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REVIEWS in MINERALOGY

and GEOCHEMISTRY
Volume 46 2002

MICAS: CRYSTAL CHEMISTRY


AND METAMORPHIC PETROLOGY
Editors
Annibale Mottana Universit degli Studi Roma Tre
Francesco Paolo Sassi Universit di Padova
James B. Thompson, Jr. Harvard University
Stephen Guggenheim University of Illinois at Chicago

FRONT COVER: Perspective view of TOT layers in Biotite down [100]


([001] is vertical), produced by CrystalMaker, Red tetrahedra contain Si
and A1, green and white octahedra contain Mg and Fe, respectively,
and yellow spheres represents the K interlayer cations. Courtesy of
Mickey Gunter, University of Idaho, Moscow. [Data: S.R. Bohlen et al.
(1980) Crystal chemistry of a metamorphic biotite and its significance in
water barometry. Am Mineral 65: 55-62]
BACK COVER: A view down [001] of lepitdolite-2M2, showing
tetrahedrally coordinated Si,A1 (blue) joined with bridging oxygens
(red thermal ellipsoids) in the T-Layer and ordered, octahedrally
coordinated A1 (gray) and Li (yellow) in the O-layer. The interlayer
cation I s12-coordinator K (green). Courtesy of Bob Downs, University
of Arizona, Tucson. [Data: S. Guggenheim (1981) Cation ordering in
lepidolite. Am Mineral 66: 1221-1232]

Series Editor for MSA: Paul H. Ribbe


Virginia Polytechnic Institute and State University

MINERALOGICAL SOCIETY of AMERICA


Washington, D.C.
ACCADEMIA NATIONALE dei LINCEI
Roma, Italia
COPYRIGHT 2002

MINERALOGICAL SOCIETY OF AMERICA


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REVIEWS IN MINERALOGY
AND GEOCHEMISTRY
( Formerly: REVIEWS IN MINERALOGY )
ISSN 1529-6466

Volume 46

MICAS: Crystal Chemistry


and Metamorphic Petrology

ISBN 0-939950-58-8

** This volume is the eighth of a series of review volumes published


jointly under the banner of the Mineralogical Society of America and
the Geochemical Society. The newly titled Reviews in Mineralogy and
Geochemistry has been numbered contiguously with the previous series,
Reviews in Mineralogy.

Additional copies of this volume as well as others in


this series may be obtained at moderate cost from:

THE MINERALOGICAL SOCIETY OF AMERICA


1015 EIGHTEENTH STREET, NW, SUITE 601
WASHINGTON, DC 20036 U.S.A.
MICAS: Crystal Chemistry and Metamorphic Petrology
Reviews in Mineralogy and Geochemistry Volume 46 2002

FORWARD
The editors and contributing editors of this volume participated in a short course on
micas in Rome late in the year 2000. It was organized by Prof. Annibale Mottana and
several colleagues (details in the Preface below) and underwritten by the Italian National
Acadmey, Accademai Nationale dei Lincei (ANL). The Academy subsequently joined
with the Mineralogical Society of America (MSA) in publishing this volume. MSA is
grateful for their generous involvement.
I am particularly thankful to Prof. Mottana for Herculean efforts in supervising the
editing of twelve manuscripts from six countries and submitting a single package
containing everything needed to compile this volume! This was a uniquely positive
experience fro me as Series editor for MSA. Assembling this volume was made tolerable
by the exceptional efforts of Steve Guggenheim. During recovery from spinal surgery he
spent three weeks painstakingly (no pun) correcting grammar and wording of the many
authors from whom English is not their first language. Special thanks to him and the
gracious and patient authors who suffered the extra work of assimilating both Steves
suggestions and mine, above and beyond those of their reviewers and the editors. MSAs
Executive Director, Alex Speer, made all the contractual arrangements with ANL.
This is the second of what we hope will be many co-operative projects with
international colleagues and members of MSA. The first was in the year 2000:
Transformation Processes in Minerals, RiMG 39, the proceedings of a short course at
Cambridge University in partnership with four European scientific societies.
Paul H. Ribbe, Series editor
Blacksburg, Virginia
April 20, 2002

PREFACE
Micas are among the most common minerals in the Earth crust: 4.5% by volume.
They are widespread in most if not all metamorphic rocks (abundance: 11%), and
common also in sediment and sedimentary and igneous rocks. Characteristically, micas
form in the uppermost greenschist facies and remain stable to the lower crust, including
anatectic rocks (the only exception: granulite facies racks). Moreover, some micas are
stable in sediments and diagenetic rocks and crystallize in many types of lavas. In
contrast, they are also present in association with minerals originating from the very
deepest parts of the mantlethey are the most common minerals accompanying diamond
in kimberlites.
The number of research papers dedicated to micas is enormous, but knowledge of
them is limited and not as extensive as that of other rock-forming minerals, for reasons
mostly relating to their complex layer texture that makes obtaining crystals suitable for
careful studies with the modern methods time-consuming, painstaking work.
Micas were reviewed extensively in 1984 (Reviews in Mineralogy 13, S.W. Bailey,
editor). At that time, Micas volume covered most if not all aspects of mica
knowledge, thus producing a long shelf-life for this book. Yet, or perhaps because of that

iii
1529-6466/02/0046-0000$05.00 DOI: 10.2138/rmg.2002.46.0
excellent review, mica research was vigorously renewed, and a vast array of new data has
been gathered over the past 15 years. These data now need to be organized and reviewed.
Furthermore, a Committee nominated by the International Mineralogical Association in
the late 1970s concluded its long-lasting work (Rieder et al. 1998) by suggesting a new
classification scheme which has stimulated a new chemical and structural research on
micas. To make a very long story short:
- the extraordinarily large, but intrinsically vague, micas nomenclature developed
during the past two centuries has been reduced from >300 to just 37 species names
and 6 series (see page xiii, preceding Chapter 1);
- the new nomenclature shows wide gaps that require data involving new chemical and
structural work;
- the suggestion of using adjectival modifiers for those varieties that deviate away from
end-member compositions requires the need fro new and accurate measurements,
particularly fro certain light elements and volatiles;
- the use of polytype suffixes based on the modified Gard symbolism created better
ways of determining precise stacking sequences. This resulted in new polytypes being
discovered.
Indeed, all this has happened over the past few years in an almost tumultuous way.
It was on the basis of these developments that four scientists (B. Zanettin, A.
Mottana, F.P. Sassi and C. Cipriani) applied to Accademia Nazionale dei Linceithe
Italian National Academyfor a meeting on micas. An international meeting was
convened in Rome on November 2-3, 2000 with the title Advances on Micas (Problems,
Methods, Applications in Geodynamics). The topics of this meeting were the crystal-
chemical, petrological, and historical aspects if the micas. The organizers were both
Academy members (C. Cipriani, A. Mottana, F.P. Sassi, W. Schreyer, J.B. Thompson Jr.,
and B. Zanettin) and Italian scientist well-known for their studies on layer silicates
(Professors M.F. Brigatti and G. Ferraris). Financial support in addition to that by the
Academy was provided by C.N.R. (the Italian National Research Council), M.U.R.S.T.
(the Italian Ministry for University, Scientific Research and Technology) and the
University of Rome III. Approximately 200 scientists attended the meeting, most of them
Italians, but, with a sizeable international participation. Thirteen invited plenary lectures
and six oral presentations were given, and fourteen posters were displayed.
The amount of information presented was large, although the organizers made it very
clear that the meeting was to be limited to only a few of the major topics of micas studies.
Other studies are promised for a later meeting. Oral and poster presentations on novel
aspects of mica research are being printed in the European Journal of Mineralogy, as
apart of an individual thematic issue: indeed thirteen papers have appeared in the
November 2001 issue. The plenary lectures, which consisted mostly of reviews, are
presented in expanded detail in this volume.
This book is the first a co-operative project between Accademia Nazionale dei Lincei
and Mineralogical Society of America. Hopefully, future projects will involve reviews of
the remaining aspects of mica research, and other aspects of mineralogy and
geochemistry.
The entire meeting was made successful through a co-operative effort. The editing of
this book was achieved by a co-operative effort of two Italian Academy members from
one side, and by two American scientists from the other side, one of them (JBT) being
also a member of Lincei Academy. The entire editing process benefited from the
goodwill of many referees, both from those attending Rome meeting and from several
who did not. In all the reviewers were distinguished expert of the international
iv
community of mica scholars. Their work, as well as our editing work, were aided greatly
by RiMG Series Editor, Professor Paul Ribbe, who continuously supported the efforts
with all his professional experience and friendly advice. We, the co-editors, thank them
all very warmly, but take upon ourselves all remaining shortcomings: we are aware that
some shortcomings may be present in spite of all our efforts to avoid them Moreover, we
are aware that there are puzzling aspects of micas that are unresolved. Please consider all
these possible avenues for future research!
Annibale Mottana (Rome)
Francesco Paolo Sassi (Padua)
James B. Thompson, Jr. (Cambridge, Mass.)
Stephen Guggenheim (Chicago)

v
Nomenclature of Micas
MICA SIMPLIFIED FORMULA: I M2-3 1-0 T4 O10 A2
where
I = Cs, K, Na, NH4, Rb, Ba, Ca
M = Li, Fe (2+, 3+), Mg, Mn, Zn, Al, Cr, V, Ti
= vacancy
T = Be, Al, B, Fe(3+), Si
A = Cl, F, OH, O, S

MICA SERIES NAMES: biotite


glauconite
illite
lepidolite
phengite
zinnwaldite

INTERLAYER-
TRUE MICAS BRITTLE MICAS
DEFICIENT MICAS
Dioctahedral Trioctahedral Dioctahedral Trioctahedral Dioctahedral Trioctahedral
muscovite annite margarite clintonite illite wonesite
aluminoceladonite phlogopite chernykhite bityite glauconite
ferro-alumino- siderophyllite anandite brammallite
celadonite
celadonite eastonite kinoshitalite
ferroceladonite hendricksite
roscoelite montdorite
chromphyllite tainiolite
boromuscovite polylithionite
paragonite trilithionite
nanpingite masutomilite
tobelite norrishite
tetra-ferri-annite
tetra-ferri-
phlogopite
aspidolite
preiswerkite
ephesite

FORWARD
The editors and contributing editors of this volume participated in a short course on micas in
Rome late in the year 2000. It was organized by Prof. Annibale Mottana and several colleagues
(details in the Preface below) and underwritten by the Italian National Acadmey, Accademai
Nationale dei Lincei (ANL). The Academy subsequently joined with the Mineralogical Society
of America (MSA) in publishing this volume. MSA is grateful for their generous involvement.
I am particularly thankful to Prof. Mottana for Herculean efforts in supervising the editing of
twelve manuscripts from six countries and submitting a single package containing everything
needed to compile this volume! This was a uniquely positive experience fro me as Series editor
for MSA. Assembling this volume was made tolerable by the exceptional efforts of Steve
Guggenheim. During recovery from spinal surgery he spent three weeks painstakingly (no pun)
correcting grammar and wording of the many authors from whom English is not their first
language. Special thanks to him and the gracious and patient authors who suffered the extra work
of assimilating both Steves suggestions and mine, above and beyond those of their reviewers
and the editors. MSAs Executive Director, Alex Speer, made all the contractual arrangements
with ANL.
This is the second of what we hope will be many co-operative projects with international
colleagues and members of MSA. The first was in the year 2000: Transformation Processes in
Minerals, RiMG 39, the proceedings of a short course at Cambridge University in partnership
with four European scientific societies.
PaulH.Ribbe,Serieseditor
Blacksburg,Virginia
April20,2002

iii
1529-6466/02/0046-0000$05.00 DOI: 10.2138/rmg.2002.46.0f

PREFACE
Micas are among the most common minerals in the Earth crust: 4.5% by volume.
They are widespread in most if not all metamorphic rocks (abundance: 11%), and
common also in sediment and sedimentary and igneous rocks. Characteristically, micas
form in the uppermost greenschist facies and remain stable to the lower crust, including
anatectic rocks (the only exception: granulite facies racks). Moreover, some micas are
stable in sediments and diagenetic rocks and crystallize in many types of lavas. In
contrast, they are also present in association with minerals originating from the very
deepest parts of the mantlethey are the most common minerals accompanying diamond
in kimberlites.
The number of research papers dedicated to micas is enormous, but knowledge of
them is limited and not as extensive as that of other rock-forming minerals, for reasons
mostly relating to their complex layer texture that makes obtaining crystals suitable for
careful studies with the modern methods time-consuming, painstaking work.
Micas were reviewed extensively in 1984 (Reviews in Mineralogy 13, S.W. Bailey,
editor). At that time, Micas volume covered most if not all aspects of mica
knowledge, thus producing a long shelf-life for this book. Yet, or perhaps because of that

excellent review, mica research was vigorously renewed, and a vast array of new data has
been gathered over the past 15 years. These data now need to be organized and reviewed.
Furthermore, a Committee nominated by the International Mineralogical Association in
the late 1970s concluded its long-lasting work (Rieder et al. 1998) by suggesting a new
classification scheme which has stimulated a new chemical and structural research on
micas. To make a very long story short:
- the extraordinarily large, but intrinsically vague, micas nomenclature developed
during the past two centuries has been reduced from >300 to just 37 species names
and 6 series (see page xiii, preceding Chapter 1);
- the new nomenclature shows wide gaps that require data involving new chemical and
structural work;
- the suggestion of using adjectival modifiers for those varieties that deviate away from
end-member compositions requires the need fro new and accurate measurements,
particularly fro certain light elements and volatiles;
- the use of polytype suffixes based on the modified Gard symbolism created better
ways of determining precise stacking sequences. This resulted in new polytypes being
discovered.
Indeed, all this has happened over the past few years in an almost tumultuous way.
It was on the basis of these developments that four scientists (B. Zanettin, A.
Mottana, F.P. Sassi and C. Cipriani) applied to Accademia Nazionale dei Linceithe
Italian National Academyfor a meeting on micas. An international meeting was
convened in Rome on November 2-3, 2000 with the title Advances on Micas (Problems,
Methods, Applications in Geodynamics). The topics of this meeting were the crystal-
chemical, petrological, and historical aspects if the micas. The organizers were both
Academy members (C. Cipriani, A. Mottana, F.P. Sassi, W. Schreyer, J.B. Thompson Jr.,
and B. Zanettin) and Italian scientist well-known for their studies on layer silicates
(Professors M.F. Brigatti and G. Ferraris). Financial support in addition to that by the

iii
1529-6466/02/0046-0000$05.00 DOI: 10.2138/rmg.2002.46.0p

Academy was provided by C.N.R. (the Italian National Research Council), M.U.R.S.T.
(the Italian Ministry for University, Scientific Research and Technology) and the
University of Rome III. Approximately 200 scientists attended the meeting, most of them
Italians, but, with a sizeable international participation. Thirteen invited plenary lectures
and six oral presentations were given, and fourteen posters were displayed.
The amount of information presented was large, although the organizers made it very
clear that the meeting was to be limited to only a few of the major topics of micas studies.
Other studies are promised for a later meeting. Oral and poster presentations on novel
aspects of mica research are being printed in the European Journal of Mineralogy, as
apart of an individual thematic issue: indeed thirteen papers have appeared in the
November 2001 issue. The plenary lectures, which consisted mostly of reviews, are
presented in expanded detail in this volume.
This book is the first a co-operative project between Accademia Nazionale dei Lincei
and Mineralogical Society of America. Hopefully, future projects will involve reviews of
the remaining aspects of mica research, and other aspects of mineralogy and
geochemistry.
The entire meeting was made successful through a co-operative effort. The editing of
this book was achieved by a co-operative effort of two Italian Academy members from
one side, and by two American scientists from the other side, one of them (JBT) being
also a member of Lincei Academy. The entire editing process benefited from the
goodwill of many referees, both from those attending Rome meeting and from several
who did not. In all the reviewers were distinguished expert of the international
community of mica scholars. Their work, as well as our editing work, were aided greatly
by RiMG Series Editor, Professor Paul Ribbe, who continuously supported the efforts
with all his professional experience and friendly advice. We, the co-editors, thank them
all very warmly, but take upon ourselves all remaining shortcomings: we are aware that
some shortcomings may be present in spite of all our efforts to avoid them Moreover, we
are aware that there are puzzling aspects of micas that are unresolved. Please consider all
these possible avenues for future research!
Annibale Mottana (Rome)
Francesco Paolo Sassi (Padua)
James B. Thompson, Jr. (Cambridge, Mass.)
Stephen Guggenheim (Chicago)

iv
MICAS: CRYSTAL CHEMISTRY
and METAMORPHIC PETROLOGY
Editors: A Mottana, F P Sassi, J B Thompson, Jr & S Guggenheim

Table of Contents

1 Mica Crystal Chemistry and the Influence of Pressure,


Temperature, and Solid Solution on Atonlistic Models
Maria Franca Brigatti, Stephen Guggenheim
OVERVIEW 1
Treatment of the data and definition of the parameters used 3
End-member crystal chemistry: New end members and new data since 1984 .4
Synthetic micas with unusual properties 11
EFFECT OF COMPOSITION ON STRUCTURE ., 1I
Tetrahedral sheet 11
Tetrahedral rotation and interlayer region 19
Tetrahedral cation ordering 25
Octahedral coordination and long-range octahedral ordering 27
Crystal chemistry of micas in plutonic rocks 37
ATOMISTIC MODELS INVOLVING HIGH-TEMPERATURE STUDIES OF THE MICAS 39
Studies of samples having undergone heat treatment 39
Dehydroxylation process for dioctahedral phyllosilicates .41
Dehydroxylation models for trans-vacant 2: 1 layers 43
Dehydroxy lation models for cis-vacant 2: 1 layers 44
Compalison of Na-rich vs. K-rich dioctahedral forms .49
Heat-treated trioctahedral samples: The O,OH,F site and in situ high-temperature studies 50
Heat-treated trioctahedral samples: Polytype comparisons 51
ACKNOWLEDGMENTS 51
APPE~DIX I: DERIV ATIONS 52
Derivation of "tetrahedral cation displacement", T di sp 52
Derivation of f1E 1, f1E 2 , f1E 3 52
Derivation of ex 53
Explanation of O[eor 54
Explanation of E M - o(4) 54
APPENDIX II: TABLES 1-4 55
Table 1a. Structural details of trioctahedral true micas-l M, space group C2/m 55
Table 1b. Structural details of trioctahedral true micas-1M, space group C2 70
Table Ie. Structural details of trioctahedral true micas-2M], space group C2/c 72
Table Id. Structural details oftrioctahedral true micas-2M J , space groups Ce. Cl 74
Table Ie. Structural details of trioctahedral true micas-2M 2 , space group C2!c 74
Table I f. Structural details of trioctahedral true micas-3T, space group P3,12 74
Table 2a. Structural details of trioctahedral true micas-I M, Mspace groups C2/m and C2 76
Table 2b. Structural details of trioctahedral true micas-1M, space group C2/c 78
Table 2c. Structural details of trioctahedral true micas-2M, space group C2/e 84
Table 2d. Structural details of trioctahedral true micas-3T, space group P3 J 12 84
Table 3a. Structural details of trioctahedral brittle micas 86
Table 3b. Structural details of dioctahedral brittle micas 88
Table 4. Structural details of boromuscovite-I M and -2M) calculated from the
Rietveld structure refinement by Liang et al. (1995) 88
REFERENCES 90

Vll
2 Behavior of Micas at High Pressure
and High Temperature
Pier Francesco Zanazzi, Alessandro Pavese

INTRODUCTION 99
Investigati ve techniques for the study of the thennoelastic behav ior of mi cas 100
p- V and P- V- T equations of state 10 1
Dioc tahed ral micas 103
Tri oc tahedral mi cas 108
ACKNOWLEDGMENTS ] 14
REFERENCES 114

3 Structural Features of Micas


Giovanni Ferraris, Gabriella Ivaldi
INTRODUCTION 117
NOMENCLATURE AND NOTATION 1] 7
MODULARITY OF MICA STRUCTURE 118
The mica module 118
CLOSEST-PACKING aspects ]20
Closest-packing and polytypism 121
COMPOSITIONAL ASPECTS 122
SYMMETRY ASPECTS 124
Metric (lattice) symmetry ] 24
Structural symmetry 124
Symmetry and cation sites 125
Two kinds of mica layer: Ml and M2Iayers 127
The interlayer configuration 128
Possible ordering schemes in the MDO polytypes 129
The phengite case 130
DISTORTIONS 130
The misfit 130
Geo metric parameters describing distortions 131
Ditngonal rotation 131
Other distortions 132
Effects of the distortions on the stacking mode 133
FURTHER STRUCTURAL MODIFICATION 135
Pressure, temperature and chemical influence 135
Thickness of the mica module 135
Ditrigonal rotation and interlayer coordination 137
Effective coordination number (ECoN) 13 8
CONCLUSIONS 138
APPENDIX I: MICA STRUCTURE AND POLYSOMATIC SERIES 140
Layer silicates as members of modular series ? 140
Mica modules in polysomatic series 140
The heterophyllosicate polysomatic series 140
The palysepiole polysomatic series 142
Conclusions 143
APPENDIX II : OBLIQUE TEXTURE ELECTRON DIFFRACTION (OTED) 144
ACKNOWLEDGMENTS 148
REFERENCES 148

Vlll
4 Crystallographic Basis of Polytypism and Twinning in Micas
Massimo Nespolo, SlavomiJ Durovic

IN1RODUCTION 155
NOTATION AND DEFINITIONS 156
The mica layer and its constituents 157
Axial settings, indices and lattice parameters 158
Symbols 158
Symmetry and symmetry operations 159
THE UNIT LAYERS OF MICA 159
Alternative unit layers 160
MICA POLYTYPES AND THEIR CHARACTERIZATION 164
Micas as 0D structures 164
SYMBOLIC DESCRIPTION OF MICA POLYTYPES 172
Orientational symbols 172
Rotational symbols 175
RETICULAR CLASSIFICATION OF POLYTYPES: 178
SPACE ORIENTATION AND SYMBOL DEFINITION 178
LOCAL AND GLOBAL SYMME1RY OF MICA POLYTYPES
FROM THEIR STACKING SyMBOLS 180
Derivation of MDO polytypes 180
The symmetry analysis from a polytype symbol 184
RELATIONS OF HOMOMORPHY AND CLASSIFICATION OF MDO POLYTYPES 189
BASIC S1RUCTURES AND POLYTYPOIDS. SIZE LIMIT FOR THE
DEFINITION OF "POLYTYPE" 191
Abstract polytypes 192
Basic structures _ 193
H1REM observations and some implications 193
IDEAL SPACE-GROUP TYPES OF MICA POLYTYPES AND
DESYMME1RIZATION OF LAYERS IN POLYTYPES 193
CHOICE OF THE AXIAL SETTING 204
GEOME1RICAL CLASSIFICATION OF RECIPROCAL LATTICE ROWS 206
SUPERPOSITION S1RUCTURES,
FAMILY S1RUCTURE AND FAMILY REFLECTIONS 209
Family structure and family reflections of mica polytypes 212
REFLECTION CONDITIONS 213
NON-FAMILY REFLECTIONS AND ORTHOGONAL PLANES 214
HIDDEN SYMME1RY OF THE MICAS: THE RHOMBOHEDRAL LATTICE 216
TWINNING OF MICAS: THEORY 217
Choice of the twin elements 219
Effect of twinning by selective merohedry on the diffraction pattern 220
Diffraction patterns from twins 223
Allotwinning 224
Tessellation of the hp lattice 224
Plesiotwinning 230
TWINNING OF MICAS. ANALYSIS OF THE GEOME1RY OF
THE DIFFRACTION PATTERN 233
Symbolic description of orientation of twinned mica individuals. Limiting symmetry 235
Derivation of twin diffraction patterns 237
Derivation of allotwin diffraction patterns 243
IDENTIFICATION OF MDO POLYTYPES FROM THEIR DIFFRACTION PATTERNS 244
Theoretical background 244
Identification procedure 245
IDENTIFICATION OF NON-MOO POLYTYPES:
THE PERIODIC INTENSITY DISTRIBUTION FUNCTION 247
PID in tenns of TS unit layers 249
Derivation of PID from the diffraction pattern 251

ix
EXPERIMENTAL INVESTIGATION OF MICA SINGLE CRYSTALS FOR
TWIN I POLYTYPE IDENTIFICATION 252
Morphological study 252
Surface microtopography 252
Two-dimensional XRD study 254
Diffractometer study 256
APPLICATIONS AND EXAMPLES 257
24-layer subfamily: A Series I Class b biotite from Ambulawa, Ceylon 257
8A 2 (subfamily ~ Series O.Class a3) oxybiotit~ from Ruiz Peak, .New Mexico 258
1M-2M] oxyblOtlte allotwm ZT = 4 from RUiZ Peak, New Mexlco 262
{3,6}[7 {3,6}] biotite plesiotwin from Sambagawa, Japan 262
APPENDIX A. TWINNING: DEFINITION AND CLASSIFICATION 267
APPENDIX B. COMPUTATION OF THE PID FROM A
STACKING SEQUENCE CANDIDATE 270
Symlnetry of the PID 271
ACKNOWLEDGMENTS 272
REFERENCES 272

5 Investigations of Micas
Using Advanced Transmission Electron Microscopy
Toshihiro Kogure
INTRODUCTION ,.281
TEMS AND RELATED TECHNIQUES FOR THE INVESTIGATION OF MICA 281
Transmission electron microscopy 281
New recording media for beam-sensitive specimens 286
Sample preparation techniques ,.287
Image processing and simulation ,288
ANALYSES OF POLYTYPES , , 289
DEFECT STRUCTURES 299
CONCLUSION 310
ACKNOWLEDGMENTS 31 0
REFERENCES 310

6 Optical and Mossbauer Spectroscopy of Iron in Micas


M. Darby Dyar
INTRODUCTION 313
OPTICAL SPECTROSCOPY 315
Current instrumentation 315
Review of existing work 316
Sunlmary 320
MOSSBAUER SPECTROSCOPY (MS) 320
Current instrumentation 320
Recoil-free fraction effects 320
Thickness effects 321
Texture effects and other sources of error 322
Techniques for fitting Mossbauer spectra 323
Review of existing Mossbauer data 325
Sumlnary 333
COMPARISON OF TECHNIQUES 334
CONCLUSIONS 336
ACKNOWLEDGMENTS 337
APPENDIX: Other techniques for measurement of Fe 3+/LFe in Micas 337
X-ray ray photoelectron spectroscopy (XPS) 337
Electron energy-loss spectroscopy (EELS) 338
X-Ray absorption spectroscopy (XAS) 338
REFERENCES , 340

x
7 Infrared Spectroscopy of Micas
Anton Beran

INTRODUCTION 351
LATTICE VIBRATIONS 352
Far-IR region 352
Mid-IR regi on 353
OH STRETCHING VIERATIONS 359
Polarized measurements 359
Quantitative water determination 360
Hydrogen bonding 360
Cation ordering 362
OH-F replacement 365
Dehydroxylati on mechanisms 366
Excess hydroxyl 367
NH4 groups 367
ACKNOWLEDGMENTS 367
REFERENCES 367

8 X-Ray Absorption Spectroscopy of the Micas


Annibale Mottana, Augusto Marcelli,
Giannantonio Cibin, and M. Darby Dyar

INTRODUCTION 371
OVERVIEW OF THE XAS METHOD 373
EXAFS 375
XANES 37 6
Experimental spectra recording 384
Optimizati on of spectra 387
Systematics 395
AC KNOWLEDGMENTS .404
REFERENCES .405

9 Constraints on Studies of Metamorphic K-Na White Micas


Charles V. Guidotti, Francesco P. Sassi
INTRODUCTION 41 3
EFFECTS OF PETROLOGIC FACTORS ON WHITE MICA CHEMISTRy .41 4
Important compOSitional vari ations 41 4
Controls of mica composition by petrologic factors .41 8
MAXIMIZING INFORMATION FROM MICA STUDIES :
SAMPLE SELECTION CONSTRAINTS .4 23
Petrologic studies 4 24
Mine ralogic studies .42 8
DISCUSSION 440
Common failing s in petrology studies .44 0
Common failings in mineralogy studies 44I
"Standard starting points" for the compositional variations of
rock-forming dioctahedral and trioctahedral micas 44 1
ACKNOWLEDGMENTS 443
REFERENCES 444

Xl
10 Modal Spaces for Pelitic Schists
James B. Thompson, Jr.

INTRODUCTION 449
NOTATIONS AND CONVENTIONS .450
THE ASSEMBLAGE QUARTZ-MUSCOVITE-BIOTITE-CHLORITE-GARNET. .451
THE ASSEMBLAGE QUARTZ-MUSCOVITE-CHLORITE-
GARNET-CHLORITOID 4 54
ASSEMBLAGES CONTAINING CHLORITOID AND BIOTITE .455
OTHER MODAL SPACES .458
ACKNOWLEDGMENTS .458
APPENDIX : INDEPENDENT NET-TRANSFER REACTIONS .460
REFERENCES 462

11 Phyllosilicates in Very Low-Grade Metamorphism:


Transformation to Micas
Peter Arkai
I.NTRODUCTION 463
MAIN METHODS OF STUDYING LOW-TEMPERATURE TRANS FORMATIONS OF
PHYLLOSILICATES 464
XRD techniques 465
TEM techniques .466
~AIN TRENDS OF PHYLLOSILICATE EVOLUTION AT LOW TEMPERATURE .467
CURRENT PROBLEMS IN STUDYING PHYLLOSILICATE EVOLUTION AT
THE LOWER CRYSTALLITE-SIZE LIMITS OF MINERALS .469
REACTION PROGRESS OF PHYLLOSILICATES THROUGH SERIES OF
METASTABLE STAGES 472
CONCLUDING REMARKS .473
ACKNOWLEDGMENTS .474
REFERENCES .474

12 Micas: Historical Perspective


Curzio Cipriani
INTRODUCTION 4 79
PRESCIENTIFIC ERA 4 79
THE EIGHTEENTH CENTURy .480
THE NINETEENTH CENTURy .483
Physical properties 4 83
Crystallography 485
Chemical composition .486
THE TWENTIETH CENTURY 491
Crystal chemistry 491
Synthesis 494
POLYTYPES 494
SYSTEMATICS 49 5
CONCLUSIONS .496
REFERENCES 497
APPENDIX I
Present-day nomenclature of the mica group and its derivation .498
APPENDIX II
Other works consulted in preparation of this historical review .499

XlI
1 Mica Crystal Chemistry and the Influence of Pressure,
Temperature, and Solid Solution on Atomistic Models
Maria Franca Brigatti
Dipartimento di Scienze della Terra
Universit di Modena e Reggio Emilia,
Via S. Eufemia, 19
I-41100 Modena, Italy
brigatti@unimo.it
Stephen Guggenheim
Department of Earth and Environmental Sciences
University of Illinois at Chicago
845 West Taylor Street, M/C 186
Chicago, Illinois 60607
xtal@uic.edu

OVERVIEW
The 2:1 mica layer is composed of two opposing tetrahedral (T) sheets with an
octahedral (M) sheet between to form a TMT layer (Fig. 1a). The mica structure has a
general formula of A M2-3 T4 O10 X2 [in natural micas: A = interlayer cations, usually K,
Na, Ca, Ba, and rarely Rb, Cs, NH4, H3O, and Sr; M = octahedral cations, generally Mg,
Fe2+, Al, and Fe3+, but other cations such as Li, Ti, V, Cr, Mn, Co, Ni, Cu, and Zn can
occur also in mica species; T = tetrahedral cations, generally Si, Al and Fe3+ and rarely B
and Be; X = (OH), F, Cl, O, S]. Vacant positions (symbol: ) are also common in the
mica structure (Rieder et al. 1998). In the tetrahedral sheet, individual TO4 tetrahedra are
linked with neighboring TO4 by sharing three corners each (i.e., the basal oxygen atoms)
to form an infinite two-dimensional hex agonal mesh pattern (Fig. 1b). The fourth
oxygen atom (i.e., the apical oxygen atom) forms a corner of the octahedral coordination
unit around the M cations. Thus, each octahedral anion atom-coordination unit is
comprised of four apical oxygen atoms (two from the upper and two from the lower
tetrahedral sheet) and by two (OH) or F, Cl, O and S anions [the X anions, usually
indicated as the OH or O(4) site]. The OH site is at the same level as the apical oxygen
but not shared with tetrahedra. In the octahedral sheet, individual octahedra are linked
laterally by sharing octahedral edges (Fig. 1c). The smallest structural unit contains three
octahedral sites. Structures with all three sites occupied are known as trioctahedral,
whereas, if only two octahedra are occupied [usually M(2)] and one is vacant [usually
M(1)], the structure is defined as dioctahedral. The 2:1 layers, which are negatively
charged, are compensated and bonded together by positively charged interlayer cations of
the A site. The layer charge ideally is -1.0 for true micas and -2.0 for brittle micas. Thus,
in true micas, the layer charge is compensated by monovalent A cations, whereas in
brittle micas it is compensated primarily by divalent A cations.
In this section, we consider and discuss the structural and chemical features of more
than 200 micas. Most are true micas (146 trioctahedral and 55 dioctahedral). Brittle-mica
crystal-structure refinements number about twenty, of which only three are dioctahedral
(Tables 1-4, at the end of the chapter). Of the six simple polytypes first derived by Smith
and Yoder (1956) and reported by Bailey (1984a, p. 7), only five (i.e., 1M, 2M1, 3T, 2M2,
and 2O) have been found and studied by three-dimensional crystal-structure refinements.

1529-6466/02/0046-0001$10.00 DOI: 10.2138/rmg.2002.46.01


2 Brigatti & Guggenheim

Figure 1. (a) The 2:1 layer; (b) the hexagonal tetrahedral ring; (c) the octahedral sheet. For site
nomenclature see text. a and b are unit cell parameters.

Most of the trioctahedral true-mica structures are 1M polytypes and a few are 2M1, 2M2,
and 3T polytypes. In dioctahedral micas, the 2M1 sequence dominates, although 3T and
1M structures have been found. Brittle mica crystal-structure refinements indicate that the
1M polytype is generally trioctahedral whereas the 2M1 polytype is dioctahedral. The 2O
structure has been found for the trioctahedral brittle mica, anandite (Giuseppetti and
Tadini 1972; Filut et al. 1985) and recently was reported for a phlogopite from Kola
Peninsula (Ferraris et al. 2000). The greatest number of the reported structures were
refined from single-crystal X-ray diffraction data, with only a few obtained from electron
and neutron diffraction experiments.
Subsequent sections of this paper present short reviews pertaining to the description
of phyllosilicates, an emphasis of the literature since the publication of MICAS, Reviews
in Mineralogy, Volume 13, edited by S.W. Bailey (1984a), and a new analysis of the
crystal chemistry of the micas. New formulae are presented to clarify how crystal
chemistry affects the mica structure. Derivations of these formulae are provided in
Appendix I. Also, please refer to other chapters in this volume that cover related topics.
For example, see Zanazzi and Pavese for the behavior of micas at high pressure and high
temperature.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 3

Treatment of the data and definition of the parameters used


To achieve standardization, all data in Tables 1-4 (Appendix II) were re-calculated
from unit-cell parameters and atomic coordinates reported by the authors of the original
articles. Information concerning rock type and sample composition was obtained from the
original works as well. Suspect refinements are discussed separately or not reported. Of
more than 200 reported crystal-structure refinements, about twenty refinements show an
agreement factor, R, greater that 9.0%. These structures are considered of poor quality
and are not considered further.
Several authors used symbols and orientations that differ from convention to
describe geometric arrangements of the layer and the stacking sequence of mica
polytypes (e.g., Radoslovich 1961; Durovc 1994; Dornberger-Schiff et al. 1982). To
make inter-structure comparisons of features easier, however, it is advantageous to define
briefly the site nomenclature adopted and the parameters used to describe and
characterize layer geometry. The direction defined by the stacking of 2:1 units defines the
[001] direction (i.e., the c axis), whereas the periodicity of the infinite two-dimensional
sheets defines [100] and [010] directions (i.e., a and b translations). The actual value of
the repeat distance in the [001] direction, as well as lateral a and b parameters, depends
on several factors, such as the layer stereochemistry and polytypism (i.e., c 10 n,
where n identifies the number of layers involved in the stacking sequence). The site-
nomenclature scheme adopted here starts from the nomenclature generally used for the
2:1 layer of the 1M polytype in C2/m symmetry: T denotes the four-coordinated site,
M(1) and M(2) indicate six-coordinated sites with (OH) groups in trans- and cis-
orientation, respectively, A refers to the interlayer cation, O(1) and O(2) represent the
basal tetrahedral oxygen atoms, O(3) is the apical oxygen atom, and O(4) refers to the
(OH), F, Cl, S or O anions (Fig. 1a). The number of sites per unit cell is: T = 8; M(1) = 2;
M(2) = 4; A = 2; O(1) = 8; O(2) = 4; O(3) = 8; O(4) = 4. The site nomenclature for other
structural variants can be derived from this nomenclature by changes that relate to space-
group differences and to the number of 2:1 layers per unit cell.
The definition of parameters reported in Tables 1-4 (Appendix II) follows. For a
more extensive review on definition and structural significance of these parameters, see
Bailey (1984b) and references therein.
Cation-anion bond lengths: (i) tetrahedral TO; (ii) octahedral MO,OH,F,Cl,S
for both M(1) and M(2) sites; and (iii) interlayer AO. Mean bond lengths were
compared to those of the original papers and vacant-site distances determined (i.e.,
vacancy-to-anion distances).
The tetrahedral OapicalTObasal angles were used to obtain the tetrahedral flattening
angle, = 3i=1 OapicalTObasal)i/3.
The internal angles of the tetrahedral ring were used to determine the tetrahedral
rotation angle, = 6i=1 i / 6 where i = |120 i|/2 and i is the angle between basal
edges of neighboring tetrahedra articulated in the ring. Basal oxygen-plane corrugation,
z, was determined by z = (zObasal(max) zObasal(min)) c sin.
The thickness of the tetrahedral and octahedral sheets was calculated from oxygen z
coordinates of each polyhedron, including the OH group (or other X anions). The
interlayer separation was obtained by considering the tetrahedral basal oxygen z
coordinates of adjacent 2:1 layers.
The octahedral flattening angle was calculated from
4 Brigatti & Guggenheim

octahedral thickness
= cos 1
2 M O, OH, F, Cl, S
Tetrahedral cation atomic coordinates, taken from the original reference, were
transformed from fractional to Cartesian to calculate the Layer Offset, the Intralayer
Shift, and the Overall Shift. The Layer Offset is based on the displacement of the
tetrahedral sheet across the interlayer from one 2:1 layer to the next, which should be
equal to zero in the ideal mica structure. The Intralayer Shift is the over-shift of the upper
tetrahedral sheet relative to the lower tetrahedral sheet of the same 2:1 layer. The Overall
Shift relates to both effects.
In true micas, the tetrahedral mean bond distance varies from 1.57(1) in
boromuscovite-2M1 (Liang et al. 1995; Table 4) to 1.750(2) in an ordered (Al vs. Si)
ephesite-2M1 (Slade et al. 1987; Table 1d); in brittle micas, the TO mean bond
distance varies from 1.620(2) to 1.799(2) , both values are from anandite-2O (Filut et
al. 1985; Table 3a).
Octahedral mean bond length ranges from about 1.882(1) in an ordered ferroan
polylithionite-1M (Guggenheim and Bailey 1977; Brigatti et al. 2000b; Table 1b) to
2.236(1) in anandite 2O (Filut et al. 1985; Table 3a). The radius of the vacant M(1) site
in dioctahedral micas (M(1)O) varies from 2.190 to 2.259 . The shortest AOinner
distance occurs in clintonite (AOinner = 2.397(2) ; Alietti et al. 1997, Table 3a),
whereas the longest distance occurs in nanpingite and synthetic Cs-tetra-ferri-annite (A
O inner of 3.370 ; Ni and Hughes 1996 and Mellini et al. 1996, Tables 1c and 1a,
respectively). These data show the great variability in bond distances which may be
ascribed not only to the local composition but also to the constraints of closest packing
within the layer and the confinement of the octahedra between two opposing tetrahedral
sheets. We consider the compositional and topological relationships in the following
analysis.
End-member crystal chemistry: New end members and new data since 1984
Boromuscovite. Boromuscovite was first reported by Foord et al. (1991). The
mineral, precipitated from a late-stage hydrothermal fluid (T: 350-400C; P: 1-2 kbar),
occurred in the New Spaulding Pocket, Little Three Mine pegmatite dike (Ramona
district, San Diego County, California), as a fine-grained coating of quartz, polylithionite,
microcline and topaz. The mineral was found also in elbaite pegmatite at Recice near
Mov Mesto na Morave, western Moravia, Czech Republic (Liang et al. 1995; Novk et
al. 1999). Relatively high B contents were also reported for muscovite and polylithionite
from polylithionite-rich pegmatites of Rozn and Dobr Voda, Czech Republic (Cerny et
al. 1995), for polylithionite-2M1 from Recice (Novk et al. 1999), and for muscovite from
metapegmatite at Stoffhtte, Koralpe, Austria (Ertl and Brandsttter 1998).
Boromuscovite (Foord et al. 1991) has the general structural formula of
KAl2 (Si3B) O10(OH)2, in which [4]Al is replaced by [4]B relative to muscovite. The
composition of Little Three Mine boromuscovite is
(K0.89Rb0.02Ca0.01)(Al1.93Li0.01Mg0.01)(Si3.06B0.77Al0.17) O9.82F0.16(OH)2.02, whereas the
composition of Recice boromuscovite shows a slightly lower [4]B content:
(K0.89Na0.01)(Al1.99Li0.01)(Si3.10B0.68Al0.22)O10F0.02(OH)1.98. The unit cell parameters, very
similar in natural and synthetic crystals (Schreyer and Jung 1997), are significantly
smaller than those reported for muscovite (a = 5.075(1), b = 8.794(4), c = 19.82(3) ,
= 95.59(3) and a = 5.077(1), b = 8.775(3), c = 10.061(2) , = 101.31(2) for Little
Three Mine boromuscovite-2M1 and boromuscovite-1M, respectively).
A boromuscovite structure determination is complicated by the fine-grained nature
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 5

of the mineral and by the presence of the mixture of 1M and 2M1 polytypes. Nonetheless
the crystal-structure determination of a mixture of 83 wt % boromuscovite-2M1 and 17
wt % boromuscovite-1M from Recice was attempted using a coupled Rietveld-static-
structure energy-minimization method (Liang et al. 1995). Although the high standard
deviation for calculated parameters suggests caution in the analysis of crystal chemical
details, Liang et al. (1995) indicated that: (i) boron is uniformly distributed between the
two polytypes, (ii) TO distances correspond well with the B-content at the
corresponding T-sites, namely TO distances linearly decrease as B occupancy
increases, and (iii) in the 2M1 polytype, slight differences between T(1)O and T(2)
O distances may imply a B preference for the T(1) site (Table 4). The 11B MAS NMR
spectra showed a single, symmetric and narrow line (about 150 Hz wide) at 20.7 ppm.
The width was interpreted as possibly relating to the coordination for B with a near-
symmetrical disposition of anions (Novk et al. 1999).
Clintonite. Clintonite is the trioctahedral brittle mica with ideal composition of
Ca(Mg2Al)(SiAl3)O10(OH)2. This structure violates the Al-avoidance principle of Loew-
enstein (1954). It crystallizes in H2O-saturated Ca-, Al-rich, Si-poor systems under wide
P-T conditions. Clintonite, usually found in metasomatic aureoles of carbonate rocks, is
rare in nature because crystallization is limited to environments characterized by both
alumina-rich and silica-poor bulk-rock chemistry and very low CO2 and K activities
(Bucher-Nurminen 1976; Olesch and Seifert 1976; Kato et al. 1997; Grew et al. 1999).
The 1M polytype and 1Md sequences are the most common forms. The 2M1 form is rare
(Akhundov et al. 1961) and no 3T forms have been reported. Many 1M crystals are
twinned by 120 rotation about the normal to the {001} cleavage. Such twinning causes
extra spots on precession photographs that simulate an apparent three-layer periodicity
(MacKinney et al. 1988).
Subsequent to an extensive review of brittle micas (Guggenheim 1984), additional
crystal-chemical details of clintonite-1M (space group C2/m) were reported by
MacKinney et al. (1988) and Alietti et al. (1997). These studies confirmed that natural
clintonite crystals do not vary extensively in composition: (i) the octahedral sites contain
predominant Mg and Al with Fe2+ to 7% of the octahedral-site occupancy; (ii) the extent
of the substitution [4]Al-1 [6]Mg-2 [4]Si [6](Al, ), which involves the solid solution of
trioctahedral with dioctahedral Ca-bearing brittle micas, is very limited; (iii) Fe3+ content
involves tetrahedral site occupancy, but at low (<1%) concentrations; (iv) the substitution
[12]
(Na, K)-1 [4]Si-1 [12]Ca [4]Al is unlikely. Potassian clintonite (e.g., Morandi et al. 1984)
is believed to represent complex interstratifications or intergrowths between phlogopite
and clintonite, and (v) significant F for (OH) substitution is common. Although the
normal ordering pattern of a large M(1) site and two smaller M(2) sites was confirmed
for all refined clintonite crystals, different octahedral Fe2+ ordering between green and
brown crystals was detected by MacKinney et al. (1988): in green clintonite crystals, Fe2+
occupies the trans M(1) site only, whereas in brown crystals, Fe2+ is randomly distributed
over M(1) and M(2) octahedra. These distributions probably occur because of the
disordered substitution of F- for (OH)- and local FeF avoidance. Tetrahedral cations are
disordered and the tetrahedra are flattened as a consequence of the large Al (plus Fe3+)
content. The large lateral misfit of the tetrahedral and octahedral sheets is compensated
by tetrahedral in-plane rotation ( varies approximately from 23 to 25). The separation
between two adjacent layers is inversely related to . As observed by MacKinney et al.
(1988), less tetrahedral rotation and less H+-Ca repulsion, which is consistent with F- for
(OH)- substitution, allow the interlayer cation to enter more deeply in to the silicate ring,
thereby reducing the c repeat distance and cell volume appreciably (Table 3a).
Chromphyllite and chromium-containing dioctahedral micas. A dioctahedral mica
6 Brigatti & Guggenheim

with [6]Cr3+ for [6]Al3+ substitution greater than 70% was described recently by Evsyunin
et al. (1997). The crystal, from the Slyudyanka (Irkutsk region) Country, showed 2M1
stacking, and its structure was refined in space group C2/c (Table 2b). Tetrahedral mean
bond distances for both T(1) and T(2) tetrahedra do not depart significantly from those of
muscovite, whereas the octahedral M(2)O mean bond length was found to be
significantly longer, suggesting a Cr preference for the M(2) site.
Combined single-crystal structure refinements and X-ray absorption spectroscopy
studies (Brigatti et al. 2001a) suggested that, in chromium-containing muscovite crystals,
the chromium valence is trivalent and that the metal shows a distorted octahedral
coordination. Cr substitution influences generally both lateral a and b axes, whereas the c
periodicity is nearly unchanged. As the octahedral substitution of Cr for Al in the M(2)
site increases, the match between tetrahedral and octahedral sheets improves, thus leading
to a decrease in . Residual areas of positive electron density close to the M(1) site
suggest that M(1) is occupied partially, and as a consequence, the M(1) cavity is reduced
in volume and is less distorted. The reduced difference between M(1) and M(2)
octahedral volumes improves the co-planarity of tetrahedral basal oxygens.
Ephesite. Ephesite is a rare trioctahedral true mica with an ideal composition of
NaLiAl2(Si2Al2)O10(OH)2. Ephesite has the maximum Al amount found in trioctahedral
true micas. In the early literature, it was considered a brittle mica (Slade and Radoslovich
1985) because of the Al2Si2 tetrahedral content. Tetrahedral cation ordering pattern of
ephesite-1M reported by Sokolova et al. (1979) was exhaustively discussed by Bailey
(1984b). Later, two crystal-structure refinements of 2M1 crystals from Postmasburg
district (South Africa) were completed in the acentric space groups Cc and C1,
respectively. The tetrahedral and octahedral cation ordering of ephesite-2M1 in symmetry
Cc (Slade and Radoslovich 1985) was found to be similar to that of margarite-2M1
(Guggenheim and Bailey 1975, 1978), i.e., compositionally similar tetrahedra in the
lower and upper sheet of the same 2:1 layer are related by a pseudo two-fold axis normal
to the direction of the intralayer shift, passing laterally through two M(2) (Al-rich)
octahedral sites. The Al distribution between the two tetrahedral sheets is asymmetric
with [4]Al content greater in the upper than in the lower sheet. M(1) octahedra are
somewhat filled by Li, whereas M(2) octahedra are occupied by Al. However, Slade and
Radoslovich (1985) indicated that the ephesite symmetry is probably lower. They found
from Weissenberg photographs of ephesite-2M1, weak h0l reflections with l = 2n + 1,
which violate the requirements of the c glide plane and which suggest triclinic C1 space
group. In this latter space group, the tetrahedral cation ordering is more complete and
accounts for the small differences in the composition of the tetrahedral sheets in the 2:1
layer (Slade et al. 1987). A slightly different occupancy of M(1) sites was also
emphasized, owing to differences of both OH vector orientation and the isotropic
displacement factor.
Ferroceladonite and ferro-aluminoceladonite. Ferroceladonite and ferro-
aluminoceladonite were found together in an altered crystal-vitric tuff from the
Gavenwood Tuff, Murihiku Supergroup, Hokonui Hills, Southland, New Zealand (Li et
al. 1997). The representative formula of ferroceladonite and alumino-ferroceladonite is
KFe3+(Fe2+,Mg) Si4O10(OH)2 and KAl3+(Fe2+,Mg) Si4O10(OH)2, respectively, with
[6]
Mg/([6]Mg + [6]Fe2+) 0.5 and with [6]Al/([6]Al + [6]Fe3+) < 0.5 in ferroceladonite and
from 0.5 to 1.0 in aluminoferroceladonite (Rieder et al. 1998). On the basis of analyses of
homogeneous packets of ferroceladonite and alumino-ferroceladonite, Li et al. (1997)
recognized a wide variation in octahedral occupancy. They emphasized that a complete
or nearly complete solid solution exists among the four end-members of the celadonite
family (i.e., aluminoceladonite, ferro-aluminoceladonite, celadonite, and ferro-
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 7

celadonite). Lattice-fringe images of a selected-area electron diffraction pattern for both


minerals indicated a well-ordered 10- periodicity consistent with the monoclinic 1M
polytype. Unit cell parameters for a composite ferroceladonite-ferro-aluminoceladonite
sample obtained by least-squares refinement of powder X-ray data are: a = 5.270(5); b =
9.106(7), c = 10.125(8) , = 100.27(4).
Ferrokinoshitalite. Iron-rich kinoshitalite [ideally BaFe 2+ 3 Si 2 Al2 O10 (OH) 2 ] occurs in
silicate-rich bands within a high-grade, metamorphic banded iron formation enclosing
massive sulfide bodies in the Broken Hill deposit, Namaqualand Metamorphic Complex
(Aggeneys, northern Cape Province, South Africa). Ferrokinoshitalite formed at the peak
of metamorphism (T: 670 20C, P: 4.5 1kbar), at a pH below the muscovite + K-
feldspar buffer, at a f(O2) buffered by quartz + fayalite + magnetite, and at f(S2) between
10-5 and 10-7 (Frimmel et al. 1995). Ferrokinoshitalite was described as a new species of
brittle mica by Guggenheim and Frimmel (1999). The crystal structure of a ferro-
kinoshitalite-1M crystal with a chemical formula of
(Ba0.47K0.33Na0.04) (Fe1.72
2+
0.15 Ti 0.17 )(Si2.44Al1.56)O10(OH1.35F0.65)
Mg 0.74 Mn 0.08 Fe3+
showed: (i) disordered Si/Al distribution, (ii) the most common trioctahedral mica
ordering with M(1) slightly larger than M(2) [M(1)-O = 2.120; M(2)-O = 2.106 ];
and (iii) low values of the tetrahedral rotation angle ( = 3.95) because the relatively
large Fe-containing octahedra allow a good fit with the Al-rich tetrahedral sheet. A
relatively small tetrahedral rotation produces a larger size of the tetrahedral ring, thus
allowing Ba to fit better within the silicate rings. The interlayer separation in
ferrokinoshitalite, although smaller than in kinoshitalite, is still sufficient to minimize T
T electrostatic interaction between adjacent tetrahedral sheets across the interlayer to
allow a complete Si / Al tetrahedral disorder.
Illite. The term illite is commonly used in several ways. The species illite
(Bailey 1986) involves a 2:1 layer with a structure that is not expandable, a dioctahedral
sheet that is aluminous, an interlayer that is primarily K, and a composition that differs
from muscovite by substitutions of the type: [4]Si + [6](Mg,Fe2+) [4]Al + [6]Al and [4]Si +
[12]
( ,H2O) [4]Al + [12]K. A representative formula is
K0.75 (Al1.75 , R 2+
0.25 )(Si3.50Al0.50)O10 (OH)2.

Bailey (1986) suggested that the layer charge may vary between -0.6 to -0.9, although the
upper limit of -0.8 was extrapolated from the data of Hower and Mowatt (1966). The
lower limit of -0.6 was judged as a reasonable minimum without leading to possible
expandability of the structure. The general term illite (Grim et al. 1937) is for a clay
mineral that is a discrete and non-expandable mica of detrital or authigenic origin, where
the exact nature of the mica is unknown. Finally, the third use is for the micaceous
component of an interstratified system, such as illite-smectite. Material that includes an
expandable component is referred to as illitic material and not illite. Rieder et al.
(1998) recognized the wide variation in possible compositions for illite and defined a
series name for illite. The layer charge with an upper limit of -0.85 for illite was
determined so that muscovite from metamorphic regimes, which generally has a layer
charge from -0.85 to -1.0, does not require reassessment. Approximate variations
in octahedral occupancy (per octahedral site) are Al/(Al + Fe3+) from 0.6 to 1.0 and
R2+/(R2+ + R3+) of <0.25. Rieder et al. (1998) classified illite as interlayer-cation
deficient.
The chemical composition of illite appears to be related to genesis. Srodon et al.
(1992) found that hydrothermally altered igneous rocks have an illite component in
interstratified illite-smectite represented by A0.89(Al1.85Fe0.05Mg0.10)(Si3.20Al0.80)O10(OH)2
where A represents fixed interlayer cations, primarily K. Note that layer charge alone
8 Brigatti & Guggenheim

should not be used to distinguish between illite and muscovite. In contrast, Lindgreen et
al. (2000) found that illite components in shales and mudstones have a representative
formula similar to that given above from Bailey (1986).
Zller and Brockamp (1997) showed that coexisting illite-1M and illite-2M1 have
different chemical compositions, with the 1M form lower in K and tetrahedral Al and
higher in Si than the 2M1 form. The composition is K0.715(Al1.635Fe0.20Mg0.165)(Si3.45Al0.55)
O10(OH)2 and K0.835(Al1.645Fe0.19Mg0.16)(Si3.34Al0.66)O10(OH)2 for the 1M and 2M1 forms,
respectively. Although the octahedral composition of both forms is very similar, there is
an apparent deficiency in charge in the octahedral sheet of the 1M structure relative to the
2M1 polytype, suggesting that a simple Si exchange for Al and K does not occur (Zller
and Brockamp 1997). Compositional control of stacking is common in the micas. For
example, in general, trioctahedral micas favor the 1M polytype and dioctahedral micas
favor 2M1 forms (Bailey 1984a, p. 10), and there are many other examples. To emphasize
that structural relationships are not truly polytypic or polymorphic in the micas, the term
polytypoid is used to describe these structures formally.
Although single crystal refinements of high quality have not been made for illite, a
structural model involving octahedral-cation order has been developed by Drits and
coworkers that accounts well for the thermal analysis of various illite samples and their
powder diffraction patterns. Dioctahedral micas of high relative crystallinity generally
form structures with the vacant site ordered at M(1), the trans site. Dioctahedral 2:1
layers with the vacant site located in the cis position, M(2), were suggested earlier for
montmorillonite and other dioctahedral smectites (e.g., Mring and Glaeser 1954; Mring
and Oberlin 1971; Besson 1980; Besson et al. 1982; Tsipursky and Drits 1984). Drits et
al. (1984, 1993) predicted and outlined the powder X-ray diffraction features of illite with
trans-vacant and cis-vacant sites and structures where there is a statistical distribution of
cations over all three sites (simulating a trioctahedral arrangement). Bailey (1984b) and
Drits et al. (1984) noted that there is a relationship between the intralayer shift (ideally
-0.333a1) and octahedral site size: an undershift occurs where M(2) is the larger site and
an overshift occurs where M(2) is the smaller site relative to M(1). Thus, a trans-vacant
illite has a value of |c(cos)/a| greater than 0.333a1 ranging from 0.38 to 0.41 and a cis-
vacant illite has a value of less than 0.333a1 ranging from 0.29 to 0.31 (Drits et al. 1993).
The effect of these intralayer shifts is to displace significantly the 11 2 , 112 , and 11 3
reflections in powder diffraction patterns of the trans- vs. cis-vacant structures, thereby
allowing the determination of the ordering pattern. Zvyagin et al. (1985), Drits et al.
(1993), and Reynolds and Thompson (1993) described illite samples containing cis-
vacant sites. Structures with cis-vacant configurations were identified also by oblique
texture electron diffraction techniques. The occurrence of the trans-vacant and cis-vacant
structures has important implications in the thermal decomposition of illite and illite-
bearing interstratifications, which are discussed in more detail in the Atomistic Models
Involving High-Temperature Studies of the Micas section.
Nanpingite. Nanpingite, ideally CsAl2 AlSi3O10(OH)2 is a dioctahedral mica,
similar in composition to muscovite, with Cs replacing K in the interlayer site. The
mineral occurs in the Nanping pegmatite field (Fujian Province, China) where it was
found in a large pegmatite vein crystallized from a residual hydrothermal fluid (Yang et
al. 1988). No other nanpingite occurrence has been reported to date. If compared to
muscovite, the nanpingite crystal structure [space group: C2/c; unit cell parameters:
a = 9.076(3), b = 5.226(2), c = 21.41(5) , = 99.48(5), Table 2c] shows two unusual
features, i.e, a 2M2 stacking sequence and a relatively small tetrahedral rotation angle
( = 5.5) ( Ni and Hughes 1996). Both these features were attributed to the large cation
in the interlayer. In nanpingite, Cs increases the interlayer separation between two
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 9

adjacent layers, thus mitigating the energetically unfavorable conditions that hinder the
formation of the 2M2 polytype in dioctahedral micas (i.e., repulsion between basal
oxygen atoms of two adjacent layers which superimpose as a result of the 2M2 stacking;
Gven 1971a). Because of the Cs coordination, the Cs polyhedron is elongated along c*
relative to a K polyhedron, and it is not enlarged along the [100] and [010] directions. In
nanpingite, the large c parameter reflects the unusual interlayer composition.
Norrishite. The only known norrishite [ideally K Li Mn3+ 2 (Si 4 O10 )O2 ] occurrence is
in the oxidized Mn-rich schists near Grenfell, New South Wales, Australia. The mineral,
described and characterized as a new trioctahedral species by Eggleton and Hasley
(1989), presents no, or very limited, [4]Al for [4]Si substitution, and the mica is anhydrous,
with O2- in the site normally occupied by (OH), and it is fully oxidized. The lack of
protons is consistent with the charge balance constraints of the octahedral sheet (i.e, to
balance the high positive charge as required by the Mn3+ oxidation state). The crystal
structure of norrishite-1M, (K0.97Na0.05)(Li1.0Mn3+1.96Mg0.025Ti0.01Al0.05)(Si3.94Al0.06)O12.11,
was refined by Tyrna and Guggenheim (1991) in C2/m symmetry. The geometry of the
2:1 layer of norrishite is complicated by polyhedral distortions, especially of the
octahedra, which results from three independent crystal chemical effects: (i) the large and
asymmetric displacement of octahedral M(2) (cis-site) produced by the presence of O2-
on a shared edge between two adjacent M(2), (ii) elongation of octahedra approximately
parallel to [100] owing to the Jahn-Teller effect, and (iii) dioctahedral-like distortions
caused by charge and size differences of Li+ and Mn3+ occurring in the M(1) and M(2)
sites, respectively. The effect of two O2- anions on a shared edge between two M(2)
octahedra results is an electrostatic attraction between M(2) and O(4), which produces an
asymmetric displacement of M(2) cations in a direction perpendicular to the O(4)O(4)
edge. O(4) anions move close to each other along the O(4)O(4) edge to moderate the
repulsion between neighboring Mn3+ cations. Therefore, the asymmetric displacement of
M(2) is required to balance the attractive forces between M(2) and O(4) and the repulsive
forces between M(2)M(2) and O(4)O(4).
The Jahn-Teller effect associated with Mn3+ controls the arrangement of anions in
the octahedra. Thus (i) octahedra are lengthened along the [100] direction and (ii)
shortened along both the [010] and [100] directions. The intralayer shift value (-0.274 a1)
is less than the ideal value of trioctahedral micas (0.333a1) and the layer offset is small
(+0.002a1). A low valence cation (Li+) and a trivalent cation (Mn3+) order in M(1) and
M(2) sites, respectively. Thus, as in the dioctahedral micas, the shift of apical O atoms is
related to the lengthening of unshared octahedral edges of the M(1) site. In norrishite,
however, the difference between M(1) and M(2) is smaller than where M(1) is vacant and
thus the shift of the apical O atom is reflected mostly in the elongation of tetrahedral
pyramidal edges (ObasalTOapical = 112.7; ObasalTObasal = 106.0) rather than in the
corrugation of the basal oxygen plane (z = 0.058 ). The basal tetrahedral face thus
contracts, and reduces the lateral dimension of the sheet. In contrast, the octahedral
flattening owing to the relatively large radii of Mn3+ and Li+ expands the octahedral
sheet. Lack of misfit between tetrahedral and octahedral sheets results from these
combined effects and accordingly the tetrahedral ring is essentially hexagonal ( = 0.6).
The large interlayer cavity and the Coulombic interaction between K+ and O2- yield the
small interlayer separation of 3.275.
Preiswerkite. Preiswerkite, a trioctahedral true mica with the ideal formula
Na(Mg2Al)(Si2Al2)O10(OH)2 was described by Keusen and Peters (1980). The sample
occurs in a metarodingite from the Geisspfald ultramafic complex, Swiss Penninic Alps.
Other occurrences include: (i) Allalin gabbro, Zermatt-Saas zone, Switzerland (Meyer
1983), (ii) Liset eclogite pod, Western Gneiss Region, Norway (Smith and Kechid 1983),
10 Brigatti & Guggenheim

(iii) Amorican massif eclogite, France (Godard 1988, Godard and Smith 1999), (iv)
serpentinite schist of Vumba schist belt, Botswana (Rammlmair et al. 1988); (v) jadeite
of Montagua fault zone, Guatemala (Harlow 1994, 1995), and (vi) tourmaline-biotite-
scapolite rock near the Blengsvatn, Bamble sector, southern Norway (Visser et al. 1999).
Excluding the sample from Blengsvatn, which was formed in a silica-undersaturated, Na-
Al-B-Cl-Mg-rich rock during prograde metamorphism, all reported occurrences of
preiswerkite involve metabasic and meta-ultramafic rocks. Preiswerkite forms both
during retrogression, following eclogite or amphibolite-granulite facies metamorphism,
or during a late to retrograde-stage amphibolite facies overprint. The stability of
preiswerkite is not restricted to extreme or unusual P-T conditions. Therefore, the rarity
of this mica is probably related to an unusual host rock composition. Preiswerkite is
relatively homogeneous in composition. Godard and Smith (1999) observed that the
mineral, associated with Na-, (Fe,Mg)-rich margarite in two eclogite occurrences,
displays slight solid solution toward aluminoceladonite and aspidolite, but no solid
solution toward more aluminous compositions.
The crystal structure of preiswerkite-1M was determined by Oberti et al. (1993) in
space group C2/m (Table 1a). Although the presence of only one independent tetrahedral
site implies complete long-range Al, Si disorder, Raman and NMR studies on natural and
synthetic preiswerkite crystals indicated the presence of strong short-range order (Tlili et
al. 1989; Sanz and Robert 1992). Clusters of Si surrounded by three Al tetrahedra (SiAl3)
together with AlSi3 clusters were recognized in Raman spectra; 29Si and 27Al NMR
indicated also the presence SiAl3 clusters together with Al2Si environments but not with
AlSi2 or Si3 environments. The Tschermaks substitution ([4]Si-1 [6]Mg-1 [4]Al [6]Al) is
associated with an increase in the size of the tetrahedra and a decrease in size of the
octahedra. The resulting misfit is minimized by values approching 20. Oberti et al.
(1993) suggested that the charge imbalance on the basal O atoms produced by the [4]Al
content was compensated both by a shortening of the TObasal bond relative to the T
Oapical distance and by some H-bonding interactions, which prevent the replacement of
OH by F. Complete cation disorder or partial Mg, Al ordering can occur between
octahedral sites, with Al preferentially sited in M(2).
Tobelite. Tobelite, ideally (NH4)Al2Si3AlO10(OH)2, was described as a new diocta-
hedral mica by Higashi (1982). The term tobelite is used to designate an illite-like species
characterized by: (i) NH4 > K, in the interlayer, (ii) Si 3 atoms per formula unit
(apfu) in tetrahedral sites, and (iii) a layer charge of less than one. Tobelite occurs as a
hydrothermal alteration product of andesite and rhyolite tuffs in pottery clay (Ohgidani
Toseki deposit, Tobe, Ehime Prefecture) and in pyrophyllite deposits (Horo, Hiroshima
Prefecture) in Japan (Higashi 1982). Tobelite shows larger (001) spacing (~0.25 ) and
unit cell parameters [a = 5.219(3), b = 8.986(2), c = 10.447(2) , = 101.31(1)] than
illite. Unfortunately reliable single-crystal refinements are at present not available for
tobelite and illite.
NH4-rich phyllosilicates with K > NH4 and with (001) spacing values intermediate
between illite and tobelite are referred to as NH4-rich illite. They occur in hydrothermal
environments (Sterne et al. 1982; Higashi 1982; Von Damm et al. 1985; Wilson et al.
1992; Bobos and Ghergari 1999); in black-shales (Sterne et al. 1984); in regionally
metamorphosed carbonaceous pelites (Juster et al. 1987; Daniels et al. 1996; Liu et al.
1996) and in diagenetic environments (Duit et al. 1986; Lindgreen et al. 1991; Drits et al.
1997).
Tobelite-like layers are often found in interstratified dioctahedral minerals having
non-expandable (mica-like) and expandable (smectite-like and/or vermiculite-like) layers.
Drits et al. (1997) demonstrated that, in interstratified illite-smectite minerals from North
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 11

Sea oil-source rocks, the mica-like component contains both K-rich end-member (illite)
and NH4-rich end-member (tobelite) layers. The amount and the distribution of fixed K
and NH4 was determined by a peak profile-fitting procedure on experimental powder
(X-ray) diffraction features (Drits et al. 1997; Sakharov et al. 1999).
Synthetic micas with unusual properties
Cesian tetra-ferri-annite and cesian annite. Fe-rich micas have the capacity to
contain radioisotopes, such as 135Cs and 137Cs. The study of these materials has been a
promising direction of mica research over the last few years; see, for example, Mellini et
al. (1996), Drbek et al. (1998), and Comodi et al. (1999). The cesian-tetra-ferri-annite
crystal structure was studied by Mellini et al. (1996) and by Comodi et al. (1999) at
ambient conditions and at high P-T conditions. Cs-tetra-ferri-annite crystallizes in the 1M
polytype (C2/m space group). It has the largest unit-cell volume reported to date for 1M
micas and coordination polyhedra are undistorted (Table 1a). The tetrahedral rotation
angle ( = 0.2), and the octahedral-distortion parameter, , involved with the counter-
rotation of upper and lower oxygen triads are near 0 (M(1) = 0; M(2) = 0.2), thus
suggesting a nearly undistorted layer with limited internal strain. No detectable internal
strain based on such parameters (e.g., and ) was observed at high pressure (to 47
Kbar) and temperature (to 582C). Above 450C, in air, the reduction of the unit cell
volume is related to the loss of H atoms required to balance the layer charge after
oxidation of octahedral iron in the M(2)-cis site.
Li for K exchange in interlayer sites. Volfiger and Robert (1979, 1980) and Robert
et al. (1983) suggested that, in synthetic trioctahedral micas, anhydrous Li can exchange
for K in interlayer sites. Although the crystal quality obtained from the run products did
not allow a complete crystal structure determination, they indicated, on the basis of the
results obtained by infrared and powder X-ray analyses, that Li is located in the interlayer
in a pseudo-octahedral cavity. This cavity is partly defined by the hexagonal ring of one
layer and by the basal oxygen atoms of two tetrahedra in the adjacent layer.
The Li solubility limit was estimated to be a function of the relation: Li/(Li+K)max =
2 [4][Al/(Al+Si)]2. Tetrahedral Al for Si substitution is essential to minimize the electro-
static repulsion between tetrahedral cations and Li, and therefore to create favorable
cavities to host Li. Robert et al. (1983) found that the unit cell parameter, c, decreases
with K for Li substitution whereas the b parameter slightly increases.
In Li-exchanged synthetic paragonite-2M1 and muscovite-2M1, repulsive forces
between O atoms across the interlayer region cause an interlayer overshift, resulting in an
anomalously high basal spacing and smaller monoclinic angle (Keppler 1990).
Complete and rapid Li exchange in the interlayer sites was obtained for natural
phlogopite, ferroan phlogopite and muscovite using cryptand [222] as a complexing
agent, and dioxane as a solvent (Bracke et al. 1995). Powder X-ray diffraction suggests
that the interlayer spacing changes with replacement of K by Li + H2O. The original
reflection at 9.93 loses intensity progressively and an additional reflection at 11.78
appears.
EFFECT OF COMPOSITION ON STRUCTURE
Tetrahedral sheet
In some naturally occurring true micas, Si nearly fills all the tetrahedral sites (e.g.,
polylithionite, tainiolite, norrishite, and celadonite), whereas in the most common mica
species (i.e., muscovite and phlogopite) Al substitutes for Si in a ratio near 1:3. In some
true micas and brittle micas, the Al for Si substitution corresponds to a ratio of Al:Si =
1:1 (e.g., ephesite, preiswerkite, siderophyllite, margarite, and kinoshitalite), whereas the
12 Brigatti & Guggenheim

trioctahedral brittle mica, clintonite, has an unusually high Al content with a ratio of
Al:Si of 3:1 (Bailey 1984a,b). Evidence of Fe3+ tetrahedral substitution was reported on
the basis of optical observations (e.g., Farmer and Boettcher 1981; Neal and Taylor
1989), spectroscopic studies (e.g., Dyar 1990; Rancourt et al. 1992; Cruciani et al. 1995)
and crystal-structure refinement (Guggenheim and Kato 1984; Joswig et al. 1986;
Cruciani and Zanazzi 1994; Brigatti et al 1996a, 1999; Medici 1996). However, only in
tetra-ferriphlogopite, tetra-ferri-annite and anandite is Fe3+ the only Si-substituting cation,
with a Fe3+:Si ratio near 1:3 (e.g., Giuseppetti and Tadini 1972; Semenova et al. 1977;
Hazen et al. 1981; Filut et al. 1985; Brigatti et al.1996a,b, 1999; Mellini et al. 1996).
Thus, the 1:3 ratio appears to be the greatest Fe3+ tetrahedral substitution possible for the
micas. Two mica end-members contain B (boromuscovite; Liang et al. 1995) and Be
(bityite; Lin and Guggenheim 1983), and some synthetic micas contain Ge in the T site
(Toraya and Marumo 1981; Toraya et al. 1978a,c). Most mica structures display a
disordered distribution of tetrahedral cations, with the exception of some brittle mica
species, such as margarite (Guggenheim and Bailey 1975, 1978; Kassner et al. 1993),
anandite (Giuseppetti and Tadini 1972; Filut et al. 1985) and bityite (Lin and Guggen-
heim 1983) and a few true micas (e.g., polylithionite-3T, Brown, 1978; muscovite-3T,
Gven and Burnham 1967). Some true micas with an apparent ordered distribution of
cations in the tetrahedra are those with a high R value and therefore these structures
should be considered tentative.
Hazen and Burnham (1973) related TO distances of trisilicic micas to tetrahedral
composition by the linear relationship (xAl and xSi represent Al and Si apfu, respectively)
x Al
T O ( A ) = 0.163 + 1.608
x Al + xSi
A more general relationship derived here including both trioctahedral and
dioctahedral true and brittle micas (Tables 1-4, Appendix II) between tetrahedral mean
bond distances TO and tetrahedral chemistry (in apfu) is:
T O () = 1.607 + 4.201 10 2 [4]
Al + 7.68 102[4] Fe
(correlation coefficient, r = 0.965)
In the regression analysis, structures containing B, Be, and Ge in tetrahedral sites
were not considered, as well as structures with symmetry lower than ideal owing to
tetrahedral cation ordering (differences in TO values greater than 5). Only structures
containing tetrahedral Si, Al, and Fe were examined.
Geometrical considerations of tetrahedral distortion parameters have been
considered earlier (e.g., Drits 1969, 1975; Takuchi 1975; Appelo 1978; Lee and
Guggenheim 1981; Weiss et al. 1992). We further discuss these relationships here and
relate them to layer composition on the basis of data from a large number of structure
determinations.
A crystal chemical study of the parameter is complex. In an ideal tetrahedron is
equal to arcos (-1/3) 109.47. For non-ideal cases, however, was found to be affected
by tetrahedral content, increasing as Si increases (Takuchi 1975) relative to Al. The
value can deviate from its ideal value as a function of the relative position along c for the
basal oxygen atoms with respect to the tetrahedral cation and with respect to the mean
basal-edge length and the mean tetrahedral-edge value. These conclusions are based on
the linearized topology of the tetrahedron. Several simple models of deformation are
considered here (Fig. 2) and only modes (3) and (4) were found to affect the value.
All dependences (over displacement from an ideal undeformed configuration) of order
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 13

Figure 2. Geometrical considerations over the dependence of from tetrahedron vertex and center
displacement. The relationships in the legend have been obtained from a linearized geometrical
model. k and e indicate the displacement and the tetrahedron edge length, respectively.

greater than one are ignored. The model, thus, provides results in good agreement with
structural data only if displacements are small relative to the characteristic length of the
system (i.e., the tetrahedral edge).
Figure 3 shows the variations of vs. [4]Si content. Although the increase of with
[4]
Si is confirmed, there are two different linear trends, one trend for true and one trend
for brittle micas. Brittle micas show values greater than expected if just the composition
of the tetrahedron is considered. Although this simple model ignores cation ordering, on
the basis of geometrical considerations derived before (Fig. 2), the higher values may
be explained by the increase in the electrostatic attraction of basal oxygen atoms by the
high-charge interlayer cation and by the concomitant increase in repulsion between the
interlayer cation and the tetrahedral cation. Note, for example, that kinoshitalite usually
tends to approach true micas in composition. Samples of kinoshitalite and ferrokino-
shitalite (Guggenheim and Kato 1984; Brigatti and Poppi 1993; Guggenheim and
Frimmel 1999) contain significant amounts of monovalent K in substitution for Ba,
whereas, kinoshitalite refined by Gnos and Armbruster (2000), marked by an arrow in
Figure 3, has nearly complete interlayer Ba occupancy and a larger value.
To better relate how the interlayer cation affects , we have developed a simple
electrostatic model. The model is comprised of four tetrahedral oxygen atoms, with the
tetrahedral and the interlayer cations located at the center of the tetrahedron and in the
14 Brigatti & Guggenheim

Figure 3. Relationships between the tetrahedral flattening angle, , and


Si content in tetrahedral coordination as determined by microprobe
analysis. Symbols used: filled circle = annite; filled circle, x-hair =
magnesian annite; open circle = phlogopite; open circle, x-hair =
ferroan phlogopite; filled circle, dotted = tetra-ferri-annite; open circle,
dotted = tetra-ferriphlogopite; open square = polylithionite; filled
square = trilithionite; filled square, x-hair = siderophyllite; open square,
x-hair = ferroan polylithionite; filled hexagon, x-hair = norrishite;
crosses = preiswerkite; open diamond = muscovite; open diamond, x-
hair = nanpingite; filled diamond = paragonite; filled diamond x-hair =
boromuscovite; open triangle up = clintonite; filled triangle up, x-hair =
ferrokinoshitalite; filled triangle up = kinoshitalite. The sample arrowed
is kinoshitalite by Gnos and Armbruster (2000). For details see text.

middle of the interlayer, respectively. The oxygen atoms were placed at the vertices of an
undistorted tetrahedron with a tetrahedral volume equal to that as considered above. A
uniform displacement along the [001] direction was then imposed on the basal oxygen
atom plane and the electrostatic energy associated with the system was then derived as a
function of this displacement. Finally, the displacement which minimizes the electrostatic
energy of the system was calculated and compared with the value obtained for a system
identical to that described, but differing in the formal charge of the interlayer cation
which was arbitrarily set equal to one. Therefore, the model takes into consideration the
differences in energy between the two configurations described, not the total energy.
The displacement obtained was used to isolate the value from the influence of
the divalent interlayer cation. The values of tetrahedrally disordered brittle micas which
was thus isolated (i.e., *) follow the same trend defined for true micas, confirming the
influence of interlayer cations on (Fig. 4).
Unlike other models reported in the literature (e.g., Giese 1984), our model intro-
duces only the Coulombic term and does not consider the repulsive energy or van der
Waals interactions. This simplification, as Giese (1984) correctly noted, does not produce
correct energy values. For this reason, energy differences between structural systems,
which are characterized by the same repulsive energy, were considered. The charge at
each position was determined from chemical data and from structural constraints.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 15

Figure 4. Relationship between * and Si tetrahedral content . * refers to


the value isolated from the influence of the interlayer cation for the
brittle micas clintonite and kinoshitalite. Regression equation: * () =
2.920 [4]Si + 101.98, r = 0.950. Symbols and samples as in Figure 3.

Figure 5. Bond energy between tetrahedral cation and tetrahedral basal


oxygen atoms compared with the bond energy between interlayer cation
and tetrahedral basal oxygen atoms. Symbols and samples as in Figure 3.
16 Brigatti & Guggenheim

Figure 5 relates the bond energy between the tetrahedral basal oxygen atoms vs.
tetrahedral cations (TObasal) and between the basal oxygen atoms vs. interlayer cations
(AObasal), respectively. In brittle mica species, the distance between the tetrahedral
cation and the basal oxygen atom plane increases, owing to the interaction with the
interlayer cation. In this way the increase in TObasal bond energy is partly compensated
by a decrease in bond energy between the cation and the oxygen atoms of the basal plane.
The displacement of the tetrahedral cation from its ideal position can be evaluated
(see Appendix I for derivation) from the tetrahedral displacement parameter, Tdisp.:

Tdisp. = T Obasal
2

O Obasal
2


(T O )
apical

3 3
Tdisp. was calculated for all structures starting from observed distances, and then plotted
against the value observed (Fig. 6).

Figure 6. Mean value vs. the displacement of the T cation from the center
of the tetrahedron mass (Tdisp.). Symbols and samples as in Figure 3.

The plane of basal oxygen atoms approaches the tetrahedral cation in flattened
tetrahedra (the distance between the tetrahedral cation and the basal oxygen-atom plane
decreases with respect to the TOapical distance), whereas the tetrahedral cation shifts
toward the tetrahedral apex (the distance between the tetrahedral cation and basal-oxygen
atom plane increases with respect to the TOapical distance) in elongated tetrahedra. In
preiswerkite and in boromuscovite the tetrahedral cation shifts from its ideal position
toward the plane of basal oxygen atoms ( < 109.47). In the brittle mica clintonite, the
tetrahedral cation more closely approaches the center of the tetrahedron ( 109.47),
whereas in other micas the cation shifts toward the tetrahedral apex ( > 109.47). The
maximum shift was observed in norrishite (Tyrna and Guggenheim 1991) and in
polylithionite (Takeda and Burnham 1969).
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 17

Figure 7. Plot of vs. O-Obasal. Symbols and samples as in


Figure 3.

In addition, reflects an adjustment for the misfit between the tetrahedral sheet and
the octahedral sheet (the regression coefficient, r, of vs. the difference between mean
basal tetrahedral edges and mean octahedral triads is r = 0.92). Furthermore, as the mean
OO basal distance decreases, the tetrahedral cation moves away from the basal
oxygen-atom plane. Thus, increases in value (Fig. 7). The deviation of the parameters
for clintonite and kinoshitalite from the trend for true micas further suggests that there is
a significant influence of the interlayer cation on the value of .
In conclusion (i) increases as the distance between the tetrahedral cation and the
basal oxygen-atom plane increases from its ideal value; (ii) increases as OObasal
decreases, thus reflecting a dimensional adjustment between the tetrahedral sheet and
octahedral sheet; and (iii) increases with [4]Si content. Differences between values of
brittle micas from the true micas are related in part to electrostatic features. It is useful to
understand why the tetrahedral cation moves from its ideal position. Drits (1969) stated
that the position of the tetrahedral cation depends not only on the degree of substitution
of Si by Al in the tetrahedra (Brown and Bailey 1963), but also in the position and
distribution in compensating positive charges. This assumption is related to electrostatic
forces in the following way (see Appendix I for derivation):
3 q T 9 q T q 2T q 2T
E1 = E3 =
d TOb T O apical (
IS + 2 d TOb IS + 2 / 3 T Oapical )


q T (q A / 4 ) q T (q A / 4)
E 2 =
(IS / 2 + (T O )/ 3) + O
2 2
(IS / 2 + d TOb )2 +
2
O apical Oapical Oapical
apical apical
18 Brigatti & Guggenheim

where qT and qA are the tetrahedral and interlayer charges, respectively; IS is the
interlayer separation; dTOb is the distance of the tetrahedral cation from the basal oxygen
atom plane; OapicalOapical is the distance between apical oxygen atoms; and TOapical is
the distance between the tetrahedral cation and apical oxygen atom. E1 relates the
electrostatic energy between the tetrahedral cation and the basal oxygen atoms. E2 is the
electrostatic energy between the tetrahedral cation and interlayer cation. E3 considers the
repulsion between tetrahedral cations of two opposing tetrahedra across the interlayer
(Fig. 8). E1 (E2, E3) is the variation of E1 (E2, E3) values in the actual structure and in
an ideal structure with the tetrahedral cation ideally spaced from the basal and apical
oxygen atoms. E1, E2, and E3 were derived by considering the set of charges
represented in Figure 9. This specific arrangement of charges was developed to describe
the electrostatic interactions between the basal oxygen atoms of the tetrahedron and
interlayer cation. All planes of atoms (i.e., the plane of interlayer cations, the plane of
basal oxygen atoms and the plane of tetrahedral cations) can be described through a rigid
displacement of the simple charge distribution in Figure 9, thus the energy involving the
oxygen-atom plane differs, to a first approximation, from the energy related to the
distribution in Figure 9 by just a scale factor. The objective of our model is to describe
the factors influencing the interlayer cation displacement from its ideal position.
However, we consider the difference in energy between the actual structure configuration
and that characterized by a tetrahedral cation-basal oxygen atom plane distance,
which is equal to (TOapical)/3. All terms in energy which do not include that distance, are
therefore excluded in this derivation because they must be equal in both the
configurations considered. In conclusion, differences in energy among configurations
which vary for very small displacements of charge can be very useful. Our model
considers van der Waals and repulsion energies equal in both configurations to simplify
the calculation.

Figure 8. Relationship between E2 + E3 vs. E1. For the definition of


energy E1, E2, and E3, see text. Regression equation [(2 + 3) =
-1.099 1 + 1.26 10-3 ; r = 0.997). Symbols and samples as in Figure
3.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 19

Figure 9. The set of charges used to derive


E1, E2, and E3.

Figure 8 clearly shows that an increase in the electrostatic energy associated with an
increase in the tetrahedral cation-basal oxygen atom distance is compensated by a
reduction in the repulsion between the interlayer cation and the tetrahedral cation and the
tetrahedral-tetrahedral cations (sited in adjacent layers). Given the high correlation
coefficient (r = 0.997), the relation may be useful as a predictive tool.
The basal oxygen atom plane corrugation effect (z) produces an out-of-plane
twisting of tetrahedra about the bridging basal oxygen atom in the [110] tetrahedral chain
and a shortening of the distance between apical oxygens along the octahedral edge
parallel to the (001) plane. Lee and Guggenheim (1981) demonstrated that the corruga-
tion of the basal oxygen atom plane reflects differences in distance between apical
oxygen atoms linked to octahedra of different size. Thus z is limited in trioctahedral
micas with M(1) M(2) in size, whereas it shows higher values in dioctahedral micas
with M(1) >> M(2) in size. Differences in z are related to the linkage of the tetrahedral
sheet by apical oxygen with octahedral sites different in size.
A strong relationship between z and M [M = MOmax MOmin] for a
structure is evident in Figure 10. This result confirms that differences in octahedral site
dimensions play an important role over tetrahedral basal oxygen-plane corrugation
[regression equation: z () = 0.647 M; r = 0.984].
Figure 11 shows the effect of Al octahedral content ([6]Al) on z. Where [6]Al
occupancy is less than 1 apfu, z is approximately zero (trioctahedral true and
trioctahedral brittle micas). In trioctahedral Li-rich micas (polylithionite, trilithionite and
siderophillite) and in preiswerkite, [6]Al occupancy is nearly 1 apfu and z is as large as
0.15 . A z of 0.24 is observed for dioctahedral micas for which [6]Al occupancy
reaches 2 apfu. Al is a cation of relatively small size. For micas with significant amounts
of octahedral Al and where Al ordering occurs, differences in size between octahedral
sites are enhanced and the value of z increases. Such differences also occur for micas
with a low charge cation (e.g., Li+ in trioctahedral polylithionite) or by vacancies (i.e., in
dioctahedral micas), where charge balance occurs within the octahedral sheet only.
Tetrahedral rotation and interlayer region
The dimensions of an ideal octahedral sheet in the (001) plane are commonly less
than those of an ideal and unconstrained tetrahedral sheet. Thus, to obtain congruence,
the difference in size of the tetrahedral and octahedral sheets must be adjusted by any one
or more of the following: (i) in-plane rotation of adjacent tetrahedra in opposite directions
about c* (parameter ); (ii) thickening of the tetrahedra (parameter ), and (iii) a flat-
20 Brigatti & Guggenheim

Figure 10. Relationship be-


tween the tilting of the basal
oxygen plane, z and M
[ = MOmax MOmin ].
Regression equation: z ()
= 0.647 M; r = 0.984.
Symbols and samples as in
Figure 3.

Figure 11. z () vs. the


octahedral Al content deter-
mined by microprobe
analysis. The arrow indicates
the dioctahedral chromium-
rich mica (Evsyunin et al.
1997) which presents an
unusual chemical composi-
tion characterized by an
important [6]Cr for [6]Al
substitution. Symbols and
samples as in Figure 3.

tening of the octahedra (parameter ) to lengthen the octahedral edges (Mathieson and
Walker 1954, Newnham and Brindley 1956; Zvyagin 1957; Bradley 1959; Radoslovich
1961; Radoslovich and Norrish 1962; Brown and Bailey 1963; Donnay et al. 1964,
Bailey 1984b, Lee and Guggenheim 1981).
McCauley and Newnham (1971) specified by multiple regression analysis that,
although the value is largely controlled by the tetrahedral-octahedral sheet lateral misfit
(90%), it also reflects the field strength of the interlayer cation. Toraya (1981) observed
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 21

two linear relationships, between and the difference in length of the octahedral and
tetrahedral sheets along the b axis, i.e., = c1 (23eb -32do) + c2 (where do is the mean
octahedral cation-anion distance, eb is the mean basal edge length of a tetrahedron, 23eb
and 32do are the lengths along the b axis, in the idealized form, of the tetrahedral and
octahedral sheet, respectively; c1 and c2 are the regression coefficients, c1 = 35.44 and
12.58, c2 = -11.09 and 4.30 for silicate and germanate micas, respectively). Weiss et al.
(1992) used a different dataset and the same assumption of Toraya and found, for Si-rich
micas, different values for c1 and c2 (c1 = 25.9 and c2 = -5.0).

Figure 12. determined by structure refinement vs. calculated by


regression equation = 25.9 (23eb -32do) 5.0 (Weiss et al. 1992).
Symbols as in Figure 2. The plot reports only structures published after
1992, i.e., structures not considered in the predictive equation of Weiss
et al. (1992).

The calculated values using the equation of Weiss et al. (1992) and data published
after 1992 (i.e., not used to derive the equation) vs. observed values are consistent
mostly in the range of 7-9, whereas the correspondence is lower for smaller and larger
angles (Fig. 12). Weiss et al. (1992) also predicted the value from sheet composition
using a vector-representation grid. They calculated a mean tetrahedral distance, d (TO),
and a mean octahedral bond distances, d (MA) (where A is any anion), from equations
d (TO) = di (TO)calc xI
d (MO) = di (MO)calc xi
d (MOH) = dI (MOH)calc xi
where di (TO), di (MO) and di (MOH) are the calculated mean bond lengths for
cations in tetrahedral and octahedral coordination, respectively, and xi represents the
atomic fraction of each cation.
To better understand the role of tetrahedral-octahedral lateral misfit for 1M, 2M1,
22 Brigatti & Guggenheim

2M2 and 3T polytypes, we have developed a geometric model (see Appendix I).
According to this model, is equal to
1 / 3 + k 4 / 3 k 2
= tan 1 60
k 2 1
and simplifying
3
= cos 1 k
2
where k is the ratio between the OO octahedral triads (OOunshared) and OO
tetrahedral basal edges, OObasal. OOunshared very closely corresponds to b/3, b3/3
and a/3 for trioctahedral-1M (and -2M1), -3T, and -2M2 polytypes, respectively, thus
indicating that the rigid octahedral sheet primarily determines the unit-cell lateral
dimensions of trioctahedral micas. This relationship is obtained with rigid tetrahedra
and deformation involves only the hexagonal silicate ring. Therefore, the deformation
of the octahedron and tetrahedron influences the value only by affecting the tetrahedral
and octahedral lengths as given in the formula above. Figure 13 reports values
observed vs. values thus calculated. The correspondence appears excellent (r = 0.994),
although the model could be improved by calculating all the six-ring tetrahedral angles
and then averaging. The relationship between calculated and k is not linear and that
structures which primarily deviate are Li-rich micas with octahedral ordering in the M(2)
and M(3) sites.
This geometric relationship is useful also to evaluate the influence of composition
over . The mean basal tetrahedral edge depends on tetrahedral cation stereochemistry

Figure 13. determined by structure refinement vs. calculated from


the equation: = cos-1 ( 3 2 k ) where the k is the ratio between
octahedral triads (OOunshared) and tetrahedral basal edges(OObasal).
Symbols and samples as in Figure 3.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 23

([4]Al and [4]Fe in apfu, r = 0.970) by:


O O basal = 2.581+ 8.836 10 2 [4 ]
Al + 0.164 [4 ]
Fe

whereas the mean length of the octahedral triads is well fitted by the following expression
([6]Al, [6]Fe2+ in apfu, r = 0.940):
O O unshared = 3.072 4.24 10 2 [ 6]
Al + 2.14 10 2 [ 6]
Fe 2+ 3.88 10 2 Ifs
where Ifs is the increase of the interlayer cation field strength (i.e., the charge of the
interlayer cation divided by radius) in brittle micas with respect to true micas (both
regression equations were obtained using chemical data reported in Tables 1-4, Appendix
II). Note that the octahedral site composition is represented in a less accurate way than
the tetrahedral composition because of the greater variability in the chemical composition
of the octahedron.
The relationship between -observed and that calculated from composition is shown
in Figure 14. The fit is fair (r = 0.922) and this low correlation is related to the influence
of octahedral, tetrahedral, and interlayer composition on . In particular, the interlayer
composition appears to affect the mean value of the octahedral triads (unshared OO
distances). This result confirms the influence of the interlayer site composition on the
tetrahedral in-plane rotation.

Figure 14. determined by single crystal structure refinement vs.


calculated by the formula
= cos-1 ( 3 2 k )
where k value was obtained by calculating OO octahedral unshared
edges (OOunshared) and OO tetrahedral basal edges (OObasal)
from chemical composition (see text). Symbols and samples as in
Figure 3.

For large cations such as Cs and Rb (e.g., Cs-tetra-ferri-annite, Rb-,Cs-rich


phlogopite, and nanpingite) the small value corresponds to a large interlayer separation,
whereas for small cations such as Na and Ca (e.g., preiswerkite, paragonite, and
24 Brigatti & Guggenheim

Figure 15. Relationships between and interlayer separation. Symbols


and samples as in Figure 3.

clintonite) large values correspond to small interlayer separations (Fig. 15). Thus, as
previously noted (Radoslovich and Norrish 1962), the shape of the interlayer-cation
cavity reflects the field strength of the interlayer cation. The cavity adjusts in size by
tetrahedral rotation or by a shift in the cation toward or away from the plane defined by
the three basal oxygen atoms (i.e., the basal plane).
In K-rich trioctahedral micas, both and interlayer separation increase from
norrishite to tetra-ferriphlogopite (and aluminian phlogopite) toward values for Fe-rich
polylithionite, Fe-rich phlogopite, Mg-rich annite, and phlogopite. Annite deviates from
the trend of trioctahedral true micas owing to a larger interlayer separation. In the Ba-rich
brittle mica, ferrokinoshitalite (M sites mainly occupied by Fe2+), - and interlayer-
separation values are smaller with respect to those of kinoshitalite (M sites mostly
occupied by Mg). With respect to trioctahedral micas, the interlayer separation in both
muscovite and celadonitic muscovite is smaller, but values are similar. To explain this
behavior, the octahedral, tetrahedral, and O(4) site chemistry must be considered.
Compared to kinoshitalite, ferrokinoshitalite shows an enlargement of the octahedral
sheet produced by the relatively large size of Fe2+ with respect to Mg and by F for OH
substitution on O(4). Therefore, the smaller value is attributed to the large size of Fe in
the octahedra, which allows a better fit to the Al-rich tetrahedral sheet. Less rotation of
the tetrahedra produces a larger size of the silicate ring, which allows Ba to better fit
within the ring, thus reducing interlayer separation (Guggenheim and Frimmel 1999). In
norrishite, the combined effects of a Si-rich tetrahedral sheet, which produces smaller
individual tetrahedra within (001), and octahedral flattening owing to the relatively large
Li and Mn3+, reduce the tetrahedral-octahedral sheet misfit, thus requiring limited
tetrahedral rotation. In addition, the narrow interlayer region is partly related to the
increase in the Coulombic interactions of O2- [in the O(4) site] and the interlayer K
(Tyrna and Guggenheim 1991). In tetra-ferriphlogopite, the lateral extension of the
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 25

tetrahedral sheet is related to Fe3+ and involves a large value to fit the Mg-rich
octahedra. The O(4) site is mostly occupied by OH-, which produces H+K+ repulsion,
thus requiring a greater interlayer separation (Brigatti et al. 1996a). A similar adjustment
occurs also in aluminian phlogopite (Alietti et al. 1995) because the composition
involving an exchange vector of [6 ] Al 3+ Mn1.96
3+ [ 4]
Al 3+ [4 ] Si4 +1 creates larger tetrahedral-sheet
and smaller octahedral-sheet dimensions with respect to phlogopite.
With respect to trioctahedral micas, dioctahedral muscovite and celadonitic
muscovite have smaller interlayer separations but similar values. In dioctahedral micas,
the proton position results in part from repulsion by the interlayer cation and the cations
in the M(2) sites. Thus, the proton is located in that portion of the structure with minimal
local positive-charge concentration, near the M(1) site (Radoslovich 1960; Guggenheim
et al. 1987). The six-fold coordination of the interlayer cation with the basal inner O atom
is distorted and elongated parallel to c*. Both effects (i.e., the distorted coordination of
the interlayer cation and the smaller H+K+ repulsion) thus control the interlayer
separation.
McCauley and Newman (1971) and Weiss et al. (1992) related to the coordination
of the interlayer cation. In an ideal structure = 0 and the interlayer cation is in 12-fold
coordination. In non-ideal structures, values of greater than 0 reduce the interlayer-
cation coordination number from 12 to 6. Weiss et al. (1992) determined the coordination
number of the interlayer cation using the equation of Hoppe (1979):
ECoN = j=12
j=1 C j ,

where ECoN is the Effective Coordination Number; (C j = exp[1.0 ( FIR j / MEFIR)6 ]);
FIRj was calculated by dividing the AOj distance by the sum of anion and cation radii
and then multiplying by the cation radii; MEFIR is a weighted mean of FIR, i.e.,
j =12
j =1 w jFIR j
MEFIR = j =12 ; w j = exp(1 (FIR j FIR min ) 6 ;
j=1 w j

FIRmin is the smallest FIRj in the interlayer cation coordination. They found that ECoN is
close to 12 in tainiolite and annite, usually varies from 11 to 9 in polylithionite, ferroan
polylithionite, phlogopite, and ferroan phlogopite, and is between 9 and 8 in muscovite
and celadonitic muscovite, whereas paragonite and most brittle micas have the lowest
ECoN (ECoN = 6). In addition to tetrahedral and octahedral site composition, the
coordination of the interlayer cation was found to be affected by the stacking of the
layers. In the most common polytypes (e.g., 1M, 2M1 and 3T, the polytypes of subfamily
A, as defined by Backhaus and Durovc 1984 and Durovc et al. 1984) the coordination
polyhedron of the interlayer cation varies from ditrigonal antiprism to octahedral,
whereas in polytypes of subfamily B (e.g., 2M2 and 6H polytypes) it varies from
ditrigonal to trigonal prismatic.
Tetrahedral cation ordering
Ordering of tetrahedral cations is quite unusual in the common mica species such as
muscovite-2M1, phlogopite-1M and annite-1M (Bailey 1975, 1984c), whereas it is
common in brittle micas. Margarite, bityite and anandite are examples of minerals with
Si,Al (or Fe3+) tetrahedral ordering (Guggenheim 1984).
Bailey (1984b) concluded that ordering of tetrahedral cations is favored for 3T
structures (Gven and Burnham 1967; Brown 1978, Sidorenko et al. 1977b), for Si:Al
ratios near to 1:1 (Guggenheim and Bailey 1975, 1978; Joswig et al. 1983; Lin and
Guggenheim 1983) and for muscovite-1M, -2M1 and -2M2 crystals with a significant
26 Brigatti & Guggenheim

celadonite component (Gven 1971b; Zhoukhlistov et al. 1973; Sidorenko et al. 1975). In
contrast, Amisano-Canesi et al. (1994) suggested that no long-range ordering of tetra-
hedral cations is present in muscovite-3T crystals and concluded that the tetrahedral
cation ordering previously found by Gven and Burnham (1967) may be an artifact
produced by the small number of independent reflections used in the crystal-structure
refinement. It is very unusual to obtain increased cation order at high temperature, where,
in most cases increasing disorder is the norm, however the results of neutron powder
diffraction studies suggest tetrahedral Si-Al ordering for celadonitic muscovite (referred
as phengite) at high temperature (Pavese et al. 1997, 1999, 2000).
Guggenheim (1984) noted the importance of two factors in determining the degree
of Si,Al ordering in crystals with Si:Al ratios of 1:1 that relate to octahedral- and the
interlayer-site composition: (i) the charge of an apical oxygen that coordinates two Al3+
octahedral cations is undersaturated with respect to positive charge if the tetrahedral
cation is Al3+, whereas it is balanced if the tetrahedral cation is Si4+; (ii) large cations in
interlayer sites prop apart two adjacent 2:1 layers, thus minimizing electrostatic
repulsions across the interlayer. Therefore Si,Al tetrahedral ordering seems to be favored
in species with small, high-charged octahedral cations and small cations in interlayer
sites. To date, long-range tetrahedral ordering has not been determined for preiswerkite
and clintonite, but was found for ephesite, margarite, bityite and anandite.
Although Raman spectra suggest the presence of strong short-range ordering in
preiswerkite-1M [NaMg2AlAl2Si2O10(OH)2], long range ordering in tetrahedral sites was
not found by crystal-structure refinement (Oberti et al. 1993). In contrast, ephesite
[NaLiAl2Al2Si2O10(OH)2], which differs in composition from preiswerkite only for
octahedral composition, is strongly ordered in space group C1 (Slade et al. 1987). In the
latter case, perhaps, the presence of monovalent and trivalent octahedral cations requires
ordering of the tetrahedral cations to achieve a suitable local charge balance on shared
apical oxygen atoms.
The possibility of tetrahedral cation ordering in kinoshitalite, characterized by a
Si:Al ratio close to 1, was addressed by Guggenheim and Kato (1984), Guggenheim
(1984), and Gnos and Armbruster (2000). Guggenheim (1984) related the lack of
tetrahedral Si,Al ordering in kinoshitalite to the large interlayer separation (3.328 ;
Guggenheim and Kato 1984) caused by the large Ba interlayer cation which increases the
separation between adjacent 2:1 layers, thus reducing any TT electrostatic interactions
across the interlayer. Lack of tetrahedral Si,Al ordering was also confirmed for
ferrokinoshitalite (3.129 ; Guggenheim and Frimmel 1999) which also has large
interlayer separation but less than that of kinoshitalite.
According to Gnos and Armbruster (2000), Si,Al ordering in kinoshitalite may be
masked by twinning. They assumed different twin models to explain the average
structure of this brittle mica in space group C2/m starting from complete Si,Al tetrahedral
ordering in C2 and C 1 symmetries. The C2-space group model assumes that each Si
tetrahedron is surrounded by three Al tetrahedra and vice-versa as consistent with
Loewensteins (1954) Al-avoidance rule. The tetrahedral sheets of two adjacent 2:1
layers are arranged above and below the interlayer to produce the pattern along the c-axis
for which Si is always adjacent to Si and Al adjacent to Al tetrahedra. The C 1 -space
group model maintains the same Si,Al distribution within the tetrahedral sheets (i.e., one
Si atom surrounded by three Al atoms and vice-versa), but differs for the Si,Al
distribution along the c-axis. In this latter model, each Si tetrahedron is always opposed
to an Al tetrahedron. Gnos and Armbruster (2000) concluded that the crystal-structure
refinement is inconsistent with the twinning models that involve completely ordered
Si,Al sheets. In contrast, the crystal-structure refinements of two disordered models to
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 27

produce C2/m symmetry (i.e., three-dimensional Si,Al disorder and one-dimensional


disorder along the c axis) suggested a pattern of one-dimensional disorder along the [001]
direction of completely Si,Al ordered tetrahedral sheets.
In margarite [CaAl2 Al2Si2O10(OH)2], Al preferentially occupies two of the four
symmetrically independent tetrahedra (Guggenheim and Bailey 1975, 1978; Joswig et al.
1983; Kassner et al. 1993). Kassner et al. (1993) found that mean tetrahedral AlO and
Si-O distances are identical in the two crystallographically independent tetrahedral
sheets. Thus there is no asymmetry in the distribution of tetrahedral Al in these sheets as
indicated by Guggenheim and Bailey (1975, 1978) based on an incompletely refined
model. An ordering pattern similar to that of margarite occurs for tetrahedral sites of
bityite with nearly complete ordering of Al, Be relative to Si (Lin and Guggenheim
1983).
Octahedral coordination and long-range octahedral ordering
Three translationally independent octahedral cation sites characterize the 2:1 layer.
One site is trans coordinated by OH (or by F and/or Cl, and rarely by S) and is called
M(1), the remaining two sites are cis-coordinated and are referred to as M(2) where the
layer contains a symmetry plane which relates the two M(2) sites. Otherwise, the two cis-
sites are labeled M(2) and M(3), respectively. M(1) is usually vacant in dioctahedral
micas, whereas all three octahedral sites are occupied in trioctahedral micas. The cation
distribution in the octahedral sites may be summarized as: (i) all the octahedra are
occupied by the same kind of crystallographic entity (i.e., the same kind of ion or by a
statistical average of different kinds of ions, including voids, referred to as homo-
octahedral micas by Durovc 1981, 1994), (ii) two octahedra are occupied by the same
kind of crystallographic entity and the third by a different entity in an ordered way
(meso-octahedral micas), or (iii) each of the three sites is occupied by a different
crystallographic entity in an ordered way (hetero-octahedral micas). The location of
the origin of the octahedral sheet corresponds to: (i) the M(1) site for homo-octahedral
micas; (ii) the site with different occupation for meso-octahedral micas; and (iii) the site
with the smallest electron density for hetero-octahedral micas (Durovc et al. 1984). As a
consequence, two kinds of layers can be defined, namely, the M(1) layer and the M(2)
layer, the first with the origin of the octahedral sheet in M(1), the latter in either the
M(2) or M(3) site (Zvyagin 1967). The M(1) layer is the more common. Weiss et al.
(1992) identified eight possible geometries of the octahedral sheet based on the size of
octahedral sites. In particular, they derived four- and three-different geometries for meso-
octahedral and for hetero-octahedral micas, respectively.
Toraya (1981) noted that the M(1) site is usually occupied by a cation of lower
charge or by a vacancy. He explained this characteristic by considering the effect on the
linkages of the polyhedra. An increase in the size of M(2) is energetically unfavorable
because the OO shared edge between two adjacent M(2) cations would be enlarged
[increasing the repulsion between octahedral M(2) cations], the OOH,F edge between
M(1) and M(2) would be reduced [thus decreasing repulsion between octahedral M(1)
and M(2) cations], and the increased repulsion between oxygen atoms on the unshared
lateral edges of M(1) would occur owing to the smaller size of this site. In contrast, the
only unfavorable factor created by an increase in M(1) would be an increase in repulsion
between M(1) and M(2) cations, which would be mitigated by the decrease in charge of
M(1). However, examples where three sites are all equal or each site differs are not
unusual in trioctahedral micas. Several phlogopite and tetra-ferriphlogopite crystals
(space group C2/m) show the same kind of cations (or a disordered cation distribution) in
M(1) and M(2) octahedra, i.e., the difference between the mean bond lengths and mean
electron counts (m.e.c.) of M(1) and M(2) sites are equal within the standard deviations
28 Brigatti & Guggenheim

( MO = |M(1)O M(2)O| < 0.004 ; m.e.c = |m.e.c.M(1) m.e.c.M(2)| < 1.0 e-;
see, for example, in Tables 1-3 (end of chapter) the data by Semenova et al. 1977; Hazen
et al. 1981; Brigatti et al. 1996a; Gnos and Armbruster 2000), whereas some Li-rich
micas (space group C2) have different cation ordering in M(1), M(2) and M(3) sites; e.g.,
zinnwaldite-1M (Guggenheim and Bailey 1977), lepidolite-1M (Backhaus 1983),
zinnwaldite-2M1 (Rieder et al. 1996), ferroan polylithionite-1M and lithian sidero-
phyllite-1M (Brigatti et al. 2000b). The octahedral sheet may show different cation
distributions in M(1), M(2), and M(3), but the size of each octahedron need not differ.
For example, the zinnwaldite-1M (polylithionite-siderophyllite intermediate) structure
refined by Guggenheim and Bailey (1977) shows M(1) M(2) M(3) on the basis of the
site scattering power, whereas M(1) = M(3) M(2) on the basis of size of the polyhedra.
Verification of ordering requires not only the analysis of cation-anion bond length but
also the refinement of octahedral-site occupancies because mean bond lengths of
octahedra with different occupancies may be similar. Therefore, this discussion of
octahedral ordering is based only on samples for which the m.e.c. of each octahedral site
is available.
For trioctahedral true micas of the phlogopite-annite join, the m.e.c. of both M(1)
and M(2) sites increases from phlogopite to annite through ferroan phlogopite and
magnesian annite. This suggests that an increase in the Mg-1 Fe exchange occurs and that
Fe occupies both the M(1) and M(2) sites (Fig. 16). However, ferroan-phlogopite and
magnesian-annite samples (Tables 1a and 1b) have differences in mean bond lengths (to
0.036 ) and in m.e.c. (to 2.5 e-) for the M(1) and M(2) sites. Thus, a slight preference
for cations with larger radii and atomic numbers for M(1) occurs. The greatest differences
between M(1) and M(2) octahedral mean bond distances occur in Al-bearing magnesian
annite from peraluminous granites where Al is ordered in M(2) (Brigatti et al. 2000a).

Figure 16. Mean electron count (m.e.c.) of M(2) [M(2) = M(3)] vs.
m.e.c. of M(1) site. Symbols: filled circles = annite; filled circles, x-
hair =magnesian annite; open circle, x-hair = ferroan phlogopite; open
circles = phlogopite. Estimated average standard deviation: 0.3 e-.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 29

Figure 17. Difference between M(1) and M(2) site mean bond distance
in mica crystals of the phlogopite-annite join. Symbols and samples as
in Figure 16. The average standard deviation on M(1)O and M(2)
O bond distances was evaluated as 0.002 .

Thus, ordering along this join seems to be enhanced where, in addition to Mg2+ and Fe2+,
cations of different size and charge occur in octahedral coordination (Fig. 17).
Although the m.e.c. of M(1) and M(2) increases with the exchange vector of Mg-1Fe
(Fig. 16), annite crystals have MO values much smaller than those for magnesian
annite. For compositions intermediate between those of phlogopite and annite, exchange
vectors that introduce cations of different charge (or vacancies) in octahedral sites
significantly affect the layer topology. In fact, in phlogopite the octahedral sites are equal
-
in size and m.e.c., annite shows octahedral sites with similar m.e.c. ( m.e.c. < 0.4 e ) and
differences in MO bond lengths ( MO < 0.02), whereas crystals of phlogopite-
annite with intermediate compositions always have one larger octahedron and two
smaller octahedra and usually differences in m.e.c. for M(1) and M(2).
The reduction of interlayer separation with Ti content (Fig. 18) is related to
the decrease in the K-O(4) [ O(4) = OH, O, F, Cl ] distance, which is ascribed to Ti-oxy
substitution, Ti-oxy = [6] Ti4 +O22 [6] Mg 2+ 1
1 (OH) 2 ). The interlayer cation is shifted deeper in-
to the interlayer cavity owing to the deprotonation of the O(4) site; thus, the KO(4)
distance decreases with a decrease in interlayer separation. Cruciani and Zanazzi (1994)
observed that the off-center shift of the cation at M(2) is associated with an increase in
the proportion of [6]Ti, and this reveals a [6]Ti preference for the M(2) site.
Li-rich micas in the siderophlyllite-polylithionite join (Fig. 19) show different
patterns of octahedral order. For example, in a synthetic polylithionite (space group
C2/m) with octahedral composition Li2Al (Takeda and Burnham 1969) the ordering
pattern results in a large M(1) site of composition Li0.89Al0.11 and two equivalent M(2)
sites of composition (Li0.55Al0.45). A similar ordering pattern was observed in natural
30 Brigatti & Guggenheim

Figure 18. Interlayer separation vs. octahedral Ti4+ content for mica
crystals along the phlogopiteannite join. Symbols and samples as in
Figure 16. The average standard deviation on the interlayer separation
was evaluated as 0.004 .

Figure 19. Ternary [6]Al3+ [6]Li+ -[6]Fe2+ diagram showing compositional


data for Li-rich micas. Symbols: filled circles = Li-containing annite
crystals; open squares, x-hair = ferroan polylithionite and crystals with
composition intermediate between polylithionite and siderophyllite; open
squares=polylithionite; filled squares, x-hair = siderophyllite; filled square
= trilithionite. The open circles indicate the composition of the end
members (from Brigatti et al. 2000b).
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 31

trilithionite-1M (Sartori 1976; Guggenheim 1981) and in polylithionite-2M1 and 2M2


(Takeda et al. 1971; Sartori et al. 1973; Swanson and Bailey 1981).
In some Li-rich micas, the ideal layer symmetry is reduced from C2/m to C2, as a
result of a different pattern in octahedral ordering in the cis-octahedral sites (Guggenheim
and Bailey 1977; Guggenheim 1981; Backhaus 1983; Mizota et al. 1986; Rieder et al.
1996; Brigatti et al. 2000b). These minerals have M(1)O M(3)O > M(2)O and
occasionally M(1)O M(2)O > M(3)O (Backhaus 1983; Brigatti et al. 2000b).
The scattering efficiency for the M(1), M(2) and M(3) sites implies ordering with M(1)
M(2) M(3), M(1) = M(3) <M(2); or M(2) = M(3) < M(1). Where all sites have different
occupancies in Li-rich crystals, both M(1) layers and M(2)- layers are present.
Brigatti et al. (2000b) studied the crystal structure of 1M micas with composition in
the polylithionite-siderophyllite-annite field. They showed that the variation in
composition follows a near-continuous trend between polylithionite and siderophyllite.
They defined the ordering parameter QM(2),M(3) as:
M(3) O M(2) O
QM ( 2),M (3) = 1
2
[ M(2) O + M(3) O ]
Using the ordering parameter, QM(2),M(3), differences in bond lengths between the
M(2) and M(3) sites are nearly constant for polylithionite and ferroan polylithionite in the
XSid-Pl range between 1.0 and 0.7 [XSid-Pl = [6](Li + Al) / [6](Li+Al+Fe2+)]. However, the
difference rapidly decreases starting at XSid-Pl 0.6 and the layer symmetry approaches
that of space group C2/m rather than C2. The ordering parameter EM(2),M(3) is a measure
of the m.e.c. in the M(2) and M(3) sites, and is defined as:
e M(2) e M(3)
E M (2 ),M ( 3) = 1
2
[e M(2) + e M(3)]
The ordering parameter, EM(2),M(3) indicates ordering in M(2) and M(3) for 0.6 XSid-
Pl 0.4. Therefore, the M(2) and M(3) sites appear to be completely disordered only when
XSid-Pl < 0.4. Although examples of polylithionite with disordered cation distributions for
M(2) and M(3) are not unusual, Brigatti et al. (2000b) concluded that Fe2+ controls the
cis-site cation distribution and that order-disorder between M(2) and M(3) sites occurs in
a narrow compositional interval (Fig. 20).
The ideal space group of polylithionite-3T allows all three octahedra to be of
different composition. This occurs for polylithionite-3T (Brown 1978) and for lithian
siderophyllite-3T (Weiss et al. 1993), which shows a different ordering pattern for each
octahedron. Masutomilite (ideally KLiAlMn2+AlSi3O10F2), the Mn analogue of ferroan
polylithionite (Mizota et al. 1986), has M(1) and M(3) sites which are nearly equal in size
and scattering power. Both the M(1) and M(3) sites contain Li and Mn2+. The greater
scattering efficiency and smaller size of the M(2) site indicate that M(2) contains Al and
Fe. In contrast, the octahedral ordering pattern in norrishite (KLiMn3+2Si4O12) is such that
low-valence cations occur in M(1) (Li+) and trivalent cations (Mn3+) in M(2) [M(2) =
M(3)] sites.
Several micas were described with total octahedral occupancy midway between
dioctahedral and trioctahedral. However, in many cases, intermediate compositions may
represent interstratified mixtures of dioctahedral and trioctahedral layers (or species). Li-
rich muscovite crystals (Brigatti et al. 2001b) have a total octahedral occupancy of 2.24
apfu. The volume of the M(2) site increases sharply with an increase in Li. The M(1)
cation site is partially occupied. These results seem to indicate a partial dioctahedral-
trioctahedral solid solution.
In trioctahedral brittle micas, octahedral cation ordering was found for bityite and for
anandite. No evidence of ordering, except for the usual mica ordering with M(1)
32 Brigatti & Guggenheim

Figure 20. Variation of (a) QM(2),M(3) and (b) EM(2),M(3) parameters as a


function of composition. The data points at QM(2),M(3) = 0 and EM(2),M(3)
= 0 correspond to C2/m symmetry. Symbols as in Figure 19 (from
Brigatti et al. 2000b).

occupied by a cation whose average charge is smaller and whose average size is larger
than that found in M(2), was detected for kinoshitalite, ferrokinoshitalite and clintonite
(see the new species and new data section). Anandite-2O,
(Ba 0.96 K0.003Na 0.01 ) (Fe 2+2.02 Fe3+0.31 Mg 0.45 Mn 2+0.04 Mn 3+0.04 ) (Fe3+1.38 Si 2.62 )O10S0.84Cl0.16F0.04(OH)0.96,
has octahedral Fe-Mg ordering with two Fe-poor octahedra near the cell corners and two
Fe-rich octahedra near the C-face center (Filut et al. 1985). The Fe-Mg ordering requires
that hydroxyl groups are associated with the Fe-poor octahedra, whereas S replaces (OH)
in the Fe-rich octahedra. Bityite-2M1,
(Ca0.95Na0.02)(Li0.550.45Al2.04 Fe 3+ 0.01 )(Al1.34Si2.02Be0.64)O10(OH)2,

has the trans-M(1) site occupied by Li and vacancies, and the two cis-M(2) sites are
occupied by Al cations (Lin and Guggenheim 1983). Coexistence of dioctahedral [with
M(1)-vacant sites] and trioctahedral [with Li-filled M(1) sites] sheets was suggested to
explain the two patterns of OH vector orientation.
The topology of each octahedron is influenced not only by local composition but
also by the constraints of closest packing within the sheet. Several authors (e.g., Toraya
1981; Lin and Guggenheim 1983; Weiss et al. 1985, 1992) examined the relationships
between composition and the octahedral topology (i.e., variations in the octahedral
dimensions and in octahedral distortions). In agreement with the observation of Hazen
and Wones (1972), who suggested that octahedral flattening is controlled by the
octahedral cation radius, Toraya (1981) suggested for 1M silicate and germanate micas,
that the octahedral flattening angle, , gradually decreases with decreasing misfit
between the tetrahedral and octahedral sheets. He noted also that the tetrahedral lateral
dimensions remain constant. Toraya also showed that the degree of octahedral flattening,
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 33

which reflects variations in octahedral thickness and lateral octahedral dimensions, is


related to lateral misfit between the sheets of tetrahedra and octahedra and, therefore, by
. Lin and Guggenheim (1983) related the counter-rotation of upper and lower octahedral
oxygen triads (the angle of Appelo 1978) to the difference between the M(1)O and
M(2)O distances. They demonstrated that is significantly affected by the field
strength of adjacent octahedral cations and less affected either by the octahedral cation
size or by the misfit between the tetrahedral and octahedral sheets. They also observed
that octahedral flattening and octahedral counter-rotation produce opposing effects.
Octahedral flattening increases mean values of the upper and lower triads, and thus
increases lateral dimensions of the octahedra, whereas the overall effect of counter-
rotation is the reduction of the lateral octahedral size. Weiss et al. (1985) also showed
that octahedral flattening and the counter-rotation of the upper and lower anion triads are
related to the interaction in the whole sheet rather than an individual octahedron, and
suggested geometrical models to predict the octahedral topology by composition.

Figure 21. Variation of M(1) vs. M(1)O bond distance. Symbols and
samples as in Figure 3.

Figure 21 shows the variation of vs. the mean bond distance for the trans M(1)
site. Both and M(1)O increase from trioctahedral micas to dioctahedral micas. As
noted previously, the distortion of an octahedral site is not a simple function of the size of
the cation residing in the octahedron. In fact, distortions in the vacant site in dioctahedral
micas and in the M(1) site in Li-rich micas are caused by the decrease in length of the
shared edges of the M(1) octahedron with respect to the mean edge value of M(1). M(1)
is required to share edges with smaller adjacent octahedra containing cations with high
field strength. In Figure 21, plotted values for the trioctahedral micas (excluding Li-rich)
show scatter, but the general trend suggests that decreases as the site size increases.
From a geometrical point of view (in space group C2/m), a displacement of O(4) along
[001] affects each octahedron in the same way, i.e., M(1)O and M(2)O mean bond
34 Brigatti & Guggenheim

Figure 22. (a) = cos-1 toct / 2MO; (b) deformation induced on


M(1) by a displacement of the O(4) oxygen atom along the [001]
direction; (c) deformation induced on M(2) by a displacement of the
O(4) oxygen atom along [001] direction; (d) deformation produced on
octahedra by a displacement in (001) plane which produces the C2/m
symmetry requirement.

distances decrease equally, whereas M(1) and M(2) values increase equally [modes (b)
and (c), Fig. 22]. Differences between M(1) and M(2) are explained by mode (d) (Fig.
22), with a displacement of the O(4) atom toward M(2). In this way, the M(1)O
distance, and the M(1) value increase at nearly two times the rate at which M(2)O
and M(2) decrease. Mode (d), therefore, does not affect MO [MO = (M(1)O +
2 M(2)O)/3] and [ = (M(1) + 2 M(2))/3] mean values. The results provided
by the geometrical model (see Appendix I) can be compared to the trend observed for the
structures in Figure 23. The parameter otcor (i.e., the difference between the value of the
observed octahedral thickness and the thickness of an ideal octahedron whose edge is
equal to OOunshared) is defined here as:
6
ot cor = ot O O unshared
3
where ot is the observed octahedral thickness and OOunshared is the mean value of the
M(1)and M(2) unshared edges [i.e, the mean octahedral triad value:
OOunshared = (OOunshared M(1) + 2 OOunshared M(2))/3].
The resulting equation of regression is
= -34.352otcor / OOunshared + 54.779 (r = 0.982).
The trend in Figure 23 indicates that the mean value depends nearly entirely on the
displacement of the O(4) atom along the [001] direction. The first-order constant in the
regression equation (i.e., -34.352) is greater than the calculated value from the
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 35

Figure 23. Variation of the mean octahedral flattening angle vs. the
otcor/OOunshared. otcor represents the difference between the octahedral
thickness (actual) value and the thickness of an ideal octahedron whose
edge is equal to OOunshared. OOunshared are the octahedral unshared
edges (i.e., the octahedral triads). Symbols used: filled circles = annite;
filled circles, x-hair = magnesian annite; open circle = phlogopite; open
circle, x-hair = ferroan phlogopite; filled circle, dotted = tetra-ferri-
annite; open circle, dotted = tetra-ferriphlogopite; filled hexagon, x-hair
=norrishite; crosses = preiswerkite; open triangle up = clintonite; filled
triangle up, x-hair =ferrokinoshitalite; filled trangle up = kinoshitalite.

geometrical model which assumes that only O(4) is displaced parallel to the [001]
direction. Thus, we assume for the O(3) position (i.e., the apical oxygen atoms) a similar
displacement along the [001] direction. This displacement suggests the existence of a
very small corrugation in the O(3) and O(4) oxygen-atom plane. Similar results can be
obtained using octahedral mean bond distances MO. For C2/m micas, the geometrical
model also predicts the effect of the O(4) atom displacement along [100] (i.e, the
difference between values of M(1) and M(2) increases concomitant with the
displacement of O(4) along [100]). Toraya (1981) used energy-based arguments to
explain the difference between the M(1) and M(2) sites and, in particular, to explain why
M(1) is usually larger than M(2). The results obtained here seem to confirm the
interpretation of Toraya. In particular, it is shown that a displacement of the O(4) oxygen
atom in the (001) plane should not change the M-O mean value, i.e.,
M(1) - O + 2 M(2) - O 1
. It can be easily shown that the value of +
3 M(1) O
1 1
+ increases. Therefore, the energy of the MO(4) bond decreases.
M(2) O M(3) O
Assuming equal charges in each of the three octahedra, the following relationship (see
Appendix I) can be derived:
36 Brigatti & Guggenheim

1 1 1
E M O(4) QO(4) QM + +
M(1) O M(2) O M(3) O
where EM-O(4) is the M-O(4) bond energy. This equation indicates that cation ordering
resulting in an increase in the charge of M(2) and M(3) and a decrease in charge in M(1)
is even more energetically favorable. In contrast, as O(4) is displaced away from the
center of the ditrigonal silicate ring, the energy related to the O(4)-O(3) bonds is expected
to increase. This mechanism may account for the difference concerning the two
octahedral sites, but further studies are needed to confirm this.
Bailey (1984b) suggested that the large dimensions of the vacant M(1) octahedral
site in dioctahedral micas cause an overshift, (i.e., the intralayer shift parameter), where
the upper tetrahedral sheet is shifted relative to the lower sheet by a value greater than
0.33a1 of the pseudo- hexagonal cell. Apical oxygen atoms of the 2:1 layer are linked to
the diagonal edges of the trans M(1) octahedron, thus causing the M(1) diagonal edge to
increase. This produces an intralayer shift. The intralayer shift results from a
displacement of the apical oxygen atoms from their ideal positions midway among the
three octahedral sites. Trioctahedral micas with all three sites equal in size have the
smallest intralayer shifts whereas the dioctahedral micas show the greatest. The anomal-
ous behavior of norrishite is related to octahedral distortions induced by the Jahn-Teller
effect (Fig. 24).

Figure 24. Differences between the M(1)O and M(2)O octahedral


mean bond distances vs. the intralayer shift. Symbols and samples as in
Figure 3.

Crystal chemistry of micas in plutonic rocks


Most rock-forming silicates have solid solution involving the substitution of
different cations in one or several symmetrically different sites. Their compositions,
cation ordering and topology are sensitive to many environmental conditions occurring
during crystallization (e.g., Ganguly 1982; Hirschmann et al. 1994). In particular, micas
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 37

are rock-forming silicates of great interest for their petrological, crystal-chemical and
thermodynamic significance. In igneous rocks, they participate in mineral-mineral,
mineral-melt, and mineral-fluid equilibria. Thus, their structures may reflect the different
reactions involved (Icenhower and London 1995, 1997; references therein). However,
rock-forming micas have received less attention by crystallographers as petrogenetic
indicators owing to the difficulty in obtaining quality data from a structure determination.
We review below the relatively few systematic studies on the crystal chemistry of
naturally occurring micas crystallized from a melt. Phlogopite-annite appears to be the
most widespread species in plutonic parageneses, whereas dioctahedral mica occurrences
are limited, typically, to peraluminous granitoids.
Many authors have suggested the dependence of the composition of igneous micas
on factors such as bulk host-rock chemistry, oxygen fugacity, H2O fugacity, and (other)
fluid activity (e.g. Arima and Edgar 1981; Barton 1979; Edgar and Arima 1983; Speer
1984). The partition coefficients (D) between micas and coexisting phases were also
recognized as important indicators for melt evolution (e.g., De Albuquerque 1975;
Monier and Robert 1986; Icenhower and London 1995; Wolf and London 1997).
The increase of Mg/(Mg+Fe) in phlogopite with increase in MgO/(MgO+FeO) of the
rock as well as with increase temperature is well-documented (Speer 1984; Puziewicz
and Johannes 1990). Figure 25a suggests that the MgO/(MgO+FeO) ratio of the rock is
related approximately to the content of the M(1) site. In particular, as the
MgO/(MgO+FeO) ratio of the rock increases, the mica composition becomes more
phlogopitic and the M(1)-O mean bond distance decreases. Different crystallization
conditions may account for the poor fit of the data in Figure 25a. For example, the Tapira
carbonatite complex crystallized at a high crustal level (e.g., lower pressure, faster
cooling rates) and is characterized by oxygen fugacity above the NNO buffer (Brigatti et
al. 1996a), whereas peraluminous granites of Sardinia and Antarctica are the products of
ultrametamorphism leading to anatexis of aluminous metasedimentary rocks in the
continental crust (Brigatti et al. 2000a).
Figure 25b shows the interlayer separation vs. bulk rock Al content. Interlayer
separation increases as the Al content of the rock decreases. This relationship is the
structural parameter which better fits the Al rock content. The micas, for which data are
shown in Figure 25b, come from different rock-types, but share a relationship of increas-
ing Ti and Al with increasing bulk-rock Al. The decrease in the interlayer separation (Fig.
25b) is therefore related to the exchange vector [6](Mg,Fe)2+-1 OH--2 [6]Ti4+ O-22 required to
achieve layer-charge neutrality.
Bigi et al. (1993) described ferroan phlogopite and magnesian annite crystals from
mafic rocks occurring at different stratigraphic levels of the Ivrea-Verbano Mafic
Complex (Western Alps, Northern Italy). They noted that some properties, such as poly-
typism with different amounts of stacking disorder coexist in all samples and do not have
a direct or simple petrological cause, whereas octahedral cation disorder in a crystal close
to the contact with metasediments may suggest the incorporation of a restitic assemblage
in the melt. The hotter melt may have preserved the mica (and other refractory minerals),
but may have induced cation disorder of the octahedral sites. Similar results were found
in the study on Fe3+-rich phlogopite from the Tapira alkaline carbonatitic complex
(Brigatti et al. 1996a). The crystal-chemical features of these micas (mostly phlogopite-
1M and tetra-ferriphlogopite-1M) are related to the variation of f(O2), a(H2O) and a(CO2),
in addition to the magma composition during fractional crystallization and cumulus
processes responsible for the generation of the rock sequence. In addition, the disorder in
octahedral cation distribution agrees with field relationships and textural features which
suggest crystallization at high crustal levels and a high cooling rate.
38 Brigatti & Guggenheim

Figure 25. (a) Compositional dependence of M(1)O bond length in trioctahedral


mica from Mg/(Mg+Fe) of the host rock; (b) dependence of interlayer separation
from Al content in the host rock. Symbols: open squares = ferroan phlogopite and
magnesian annite crystals from Diorites of Ivrea-Verbano Zone, Italy (Bigi et al.
1993); open circles = ferroan phlogopite crystals from synitic complex of Valle del
Cervo, Northwestern Italy (Brigatti and Davoli 1990; Bigi and Brigatti 1994);
crosses = magnesian annite from UZ gabbros of Ivrea Verbano Zone, Italy (Bigi et
al. 1993); filled triangles up = ferroan phlogopite from monzonitic complex of Valle
del Cervo, Nortwestern Italy (Brigatti and Davoli 1990); open diamonds =
magnesian annite crystals from peraluminous granites of Sardinia Island (Italy) and
Antarctica (Brigatti et al. 2000a); open triangles down = phlogopite, tetra-
ferriphlogopite and ferroan phlogopite crystals from Tapira carbonatite complex,
Brazil (Brigatti et al. 1996a).

The partition coefficients of major and trace elements between trioctahedral Mg-,
Fe-rich micas and dioctahedral muscovite are a key to understanding thermodynamic
relationships. In addition, the coefficients can lead to an understanding of detailed
kinetics of anatexis of aluminous metasediments and the evolution of peraluminous
granitic suites (De Albuquerque 1975; Tracy 1978; Speer 1984; Dymeck 1983; Monier
and Robert 1986; Patio Douce and Johnston 1991,1993; Icenhover and London 1995).
The octahedral site intercrystalline partitioning between coexisting magnesian annite and
muscovite was recognized as a good indicator of chemical processes during
crystallization (Brigatti et al. 2000a). In peraluminous granites, the compositions of
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 39

trioctahedral micas (mostly magnesian annite) are characterized by significant [6]Al


contents, whereas dioctahedral mica (muscovite) has noticeable celadonite-like
substitutions. Structure refinements of magnesian annite suggest that the M(2) site
topology is largely controlled by [6]Al, whereas M(1) topology is related to both the
Fe/(Fe+Mg) ratio and to [6]Al content. In addition, crystals have significant cation
ordering which is attributed to either crystal-chemical constraints (i.e., the preference of
small high-charge cations for octahedra with OH in cis-orientation), or to intensive
variables acting during crystallization. Corresponding features found in magnesian annite
and in muscovite indicate equilibrium during subsolidus crystallization. For example, the
unit-cell volumes of coexisting micas increase in similar ways and the variation of the
cell volume of magnesian annite depends on the Al intercrystalline partition coefficient
between the M(2) sites of trioctahedral and dioctahedral mica [(D(Al)M(2)Ma/Ms (Figs. 26a
and 26b)]. The volumes of the M sites of both micas decrease with decrease of the Al
saturation index of the rock, thus reflecting the influence of melt composition (Fig. 26c).
In contrast, the behavior of Ti is opposite to that of Al. An increase in Ti content
produces an increase in volume of the M(2) sites and an increase in the volume of the
unit cell in coexisting micas (Fig. 26d) and this, according to Patio Douce et al. (1993),
is related to the temperature during mica growth.

ATOMISTIC MODELS INVOLVING


HIGH-TEMPERATURE STUDIES OF THE MICAS
Studies of samples having undergone heat treatment
Where a transformation occurs in the solid state and the rearrangement of the atoms
in the product is limited relative to the reactant, the use of Paulings electrostatic valency
principle may delineate the transformation process in detail. Dehydroxylation reactions
are topotactic in dioctahedral micas, complete recrystallization does not occur, and thus
there is strong crystallographic control, thereby allowing the use of the electrostatic
valency principle (e.g., Guggenheim et al. 1987 for muscovite). This procedure follows a
transformation step-by-step and describes how bond lengths and bond strengths are
affected at each transitional step. In contrast, decomposition and recrystallization occur
nearly simultaneously with dehydroxylation in trioctahedral micas, and transitional forms
are not known. Thus, the electrostatic valency principle cannot readily be applied to these
materials.
Takeda and Ross (1975) compared two polytypes (1M, 2M1) of Fe-rich phlogopite
(previously referred to as biotite) after passing hydrogen gas at 700C over the sample
to produce reduced and hydrogenated products, and Ohta et al. (1982) used hot argon gas
to produce oxidized (oxy-mica) and hydrogen-depleted versions of each polytype for
comparison. Thus, the effect of iron oxidation/reduction and hydrogenated/deprotoni-
zation was examined for each polytype. A similar study was made by Russell and
Guggenheim (1999) for Fe-rich phlogopite-1M for comparison with Mssbauer data for
the same material.
Another approach is to examine how thermal behavior differs for apparently similar
materials to deduce how the materials may differ (as in the case of smectite and illite,
Tsipursky and Drits 1984; Drits et al. 1993). For these materials, single-crystal structural
studies have not been attempted because the structures have considerable (stacking)
disorder. Thus, thermal behavior was used initially to determine that some aspect of the
structure, in this case cation or vacancy ordering, may differ for different samples of the
same species. Powder X-ray diffraction was then used to confirm that these differences
existed.
40

Figure 26. Relationships


between coexisting magnesian
annite-1M and muscovite-2M1
crystals in peraluminous
granites from Sardinia Island
and Antarctica (Brigatti et al
2000a). (a) unit cell volume of
magnesian annite vs. unit cell
volume of muscovite; (b)
magnesian annite unit cell
volume vs. D(AlM(2))Ma/Ms
partition coefficients (AlM(2) =
Al in M(2) sites; Ma =
magnesian annite; Ms
muscovite); (c) ratio between
M(1) and M(2) site volumes in
magnesian annite vs. the Al
saturation index (A.S.I.). of the
Brigatti & Guggenheim

host rock; (d) Muscovite cell


volume vs. the M(2) site
titanium content of magnesian
annite and muscovite (TiMa /
(TiMa + TiMs) (from Brigatti et
al. 2000a).
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 41

Dehydroxylation process for dioctahedral phyllosilicates


Bailey (1984b) described the general differences between the orientation of the OH
vector between trioctahedral and dioctahedral micas. In trioctahedral micas where each of
the three octahedral sites is occupied by the same cation, the OH vector points nearly
vertical to the (001) plane. In this way, the proton is nearly equidistant from the three
octahedral cations, and thus, equidistant from the sources of the positive charges
originating from the octahedral sheet. The interlayer cation sits directly above the OH
group so that the proton is between the oxygen atom of the OH and the interlayer cation.
Because they are of like charge, the interlayer cation and the proton interact (repulsion),
but the repulsions are directed along the vertical to the (001) plane, thereby positioning
the interlayer cation away from the proton and creating an increased separation between
adjacent 2:1 layers. Hence, fluorine substitution for OH in trioctahedral micas produces a
smaller interlayer separation and smaller c-axis dimension because the negatively
charged F anion attracts, rather than repulses, the interlayer cation. This is also why F-
rich trioctahedral micas generally have a greater thermal stability than a mica of equal
composition, but F-poor.

Figure 27. Projection near the (001) plane to


illustrate the relation between the interlayer cation
(K), the (underlying) O-H vector, and the O(2)
atom. Note that the hydrogen is closely associated
with the K-O(2) bond. The K-O(2) bond is weaker
than the other K-O bonds and weakens further at
high temperature. Note also that the silicate ring is
ditrigonal and not hexagonal.

In contrast to trioctahedral forms, dioctahedral micas with the vacant site located in
the trans position (trans-vacant or tv 2:1 layers) have a relatively non-symmetric
distribution of positive charges around the OH (Fig. 27). The OH vector is directed
away from the two occupied sites containing trivalent cations and points, in plan view,
toward the vacant site. Thus, in muscovite, the OH vector does not point directly toward
the interlayer cation, and instead the proton is near the interlayer cation, K, and a bonded
oxygen [KO(2)] of the basal oxygen-atom plane. In muscovite (Rothbauer 1971), the O
H vector is inclined by 12 from the basal oxygen plane and, in plan, a straight line may
be drawn from the oxygen of the OH group, through the proton, and to O(2). Of the three
symmetry-unique nearest-neighbor KO bond distances, Guggenheim et al. (1987) found
that the KO(2) bond distance is the longest at room temperature, and therefore, the
weakest. At all elevated temperatures studied (to 650C), this bond remains longer and
increases in length at a faster rate than the other KO bonds. The proximity of the proton
to the KO(2) bond and the rate at which this bond weakens at high temperatures suggest
a preferred path for dehydroxylation, although the actual mechanism is not known.
Dehydroxylation is not a result of destabilization of the structure owing to an increase in
misfit between the tetrahedral and octahedral sheets at higher temperatures
as was suggested by Hazen (1977), because the measured rotation angle, , indicates
that the tetrahedral and octahedral sheets mesh comfortably at temperatures to
dehydroxylation.
42 Brigatti & Guggenheim

The initial process of dehydroxylation in dioctahedral micas remains problematic. In


muscovite, Guggenheim et al. (1987) noted that the weakening of the KO(2) bond with
temperature is consistent with (i) the angular relationship of the OH vector to K and
O(2), and (ii) the O(2) atom deviating from the mean basal plane by an out-of-plane
tetrahedral corrugation as measured by z (see above). Results from a high-temperature
study of paragonite (see below) suggest that the weakening of the KO(2) bond in
muscovite is probably related to an increase in tetrahedral corrugation at high
temperatures. Guggenheim et al. (1987) noted also that mean interatomic distances of the
Al octahedral site do not vary greatly with temperature and that the AlOH bond expands
in a limited way (from 1.906 at 20C to 1.918 at 650C). However, the latter
expansion is greater than the other AlO bonds of the octahedra.
These results clearly indicate that the OH bond does not weaken as a simple
function of temperature below the dehydroxylation temperature. If the length of the OH
bond did expand, the charge on the oxygen atom would be affected (i.e., the proton, as it
moves away from the oxygen atom, would cause undersaturation of the oxygen atom
with respect to positive charge) and the AlOH bond distance would be expected to either
decrease or increase less rapidly than those of the other AlO bonds. Drits (pers. comm.)
suggested that the tetrahedral bridging and non-bridging bond lengths would be affected
also, in accord with Bookin and Smoliar (1985), if the OH bond weakens. It is possible
that the OH bond length is affected only at conditions immediately below the
dehydroxylation event such that, at a critical temperature, the OH bond of muscovite
destabilizes with the formation of H2O molecules. This is consistent with the high-
temperature study of Guggenheim et al. (1987). Other processes are possible and careful
optical (infrared, etc.) studies at high temperature would be useful to obtain a better
understanding. A potential problem of such studies, however, is that the dehydroxylation
process does not appear to occur uniformly within a crystal, and the proton interactions
are complex. Some of these interactions are discussed below.
Dehydroxylation, for example in muscovite, involves H2O loss, and not (OH)- or H2
loss alone. Therefore, it is likely that the OH group that destabilizes initially must attract
the H+ from the adjacent OH group following the reaction: 2(OH) H2O() + Or. The
remaining oxygen, Or, is referred to as the residual oxygen and remains in a muscovite-
like dehydroxylate structure where the Al cations are in five-coordination (Fig. 28). This
rearrangement, to maintain a dioctahedral configuration after H2O loss, distinguishes
the dioctahedral micas from trioctahedral varieties, because there is insufficient room in
trioctahedral micas for such an adjustment and recrystallization occurs upon
dehydroxylation. The muscovite dehydroxylate structure and the corresponding dehy-
droxylate of pyrophyllite were described by Udagawa et al. (1974) and Wardle and
Brindley (1972), respectively.
In addition to comparing bond lengths as a measure of bond strength, the strength of
an electrostatic bond (Pauling bond strength, PBS) is defined as the ratio of the valence,
v, of the cation and the (first) coordination number, n. Guggenheim et al. (1987) used
Pauling bond strengths and the second rule to examine the muscovite structure, the
transitional forms by simulating structures by considering the loss of H2O groups one at
time, and the dehydroxylate structure. More sophisticated models involving bond
strengths and bond lengths are not suitable because these structures have not been refined
and bond lengths are unavailable. Although OH groups are initially equal with respect to
energy in muscovite and would be expected to respond to temperature in identical ways,
the implication here is that dehydroxylation is temporal in that as H2O evolves, the
structure changes to compensate for changes in charge distribution. Evidence for a non-
homogeneous loss of H2O in dioctahedral 10- phyllosilicates was found by Heller-
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 43

Figure 28. A fragment of the crystal structure of an Al-rich dioctahedral mica with the trans
octahedral sites vacant. Part (A) shows the octahedral sheet of muscovite, part (B) shows the
corresponding portion of the muscovite dehydroxylate, and part (C) is muscovite in transition
between a hydroxylate to a dehydroxylate structure. Values refer to the summations of the
contributing positive charge of neighboring cations to the anion. For simplicity, tetrahedral sites
(not shown) have an occupancy that is considered to be Si only (from Guggenheim et al. 1987).

Kallai and Rozenson (1980) by Mssbauer analysis in Fe-containing muscovite and by


Guggenheim et al. (1987) in the thermal analysis of muscovite and by MacKenzie et al.
(1985), as reinterpreted by Guggenheim et al. (1987), in the thermal analysis of
pyrophyllite.
Guggenheim et al. (1987) and Evans and Guggenheim (1988) showed that analogous
processes are found in both muscovite and pyrophyllite, suggesting that the process may
be described by considering Si tetrahedra rather than partially Al-substituted tetrahedra.
Thus, for simplicity in illustration, we assume that the tetrahedral sites contain only Si to
explain the dehydroxylation process atomistically in dioctahedral mica-like phyllo-
silicates. Otherwise, we must consider each oxygen atom as having electrostatic bond
strengths with values dependent on the probability of Al0.25Si0.75 occupancy, as was done
by Guggenheim et al. (1987).
Dehydroxylation models for trans-vacant 2:1 layers
Figure 28A shows a dioctahedral 2:1 layer. Each oxygen atom has a formal charge of
-2.0 electrostatic valence units (evu). In the case of a dioctahedral sheet that is not
undergoing dehydroxylation, each oxygen atom is fully charge-balanced by neighboring
cations, and selected atoms in Figure 28A have associated summations of positive charge
contributions shown. The sums for all the oxygen atoms in the structure shown in Figure
28A indicate that each is balanced also.
In contrast, however, the forms undergoing either complete dehydroxylation (Fig.
28B) or partial dehydroxylation (Fig. 28C) do not have fully charge-balanced oxygen
atoms. For the dehydroxylate form, the residual oxygen atom is greatly undersaturated
with respect to positive charge (e.g., Or has a coordination of two Al3+ cations only, each
in five-coordination, thus PBSOr = 2 PBSAl = 2 3/5 = 1.2 evu). The other oxygen
44 Brigatti & Guggenheim

atoms are each bonded to five-coordinated Al cations and one four-coordinated (Si4+)
cation and thus are oversaturated at 2.2 evu (PBSO = 2 PBSAl + 1 PBSSi = 1.2 + 4/4
= 2.2 evu). The arrow in Figure 28B emanating from the Al cations shows the resulting
direction of movement of the Al cation away from the oversaturated oxygen atoms. This
cation has a high positive charge (3+), which helps saturate the (undersaturated) Or atom.
The PBS involves only approximate electrostatic relationships and it is not an
accurate measure of bond strength in comparison to bond length. However, the
anticipated movement of the Al toward the Or atom will produce a stronger AlOr bond
based on the bond length and the simultaneous movement away from the oversaturated
oxygen atoms produce weaker AlO bonds.
Figure 28C shows a partially dehydroxylated form where some aluminum cations are
in five coordination and others are in six coordination. In the latter case, the distribution
of oversaturated oxygen atoms (labeled 2.1 evu) are such that the direction of anticipated
Al movement (note arrows) is toward the OH group and away from the oversaturated
oxygen atoms. Moving a charged atom closer to an OH group that is balanced (at 2.0 evu
for the oxygen atom of the OH) must result in a readjustment which, in this case, requires
the H+ ion to move further away from its oxygen-atom neighbor, thereby weakening the
OH bond. Aines and Rossman (1985) and Gaines and Vedder (1964) showed that
heating of muscovite produces a shift to lower wave numbers for the OH stretching
frequency, indicating an overall weakening of the OH bond during dehydroxylation over
the average structure of the crystal. Thermal analysis (TGA, DTA, DTG) curves are
consistent with the model in that dehydroxylation does not occur homogeneously
throughout the sample. Thus, dehydroxylation initially occurs relatively rapidly.
However, as some OH groups are lost and sections of the structure contain five-
coordinated Al cations, the remaining OH groups become more tightly bound as AlOH
bonds strengthen, thereby slowing further dehydroxylation. As temperature increases, the
number of five-coordinated Al atoms increases to a point where the AlOH bonds have
all been affected and dehydroxylation proceeds rapidly again. The model predicts that
there is a bimodal loss of H2O involving dehydroxylation and the temperature interval
will be large, as is observed (Fig. 29). Because the thermal energy required to produce
dehydroxylation changes with variations in the bond strength during the process, the area
under the curve of the DTA (or DTG) cannot be used as an estimate of the number of OH
groups involved in either of the two distributions.
Mazzucato et al. (1999) examined the kinetics of muscovite dehydroxylation by in
situ powder X-ray diffraction. They found that the results were compatible with the above
structural model and followed a multi-step process where (i) two adjacent OH groups
form a H2O molecule within the octahedral sheet, followed by (ii) diffusion along the c*
axis through the six-fold silicate ring (Rouxhet 1970), and then (iii) diffusion of H2O in
the interlayer to the crystal surface. The rate limiting step is step (ii). However, this study
is consistent with Heller-Kallai and Rozenson (1980), who advocated nonhomogenous
loss of H2O (see above), and Kalinichenco et al. (1997), who suggested a continuous
nucleation process.
Dehydroxylation models for cis-vacant 2:1 layers
Guggenheim and co-workers considered only trans-vacant dioctahedral micas in the
dehydroxylation process. The possibility of dioctahedral 2:1 layers with the vacant site
located in the cis position (cis-vacant or cv 2:1 layers) had been suggested for mont-
morillonite and other dioctahedral smectites (e.g., Mring and Glaeser 1954; Mring and
Oberlin 1971; Besson 1980; Besson et al. 1982; Drits et al. 1984; Tsipursky and Drits
1984). Although most illite consist of trans-vacant layers, Zvyagin et al. (1985), Drits et
al. (1993), and Reynolds and Thompson (1993) described illites with cis-vacant sites.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 45

Figure 29. Thermal analysis curves


[thermal gravimetric analysis (DTA) and
derivative thermal gravimetric (DTG)] of
muscovite (A) and pyrophyllite (B)
showing two thermal analysis events in
each phase. See text for discussion (from
Guggenheim et al. 1987).

The postulated configuration (Drits et al. 1995) of the cis-vacant 2:1 layer is shown
in Figure 30. In this configuration, the shared edge between any two Al-containing
octahedra is either two oxygen atoms or an oxygen atom and a hydroxyl group. This
differs significantly from the configuration involving the trans-vacant site by both the
position of the vacancy and the shared edge between Al octahedra which consists of
either two oxygen atoms or two hydroxyl groups. Dehydroxylation is still expected to
involve adjacent OH groups, so that a residual oxygen atom is retained in the structure
and one oxygen atom and two hydrogen atoms are liberated (= H2O).
For a cis-vacant 2:1 layer, dehydroxylation produces a structure where there is a
five-coordinated Al(2) site, with one Or atom and four additional oxygen atoms, and an
octahedral site [Al(2)] in trans-orientation with respect to Or (Fig. 31). Paulings
electrostatic valency rule may be used to predict how the structure responds to
dehydroxylation. As before, the tetrahedral sites may be assumed to contain only Si.
Figure 31 shows the postulated structure with each oxygen atom labeled with the sum of
the bond strengths that reach the atom from the neighboring cations (including the Si
cations, which are not shown). Al(2) cations are surrounded by oversaturated oxygen
atoms, except for one very undersaturated Or. Thus, it is expected that the position of this
cation will be further away from the oversaturated oxygen atoms and closer to the
residual oxygen atom.
In contrast, the Al(1) cation is located in a very distorted and large site with two
opposing under-saturated residual oxygen atoms, and this arrangement is inherently
unstable. To compensate, the Al cation positions itself closer to one of the residual
oxygen atoms (illustrated in Fig. 31 as the upper Or). Thus, each Or is partly
46 Brigatti & Guggenheim

Figure 30 (left). The octahedral sheet of an Al-rich dioctahedral mica with the cis octahedral sites
vacant (after Drits et al. 1995).
Figure 31 (right). The structural model of a cis-vacant Al-rich octahedral sheet after initial heating.
The OH groups have been lost and a residual O atom remains. Compare this figure to Figure 30.
Al(1) atom is located in a very distorted octahedral site, and this atom will readjust its position to a
structure as depicted in Figure 32 (after Drits et al. 1995).

compensated by an adjacent Al(1) and the resultant nearest neighbor arrangement around
Al(1) becomes five-coordinated (Fig. 32). Drits et al. (1995) noted that the movement of
Al(1) toward Or also requires a closer approach to O(5), which is destabilizing. They
suggested that this structure (Fig. 32) transforms to the trans-vacant dehydroxylated
structure (Fig. 28) with increasing temperature by the migration of Al(1) to the vacant
site depicted in Figure 32.
The models as presented in Figures 28 and 32 are significantly different and thus
they have unique diffraction patterns and different a and b cell parameters. Drits et al.
(1995) considered several dioctahedral cis-vacant phyllosilicates, including illite and
montmorillonite. In montmorillonite, the b value initially increases with increasing
temperature, but decreases from 500 to ~650C, after which it again increases with
increasing temperature. The decrease in the b value is related to the change in structure
illustrated from Figure 31 to Figure 32. Drits et al. (1995) suggested that the interlayer
cation prevents tetrahedral rotation in illite, but because montmorillonite does not have an
interlayer cation that resides within the silicate ring, tetrahedral rotation is not inhibited.
Thus, unlike cis-vacant illite, the lateral dimensions in cis-vacant montmorillonite can
decrease, and cis-vacant montmorillonite can more easily adjust to dehydroxylation than
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 47

Figure 32. The Al(1) atom has move closer to the


residual oxygen atom and the octahedral coordination of
Al(1) (Fig. 31) becomes five-coordinated. As tempera-
ture increases, Al(1) moves to the vacant site (note
arrow) and the structure becomes trans vacant.

cis-vacant illite. At temperatures greater than ~ 700C, both cis-vacant illite and cis-
vacant montmorillonite transform to the model shown in Figure 28 (derived from the
dehydroxylation of the trans-vacant dioctahedral phyllosilicate) by the migration of Al(1)
of Figure 32 into the vacant site.
Drits et al. (1995) argued that although crystallinity and particle size effects are
important considerations for the dehydroxylation temperatures for illite and
montmorillonite, these effects do not explain why cis-vacant forms dehydroxylate at
higher temperatures (by 150-200C) than trans-vacant forms. Drits et al. (1995)
suggested that one possible reason involves the probability for hydrogen to jump to the
nearest OH group to form a water molecule strongly depends on the distance between the
adjacent OH groups. The shorter the distance, the lesser the thermal energy required for
the dehydroxylation of OH pairs. Studies involving electrostatic modeling would be
useful to relate how the proximity between adjacent OH pairs affects the path the proton
must travel to form an H2O molecule.
A thermodynamic assessment for aluminum-rich cis-vacant and trans-vacant
dehydroxylation reactions is useful. Figure 33 shows a schematic reaction path for both
reactions with respect to temperature. The low-temperature, cis-vacant hydroxyl-rich
form (phase a) appears to have a greater thermal stability than the corresponding trans-
vacant form (phase b). The trans-vacant dehydroxylate structure (c) is the end product in
Figure 33 for both reactions, and this phase appears also to have a different thermal
stability for the two reaction series.
48 Brigatti & Guggenheim

Temperature increasing
Figure 33. A schematic showing two reactions, A and B, with apparent
stability fields with respect to temperature. Reaction A involves phase (a),
which is cis-vacant, and Reaction B involves a trans-vacant reactant, (b).
Reaction A produces a transition phase, a, that is OH poor before
transforming to a trans-vacant dehydroxylate, phase (c). Reaction B
transforms directly to phase (c). Phase (c) appears to have two different
thermal stability ranges depending on the reaction involved, which is a clear
indication that kinetic effects are important in determining where the
transformation to phase (c) occurs. Likewise, the upper temperature limits for
phase (a) and phase (b) are not related to stability, but must be related to
kinetic effects. Note that Pauling bond strength calculations for the residual
oxygen atom (note the values, in evu, at the top right corner above each box)
are consistent with decreasing PBS at elevated temperatures.

Muller et al. (2000c) showed that rehydroxylated illite consisted of only trans-vacant
layers, regardless of the nature of the starting material. Thus, reaction B involves a
(metastable) equilibrium reaction phase b phase c, which is reversible. In contrast,
reaction A has not been reversed, suggesting that if this is an equilibrium reaction, a
significant kinetic barrier prevents a reversal. Thus, the different temperatures for phase a
phase a and phase b phase c are a consequence of resultant processes where the
two forms (a and b) follow separate paths to phase c. This may be the reason why there is
a significant difference in thermal stability for phase c for reaction A vs. reaction B. The
reaction series for reaction A and reaction B must follow a structural pathway consistent
with Paulings second rule. Note that increasing temperature produces structures where
the charge on the residual oxygen atom (Fig. 33) deviates from 2.0 by greater amounts
with increasing temperature for each structure in a given series.
The situation differs, however, for dioctahedral micas containing significant amounts
of divalent cations, and this would be expected, considering the differences in
composition. Tsipursky et al. (1985) inferred that dehydroxylation of celadonite and
glauconite is accompanied by cation migration from cis to trans sites, with cation
migration occurring if Fe is greater than Al. For celadonite, Muller et al. (2000a) found
that trans-vacant layers are transformed to cis-vacant layers upon dehydroxylation and
both types of layers exist upon rehydration (at 80% cis-vacant, 20% trans-vacant). The
transformation involves cation migration and several intermediate structures (see below).
For the glauconite sample studied, which had a significant amount of octahedral
aluminum, the trans-vacant layers were transformed to cis-vacant layers by
dehydroxylation and then to trans-vacant layers upon rehydroxylation.
Muller et al. (2000b) suggested that the dehydroxylated structure of Fe- and Mg-
bearing dioctahedral micas contains structural fragments with different cation occupancy
within the same layer, with each fragment being dioctahedral. In a study using selected-
area electron diffraction, Muller et al. (2000c) found that at near 650C, Mg
preferentially migrates unequally to trans sites, after which it remains fixed. After Mg
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 49

migration, Fe3+ ions redistribute unequally over all cis sites and one of the two trans sites
(a reduction in symmetry from a C cell to a P cell, which occurs here, requires two trans
sites per cell on average). Because the mica structure has partial site occupancy over both
cis and trans sites, the residual oxygen atoms (Muller et al. 2000b) partially occupy
former OH-group sites (instead of the average position between two former OH-group
sites). Perhaps this is related in part to iron oxidation where an oxy-component forms by
loss of hydrogen rather than by a dehydroxylation process only, although some of the
studied materials have relatively low Fe2+-content. Muller et al. (2000b) suggested that
misfit between the octahedral sheet and the tetrahedral sheet may play a role in the cation
migration at high temperatures; the octahedral cations (Fe, Mg) are considerably larger in
size than Al. Thus, if the tetrahedral sheet limits thermal expansion of an Fe, Mg-rich
octahedral sheet, then rearrangement of the octahedral cations is required to produce a
more efficient packing of cations and anions. Muller et al. (2000b) noted that cation
migration is dependent on Al content of the octahedra, with cation migration absent
where octahedral Al-content is greater than that of the other octahedral cations. At
temperatures near 750C, cation migration of a different type was inferred to occur.
Superlattice reflections appear in hk0 electron diffraction patterns, with different crystals
showing that two superstructures may form, some with superperiodicity along a and
some with superperiodicity along b. For the latter it was suggested that the scattering
efficiencies of alternating domains of Mg-rich and Fe-rich regions may produce the
structural modulation.
In a study of interstratified illite-smectite minerals to determine cis-vacant vs. trans-
vacant content of natural and untreated samples, McCarty and Reynolds (1995)
determined that there is a linear trend with a decrease in cis-vacant layers with an
increase in Mg and Fe substitution of octahedral Al, although such trends are not
universally observed (e.g., Ylagan et al. 2000). Characterizing the octahedral ordering
pattern is of potential value in determining if the smectite to illite transformation occurs
dominantly by a solid-state transformation or by dissolution and crystallization. If the
latter mechanism dominates, then cis-vacant illite-smectite may form crystallites
containing greater proportions of trans-vacant sites with increasing illitization, for
example, as a result of temperature changes.
Comparison of Na-rich vs. K-rich dioctahedral forms
High-temperature studies of paragonite-2M1 (Comodi and Zanazzi 2000) showed
that the dehydroxylation process in this Na-rich mica is analogous to that of muscovite-
2M1 and trans-vacant micas. Like muscovite, the OH vector points toward a basal
oxygen atom; in paragonite, this oxygen atom is defined as O(4) (Comodi and Zanazzi
2000), rather than O(2) as in muscovite. Thus, the Na-O(4) bond is the longest nearest-
neighbor bond and remains such to 600C, the highest temperature studied for
paragonite. The increase in the Na-O(4) bond appears related to tetrahedral corrugation
(with z increasing from 0.232 to 0.243). A similar result was suggested by
Guggenheim et al. (1987) for muscovite, although the trend in muscovite was equivocal.
The weakening of Na-O(4) suggests a possible path for H2O migration during
dehydroxylation. Upon dehydroxylation, paragonite transforms to a dehydroxylate
structure much like the muscovite-dehydroxylate and the pyrophyllite-dehydroxylate
structures (see above). With increasing temperature, the interlayer separation increases.
Also, the tetrahedral rotation angle, , for both muscovite and paragonite decreases
(muscovite, 11.8 to 9.2 at 650C, paragonite, 16.2 to 12.9 at 650C) indicating that the
tetrahedral sheet must extend laterally in both structures to compensate for an expanding
octahedral sheet.
Differences between the two structures are more apparent by comparing layer offset.
50 Brigatti & Guggenheim

Lin and Bailey (1984), in a study of the room-temperature structure of paragonite-2M1,


noted that the large layer offset in paragonite in comparison to that in muscovite is related
to both the smaller size of Na relative to K and the corrugation of the basal oxygen-atom
surfaces owing to tetrahedral tilting around the vacant M(1) site. The tetrahedral tilting
places the O(3) basal oxygen atoms of adjacent layers in paragonite close to each other,
thereby producing repulsion that causes a layer offset. The high-temperature study of
Comodi and Zanazzi (2000) appears to confirm this explanation because the corrugation
of the basal oxygen atoms, z, increases at higher temperatures and produces a greater
layer offset. In contrast, the K in muscovite is much larger than Na in paragonite and the
adjacent 2:1 layers are sufficiently separated so that O(3)-O(3) repulsions are minimized.
Heat-treated trioctahedral samples: the O,OH,F site
and in situ high-temperature studies
Takeda and Morosin (1975) obtained cell dimensions to 802C and refined the
crystal structure of a synthetic F-rich phlogopite-1M at 700C. They developed a model
involving misfit between the octahedral and tetrahedral sheets to explain thermal
decomposition. In this model, the octahedral sheet expands at high temperature and the
tetrahedral sheet responds to this expansion by becoming more hexagonal in symmetry
(i.e., the tetrahedral rotation angle, , approaches zero) because the apparent size of the
individual tetrahedra does not expand commensurately. Takeda and Morosin (1975)
stated that thermal decomposition resulted from loss of contact of the anions around the
interlayer cations as approaches zero. Hazen (1977) suggested that misfit and the lack
of congruency between the tetrahedral and octahedral sheets results in decomposition as a
general mechanism. However, this general mechanism has since been discredited by
Guggenheim et al. (1987), although it may apply for certain unusual compositions.
Toraya (1981) noted that a fully extended tetrahedral sheet may not be the only condition
for establishing an upper-temperature limit before decomposition, and he also discussed
how octahedra may change in size and shape in response to thermal effects.
Russell and Guggenheim (1999) studied a near-OH end-member, natural phlogopite-
1M crystal to 600C and found that the KO bond distances increased similarly with
increasing temperature. In trioctahedral micas where each octahedral site is similarly
occupied and the OH vector points along the [001] toward the interlayer cation, all the
KO bond distances would be expected to lengthen as the proton moves away from the
oxygen atom of the OH group (owing to H+ to K+ repulsions). Thus, it is not apparent
from a structural analysis how dehydroxylation is initiated. Dehydroxylation in
phlogopite, however, is consistent with generally higher thermal stabilities for F-rich
trioctahedral micas compared to OH-rich trioctahedral micas of otherwise similar
compositions.
Comparison of the F vs. OH end-member phlogopite structures at high temperatures
showed that the effect of this substitution produced different modes of octahedral
expansion with increasing temperature. For F-rich octahedra, Takeda and Morosin (1975)
found that the octahedra become elongate parallel to the c axis above 400C and there is
a change in thermal expansion for each cell parameter (a, b, or c) at this temperature. In
contrast, although the OH-rich octahedra are larger at elevated temperatures, these
octahedra do not change shape, and there is no change in the rate of linear expansion of
the cell parameters (Russell and Guggenheim 1999). The attractive forces between K+
and F- and the repulsive forces between K+ and H+ affect the interlayer K octahedron for
these two phases: in accordance, the KO octahedron in phlogopite is elongate parallel to
c*, but in fluorophlogopite the octahedron is compressed along c*. The octahedral
distortions for both the Mg-rich octahedra and the K-rich octahedron attributed by
Russell and Guggenheim (1999) to the difference in composition between the OH-rich
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 51

vs. F-rich site assumes that the substitutions of Na, Al and Fe in the natural sample
(K0.82Na0.115)= 0.935(Mg2.28Al0.495Fe0.12)=2.895 do not greatly affect the results.
Heat-treated trioctahedral samples: polytype comparisons
The location and influence of the proton in micas is important in understanding how
mica structures alter (e.g., Bassett 1960; Norrish 1973), the formation of mica polytypes
(e.g., Takuchi 1965), and thermal decomposition (e.g., Guggenheim et al. 1987). Mica-
polytype derivations and descriptions are included in detail elsewhere in this volume.
However, heat-treatment studies have been useful in understanding the influence of the
OH site on mica polytypes. These studies have involved structure determinations of iron-
bearing phlogopite (biotite) that have been reduced (hydroxy component with Fe2+
production) or oxidized (oxy component with Fe3+ production), so that the OH site
may or may not contain H+, respectively. Using samples heated under hydrogen for an
unreported period at 700C, Takeda and Ross (1975) studied 1M and 2M1 polytypes of
similar compositions to determine the effect of stacking on atom positions. They found
that adjacent layers exert an influence on the 2:1 layer and that two oxygen atoms
associated with the octahedra are displaced in the 2M1 polytype relative to the 1M
polytype within the (001) plane. This causes the octahedra to have a deformation that
results in variations in the octahedral bond distances (some longer and some shorter than
most octahedra). In a follow-up study using similar material from the same locality but
with treatment by hot argon gas (oxy-micas), Ohta et al. (1982) found that the interlayer
separation increased significantly for the hydrogenated material relative to the oxy-mica;
this is caused by H+ to K+ repulsions. Ohta et al. (1982) found also that for both
polytypes, Fe was incorporated in the tetrahedral sites upon oxidation. In contrast, in a
study involving heat-treatment and oxidation, Russell and Guggenheim (1999) did not
find a change in tetrahedral-site occupancy by oxidation and heat-treatment, although
they did find results similar to those of Ohta et al. (1982). Russell and Guggenheim
suggested that the apparent change in the tetrahedral site occupancy as found by Ohta et
al. (1982) was a result of using crystals of different starting composition.

ACKNOWLEDGMENTS
We thank V.A. Drits for comments on an early version of this manuscript and D.R.
Peacor and G. Ferraris for comments on the final version. Special thanks to Marco Poppi
for helping in deriving models of mica crystal chemistry. Partial support for this work
was made possible by the donors of The Petroleum Research Fund, administered by The
American Chemical Society, under grant PRF-32858-AC5 and by the U.S. National
Science Foundation, under grant #EAR-0001122. We also thank the Italian MURST
(project Layer silicates: Crystal chemical, structural and petrological aspects) and the
CNR for financial support.
52 Brigatti & Guggenheim

APPENDIX I: DERIVATIONS
This section shows the derivation of some formulae reported in the text.
Derivation of tetrahedral cation displacement, Tdisp.
(OO )2 (T O apical )
T d isp . ( A ) = ( T O basal )2 basal

3 3

Figure A1. Geometrical considerations to derive Tdisp.


T represents the tetrahedral cation, the three Obasal
atoms define the basal oxygen-atom plane and Oapical
repre-sents the oxygen atom of the tetrahedral apex.
OapicalH is the height of the tetrahedron.

The variable Tdisp. is the displacement of the tetrahedral cation from its ideal position (i.e.,
from the center of mass of the tetrahedron). In a tetrahedron (Fig. A1), the center of mass
divides the tetrahedral height (OapicalH) into two parts. The part containing the vertex
(TOapical) is three times larger than the distance of the tetrahedral (T) cation from the
basal oxygen-atom plane (T - H). In the above formula the part under square root is T-H.
Using The Pythagorean theorem and assuming that all ObasalObasal edges are equal, we
obtain:
2 3
(O basal H) = (O basal O basal )
3 2
By equating the two latter relations:
1
(T H) = (T O basal ) (O basal O basal )
2 2

3
For a regular tetrahedron:
(T H) = (T Oapical ) 3
Thus, for a regular tetrahedron Tdisp. is zero. If the tetrahedral cation shifts from the center
of mass of the tetrahedron Tdisp. differs from zero and relates to the modulus of the shift.
Derivation of E1, E2, E3

3 q T 9 q T q 2T q 2T
E1 = E3 =
d TOb T O apical (
IS + 2 d TOb IS + 2 / 3 T Oapical )


q T (q A / 4 ) q T (q A / 4)
E 2 =
(IS / 2 + (T O )/ 3) + O
2 2
(IS / 2 + d TOb )2 +
2
O apical Oapical Oapical
apical apical
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 53

The asymmetric unit and charge distribution produces a pattern of charge as


shown in Figure 9 (see text). The electrostatic energy (E) associated with two charged
atoms is directly proportiol to the product of charges (Q) and inversely proportional
to the distance (d12) between atoms (1,2). The energy E can be estimated as
E = Q1 Q2 d12, where is a constant set equal to 1 (Coulombs law).
Energy E1 is the electrostatic interaction between the tetrahedral cation and the basal
oxygen atoms. Each oxygen atom contributes 1 q t d pob where -1 is the formal
oxygen-atom charge (i.e., the charge of the basal oxygen atom divided by the number of
nearest neighbor tetrahedral cations, qt is the tetrahedral-cation charge, and dpob is the
distance between the tetrahedral cation and the basal oxygen atom. E1 represents the
difference between the E1 calculated for the configuration vs. an ideal configuaration.
The ideal configuration occurs where the position of the tetrahedral cation is located in
the center of mass of the tetrahedron [ i.e., dTOb is substituted by (T-Oapical)/3 ]. Thus, for
a regular tetrahedron, E1 is equal to zero. If the tetrahedron is distorted, E1 differs from
zero and increases (in absolute value) as the tetrahedral cation shifts from the center of
mass of the tetrahedron. E2, E3 can be calculated similarly.
E2 is the electrostatic interaction between the tetrahedral cation and the interlayer
cation. Each tetrahedral cation interacts with three neighboring interlayer cations
(contributions from more distant interlayer cations are omitted). Each interlayer cation
contributes
q T (q A / 12)

(IS / 2 + d T Ob )2 + ( Oapical Oapical )


2

where each interlayer cation is surrounded by 12 tetrahedral cations and the term
involving the square root is the distance between the interlayer cation and the tetrahedral
cation). An expression for E2 is obtained similarly to E1 (i.e., substi-tuting in the
second term (T-Oapical)/3 for dTOb).
E3 is the electrostatic interaction between two opposing tetrahedral cations (the
influence of additional surrounding tetrahedral cations is omitted). The atoms involved
here have the same charge (qT). The product of the charges ( q T2 ) is thus divided by the
distance between atoms (as for E1 and E2). E3 is obtained the same way as E1 and E2.
Derivation of
1 / 3 + k 4 / 3 k2 3
= tan 1 60 or = cos 1 k
k2 1 2
The following assumptions are made:(1) The hexagonal ring distorts by varying the
internal-angle value from 120 by an amount of either +2 or -2 alternating around
the ring. (2) Symmetry plane is present. (3) Each tetrahedron is rigid (i.e., with constant
tetrahedral edges and with each tetrahedral oxygen atom and with each tetrahedral cation
occupying ideal positions).
Thus tetrahedral and octahedral coordinates for the basal and apical oxygen atoms in
a (001) plane (Fig. A2) may be written. From this, as expression for k as a function of ,
can be obtained
60 + 60 60 + 60 2 2

3 cos sin + cos cos + 2 cos + cos +


3 180 180 180 180 180 180
k=
3 60 + 60 + 60 + 60 60 +
+ 3 sin cos + 3 sin cos + sin sin
180 180 180 180 180 180

and simplifying:
54 Brigatti & Guggenheim

2
k= cos .
3 180

Figure A2. The distribution of basal and apical


oxygen atoms for a six-fold silicon tetrahedral
ring with = 0. Black circles represent tetrahedral
basal-oxygen atoms whereas gray circles
represent tetrahedral apical-oxygen atoms.

Explanation of otcor
6
ot cor = ot O O unshared
3
In a regular octahedron, the thickness is equal to 6 3 l , where l is the length of an
octahedral edge. The parameter otcor is the difference between the observed value for the
octahedral thickness of an octahedron with a given mean basal edge and the octahedral
thickness of an ideal octahedron with each edge being the same length as the mean basal
edge.
Explanation of (4)
1 1 1
E M O (4 ) QO ( 4) QM + +
M(1) O M(2) O M(3) O
The energy related to two charged points is proportional to the product of the magnitude
of the charges divided by the distance between the charged particles (Coulombs law).
The energy related to the interaction between the octahedral cation (M) and the O(4)
atom can be estimated from the above formula.
Mica Crystal Chemistry and Influence of P-T-X on Atomistic Models 55

APPENDIX II: TABLES 1-4


TABLE 1. STRUCTURAL DETAILS OF TRIOCTAHEDRAL TRUE MICAS
56 Brigatti & Guggenheim

Table 1a. Structural details of trioctahedral true Micas-1M, space group C2/m

Cell parameters R
Reference Species, locality Rock type Composition A b c E
(sample number)
() () () () (%)
3+ 2+
1. Alietti et al. 1995 Phlogopite, Mt. Skarn (K0.93Na0.04) (Al0.24Fe 0.09 Fe 0.12 5.306(1) 9.195(3) 10.272(3) 100.01(2) 2.9
(n # 1a) Monzoni (Italy) Mg2.48Mn0.01Ti0.02) (Si2.74Al1.26)
O9.99 F0.06 (OH)1.95

2. Alietti et al. 1995 Phlogopite, Mt. Skarn (K0.93Na0.04) (Al0.24Fe3+0.07 Fe2+0.11 5.309(2) 9.180(5) 10.291(4) 100.00(4) 2.8
(n # 1b) Monzoni (Italy) Mg2.55Mn0.01Ti0.02) (Si2.65Al1.35)
O9.96 F0.09 (OH)1.95

3. Alietti et al. 1995 Phlogopite, Mt. Skarn (K0.95Na0.02Ba0.01) (Al0.18Fe3+0.15 5.305(2) 9.189(3) 10.286(3) 99.96(2) 2.9
(n # 2a) Monzoni (Italy) Fe2+0.03Mg2.63Ti0.01) (Si2.60Al1.40)
O9.93 F0.11 (OH)1.96

4. Alietti et al. 1995 Aluminian phlogopite Skarn (K0.95Na0.02Ba0.01) (Al0.47Fe3+0.15 5.299(1) 9.179(2) 10.279(3) 99.90(2) 3.0
(n # 3a) Mt. Monzoni (Italy) Fe2+0.07Mg2.23Mn0.04 Ti0.01) (Si2.50
Al1.50) O10.02 F0.04 (OH)1.94

5. Alietti et al. 1995 Phlogopite, Mt. Skarn (K0.90Na0.02Ba0.02Ca0.02) (Al0.20 5.307(2) 9.199(2) 10.291(2) 99.89(2) 2.5
(n # 4a) Monzoni (Italy) Fe3+0.11Fe2+0.04 Mg2.64Mn0.01)
(Si2.60Al1.40) O9.92 F0.06 (OH)2.02

6. Bigi and Brigatti Ferroan phlogopite, Syenite (Na0.02K0.95) (Al0.05Fe3+0.50 Fe2+0.70 5.335(2) 9.244(2) 10.206(3) 100.08(2) 3.3
1994 (n # M7) Valle Cervo (Italy) Mg1.54Mn0.02Ti0.20) (Si2.81Al1.19)
O10.73 (OH)1.27

7. Bigi et al. 1993 (n Magnesian annite, Gabbro (Na0.02K0.81Ba0.10) (Fe2+1.05 Mg0.92 5.349(2) 9.244(6) 10.132(7) 100.38(4) 3.1
# MP9) Ivrea (Italy) Mn0.01Ti0.67) (Si2.50Al1.37 Fe0.13)
O9.99 F0.06 (OH)1.95

8. Brigatti and Ferroan phlogopite, Monzonite (K0.90Na0.03) (Fe3+0.45Fe2+0.79 5.343(3) 9.258(1) 10.227(2) 100.26(2) 3.3
Davoli 1990 (n # Valle Cervo (Italy) Mg1.43Mn0.01Ti0.23 Li0.01) (Si2.78
M14) Al1.19 Fe3+0.03) O10.44 Cl0.04 (OH)1.52

9. Brigatti and Ferroan phlogopite, Syenite (K0.92Na0.01Ca0.01) (Al0.01Fe3+0.46 5.346(2) 9.252(2) 10.238(4) 100.02(3) 2.4
Davoli 1990 (n # Valle Cervo (Italy) Fe2+0.71Mg1.50Mn0.03 Ti0.15Li0.01)
M32) (Si2.80Al1.20) O10.25 Cl0.02 (OH)1.73

10. Brigatti and Ferroan phlogopite, Granite-monzo- (K0.94Na0.02) (Al0.05 Fe3+0.39 Fe2+0.95 5.337(1) 9.242(2) 10.211(2) 100.15(2) 3.5
Davoli 1990 (n # Valle Cervo (Italy) nite transition Mg1.35Mn0.03Ti0.20 Li0.01) (Si2.79
M62) Al1.21) O10.55 Cl0.01 (OH)1.44

11. Brigatti and Ferroan phlogopite, Monzonite (K0.91Na0.02) (Al0.02 Fe3+0.36 Fe2+0.86 5.345(1) 9.258(2) 10.222(2) 100.23(2) 2.1
Davoli 1990 (n # Valle Cervo (Italy) Mg1.39Mn0.02Ti0.25 Li0.01) (Si2.74
M73) Al1.26) O10.32 Cl0.05 (OH)1.63

12. Brigatti and Ferroan phlogopite, Granite (K0.99Na0.01) (Al0.05Fe3+0.34Fe2+0.91 5.355(1) 9.251(4) 10.246(4) 100.15(3) 6.2
Davoli 1990 (n # Valle Cervo (Italy) Mg1.35Mn0.03 Ti0.23Li0.02) (Si2.85
M13) Al1.15) O10.54 Cl0.01 (OH)1.45

13. Brigatti and Poppi Titanian phlogopite, Lamproite (K0.93Na0.06Ba0.01) (Al0.01Fe3+0.18 5.320(2) 9.207(3) 10.100(2) 100.24(2) 2.0
1993 (n # 18) Jumilla (Spain) Fe2+0.06Mg2.33Mn0.01 Ti0.41) (Si2.94
Al1.06) O10.96 F0.79 (OH)0.25

14. Brigatti and Poppi Aluminian phlogopite, Leucitic (K0.88Na0.07Ca0.03Ba0.03) (Al0.93 5.323(1) 9.219(1) 10.219(4) 100.03(2) 2.7
1993 (n # 20) Grotta dei Cervi basanite Fe3+0.41Fe2+0.39 Mg1.10Mn0.03Ti0.14)
(Italy) (Si2.68 Al1.32) O11.36 F0.14 (OH)0.50

15. Brigatti and Poppi Ferrian phlogopite, Leucitic (K0.92Na0.05Ba0.03) (Al0.14Fe3+0.38 5.326(1) 9.222(1) 10.223(2) 100.04(1) 2.3
1993 (n # 21) Grotta dei Cervi basanite Fe2+0.31Mg2.00Mn0.01Ti0.17) (Si2.68
(Italy) Al1.32) O10.57 F0.16 (OH)1.27
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 57

Tetrahedral Octahedral Sheet thickness Interlayer Basal Mean bond lengths A - O Intralayer Layer Overall
D W <M1 <M2 Tetra- Octa- Separa- oxygen T-O M1-O M2-O Inner Outer shift offset shift
hedral hedral tion 'z a1 a1 a1
()
(u 2)
() ()
(u 2)
() () () () ()
(u 2)
() ()
(u 2)
() (A)
10.2 110.1 59.0 59.0 2.252 2.129 3.482 0.008 1.660 2.066 2.065 2.947 3.408 -0.336 -0.001 -0.337 1.

10.7 110.3 58.9 58.9 2.259 2.134 3.482 0.005 1.662 2.066 2.065 2.935 3.417 -0.335 -0.002 -0.337 2.

11.1 110.1 59.0 58.9 2.258 2.130 3.485 0.003 1.663 2.067 2.064 2.927 3.429 -0.335 0.000 -0.335 3.

12.5 109.6 59.3 59.1 2.251 2.112 3.512 0.006 1.666 2.067 2.054 2.903 3.466 -0.334 0.000 -0.334 4.

10.7 110.3 58.8 58.7 2.253 2.149 3.483 0.002 1.661 2.072 2.070 2.937 3.420 -0.334 0.001 -0.333 5.

6.4 110.4 58.8 58.5 2.247 2.169 3.386 0.005 1.654 2.095 2.078 3.016 3.306 -.0.334 -0.001 -0.335 6.

7.1 110.1 58.7 59.0 2.248 2.151 3.319 0.021 1.667 2.067 2.088 2.983 3.311 -0.336 -0.005 -0.341 7.

5.6 110.4 59.0 58.7 2.257 2.160 3.391 0.008 1.657 2.095 2.077 3.037 3.294 -0.337 -0.004 -0.341 8.

6.4 110.4 58.9 58.7 2.255 2.164 3.408 0.014 1.657 2.092 2.081 3.026 3.316 -0.333 0.000 -0.333 9.

6.3 110.3 58.8 58.6 2.248 2.164 3.391 0.017 1.655 2.088 2.079 3.020 3.306 -0.334 -0.003 -0.337 10.

5.6 110.4 58.9 58.6 2.252 2.169 3.386 0.006 1.656 2.097 2.081 3.037 3.292 -0.336 -0.004 -0.340 11.

6.0 110.6 58.9 58.7 2.270 2.164 3.382 0.026 1.663 2.096 2.080 3.028 3.302 -0.335 -0-002 -0.337 12.

5.9 110.6 59.6 59.2 2.275 2.104 3.286 0.018 1.652 2.077 2.054 2.993 3.261 -0.335 -0.002 -0.337 13.

9.1 110.2 59.1 58.9 2.258 2.136 3.411 0.015 1.659 2.077 2.068 2.956 3.371 -0.333 -0.001 -0.334 14.

9.3 110.2 59.1 58.9 2.261 2.135 3.410 0.008 1.660 2.076 2.070 2.952 3.377 -0.334 -0.001 -0.335 15.
58 Brigatti & Guggenheim

16. Brigatti and Poppi Ferroan phlogopite Leucitite (K0.85Na0.11Ba0.04) (Fe2+0.74Mg1.70 5.330(3) 9.245(2) 10.192(9) 100.35(6) 3.4
1993 (n # 22) (Antartica) Mn0.01Ti0.49) (Si3.25Al0.75) O11.14
F0.31 (OH)0.55

17. Brigatti and Poppi Ferroan phlogopite, Trachyte (K0.90Na0.07Ba0.03) (Al0.02Fe3+0.39 5.331(1) 9.230(2) 10.160(2) 100.19(1) 3.2
1993 (n # 19) Colli Euganei (Italy) Fe2+0.60Mg1.61Mn0.01 Ti0.37) (Si2.75
Al1.25) O11.93 F0.23 (OH)0.84

18. Brigatti and Poppi Ferrian phlogopite, Lamprophire (K0.88Na0.08Ba0.04) (Al0.12Fe3+0.47 5.328(3) 9.219(2) 10.233(3) 99.88(3) 3.4
1993 (n # 23) Alto Adige (Italy) Fe2+0.42Mg1.85Mn0.01 Ti0.14) (Si2.65
Al1.35) O10.56 F0.01 (OH)1.43

19. Brigatti and Poppi Ferrian phlogopite, Lamprophire (K0.91Na0.06Ba0.04) (Al0.13Fe3+0.72 5.328(1) 9.224(2) 10.247(3) 100.01(2) 2.7
1993 (n # 24) Alto Adige (Italy) Fe2+0.30Mg1.67Mn0.01 Ti0.18) (Si2.62
Al1.38) O10.87 F0.04 (OH)1.09

20. Brigatti and Poppi Ferroan phlogo-pite, Leucitic (K0.89Ba0.12) (Al0.24Fe3+0.23Fe2+0.76 5.333(1) 9.241(1) 10.180(1) 100.10(1) 2.2
1993 (n # 25) Grotta dei Cervi basanite Mg1.58Ti0.17) (Si2.59Al1.41) O10.52
(Italy) F0.26 (OH)1.22

21. Brigatti et al. Ferroan phlogopite, Lamproite (K0.96Na0.02Ca0.03) (Al0.22Cr0.05 5.317(1) 9.207(1) 10.232(2) 99.98(2) 2.5
1991 (n # 8) Puebla de Mula Fe2+0.39Mg2.17Mn0.02 Ti0.14) (Si2.86
(Spain) Al1.14) O10.43 F0.20 (OH)1.37

22. Brigatti et al. Phlogopite, Cancarix Lamproite (K0.95Na0.02Ca0.01) (Cr0.03Fe2+0.28 5.306(1) 9.190(1) 10.163(1) 100.11(1) 2.2
1991 (n # 9) (Spain) Mg2.42Mn0.01Ti0.18) (Si2.91Al1.09)
O10.12 F0.72 (OH)1.16

23. Brigatti et al. Ferroan phlogopite, Lamproite (K0.96Na0.02) (Al0.09 Cr0.05Fe2+0.59 5.322(1) 9.228(3) 10.102(1) 100.25(1) 2.2
1991 (n # 10) Fortuna (Spain) Mg1.60Mn0.03Ti0.52) (Si2.93Al1.07)
O10.88 F0.57 (OH)0.55

24. Brigatti et al. Ferroan phlogopite, Lamproite (K0.96Na0.03Ca0.01) (Al0.15Cr0.07 5.315(1) 9.204(1) 10.168(1) 100.13(2) 1.9
1991 (n # 11) Jumilla (Spain) Fe2+0.50Mg1.90Mn0.03 Ti0.33) (Si2.87
Al1.13) O10.71 F0.30 (OH)0.99

25. Brigatti et al. Ferroan phlogopite, Lamproite (K0.95Na0.03) (Al0.04Cr0.05Fe2+0.50 5.314(1) 9.190(1) 10.160(3) 100.18(2) 2.1
1991 (n # 12) Jumilla (Spain) Mg2.09Mn0.02 Ti0.27) (Si2.90Al1.10)
O10.43 F0.44 (OH)1.13

26. Brigatti et al. Ferroan phlogopite, St. Alkaline (K0.92Na0.01Ca0.01) (Al0.01Cr0.01 5.329(1) 9.235(2) 10.190(3) 100.20(2) 2.3
1991 (n # 15) Hilaire (Canada) gabbro- Fe2+0.94Mg1.48Mn0.02 Ti0.39) (Si2.73
peralkaline Al1.27) O10.15 F0.07 (OH)1.78
syenite
27. Brigatti et al. Ferroan phlogopite, Monzonite- (K0.97Na0.02Ca0.01) (Al0.08Cr0.01 5.333(1) 9.256(6) 10.186(4) 100.17(3) 3.0
1991 (n # 16) Sande (Norway) alkali syenite Fe2+1.24Mg1.40Mn0.02 Ti0.23) (Si2.81
Al1.19) O10.32 F0.31 (OH)1.37

28. Brigatti et al. Magnesian annite, Quartz diorite (K0.91Na0.02) (Al0.19 Cr0.01Fe2+1.30 5.323(1) 9.215(2) 10.210(2) 100.14(2) 2.6
1991 (n # 17) Capo Vaticano (Italy) Mg1.24Mn0.01 Ti0.20) (Si2.76Al1.24)
O10.18 F0.02 (OH)1.80

29. Brigatti et al. Phlogopite, Tapira Alkaline carbo- (K0.93Na0.05Ba0.02) (Fe3+0.16Fe2+0.09 5.321(1) 9.211(2) 10.287(1) 99.93(1) 2.7
1996a (n # Tae (Brazil) natitic complex: Mg2.65 Ti0.08) (Si2.84Al1.04Fe3+0.12)
23-1a) bebedourite O10.17 F0.01 (OH)1.82

30. Brigatti et al. Phlogopite, Tapira Alkaline carbo (K0.88Na0.05Ba0.01) (Fe3+0.22Fe2+0.09 5.330(2) 9.230(3) 10.256(4) 99.92(3) 2.7
1996a (n # Tae (Brazil) natitic complex: Mg2.60Ti0.09) (Si2.82Al1.13 Fe3+0.05)
23-1b) bebedourite O10.18 F0.01 (OH)1.81

31. Brigatti et al. Phlogopite, Tapira Alkaline carbo- (K0.87Na0.05Ba0.02) (Fe3+0.23Fe2+0.09 5.318(1) 9.219(3) 10.274(4) 99.88(3) 3.0
1996a (n # Tae (Brazil) natitic complex: Mg2.57Ti0.10) (Si2.81Al1.14Fe3+0.05)
23-1c) bebedourite O10.18 F0.01 (OH)1.81

32. Brigatti et al. Ferroan phlogopite, Alkaline carbo (K0.98Ba0.02) (Fe3+0.24Fe2+0.62Mg1.90 5.341(1) 9.244(2) 10.253(3) 100.09(2) 2.3
1996a (n # Tpg Tapira (Brazil) natitic complex: Mn0.02 Ti0.18) (Si2.71Al1.20Fe3+0.09)
63-2B) bebedourite O10.25 F0.02 (OH)1.73
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 59

4.4 110.3 59.0 58.7 2.270 2.154 3.332 0.020 1.655 2.093 2.072 3.045 3.245 -0.336 -0.007 -0.344. 16.

7.6 110.0 59.3 59.0 2.261 2.125 3.353 0.008 1.657 2.083 2.064 2.976 3.325 -0.335 -0.002 -0.337 17.

9.3 110.2 58.9 58.7 2.250 2.154 3.426 0.010 1.659 2.083 2.074 2.957 3.380 -0.331 0.001 -0.330 18.

9.1 110.3 58.9 58.7 2.262 2.153 3.413 0.001 1.662 2.084 2.073 2.959 3.373 -0.334 0.000 -0.334 19.

8.6 110.4 59.1 59.0 2.271 2.135 3.344 0.007 1.663 2.080 2.071 2.953 3.347 -0.334 -0.001 -0.335 20.

7.6 110.5 58.9 58.8 2.259 2.145 3.413 0.005 1.654 2.079 2.068 2.989 3.333 -0.333 -0.001 -0.334 21.

6.6 110.7 59.2 59.1 2.269 2.116 3.352 0.010 1.650 2.067 2.058 2.989 3.289 -0.335 -0.001 -0.336 22.

5.3 110.0 59.6 59.2 2.261 2.107 3.313 0.010 1.648 2.081 2.056 3.017 3.256 -0.336 -0.002 -0.338 23.

6.8 110.5 59.2 59.0 2.265 2.122 3.357 0.009 1.652 2.074 2.061 2.989 3.300 -0.334 -0.002 -0.336 24.

6.7 110.5 59.2 59.0 2.258 2.123 3.360 0.009 1.649 2.071 2.061 2.990 3.297 -0.335 -0.003 -0.338 25.

7.5 110.2 59.0 58.7 2.252 2.150 3.374 0.013 1.656 2.089 2.071 2.985 3.327 -0.335 -0.004 -0.339 26.

5.3 110.5 58.9 58.6 2.248 2.164 3.365 0.000 1.653 2.094 2.077 3.036 3.276 -0.335 -0.002 -0.337 27.

8.0 110.1 58.7 58.5 2.230 2.170 3.421 0.015 1.650 2.085 2.077 2.984 3.346 -0.336 -0.002 -0.338 28.

8.9 110.6 58.7 58.7 2.259 2.161 3.453 0.000 1.659 2.077 2.077 2.972 3.376 -0.333 0.000 -0.333 29.

8.9 110.3 58.7 58.7 2.248 2.158 3.449 0.000 1.658 2.079 2.079 2.974 3.380 -0.332 0.001 -0.331 30.

8.9 110.3 58.8 58.8 2.255 2.149 3.462 0.006 1.659 2.076 2.073 2.975 3.378 -0.333 0.002 -0.331 31.

8.1 110.2 58.9 58.7 2.254 2.159 3.428 0.009 1.659 2.087 2.079 2.990 3.359 -0.335 -0.001 -0.336 32.
60 Brigatti & Guggenheim

33. Brigatti et al. Tetra-ferriphlogopite, Alkaline carbo (K0.99Na0.01) (Fe3+0.05Fe2+0.17Mg2.70 5.357(2) 9.270(4) 10.319(4) 99.96(3) 3.2
1996a (n # Tas Tapira (Brazil) natitic complex: Ti0.01) (Si3.11Fe3+0.89) O10.08 F0.14
22-1a) glimmerite (OH)1.78

34. Brigatti et al. Tetra-ferriphlogopite, Alkaline carbo (K0.98Na0.02) (Fe3+0.06Fe2+0.17Mg2.75 5.358(2) 9.277(3) 10.308(2) 99.99(4) 3.3
1996a (n # Tas Tapira (Brazil) natitic complex: Mn0.01Ti0.01) (Si3.07Fe3+0.93) O10.17
22-1b) glimmerite F0.05 (OH)1.78

35. Brigatti et al. Phlogopite, Tapira Alkaline carbo- (K0.98Na0.01Ba0.02) (Fe3+0.15Fe2+0.08 5.332(1) 9.239(2) 10.291(2) 99.94(2) 2.8
1996a (n # Tpt (Brazil) natitic complex: Mg2.68Mn0.01 Ti0.08) (Si2.82Al1.11
17-1) perovskite- Fe3+0.07) O10.16 F0.11 (OH)1.73
magnetitite
36. Brigatti et al. Phlogopite, Tapira Alkaline carbo (K0.96Na0.03Ba0.01) (Fe3+0.19Fe2+0.07 5.318(2) 9.214(1) 10.279(2) 100.01(2) 2.8
1996a (n # Tas (Brazil) natitic complex: Mg2.68Ti0.05) (Si2.85Al1.07Fe3+0.08)
27-2Ba) dunite O10.16 F0.03 (OH)1.81

37. Brigatti et al. Phlogopite, Tapira, Alkaline carbo (K0.96Na0.03Ba0.01) (Fe3+0.21Fe2+0.07 5.330(1) 9.235(1) 10.301(1) 99.92(1) 2.5
1996a (n # Tas (Brazil) natitic complex: Mg2.64Mn0.01Ti0.06) (Si2.85Al1.10
27-2Bb) dunite Fe3+0.05) O10.13 F0.06 (OH)1.81

38. Brigatti et al. Ferroan phlogopite, Alkaline carbo (K0.92Ba0.04) (Fe3+0.30Fe2+0.38Mg2.17 5.333(1) 9.238(2) 10.267(2) 99.96(2) 2.8
1996a (n # Tag Tapira (Brazil) natitic complex: Mn0.01Ti0.13) (Si2.76Al1.19Fe3+0.05)
15-4) bebedourite O10.26 F0.06 (OH)1.68

39. Brigatti et al. Ferroan phlogopite, Alkaline carbo (K0.92Ba0.02) (Fe3+0.25Fe2+0.34Mg2.19 5.329(2) 9.228(2) 10.258(3) 100.03(3) 2.8
1996a (n # Tag Tapira (Brazil) natitic complex: Mn0.01 Ti0.13) (Si2.74Al1.15Fe3+0.11)
15-3) bebedourite O10.04 F0.05 (OH)1.91

40. Brigatti et al. Tetra-ferriphlogopite, Alkaline carbo- K0.99 (Fe3+0.10Fe2+0.22Mg2.64Mn0.01 5.338(2) 9.247(1) 10.300(2) 99.96(2) 2.8
1996a (n # Tpq Tapira (Brazil) natitic complex: Ti0.03) (Si2.91Al0.71Fe3+0.38) O10.06
16-4A) perovskite- F0.08 (OH)1.86
magnetitite
41. Brigatti et al. Tetra-ferriphlogopite, Alkaline carbo (K0.95Na0.02) (Fe3+0.23Fe2+0.20 5.356(1) 9.284(2) 10.309(3) 100.03(2) 3.1
1996a (n # Tpq Tapira (Brazil) natitic complex: Mg2.54Ti0.02) (Si3.15Al0.04Fe3+0.81)
16-6B) glimmerite O10.34 F0.10 (OH)1.56

42. Brigatti et al. Tetra-ferriphlogopite, Alkaline carbo (K0.99Na0.01) (Fe3+0.08Fe2+0.17Mg2.73 5.362(1) 9.288(1) 10.321(2) 99.99(1) 3.1
1996b (n # Tas Tapira (Brazil) natitic complex: Ti0.01) (Si3.05Fe3+0.95) O10.17 F0.04
22-1c) glimmerite (OH)1.79

43. Brigatti et al. Tetra-ferriphlogopite, Alkaline carbo K1.02 (Fe3+0.11Fe2+0.20Mg2.68Mn0.01) 5.365(1) 9.292(1) 10.326(1) 99.99(1) 2.5
1996b (n # Tpq Tapira (Brazil) natitic complex: (Si3.05Fe3+0.95) O10.18 F0.07 (OH)1.75
16-6B) glimmerite

44. Brigatti et al. Ferroan phlogopite, Granodiorite (K0.92Na0.03Ca0.02Ba0.04) (Al0.18 5.341(1) 9.252(1) 10.229(2) 100.17(2) 2.9
1998 (n # wa3H) Warburton (Australia) Fe3+0.18Fe2+1.01Mg1.26Mn0.02 Ti0.28)
(Si2.77Al1.23) O10.58 F0.08 Cl0.02)
(OH)1.32
45. Brigatti et al. Magnesian annite, Microgranitoid (K0.93Na0.03Ca0.02Ba0.01) (Al0.21 5.345(1) 9.263(4) 10.234(6) 100.11(2) 3.9
1998 (n # wa8E) Warburton (Australia) enclave in Fe2+1.37Mg1.15Mn0.03 Ti0.25) (Si2.85
granodiorite Al1.15) O10.61 F0.16 Cl0.06 (OH)1.17

46. Brigatti et al. Magnesian annite, Granodiorite (K0.89Na0.03Ca0.03Ba0.02) (Al0.18 5.344(1) 9.258(1) 10.232(1) 100.15(1) 3.3
1998 (n # wa8H) Warburton, (Australia) Fe3+0.13Fe2+1.20Mg1.19Mn0.02 Ti0.29)
(Si2.82Al1.18) O10.76 F0.14 Cl0.05
(OH1.05)
47. Brigatti et al. Ferroan phlogopite, Microgranitoid (K0.92Na0.03Ca0.04Ba0.01) (Al0.31 5.347(1) 9.260(2) 10.229(3) 100.07(3) 2.8
1998 (n # wa23e) Warburton (Australia) enclave in Fe3+0.16Fe2+1.10Mg1.23Mn0.01 Ti0.19)
granodiorite (Si2.77Al1.23) O10.67 F0.12 Cl0.02
(OH)1.19
48. Brigatti et al. Ferroan phlogopite, Alkaline carbo (K0.95Na0.02Ba0.03) (Fe3+0.23Fe2+0.38 5.332(1) 9.230(2) 10.267(1) 99.99(1) 2.8
1999 (n # Tapira (Brazil) natitic complex: Mg2.25Mn0.01 Ti0.13) (Si2.76Al1.17
TAG15-4b) bebedourite Fe0.07) O10.28 F0.05 (OH)1.68

49. Brigatti et al. Phlogopite, Tapira Alkaline carbo- (K0.97Na0.01Ba0.02) (Fe3+0.20Fe2+0.11 5.323(1) 9.219(1) 10.282(1) 99.93(1) 2.4
1999 (n # TpQ16- (Brazil) natitic complex: Mg2.59Mn0.01 Ti0.05) (Si2.90Al1.06
4Ab) perovskite- Fe0.04) O10.12 F0.06 (OH)1.82
magnetitite
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 61

10.8 109.6 58.7 58.7 2.254 2.168 3.487 0.002 1.670 2.088 2.089 2.952 3.446 -0.334 0.001 -0.333 33.

10.9 110.1 58.9 58.9 2.271 2.156 3.454 0.000 1.677 2.087 2.085 2.941 3.440 -0.333 -0.001 -0.334 34.

8.8 110.7 58.8 58.7 2.265 2.159 3.447 0.001 1.663 2.081 2.080 2.977 3.379 -0.333 0.000 -0.333 35.

8.5 110.7 58.6 58.6 2.256 2.164 3.448 0.000 1.656 2.078 2.077 2.980 3.364 -0.335 -0.001 -0.336 36.

8.5 110.7 58.6 58.6 2.261 2.167 3.457 0.001 1.660 2.081 2.082 2.987 3.372 -0.333 0.000 -0.333 37.

8.6 110.2 58.8 58.7 2.257 2.157 3.442 0.005 1.660 2.083 2.078 2.981 3.372 -0.333 0.000 -0.333 38.

8.5 110.4 58.7 58.6 2.252 2.167 3.431 0.001 1.658 2.085 2.079 2.977 3.365 -0.335 0.000 -0.335 39.

9.1 110.2 58.7 58.7 2.257 2.164 3.467 0.003 1.662 2.084 2.083 2.978 3.394 -0.334 0.000 -0.334 40.

10.2 110.2 58.8 58.7 2.268 2.168 3.447 0.004 1.673 2.091 2.089 2.955 3.422 -0.334 -0.001 -0.335 41.

11.5 109.9 59.0 59.0 2.274 2.151 3.465 0.001 1.680 2.087 2.087 2.931 3.462 -0.334 0.000 -0.334 42.

11.5 119.9 58.9 58.9 2.271 2.159 3.469 0.001 1.679 2.091 2.089 2.934 3.464 -0.333 -0.001 -0.334 43.

7.0 110.3 59.1 58.8 2.257 2.148 3.407 0.009 1.658 2.091 2.073 3.010 3.330 -0.336 -0.002 -0.338 44.

6.6 109.7 58.5 58.5 2.229 2.186 3.431 0.026 1.654 2.092 2.090 3.027 3.329 -0.336 0.000 -0.336 45.

7.1 110.2 59.0 58.8 2.256 2.152 3.408 0.012 1.659 2.091 2.076 3.010 3.332 -0.335 -0.002 -0.337 46.

6.8 110.3 59.0 58.8 2.262 2.153 3.395 0.010 1.657 2.090 2.075 3.010 3.319 -0.333 -0.001 -0.334 47.

9.1 110.5 58.7 58.7 2.260 2.163 3.428 0.000 1.662 2.082 2.079 2.965 3.378 -0.334 0.000 -0.334 48.

8.8 110.7 58.6 58.6 2.259 2.164 3.446 0.002 1.659 2.078 2.078 2.974 3.372 -0.333 0.000 -0.333 49.
62 Brigatti & Guggenheim

50. Brigatti et al. Ferroan tetra- Alkaline carbo- (K0.99Na0.01) (Fe3+0.30Fe2+0.54Mg1.99 5.370(1) 9.306(1) 10.319(1) 100.00(1) 3.0
1999 (n #TPQ16- ferriphlogopite, Tapira natitic complex: Mn0.02 Ti0.01) (Si3.01Al0.13Fe0.86)
4Ac) (Brazil) perovskite- O10.04 (OH)1.96
magnetitite
51. Brigatti et al. Magnesian annite, Sos Peraluminous (K0.95Na0.04) (Al0.35Fe3+0.01Fe2+1.45 5.352(1) 9.268(3) 10.255(3) 100.27(2) 3.2
2000a (n # a4) Canales pluton, granite Mg0.77Mn0.04 Ti0.21) (Si2.71Al1.29)
Sardinia (Italy) O10.15 F0.05 (OH)1.80

52. Brigatti et al. Magnesian annite, Peraluminous (K0.93Na0.03Ca0.01) (Al0.54Fe3+0.01 5.336(1) 9.239(2) 10.200(2) 100.29(2) 2.7
2000a (n # b1) Tinker Glacier granite Fe2+1.41Mg0.83Mn0.03 Ti0.17) (Si2.62
(Antarctica) Al1.38) O10.46 (OH)1.54

53. Brigatti et al. Magnesian annite, Peraluminous (K0.96Na0.03Ca0.01Ba0.01) (Al0.48 5.347(2) 9.257(1) 10.211(1) 100.27(2) 3.1
2000a (n # c3-31) Tinker Glacier granite Fe2+1.48Mg0.70Mn0.06 Ti0.20) (Si2.63
(Antarctica) Al1.37) O10.38 F0.01 (OH)1.61

54. Brigatti et al. Magnesian annite, Peraluminous (K0.96Na0.01) (Al0.64Fe2+1.33Mg0.73 5.328(1) 9.222(2) 10.197(2) 100.26(1) 3.2
2000a (n # cc1) Tinker Glacier granite Mn0.04Ti0.17) (Si2.68Al1.32) O10.44
(Antarctica) (OH)1.32

55. Brigatti et al. Magnesian annite, Sos Peraluminous (K0.96Na0.02Ca0.03Ba0.01) (Al0.60 5.339(1) 9.232(2) 10.208(2) 100.30(2) 3.6
2000a (n # Canales pluton, granite Fe2+1.36Mg0.73Mn0.02Ti0.14) (Si2.69
Gfs15a) Sardinia (Italy) Al1.31) O10.31 F0.12 (OH)1.57

56. Brigatti et al. Magnesian annite, Riu Peraluminous (K0.98Na0.02) (Al0.50Fe2+1.46Mg0.70 5.344(2) 9.256(3) 10.237(2) 100.27(2) 3.2
2000a (n # H87) Morunzu, Sardinia granite Mn0.03Ti0.16) (Si2.72Al1.28) O10.25
(Italy) F0.15 Cl0.03 (OH)1.57

57. Brigatti et al. Annite, Pikes Peak, Granitic (K0.99Na0.01) (Al0.13Fe3+0.21Fe2+2.29 5.384(1) 9.324(1) 10.254(1) 100.86(1) 2.6
2000b (n # 120) Colorado pegmatite Mg0.10Mn0.01Ti0.25) (Si3.14Al0.86)
F0.26 O10.95 (OH)0.79

58. Brigatti et al. Siderophyllite, Pikes Granitic (K0.95Rb0.02Na0.05) (Al0.84Fe3+0.24 5.358(2) 9.280(3) 10.151(2) 100.10(1) 3.3
2000b (n # 26 ) Peak, Colorado pegmatite Fe2+1.63Mg0.10 Zn0.01 Li0.17Ti0.02)
(Si2.94Al1.06) O10.93 F0.90 (OH)0.17

59. Brigatti et al. Aluminian annite, Granitic (K1.00Na0.01) (Al0.35Fe3+0.16Fe2+2.22 5.372(1) 9.313(1) 10.204(1) 100.52(1) 3.6
2000b (n # 33 ) Pikes Peak, Colorado pegmatite Mn0.08Ti0.11 Li0.08) (Si3.09Al0.91)
O10.95 F0.26 (OH)0.79

60. Comodi et al. Cesian, tetra-ferri- Synthetic Cs0.89 (Fe3+0.03Fe2+2.97) (Si3.07 5.486(1) 9.506(1) 10.818(1) 99.67(6) 3.7
1999 annite Fe3+0.90Al0.03) O10 OH2

61. Donnay et al. Tetra-ferri-annite Synthetic K1.00 Fe2+3.00 (Si3.00Fe3+1.00) O10 5.430(2) 9.404(5) 10.341(3) 100.1(1) 9.3
1964 (OH)2

62. Guggenheim 1981 Trilithionite, Pegmatite (K0.79Rb0.07Cs0.03Na0.03Ca0.01) 5.209(2) 9.011(5) 10.149(5) 100.77(4) 3.5
Radkovice, Jihlava, (Li1.48Fe2+0.02Fe3+0.008 Mg0.05
Moravia (Czech Mn0.03Al1.30) (Si3.49Al0.51) O10
Republic) (OH,F)2
63. Guggenheim and Manganoan Metamorphosed (K0.85Na0.19Ba0.06) (Fe3+0.06Mg1.74 5.380(2) 9.295(2) 10.318(4) 99.96(2) 5.4
Kato 1984 (n # 1) phlogopite, manganese Mn2+0.95Mn3+0.18) (Si2.75Al1.15
Nodatamagawa, Iwate deposit Ti0.03Fe3+0.07) O10.01 F0.09 (OH)1.90
Prefecture (Japan)
64. Guggenheim and Barian, manganoan, Metamorphosed (K0.58Na0.09Ba0.35) (Fe3+0.04Al0.35 5.330(2) 9.245(3) 10.240(3) 99.92(2) 3.8
Kato 1984 (n # 5) phlogopite, manganese Mg2.10 Mn2+0.52 Mn3+0.22) (Si2.33
Nodatamagawa, Iwate deposit Al1.65Ti0.01) O10.75 F0.07 (OH)1.18
Prefecture (Japan)
65. Hawthorne et al. Rubidian, cesian, Granitic K0.46Cs0.23Rb0.28 (Al0.38Fe2+1.00 5.343(1) 9.247(2) 10.397(3) 100.04(2) 4.5
1999 phlogopite, Red Cross pegmatite Mn0.04Ti0.04Mg1.20 Li0.34) (Si2.91
Lake, Manitoba Al1.09) O10 F0.45 (OH)1.55
(Canada)
66. Hazen and Annite, Pikes Peak, Granite (K0.88Na0.07Ca0.03) (Al0.09Fe3+0.19 5.3860(9) 9.3241(7) 10.2683(9) 100.63(1) 4.5
Burnham 1973 Colorado Fe2+2.22Mg0.12Mn0.05 Ti0.22) (Si2.81
Al1.19) O10.35 F0.22 Cl0.05 (OH)1.38
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 63

10.8 110.0 58.9 58.8 2.269 2.170 3.455 0.006 1.678 2.097 2.092 2.948 3.446 -0.334 0.000 -0.334 50.

8.5 110.1 59.3 58.8 2.259 2.148 3.424 0.011 1.665 2.101 2.073 2.985 3.373 -0.338 -0.004 -0.342 51.

7.6 110.1 59.4 58.9 2.255 2.130 3.395 0.019 1.658 2.094 2.063 2.991 3.337 -0.338 -0.003 -0.341 52.

7.6 110.2 59.3 58.9 2.258 2.140 3.391 0.019 1.661 2.097 2.070 2.993 3.341 -0.338 -0.002 -0.340 53.

8.1 110.2 59.5 58.9 2.251 2.128 3.404 0.021 1.657 2.093 2.058 2.978 3.348 -0.338 -0.003 -0.341 54.

7.7 110.2 59.3 58.9 2.251 2.137 3.404 0.008 1.658 2.091 2.067 2.992 3.340 -0.339 -0.003 -0.342 55.

8.1 110.1 59.4 58.8 2.260 2.138 3.415 0.015 1.663 2.101 2.066 2.989 3.357 -0.338 -0.004 -0.342 56.

1.5 110.2 58.8 58.4 2.250 2.196 3.374 0.000 1.658 2.117 2.098 3.143 3.212 -0.336 -0.023 -0.359 57.

5.0 110.1 59.0 59.4 2.252 2.123 3.367 0.009 1.668 2.059 2.087 3.051 3.279 -0.333 0.001 -0.332 58.

2.0 110.2 58.5 58.4 2.241 2.201 3.349 0.002 1.656 2.109 2.100 3.122 3.211 -0.338 -0.009 -0.347 59.

0.3 110.5 59.3 59.2 2.293 2.180 3.899 0.013 1.688 2.132 2.128 3.359 3.372 -0.333 +0.002 -0.331 60.

6.4 110.3 59.3 59.3 2.318 2.152 3.394 0.010 1.687 2.107 2.106 3.055 3.351 -0.334 0.001 -0.333 61.

7.3 112.1 61.0 58.6 2.259 2.056 3.397 0.070 1.632 2.118 1.970 2.950 3.270 -0.357 -0.007 -0.364 62.

6.8 110.8 58.1 57.9 2.254 2.245 3.409 0.008 1.663 2.122 2.110 3.027 3.337 -0.331 -0.001 -0.332 63.

11.0 110.6 58.8 58.7 2.273 2.161 3.380 0.002 1.672 2.086 2.078 2.910 3.413 -0.332 0.001 -0.331 64.

3.5 110.8 59.5 59.0 2.261 2.125 3.591 0.017 1.652 2.093 2.064 3.141 3.296 -0.338 -0.001 -0.339 65.

1.6 110.4 58.6 58.3 2.252 2.207 3.380 0.014 1.660 2.121 2.101 3.143 3.215 -0.334 -0.018 -0.352 66.
64 Brigatti & Guggenheim

67. Hazen and Phlogopite, Franklin, Marble (K0.77Na0.16Ba0.05) Mg3.00 5.3078(4) 9.1901(5) 10.1547(8) 100.08(1) 4.1
Burnham 1973 New Jersey (Si2.95Al1.05) O10 F1.30 (OH)0.70

68. Hazen and Finger Phlogopite, Franklin, Marble (K0.77Na0.16Ba0.05) Mg3.00 5.260(1) 9.100(1) 9.791(9) 100.68(4) 14.7
1978 (high New Jersey (Si2.95Al1.05) O10 F1.30 (OH)0.70
pressure)

69. Hazen et al. 1981 Tetra-ferriphlogopite, Volcanic (K0.97Na0.01Ba0.02) (Fe2+0.03Mg2.46 5.329(1) 9.230(2) 10.219(1) 99.98(1) 3.0
(n # Y253) Cupaello (Italy) melilite Ti3+0.09 Li0.23Na0.11) (Si3.31Al0.04
Fe3+0.65) O10 F2.00

70. Joswig 1972 Phlogopite (K0.90Na0.02) (Al0.07Fe2+0.16Mg2.70 5.314(1) 9.2024(5) 10.1645(7) 100.05(1) 2.0
(Madagascar) Ti0.03) (Si2.91Al1.09) O9.90 F1.13
(OH)0.97

71. Kato et al. 1979 Manganoan Metamorphosed (K0.73Na0.32Ba0.11) (Fe3+0.03Mg2.27 5.349(2) 9.241(2) 10.282(4) 99.96(2) 10.6
(n # 2) phlogopite, manganese Mn2+0.49) (Si2.86Al1.07Ti0.02 Fe3+0.05)
Nodatamagawa, Iwate deposit O10.34 F0.09 (OH)1.57
Prefecture (Japan)
72. McCauley et al. Fluoro phlogopite Synthetic (K0.98Na0.04) Mg2.97 (Si2.98Al1.02) 5.308(2) 9.183(3) 10.139(1) 100.07(2) 6.1
1973 O9.90 F1.94 (OH)0.16

73. Medici 1996 (n # Phlogopite, Tapira Alkaline carbo (K0.98Na0.01) (Fe3+0.08Fe2+0.13Mg2.73 5.330(1) 9.239(1) 10.305(1) 99.89(1) 3.3
TPP16-6a) (Brazil) natitic complex: Ti0.06) (Si2.82Al1.04Fe3+0.14) O10.01
garnet magnetite F0.11 (OH)1.88

74. Medici 1996 Octa-ferroan tetra- Alkaline carbo (K1.00Ba0.01) (Fe3+0.01Fe2+0.60Mg2.36 5.360(1) 9.293(1) 10.314(2) 100.01(1) 2.8
ferriphlogopite, Tapira natitic complex: Mn0.01 Ti0.01) (Si3.03Al0.07Fe3+0.90)
(n # TPP16-6b) (Brazil) garnet magnetite O10.08 F0.01 (OH)1.91

75. Medici 1996 (n # Octa-ferroan tetra- Alkaline carbo (K1.97Ca0.03 Ba0.01) (Fe2+0.60Mg2.38 5.3637(5) 9.2908(8) 10.321(1) 99.995(9) 2.5
TPP16-6c) ferriphlogopite, Tapira natitic complex: Mn0.01Ti0.01) (Si3.02Al0.06Fe3+0.92)
(Brazil) garnet magnetite O10.05 F0.04 (OH)1.91

76. Medici 1996 (n # Ferroan phlogopite, Alkaline carbo (K0.95Na0.03) (Fe3+0.04Fe2+0.43Mg2.39 5.351(1) 9.267(2) 10.311(1) 99.99(1) 2.6
TAX27-1) Tapira, Brazil natitic complex: Mn0.01Ti0.08) (Si2.94Al0.78Fe3+0.28)
clinopyroxenite O10.00 F0.05 (OH)1.95

77. Medici 1996 (n # Ferroan phlogopite, Alkaline carbo (K0.98Na0.02Ba0.01) (Fe3+0.10Fe2+0.44 5.3355(8) 9.2457(7) 10.294(2) 99.94(1) 2.5
TAI17-1) Tapira (Brazil) natitic complex: Mg2.36Mn0.01 Ti0.09) (Si2.82Al1.10
bebedourite Fe3+0.08) O10.12 (OH)1.88

78. Medici 1996 (n # Ferroan phlogopite, Alkaline carbo (K0.98Na0.02) (Fe3+0.06Fe2+0.60 5.329(2) 9.244(2) 10.271(3) 99.97(2) 3.6
TAA11-1a) Tapira (Brazil) natitic complex: Mg2.23Mn0.01 Ti0.10) (Si2.84Al1.14
bebedourite Fe3+0.02) O10.11 F0.05 (OH)1.84

79. Medici 1996 (n # Ferroan phlogopite, Alkaline carbo (K0.98Ba0.02) (Fe2+1.14Mg1.73Mn0.04 5.344(1) 9.259(2) 10.280(2) 100.01(1) 2.8
TA9) Tapira (Brazil) naitic complex: Ti0.09) (Si3.00Al0.90Fe3+0.10) O10.17
garnet magnetite F0.01 (OH)1.82

80. Medici 1996 (n # Ferroan phlogopite, Kamafugite (K0.95Na0.04) (Fe2+0.44Mg2.51Ti0.05) 5.331(1) 9.227(1) 10.275(2) 99.96(2) 3.9
LI12a) Limeira, Brazil (Si3.01Al0.92Fe3+0.07) O10.11 F0.18
(OH)1.71

81. Medici 1996 (n # Phlogopite, Malaquias Kamafugite (K0.97Na0.02 Ba0.02) (Fe3+0.03Fe2+0.35 5.317(1) 9.208(2) 10.118(2) 100.15(1) 2.9
MA-1) (Brazil) Mg2.07Ti0.33) (Si2.94Al1.06) O10.21
F0.93 (OH)0.86

82. Mellini et al. 1996 Cesian tetra-ferri- Synthetic Cs0.89 (Fe3+0.03Fe2+2.97) (Si3.07 5.487(1) 9.506(2) 10.826(6) 99.83(3) 5.5
annite Fe3+0.90Al0.03) O10 (OH)2

83. Oberti et al. 1993 Preiswerkite, Ultramafic (K0.02Na0.83) (Al0.93 Fe0.17Mg1.90 5.225(4) 9.050(8) 9.791(9) 100.27(6) 3.8
(n # KP9) Geisspfad complex Cr0.01) (Si2.12Al1.88) O9.99 (OH)2.01
(Switzerland) mean composition
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 65

7.5 110.5 59.0 59.0 2.261 2.125 3.352 0.002 1.650 2.063 2.065 2.969 3.312 -0.334 -0.001 -0.335 67.

9.7 109.3 60.1 59.3 2.280 2.059 3.002 0.000 1.66 2.07 2.02 2.81 3.26 -0.345 0.000 -0.345 68.

5.7 110.8 58.8 58.8 2.275 2.151 3.364 0.003 1.655 2.077 2.077 3.021 3.282 -0.332 0.000 -0.332 69.

7.7 110.6 59.2 59.1 2.268 2.116 3.356 0.001 1.654 2.066 2.063 2.970 3.319 -0.334 0.000 -0.334 70.

6.2 111.3 58.4 58.2 2.265 2.202 3.395 0.018 1.657 2.101 2.090 3.025 3.307 -0.330 -0.002 -0.332 71.

5.9 110.1 59.0 59.0 2.252 2.124 3.356 0.004 1.642 2.062 2.064 3.006 3.273 -0.334 0.000 -0.334 72.

8.6 110.7 58.7 58.6 2.263 2.168 3.458 0.008 1.661 2.084 2.081 2.986 3.374 -0.333 0.001 -0.332 73.

10.3 110.0 58.8 58.8 2.265 2.170 3.457 0.001 1.674 2.092 2.091 2.953 3.435 -0.334 0.000 -0.334 74.

10.4 110.1 58.8 58.8 2.270 2.165 3.460 0.003 1.675 2.091 2.090 2.958 3.433 -0.334 0.000 -0.334 75.

8.0 110.5 58.7 58.6 2.265 2.174 3.451 0.006 1.664 2.091 2.089 3.004 3.367 -0.334 0.000 -0.334 76.

9.0 110.6 58.7 58.7 2.269 2.162 3.440 0.002 1.665 2.084 2.081 2.973 3.382 -0.333 0.000 -0.333 77.

8.5 110.4 58.5 58.5 2.245 2.178 3.447 0.007 1.658 2.087 2.084 2.983 3.372 -0.333 -0.001 -0.334 78.

6.7 110.7 58.6 58.5 2.259 2.178 3.428 0.005 1.659 2.092 2.087 3.024 3.329 -0.334 0.000 -0.334 79.

6.7 110.8 58.6 58.6 2.258 2.169 3.435 0.018 1.655 2.082 2.081 3.019 3.324 -0.333 0.000 -0.333 80.

4.5 110.8 59.3 59.0 2.271 2.123 3.294 0.011 1.648 2.077 2.061 3.026 3.230 -0.334 -0.001 -0.335 81.

0.2 110.0 59.4 59.3 2.284 2.168 3.930 0.015 1.688 2.130 2.125 3.370 3.380 -0.335 -0.002 -0.337 82.

20.0 107.7 59.6 59.5 2.255 2.051 3.073 0.005 1.695 2.025 2.020 2.573 3.514 -0.334 0.000 -0.334 83.
66 Brigatti & Guggenheim

84. Oberti et al. 1993 Preiswerkite, Ultramafic (K0.02Na0.83) (Al0.93 Fe0.17Mg1.90 5.228(7) 9.049(10) 9.819(12) 100.41(13) 4.6
(n # KP17) Geisspfad complex Cr0.01) (Si2.12Al1.88) O9.99 (OH)2.01
(Switzerland)
mean composition

85. Otha et al. 1982 Ferrian phlogopite, Rhyodacite (K0.77Na0.16Ba0.02) (Al0.16Fe3+0.86 5.320(4) 9.210(1) 10.104(1) 100.10(1) 5.0
Ruiz Peak, Valles Fe2+0.01Mg1.67Mn0.01Ti0.34) (Si2.84
Mountains, New Al1.16) O11.62 F0.17 (OH)0.21
Mexico
86. Rayner 1974 Phlogopite (K0.93Na0.04Ca0.03) (Fe2+0.10Mg2.77 5.322 9.206 10.240 100.03 6.6
Ti0.11) (Si2.88Al1.12) O10 F0.51
(OH)1.49

87. Russell and Aluminian phlogopite, Metamorphosed (K Na ) (Al Fe Mg ) 5.3030(4) 9.1805(6) 10.2483(7) 100.05(6) 9.7
0.82 0.12 0.50 0.12 2.28
Guggenheim 1999 White Well (Australia) ultrabasic schist (Si Al ) O F (OH)
2.79 1.21 10 0.07 1.93
(TC = 20)

88. Russell and Aluminian phlogopite, Metamorphosed (K Na ) (Al Fe Mg ) 5.3193(7) 9.207(1) 10.286(1) 100.042(9) 12.8
0.82 0.12 0.50 0.12 2.28
Guggenheim 1999 White Well (Australia) ultrabasic schist (Si Al ) O F (OH)
2.79 1.21 10 0.07 1.93
(TC = 300)

89. Russell and Aluminian phlogopite, Metamorphosed (K Na ) (Al Fe Mg ) 5.3331(7) 9.2316(9) 10.3159(8) 100.004(8) 11.9
0.82 0.12 0.50 0.12 2.28
Guggenheim 1999 White Well (Australia) ultrabasic schist (Si Al ) O F (OH)
2.79 1.21 10 0.07 1.93
(TC = 450)

90. Russell and Aluminian phlogopite, Metamorphosed (K Na ) (Al Fe Mg ) 5.342(3) 9.238(4) 10.357(5) 99.99(1) 6.9
0.82 0.12 0.50 0.12 2.28
Guggenheim 1999 White Well (Australia) ultrabasic schist (Si Al ) O F (OH)
2.79 1.21 10 0.07 1.93
(TC = 600)

91. Russell and Ferroan phlogopite Calcite veins (K0.93Na0.08) (Mg1.57Fe2+1.07Fe3+0.10 5.3346(7) 9.2417(8) 10.182(2) 100.26(1) 3.9
Guggenheim 1999 Silver Crater Mine, hosted within Ti0.10 Mn0.06) (Si2.97Al1.00Ti0.03) O10
(room Bancroft (Ontario) nepheline F0.94 Cl0.01 (OH)1.05
temperature) syenites
92. Russell and Ferroan phlogopite Calcite veins (K0.93Na0.08) (Mg1.57Fe2+1.07Fe3+0.10 5.3099(5) 9.185(1) 10.093(2) 100.07(1) 3.9
Guggenheim 1999 Silver Crater Mine, hosted within Ti0.10 Mn0.06) (Si2.97Al1.00Ti0.03) O10
(heated) Bancroft (Ontario) nepheline F0.94 Cl0.01 (OH)1.05
syenites

93. Sartori 1976 Trilithionite, Elba Granitic (K0.88Na0.06Rb0.05Ca0.01) (Al1.13 5.20(2) 9.01(1) 10.09(1) 99.3(3) 6.7
Island (Italy) pegmatite Li1.31) (Si3.36Al0.64) O10 F1.53
(OH)0.47

94. Semenova et al. Tetra-ferriphlogopite, Ultrabasic and (K1.03Na0.09Ca0.04) (Mg2.89Fe2+0.16 5.358(3) 9.297(3) 10.318(2) 100.02(5) 4.2
1977 Kovdor massif alkaline rocks Mn0.01) (Al0.08Fe3+0.85Ti0.03Si2.98)
O10 (OH)2

95. Steinfink 1962 Tetra-ferriphlogopite, (K0.90Mn0.10) Mg3.00 [Si3.00 (Fe3+, 5.36(1) 9.29(2) 10.41(2) 100.0(2) 13.1
Langhan (Sweden) Mn)1.00] O10 (OH)2.0

96. Takeda and Polylithionite Synthetic K1.00 (Li2.00 Al1.00) Si4.00 O10.00 F2.00 5.188(4) 8.968(3) 10.029(5) 100.45(1) 5.1
Burnham 1969

97. Takeda and Lithium-containing Synthetic (K0.95) (Mg2.80Li0.20) (Si3.25Al0.75) 5.31 9.21 10.13 100.02 7.5
Donnay 1966 phlogopite O10 F2

98. Takeda and Fluoro phlogopite Synthetic (K0.98 Na0.04) Mg2.97 (Si2.98Al1.02) 5.3074(6) 9.195(2) 10.134(1) 100.08(1) 4.3
Morosin 1975 (room temperature) O9.90 (OH0.16,F1.94)

99. Takeda and Ross Ferroan phlogopite, Rhyodacite (K0.78 Na0.16Ba0.02) (Al0.19Fe3+0.19 5.331(2) 9.231(4) 10.173(4) 100.16(3) 4.4
1975 Ruiz Peak, Valles Fe2+0.71Mg1.68Mn0.01 Ti0.34) (Si2.86
Mountains, New Al1.14) O11.12 F0.17 (OH)0.71
Mexico
100. Tateyama et al. Tetra-magnesian Synthetic (K0.96Na0.03) Mg2.84 (Si3.63Mg0.31 5.321(2) 9.238(1) 10.287(1) 100.06(1) 10.4
1974 phlogopite Fe0.03Al0.03) O10 (OH)2
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 67

19.6 107.8 60.0 59.1 2.247 2.061 3.103 0.065 1.688 2.059 2.007 2.592 3.512 -0.342 0.003 -0.339 84.

7.3 110.3 59.5 59.2 2.275 2.112 3.287 0.021 1.655 2.077 2.059 2.962 3.294 -0.331 -0.002 -0.333 85.

8.7 109.0 59.2 59.0 2.270 2.126 3.418 0.005 1.659 2.076 2.064 2.967 3.360 -0.332 -0.003 -0.335 86.

11.2 110.2 59.1 58.9 2.252 2.192 3.459 0.001 1.662 2.072 2.059 2.915 3.424 -0.328 -0.009 -0.337 87.

9.6 110.2 59.1 58.9 2.252 2.130 3.495 0.014 1.660 2.074 2.065 2.968 3.402 -0.336 -0.001 -0.337 88.

8.7 110.2 59.1 59.0 2.252 2.138 3.517 0.006 1.660 2.076 2.072 3.000 3.393 -0.335 -0.001 -0.336 89.

6.7 110.5 58.9 58.8 2.257 2.154 3.532 0.001 1.658 2.085 2.078 3.051 3.352 -0.324 -0.012 -0.336 90.

4.3 110.7 58.7 58.5 2.250 2.175 3.345 0.002 1.650 2.090 2.082 3.051 3.247 -0.336 -0.004 -0.340 91.

4.7 110.6 59.2 59.0 2.269 2.119 3.280 0.016 1.645 2.070 2.059 3.013 3.227 -0.331 -0.001 -0.332 92.

7.4 112.2 60.8 58.5 2.255 2.060 3.387 0.062 1.631 2.113 1.972 2.942 3.269 -0.330 0.017 -0.313 93.

11.5 109.9 59.0 59.0 2.277 2.146 3.460 0.008 1.680 2.086 2.085 2.933 3.458 -0.334 -0.001 -0.335 94.

11.1 110.2 58.1 58.2 2.280 2.218 3.475 0.008 1.681 2.101 2.105 2.945 3.452 -0.338 0.001 -0.337 95.

3.0 113.8 60.2 58.1 2.247 2.095 3.274 0.036 1.619 2.106 1.981 3.000 3.132 -0.351 0.000 -0.351 96.

6.2 110.6 59.4 59.3 2.273 2.102 3.328 0.006 1.651 2.061 2.060 2.995 3.278 -0.333 0.001 -0.332 97.

6.5 110.7 59.4 59.4 2.277 2.095 3.329 0.008 1.650 2.056 2.058 2.987 3.282 -0.335 0.001 -0.334 98.

7.6 110.4 59.2 58.9 2.271 2.138 3.334 0.014 1.659 2.086 2.068 2.972 3.318 -0.335 -0.002 -0.337 99.

7.4 110.8 58.0 58.2 2.230 2.204 3.465 0.016 1.65 2.08 2.09 3.01 3.34 -0.335 -0.003 -0.338 100.
68 Brigatti & Guggenheim

101. Tepikin et al. Annite (K0.88Na0.02Ca0.02) (Fe2+2.31Mg0.28 5.366(5) 9.311(5) 10.16(1) 100.2(2) 13.5
1969 Mn0.02Al0.18Fe3+0.01 Ti0.10Li0.04)
(Si2.71Al1.29) (H3O)0.04 O10 F0.14
(OH)1.86
102. Toraya and Tetra-germanatian, Synthetic K1.0 (Mg1.04Mn1.96) (Ge3.00Al1.00) 5.489(1) 9.509(1) 10.462(3) 100.12(2) 5.0
Marumo 1981 (n manganoan fluoro O10 F2
# X1.96) phlogopite

103. Toraya and Tetra-germanatian, Synthetic K1.00 (Mg2.36Mn0.64) (Ge3.00Al1.00) 5.435(1) 9.413(2) 10.458(3) 100.03(3) 4.0
Marumo1981 (n # manganoan fluoro O10 F2
X0.68) phlogopite

104. Toraya et al. 1976 Tetra-silicic Synthtetic K Mg2.5 Si4O10 F2 5.253(1) 9.086(2) 10.159(1) 99.89(3) 3.8
fluorophlogopite

105. Toraya et al. 1977 Tainiolite Synthetic K (Mg2Li) Si4O10 F2 5.231(1) 9.065(2) 10.140(1) 99.86(2) 2.4

106. Toraya et al. Tetra-germanatian Synthetic K1.00 Mg2.50 Ge4.00 O10 F2 5.421(2) 9.353(4) 10.533(2) 100.14(4) 5.5
1978a (n # 1) fluoro phlogopite

107. Toraya et al. Tetra-germanatian Synthetic K1.00 (Mg2.00Li1.00) Ge4.00 O10 F2 5..395(1) 9.341(2) 10.547(1) 99.87(2) 3.8
1978a (n # 2) tainiolite

108. Toraya et al. Fluoro phlogopite Synthetic K Mg2.75 (Si3.5Al0.5) O10 F2 5.292(1) 9.164(5) 10.143(1) 100.07(2) 2.9
1978b (n # c)

109. Toraya et al. Tetra-germanatian Synthetic K Mg3 (Ge3Al) O10 F2 5.417(6) 9.345(5) 10.468(1) 100.03(3) 3.7
(1978c) fluoro phlogopite

110. Toraya et al. 1983 Fluoro phlogopite Synthetic K (Mg2.44Mn0.24) (Si3.82Mn0.18) 5.285(1) 9.157(1) 10.190(2) 99.97(2) 4.3
O10 F2

111. Tyrna and Norrishite, Grenfell Metamorphosed K (Li Mn3+2) Si4 O12 5.289(3) 8.914(3) 10.062(7) 98.22(5) 7.8
Guggenheim 1991 New South Wales stratiform unit
(Australia)

112. Weiss et al. 1993 Aluminian fluoro (K0.92Na0.09Ca0.01Rb0.01) (Fe2+2.02 5.3655(6) 9.293(1) 10.198(2) 100.47(1) 3.8
annite, Brooks Al0.47Li0.33Mn0.07Mg0.03) (Si2.98
Mountain, Seward Al1.02) O10 F0.99 Cl0.03 (OH)0.98
(Alaska)
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 69

1.3 110.5 59.6 59.6 2.277 2.107 3.340 0.060 1.668 2.080 2.078 3.134 3.191 -0.330 -0.004 -0.334 101.

13.2 111.4 59.5 59.5 2.419 2.158 3.304 0.006 1.749 2.128 2.123 2.892 3.527 -0.335 0.000 -0.335 102.

15.0 111.5 59.9 59.9 2.421 2.102 3.354 0.004 1.746 2.094 2.095 2.846 3.557 -0.335 0.000 -0.335 103.

1.4 111.8 58.0 58.0 2.243 2.186 3.337 0.003 1.625 2.062 2.064 3.079 3.142 -0.333 +0.001 -0.332 104.

1.1 112.7 57.8 57.9 2.251 2.192 3.297 0.000 1.625 2.058 2.061 3.068 3.116 -0.332 0.000 -0.332 105.

12.9 114.3 60.1 58.4 2.446 2.170 3.306 0.051 1.744 2.178 2.070 2.872 3.480 -0.339 -0.003 -0.342 106.

13.5 114.3 59.3 59.3 2.458 2.138 3.338 0.009 1.744 2.093 2.092 2.861 3.494 -0.333 -0.002 -0.335 107.

3.6 111.1 58.8 58.8 2.258 2.137 3.334 0.000 1.638 2.062 2.063 3.045 3.209 -0.335 0.000 -0.335 108.

15.9 111.5 60.2 60.2 2.425 2.063 3.395 0.005 1.744 2.076 2.078 2.824 3.577 -0.335 -0.002 -0.337 109.

1.7 111.2 58.4 58.4 2.246 2.172 3.372 0.000 1.632 2.071 2.070 3.097 3.174 -0.333 -0.001 -0.334 110.

0.6 112.9 58.6 57.2 2.246 2.213 3.253 0.055 1.621 2.123 2.040 3.063 3.086 -0.274 0.002 -0.272 111.

1.3 110.6 58.9 58.5 2.247 2.180 3.355 0.005 1.656 2.108 2.088 3.133 3.195 -0.341 -0.004 -0.345 112.
70 Brigatti & Guggenheim

Table 1b. Structural details of trioctahedral true Micas-1M, space group C2

Cell parameters R

Reference Species, locality Rock type a b c E


Composition
(sample number) () () () () (%)

113. Backhaus 1983 Polylithionite, (K0.90Na0.08Rb0.04 Cs0.003) (Al1.10 5.216(3) 9.005(4) 10.084(3) 100.72(5) 7.3
Wakefield (Canada) Li1.51Fe3+0.03Fe2+0.15 Mn0.16 Ti0.01)
(Si3.48 Al0.53) O10.38 (OH)0.41 F1.67

114. Brigatti et al. Ferroan polylithionite, Miarolitic cavity (K0.91Na0.01Rb0.05) (Al1.06Li1.41 5.262(1) 9.085(2) 10.099(2) 100.72(1) 3.4
2000b (n # 114) Sentinel Rock, Pikes in granitic Fe3+0.05Fe2+0.40Mn0.04 Mg0.002Zn0.002)
Peak (Colorado) pegmatite (Si3.54Al0.46) O10.11 (OH)0.14 F1.75

115. Brigatti et al. Ferroan polylithionite, Miarolitic cavity (K0.94Na0.002Rb0.003) (Al1.11Li1.11 5.270(1) 9.092(1) 10.080(2) 100.70(1) 3.7
2000b (n # 55a) Wigwam Creek, Pikes in granitic Fe3+0.05Fe2+0.53Mg0.01Mn0.04Ti0.01
Peak (Colorado) pegmatite Zn0.003) (Si3.41Al0.59) O10.17 (OH)0.20
F1.63
116. Brigatti et al. Ferroan polylithionite, Miarolitic cavity (K0.96Na0.01Rb0.02) (Al1.06Li1.22 5.263(1) 9.085(1) 10.078(1) 100.75(1) 3.2
2000b (n # 55b) Wigwam Creek, Pikes in granitic Fe3+0.06Fe2+0.55 Mg0.005Mn0.05
Peak (Colorado) pegmatite Zn0.01Ti0.005) (Si3.41Al0.59) O10.23
(OH)0.24 F1.53
117. Brigatti et al. Ferroan polylithionite, Miarolitic cavity (K0.97Na0.02Ca0.01) (Al1.01Li1.08 5.290(1) 9.128(1) 10.093(1) 100.80(1) 3.0
2000b (n # 130-1) Devils Head area, Pikes in granitic Fe3+0.09Fe2+0.70Mg0.02 Mn0.06Zn0.005
Peak (Colorado) pegmatite Ti0.002) (Si3.30Al0.70) O10.26 (OH)0.19
F1.55
118. Brigatti et al. Ferroan polylithionite, Miarolitic cavity (K0.96Na0.02Ca0.006) (Al1.02Li1.09 5.275(2) 9.105(2) 10.084(1) 100.70(1) 3.9
2000b (n # 130-2) Devils Head area, Pikes in granitic Fe3+0.06Fe2+0.71Mg0.02Mn0.06Zn0.005
Peak (Colorado) pegmatite Ti0.005) (Si3.33Al0.67) O10.27 (OH)0.19
F1.54
119. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.94Na0.02) (Al1.05Li0.97Fe3+0.07 5.279(1) 9.114(2) 10.077(2) 100.79(1) 3.6
2000b (n # 137) phyllite intermediate, in granitic Fe2+0.67 Mg0.01Mn0.07Zn0.006Ti0.005)
Lake George Ring, pegmatite (Si3.21Al0.79) O10.02 (OH)0.24 F1.74
Pikes Peak (Colorado)
120. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.96Na0.02Ca0.001) (Al1.03Li0.97 5.285(1) 9.122(2) 10.101(2) 100.85(1) 3.3
2000b (n # 104) phyllite intermediate, in granitic Fe3+0.14Fe2+0.64 Mg0.01 Mn0.01
Crystal Park, Pikes pegmatite Zn0.005Ti0.01) (Si3.30Al0.70) O10.15
Peak (Colorado) (OH)0.24 F1.61
121. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.94Na0.02Rb0.004) (Al1.05Li0.94 5.283(1) 9.123(2) 10.072(2) 100.76(1) 3.8
2000b (n # 54b) phyllite intermediate, in granitic Fe3+0.12Fe2+0.61Mg0.01Mn0.06Ti0.006
Harris Park, Pikes Peak pegmatite Zn0.002) (Si3.31Al0.69) O10.10 (OH)0.25
(Colorado) F1.65
122. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.94Na0.04Rb0.003) (Al0.88Li0.86 5.288(1) 9.133(1) 10.088(1) 100.81(1) 3.4
2000b (n # 177) phyllite intermediate, in granitic Fe3+0.24Fe2+0.65Mg0.01 Mn0.06
Wigwam Creek, Pikes pegmatite Zn0.01Ti0.005) (Si3.23Al0.77) O9.93
Peak (Colorado) (OH)0.15 F1.92
123. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.96Na0.01) (Al1.02Li0.86Fe3+0.04 5.283(1) 9.118(1) 10.092(1) 100.78(1) 2.9
2000b (n # 140-1) phyllite intermediate, in granitic Fe2+0.81Mg0.05Mn0.06 Zn0.01Ti0.03)
Lake George Ring , pegmatite (Si3.17Al0.83) O10.13 (OH)0.25 F1.62
Pikes Peak (Colorado)
124. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.96Na0.01) (Al0.98Li0.85Fe3+0.05 5.297(1) 9.146(1) 10.102(1) 100.81(1) 2.7
2000b (n # 140-2) phyllite intermediate, in granitic Fe2+0.80Mg0.05 Mn0.06 Zn0.01Ti0.025)
Lake George Ring, pegmatite (Si3.24Al0.76) O10.11 (OH)0.25 F1.64
Pikes Peak (Colorado)
125. Brigatti et al. Polylithionite-sidero- Miarolitic cavity (K0.82Na0.03Rb0.09) (Al1.11Li0.77 5.295(1) 9.139(2) 10.077(2) 100.83(2) 3.7
2000b (n # 24) phyllite intermediate, in granitic Fe3+0.05Fe2+0.78Mn0.08 Ti0.006Mg0.004
Wigwam Creek, Pikes pegmatite Zn0.002) O10.24 (Si3.31Al0.69) (OH)0.17
Peak (Colorado) F1.59
126. Brigatti et al. Lithian siderophyllite, Quartz core, (K0.99Na0.01) (Al0.81 Li0.41Fe3+0.09 5.339(1) 9.233(1) 10.135(2) 100.73(1) 3.3
2000b (n # 47) Lake George Ring granitic Fe2+1.40Mg0.04 Mn0.08Zn0.02Ti0.10)
complex, Pikes Peak pegmatite (Si3.06Al0.94) O10.64 (OH)0.28 F1.08
(Colorado)
127. Brigatti et al. Lithian siderophyllite, Quartz core, (K0.99Na0.04Rb0.002) (Al0.90Li0.62 5.300(1) 9.144(1) 10.089(2) 100.74(1) 3.6
2000b (n # 103) Crystal Park, Pikes granitic Fe3+0.09Fe2+1.19 Mg0.02 Mn0.05Zn0.01
Peak (Colorado) pegmatite Ti0.03) (Si3.23Al0.77) O10.55 (OH)0.15
F1.29
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 71

Tetrahedral Octahedral Sheet thickness Interlayer Basal Mean bond lengths A - O Intralayer Layer Overall
D WT1 <M1 <M2 Tetra- Octa- Separa- oxygen T1-O M1-O M2-O Inner Outer shift offset shift
WT2 <M3 hedral hedral tion 'z T2-O M3-O a1 a1 a1
() () () () () () () () () () ()
6.0 112.3 60.5 59.9 2.257 2.066 3.328 0.109 1.631 2.098 2.058 2.958 3.226 -0.356 -0.004 -0.360 113.
112.3 57.3 1.633 1.914

3.7 111.9 60.6 60.6 2.252 2.086 3.333 0.131 1.632 2.124 2.122 3.029 3.195 -0.355 -0.002 -0.357 114.
111.9 56.4 1.640 1.885

4.0 111.8 60.6 56.5 2.249 2.087 3.319 0.134 1.641 2.125 1.888 3.022 3.199 -0.354 -0.001 -0.355 115.
111.7 60.6 1.635 2.124

3.8 112.0 60.6 56.2 2.246 2.092 3.316 0.135 1.634 2.129 1.882 3.022 3.193 -0.355 -0.002 -0.357 116.
111.8 60.5 1.636 2.127

5.0 111.2 60.8 56.7 2.255 2.075 3.331 0.129 1.649 2.128 1.890 3.009 3.236 -0.354 -0.004 -0.358 117.
111.3 60.8 1.640 2.127

4.1 111.7 60.7 56.6 2.252 2.082 3.323 0.144 1.641 2.125 1.890 3.023 3.206 -0.353 -0.002 -0.355 118.
111.6 60.7 1.637 2.125

4.3 111.6 60.7 56.4 2.250 2.084 3.314 0.109 1.638 2.129 1.885 3.018 3.209 -0.355 -0.002 -0.357 119.
111.5 60.7 1.641 2.131

4.6 111.4 60.8 56.6 2.252 2.081 3.336 0.130 1.644 2.133 1.890 3.018 3.226 -0.356 -0.004 -0.360 120.
111.4 60.7 1.640 2.123

3.6 111.5 60.8 56.3 2.250 2.087 3.308 0.133 1.642 2.136 1.883 3.033 3.195 -0.354 -0.002 -0.356 121.
111.5 60.7 1.639 2.132

4.5 111.3 60.7 56.6 2.250 2.083 3.326 0.128 1.643 2.130 1.891 3.021 3.222 -0.355 -0.003 -0.358 122.
111.2 60.7 1.641 2.131

4.0 111.5 60.6 56.4 2.250 2.093 3.323 0.137 1.643 2.133 1.891 3.028 3.208 -0.354 -0.003 -0.357 123.
111.6 60.6 1.637 2.129

4.4 111.3 60.7 56.6 2.254 2.088 3.326 0.127 1.646 2.135 1.896 3.026 3.224 -0.354 -0.004 -0.358 124.
111.3 60.7 1.643 2.131

4.8 111.1 60.9 56.6 2.250 2.077 3.320 0.141 1.645 2.134 1.885 3.015 3.230 -0.355 -0.003 -0.358 125.
111.1 60.9 1.643 2.133

3.4 110.5 59.8 58.0 2.241 2.138 3.339 0.058 1.658 2.126 2.017 3.070 3.224 -0.348 -0.005 -0.353 126.
110.5 59.2 1.637 2.085

3.5 111.3 60.4 56.6 2.247 2.107 3.310 0.125 1.643 2.131 1.916 3.043 3.201 -0.352 -0.003 -0.355 127.
111.3 60.3 1.641 2.129
72 Brigatti & Guggenheim

128. Guggenheim 1981 Polylithionite, (K1.01Na0.01 Rb0.03) (Si3.87Al0.13) 5.242(3) 9.055(6) 10.097(7) 100.77(5) 6.2
Tanakamiyama, Ohtsu, (Al1.13 Li1.41Fe2+0.07Mn0.05) O10
Japan (OH, F)2

129. Guggenheim and Polylithionite-sidero- (K0.90Na0.05) (Al1.05Li0.67Fe3+0.16 5.296(1) 9.140(2) 10.096(3) 100.83(2) 5.7
Bailey 1977 phyllite intermediate, Fe2+0.77Mg0.01Mn0.05 Ti0.01)
Sadisdorf Mine, (Si3.09Al0.91) O10 (OH)0.79 F1.21
Germany
130. Mizota et al. 1986 Masutomilite,Tanaka- (K0.90Na0.08 Rb0.07) (Si3.33Al0.67) 5.262(2) 9.102(3) 10.094(3) 100.83(2) 4.6
miyama, Ohtsu, Japan (Al0.98Li1.27Mn0.50Fe3+0.03Fe2+0.09
Ti0.005) O9.82 (OH0.60F1.58)

Table 1c. Structural details of trioctahedral true Micas-2M1, space group C2/c

Cell parameters R

Reference Species, locality Rock type Composition a b c E


(sample number)
() () () () (%)
3+ 2+
131. Bigi and Brigatti Ferroan phlogopite Syenite (K0.95Na0.03) (Mg1.55Fe 0.52Fe 0.70 5.339(1) 9.249(1) 20.196(1) 95.06(1) 2.7
1994 (n # M7) Valle del Cervo (Italy) Mn0.02Ti0.22) (Si2.78Al1.22) O10.73
(OH)1.27

132. Bigi e al. 1993 (n # Magnesian annite, Gabbroic calc- (K0.92Na0.01Ca0.001Ba0.04) (Fe2+1.36 5.335(2) 9.242(3) 20.106(7) 95.07(3) 3.7
MP16) Ivrea-Verbano Zone alkaline rock Mg0.80 Al0.40Fe3+0.17Mn0.01Ti0.26)
(Italy) (Si2.84 Al1.16) O10.95 (OH)1.05

133. Bigi et al. 1993 (n Ferroan phlogopite Gabbroic calc- (K0.98 Ca0.001 Ba0.02) (Mg1.63Al0.23 5.328(4) 9.220(3) 20.118(3) 95.11(3) 2.7
# MP17a) Ivrea-Verbano Zone alkaline rock Fe2+0.81 Mn0.002Ti00.33) (Si2.79 Al1.21)
(Italy) O10.70 F0.31 (OH)0.99

134. Bigi et al. 1993 (n Ferroan phlogopite Gabbroic calc- (K0.95Na0.02Ca0.003Ba0.02) (Mg1.57 5.323(1) 9.222(3) 20.130(5) 95.06(2) 3.4
# MP17b) Ivrea-Verbano Zone alkaline rock Al0.34Fe2+0.79Ti0.30Mn0.002) (Si2.87
(Italy) Al1.13) O10.83 F0.26 (OH)0.91

135. Bohlen et al. 1980 Magnesian annite, Au Orthogneiss (K0.99 Ca0.003Na0.02) (Al0.12Mg1.16 5.357(6) 9.245(5) 20.234(5) 94.98(4) 4.2
Sable Forks, New York Fe2+1.39 Mn0.007 Ti0.32) (Si2.79 Al1.21)
(Northeast O10.56 F0.08Cl0.14 (OH)1.22
Adirondacks)

136. Brigatti et al. Magnesian annite, Peraluminous (K0.98Na0.02Ca0.01) (Fe2+1.36Al0.60 5.335(1) 9.242(2) 20.181(4) 95.20(2) 2.8
2000a (n # C6c) Tinker Glacier, granite Mg.0.71Mn0.04Ti0.16) (Si2.71Al1.29)
Antarctica O10.36 (OH)1.64

137. Otha et al. 1982 Ferrian phlogopite, Rhyodacite (K0.77Na0.16Ba0.02) (Mg1.67Fe3+0.86 5.3175(7) 9.212(2) 19.976(3) 95.09(1) 3.9
Ruiz Peak, Valles Fe2+0.01Mn0.01Ti0.34 Al0.16) (Si2.84
Mountains, New Al1.16) O11.62 F0.17 (OH)0.21
Mexico

138. Swanson and Polylithionite, (K0.80Na0.004Cs0.02Rb0.06) (Li1.65 5.199(1) 9.026(2) 19.969(5) 95.41(2) 9.1
Bailey 1981 Biskupice, Czech Al1.24Mg0.002Fe2+0.002Ti0.001 Mn0.04)
Republic (Si3.62Al0.38) O10 F1.52 (OH)0.48

139. Takeda and Ross Hydrogenated, ferroan Rhyodacite (K0.78Na0.16Ba0.02) (Mg1.68Fe3+0.19 5.329(2) 9.234(3) 20.098(7) 95.09(3) 5.6
1975 phlogopite, Ruiz Peak, Fe2+0.71Mn0.01Ti0.34 Al0.19) (Si2.86
Valles Mountains, New Al1.14) O11.12 F0.17 (OH)0.71
Mexico
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 73

3.5 112.6 60.4 56.2 2.254 2.092 3.318 0.087 1.64 2.12 1.88 3.02 3.18 -0.356 -0.004 -0.360 128.
112.5 60.5 1.63 2.12

5.8 111.0 60.8 56.5 2.252 2.078 3.333 0.127 1.646 2.132 1.882 2.990 3.251 -0.354 -0.004 -0.358 129.
111.1 60.8 1.639 2.131

4.4 108.8 60.5 56.4 2.238 2.098 3.340 0.115 1.626 2.128 1.893 3.017 3.215 -0.356 -0.004 -0.360 130.
111.3 60.4 1.641 2.123

Sheet Inter- Intra-


Tetrahedral Octahedral Thickness layer Basal Mean bond lengths A- O layer Layer Overall
D WT1,T2 <M1 <M2 Tetra- Octa- separa- Oxygen T1-O M1-O M2-O Inner Outer shift offset shift
(u2) hedral hedral tion 'z T2-O (u2) a2, 3 a1, 1 a1
() () () () () () () () () () () () ()

6.0 110.6 58.9 58.6 2.257 2.170 3.376 0.018 1.657 2.097 2.082 3.023 3.297 0.333 -0.001 -0.334 131.
110.7 1.654

6.8 109.8 59.3 58.8 2.255 2.144 3.359 0.026 1.639 2.100 2.071 3.006 3.317 0.330 -0.002 -0.333 132.
109.9 1.677

7.8 110.2 59.3 59.0 2.258 2.128 3.374 0.020 1.656 2.085 2.064 2.977 3.331 0.336 -0.001 -0.336 133.
110.2 1.658

7.8 110.1 58.9 58.9 2.244 2.146 3.393 0.006 1.662 2.074 2.076 2.980 3.337 0.332 0.000 -0.334 134.
110.0 1.661

5.3 110.2 58.7 58.4 2.250 2.185 3.393 0.008 1.661 2.106 2.086 3.046 3.289 0.334 0.001 -0.328 135.
110.4 1.656

7.8 110.2 59.4 58.8 2.254 2.135 3.406 0.024 1.658 2.099 2.063 2.988 3.346 0.338 -0.002 -0.343 136.
110.1 1.660

7.4 110.2 59.4 59.1 2.270 2.113 3.295 0.026 1.653 2.076 2.060 2.960 3.300 0.331 -0.001 -0.333 137.
110.2 1.656

6.2 112.3 60.7 58.6 2.256 2.061 3.366 0.072 1.628 2.107 1.977 2.964 3.237 0.357 -0.003 -0.362 138.
112.2 1.631

7.7 110.2 59.2 58.9 2.269 2.135 3.337 0.020 1.662 2.087 2.068 2.970 3.323 0.334 -0.001 -0.335 139.
110.3 1.657
74 Brigatti & Guggenheim

Table 1d. Structural details of trioctahedral true Micas-2M1, space group Cc, C1

Cell parameters R

Reference Species, locality Rock type Composition a b c D, E, J


(sample number)
() () () () (%)

140. Rieder et al. 1996 Lithian siderophyllite, (K0.80Na0.04Rb0.05Ca0.02) (Fe2+1.07 5.292(1) 9.187(2) 19.935(3) 90 5.8
Space group Cc Barbora mine, Krupka, Al0.97Li0.50Fe3+0.14 Mn2+0.03Mg0.02) 95.40(1)
Czech Republic. (Si3.00 Al1.00) O10.00 F0.91 (OH)1.09 90

141. Slade et al. 1987 Ephesite, Postmasburg (Na0.94K0.001Ca0.03) (Al2.01Li0.85 5.123(2) 8.872(3) 19.307(3) 89.97(2) 4.7
Space group C1 district, South Africa. Fe3+0.01Mn0.005Mg0.03) (Si2.01 Al1.99) 95.15(2)
O10.00 (OH)2 89.96(2)

Table 1e. Structural details of trioctahedral true Micas-2M2, space group C2/c
Cell parameters R

Reference Species, locality Rock type Composition a b c E


(sample number)
() () () () (%)

142. Guggenheim 1981 Trilithionite, Radkovice, (K0.79Rb0.07Cs0.03Na0.03Ca0.01) 9.023(2) 5.197(2) 20.171(3) 99.48(2) 4.8
Jihlava, Moravia (Czech (Li1.48Al1.30Mg0.05Fe3+0.008Fe2+0.002
Republic) Mn0.03) (Si3.49Al0.51) O10 (F, OH)2

143. Sartori et al. 1973 Polylithionite, Elba Pegmatite (K0.92Rb0.06Na0.06Cs0.004Ca0.01) 9.04(2) 5.22(2) 20.210(1) 99.6(3) 9.6
Island, Italy (Li1.76Al1.26Fe3+0.003Mn0.003 Mg0.007)
(Si3.36Al0.64) O10 F1.53, (OH)0.47

144. Takeda et al. 1971 Trilithionite, Rozna, (K0.87Rb0.06Na0.12Cs0.005Ca0.02) 9.032(2) 5.200(3) 20.15(4) 99.8(2) 7.2
Moravia, (Czech (Li1.05Al1.40Fe2+0.07Mn0.03 Mg0.05)
Republic) (Si3.39Al0.61) O10 F1.2 (OH)0.8

Table 1f. Structural details of trioctahedral true Micas-3T, space group P3112

Cell parameters R

Reference Species, locality Rock type a c


Composition
(sample number) () () (%)

145. Brown 1978 Polylithionite, (K0.85Na0.11 Rb0.05) (Al1.25Li1.62 5.200(5) 29.76(1) 4.7
Coolgardie (Australia) Mg0.01Fe0.015Mn0.09) (Si3.48Al0.52)
O10 (OH)0.44 F1.54

146. Weiss et al. 1993 Lithian siderophyllite, Granitic rock (K0.92Na0.03Rb0.04Ca0.01) (Al0.68 5.309(2) 29.818(6) 3.0
Kymi stock, Finland Li0.37Fe2+1.25Fe3+0.34 Zn0.02Mn2+0.04)
(Si2.97Al1.03) O10 (OH)0.94 F1.06
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 75

Sheet Inter- Intra-


Tetrahedral Octahedral thickness layer Basal Mean bond lengths A- O layer Layer Overall
D WT1 WT2 <M1 <M2 <M3 Tetra- Octa- sepa- oxygen T1-O T2-O M1-O M2-O M3-O Inner Outer shift offset shift
hedral hedral ration 'z a2, 3 a1, 1 a1
() () () () () () () () () () () () () () () () ()

5.9 109.0 109.7 60.8 56.9 60.8 2.241 2.077 3.401 0.123 1.642 1.645 2.131 1.901 2.131 3.002 3.265 0.334 -0.002 -0.355 140.
5.5 109.1 108.0 2.204 0.075 1.651 1.650

22.1 108.8 108.1 61.6 58.0 58.4 2.277 2.024 3.077 0.158 1.653 1.734 2.128 1.910 1.933 2.491 3.522 0.348 -0.036 -0.338 141.
21.8 108.1 108.5 61.8 58.4 58.2 2.235 2.018 3.081 0.165 1.750 1.625 2.132 1.925 1.914 2.494 3.520
22.6 107.6 108.2 2.237 0.138 1.732 1.641
22.5 108.0 107.7 2.280 0.148 1.633 1.748

Sheet Inter- Intra-


Tetrahedral Octahedral Thickness layer Basal Mean bond lengths A- O layer Layer Overall
D WT1,T2 <M1 <M2 Tetra- Octa- separa- Oxygen T1-O M1-O M2-O Inner Outer Shift offset shift
(u2) hedral hedral tion 'z T2-O (u2) b3 a1 a1
() () () () () () () () () () () () () b2 a1

6.6 112.1 61.1 58.6 2.254 2.052 3.387 0.083 1.629 2.121 1.967 2.961 3.251 -0.358 -0.005 -0.368 142.
112.1 1.629 +0.358 -0.005

6.5 111.9 60.8 58.4 2.241 2.074 3.409 0.094 1.630 2.123 1.980 2.976 3.262 -0.361 -0.005 -0.372 143.
112.0 1.627 +0.361 -0.005

5.4 112.2 61.1 58.2 2.246 2.076 3.360 0.095 1.620 2.144 1.967 2.980 3.220 -0.364 -0.007 -0.380 144.
112.3 1.633 +0.364 -0.007

Tetrahedral Octahedral Sheet thickness Interlayer Basal Mean bond lengths A - O Intralayer Layer Overall
D WT1 <M1 <M2 Tetra- Octa- Separa- oxygen T1-O M1-O M2-O Inner Outer shift Offset Shift
WT2 <M3 hedral hedral tion 'z T2-O M3-O a2,3,1 a1,2,3
() () () () () () () () () () ()

7.6 112.6 59.6 60.8 2.257 2.059 3.347 0.131 1.652 2.036 2.113 2.925 3.265 -0.355 -0.006 0 145.
111.8 57.6 1.617 1.920

4.1 110.7 60.5 56.8 2.251 2.109 3.328 0.110 1.651 2.143 1.926 3.041 3.225 -0.347 -0.003 0 146.
111.1 60.2 1.644 2.123
76 Brigatti & Guggenheim

TABLE 2. STRUCTURAL DETAILS OF DIOCTAHEDRAL TRUE MICAS

Table 2a . Structural details of trioctahedral true Micas-1M,

space groups C2/m and C2

Cell parameters R
Reference Species, locality Rock type Composition a b c E
(sample number)
() () () () (%)

1. Sidorenko et al. Muscovite, (K0.65Na0.03) (Al1.83Fe3+0.03Fe2+0.04 5.186 8.952 10.12 101.8 10.9
1975 (Space group Transbaikal, Siberia, Mg0.10 Mn0.04) (Si3.51Al0.49) O10.13
C2) Russia F0.07 (OH)1.80

2. Soboleva et al. Paragonite Synthetic Na0.91 Al1.88 (Si3.45Al0.55) O10 (OH)2 5.135 8.890 9.74 99.7 12.1
1977 (Space group
C2/m)

3. Zhukhlistov et al. Celadonite, Krivoj Iron-ore basin (K0.83Na0.01Ca0.04) 5.23 9.05 10.15 100.5 10.8
1977 (Space group Rog, Ukraine (Al0.05Fe3+1.15Fe2+0.36 Mg0.41Ti0.01)
C2/m) (Si3.94Al0.06) O10 F0.01 (OH)1.99
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 77

Basal
Tetrahedral Octahedral Sheet thickness Interlayer oxygen Mean bond lengths A - O Intralayer Layer Overall
D W <M1 <M2,M3 Tetra- Octa- separa- 'z T-O M1-O M2-O Inner Outer shift offset shift
vacancy hedral hedral tion vacancy M3-O a1 a1 a1
() () () () () () () () () () ()

9.3 110.1 61.6 56.6 2.196 2.113 3.399 0.220 1.614 2.221 1.920 2.897 3.306 -0.376 -0.024 -0.400 1.
111.1 57.3 1.633 1.957

19.1 110.4u2 59.9 57.8u2 2.222 2.099 3.059 0.096 1.659u2 2.091 1.971u2 2.561 3.441 -0.338 0.020 -0.319 2.

1.3 112.6u2 58.3 56.6u2 2.248 2.249 3.233 0.000 1.636u2 2.141 2.043u2 3.044 3.103 -0.354 -0.002 -0.356 3.
78 Brigatti & Guggenheim

Table 2b. Structural details of trioctahedral true Micas-1M, space group C2/c

Cell parameters R
Reference Species, locality Rock type Composition a b c E
(sample number)
() () () () (%)

3+
4. Birle and Muscovite, Hartz (K0.94Na0.06) (Al1.83Mg.0.06 Fe 0.12 ) 5.194(6) 8.996(6) 20.10(2) 95.2(1) 12
Tettenhorst 1968 Range, Australia (Si3.11Al0.89) O10 (OH)2

5. Brigatti et al. 1998 Muscovite, Maddalena Pegmatite (K0.99Na0.01Ba0.01) (Al1.65Fe2+0.29 5.226(1) 9.074(2) 20.039(2) 95.74(1) 2.5
(n # GA1) Island, Italy Mn0.07Ti0.01) (Si3.30Al0.70) O10.01
F0.22 (OH)1.77

6. Brigatti et al. 1998 Muscovite, Antarctica Pegmatite (K0.92Na0.09) (Al1.78Mg.0.06 Fe2+0.12 5.182(3) 8.982(5) 20.002(5) 95.72(2) 3.0
(n # RA1) Ti0.04) (Si3.18Al0.82) O10.08 F0.07
(OH)1.85

7. Brigatti et al. 1998 Muscovite, Sos Peraluminous (K0.92Na0.09) (Al1.88Mg.0.05 Fe3+0.09 5.186(1) 8.991(3) 20.029(7) 95.77(3) 3.6
(n # A4b) Canales pluton, Central granite Ti0.02) (Si2.92Al1.08) O10.01 F0.11
Sardinia, Italy (OH)1.88

8. Brigatti et al. 1998 Muscovite, Sos Peraluminous (K0.92Na0.08) (Al1.86Fe3+0.01Mg.0.07 5.192(2) 9.013(5) 20.056(7) 95.83(3) 2.9
(n # GFS15Ab) Canales pluton, Central granite Fe2+0.06Ti0.02) (Si3.03Al0.97) O10 F0.09
Sardinia, Italy (OH)1.91

9. Brigatti et al. 1998 Muscovite, Riu Two-mica (K0.96Na0.05) (Al1.71Fe3+0.16 Fe2+0.13 5.209(3) 9.035(6) 20.066(9) 95.68(3) 3.9
(n # H87b) Morunzu, Sardinia, leucogranite Mn0.01) (Si3.09Al0.91) O10.01 F0.22
Italy (OH)1.77

10. Brigatti et al. 1998 Muscovite, Frontier Peraluminous (K0.93Na0.08) (Al1.83Mg.0.07 Fe2+0.07 5.186(1) 9.005(1) 20.031(3) 95.78(1) 2.9
(n # CC1b) Mountains Area, granite Ti0.06) (Si3.18Al0.82) O10.21 (OH)1.79
Antarctica

11. Brigatti et al. 1998 Muscovite, Tinker Peraluminous (K0.88Ca0.06Na0.06) (Al1.88Mg.0.06 5.188(1) 8.996(3) 20.082(2) 95.78(1) 2.8
(n # C3-29b) Glacier, Antarctica granite Fe2+0.07Ti0.03) (Si3.07Al0.93) O10.17
F0.19 (OH)1.64

12. Brigatti et al. 1998 Muscovite, Tinker Peraluminous (K0.94Na0.07) (Al1.83Mg.0.07 Fe2+0.07 5.187(2) 9.004(2) 20.036(2) 95.73(2) 2.1
(n # B1b) Glacier, Antarctica granite Ti0.06) (Si3.09Al0.91) O10.12 F0.23
(OH)1.65

13. Brigatti et al. 1998 Muscovite, Tinker Peraluminous (K0.92Na0.09) (Al1.78Mg.0.15 Fe2+0.13 5.186(1) 9.003(1) 20.030(4) 95.84(2) 3.9
(n # C6Cb) Glacier, Antarctica granite Ti0.04) (Si3.17Al0.83) O10.25 F0.19
(OH)1.56

14. Brigatti et al. 1998 Muscovite, Tinker Peraluminous (K0.93Na0.05) (Al1.80Mg.0.15 Fe2+0.07 5.196(2) 8.997(3) 20.034(4) 95.80(2) 3.1
(n # C6Bb) Glacier, Antarctica granite Ti0.05) (Si2.87Al1.13) O9.91 F0.41
(OH)1.68

15. Brigatti et al. 1998 Muscovite, Tinker Peraluminous (K0.93Na0.05Ca0.01) (Al1.64Fe3+0.08 5.197(1) 9.022(2) 20.076(4) 95.79(2) 2.8
(n # C3-31b) Glacier, Antarctica granite Fe2+0.08Mg0.16Ti0.02) (Si3.18Al0.82)
O9.93 (OH)2.07

16. Brigatti et al. 2001 Chromium-containing In glacial (K0.86Na0.10Ba0.04) (Al1.86Mg0.08 5.192(1) 9.011(1) 20.028(2) 95.74(1) 2.5
(Westland) muscovite, Westland, moraines Fe2+0.04Cr0.06) (Si3.11Al0.89) O10.17
New Zealand. (OH)1.83

17. Brigatti et al. 2001 Chromium-containing Biotite schist (K0.73Na0.27) (Al1.84Mg0.02 Fe2+0.02 5.175(1) 8.979(2) 19.915(2) 95.66(1) 3.1
(Campbell Creek) muscovite, Northwest Cr0.10Ti0.02) (Si3.07Al0.93) O10.05 F0.03
Nelson, Campbell (OH)1.92
Creek, New Zealand

18. Brigatti et al. 2001 Chromium-containing Quartz schist (K0.96Na0.03Ba0.01) (Al1.83Mg0.11 5.206(1) 9.040(3) 20.058(9) 95.79(4) 3.3
(Anatoki River) muscovite, Northwest
Nelson, Anatoki River,
Fe2+0.10Cr0.11Ti0.03) (Si3.14Al0.86)
O10.50 F0.04 (OH)1.46
New Zealand
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 79

Table 1a . Structural details of trioctahedral true micas-2M1, C12/c(1) layer symmetry (May 20, 2000)

Inter- Basal Intra-


Tetrahedral Octahedral Sheet thicknesslayer oxygen Mean bond lengths A- O layer Layer Overall
D WT1, <M1 <M2 Tetra- Octa- separa- 'z T1-O M1-O M2-O Inner Outer shift offset shift
WT2 vacancy (u2) hedral hedral tion T2-O vacancy (u2) a2, 3 a1, 1 a1
() () () () () () () () () () () () ()

12.0 110.6 62.4 57.0 2.243 2.097 3.427 0.236 1.660 2.259 1.925 2.852 3.385 0.368 0.002 -0.349 4.
111.2 1.636

7.7 111.5 61.8 57.4 2.247 2.107 3.368 0.179 1.640 2.230 1.953 2.943 3.287 0.374 -0.005 -0.384 5.
111.5 1.640

11.3 111.0 62.3 57.1 2.242 2.088 3.378 0.223 1.643 2.243 1.923 2.849 3.351 0.378 -0.002 -0.385 6.
111.1 1.639

11.2 111.1 62.1 57.1 2.242 2.095 3.385 0.223 1.642 2.242 1.928 2.854 3.354 0.378 -0.005 -0.388 7.
111.1 1.640

11.2 110.9 62.3 57.2 2.242 2.087 3.405 0.225 1.644 2.244 1.928 2.864 3.362 0.379 -0.006 -0.392 8.
110.8 1.643

10.1 111.2 62.0 57.3 2.251 2.099 3.383 0.214 1.641 2.237 1.941 2.887 3.336 0.374 -0.004 -0.381 9.
111.1 1.647

11.1 111.0 62.2 57.2 2.242 2.090 3.391 0.221 1.642 2.243 1.928 2.860 3.354 0.377 -0.006 -0.389 10.
111.0 1.642

11.4 111.0 62.3 57.2 2.246 2.089 3.409 0.230 1.645 2.247 1.925 2.858 3.364 0.377 -0.006 -0.390 11.
111.0 1.644

10.8 111.1 62.3 57.1 2.245 2.091 3.388 0.219 1.642 2.245 1.927 2.865 3.347 0.376 -0.005 -0.386 12.
111.1 1.641

11.3 111.0 62.3 57.2 2.241 2.088 3.393 0.225 1.644 2.245 1.926 2.857 3.358 0.378 -0.007 -0.393 13.
110.9 1.642

11.0 111.1 62.2 57.2 2.242 2.090 3.391 0.219 1.641 2.244 1.928 2.863 3.353 0.377 -0.006 -0.390 14.
111.0 1.644

10.9 111.2 62.2 57.1 2.248 2.097 3.393 0.224 1.647 2.251 1.931 2.868 3.356 0.377 -0.006 -0.390 15.
111.1 1.645

11.4 111.1 62.2 57.1 2.250 2.095 3.369 0.223 1.646 2.244 1.931 2.848 3.358 0.377 -0.005 -0.386 16.
111.1 1.646

12.3 111.0 62.2 57.0 2.242 2.095 3.329 0.228 1.645 2.244 1.925 2.810 3.361 0.376 -0.002 -0.380 17.
110.9 1.644

10.5 111.5 62.1 57.2 2.252 2.099 3.374 0.196 1.642 2.246 1.937 2.875 3.344 0.379 -0.006 -0.389 18.
111.2 1.650
80 Brigatti & Guggenheim

19. Catti et al. 1989 (T Muscovite, Monte Pegmatite (K0.86Na0.11) (Al1.93 Fe0.07Mg.0.02) 5.191(1) 9.006(3) 20.068(6) 95.77(2) 4.8
= 25C) Botte Donato, Calabria, (Si3.08Al0.92) O10 (OH)2
Italy

20. Catti et al. 1989, Muscovite, Monte Pegmatite (K0.86Na0.11) (Al1.93 Fe0.07Mg.0.02) 5.229(1) 9.076(3) 20.322(8) 95.74(3) 6.0
(T = 700C) Botte Donato, Calabria, (Si3.08Al0.92) O10 (OH)2
Italy

21. Catti et al. 1994 Muscovite, Effingham Granite (K0.90Na0.07) (Al1.63Fe0.23Mg0.16 5.2108(4) 9.0399(8) 20.021(2) 95.76(1) 4.0
(Room pressure) Township, Ontario pegmatite Ti0.03) (Si3.20Al0.80) O10 (OH)2

22. Comodi and Paragonite, Western (Na0.88K0.10Ca0.01Ba0.01) (Al1.97 5.135(1) 8.906(1) 19.384(4) 94.6(1) 2.1
Zanazzi 1997 (n # Alps, Italy Fe0.01Mn0.002Mg0.006Ti0.007) (Si3.01
AL433, 0.001 Al0.99) O10 (OH)2
Kbar)
23. Comodi and Paragonite, Western (Na0.88K0.10Ca0.01Ba0.01) (Al1.97 5.134(3) 8.906(5) 19.32(1) 94.5(2) 6.1
Zanazzi 1997 (n # Alps, Italy Fe0.01Mn0.002Mg0.006Ti0.007) (Si3.01
AL433, 0.5 Kbar) Al0.99) O10 (OH)2

24. Comodi and Paragonite, Western (Na0.88K0.10Ca0.01Ba0.01) (Al1.97 5.082(2) 8.813(5) 18.91(1) 94.7(2) 7.0
Zanazzi 1997 (n # Alps, Italy Fe0.01Mn0.002Mg0.006Ti0.007) (Si3.01
AL433, 25.4 Kbar) Al0.99) O10 (OH)2

25. Comodi and Paragonite, Western (Na0.88K0.10Ca0.01Ba0.01) (Al1.97 5.062(2) 8.769(3) 18.64(2) 95.2(2) 6.5
Zanazzi 1997 (n # Alps, Italy Fe0.01Mn0.002Mg0.006Ti0.007) (Si3.01
AL433, 40.5 Kbar) Al0.99) O10 (OH)2

26. Comodi and Paragonite, Guatemala (Na0.91K0.07Ca0.01Ba0.01) (Al1.99 5.140(2) 8.911(5) 19.38(1) 94.62(1) 3.7
Zanazzi 2000 (n # Fe0.01Mn0.001Mg0.02Ti0.005) (Si2.92
AMNH104213) (T Al1.08) O10 (OH)2
= 25C)
27. Comodi and Paragonite, Guatemala (Na0.91K0.07Ca0.01Ba0.01) (Al1.99 5.152(2) 8.941(5) 19.46(1) 94.26(1) 2.5
Zanazzi 2000 (n # Fe0.01Mn0.001Mg0.02Ti0.005) (Si2.92
AMNH104213) (T Al1.08) O10 (OH)2
= 210C)
28. Comodi and Paragonite, Guatemala (Na0.91K0.07Ca0.01Ba0.01) (Al1.99 5.173(2) 8.985(5) 19.55(1) 93.58(1) 2.9
Zanazzi 2000 (n # Fe0.01Mn0.001Mg0.02Ti0.005) (Si2.92
AMNH104213) (T Al1.08) O10 (OH)2
= 450C)
29. Comodi and Paragonite, Guatemala (Na0.91K0.07Ca0.01Ba0.01) (Al1.99 5.190(3) 9.011(6) 19.60(2) 92.96(1) 4.4
Zanazzi 2000 (n # Fe0.01Mn0.001Mg0.02Ti0.005) (Si2.92
AMNH104213) (T Al1.08) O10 (OH)2
= 600C)
30. Evsyunin et al. Chromphyllite, (K0.82Ba0.14Na0.04) (Cr3+1.42Al0.27 5.240(3) 9.103(2) 19.93(4) 95.59(3) 4.8
1997 Slyudyanka, Irkutsk V3+0.13Mg0.18Fe2+0.01) (Si3.02 Al0.98)
region O10 F0.30 (OH)1.66

31. Guggenheim et al. Muscovite, Diamond Pegmatite (K0.93Na0.08Ca0.01) (Al1.83Fe0.16 5.200(4) 9.021(7) 20.07(2) 95.71(7) 4.0
1987 (T = 20C) mine, Keystone, South Mg0.01Mn0.01) (Si3.10Al0.90) O10 F0.17
Dakota (OH)1.83

32. Guggenheim et al. Muscovite, Diamond Pegmatite (K0.93Na0.08Ca0.01) (Al1.83Fe0.16 5.215(2) 9.053(4) 20.15(1) 95.72(3) 5.3
1987 (T = 300C) mine, Keystone, South Mg0.01Mn0.01) (Si3.10Al0.90) O10 F0.17
Dakota (OH)1.83

33. Guggenheim et al. Muscovite, (K1.00Na0.03Ca0.01) (Al1.93Fe2+0.01 5.1579(9) 8.9505(8) 20.071(5) 95.75(2) 5.2
1987 (T = 20C) Panasqueira, Portugal Mg0.01Mn0.01) (Si3.09Al0.91) O10 F0.12
(OH)1.88

34. Guggenheim et al. Muscovite, (K1.00Na0.03Ca0.01) (Al1.93Fe2+0.01 5.182(1) 8.993(1) 20.232(5) 95.75(2) 6.9
1987 (T = 525C) Panasqueira, Portugal Mg0.01Mn0.01) (Si3.09Al0.91) O10 F0.12
(OH)1.88

35. Guggenheim et al. Muscovite, (K1.00Na0.03Ca0.01) (Al1.93Fe2+0.01 5.189(1) 9.004(1) 20.256(6) 95.74(2) 7.3
1987 (T = 650C) Panasqueira, Portugal Mg0.01Mn0.01) (Si3.09Al0.91) O10 F0.12
(OH)1.88
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 81

11.8 111.0 62.4 57.2 2.248 2.089 3.398 0.232 1.647 2.251 1.925 2.848 3.373 0.377 -0.005 -0.389 19.
111.0 1.647

8.2 111.2 62.5 57.2 2.257 2.100 3.495 0.212 1.642 2.274 1.936 2.970 3.332 0.380 -0.005 -0.389 20.
111.1 1.646

9.5 109.8 62.0 57.2 2.241 2.108 3.370 0.229 1.645 2.241 1.943 2.897 3.322 0.372 -0.005 -0.386 21.
110.7 1.640

16.0 110.4 62.0 56.9 2.243 2.085 3.089 0.234 1.654 2.225 1.912 2.642 3.375 0.373 0.036 -0.303 22.
110.4 1.651

16.3 110.3 62.1 57.0 2.247 2.080 3.056 0.193 1.65 2.22 1.91 2.63 3.37 0.372 0.036 -0.295 23.
110.0 1.65

17.9 111.5 62.6 57.9 2.306 1.998 2.814 0.188 1.68 2.17 1.88 2.50 3.30 0.364 0.024 -0.305 24.
112.7 1.67

18.4 111.5 62.5 57.8 2.252 1.980 2.797 0.167 1.68 2.14 1.86 2.48 3.33 0.366 0.015 -0.334 25.
112.1 1.65

16.2 110.4 62.0 56.9 2.246 2.092 3.074 0.232 1.656 2.225 1.915 2.634 3.378 0.373 0.037 -0.304 26.
110.4 1.654

15.3 110.4 62.1 57.0 2.247 2.091 3.118 0.225 1.655 2.233 1.918 2.672 3.375 0.374 0.049 -0.281 27.
110.4 1.652

14.3 110.4 62.2 57.0 2.248 2.096 3.167 0.238 1.655 2.243 1.925 2.722 3.372 0.374 0.070 -0.236 28.
110.5 1.651

12.9 110.3 62.2 57.1 2.244 2.101 3.200 0.243 1.652 2.256 1.932 2.768 3.359 0.374 0.090 -0.195 29.
110.3 1.648

7.3 111.6 61.2 57.3 2.252 2.136 3.278 0.155 1.644 2.213 1.976 2.933 3.260 0.368 -0.002 -0.370 30.
111.6 1.643

11.3 111.0 62.1 57.2 2.249 2.098 3.388 0.216 1.646 2.243 1.935 2.858 3.364 0.376 -0.004 -0.384 31.
111.2 1.647

10.3 111.0 62.2 57.1 2.246 2.105 3.427 0.229 1.649 2.256 1.939 2.898 3.358 0.377 -0.004 -0.385 32.
111.0 1.645

11.8 110.9 62.2 57.1 2.234 2.081 3.436 0.218 1.635 2.234 1.916 2.848 3.368 0.377 -0.006 -0.390 33.
110.8 1.637

9.8 111.2 62.3 57.1 2.241 2.091 3.492 0.213 1.637 2.246 1.925 2.916 3.347 0.379 -0.006 -0.391 34.
111.1 1.635

9.2 111.1 62.3 57.1 2.241 2.091 3.506 0.220 1.636 2.249 1.926 2.935 3.340 0.379 -0.006 -0.390 35.
111.2 1.634
82 Brigatti & Guggenheim

36. Gven 1971b Muscovite, Georgia Pegmatite [K0.86Na0.10 (H+3)0.01] (Al1.90 5.1906(2) 9.0080(3) 20.0470(6) 95.757(2) 3.5
Mg.0.06Fe3+0.02Fe2+0.05 Ti0.01)
(Si3.02Al0.98) O10 F0.01 (OH)1.99

37. Gven 1971b Magnesian muscovite, Schist (K0.87Na0.07Ba 0.01Ca 0.02) (Al1.43 5.2112(3) 9.0383(4) 19.9473(6) 95.769(5) 4.5
Tiburon Peninsula, Mg.0.50Fe3+0.05Fe2+ 0.09 Ti0.01)
California (Si3.39Al0.61) O10.08 (OH)1.92

38. Knurr and Bailey Muscovite, Minas Metamorphosed (K Na Ba


0.93 0.05 0.007) (Al1.72Mg.0.10 5.2044(8) 9.018(2) 20.073(5) 95.82(2) 2.7
1986 Gerais, Brazil sedimentary Fe3+0.15Mn3+0.02Ti0.02) (Si3.06 Al0.94)
manganese O10 (OH)2
deposits

39. Lin and Bailey Paragonite, Zermatt- Glaucophane- (Na0.92K0.04Ca 0.02) (Al1.99Mg.0.01 5.128(2) 8.898(3) 19.287(9) 94.35(3) 4.5
1984 (n # PWB Saas Fee, Swiss Alps bearing Fe0.03Ti0.003) (Si2.94Al1.06) O10
1705) metamorphosed (OH)
2
eclogite

40. Brigatti et al. 2001 Muscovite, Fregeneda, Granitic (K0.94Na0.05Rb0.01) (Al1.94Fe2+0.08 5.193(1) 9.016(3) 20.114(5) 95.77(2) 3.5
(n # 39) Portugal pegmatite Mg0.02Li0.03) (Si3.07Al0.93) O10.12
F0.09 (OH)1.79

41. Brigatti et al. 2001 Lithian, ferroan Granitic (K0.96Na0.01Rb0.03) (Al1.49Fe3+0.07 5.209(2) 9.038(3) 19.997(5) 95.70(3) 4.1
(n # 147) muscovite, Pikes Peak, pegmatite Fe2+0.39Mn0.01Li0.28) (Si3.24Al0.76)
Colorado O10.0 F0.43 (OH)1.57

42. Brigatti et al. 2001 Lithian, ferroan Granitic (K0.98Na0.02Rb0.02) (Al1.45Fe3+0.08 5.224(1) 9.081(3) 19.952(4) 95.63(2) 3.5
(n # 129) muscovite, Pikes Peak, pegmatite Fe2+0.33Mn0.03Ti0.01 Li0.37) (Si3.28
Colorado Al0.72) O10.0 F0.57 (OH)1.43

43. Brigatti et al. 2001 Muscovite, Argemela, Granite (K0.86Na0.15Rb0.02) (Al1.79Fe2+0.13 5.190(2) 9.022(3) 20.057(4) 95.60(7) 3.3
(n # 2b) Portugal Mg0.01Mn0.01Li0.12) (Si3.19Al0.81)
O10.0 F0.29 (OH)1.71

44. Brigatti et al. 2001 Muscovite, Argemela, Granite (K0.86Na0.15Rb0.02) (Al1.81Fe2+0.13 5.197(1) 9.019(2) 20.068(3) 95.71(1) 4.2
(n # 2a) Portugal Mg0.01Mn0.01Li0.12) (Si3.13Al0.87)
O10.0 F0.29 (OH)1.71

45. Richardson and Muscovite, Archers (K0.88Na0.03Ca0.01) (Al1.87Ti0.03 5.199(2) 9.027(2) 20.106(4) 95.78(4) 9.9
Richardson 1982 Post, Kenya Mg0.06 Mn3+0.03) (Si3.01Al0.85
Fe3+0.14) O10 (OH)2

46. Rothbauer 1971 Muscovite, Diamond Pegmatite (K0.85Na0.09) (Al1.81Fe2+0.14 Mg0.12) 5.1918(2) 9.0155(5) 20.0457(7) 95.735(3) 2.7
Mine, Black Hills, (Si3.09Al0.91) O9.81 F0.19 (OH)2
South Dakota

47. Rule and Bailey Magnesium-containing (K0.95Na0.05Ba0.03) (Al1.51Mg0.27 5.2153(5) 9.043(2) 19.974(9) 95.789(9) 3.3
1985 muscovite, Rio de Oro, Fe0.14Cr0.10Ti0.01Mn0.003) (Si3.25
Sahara Al0.75) O10 (OH)2

48. Sidorenko et al. Paragonite, Southern Pyroclastic rock (K0.10Na0.60Ca0.03) (Al1.93 Mg0.10 5.135 8.894 19.365 94.10 11.1
1977a Urals Fe2+0.02) (Si2.98 Al1.02) O8.78 (OH)2.22
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 83

11.4 111.0 62.1 57.0 2.239 2.104 3.392 0.227 1.643 2.245 1.933 2.855 3.362 0.377 -0.005 -0.387 36.
111.1 1.642

6.0 111.5 61.4 57.1 2.219 2.126 3.359 0.161 1.621 2.222 1.956 2.971 3.236 0.376 -0.004 -0.385 37.
111.4 1.634

10.8 111.1 62.1 57.0 2.243 2.106 3.394 0.224 1.644 2.252 1.935 2.873 3.353 0.378 -0.006 -0.391 38.
111.0 1.644

16.2 110.3 62.1 57.0 2.243 2.077 3.053 0.231 1.653 2.221 1.908 2.457 3.370 0.376 0.045 -0.285 39.
110.3 1.652

11.4 110.9 62.4 57.2 2.249 2.087 3.422 0.232 1.647 2.249 1.927 2.866 3.372 0.378 -0.006 -0.389 40.
110.9 1.646

8.7 111.9 61.7 57.2 2.241 2.110 3.356 0.179 1.634 2.226 1.949 2.911 3.297 0.377 -0.006 -0.381 41.
111.6 1.638

5.9 111.7 61.5 57.4 2.238 2.114 3.337 0.147 1.629 2.214 1.963 2.973 3.237 0.374 -0.004 -0.375 42.
111.6 1.637

9.7 111.5 61.8 57.8 2.255 2.072 3.399 0.172 1.639 2.190 1.944 2.896 3.324 0.369 -0.005 -0.377 43.
111.6 1.639

10.6 111.3 62.1 57.5 2.252 2.081 3.399 0.198 1.643 2.219 1.937 2.877 3.347 0.373 -0.005 -0.384 44.
111.2 1.643

11.0 111.1 61.9 56.8 2.236 2.123 3.406 0.218 1.639 2.253 1.941 2.871 3.361 0.378 -0.005 -0.389 45.
110.9 1.646

11.3 111.0 62.2 57.2 2.245 2.089 3.393 0.217 1.645 2.241 1.930 2.857 3.362 0.376 -0.005 -0.386 46.
110.9 1.644

7.9 111.6 61.7 57.1 2.237 2.121 3.341 0.185 1.636 2.233 1.952 2.924 3.278 0.376 -0.005 -0.386 47.
111.6 1.637

17.4 111.0 60.6 2.264 2.125 3.005 0.13 1.671 2.161 1.950 2.586 3.386 0.355 0.053 -0.274 48.
112.3 57.0 1.661
84 Brigatti & Guggenheim

Table 2c. Structural details of trioctahedral true Micas-2M2, space group C2/c

Cell parameters R

Reference Species, locality Rock type Composition a b c E


(sample number)
() () () () (%)

49. Ni and Hughes Nanpingite, Nanping, Granitic (Cs0.88K0.06Rb0.01) (Al1.64 9.076(3) 5.226(2) 21.41(5) 99.48(6) 5.8
1996 Fujian, China pegmatite Fe2+0.17Mg0.22Li0.15) (Si3.16Al0.84)
O10 (OH)1.79 F0.21

50. Zhoukhlistov et al. Muscovite, North Metasomatized (K0.68Na0.09) Al1.93 (Si3.5Al0.5) O10.06 8.965 5.175 20.31 100.66 11.7
1973 Armenia. pyrite deposits (OH)1.94

Table 2d. Structural details of trioctahedral true Micas-3T, space group P3112

Cell parameters R

Reference Species, locality Rock type a c


Composition
(sample number) () () (%)

51. Amisano Canesi et Muscovite, (North Shist, (K0.93Na0.03) (Al1.54 5.212(1) 29.804(6) 3.6
al. 1994 (n # KZ) Kazakhstan) conditions: 6 Fe0.25Mg0.21Ti0.04) (Si3.34Al0.56) O10
<p<9 kbar; (OH)2
T=600C
52. Amisano Canesi et Magnesian muscovite, Pyrope-bearing (K0.92Na0.01) (Al1.41Mg0.60Ti0.02) 5.215(1) 29.755(5) 4.5
al. 1994 (n # DM) Dora Maira massif white shist (Si3.54Al0.46) O10 (OH)2
(Italy) (P=30kbar,
T=700C)
53. Gven and Muscovite, Sultan (K0.90Na0.06Ca0.01Ba0.01) (Al1.83 5.1963(4) 29.971(2) 2.4
Burnham 1967 Basin, Snohomish Fe2+0.04F3+0.04Mg0.09Ti0.01)
County, Washington (Si3.11Al0.89) O10 (OH)1.98 F0.03

54. Sidorenko et al. Paragonite (Na0.71K0.16Ca0.03) (Al2.02 5.132 28.72 13.0


1977b Fe3+0.01Mg0.01) (Si2.96Al1.04) O9.98
(OH)2.02
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 85

Sheet Inter- Intra-


Tetrahedral Octahedral Thickness layer Basal Mean bond lengths A- O layer Layer Overall
D WT1,T2 <M1 <M2 Tetra- Octa- separa- Oxygen T1-O M1-O M2-O Inner Outer Shift offset shift
(u2) hedral hedral tion 'z T2-O (u2) b3 a1 a1
() () () () () () () () () () () () () b2 a1

5.7 111.4 62.4 57.6 2.241 2.079 3.997 0.215 1.634 2.244 1.939 3.174 3.416 -0.379 -0.005 -0.389 49.
111.5 1.633 +0.379 -0.005

11.2 111.4 60.9 57.0 2.216 2.133 3.414 0.233 1.619 2.195 1.956 2.860 3.354 -0.380 -0.018 -0.419 50.
111.6 1.653 +0.380 -0.018

Tetrahedral Octahedral Sheet thickness Interlayer Basal Mean bond lengths A - O Intralayer Layer Overall
D WT1 <M1 <M2 Tetra- Octa- Separa- oxygen T1-O M1-O M2-O Inner Outer shift Offset Shift
WT2 <M3 hedral hedral tion 'z T2-O M3-O a2,3,1 a1,2,3
() () () () () () () () () () ()

7.4 111.9 61.7 57.0 2.247 2.116 3.305 0.182 1.637 2.231 1.943 2.928 3.259 0.379 -0.003 0 51.
111.8 57.2 1.638 1.953

5.4 112.1 61.4 57.1 2.235 2.130 3.305 0.162 1.628 2.228 1.954 2.972 3.213 0.378 -0.003 0 52.
112.1 57.3 1.631 1.971

11.8 110.0 61.8 57.6 2.207 2.112 3.465 0.156 1.670 2.231 1.973 2.868 3.389 0.383 -0.004 0 53.
110.3 56.5 1.603 1.913

15.7 111.6 59.8 58.1 2.249 2.075 3.001 0.092 1.609 2.061 1.965 2.621 3.341 -0.349 -0.025 0 54.
110.4 58.4 1.684 1.981
86 Brigatti & Guggenheim

TABLE 3a. STRUCTURAL DETAILS OF TRIOCTAHEDRAL BRITTLE MICAS

Cell parameters R

Reference Species, locality Rock type Composition a b c E


(sample number)
() () () () (%)

1M polytype, space group C2/m


1. Alietti et al. 1997 Clintonite, Valle di Skarn (Na0.01Ca0.99) (Al0.68Fe3+0.04Fe2+0.11 5.200(1) 9.005(2) 9.795(2) 100.24(2) 3.5
(n # cli5a) Stabio (Italy) Mg2.21) (Si1.20Al2.76) O9.88 F0.14
(OH)1.98

2. Alietti et al. 1997 Clintonite, Mt. Skarn (Na0.01Ca0.99) (Al0.64Fe2+0.22Mg2.14) 5.198(1) 9.006(1) 9.796(1) 100.21(1) 3.7
(n # cli7c) Monzoni (Italy) (Si1.19Al2.79Fe3+0.02) O9.82 F0.11
(OH)2.07

3. Alietti et al. 1997 Clintonite, Mt. Skarn (Na0.02Ca0.96) (Al0.76Fe2+0.15Mg2.09) 5.194(1) 8.995(2) 9.788(2) 100.23(3) 3.1
(n # cli8a) Monzoni (Italy) (Si1.25Al2.75) O9.94 F0.09 (OH)1.97

4. Alietti et al. 1997 Clintonite, Mt. Skarn (Na0.02Ca0.97) (Al0.65Fe2+0.13Mg2.22) 5.203(1) 9.026(2) 9.811(1) 100.27(1) 3.2
(n # cli8d) Monzoni (Italy) (Si1.24Al2.76) O9.86 F0.17 (OH)1.97

5. Alietti et al. 1997 Clintonite, Mt. Skarn Ca0.98 (Al0.67Fe2+0.16Mg2.17Ti0.01) 5.192(2) 9.003(2) 9.794(2) 100.17(2) 3.3
(n # cli9a) Monzoni (Italy) (Si1.19Al2.78Fe3+0.03) O9.83 F0.19
(OH)1.98

6. Alietti et al. 1997 Clintonite Valle di Skarn (Na0.01Ca0.95) (Al0.63Fe2+0.16Mg2.20 5.202(1) 9.005(2) 9.816(2) 100.30(1) 2.7
(n # cli9b) Stabio, Italy Ti0.01) (Si1.28Al2.7Fe3+0.02) O9.84 F0.18
(OH)1.98

7. Brigatti & Poppi Potassium kinoshitalite Skarn (K0.41Na0.04Ca0.01Ba0.54) 5.318(1) 9.214(1) 10.164(2) 100.11(1) 2.5
1993 (n #27) (Alaska) (Al0.17Fe2+0.27Mg2.53Ti0.03) (Si2.17
Al1.83) O9.94 F0.71(OH)1.35

8. Gnos and Kinoshitalite Metamorphic (Ba0.99K0.06Na0.01) (Al0.04Mg2.64 5.316(1) 9.230(2) 10.197(2) 100.06(1) 3.4
Armbruster 2000 manganese Mn0.31) (Si2.03Al1.97) O10 F0.37 Cl0.02
deposit (OH)1.61

9. Guggenheim & Ferrokinoshitalite, Sulfide ore body (Ba0.47K0.33Na0.04) (Fe2+1.72Fe3+0.15 5.389(1) 9.337(2) 10.054(2) 100.53(2) 3.2
Frimmel 1999 Brooken Hill (South in iron Mg0.74Mn0.08 Ti0.17) (Si2.44Al1.56)
Africa) formation O10 F0.65 (OH)1.35

10. Joswig et al. 1986 Clintonite, Lago della Skarn (Ca1.00Na0.007) (Mg2.29Al0.70Fe2+0.05 5.2037(9) 9.0126(5) 9.8145(9) 100.26(1) 2.0
Vacca, Adamello Ti0.006) (Si1.20Al2.69Fe3+0.11) O10
(Italy) (OH)2

11. Kato et al. 1979 Manganoan Metamorphic (K0.35Na0.11Ba0.58) (Fe3+0.05Al0.22 5.345(3) 9.250(4) 10.256(8) 99.99(5) 7.8
(n# 6) kinoshitalite, manganese Mg2.07Mn2+0.52 Mn3+0.21)
Nodatamagawa, Iwate deposit (Si2.05Al1.94 Ti0.01) O10.33 F0.05
Prefecture (Japan) (OH)1.62

12. MacKinney et al. Clintonite, Ertsberg Skarn Ca1.00 (Mg2.08Al0.74Fe2+0.18) 5.199(2) 9.005(3) 9.812(3) 100.30(2) 2.2
1988 (n # (Jaya) (Si1.10Al2.90) O10 (OH)2
2U.W.1782/5)

13. MacKinney et al. Clintonite, Edenville Marble Ca0.97 (Mg2.18Al0.70Fe2+0.11Ti0.01) 5.200(1) 9.005(2) 9.779(2) 100.30(2) 4.0
1988 (n # (New York) (Si1.32Al2.68) O10 (OH)2
3USNM94594)

14. MacKinney et al. Clintonite, Chichibu Ca1.00 (Mg2.11Al0.82Fe2+0.07) 5.197(1) 9.002(2) 9.812(2) 100.32(2) 2.2
1988 (n# 1USNM mine (Japan) (Si1.08Al2.92) O10 (OH)2
105455)

15. McCauley and Lithian kinoshitalite synthetic Ba0.97 (Mg2.23Li0.77) (Si2.84Al1.16) 5.2858(2) 9.1575(6) 10.0375(5) 100.124(4) 7.1
Newnham 1973 O9.9 F2.08
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 87

Tetrahedral Octahedral Sheet thickness Interlayer Basal Mean bond lengths A - O Intralayer Layer Overall
D W <M1 <M2 Tetra- Octa- Separa- oxygen T-O M1-O M2-O Inner Outer shift offset Shift
hedral hedral tion 'z
() () () () () () () () () () ()

23.4 109.2u2 59.1 58.8u2 2.319 2.092 2.908 0.004 1.731u2 2.034 2.020u2 2.432 3.561 -0.335a1 0.000a1 -0.335a1 1.

24.4 109.2u2 58.8 58.7u2 2.316 2.106 2.903 0.002 1.742u2 2.030 2.027u2 2.407 3.585 -0.334a1 0.000a1 -0.334a1 2.

23.9 109.2u2 58.8 58.6u2 2.309 2.106 2.908 0.007 1.733u2 2.033 2.023u2 2.417 3.572 -0.334a1 -0.001a1 -0.335a1 3.

23.4 109.4u2 59.1 58.8u2 2.327 2.094 2.906 0.012 1.735u2 2.037 2.022u2 2.435 3.563 -0.336a1 -0.001a1 -0.336a1 4.

24.9 108.9u2 58.8 58.7u2 2.309 2.102 2.920 0.027 1.749u2 2.029 2.024u2 2.397 3.603 -0.334a1 0.001a1 -0.333a1 5.

23.1 109.3u2 59.0 58.6u2 2.317 2.103 2.921 0.006 1.725u2 2.042 2.021u2 2.444 3.554 -0.337a1 0.000a1 -0.337a1 6.

11.4 111.1u2 59.0 59.0u2 2.298 2.131 3.280 0.003 1.676u2 2.071 2.067u2 2.866 3.391 -0.336a1 0.001a1 -0.335a1 7.

12.0 112.1u2 58.6 58.6u2 2.324 2.167 3.226 0.002 1.686u2 2.080 2.079u2 2.837 3.396 -0.335a1 0.000a1 -0.335a1 8.

4.0 111.3u2 58.5 58.3u2 2.269 2.216 3.130 0.008 1.672u2 2.120 2.106u2 3.024 3.210 -0.340a1 -0.001a1 -0.341a1 9.

23.1 109.3u2 59.1 58.6u2 2.322 2.103 2.911 0.013 1.727u2 2.046 2.021u2 2.443 3.553 -0.336a1 0.000a1 -0.336a1 10.

12.4 110.9u2 58.6 58.4u2 2.294 2.184 3.328 0.019 1.684u2 2.095 2.087u2 2.866 3.438 -0.334a1 0.001a1 -0.333a1 11.

23.4 109.0u2 59.2 58.8u2 2.317 2.088 2.931 0.014 1.728u2 2.041 2.015u2 2.440 3.564 -0.336a1 -0.001a1 -0.337a1 12.

22.8 109.3u2 59.1 58.7u2 2.317 2.097 2.892 0.008 1.722u2 2.040 2.019u2 2.444 3.538 -0.336a1 0.000a1 -0.336a1 13.

23.3 109.1u2 59.4 58.9u2 2.323 2.080 2.926 0.011 1.728u2 2.042 2.011u2 2.440 3.560 -0.337a1 -0.001a1 -0.338a1 14.

4.7 112.6u2 58.7 58.5u2 2.280 2.155 3.165 0.011 1.645u2 2.074 2.062u2 2.975 3.192 -0.333a1 -0.001a1 -0.334a1 15.
88 Brigatti & Guggenheim

2M1 polytype, space group Cc


16. Lin and Bityite, Mops, Pegmatite (Ca0.95Na0.02K0.001) (Al2.04Li0.55 0.45 5.058(1) 8.763(3) 19.111(7) 95.39(2) 3.0
Guggenheim 1983 (Zimbabwe) Fe3+0.007) (Si2.02Be0.64 Al1.34)
O10(OH)2

2Or polytype, space group Pnmn


17. Giuseppetti and Anandite, Wilagedera, Magnetite ore (Ba0.87K0.05Na0.04Mn0.04Ca<0.01) 5.468(9) 9.49(2) 19.96(1) 6.1
Tadini 1972 (North Western Sri zone, iron-ore (Fe2+2.46 Mg0.48 Mn0.06)
Lanka) body (Si2.64Fe3+0.7Fe2+0.58 Al0.08) O10
(OH) S0.85 Cl0.15

18. Filut et al. 1985 Anandite, Wilagedera, Magnetite ore (Ba0.96K0.03Na0.01) (Fe2+2.01Fe3+0.28 5.439(1) 9.509(2) 19.878(6) 6.4
(North Western Sri zone, iron-ore Al0.10Mg0.46 Mn3+0.04 Mn2+0.04Ti0.01)
Lanka) body (Si2.60Fe3+1.40) O10 (OH) F0.04 S0.84
Cl0.16

TABLE 3b. STRUCTURAL DETAILS OF DIOCTAHEDRAL BRITTLE MICAS

Cell parameters R
Reference Species, locality Rock type Composition a B c E
(sample number)
() () () () (%)

2M1 polytype, Space group Cc

19. Guggenheim and Margarite, Corundum (Ca0.81Na0.19K0.01) (Al1.99 5.1038(4) 8.8287(7) 19.148(1) 95.46(3) 4.0
Bailey 1975, 1978 Hill, Unionville, Fe2+0.01Mg0.03) (Si2.11Al1.89) O10
Chester County (OH)2
(Pennsylvania)

20. Joswig et al. 1983 Margarite, Greiner, (Ca0.73Na0.21) (Al1.96 Fe0.03Mg0.10 5.108(1) 8.844(2) 19.156(3) 95.48(2) 1.7
Zillertal, Tirol, Austia Li0.12) (Si1.92Al2.08) O10 (OH)2.12

21. Kassner et al. 1993 Margarite, Greiner, (Ca0.73Na0.21) (Al1.96 Fe0.03Mg0.10 5.1138(2) 8.8569(4) 19.185(1) 95.484(4) 2.7
Zillertal, Tirol, Austia Li0.12) (Si1.92Al2.08) O10 (OH)2.12

TABLE 4. STRUCTURAL DETAILS OF BOROMUSCOVITE-1M AND -2M1


calculated from the rietveld structure refinement by Liang et al. (1995)
Cell parameters R Tetrahedral Octahedral Sheet
thickness
a b c E D WT1 <M1 <M2 Tetra- Octa-
% WT2 (u2) hedral hedral
() () () ()
() () () () () ()

Boromuscovite-1M 5.102(4) 8.788(7) 10.076(7) 101.23(3) 3.8 10.5 106.2 62.5 54.6 2.03 2.19
(u2)

Boromuscovite-2M1 5.090(1) 8.822(2) 19.819(5) 95.62(1) 3.8 8.4 108.2 61.8 57.4 2.14 2.05
108.9
Mica Crystal Chemisrty and Influence of P-T-X on Atomistic Models 89

21.6 109.8T1 61.4 57.3M2 2.276 2.050 2.910 0.169 1.723T1 2.14 1.902M2 2.432 3.437 0.355a2,3 0.002a1,1 -0.355a1 16.
21.7 110.1T11 57.3M3 2.277 0.167 1.632T11 1.903M3
109.5T2 1.628T2
110.3T22 1.721T22

2.1 112.9T1 59.0M1 56.2M3 2.301 2.338 3.041 0.207 1.68T1 2.267M1 2.096M3 3.026 3.241 r0.331a1 0 0 17.
3.0 113.7T2 56.2M2 58.7M4 1.77T2 2.104M2 2.250M4

0.9 112.5 59.8M1 55.2M3 2.265 2.327 3.083 -0.13 1.620(2) 2.097M1 2.228M3 3.054 3.228 r0.337 a1 0 0 18.
0.9 112.6 55.3M2 60.2M4 +0.18 1.799(2) 2.236M2 2.120M4

Sheet Inter- Intra-


Tetrahedral Octahedral Thickness layer Basal Mean bond lengths A- O layer Layer Overall
D W <(M1) < Tetra- Octa- separa- Oxygen T-O M1-O M2-O Inner Outer shift offset shift
(T1, T11, vacancy (M2,M3) hedral hedra tion 'z (T1, T11, vacancy M3-O a2,3 a1, ,1 a1
T2, T22) T2, T22)
() () () () () () () () () () () ()

21.0 107.5 56.9 2.305 2.080 2.875 0.202 1.747 1.903 2.456 3.432 0.365 0.006 -0.359 19.
20.8 109.0 57.1 2.272 0.202 1.623 1.915
109.3 1.633
109.1 1.736
20.9 110.6 61.7 57.0 2.288 2.079 2.874 0.194 1.748 2.193 1.909 2.454 3.438 0.365 0.006 -0.358 20.
20.9 110.5 57.1 2.293 0.208 1.628 1.912
110.6 1.748
110.6 1.626
20.8 110.7 61.7 57.0 2.294 2.080 2.879 0.203 1.750 2.196 1.910 2.459 3.441 0.366 0.006 -0.359 21.
20.8 110.7 57.1 2.296 0.204 1.750 1.915
110.6 1.630
110.6 1.629

Mean bond lengths A - O


Interlayer Basal Intralayer Layer Overall
Separa- oxygen T1-O M1-O M2-O Inner Outer shift offset shift
tion 'z T2-O (u2) a1 a1 a1
() () () () ()
3.64 0.43 1.58 2.37 1.89 2.92 3.37 -0.335a1 -0.049a1 -0.385a1
(u2)

3.52 0.24 1.59 2.17 1.91 2.92 3.28 0.374a2,3 0.016a1,1 -0.381a1
1.57
90 Brigatti & Guggenheim

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2 Behavior of Micas at High-Pressure
and High-Temperature
Pier Francesco Zanazzi
Dipartimento di Scienze della Terra
Universit degli Studi di Perugia
Piazza Universit, Perugia, Italy
e-mail: zanazzi@unipg.it

Alessandro Pavese
Dipartimento di Scienze della Terra
Universit degli Studi di Milano
Via Botticelli 23, 20133 Milano, Italy
e-mail: alessandro.pavese@unimi.it
INTRODUCTION
Micas have been long known to play a crucial role in most petrologic and
petrogenetic processes, both in magmatic and metamorphic environments. Understanding
the crystal-chemical and thermoelastic behavior of this mineral family with variations in
pressure (P), temperature (T) and composition (X) is crucial to provide a reliable basis for
further interpretation and prediction of phase equilibria, transformations and most
reactions occurring in a variety of rocks. In addition, the development of geothermom-
eters and geobarometers has extensively made use of compositional (Fe/Mg+Fe ratio,
K/Na+K ratio, Tschermak substitution, etc.) and structural (cation ordering, polytypic
occurrence, etc.) properties of micas, or of their occurrence in assemblages at equilibrium
with other phases. A few studies by in situ high-pressure, high-temperature and high-
pressurehigh-temperature experiments are available (see e.g., Chapter 8 in Reviews in
Mineralogy and Geochemistry, Volume 41). The objectives of these studies are to
determine structural and thermoelastic properties of micas and to understand the
microscopic mechanisms ruling their responses to thermobaric stress.
Following these objectives, we partition such investigations into two categories:
1. Those which do not lead to a breakdown or permanent change of the structure of
the reactant phase or of its chemical composition.
High-pressure studies (single crystal, SC, and/or powder diffraction, PD) within
the elastic boundaries of response are required for the determination of P-V
equations of state, of compressibilities of bond lengths, of polyhedral volumes
and similar parameters for any other structural building units. These studies lead
to the understanding of compression mechanisms and to the estimate of the PV-
contribution to the Gibbs energy for correct interpretation of stability fields.
High-temperature studies (SC, PD) are aimed at determining bulk/polyhedral/
bond-length thermal expansions, or at obtaining insight into cation rearrange-
ments triggered by temperature. Results from these studies produce information
on the structural response to heating, on the bulk/tensorial thermal-expansion
coefficients used in thermodynamic calculations and on the cation order-disorder
reaction mechanisms.
High-pressure/high-temperature studies (SC, PD) for determination of P-V-T
equations of state. These results lead to an understanding of thermoelastic
properties, of exsolution phenomena and of phase diagrams.

1529-6466/02/0046-0002$05.00 DOI:10.2138/rmg.2002.46.02
100 Zanazzi & Pavese

Measurements at ambient conditions of elastic constants contribute to refining the


equation of state.
2. Those which cause significant change of the structure, or of the chemical
composition.
High-pressure studies (PD) involving the tracking of transformations to
amorphous phases. These studies contribute to the understanding of breakdown
reactions in high-pressure metamorphic environments.
High-temperature studies (SC, PD) are mostly devoted to investigations on
oxidization reactions in Fe-bearing micas, and on dehydroxylation/dehydration
processes. These studies lead to the understanding of mechanisms of storage and
release of H2O in hydrated sheet silicates through thermal activation and the
effects of the oxygen fugacity upon phase relation diagrams.
Given the variety of topics targeted by studies at non-ambient conditions on micas,
many methodologies are used, both of experimental and of theoretical nature. These
methodologies are:
3. Experimental diffraction techniques (sealed-source X-ray tube; synchrotron radiation
source; pulsed/steady neutron sources) with conditioning chambers, properly
designed to achieve high-pressure, high-temperature, and high-pressurehigh-
temperature conditions. [See Chapters 14, 15, and 16 in Hi gh Temperature and
High-Pressure Crystal Chemistry, Reviews in Mineralogy and Geochemistry Vol.
41 (R.M. Hazen and R.T. Downs, editors, 2000) for detailed descriptions.]
4. Experimental shock-wave methods, or Brillouin scattering techniques used to
measure elastic constants at either ambient, or non-ambient conditions.
5. Theoretical models to develop P-V and P-V-T equations of state, which provide links
between thermodynamics, structural data and thermoelasticity.
As discussed above for the objectives and methodologies, we consider trioctahedral
and dioctahedral micas. We stress the differences of behavior as a function of
environmental variables exhibited by these two subgroups.
Investigation techniques for the study of the thermoelastic behavior of micas
Among the techniques concerning crystallography and spectroscopy under static high
pressure, the diamond anvil cell (DAC) is a powerful device. The best system for obtaining
high pressures involves the use of two gem-quality single-crystal diamonds with flat
surfaces to serve as anvil faces. Diamond is used because of its high degree of hardness,
and because it is transparent to most electromagnetic radiations. The diamonds are set so
that a sample (a powder or a crystal) can be mounted between the anvil faces. The area of
the culet face is small, thereby allowing very high pressures to be reached with small loads.
A thick sheet of metal having a hole with a diameter smaller than that of the diamond faces
is used as a gasket between the two diamonds: the hole is the chamber in which the sample,
generally together with a fluid as a hydrostatic medium, is located. The apparatus must be
small to be mounted on a diffractometer. Larger cells have been used in connection with
neutron studies (Catti et al. 1994). Detailed descriptions of different DACs are given by
Ahsbahs (1987) and Hazen and Finger (1982), and updated in Chapters 14 and 16 in
High-Temperature and High-Pr essure Crystal Chemistry, Reviews in Mineralogy and
Geochemistry Vol.41 (R.M. Hazen and R.T. Downs, editors, 2000).
Several methods for measuring pressure have been developed. By far the most
popular method for high-pressure calibration is based on the wavelength shift of the
fluorescence lines of some elements excited by an intense source. One frequently used
Micas at High Temperature and High Pressure 101

sensor is ruby (Barnett et al. 1973): when excited by blue light, Cr3+ in the matrix of
Al2O3 undergoes a 2E-4A2 transition, generating a doublet whose wavelength increases
with pressure.
Single-crystal diffractometry under high pressure presents several experimental
problems, which generally produce low-quality intensity data, and hence, inferior
structural refinement results (Zanazzi 1996, Angel et al. 2001). Generally, diffractometry
studies were performed with sealed-source X-ray tubes, synchrotron, or neutron
radiation.
The thermoelastic behavior of micas was also studied by dynamic methods, namely
shock wave compression (Sekine et al. 1991), or by techniques involving resonant
ultrasound spectroscopy (Aleksandrov and Ryzhova 1961) or by Brillouin spectrometry
(Vaughan and Guggenheim 1986).
For a description of the devices and methods for high-temperature studies, see
Chung et al. (1993) and see Chapter 13 in H igh-Temperature and High-Pressure Crystal
Chemistry, Reviews in Mineralogy and Geochemistry Vol. 41 for more recent
techniques.
Heating methods can be grouped into three main categories:
(1) Hot gas. The sample is heated by a gas flow (N2) passing over a coiled electric
heating element. Maximum temperature is about 900C, and stability is poor.
(2) Radiative furnaces. A resistance wire is embedded in a refractory cement or ceramic
with conical openings for accessibility to the sample. Furnaces are normally
designed to operate in air, although the crystal itself may be sealed in a glass
capillary. Some heaters operate either in vacuum or in a controlled atmosphere
(especially for neutron diffraction).
(3) Laser heating. This heating method is based on the use of laser (Nd-YAG, or CO2).
This method involves the local heating of the sample in connection with the diamond
anvil cell for high P and high T studies in the simulation of geophysical conditions.
[See Chapter 13 in High-Temperature and High-Pressure Crystal Chemistry,
Reviews in Mineralogy and Geochemistry Vol. 41 for additional refs.]
P-V and P-V-T equations of state
One of the main goal of studies at non-ambient conditions involves the derivation of
the equations of state (EoS) of minerals, which are crucial for the prediction and
interpretation of high-pressure and high-temperature processes. The EoS relates
volumetric changes to intensive environmental variables, such as P and/or T [see Wallace
(1972) for a survey]. In particular, EoS are the one way to determine the contribution PV
to the Gibbs energy, which fixes stability of phases at given thermobaric conditions.
EoSs are also able, at least in principle, to predict the behavior of the bulk modulus as a
function of pressure and temperature for wide P-T ranges. Furthermore, data involving P-
V-T can be used to obtain the bulk thermal expansion as a function of pressure and
temperature simultaneously. Thus equations of state are fundamental in investigating
materials in general at non-ambient conditions.
We report and discuss briefly some of the most used EoS, although the reader should
refer to Angel (2001), Duffy and Wang (1998), and Anderson (1995) for a more detailed
presentation. EoS can broadly be divided into two categories:
f(P,V) = 0 and f(P,V,T) = 0
where the former is commonly called P-V EoS (i.e., isothermal EoS), and the latter
102 Zanazzi & Pavese

P-V-T EoS. P-V equations of state are in most applications described by the Birch-
Murnaghan (1986) expression, such that:
P(V ) = 3 fE (1 + 2 fE )5/2 ( A + BfE + CfE 2 ) (1)
2 2
where A = K0, B = 3/4 K0(K0 - 4), and C = 3/2 K0 K0 + 3/2 K0 K0 - 21/2 K0K0 + 143/6;
K0, K0 and K0 are the bulk modulus, its first and second derivatives versus pressure at
room conditions, respectively; fE is the Eulerian strain, defined as
fE = 1 (V0 / V0 )2/3 1 (2)
2
where V and V0 are the volume at P and at ambient conditions, respectively.
A truncation with C = 0 in Equation (1) is in general sufficient to describe the
behavior of minerals at very high pressure. Values for measured P-V data are generally
not needed for C [for more details, see Angel (2001)].
An alternative P-V EoS was provided by Vinet et al. (1986; 1987), and derived from
very general principles. Its form is as follows
3K 0 (1 W ) 3
P(V ) = exp ( K 0 1)(1 W ) (3)
2
2
W
where W =( V/V0)1/3.
Extensions of Equation (3) were provided by Vinet et al. (1989) and by Moriarty
(1995). These formalisms, however, are beyond the introductory purposes of this
presentation. The Vinet EoS is well suited to cope with structurally simple materials
(Jeanloz 1988), and results more appropriate than the Birch-Murnaghan function for
cases involving very high compression, when W < 0.6 (Vinet et al. 1986).
The experimental P-V data are fitted by Equation (1) or Equation (3) to infer the
elastic parameters which, for the reasons stated above, are commonly restricted to K0 and
K0. The extension of the P-V EoSs to the high-temperature regime can be made by
replacing K0, K0 and V0 with K0(T), K0(T) and V0(T), which represent the corresponding
quantities at T and ambient pressure. K0(T), K'0(T) and V0(T) are parametrized as a
function of T in several ways [for instance, see Saxena and Zhang, 1990]. K0(T) is well
known to have a quasi-linear behavior at high temperature, whereas for K'0(T) Saxena
and Zhang (1990) proposed a logarithmic dependence on T. V0(T) fulfils the standard
relationship
T
V0 (T ) = V0 exp V (T )dT (4)
T0
where V is the bulk thermal expansion coefficient. Applications of such a sort of EoSs
have been hitherto reported, for example, by Shinmei et al. (1999), Pavese et al. (1999b)
and Utsumi et al. (1998).
An alternative way of introducing the thermal dependence on T in an EoS consists in
splitting P into two components, that is
P = PS + PTH (5)
where PS has a purely static origin and can be calculated as above [(Eqn.1) or (Eqn.3)],
while PTH is a temperature dependent part (ther mal pressure). In turn, one has that
T
PTH = V KT dT (6)
T0
Micas at High Temperature and High Pressure 103

A remarkable simplification (Vinet et al. 1987; Birch, 1986) occurs if T > D, where
D is the Debye temperature of the compound under study, given that PTH can be
approximated as
Pt = V ,0 K 0 (T T0 ) (7)
where V,0 stands for the bulk thermal expansion coefficient at a reference temperature
(T0) and ambient pressure. Such an approximation, which was empirically proven
(Anderson and Isaak 1995) to hold below D for many materials, allows one to linearize
the dependence of the EoS on T, and leads to a significant numerical simplification.
Other EoS have not been considered in this brief outline for the sake of brevity:
Poirier and Tarantola (1998), Jackson and Rigden (1996), Kumar and Bedi (1996),
Holzapfel (1996), Kumar (1995). Also the use of the Rankine-Hugoniot equations related
to shock wave methods (Ahrens 1987) is not discussed here.
Dioctahedral micas
Compressibility of white mica . Several methods were used to study the elastic
behavior of dioctahedral micas. After the first compression data of Bridgman (1949),
Aleksandrov and Ryzhova (1961) measured an incomplete set of elastic constants of
muscovite by ultrasonic methods, assuming a hexagonal symmetry for mica. Vaughan
and Guggenheim (1986) measured muscovite elasticity by Brillouin spectrometry in its
proper monoclinic symmetry. Sekine et al. (1991) obtained the EoS of muscovite by a
shock wave method. Faust and Knittle (1994) studied muscovite under pressure by
powder X-ray methods to 270 kbar, where complete amorphization of mica occurs. Catti
et al. (1994) determined the compressibility of muscovite 2M1 by powder neutron
diffraction up to 20 kbar. Comodi and Zanazzi (1995, 1997) measured the compressibility
of two samples of muscovite with different Na content, and that of paragonite by single-
crystal diffraction methods in the range of 0-40 kbar. The EoS of a phengite 3T was
modeled by Pavese et al. (1999b) on the basis of synchrotron powder diffraction
measurements, performed at high P and T (P in the range of 0-50 kbar, T to 1000K).
Finally, Smyth et al. (2000) determined the bulk elastic properties of synthetic 2M1 and
3T Si-rich phengites. No data are available for brittle micas.
Figure 1 plots the equations of state of muscovite on the basis of the literature data.
Differences in samples and methodologies produce scattered values of the
compressibility (Table 1). The main observed features, however, show the strong control
the atomic arrangement has on the anisotropy of the elastic behavior. The compressibility
along [0 0 1] direction is between three and five times (depending on chemical
composition) greater than that along the a or b axes.
The main deformation mechanisms based on the single-crystal structural refinements
under pressure for muscovite and paragonite-2M1 (Comodi and Zanazzi 1995, 1997) are:
1. The high compressibility along the [001] direction, largely related to the reduction in
the interlayer thickness. This behavior is expected because of the weak bonding of the
interlayer cation. The effect is more evident if the cation is potassium, and decreases
if potassium is substituted by sodium (Fig. 2).
2. The smaller compressibility observed as Na increases relative to K is explained by
stronger repulsion between the basal oxygen atom planes on both sides of the Na
interlayer cation, owing to shorter csin and greater tetrahedral rotation than for
samples containing K.
3. (Si,Al)-O bond lengths do not vary significantly in the P range of 0-40 kbar. On the
whole, tetrahedral volume increases slightly. Tetrahedral thickness also apparently
increases, probably owing to tetrahedral tilting out of the (001) plane. A reduction of
104 Zanazzi & Pavese

the corrugation parameter, z, as defined by Gven (1971), is observed as P


increases.
4. In the octahedral sheet there is a small decrease in the volume of the octahedra. A
larger decrease is observed in the nominally vacant M1 octahedron, whereas in M2,
which is Al rich, a smaller decrease occurs. On the whole, the octahedral sheet is
thinned along the [0 0 1] direction.
5. The compressibility of the octahedra is greater than that of the tetrahedra. This results
in an increased dimensional misfit between tetrahedral and octahedral sheets, so that
there is an increase in the tetrahedral rotation angle, , with P (from 16.0 to 18.4 at
41 kbar for paragonite, and from 11.5 to 12.7 at 28 kbar for muscovite).
6. The partial occupancy of the M1 site by divalent cations, and a greater Si content in
the tetrahedral sheet, should decrease the compressibility. Therefore the presence of a
phengitic component probably increases the mica stiffness, as shown by the increased
bulk modulus of phengite-3T in comparison with that of end-member muscovite
(Pavese et al. 1999b). The difference found, however, could be partially ascribed to
the different mica polytype. A statistical study on the occurrence of metamorphic
phengites by Sassi et al. (1994) seems to show that the crystallization of the 3T
polytype is mainly favored by high P/T ratio conditions.

Figure 1. Equation of state of muscovite.


Elastic parameters from Table 1. Full line:
Vaughan and Guggenheim (1986); dashed line:
Sekine et al. (1991); dot-dashed line: Faust and
Knittle (1994); dotted line: Catti et al. (1994)
and Comodi and Zanazzi (1994).

Presently, the lack of reliable compressibility data precludes any affirmation about
the relative stiffness of the various polytypes of mica, and hence any speculation on their
relative stability under high-pressure conditions.
The progressive Si-Al ordering in tetrahedral sites of muscovites with increasing
pressure, as claimed by Velde (1980), was not confirmed by Flux et al. (1984) on the
basis of infrared (IR) spectra of synthetic 2M1 samples crystallized under different
pressures.
Above 180 kbar, at ambient temperatures, muscovite begins to amorphize (Faust and
Knittle 1994). The amorphization is complete near 270 kbar. In a diamond anvil cell
heated at about 800C by laser, muscovite transforms between 18 and 37 kbar into an
assemblage containing sanidine, corundum, H2O, and a cymrite phase KAlSi3O8.H2O.
Between 37 and 40 kbar, muscovite breaks down to wadeite, kyanite, corundum and
H2O. Over 109, and to ~210 kbar, an assemblage of hollandite, corundum and H2O is
stable (Faust and Knittle 1994).
Micas at High Temperature and High Pressure 105

Table 1. Bulk modulus at P = 0 (K0 in kbar)* and its first derivative versus pressure
for dioctahedral micas.
* K0 values obtained from static compression measurements are the isothermal moduli,
values obtained from Brillouin spectroscopy and shock wave measurements are the
adiabatic moduli.

Sample K0 K 0 Technique

Muscovite-2M1 582 - Brillouin spectroscopy


(Vaughan & Guggenheim 1986)
Muscovite-2M1 520 3.2 shock wave
(Sekine et al. 1991)
Muscovite-2M1 614 6.9 static compression powder
(Faust and Knittle 1994) diffraction
Muscovite-2M1 560 4 static compression neutron
(Catti et al. 1994) powder diffraction
Muscovite-2M1 560 - static compression single
(Comodi and Zanazzi 1995) crystal diffraction ( -1)
Na-Muscovite-2M1 600 - static compression single
(Comodi and Zanazzi 1995) crystal diffraction ( -1)
Paragonite-2M1 655 - static compression single
(Comodi and Zanazzi 1997) crystal diffraction ( -1)
Phengite-3T 583 6.6 static compression
(Pavese et al. 1999) synchrotron X-ray diffraction
Phengite-3T 620 9 static compression single
(Smyth et al. 2000) crystal diffraction
Phengite-2M1 570 9.2 static compression single
(Smyth et al. 2000) crystal diffraction

Figure 2. -1 (kbar) as a function of


Na/(Na+K) in dioctahedral micas. Data
from Comodi and Zanazzi (1997).
106 Zanazzi & Pavese
-1
Table 2. Axial thermal expansion coefficients (x in C ) for the cell edges and the volume,
and the first derivative of tetrahedral rotation angle versus T in dioctahedral micas.
Sample a b c V d/dT
Muscovite-2M1 0.9910-5 1.1110-5 1.3810-5 3.5410-5 - 4.1210-3
(Guggenheim et al. 1987)
Muscovite-2M1 1.1210-5 1.1810-5 1.8910-5 4.210-5 -5.310-3
(Catti et al. 1989)
Muscovite-2M1 1.410-5 1.410-5 1.910-5 4.710-5 -
(Symmes 1986)
Phengite-2M1 0.8910-5 0.9810-5 1.6610-5 3.4310-5 -
(Pavese et al. 1999)
Phengite-2M1 0.8610-5 0.9910-5 2.1510-5 4.0510-5 -
(Mookherjee et al. 2000)
Phengite-3T 0.5710-5 - 2.5310-5 4.2610-5 -4.510-3
(Amisano Canesi 1995)
Phengite-3T 0.5710-5 - 2.1410-5 3.3110-5 -
(Pavese et al. 1997)
Paragonite-2M1 1.5110-5 1.9410-5 2.1510-5 5.910-5 -5.7410-3
(Comodi and Zanazzi 2000)
Paragonite-2M1 1.510-5 1.410-5 1.710-5 4.910-5 -
(Symmes 1986)
Margarite 0.8610-5 0.6510-5 1.210-5 2.810-5 -
(Symmes 1986)
Thermal expansion of dioctahedral micas. The thermal behavior of dioctahedral
micas has been studied with single-crystal methods by Guggenheim et al. (1987) and
Catti et al. (1989) for muscovite, by Comodi and Zanazzi (2000) for paragonite, and by
Amisano Canesi et al. (1994) for phengite. Symmes (1986) reported isobaric expansion
data from the powder diffraction method for muscovite, paragonite, margarite, and other
phyllosilicates to 500C. The structural response of phengite to temperature by in situ
powder neutron diffraction studies was reported by Pavese et al. (1999a) and Mookherjee
et al. (2000) for the 2M1 polytype, by Amisano Canesi et al.(1994), Amisano Canesi et al.
(1995) and Pavese et al. (1997) for the 3T polytype. Results on the thermal expansion of
micas are summarized in Table 2.
The study of thermoelastic properties is more difficult for micas than for other rock-
forming silicates, because of the partial hydroxyl loss at high temperature. The
mechanism of this reaction is 2OH- H2O + O2-, with H2O diffusing through the
tetrahedral sheets and the interlayer region. A kinetic analysis of the process was
performed by Mazzucato et al. (1999) (and references therein) by in situ powder X-ray
diffraction. Dehydroxylation of (Fe3+, Mg)-rich dioctahedral micas [celadonite and
glauconite samples] was studied by Muller et al. (2000a,b) both in terms of structural
transformations and of cation migration, combining powder X-ray diffraction, selected
area electron diffraction and modeling. Such an investigation was performed by in situ
and ex-situ measurements, and revealed migration of cations, mostly Mg, from the cis-
sites to the empty trans-sites, which acquire 5-fold coordination. This reaction causes a
transformation of the C-centered cell into primitive. The dehydroxylation path of
muscovite was modeled by Abbott (1994) on the basis of theoretical energy calculations.
Results suggest that the release of OH depends on the [4]Al/Si ratio of the environment.
Since this ratio is variable, owing to the many possible patterns of Al-Si tetrahedral order,
it is not surprising that muscovite dehydroxylation takes place over a wide temperature
range. This conclusion is however to be assessed with due care, as it relies upon the
Micas at High Temperature and High Pressure 107

assumption of a precise knowledge of the hydrogen position, which thing is hard to be


determined at an adequate level of precision.
The formation of a metastable dehydroxylated phase is shown by a marked change in
slope of the lattice constants and cell volume upon increasing T. This was found in
muscovite above 800C (Guggenheim et al. 1987) and in paragonite above 600C
(Comodi and Zanazzi 2000). This is in agreement with the greater thermal stability of
muscovite than paragonites obtained from petrographic evidence (Guidotti 1984) and
experimental phase relations (Hewitt and Wones 1984). However, the temperature range
of dehydroxylation is variable, depending on the rate of the change in T and the possible
non-equilibrium conditions of the sample, e.g. those occurring during thermal analysis, or
on a hypothetic locally different Al-Si order in tetrahedral sites (Abbott 1994).
For paragonite, the dehydroxylation process is completed below 700, as shown by
Raman spectra. Structure refinements by single-crystal method (Comodi and Zanazzi
2000) show that the dehydroxylated phase is similar to the dehydroxylation product of
muscovite (Udagawa et al. 1974). In this phase, the octahedral sheets undergo the
greatest changes, because the Al ions become five-fold coordinated to form distorted
trigonal bipyramids. The sheet of these polyhedra is sandwiched between two tetrahedral
sheets, with an atomic arrangement similar to that of the precursor mica. This reaction is
topotactic. Because of the enlarged dimensions of the Al sheet, tetrahedral rotation angle
decreases, going from 16.2 in paragonite to 13.3 in the anhydrous phase.
The effects of temperature on the mica structure, based on the single-crystal
refinements of muscovite at 650C (Guggenheimet al. 1987) and of paragonite at 600C
(Comodi and Zanazzi 2000), can be summarized as follows:
1. the expansion of dioctahedral micas, like that of other phyllosilicates, is strongly
anisotropic, with maximum value along the [001] direction (Table 2). The anisotropy
is slightly smaller in paragonite than in muscovite. The effect on the c-cell parameter
is mainly related to the expansion of the interlayer thickness. The variation in the
interlayer thickness is 0.07 in muscovite and 0.13 in paragonite. The angle
does not change with T in muscovite, but decreases in paragonite.
2. the tetrahedral (Si,Al) volume does not change significantly in the investigated
interval (25-650C for muscovite; 25-600 C for paragonite). The Al octahedra
expand slightly: the volume of M2 increases by 1.5% in muscovite, and by 2.5% in
paragonite. The volume of the M1 vacant site increases by 1.8% in muscovite and by
4% in paragonite. The resulting total increase of the [2:1] layer thickness is 0.02 in
muscovite and 0.013 in paragonite.
3. the effects of intensive variables P and T on the structure of mica are roughly
similar, but opposite in sign. This applies to variations in cell edges and to their
anisotropy, as well as to polyhedral deformations. The greatest effects concern the
interlayer region, where the difference of the six "inner" and six "outer" distances in
the interlayer cation polyhedron decreases with T and increases with P. The same
trend is observed for the tetrahedral rotation angle , going from 11.8 to 9.2 in
muscovite and from 16.2 to 12.9 in paragonite.
Assuming that
1. the variations induced by T and P are cumulative,
2. the derivative of the thermal expansion coefficient versus P at constant T, (/P)T ,
is negligible,
3. the derivative of the compressibility coefficient versus T at constant P, (T)P , is
negligible,
108 Zanazzi & Pavese

the conditions which do not change the structure with respect to ambient conditions can
be determined, at least volumetrically. At first approximation, the resulting EoS in the
PTV space for paragonite and muscovite are: V/V0 = 1 + 5.910-5 T 0.00153 P and V/V0
= 1 + 4.310-5 T 0.0017 P (T is in C andP is in kilobars), showing that paragonite is
more expandible and less compressible than muscovite. This is a significant datum
concerning the shape of the Pg-Ms solvus at high P and T.
Order-disorder of Si and Al in tetrahedral sites as a function of temperature was the
object of several studies, with controversial results. The behavior of phengite-3T from
Dora Maira at high T was studied by in situ single-crystal X-ray diffraction (Amisano-
Canesi et al. 1994; Amisano-Canesi 1995) and powder neutron diffraction (Pavese et al.
1997, 2000). These authors found that this sample seems to exhibit cation ordering both
on the tetrahedral and on the octahedral sites, supporting the hypothesis of Sassi et al.
(1994) that a high P/T ratio induces cation order. Powder neutron diffraction on a Fe-rich
phengite-2M1 (Pavese et al. 1999a) showed that cation partitioning is disordered at room
temperature, but Al fully orders into the T1 site at 600C. This resultis in contrast with
the findings of Mookherjee et al. (2000) on phengite-2M1 from Greece, who find no
evidence for changes in tetrahedral cation order on heating (in situ powder neutron
diffraction to 650C).
Low-temperature powder neutron diffraction measurements were used by Pavese et
al. (2001) to investigate the fractional occupancy of the M1 site of phengite-3T and -2M1,
commonly assumed to be empty.
Trioctahedral micas
High pressure studies. High pressure investigations on trioctahedral micas are
hitherto very scarce. Hazen and Finger (1978) first pioneered the crystal structures and
compressibilities of layer minerals at high pressure, investigating natural phlogopite and
chlorite. There was a twenty-year long lack of high pressure studies on trioctahedral
micas until the work of Comodi et al. (1999), who dealt with high-pressure and high-
temperature behavior of Cs-tetra-ferri-annite-1M (composition: Cs1.78(Fe2+5.93Fe3+0.07)
(Si6.15Fe3+1.80Al0.05)O20(OH)4), and Comodi et al. (2001), who studied the compressibility
of Rb-tetra-ferri-annite-1M; hereafter, referred to C s-annite and Rb-annite,
respectively. Note that (1) the investigated samples are synthetic, and that (2) the results
therein reported can only be extrapolated to natural micas (i.e., K- and Na-rich micas)
with care. The above studies provide indications about the microscopic mechanisms
governing the behavior of trioctahedral micas under pressure and explore the baric range
to 50 kbar, which is sufficient for applications of geological interest.
In Table 3, the compressibility of the lattice parameters and of the polyhedral
building units are reported, along with other structural parameters useful to understand
the high-pressure behavior of Cs-annite, Rb-annite and phlogopite. The points outlined
below show the effect of how different structural units of trioctahedral micas relate with
one another, and then respond as a whole to pressure:
1. Most of the volume reduction under pressure occurs along the [001] direction. This
is readily understood by observing, in Table 3, the remarkable anisotropy of the
axial compressibilities. The shortening of the c axis is responsible of about 81%
(Cs-annite) and 70% (phlogopite and Rb-annite) of the reduction in volume. An
analysis of the change of the tetrahedral, octahedral and interlayer thicknesses as a
function of pressure reveals that the interlayer thickness undergoes a shortening at
least ten times as large as the others, which, in turn, are comparable with one
another.
2. The interlayer site exhibits a significantly smaller bulk modulus than the other sites,
Micas at High Temperature and High Pressure 109

Table 3. Polyhedral bulk modulus for T1, T2, M1, M2 and interlayer sites, in kbar. Axial and
-1
volume compressibilities (a,b,c,V), in kbar-1, and first derivative versus P of /0, in kbar .
Bulk modulus at P = 0 (K0, in kbar) calculated by the Birch-Murnaghan EoS, constraining its
first derivative versus P (K0) to be equal to 4. Tetrahedral rotation angle () and tetrahedral
-1 -1
tilting (z) first derivative versus P, in kbar and kbar , respectively.

phlogopite Cs-annite Rb-annite


(Hazen & Finger 1978) (Comodi et al. 1999) (Comodi et al. 2001)
T1 negligible 1370(400)
T2 negligible 1370(400)
M1 1200(2000) 1040(300)
M2 1200(2000) 1190(300)
K/Cs 200(30) 260(70)

a 2.510-4 1.6(2) 10-4 1.6(1) 10-4


b 2.810-4 1.7(1) 10-4 2.13(7) 10-4
c 11.710-4 14.0(5) 10-4 10.1(4) 10-4
d(/0)/dP 1.7(5) 10-4 1.5(1) 10-4 negligible

K0 510(14) 419(6) 500(3)


K 0 4 4 4

d/dP 51.410-3 4.110-3


dz/dP 2.110-4 6.910-4

in keeping with the fact that the contraction along the [001] direction occurs mainly
at the expense of the interlayer polyhedron, which yields under load.
3. The discrepancies of the c values are likely related to differences of the interlayer
composition. Note that Cs- and Rb-cations are expected to be softer than K [Cs, Rb
and K have the same oxidation state, but decreasing ionic radius, leading to
decreasing cation-oxygen bond lengths], which is consistent with the
compressibilities of the c-axis. This conclusion is consistent also with the polyhedral
bulk-modulus values of the interlayer sites, although care is required because of the
large uncertainties.
4. The polyhedral bulk moduli of the octahedral sheet do not allow a reliable
comparison between the Fe-bearing sites and the Mg-bearing ones because of the
large uncertainties affecting the issues of Hazen and Finger (1978). The a and b
values, which are reflective of the compliance of the T-O-T layer across the (001)
plane, indicate Cs-annite behaves more rigidly than phlogopite. This observation is
in keeping with Zhang et al. (1997) who maintain, for clinopyroxenes, that sites
containing Mg are softer than those occupied by Fe. Rb-annite exhibits a value of b
in disagreement with the one of Cs-annite, presumably owing to the structural
transition from A type to B type (Franzini 1969; see next point 5), which mainly
affects the compressibility of a and b lattice parameters.
5. The tetrahedra are nearly rigid units, and tend to relax under pressure by rotations
described by the angle. These rotations are sensitive to composition, as Table 3
shows. In particular, the tetrahedral sheets adjacent to the Fe-bearing octahedral
sheet, in Cs-annite, exhibit a significantly smaller rotation than in phlogopite. This
110 Zanazzi & Pavese

is consistent with point (4): the rigidity of the Fe-rich octahedral sheet seriously
limits the rotational degree of freedom of the tetrahedral sheet to comply with
pressure. The value and the tetrahedral sheet corrugation (z) increase upon
increasing pressure, regardless of the composition; such an observation suggests that
the tetrahedral rotation and the corrugation of the basal oxygen atom plane are a very
general way of relaxation of the tetrahedral sheet in micas. The structural evolution
of Rb-annite with pressure (Comodi et al. 2001) shows a peculiar behavior of the
tetrahedral rotation angle : although it increases with pressure as well as in other
micas, it assumes positive values at pressures lower than about 45 kbar and negative
values at higher pressure, indicating a phase transition from a type A to a type B
structure (Franzini 1969).
6. The differences on the bulk-modulus values must be assessed with care, because of
the small number of points obtained by Hazen and Finger (1978) in deriving K0 for
phlogopite. Taking into account the large uncertainties on the data, the difference in
K0 reflects the greater softness of Cs/Rb-annites than phlogopite because of the
replacement of K with Cs/Rb in the interlayer. In particular, note that the larger K0 of
Rb-annite than that of Cs-annite is consistent with predictions based on the ionic
radii, as discussed in point (3) above.
7. The obliquity of the monoclinic cells of trioctahedral micas increases upon pressure.
High-temperature studies. In this section we discuss in situ high-temperature
investigations, and studies with heat-treated samples to induce oxidation and dehydration/
dehydroxylation processes.
Takeda and Morosin (1975) compared the behavior at high temperature of a
synthetic fluorphlogopite with predictions relying upon the geometrical approach of
Donnay et al. (1964). Hogg and Meads (1975) investigated by Mssb auer spectroscopy
the thermal decomposition of biotites, owing to Fe2+ Fe3+ oxidation accompanied by
dehydroxylation on specimens previously heated. Tripathi et al. (1978) studied the effects
of high-temperature reactions in biotite and phlogopite by Mssbauer spectroscopy.
Rancourt et al. (1993) reported the first kinetic study of iron oxidation in biotite by
Mssbauer spectroscopy. They also suggested a simple activation model accounting for
iron oxidation and ordinary dehydroxylation, based on the following reactions:
OH- O2- + H+, i.e., local dissociation of OH-groups either by Fe2+ + H+ Fe3+ + H,
i.e., Fe-oxidation, or by O2- + 2 H+ H2O, i.e., dehydroxylation. Twenty-four years after
the Takeda and Morosins investigation, Russell and Guggenheim (1999), and Comodi et
al. (1999) discussed the high-temperature behavior of a near end-member phlogopite and
of a Cs-annite, respectively. These investigations consider structural aspects observed
in situ and Fe-oxidation mechanisms in heat-treated specimens. The latter topic is
discussed in the light of bond-length changes and cell volume versus heating-time curves.
Tutti et al. (2000) studied the thermal expansion of a natural phlogopite from Pargas
(Finland) and monitored by TGA and DTG the Fe-oxidation and dehydroxylation
processes triggered by temperature. They observed that the curves of a, b and c as a
function of temperature are split by a discontinuity slightly above 400C into two regions
exhibiting quite different thermal expansion coefficients. Such a behavior upon heating is
presumably related to the different mechanisms governing the structural rearrangements
of phlogopite below and above the oxidation temperature of Fe, which takes place about
500-600C. Note that the discontinuity observed by Tutti et al. (2000) is consistent with
that reported by Takeda and Morosin (1975) for F-phlogopite. It is worthy of interest to
analyse how the structure of trioctahedral micas responds to heating, to achieve a full
understanding of the mechanisms driving the high-temperature processes in these
Micas at High Temperature and High Pressure 111

-1
Table 4. Axial thermal expansion coefficients (a,b,c,V), in C , and first derivative of /0 angle
-1
of the monoclinic cell versus T, in C . Tetrahedral rotation angle () and octahedral flatness
-1
angle () first derivatives versus T, in degC . The results from Tutti et al. (2000) are reported on
two rows: the upper and the lower refer to thermal expansion coefficients below and above
412C, respectively.
F-phlogopite phlogopite phlogopite Cs-annite
(Takeda and (Russell and Gug- (Tutti et al. 2000) (Comodi et al.
Morosin 1975) genheim 1999) 1999)
a 0.8910-5 1.4010-5 3.7410-5 negligible
0.8610-5
b 0.7710-5 1.3410-5 1.0910-5 negligible
0.8010-5
c 1.810-5 1.8110-5 1.1910-5 3.1210-5
1.9310-5
d(/0)/dT -1.3 -1.5 -0.36
d/dT -5.610-3 -7.910-3 -1.010-3
d/dT -0.710-3 -0.310-3 -0.710-3

minerals. In Table 4, we report some of the parameters required to understand structural


adjustments occurring as a function of temperature:
1. All trioctahedral micas (Table 4) expand mainly along the [001] direction, although at
quite different rates according to the compositions of the octahedral sheet and,
principally, of the interlayer sites. For Cs-annite, the Fe(O,OH)6 octahedra are
moderately sensitive to heating, so that the thermal expansion coefficients along the
[100] and [010] directions are negligible and the volume expansion occurs entirely
along the [001] direction. The soft Cs-cation in the interlayer site causes c in Cs-
annite to be nearly twice as large as the corresponding value in phlogopite. This
conclusion is consistent with the linear thermal expansion coefficients of the interlayer
at approximately 6.3 10-5 and 3.7 10-5 per C for Cs-annite and phlogopite,
respectively. In Figure 3, the relative change of the c cell dimension for Cs-annite and
phogopite is reported as a function of T.
2. The octahedral flatness angle, , decreases upon heating for both Mg- and Fe-bearing
trioctahedral micas, which reduces the diagonal elongation versus the sheet thickness.
Note that the d/dT values are not simply related to the cation occupancy of the M-
sites. For example Mg(O,OH)6 shows remarkable differences in phlogopite or in F-
rich phlogopite.
3. The tetrahedral rotation angle as a function of T exhibits a negative slope, and changes
at different rates in Mg- or Fe-bearing trioctahedral micas. In particular, the rotation
angle changes slightly in the latter, and this result is related to the inertness of the
Fe(O,OH)6 or Fe(O,F)6 octahedra and implies a modest rearrangement in the T-sheet.
4. The obliquity of the cell decreases on heating, indicating a tendency to approach a 90
angle.
In brief, from the discussion above, trioctahedral micas, under thermal or baric
conditions, respond as follows:
1. structural changes occur mainly along the [001] direction, at the expense of the
interlayer site, owing to the weaker interactions. The axial thermal expansion or
compressibility coefficients reflect this aspect.
112 Zanazzi & Pavese

Figure 3. (c-c0)/c0 ratio as a function of


temperature, for Cs-annite (Comodi et al.
1999) and phlogopite (Russell and
Guggenheim 1999). c0 is the value of c at
ambient conditions.

Figure 4. (a) <T-O> (filled squares) and <M-O> (M1 and M2, filled and empty diamonds respectively) bond lengths
versus pressure, normalized to their values at room conditions. pg: paragonite. Data from Comodi and Zanazzi
(1997). Subscripts HP and RP stand for high pressure and room pressure, respectively. (b) <T-O> (T1 and T2, filled
and empty circles, respectively) and <M-O> (M1 and M2, filled and empty diamonds, respectively) bond lengths
versus temperature, normalized to their values at room conditions. pg: paragonite. Data from Comodi and Zanazzi
(2000). Subscripts RT and HT stand for room temperature and high temperature, respectively.

2. the adjustment of the T-O-T layer is accomplished by volumetric changes of the


octahedra by either expansion or compression, and by rotations and corrugations of
the tetrahedral sheets. The tetrahedra behave as quasi-rigid bodies, to achieve
matching lateral dimensions between tetrahedral and octahedral sheets.
3. the obliquity of the unit cell increases under pressure, and decreases upon heating.
The behavior of micas as a function of P and/or T is therefore strictly dependent on
the stacking structural features of these minerals. Thus, trioctahedral and dioctahedral
micas show similar responses to thermobaric stress. Most of the compression/expansion
occurs along c*, at the expense of the interlayer polyhedra. The changes occurring across
the (0 0 1) plane are out-of-plane tilting and in-plane rotation of the tetrahedra of the
tetrahedral sheets, to minimize the misfit between the tetrahedral and octahedral sheets,
Micas at High Temperature and High Pressure 113

the latter accounting for the most significant bond-length variations in the 2:1 layer. As
an example, in Figures 4a and 4b the average T-O and M-O bond lengths in paragonite
are plotted as a function of pressure and temperature, respectively, to illustrate the
sensitivity of the tetrahedra and octahedra to thermobaric stress. The results are consistent
with the general rule that temperature promotes regularity whereas pressure favors
distortion in structures: Figures 5a and 5b show the difference between the average of the
interlayer cation-oxygeninner and cation-oxygenouter bond lengths in paragonite and
muscovite, normalized to ambient conditions, versus P and T, respectively. Note that
pressure tends to increase the twelve-fold site strain, whereas temperature shows the
reverse trend, where atoms produce a more regular arrangement. Note also the
remarkable dependence of the thermoelastic parameters on the chemical composition,
apparent in the case of the interlayer cation replacement. Figure 6 shows the bulk
modulus plotted as a function of the interlayer cation size. The figure is computed as an
average of the interlayer chemical composition, assuming a twelve-fold coordination. A
shift of approximately 0.5 in ionic radius corresponds to more than 100-kbar decrease
in K0.

Figure 5. (a). |<K-O>inner-<K-O>outer| versus pressure, normalized to their values at room conditions. pg
(filled circles): paragonite (Comodi and Zanazzi 1997); ms (empty circles): muscovite (Comodi and
Zanazzi 1995). Subscripts i and o stand for inner and outer; HP and RP for high pressure and room
pressure, respectively. (b)|<K-O>inner-<K-O>outer| versus temperature, normalized to their values at room
conditions. pg (open circles): paragonite (Comodi and Zanazzi 2000); ms (filled circles): muscovite
(Guggenheim et al. 1987). Subscripts i and o stand for inner and outer; HT and RT for high temperature
and room temperature, respectively.

The modest number of experimental studies on the behavior of micas as a function


of pressure and/or temperature and the difficulty in the experiments that leads to lack of
precision, make a statistically reliable comparison between trioctahedral and dioctahedral
micas difficult. The main differences between the two originate from the octahedral sheet
behavior. Differences between the two forms would be expected between the
rearrangements of the 2:1 layers upon P and/or T.
Based on the current data, and assuming a K-bearing interlayer sheet, the following
conclusions can be drawn:
1. Dioctahedral micas are less thermally stable, and have larger bulk thermal expansion
than trioctahedral micas, presumably as a consequence of the vacant M1 site.
114 Zanazzi & Pavese

2. Dioctahedral micas have a slightly larger bulk modulus than trioctahedral micas (i.e.
are slightly stiffer), because of the presence of trivalent cations instead of divalent
cations in octahedral coordination. This produces a larger polyhedral bulk modulus
(Hazen and Finger 1982).

Figure 6. Bulk modulus as a function of


interlayer cation size, calculated using the
interlayer chemical composition. Na(Pg):
paragonite (Comodi and Zanazzi 1997);
Na(mu): Na-rich muscovite (Comodi and
Zanazzi 1995); K(phl): phlogopite (Hazen
and Finger 1978); K(mu): K-muscovite
(Comodi and Zanazzi 1995); Cs(Cs-tfa): Cs-
tetra-ferri-annite (Comodi et al. 1999);
Rb(Rb-tfa): Rb-tetra-ferri-annite (Comodi et
al. 2001).

ACKNOWLEDGMENTS
We are grateful to Steve Guggenheim for reviewing this chapter and for his
comments on the manuscript.
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3 Structural Features of Micas
Giovanni Ferraris1 and Gabriella Ivaldi2
1,2
Dipartimento di Scienze Mineralogiche e Petrologiche
Universit di Torino
10125 Torino, Italy
and
1
Istituto di Geoscienze e Georisorse
Consiglio Nazionale delle Ricerche
10125 Torino, Italy
ferraris@dsmp.unito.it ivaldi@dsmp.unito.it

INTRODUCTION
The large number of mica species (end-members) and varieties is based on chemical
variability and peculiar structural features like polytypism, local and global symmetry. In
addition, mainly because of an inherent misfit between the constituent tetrahedral and
octahedral sheets, in the specific mica structures several structural parameters undergo
adjustments relative to their ideal values. Consequently, the mechanisms ruling distor-
tions from ideal models must be considered when investigating a mica behavior under
geological conditions.
Micas are important rock-forming minerals and petrographers consider them mainly
for their chemical aspects. The importance of the chemical composition is well known to
all researchers dealing with minerals. To give emphasis to the chemical composition, the
official classification of the micas (Rieder et al. 1998; Rieder 2001) allows exceptions
(note the introduction of species that are not end member in Rieder et al. 1998) to the
rules which are normally used to define mineral species (Nickel and Grice 1998).
However, as shown throughout this book, the role of structure features (including some
aspects of polytypism) in determining fields of stability of micas and, therefore, in
providing geological insights, is increasingly recognized as crucial. Thus, it seems
justified that a chapter dedicated to the description of the general structural background
of micas should be presented independently from specific cases, which are discussed in
other chapters.
This chapter is an introduction to the symmetry and geometric aspects of micas.
Nevertheless, some less conventional topics not covered in other chapters are reported in
appendices. Appendix I concerns the wide presence of mica-like modules in the growing
group of natural, layer titanosilicates (Khomyakov 1995; Ferraris et al. 2001b,d) and
other more or less exotic structures belonging to the expanding field of modular
crystallography (Merlino 1997). Important results have been obtained by the oblique-
texture electron diffraction method (OTED; cf. Zvyagin et al. 1996, and references
therein). Only a few, limited treatments are in English. Thus, this method is discussed in
Appendix II.

NOMENCLATURE AND NOTATION


Bailey (1984c) recommended a notation system for structural sites in micas.
However, there is no agreement to the labeling of these sites; e.g., either an italic or
roman font is used with or without parentheses to separate the alphanumeric parts.
Following recent papers (Nespolo et al. 1999c: Nespolo 2001) and in agreement with the
chapter of Nespolo and Durovic (this volume), the nomenclature of the OD theory of
polytypes (Dornberger-Schiff et al. 1982; Durovic 1994) is here adopted to label sites,

1529-6466/02/0046-0003$05.00 DOI:10.2138/rmg.2002.46.03
118 Ferraris & Ivaldi

planes, sheets and layers. Emphasis is given to symmetry aspects more than to structural
and chemical features. Thus, rather than to a distinction between dioctahedral and
trioctahedral micas, preference is given to a classification in homo-octahedral, meso-
octahedral and hetero-octahedral families according to the layer symmetry [H`( 3 )1m,
P`( 3 )1m and P(3)12; see Table 1 below] of the octahedral sheet in the TOT or 2:1 layer,
here referred to as the M layer. Two types of M layers are introduced according to the
position of the origin assigned to the reference system in the octahedral sheet: layer M1 if
the origin is in the octahedral trans site M1, and layer M2 if the origin is in the octahedral
cis sites M2 or M3. Trans and cis refer to the position of the OH groups (cf. Fig. 5
below). The distinction between M1 and M2 is necessary also because of the different
role played by these two types of layer in generating polytypes (Nespolo 2001). The
introduction of the notation M1 and M2 for the M layer follows directly from the letter
M which is previously used to indicate the TOT layer (e.g., Takuchi and Haga 1971),
before the existence of two types of layer was recognized. Because the roman font is
reserved for the layer, we adopt the italic font to indicate the octahedral sites, namely M1,
M2 and M3. For the ordinal label 1, 2 and 3 see the below Structural symmetry below.
Summarizing: roman font is used for planes (cf. Fig. 2 below), sheets (O octahedral, T
tetrahedral) and layers (M, TOT); italics font is used for structural sites (M octahedral, T
tetrahedral) and cations occupying them (Y octahedral, Z tetrahedral, I interlayer).

MODULARITY OF MICA STRUCTURE


Thanks to the pioneering paper on the biopyribole polysomatic series by Thompson
(1978), the structure of micas, together with those of amphiboles and pyroxenes, lead to
the development of the modern modular description of the crystal structures. According
to the modular crystallography principles (Merlino 1997), the same structural modules
(fragments) larger than single coordination polyhedra may occur in different structures.
The emphasis on modules is not only important in describing series, it is also useful in
describing aspects ranging from a single structure to classification, genesis, solid state
reactions (e.g., Baronnet 1997; Ferraris et al. 2000), structural modeling, and defect
structures (cf. chapter by Kogure, this volume).
Micas are layer silicates (phyllosilicates) whose structure is based either on a
brucite-like trioctahedral sheet [Mg(OH)2 which in micas becomes Mg3O4(OH)2] or a
gibbsite-like dioctahedral sheet [Al(OH)3 which in micas becomes Al2O4(OH)2]. This
module is sandwiched between a pair of oppositely oriented tetrahedral sheets. The latter
sheet consists of Si(Al)-tetrahedra which share three of their four oxygen apices to form a
two-dimensional hexagonal net (Fig. 1). In micas, the association of these two types of
sheet produces an M layer, which is often referred as the 2:1 or TOT layer.
As mentioned in the Introduction, the wide variety of micas (Rieder et al. 1998)
derives not only from chemical composition but also from structural features such as the
many (infinite, in principle) possibilities of stacking the M layer, particularly the special
type of polymorphism known as polytypism, discussed by Nespolo and Durovic (this
volume).
The mica module
The mica module, consisting of an M (TOT or 2:1) layer plus an interlayer cation, is
conveniently considered to be built by eight atomic planes in the following sequence,
starting from the bottom in Figure 2.
Obl Lower (l) plane of the basal (b) oxygen atoms (O) belonging to the tetrahedra;
these oxygen atoms also participate in the coordination of the interlayer cation I.
Zl Lower plane of the four-coordinated tetrahedral cations Z (these cations are
Structural Features of Micas 119

often indicated by T, but here this letter is used to indicate a tetrahedral site T and a
tetrahedral sheet T).
Oal Plane of the lower apical (a) oxygen atoms of the tetrahedra; these oxygen
atoms are shared between one tetrahedral and one octahedral sheet. The Oal plane
contains also hydroxyl (OH)- groups (and their substitutions) which belong only to
the octahedral sheet.
Y Plane of the octahedral cations Y which are often indicated by M (here this
letter is used to indicate an octahedral site M and the M layer; the symbol O is used
to indicate the sheet containing the M sites).
Oau Plane of the upper (u) apical oxygen atoms (Oa) of the tetrahedra (cf. Oal).
Zu Upper (u) plane of the tetrahedral cations (cf. Zl).
Obu Upper (u) plane of the basal (b) oxygen atoms (Ob) belonging to the tetrahedra
(cf. Obl).
I Plane of the interlayer cations I (interlayer sites).

Figure 1. Ideal trioctahedral brucite-like (a) and dioctahedral gibbsite-like (b) sheets. Two ideal
tetrahedral sheets (c) share their apical oxygen atoms with an octahedral sheet to form an M layer (d)
which is also known as 2:1 or TOT layer. Hydroxyl (OH)- groups are represented by black circles.

Planes are combined to form three types of sheets: Ob + Z + Oa form two tetrahedral
sheets (Tl and Tu); Oa + Y + Oa form one octahedral (O) sheet. The whole M mica layer
corresponds to the Tl-O-Tu (also termed 2:1) sequence; this layer is also called the
conventional mica layer and is often designated as the TOT layer. The interlayer cations
are located between two successive M layers in the I plane and their coordination is
discussed below. The separation between two I planes is about 10 .
120 Ferraris & Ivaldi
CLOSEST-PACKING ASPECTS
The apical oxygen atoms and the hydroxyl (OH)- groups forming the Oa plane (Fig.
2) are arranged according to a two-dimensional closest-packing of spheres; Oa is also
called the hydroxyl plane. In this plane, the packing is however not tight; in fact, the
spacing between the oxygen anions is about 3.1 compared to 2.6 in a typical closest-
packing of oxygen atoms (e.g., in olivine or spinel). Between two adjacent hydroxyl
planes (Oal and Oau), the octahedral and tetrahedral sites that are typical of a three-
dimensional closest-packing of spheres occur (Fig. 3). This type of tetrahedral sites is
vacant in micas; the octahedral sites M instead are fully (trioctahedral micas) or partially.

Figure 2. Cross-section perpendicular to the M layer of the mica structure seen along
[110]. Sequence and labeling of eight distinct building atomic planes are shown.
Hydroxyl (OH)- groups are represented by black circles (see text for explanation of
labeling).

Figure 3. Projection of a closest-packing AB sequence along the planes formed by apical


oxygen atoms Oa. Positions of the octahedral (M) and tetrahedral (small circles) sites are
shown. These tetrahedral sites are not occupied in the octahedral sheets of micas.
Structural Features of Micas 121

Figure 4. Stacking of two closest-packing planes of spheres (plane A dark gray, plane B
light gray) consisting of oxygen atoms and (OH)- groups. The primitive hexagonal cell
(A1 = A2) and the conventional C-centred orthohexagonal cell [(a, b) in the C1 orientation
according to Arnold (1996)] normally used for phyllosilicates are shown. Cells are
shown also for a closest-packing of equal spheres [smaller (ah, bh) cells]. Each n-th plane
of spheres (e.g. B) is a/3 staggered relative to the (n-1)-th plane (A). The interstitial sites
between the spheres appear either as open holes or as gray triangles. Each interstice is
surrounded by three packing spheres in its plane; between the two planes A and B
tetrahedral and octahedral sites occur (Fig. 3).

(dioctahedral micas) occupied by Y cations. Note (Fig. 4) that in the Oa plane each (OH)-
group is surrounded by six oxygen ions which, in turn, are surrounded by three (OH)-
groups, and three oxygen atoms.
The distances (2.7 ) between the anio ns within the basal Ob plane are closer to the
expected value for a closest-packing of oxygen ions (2.6 ). However, relative to real
closest-packing, the Ob plane shows vacancies. In fact, this plane can be formally derived
from a closest-packing of spheres by removing one third of the spheres which, otherwise, in
a (001) projection would occupy the center of the hexagonal rings (Fig. 1). The same
configuration of the Ob plane is obtained by removing the (OH)- groups in Figure 4. The Ob
plane shows ideal closest-packing without vacancies if the maximum value (30) of the
ditrigonal rotation occurs (cf. the paragraph Ditrigonal rotation and Fig. 8 below).

Closest-packing and polytypism


The pseudo-closest-packing feature of the Oa planes is key to the understanding of
widespread polytypism of micas (Bailey 1984a). A plane closest-packing of equal
spheres (Fig. 4) is based upon a plane hexagonal Bravais lattice with cell parameter ah
which is equal to the diameter of the packed sphere. In the plane, each sphere is in
contact with six translationally equivalent spheres and two translationally independent
sets of small vacant sites; each of these two sets (open circles and gray triangles in Fig.
4) contains three translationally equivalent vacant sites. To maintain a closest-packing
arrangement in three dimensions, the stacking of two successive planes of spheres (A and
B) implies that the upper plane (e.g., B) is staggered (shifted) in such a way that its
spheres overlie one set of vacant sites belonging to the lower plane (A). Owing to the
hexagonal symmetry in the plane, six equivalent staggers are possible along six directions
separated by 60 (cf. Ferraris 2002).
122 Ferraris & Ivaldi

The possibility of multiple staggering is the basis for different periodicities along c, a
structural aspect known as polytypism (Verma and Krishna 1966). In the case of micas
(and, generally, of phyllosilicates) there are two types of packing spheres: oxygen ions
and (OH)- groups. A larger, orthohexagonal C-centered cell (a,b) must be chosen, as
shown in Figure 4, and the typical closest-packing stagger between Oal and Oau
corresponds to an a/3 shift (intralayer stagger). Note that, in module, the parameter a in
micas corresponds to the parameter bh of the orthohexagonal cell in a standard closest-
packing plane of equal spheres. The a/3 stagger between Oal and Oau reflects in the
mutual postion of the Tl and Tu sheets as shown in Figure 5. Particularly in K-micas
(Radoslovich 1960) and in dioctahedral micas (Bailey 1975) the intralayer stagger may
slightly differ from a/3. This effect is related either to the size of the I cation or to the
distortion of the vacant M1 site, as defined below.

Figure 5. Reference axes in the M layer plane. Hydroxyl (OH)- groups are
represented by black circles. The OH groups are in trans position in M1
and in cis position in M2 and M3. The stagger (offset) a/3 between lower
and upper T sheets is shown. The T1u and T2u tetrahedra are
translationally independent; the same for the M1, M2 and M3 octahedra.

To build the crystal structures of the mica polytypes, the M layer is stacked along c
in steps of about 10 . Commonly, at least in the homo-octahedral (i.e., all octahedra are
equal in content and size; cf. below) approximation, the derivation of the mica polytypes
is achieved by considering rotations between adjacent M layers (Smith and Yoder 1956)
rather than stacking directions. These rotations are performed around the normal to the
layer and leave the layer unchanged if multiples are of 60. The insertion between two Ob
planes of interlayer cations I is possible only if each (ideally) hexagonal ring of the
atomic plane Obu, belonging to the nth layer, faces an (ideally) hexagonal ring of the
plane Obl belonging to the (n+1)th layer. Because this structural requirement can be
achieved by different relative rotations between two adjacent layers, different mica
polytypes are possible.
COMPOSITIONAL ASPECTS
Ideally, the crystal-chemical formula of micas can be written as I(Y3-xx)[Z4O10]A2
Structural Features of Micas 123

(Rieder et al. 1998). Labels represent the following chemical elements and groups [the
commonest elements and groups are shown in bold face and their ionic radii ()
according to Shannon (1976) are given in parentheses].
I = Cs, K (1.38), Na (1.02), NH4, Rb, Ba, Ca (1.00), .
Y = Li (0.76), Fe2+ (0.78), Fe3+ (0.645), Mg (0.72), Mn2+, Mn3+, Zn, Al (0.535), Cr, V,
Ti (0.605), Na (unpublished results on the occurrence of an analogue of tainiolite with
octahedral Na instead of Li). In the crystal-chemical formula, the coefficient 3-x
together with the symbol of vacancy () means that in principle the occupancy of the
octahedral sheet (O) can span from 2/3 (x = 1, dioctahedral micas) to all the available
sites (x = 0, trioctahedral micas). Actually, not many examples of intermediate di-
/trioctahedral micas are known. Some of the examples might leave doubts on their
intermediate nature because of unsatisfactory chemical (cf. below) and/or structural
data. A 2M2 lepidolite with (Li0.35Al0.100.55) in M1 (Takeda et al. 1971) and a Li-Be-
rich mica bityite with (Li0.550.45) in M1 (Lin and Guggenheim 1983) should be true
octahedrally intermediate micas. Cases as the M1-deficient Li-rich micas refined by
Brigatti et al. (2000), where the maximum vacancy in M1 is 0.23, look more like
octahedrally-deficient trioctahedral micas than intermediate di-/trioctahedral micas.
On chemical basis only, a Si-rich mica with slightly less than two Y cations has
recently been reported (Burchard 2000).
Z = Be, Al (0.39), B, Fe3+ (0.49), Si (0.26), Ti (?) (no vacancies have been reported).
A = Cl, F, OH, O, S (no vacancies have been reported).
It should be noted that:
1. The same site may be occupied (either in an ordered or a disordered way) by different
ions.
2. At least two elements (Al and Fe3+) may occupy both octahedral and tetrahedral sites;
as mentioned above, Na is reported also in octahedral coordination.
3. The same element (e.g., Fe) may be present in different oxidation states.
4. Most of the recent chemical data are obtained by electron microprobe analysis;
consequently, they are often incomplete because oxidation state, light elements and
water (hydrogen) are not analyzed [cf. Dyar (this volume) and Pavese et al. (2002) for
a recent case of synergic use of neutron-diffraction data and Mssabauer
spectroscopy].
Features 1-4 imply that the crystal-chemical formula of a mica cannot be established
on the basis of a chemical analysis only (even if it is complete); detailed structural knowl-
edge is necessary. Structurally, the occupancy of a site can be obtained by combining
chemical constraints (chemical analysis) with other information like the following.
Scattering power of a site (Sp ). If a site is fully occupied by two elements with
scattering power S1 and S2 and occupancy x and 1-x, respectively, the distribution of the
elements can be obtained by solving the equation Sp = xS1 + (1-x)S2. This procedure
cannot be applied without further information when (1) vacancy and/or more than two
elements occur in the same site; (2) the difference in the scattering power is small as,
with X-ray diffraction, in the common cases of substituting elements differing by only
one electron (Na-Mg, Mg-Al, Al-Si, Mn-Fe). If suitable wavelengths are available (e.g.,
synchrotron radiation) anomalous scattering may be used to recognize different atoms
that randomly occupy the same site. For case (2), neutron-diffraction data would
represent the best solution; but, for powder-diffraction data, cf. a discussion in Pavese et
al. (2000). Note that the occurrence of stacking faults in the structure may create peculiar
problem in the refinement procedure (Nespolo and Ferraris 2001).
124 Ferraris & Ivaldi

Distributions of the bond lengths . Good quality structural data allow the use of the
average bond length of a coordination polyhedron to determine quantitatively the fraction
of occupying atoms. In micas, a reasonable determination of the tetrahedral Si (xSi) and
Al (xAl) fractional contents as a function of the average tetrahedral bond lengths (Z-O)av
can be obtained by the equation (Z-O)av = 0.163[xAl /( xSi + xAl )] + 1.608 (Hazen and
Burnham 1973; cf. Brigatti and Guggenheim (this volume) for an equation which also
takes into account tetrahedral Fe).

SYMMETRY ASPECTS
Metric (lattice) symmetry
Because of the pseudo-closest-packing nature of the atomic planes mentioned above,
the two-dimensional Bravais lattice of both the T and the O sheets (Fig. 1), idealized and
undeformed according to the Pauling (1930) structural model of micas, is hexagonal
6mm. Both sheets can be described in terms of a primitive hexagonal lattice, defined by
two hexagonal axes A1 and A2, or of a C-centered orthohexagonal lattice defined by the
two shortest perpendicular translation vectors, a and b, between which the ortho-
hexagonal relation b = a3 ideally holds (Fig. 5; Nespolo et al. 1997a, 1998).
The two-dimensional lattice of the real sheets, as well as of the whole M layer they
form, is no longer hexagonal. The A1 and A2 axes are no longer exactly identical in length
and their interaxial angle is no longer exactly 120: they define a lattice that is only
pseudo-hexagonal and corresponds to a centered rectangular lattice whose a and b axes
only approximately obey the orthohexagonal relation b = a3.
Structural symmetry
The T sheet. In an ideal T sheet (Fig. 1), the tetrahedra are regular polyhedra and
their centers (Z cations) coincide with the nodes of a hexagonal plane lattice; the
corresponding point group symmetry is 6mm. The layer symmetry (-symmetry) of this
sheet is P(6)mm; the symmetry of the direction without periodicity, which is
perpendicular to the layer, is shown in parentheses according to the layer group notation
(Dornbenger-Schiff 1959). In each T sheet there are two translationally independent
tetrahedral sites (Fig. 5). On the whole there are four T sites in the M layer: T1u, T2u, T1l
and T2l (u = upper; l = lower). Following Bailey (1984), tetrahedral sites in the upper
sheet that, in the (001) projection, are at -1/3[010], +1/3[310] and 1/3[310] from the
upper OH group are labeled T1, whereas those at +1/3[010], -1/3[310] and +1/3[310] are
labeled T2. The same definition applies to the lower T sites with respect to the lower OH
group.
The O sheet . In the O sheet (Fig. 5) the number of translationally independent M
sites is three: one site (M1) has two (OH)- groups in trans configuration, whereas the
other two sites (M2 and M3) have two (OH)- groups in cis configuration. The definition
of M2 and M3 is however not straightforward. Bailey (1984c) suggested labeling M3 the
site on the left of the (pseudo)-mirror plane, but most authors have labeled that site as
M2. Here we retain the definition prevailing in the literature, calling M2 (M3) the site
with negative (positive) y coordinate in the layer-fixed reference, namely on the left
(right) of the (pseudo)mirror plane looking down the positive direction of the c axis.
Families of micas accordin g to the symmetry of the O sheet . The type of occupancy
(number of electrons in the site, if the exact cation composition of the site is unknown) of
the three M octahedral sites defines the three following families of micas as introduced by
OD theory (Dornberger-Schiff et al. 1982; Durovic 1994). The -symmetry of the O
sheet is different in the three families (Table 1): homo-octahedral family (the three M
sites have the same cation occupancy), meso-octahedral family (two M sites are identical,
Structural Features of Micas 125

one is different), and hetero-octahedral family (the three M sites are differently
occupied). The distinction in three families is based on structural features and reflects the
symmetry of the O sheet; it is operatively determined on the basis of the number of
electrons filling each of the three M sites, and it is used by the OD theory to fix
unequivocally the origin in the layer. Table 1 contains a comparison of the common
division of the mica families into tri- and dioctahedral classifications.

Table 1. Families of micas based on the symmetry of the octahedral sheet. Comparison
with dioctahedral and trioctahedral classification is given. (Modified after Durovic 1994).

Family -symmetyr Trioctaeh dral Dioctaeh dral


Homo-octahedral H`( 3 )1m ---

Meso- octaeh dral P`( 3 )1m

Heteor - octaeh dral P(3)12

= different electron occupancy of the M sites; = vacancy

Dioctahedral/tir octahedral distinction. As mentioned above, the O sheet of micas is


traditionally described with reference to the minerals brucite (brucite-like sheet or
trioctahedral sheet, namely homo-octahedral sheet) and gibbsite (gibbsite-like sheet or
dioctahedral sheet, namely meso-octahedral sheet). This description is helpful to
emphasize the modular nature of the mica layer; however, whereas the brucite-like sheet
corresponds to the highest symmetry (homo-octahedral), the gibbsite- sheet does not
correspond to the lower symmetry, being only meso-octahedral.
Symmetry of the O sheet . The plane point group symmetry of the ideal O sheet (Fig.
1) is 3m (a subgroup of 6mm) and its layer-symmetry is either H`( 3 )1m (brucite-like
sheet) or P( 3 )1m (gibbsite-like sheet). In fact, the symmetry of the two types of
octahedral sheets differs at least for the following reasons.
1. In the ideal brucite-like sheet (Fig. 1) all the octahedral sites are metrically
equivalent; each oxygen atom has coordination number three and the O-H bonds of
the hydroxyl (OH)- groups are perpendicular to the sheet.
2. In the ideal gibbsite-like sheet (Fig. 1) only 2/3 of the octahedral sites are occupied
by the same cation and the other 1/3 is vacant; each oxygen atom has coordination
number two and the O-H bond is parallel to the sheet and directed towards the
vacant site.
Symmetry of the M layer . Because Oal and Oau correspond to two successive planes
of a (pseudo)-closest-packing of spheres, Tl and Tu of an M layer are a/3 staggered (Fig.
5); consequently, both in the brucite-like and in the gibbsite-like case, the -symmetry of
the entire M layer is lowered to C12/m(1).
Symmetry and cation sites
Mainly because of a dimensional misfit between the T and O sheets (cf. below), in
real mica structures the Pauling model (in which there are no structural distortions) is too
abstract and must be replaced at least by a model which takes into account a rotation of
the tetrahedra within the (001) plane. This ditrigonal rotation is discussed below; the
resulting model has been called the trigonal model by Nespolo et al. (1999c).
126 Ferraris & Ivaldi

In the homo-octahedral family, the three M sites are by definition identical in content
and size. Any difference in one of the M sites violates the H centering, lowering the
symmetry of the O sheet to that of the meso-octahedral family. A difference between the
other two M sites destroys also the inversion center and lowers the symmetry of the O
sheet to that of the hetero-octahedral family. From the practical viewpoint, differences
among the M sites are often small and must be evaluated on statistical grounds. As
discussed by Bailey (1984c) for the specific case of micas [cf. an application in Amisano-
Canesi et al. (1994)], if l is taken as the estimated standard deviation (esd) of an
individual quantity and n = l/n1/2 is the esd of the mean of n values, the esd of a
difference () between two mean values is given by = 21/2n. Two quantities are
considered different at the 0.1% level of significance if > 3.1 (usually known as the
3 rule).
In both the Pauling and the trigonal models, the stagger of the two T sheets reduces
the symmetry of the M layer to monoclinic (Fig. 5). Within the highest layer-group
C12/m(1), M2 = M3 and only one symmetrically independent tetrahedral site exists (most
of 1M polytypes have this symmetry). Depending on the cation distribution and the
presence of structural distortions, the M layer may however have a lower -symmetry
corresponding to a subgroup of C12/m(1). In principle the following lower symmetries
can occur.
Layer group symmetry C1m(1). The m mirror plane coincides with the ac plane of the
layer, M2 = M3 and two symmetrically independent tetrahedral sites occur
according to the following scheme: T1u = T2u and T1l = T2l. No structures are
known with this symmetry.
Layer group symmetry C12(1). The two-fold axis is along the b axis of the layer and
the M2 and M3 sites are no longer equivalent. Two symmetrically independent
tetrahedral sites are present in each sheet, but the two T sheets of a layer are
symmetrically equivalent: T1u = T1l and T2u = T2l. This symmetry occurs in some
meso- and hetero-octahedral 1M polytypes and in the hetero-octahedral 3T
polytypes.
Layer group symmetry C 1 . The M2 and M3 sites are equivalent. There are two
symmetrically independent tetrahedral sites in the M layer according to the
following scheme: T1u = T2l and T2u = T1l. Most of the known 2M1 polytypes
show this symmetry.
Layer group symmetry C1. The three M sites and the four T sites are all symmetrically
independent. This symmetry occurs, e.g., in ephesite-2M1 (Slade et al. 1987).
In real structures, the -symmetry of the M layer with a given pattern of cation
ordering may be lower than the ideal one described by the trigonal model as a function of
the concrete stacking mode in a polytype: this phenomenon is known as
desymmetrization (Durovic 1979). A primitive P lattice for the layer occurs in the unique
example of anandite-2O (space group Pnmn; Giuseppetti and Tadini 1972, Filut et al.
1985). However, anandite-2O cannot be considered a real mica polytype (Ferraris et al.
2001c) for the following reasons: its P cell is not compatible with the C-centered cell
common to all mica polytypes; its space group is not that expected (Ccmm) for the 2O
mica polytype according to the OD theory; S substituting OH is coordinated by the
interlayer cation which thus has coordination number 13.
Summarizing, in an M layer:
1. The maximum of symmetrically independent M sites is three.
2. At least two symmetrically independent M sites are always present; in dioctahedral
micas an independent site is always represented by the vacant M1 site.
Structural Features of Micas 127

3. In real polytypes the maximum number of independent T sites is two.


4. If the lattice of the layer is P, the maximum number of independent T sites can reach
four, but the resulting structure is no longer strictly polytypic (cf. anandite-2O).
Table 2. -symmetry (S) and type of layer (L) in the three families of mica polytypes within the
Trigonal model. indicates the electron density of the octahedral site (site occupancy).
Origin
Family
S of S of in L
O sheet M layer O sheet
Homo-octahedral

(M1 = M2 = M3) H`( 3 )1m (M1) = (M2) = (M3) C12/m(1) --- M1


Meso-octahedral

M1 M2 = M3 P`( 3 )1m (M1) (M2) = (M3) C12/m(1) M1 M1

M1 = M2 M3 P`( 3 )1m (M1) = (M3) (M2) C12(1) M2 M2

M1 = M3 M2 P`( 3 )1m (M1) = (M2) (M3) C12(1) M3 M2


Hetero-octahedral

(M1 M2 M3) P(3)12 (M1) (M2), (M1) (M3) C12(1) M1 M1

P(3)12 (M2) < (M1), (M2) < (M3) C12(1) M2 M2

P(3)12 (M3) < (M1), (M3) < (M2) C12(1) M3 M2


Two kinds of mica layer: M1 and M2 layers
The -symmetry of the M layer depends on the number of identical M sites in the O
sheet. The origin of this sheet is fixed by the OD theory and taken at the site with the
point symmetry corresponding to the -symmetry of the sheet (Dornberger-Schiff et al.
1982). The complete scheme is given in Table 2 and is summarized as follows.
Homo-octaeh dral family . In this family any of the three M sites has 3 1m point group
symmetry.
Meso-octahedral family . In this family only one of the M sites has symmetry 3 1m: it is
the site with different occupancy/size. Depending on whether this site is M1 (trans)
or M2/M3 (cis), the layer itself is termed M1 or M2 respectively; the highest layer-
group for these two layers is C12/m(1) (M1) and C12(1) (M2). There is thus a basic
difference in the nature of these two types of layer.
Hetero-octaeh dral family . In this family, because of the chemical/size difference of the
three M sites, the highest layer-group is C12(1) for both kinds of layer and any of
the three M sites has point symmetry 312. In the hetero-octahedral family the origin
can in principle be chosen in any of the M sites. In the case of dioctahedral micas,
the origin of the O sheet is taken in the vacant octahedral site. By extending this
criterion, in the case of hetero-trioctahedral micas the origin of the O sheet is taken
as the site showing the lowest electron density (lowest X-ray scattering power;
Durovic et al. 1984), which often corresponds to the largest M site (in most cases
that site is M1). However, some examples are known (cf. Nespolo and Durovic, this
volume) in which the site containing the lowest electron density is either M2 or M3,
and the origin of the O sheet is thus in one of the two cis sites. Thus, as in the meso-
octahedral family, two kinds of layer, M1 and M2, are distinguished.
128 Ferraris & Ivaldi

Examples . Although the M1 layer is much more common, several examples of


micas constructed of M2 layers are known. So far, in dioctahedral micas constructed of
M2 only examples of 1M polytype have been reported; in them the vacancy is ordered
into one of the two cis sites (Zvyagin et al. 1985; Bloch et al. 1990; Zhukhlistov and
Zvyagin 1991; Zhukhlistov et al. 1996). On the contrary, trioctahedral micas constructed
of M2 layers are known for all the three most common polytypes (1M, 2M1 and 3T)
(Guggenheim and Bailey 1977; Brown 1978; Guggenheim 1981; Mizota et al. 1986;
Rieder et al. 1996; Brigatti et al. 2000). Both the M1 and the M2 layers can undergo the
mentioned desymmetrization (Durovic 1979); a corresponding reduction to a space
subgroup of the whole polytype may or may not occur. To distinguish the two kinds of
layer, the occupancy and the size of the three octahedral sites must be known as a result
of the refinement of the crystal structure. This knowledge is available only in a few cases
and most of the mica structural studies are just based on the assumption that the crystal
under investigation is built by M1 layers. For this assumption, Nespolo et al. (1999c),
following a suggestion by S. Durovic (pers. comm.), introduced the term homo-
octahedral approximation.
The interlayer configuration
In the Pauling model, the -symmetry of the interlayer is P(6/m)mm: the interlayer
cations have twelve nearest neighboring oxygen atoms at the corners of a hexagonal
prism, which is not modified by an n 60 rotation between adjacent layers. On the other
hand, in the trigonal model the ditrigonal rotation modifies the symmetry of the interlayer
depending on the parity of n in the n 60 rotation. This symmetry becomesP( 3 )1m for
even n and P`( 6 )2m for odd n. In both cases the I cations have six oxygen atoms as
nearest neighbors and other six oxygen atoms as next-nearest neighbors (Fig. 6).

Figure 6. The interlayer cation I (large circles) displays antiprismatic coordination and
prismatic coordination in the subfamily A and B polytypes, respectively. First and
second neighbor bonds are indicated by full and dashed lines respectively. For
maximum ditrigonal rotation (30), the first six neighbors form either a trigonal
antiprism (subfamily A) or a trigonal prism (subfamily B).

Subfamilies A and B of polytyep s . Even rotations between adjacent layers lead to a


trigonal (considering only the nearest neighbors oxygen atoms) or ditrigonal (considering
also the next-nearest neighbors oxygen atoms) antiprismatic coordination for the
interlayer cations I, whereas odd rotations lead to trigonal or ditrigonal prismatic
coordination. The antiprismatic coordination of the nearest neighbors is often quoted as
octahedral coordination and, as discussed below, is presumed to be a stabilizing factor
of the subfamily A polytypes, as are called those based on 2 n 60 rotations. Instead, the
subfamily B polytypes, which are based on (2n +1) 60 rotations, are rarer and are
Structural Features of Micas 129

considered less stable.


MDO polytypes . The subfamily A polytypes 1M (n = 0), 2M1 (n = 1 and 2), and
3T (n = 1 or 2) and the subfamily B polytypes 2O (n = 1), 2M2 (n = 0 and 2), and 6H
(n = 0 or 2; never found) are called homogeneous (Zvyagin 1988), MDO (Durovic et al.
1984), simple (Smith and Yoder 1956) or standard (Bailey 1980) polytypes. The ideal
space groups of the six MDO polytypes are: C2/m (1M), C2/c (2M1 and 2M2), P31,212
(3T), Ccmm (2O) and P61,522 (6H) (Fig. 7).

Figure 7. Crystal structures of the five known MDO (homogeneous) polytypes of mica: 1M (a), 2M1 (b),
2M2 (c), 3T (d), and 2O (e).

Possible ordering schemes in the MDO polytypes


The actual -symmetry (maximum symmetry) of the M layer in a polytype can be
any subgroup of C12/m(1) which is not lower than the -symmetry required (minimum
symmetry) to the M layer by the space-group of the structure. For the five known
MDO (homogeneous) polytypes the minimum symmetry is as follows.
Space groups C2/m and Ccmm. The minimum symmetry required by these two space
groups is C12/m(1). The O sheet contains the global twofold axis in both space
groups. One tetrahedral and two octahedral independent sites are allowed and no
ordering of the tetrahedral cations is possible. The 1M and 2O polytypes show this
symmetry.
130 Ferraris & Ivaldi

Space group C 2/c. The minimum symmetry required by this space group is C 1 ; the
global twofold axis passes through the interlayer cation. Two tetrahedral and two
octahedral independent sites are allowed; consequently, both tetrahedral and, for
trioctahedral micas, octahedral cation ordering are possible. The 2M1 and 2M2
polytypes show this symmetry.
Space group P 31,212. The minimum symmetry required by this space group is C12(1)
with the O sheet containing a set of global twofold axes; the interlayer cation lies on a
second set of global twofold axes. The 3T polytypes show this symmetry. Most of the
3T micas are dioctahedral and both tetrahedral (two independent T sites) and
octahedral (three independent M sites, including the vacant one) cation ordering is
possible.
Summarizing: among the five known MDO polytypes with ideal space-group,
tetrahedral ordering is not possible in 1M and 2O polytypes. Octahedral ordering is
instead possible in all five trioctahedral polytypes; for dioctahedral polytypes cf. phengite
below. Note that there are some hints of a limited occupancy of M1 in strictly
dioctahedral micas (Brigatti et al. 1998, 2001; Pavese et al. 2001).
The phengite case
The possibility of chemical order/disorder allowed by crystallographically
independent M and T sites is a feature influencing the polytype stability (Pavese et al.
1997, 1999a,b; 2000), together with the interlayer coordination and the T/O dimensional
mismatch as discussed later. The dioctahedral phengite micas are typical of high-pressure
environment (Sassi et al. 1994) and represent a good example for this type of discussion.
Owing to an optimum octahedral Mg/Al and tetrahedral Si/Al substitution, a good T/O
match with very small ditrigonal rotation (see below) is possible in both 2M1 and 3T
polytypes. Because this rotation increases with pressure P (cf. Zanazzi and Pavese's
chapter), a small starting value at room-condition allows to maintain a still reasonable
rotation at higher P. Whereas this feature is present also in trioctahedral micas, only
dioctahedral micas (and phengites in particular) show the following characteristics which
favor stability at high P (Ferraris et al. 1995; Ferraris and Ivaldi 1993, 1994a,b).
1. The O-H bond tends to be parallel to (001) and in the direction of the vacant M site
and does not hinder the compressibility of the interlayer. The O-H pointing towards
the interlayer cation is instead an obstacle to this compressibility in the trioctahedral
micas.
2. A higher structural flexibility In 3T following from the presence of more than one
crystallographically independent octahedral site.
3. A spiral disposition in 3T of the O-H directions across the three M layers of a cell
compared to the antiparallel disposition in the 2M1 polytype; consequently, a minor
interlayer repulsion can be expected in 3T.
In particular, the stability of 3T phengite at high P relative to the 2M1 polytype occurs by
3T phengite possessing the characteristics 2. and 3.

DISTORTIONS
The misfit
As already mentioned, in real mica structures the Pauling model is too abstract and
must be replaced at least by the trigonal model, which considers a rotation of the
tetrahedra around the perpendicular to (001). In fact, b being about 9.4, 8.6 and 9.3 in
brucite, gibbsite and T sheet (with Si:Al = 3:1), respectively, the dimensions of the T and
of the O sheets do not match. Consequently, as discussed below, some structural
distortions are needed to overcome the misfit and to form these two sheets into a layer.
Structural Features of Micas 131

Geometric parameters describing distortions


Practically, in all crystal structures, strictly regular coordination polyhedra occur
only if regularity is constrained by the symmetry, i.e., in micas, if the coordinated cation
occupies a crystallographic position with point symmetry 4 3m for a tetrahedron and
m 3 m for an octahedron. That does not happen because the tetrahedral and octahedral
sites occurring in micas, even in the ideal Pauling model, have maximum symmetry 1 and
2/m, respectively. Consequently, the polyhedra on which the M layer is comprised have
some degrees of freedom to differentiate their bond lengths and angles. This freedom is
exploited to compensate, at least in part, both internal strains, connected with the
chemical composition and the misfit between T and O sheets, and external strains, like
pressure and temperature variations. In dioctahedral micas, the vacant octahedron is by
far larger (M-O ~ 2.2 ) than the occupied ones ( M-O ~ 1.9 ) because of the
repulsion between the unshielded Oa apical oxygen atoms forming the vacant octahedron.
Because two types of quite different Oa-Oa octahedral edges occur in the O sheet of the
dioctahedral micas, two different types of Oa-Oa distances are necessary also in the T
sheet to fit with the O sheet. Larger distortions must therefore be expected in dioctahedral
micas than in trioctahedral micas.

Figure 8. From left to right, undistorted, moderately and fully distorted tetrahedral sheets are shown.
The distortion (ditrigonal rotation ) is obtained by rotation of the tetrahedra around the perpendicular to
the sheet. As shown, the angle 2 is defined by the directions of two tetrahedral edges sharing a corner.
In a fully distorted tetrahedral sheet, the basal oxygens form an ideal closest packing without vacancies.

Ditrigonal rotation
The trigonal model is the most important modification of the simple Paulings
model; it was introduced in 1949 by Belov, although a later paper by Radoslovich (1961)
is usually quoted. To match the T and O sheets into a TOT layer, structural distortions
must be introduced. The most important of these distortions is the ditrigonal (or in plane)
rotation, , of the tetrahedra around the perpendicular to (001) (Fig. 8). This distortion
was theoretically related to the misfit between T and O by several authors (cf. Bailey
1984c) and was first experimentally confirmed in the structure of clintonite (Takuchi
and Sadanaga 1959; these authors used the variety name xanthophyllite). The rotation
reaches its maximum value (30) when thehexagonal ring becomes a perfect ditrigonal
ring; in this case the Ob oxygen atoms form an ideal closest-packing. In both Pauling and
trigonal models, the tetrahedra have a triangular base exactly parallel to the (001) plane
and the Ob oxygen atoms form a flat (001) surface. The angle between the prolongation
of one edge of a triangular base and the corresponding edge of the triangular base sharing
the same oxygen atom corresponds to 2 (Fig. 8). Calling i the internal angles of the
basal hexagon, the angle 2 is obtained by the equation 2 = i = 1,6 (|120 i|)/6 (e.g.,
Weiss et al. 1992). The -symmetry of the tetrahedral sheet is reduced to trigonal by the
ditrigonal rotation [layer-group P( 3 )1m] but the entire M layer maintains the C12/m(1)
symmetry.
The physical limits for are 0 (the fit between T and O is perfect) and 30
132 Ferraris & Ivaldi

(maximum ditrigonalization). The effects of the two possible directions of the ditrigonal
rotation are as follows (Franzini 1969):
Type-A layer. The triangular bases of the tetrahedra are oriented in the opposite way
relative to the underlying, parallel triangular faces of the octahedral sheet (Fig. 9A).
Type-B layer. The triangular faces of the tetrahedral and octahedral sheets have the
same orientation (Fig. 9B).

Figure 9. Type-A and type-B mica layers according to Franzini (1969) seen down the positive
direction of the c axis. In type-A the triangular bases of the tetrahedra are oriented in the opposite way
relative to the underlying, parallel triangular faces of the octahedral sheet. In type-B the triangular
faces of the tetrahedral and octahedral sheets have the same orientation. The trans octahedra are
shadowed.

In the type-A layer, the oxygen atoms of the Ob plane approach the perpendiculars
passing through the octahedral cations because, according to Bailey (1984a), they are
attracted by these cations. Thus a shielding effect between the Y octahedral cations and
the I interlayer cations occurs. In the type-B layer the opposite situation arises and the
shielding effect is reduced with respect to the undistorted Paulings model. In both cases,
the b parameter of the distorted T sheet shortens with respect to that of an ideal T sheet
and the T/O match is improved. As noted by Zvyagin (1967), and shown by the
orientation of the triangles in Figure 9, the packing sequence of three apical sheets
Oal-Oau-Obl approaches cubic-closest-packing (ccp) in type-A and hexagonal-closest-
packing (hcp) in type-B. Contrary to Griffens (1992) statement that, although rarely, the
type-B has been observed in dioctahedral micas, we have found no cases of this layer in
micas. It occurs instead in other phyllosilicates, e.g., in 1:1 layer silicates such as lizardite
(Mellini 1982) and in cronstedtite (Hybler et al. 2000) [actually, in these silicates the
occurrence of unshielded octahedral cations is not a problem because there are no
isolated interlayer cations].
Other distortions
Because of the sheet dimensions, which are determined by the Y-O and Z-O
distances, the misfit between the T (b ~ 9.3 for tetrahedral occupancy Al:Si = 1:3) and
O sheets is minimum and maximum when the octahedral sheet corresponds to a brucite-
like (b ~ 9.4 ) or a gibbsite-like ( b ~ 8.6 ) layer, respectively. These two cases occur in
the pure end-members micas phlogopite (trioctahedral), KMg3[AlSi3O10](OH)2, and
muscovite (dioctahedral), KAl2[AlSi3O10](OH)2. Therefore, besides ditrigonal rotation,
the chemical composition can contribute to match the dimensions between the T and O
sheets. As seen in the paragraph C ompositional aspects, whereas in the T sites
practically only Al and Si (sometimes Fe3+) can occur, a larger variety of cations, with
octahedral ionic radii ranging from 0.535 (Al) to 0.76 (Li), can occur in the M sites.
An appropriate distribution of cations can therefore favor the fitting between T and O
sheets. The introduction of chemical substitutions at least in part contributes to various
types of polyhedral distortions. These, besides the discussed ditrigonal rotation, are
classified here below (Fig. 10). Some specific structural reasons for the appearance of
Structural Features of Micas 133

Figure 10. Definition of the octahedral flattening (), octahedral


thickness (t0), tetrahedral elongation (), tetrahedral tilting (z) and
octahedral counter-rotation () which is related to i as shown in the text.

these distortions are given here but more details can be found in Brigatti and Guggenheim
(this volume).
Tetrahedral elongation . This distortion is also known as tetrahedral thickening and
implies an expansion for the tetrahedra in the direction perpendicular to the T sheet
and a lateral compression (Radoslovich and Norrish 1962). The effect is measured
by the angle = i=1,3(Ob-T-Oa)i /3 (ideal = 109.47). It is particularly active in
dioctahedral micas where it is related to the presence of the vacant octahedral site
(Lee and Guggenheim 1981).
Tetar eh dral it lting . Practically, this distortion is only found in dioctahedral micas
because is caused by a great difference between the sizes of the octahedral sites.
The tetrahedra rotate around a direction parallel to the (001) plane determining a
departure from coplanarity of the Ob oxygen atoms (out-of-plane tilting). This
tilting produces a corrugation of the basal plane which is measured by the parameter
z = [zOb(max) zOb(min)]csin.
Octaeh dral flatet ning (or iht ckening) . This distortion is measured by the angle
between the body diagonal and the base of the octahedron (Donnay et al. 1964).
Given the thickness t0 of the O sheet and the average octahedral distance Y-O,
is calculated as = cos-1[t0/(2 Y-O)]. Because ideal = 54.73, a flattening
results in a larger value of ; vice versa for a thickening.
Counter-rotation . This distortion (Newnham 1961) is measured as the
angle of rotation between the two triangular octahedral faces parallel to (001)
belonging to the same octahedron; it is calculated by = |( 1 + 3 + 5)/3 - 60| =
|( 2 + 4 + 6)/3 60| (ideal = 60 and 0). The anglesi correspond to the O-Y-
O angles measured in the projection of the octahedron onto (001); in a regular
octahedron i = 60. Generally, for all micas this effect is related to the difference in
size of neighboring octahedra (Lin and Guggenheim 1983).
These distortions are not independent variables. In fact, besides specific aspects in part
mentioned above, all of them are to some extent correlated with chemical substitutions and
T/O misfit. Several correlations have been proposed, particularly for the ditrigonal rotation
(e.g., Lin and Guggenheim 1983; McCauley and Newnham 1971; Toraya 1981; Weiss et al.
1985).

Effects of the distortions on the stacking mode


All the distortions decrease in the order hetero-octahedral > meso-octahedral >
homo-octahedral, because of the corresponding reduction in the size difference of
134 Ferraris & Ivaldi

different octahedra. All octahedra in micas are more or less distorted (they should thus
more rigorously be termed trigonal antiprisms) and the distortions can be fully described
by the flattening and the counter-rotation (Weiss and Rieder 1997). It has been
shown (Weiss and Wiewira 1986; Weiss and Rieder 1997) that the ditrigonal rotation is
most effective in influencing the diffraction intensities, in particular 20l and 13l
reflections (i.e., the second ellipse in the OTED described in Appendix II); instead the
counter-rotation affects mainly the basal diffractions.

Figure 11. Adjacent basal Ob oxygen atoms in the case of 1M and 2O polytypes,
that show 0 and 180 rotations betweenadjacent M layers (left), and (right) of
2M1, 3T, 2M2 and 6H polytypes where instead the rotation between adjacent M
layers is 120 (2M1, 3T) or 60 (2M2 and 6H). The tetrahedral tilting z (Fig. 10)
is exaggerated.

z and stability of polytypes . The tetrahedral tilting z seems to have the most
marked influence on the relative stability of the 1M and 2M1 polytypes, the latter
becoming energetically favored when z increases (Appelo 1978 and 1979, Abbott and
Burnham 1988). A general influence of z 0 on the relative stability of different
polytypes can also be expected on geometric grounds by considering the interlayer
configuration (Fig. 11) for different values of the n 60 rotation between adjacent M
layers (Gven 1971, Soboleva 1987). For polyt ypes based on 0 or 180 rotations (the
MDO polytypes are1M and 2O), both the Ob planes delimiting the interlayer region have
negative z in correspondence of the I cation. For polytypes based on 120 (2M1 and
3T) or 60 (2M2 and 6H) rotations, the two Ob sheets delimiting the interlayer region
have opposite signs of z in correspondence of the I cation. In presence of a large z, the
polytypes based on 0 and 180 rotations offer too a large cavity for theI cation and, e.g.,
2M1 (but also 3T) is favored relative to 1M. At high z, (2n+1) 60 rotations become
favored and the relative stability of 2M2 and 2O seems then to depend on the ditrigonal
rotation of the tetrahedra (Bailey 1984c; Abbott and Burnham 1988).

Figure 12. Stacking of the M octahedral sites for


subfamily A and subfamily B polytypes. These sites
lie on the same perpendicular to (001) in subfamily
B but not in subfamily A polytypes.
Structural Features of Micas 135

Relatiev rotation of two adjacent M layers . This plays a role in stabilizing polytypes
also in connection with the relative positions of the M sites. In fact (Fig. 12), whereas for
a 2n 60 rotation (subfamily A) the octahedral sites in two adjacent M layers are
staggered by a/3 and thus not overlapped in the (001) projection, in the case of a (2n+1)
60 rotation (subfamily B) they are staggered b/3 and thus lie on the same
perpendicular to (001) [Soboleva 1987; cf. also the polytypic stacking discussed in terms
of configurations I and II of the octahedral cations in Bailey (1984a)]. Although a direct
influence of the relative positions of octahedral cations belonging to adjacent layers is
hardly conceivable, because of the large separation (~10 ), the stacking of octahedra
along the perpendicular becomes an indirect destabilizing factor through its effect on
tetrahedral tilting z. This would be clear in the case of a hypothetical 2O dioctahedral
mica, where the large and vacant octahedral sites would stack on the same perpendicular.
As a consequence, tetrahedra on the opposite sides of the I cations are tilted in the same
direction, increasing the repulsion between approaching Ob atoms. In the other two MDO
subfamily B dioctahedral polytypes (2M2 and 6H), the stacking along a perpendicular
alternates vacant and filled octahedral sites, reducing the Ob-Ob repulsion with respect to
the 2O polytype. Dioctahedral 2M2, although rare, has been found (Zhukhlistov et al.
1973), whereas neither 2O nor 6H have been discovered so far in dioctahedral micas. The
complete absence of the 6H polytype in any family of mica likely derives both from
energetic factors (e.g., odd rotations) and kinetic reasons (low probability of formation
and inheritance of a 6-layer period with hexagonal symmetry; Nespolo 2001).

FURTHER STRUCTURAL MODIFICATION


Pressure, temperature and chemical influence
Generally pressure (P) and temperature (T) have a major influence on the distortions
of coordination polyhedra (cf. Zanazzi and Pavese, this volume). The tetrahedral dimen-
sions are the ones least sensitive to P and T, whereas the compressibility and expansion
of the octahedra are large, so the fit between tetrahedral and octahedral sheets improves
with increasing T (larger O sheet) and worsen with increasing P (smaller O sheet).
Therefore, in a first approximation, P and T shows an opposite behavior (Hazen and
Finger 1982). The knowledge of the P-V-T equation of state would allow the calculation
of the isochor, i.e., the P-T path which maintains constant the cell volume (cf. Pavese et
al. 1999b) and, reasonably, also the distortions. For a rough estimate of the isochor, the
values of the expansion at constant P (isobar) and of the compression at constant T
(isotherm) can be combined (e.g., Comodi and Zanazzi 1995; Mellini and Zanazzi 1989).
The main effect of P and T are on the interlayer because the I-Ob bonds are weak.
Both the effect of modifying the length of the c parameter and the ditrigonal rotation are
discussed below. Note that any change in the T/O match because of P and T variations
modifies the ditrigonal rotation and consequently the interlayer coordination. Other
sources of change for the I-Ob distances are tetrahedral substitutions (which modify the
length l of the tetrahedral edge). Summarizing, for a given I, the parameter c modifies
mainly under the following factors:
1. temperature T (expansion longer c);
2. pressure P (compression shorter c);
3. ditrigonal rotation (I-Ob distances are modified).
Thickness of the mica module
As mentioned at the beginning of this chapter, a mica module is intended to consist of
an M layer plus the interlayer cation. The use of the module thickness tm = csin/n (n is the
number of M layers in a unit cell) allows the comparison of data from different polytypes.
136 Ferraris & Ivaldi

Figure 13. Decreasing trend of the


mica module thickness (top) and
ditrigonal rotation vs the increasing
content of Si in 2M1 (rhombi and
crosses) and 3T (open triangles and
circles) natural phengitic micas. To
obtain the knowledge of the crystal
structure is necessary. The values cor-
responding to samples with known
structure are indicated by rhombi (2M1)
and circles (3T). The values at 3.81Si
represent the only two synthetic phen-
gites which are included because their
crystal structures are known (Smyth et
al. 2000). R represents the correlation
coefficients of the shown regression
lines.

Sinking effect of the I cation . The smaller the ditrigonal rotation , the larger is the
more or less hexagonal cavity where the interlayer cation I can sink; consequently a
shorter c parameter is expected. This effect has been observed by several authors.
Guidotti et al. (2000) noted that a shorter c parameter is observed in the low pressure Fm-
rich muscovites [Fm = (Fe + Mg)/(Fe + Mg + Al)]. In fact, as expected from the values of
the cation ionic radii, the Fm substitution for Al in muscovites (and the parallel Si/Al
tetrahedral substitution) improves the T/O fit and, consequently, the ditrigonal rotation
decreases. assonne and Schreyer (1986, 1989) and, recently, Schmidt et al. (2001)
showed, in synthetic phengites, a contraction of the c parameter with the increase of the
Si content. Ivaldi et al. (2001a) have found the same result on natural samples (Fig. 13;
the thickness of the mica module tm instead of c is used). The ditrigonal rotation
behaves as tm. The decrease of the ditrigonal rotation with the increase of the Si content
is well explained by the improvement of the fit between the tetrahedral and octahedral
sheets promoted by the aluminoceladonitic substitution (Mg for VIAl and Si for IVAl). By
decreasing , more-hexagonal rings occur in the Ob plane where the interlayer cation can
sink.
Structural Features of Micas 137

Figure 14. A shift (exaggerated) of the basal


plane Ob from the full line to the dashed line
position reduces more (CD) the I-Ob(outer)
distances than (AB) the I-Ob(inner) ones.

Interlayer separation and coordination. Ferraris and Ivaldi (1994b) showed that a
variation of the interlayer separation influences the outer I-Ob distances more greatly than
the inner I-Ob distances. This geometric effect appears clear in Figure 14. Therefore, an
at first sight unexpected behavior occurs under variation of P and/or T: the I-Ob(inner)
distances, which represent shorter and thus stronger bonds, change by far more than the I-
Ob(outer) ones, which instead represent longer and thus weaker bonds.

Figure 15. Undistorted (a) hexagonal ring of a T sheet showing that all basal Ob
atoms have the same distance DA = l from the ring center D; D represents the
intersection of the drawing plane with the perpendicular to the ring. In a ring (b) with
maximum ditrigonal rotation , the inner Ob atoms are closer (DC = l/31/2) to D than
the outer Ob atoms (DB = 2l/31/2). The values of the internal ring angles are related to
as follows: BCB' = 120 + 2, CBC' = 120 - 2.

Ditrigonal rotation and interlayer coordination


In presence of the ditrigonal rotation, six Ob basal oxygen atoms are closer to (inner
Ob oxygens) and six are farther from (outer Ob oxygens) the interlayer cation I. By
increasing from its minimum value (0, absence of distortion) to its maximum value
(30), the distance d of the Ob oxygen atoms from the perpendicular to the layer
containing I, expressed as a function of the tetrahedral edge l, changes (Fig. 15) from d =
l to dinner = l/31/2 and douter = 2l/31/2. In other words, while the Ob(inner) atoms decrease their
undistorted distance from the perpendicular by (dinner d)/d = -42.3%, the Ob(outer) atoms
move very little and increase the same distance by (douter d)/d = 15.5%. Therefore, the
consequence of the ditrigonal rotation on the interlayer coordination is dramatic.
Precisely:
138 Ferraris & Ivaldi

Increase of the ditir gonal or at tion . An increase of (e.g., under compression) causes
the difference between I-Ob(outer) and I-Ob(inner) distances to become larger. Thus both
the trigonal antiprismatic (ideally octahedral) coordination (subfamily A polytypes
such as 1M, 2M1 and 3T ) and the trigonal prismatic coordination (subfamily B
polytypes such as 2O, 2M2 and 6H) become more dominant. As far as the
antiprismatic coordination is a stabilizing factor, the increase of the ditrigonal
rotation at high P should not weaken a structure.
Decrease of eht ditir gonal or at it on . A decrease of (e.g., under expansion) causes the
difference between I-Ob(outer) and I-Ob(inner) distances to become smaller: the interlayer
coordination approaches the hexagonal prismatic coordination for both polytype
subfamilies A and B. As far as the antiprismatic coordination is a stabilizing factor,
the decrease of the ditrigonal rotation at high T should weaken a structure.
Note that, under the combined causes which influence the I-Ob distances and
discussed above, overall decreases of the I-Ob(inner) has been reported in high-temperature
refinements of micas (Catti et al. 1989, Guggenheim et al. 1987; Ivaldi et al. 1998; Russel
and Guggenheim 1999; Takeda and Morosin 1975).
Effective coordination number (ECoN)
ECoN is a useful generalization of the classical definition of coordination number
(number of anions in contact with a cation); it considers the lengths of the bonds (Hoppe
1979). For a cation X establishing R(X)i bonds with equal anions, ECoN is defined as
[Nespolo et al. (1999a) on the basis of Hoppe et al. (1989)]:
ECoN(X) = iexp{1 [R(X)i /R(X)av]6}; (1)
R(X)av represents a weighted average bond distance for the coordination polyhedron
around the cation X and is defined as
Rav(X) =i R(X)iexp{1 [R(X)i /R(X)min]6}/iexp{1 [R(X)i /R(X)min]6} (2)
R(X)min being the shortest R(X)i distance (the exponent 6 is valid when the anion is O2-).
The sum over i is in principle extended to all the oxygen atoms; practically, however,
note that the contribution falls to zero as R(X)i exceeds R(X)av [Eqn. (1)] or R(X)min [Eqn.
(2)] by more than about 20%. ECoN defined by Equation (1) is a non-integer number
approaching the Pauling's coordination number (i.e., the number of first neighbor anions)
and equal to it for regular coordination polyhedra where R(X)i = R(X)av = R(X)min.
Recently the method has been extended to distorted and hetero-ligand polyhedra
(Nespolo et al. 2001).
A correlation between ECoN calculated for the interlayer cation I and the ditrigonal
rotation can intuitively be expected from the discussion of this section. Such
correlation has been investigated by Weiss et al. (1992) and found to be quite regular
(Fig. 16). In fact, ECoN for I smoothly decreases from about 12 (null ditrigonal rotation)
to 6 (for a ditrigonal rotation higher than about 16).

CONCLUSIONS
Even if the discussion is still open, the basic features of the mica structure
reasonably explain a wide range of the micas properties, from polytypism and twinning
(Nespolo et al. 1997b; Nespolo et al. 1999b; details in Nespolo and Durovic', this
volume) to chemical variability and stability in a range of geological conditions. The
matter of stability fields is of paramount interest in Earth sciences and concerns both the
occurrence of a polytype more than others and the capability for a mica of existing at
high P and/or T values. For a list of references to occurrences of associated polytypes of
Structural Features of Micas 139

Figure 16. Correlation be-


tween ECoN (effective coor-
dination number) of the inter-
layer cation I and the di-
trigonal rotation in micas.
[Modified after Weiss et al.
(1992)].

micas; cf. Ivaldi et al. (2001b) and Ferraris et al. (2001c).


The following basic structural features play a role in structure stabilization.
1. The type of interlayer coordination, which is connected with the parity n of rotation
(n 60) between adjacent M layers, justifies a wider occurrence of family A
polytypes (not limited to the MDO polytypes 1M, 2M1, 3T) which show even
rotations only. The amount of rotation between two adjacent M layers influences
the relative stability of polytypes independently of the parity n.
2. A phengitic composition favors stability at high P/T values because the
aluminoceladonitic substitution provides a good T/O fit and consequent small
ditrigonal rotation at high P/T also.
3. The argument of a small ditrigonal rotation cannot stand alone (cf. the
trioctahedral micas). It becomes effective as stabilizing factor at high P for
dioctahedral micas because other aspects concur as: (1) the O-H bond points
towards the vacant octahedral site and assumes a direction (almost) parallel to (001)
thus minimizing its interaction with the interlayer cation; (2) the presence both of a
pair of independent tetrahedral sites and of independent M2 and M3 octahedral sites
in the 3T polytype which, with phengitic composition, is the most stable form of
mica at high P/T.
4. In trioctahedral micas, the O-H bond is pushed away from the (001) Ob plane and
tends to lie along the perpendicular to this plane. Thus, some repulsive interaction
with the interlayer cation occurs that weaken the stability of the structure. However,
in oxidized (e.g., Ohta et al. 1982) or fluorinated micas (e.g., Takeda et al. 1971)
this repulsion is reduced proportionally to the O2- OH- or F- OH- substitution.
This is particularly evident in synthetic fluoro-micas (e.g., Takeda and Burnham
1969).
5. Geometric effects connected with the variation of the ditrigonal rotation and of the
interlayer separation are as important as energetic factors in determining the
variation of the interlayer bonds under compression, dilatation and effects in that
produce changes in the coordination (i.e., sinking effect) of the interlayer cation.
6. The presence of two types of M layer, M1 and M2, may play a role in the growth of
long period polytypes (Nespolo 2001).
140 Ferraris & Ivaldi
APPENDIX I:
MICA STRUCTURE AND POLYSOMATIC SERIES
Layer silicates as members of modular series?
The T and O sheets occurring in the mica structure are present in all layer silicates
(phyllosilicates); the entire M (TOT) mica layer is present in 2:1 layer silicates only. The
description of layer silicates is often given by emphasizing different stacking of T and O
sheets, even if an explicit discussion in terms of modular series is absent from the
literature.
Several types of modular series have been defined (Makovicky 1997):
Polysomatic (homologous accretional) series. The crystal structures of the members of
these series are based on the same modules. Biopyriboles are a well known example
(Thompson 1978).
Merotyip c series . Both common and peculiar modules are present in the crystal
structures of the members. The case of bafertisite-derivative structures, belonging to
the heterophyllosilicate group of titanosilicates, is described below.
Plesiotypic series. The crystal structures of the members of these series are based on
modules which have common features but may contain additional peculiar details.
The family of serpentine-like structures (lizardite, chrysotile, antigorite,
carlosturanite) is an example reported by Makovicky (1997). The members of this
plesiotypic series are based on variously curled, reversed and/or interrupted TO
(serpentine) layers.
From a topologic viewpoint, namely without considering the actual composition of
the M layer but only that of the interlayer, the following modules are necessary to obtain
all the structures of the 2:1 layer silicates:
1. three types of M layer: homo- meso- and hetero-octahedral layers;
2. interlayer modules of different chemical and structural nature ranging from single
cations (micas), to octahedral sheets (chlorites) and a mixture of layers and various
chemical groups (interstratified clay minerals).
The entire group of layer silicates could therefore be classified as a mero-plesiotypic
series in the sense that both structural details and nature of the building modules varies.
Mica modules in polysomatic series
The M mica module occurs not only in biopyriboles, chlorites and interstratified clay
minerals as mentioned above, but also in some other polysomatic series. Because these
series represent different possibilities for the presence of mica-like structures in minerals,
it seems useful to shortly describe some of them.
The heterophyllosicate polysomatic series
By analogy with phyllosilicates, a group of titanium silicates whose structures are
based on TOT-like layers have been called heterophyllosilicates (Ferraris et al. 1997). In
these structures, rows of Ti(Nb)-octahedra (hereafter, Ti-octahedra) are introduced in a T
sheet along the direction which is parallel to a pyroxene tetrahedral chain (Fig. 17). HOH
layers are thus obtained where H stands for hetero to indicate the presence of the Ti-
octahedra in a sheet corresponding to the T sheet of the layer silicates. Because the edges
of the Ti-octahedra and Si-tetrahedra have close lengths dimensions, the insertion of the
octahedra in a T sheet does not produce strain. As summarized by Ferraris (1997), three
types of HOH layers (Fig. 18) are known so far.
Bafertisite-like ( HOH)B layer . A bafertisite module B, I2Y4[Ti2(O)4Si4O14](O,OH)2,
is one-to-one intercalated with a one-chain-wide mica-like module
Structural Features of Micas 141

Figure 17. Different types of H sheets which are obtained by periodically


introducing Ti-octahedra (light gray) in a tetrahedral T sheet: bafertisite-like (B),
astrophyllite-like (A) and nafertisite-like (N) H sheets.

M,IY3[Si4O10](O,OH)2 (I and Y represent interlayer cations and octahedral cations,


respectively).
Astrophyllite-like ( HOH)A layer . With respect to the bafertisite-like layer, a second
one-chain-wide mica-like module M is present between two bafertisite-like
modules.
Nafertisite-like ( HOH)N layer. With respect to the bafertisite-like layer, a second and a
third one-chain-wide mica-like module M are present between two bafertisite-like
modules [or, a second M module is added to (HOH)A].
The series. Bafertisite (Guan et al. 1963, Pen and Shen 1963, Rastsvetaeva et al.
1991), astrophyllite (Woodrow 1967) and nafertisite (Ferraris et al. 1996) are members of
a polysomatic series BmMn which is based on B (bafertisite-like) and M (mica-like)
modules and has a general formula I2+nY4+3n[Ti2(O)4Si4+4nO14+10n](O,OH)2+2n. In the
formula, atoms belonging, even in part, to the H sheet are shown in square brackets; for n
= 0, I = Ba and Y = (Fe,Mn) the formula of bafertisite is obtained. The
heterophyllosilicates have also been described by using differently defined B and M
modules (Christiansen et al. 1999), a possibility which is not rare in modular
crystallography (Merlino 1997).
142 Ferraris & Ivaldi

Figure 18. Bafertisite-like (B),


astrophyllite-like (A) and naf-
ertisite-like (N) HOH layers.

Seidozerite derivatives . The bafertisite-like module (HOH)B is the building fragment


of several layer titanosilicates (seidozerite or bafertisite derivatives; Ferraris et al. 1997)
where only the interlayer content varies. These titanosilicates are B1M0 members of the
heterophyllosilicate series with a peculiar interlayer content. They are represented by the
formula XY4[Ti2(O)4Si4O14](O,OH)2, where X indicates the interlayer content which may
consist of H2O, tetrahedral anions and cations. All the seidozerite derivatives are based
on a common two-dimensional (sub)cell with a ~ 5.4 and b ~ 7 , whereas the value of
the stacking c parameter depends on the nature of X. The set of seidozerite derivatives
forms a merotype [or mero-plesiotype (Ferraris 2001d) series]. In the seidozerite
derivatives, (HOH)B represents the common building layer and the X inter-layer content
is variable.
The palysepiole polysomatic series
The palysepiole polysomatic series PpSs (Ferraris et al. 1998) includes minerals
whose structures contain one or both the types of TOT ribbons (modules) which are
present in palygorskite and sepiolite; these ribbons are reminiscent of the TOT modules
occurring in amphiboles (Fig. 19). The two modules are:
P = Ax(Y2+,Y3+,)5[Si8O20(OH)2]nH2O (palygorskite module; in palygorskite Y is
mainly Mg and n 8);
S = Ax(Y2+,Y3+,)8[Si12O30(OH)4]mH2O (sepiolite module; in sepiolite Y is
mainly Mg and m 12).
The structures of sepiolite and palygorskite are based on chess-board arranged [001]
TOT ribbons and intercalated channels. Each ribbon occurring in sepiolite, (TOT)S, is six
pyroxene-chain wide and 50% wider than that occurring in palygorskite, (TOT)P, which
in turn is four pyroxene-chain wide. A variable amount of alkali A cations and
water molecules occurs in the channels. The third known mineral of the group,
kalifersite, corresponds to the member P1S1 of the series and has formula
K5(Fe73+,2)[Si20O50(OH)6]12H2O. Its structure is based on an alternation, in the [010]
direction, of (TOT)S and (TOT)P ribbons. Each of two types of [001] channels, which
occur within the mixed palygorskite/sepiolite framework, is filled with a different strip of
alkali-octahedra (not shown in Fig. 19).
Structural Features of Micas 143

Figure 19. View along [001] of the crystal


structures of palygorskite (P), kalifersite (K) and
sepiolite (S). Kalifersite is based on a chess-
board arrangement of ribbons (TOT)S (sepiolite)
and (TOT)P (palygorskite). Cations and water
molecules occurring in the channels are not
shown.

Other modular structures


Guggenheim and Eggleton (1987, 1988) described some modular 2:1 layer silicates
in terms of fragments of the M (TOT) mica module, with or without interlayer cations.
The modularity of these silicates originates by the inversion of part of the tetrahedral
linkage. On the basis of the inversion fragments, the basic TOT layers may form either
islands (e.g., stilpnomelane and zussmanite) or strips (where the octahedral sheets
remains continuous as in ganophyllite and minnesotaite, or discontinuous as in the above
mentioned palysepioles).
Conclusions
TOT modules occur in different mineral structures and the following examples have
been discussed in this Appendix.
Infinite two-dimensional layers occur in micas, talc, pyrophyllite, chlorites and
interstratified clay minerals.
Slices of the mica (talc) structure cut perpendicularly to the layer are present in
amphiboles and palysepioles; they are inclined on the layer in
heterophyllosilicates, according to the description of Ferraris et al. (1996).
It seems reasonable to connect variety and frequency of occurrence with structural
stability. The wide range of conditions under which the TOT layer is stable on its own
occurs in talc and pyrophyllite, built up by this layer only. The TOT layers are even able
to survive through reactions generating other minerals [cf. Baronnet (1997) and Buseck
(1992) and references therein] including other micas (cf. Ferraris et al. 2001a).
Probably features other than crystal chemistry concur to explain the wide distribution
and persistence of variously sliced mica modules. The high symmetry of the mica
modules could be a key feature, in the sense that it favors different stacking and
connections with other modules both of the same kind and different nature. Mica
polytypes and twins are clear examples of symmetry-assisted structures. The flexibility of
144 Ferraris & Ivaldi

the T and O sheets and of the TOT layer as a whole has been widely discussed in this
chapter. This flexibility is usefully exploited to match mica modules with other modules,
a role which can be played also by closeness of polyhedral dimensions (cf. the
heterophyllosilicates case).

APPENDIX II:
OBLIQUE TEXTURE ELECTRON DIFFRACTION (OTED)
In addition to powder X-ray (Bailey 1988) and single-crystal X-ray diffraction
methods, electron diffraction is widely used to characterize micas. In particular, the
oblique-texture electron diffraction (OTED) method here described has been used to
obtain important results from micro grained samples of layer silicates (cf. references
below). A part some earlier sporadic papers, the OTED method was developed by
Vainshtein (1956, 1964), following Pinsker (1953), and further improved during
following years (Zvyagin 1967, Zvyagin et al. 1979, Vainshtein et al. 1992, Zvyagin et al.
1996). OTED has been used to obtain diffracted intensities for solving crystal structures
(cf. quoted papers and Zhukhlistov et al. 1997), spite of the dynamic effects affecting the
electron diffraction intensities. In the present context, however, we are interested in the
application of OTED for polytype identification and follow Zvyagin (1967). The method
is suitable for materials that show a very good cleavage where thin mounts can be
prepared so that the cleavage planes are more or less perfectly parallel to the plane of the
mount.

Figure 20. Cylindrical reciprocal lattice generated by rotation of


reciprocal lattice rows around c* (left) and its elliptical intersection with
the Ewald sphere (right) which, in the case of electron diffraction (only
small Bragg angles are possible), can be approximated by a plane. At
right, the effect of a non perfect planarity of the sample is shown by
substituting the circles of the left figure with tori; the intersection of a
torus with the Ewald sphere is an arc (Fig. 22). Modified after Zvyagin
(1967).

Let us suppose that the exploited cleavage is {001} and the cleavage lamellae are
textured in a planar mount so that their orientations have a common perpendicular to (001),
i.e., around c*. Under these conditions, each reciprocal row hkl (h and k are fixed) parallel to
c* describes a so called cylindrical reciprocal lattice (Fig. 20). The nodes with the same hk
indices are at a distance [(h/a)2 + (k/b)2]1/2 from c*. All the circles have their center on the
rotation axis but not at the corresponding 00l node, except when the lattice is orthogonal.
The projection of these circles on the ab plane is shown in Figure 21 together with the hk
Structural Features of Micas 145

Figure 21. Distribution in the ab plane of the hkl reflections on concentric circles
with radius [(h/a)2 + (k/b)2]1/2 in the case of a lattice with b = a31/2, as occurs in
layer silicates. Modified after Zvyagin (1967).

indices for the case of those layer silicates where the relations b = a3 holds. These circles
correspond to the orbits which are defined in Figure 16 in the chapter by Nespolo and
Durovic (this volume) in connection with the S, D and X classification of the rows (cf.
below). However, whereas the orbits are the loci containing S, D or X rows with their
individual nodes, in the cylindrical lattice one circle carries intensity contributed by all hkl
nodes falling on that circle.
Because of the small electron wavelength (10-2 ) and a substantial diffraction
intensity limited to quite small Bragg angles around the incident beam, the Ewald sphere
can locally be approximated by a plane. For a given inclination angle between the
incident beam and the plane of the mount, the intersection of the Ewald plane with the
cylindrical lattice results in a series of ellipses which represent the loci of the diffracting
nodes (Figs. 20, 22). The length of the minor axis bhk of each ellipse is independent of the
inclination angle and corresponds to the intersection of the ellipse with the ab plane;
the major axis ahk is given by bhk/cos. plane detector behind the sample, set at a
distance L from the sample and parallel to it, is parallel to the diffracting ellipses and
registers an undistorted image of the position of the diffracting nodes together with their
diffraction intensities. The scale factor between the reciprocal lattice ellipse and the
image ellipse is L, where is the electron wavelength. For each hk image ellipse, the
distance of a diffraction spot from the minor axis is
Dhkl = (L/sin)(ha*cos* + kb*cos* + lc*) = hp + ks + lq (3)
and the length of the minor axis is
146 Ferraris & Ivaldi

Figure 22. Theoretical OTED diffraction pattern [for a 1M mica polytype for which b =
a31/2] showing the spots (arcs) arranged on ellipses. According to its order, each ellipse
contains reflections with the type of indices shown in this Figure and in Table 3. The
spots are represented as arcs because in practice the lamellae of the sample can be
slightly inclined relative to the average plane of the sample (Fig. 20). The distance of
each spot from the trace O of the incident beam (origin of the lattice) corresponds to
d*(hkl); the case of d*(112) is shown in the figure. Modified after Zvyagin (1967).

bhk = L(h2/a2 + k2/b2)1/2. (4)


1/2
Because in the layer silicates b = a3 , Equation (4) becomes
bhk = L(3h2 + k2)1/2/b. (5)
Note that in the OTED method the overlap of reflections is limited to those
reflections with the same value of Dhkl (Eqn. 3) and belonging to the same ellipse; thus a
dramatic improvement is obtained relative to the classic powder diffraction methods.
Note also that, in the most general case, the reflections with l = 0 do not lie on the minor
axis because the a*b* and ab planes are not coincident. These two planes coincide in
orthogonal crystal systems where Equations (3) and (4) become, in the order,
Dhkl = (L/sin)lc* = lq (6)
and
bhk = L[h2(a*)2 + k2(b*)2]1/2. (7)
Some simplification is also obtained in the monoclinic case (* = 90) where
Dhkl = (L/sin)(ha*cos* + lc*) = hp + lq. (8)
Each ellipse is characterized by 3h2 + k2 = constant. Table 3 reports the absolute
values of hk which occur when b = a31/2. According to their h and k values, the rows
parallel to c* have been classified in the following way (Nespolo et al. 2000; cf. below
and Nespolo and Durovic, this volume, for details).
S or sw . These are the rows with h = 0(mod3) and k =0(mod3); they are family rows in
the Pauling model and are common to all polytypes of the same family.
Structural Features of Micas 147

Table 3. Absolute values allowed for the hk indices of the spots appearing, in an OTED pattern,
on the ellipses with the shown order.
Ellipse |h||k| 3h2 + k2 Type of Ellipse |h||k| 3h2 + k2 Type of
order ellipse order ellipse

1 02, 11 4 7 17, 35, 42 52


X X
2 13, 20 12 D 8 08, 44 64
X
3 04, 22 16 X 9 28, 37, 51 76 X
4 15, 24, 31 28 X 10 19, 46, 53 84 D
5 06, 33 36 S 11 0.10, 55 100 X
6 26, 40 48 D 12 39, 60 108 S

D or sw . These are the rows with h 0(mod3) and k = 0(mod3). They may identify the
general symmetry principle on which a polytype is comprised, distinguishing
subfamily A polytypes (for which D rows are family rows in the trigonal model),
subfamily B polytypes (for which D rows are again family rows in the trigonal
model ) and mixed-rotations polytypes (for which D rows are non-family rows in
both the Pauling and the trigonal model).
X or sw . These are the rows with h 0(mod3); they are non-family rows in both the
Pauling and trigonal model and are characteristic of each polytype.
Because of the condition 3h2 + k2 = constant, which constrains the values of h and k,
each ellipse of OTED bears only reflections corresponding to one type of row (S, D or
X). Consequently, the ellipses themselves can be usefully classified into S, D and X
ellipses (Table 3).
By using the equations shown above, indexing and cell parameters of the reflections
registered on an OTED pattern can be obtained. Whereas in two-dimensional X-ray
diffraction (XRD) studies (e.g., precession method), reciprocal central planes containing
two types of rows (SD planes and SX planes) are recorded, in OTED each ellipse
contains only one type of the S, D or X rows, as said above. Although the recording
technique is different, the general principle of polytype identification is the same. Both
techniques can identify polytypic and structural features upon inspection of specific rows
(XRD) or ellipses (OTED), at least in the homo-octahedral approximation. This
identification can be obtained not only for MDO polytypes of micas, but also for non
MDO (inhomogeneous) polytypes [cf. examples in Borutsky et al. (1987) and
Zhukhlistov et al. (1990, 1993)]. For polytypes with longer period (longer stacking
sequence), a simplified procedure to analyze the intensity distribution is necessary, but
the general principle of polytype (and twin) identification is the same, and consists in the
inspection of D and X rows.
The OTED patterns can be analyzed as follows in terms of S, D, and X rows (cf.
Nespolo and Durovic, this volume, for details).
Ellipses of 2+2n order . The D character of the rows belonging to the 2nd (as well as
6th, 10th) ellipse can discriminate among subfamily A polytypes, subfamily B
polytypes and mixed-rotation polytypes by observing the number N of reflections in
the c*1 repeat (about 0.1 -1): one reflection for subfamily A polytypes, two equally
spaced reflections for subfamily B polytypes, N > 2 reflections for mixed-rotation
148 Ferraris & Ivaldi

polytypes. When indexing the reflections in the unit cell of a polytype, they
correspond to the following presence criteria for the index l: 1M (no systematic
absences of l), 2M1 (l = 2n), 3T (l = 3n), 2M2 (no absences of l), 2O (no absences of
l), 6H (l = 3n), mixed-rotation (no absences of l).
X-type ellipses . The intensity distribution in the 1st ellipse (as well as other X-type
ellipses) is typical of each mica polytype. Knowing the symmetry principle
(subfamily A or B, or mixed-rotation, revealed by the 2nd ellipse) helps to obtain
the stacking sequence from the intensity distribution in the 1st ellipse. Because the
X rows are non-family rows in both the Pauling and trigonal model, the
computation of the intensities in the X-type ellipses, to be compared with those
experimentally measured, can be performed even in the simplest Pauling model.
Other ellipses . The intensity distribution on the 6th and 7th ellipses (and on the 2nd
ellipse in some cases) can distinguish between di- and trioctahedral phyllosilicates
(Zvyagin 1993). The ditrigonal rotation is most effective in influencing the
diffraction intensities of the 2nd ellipse (Weiss and Wiewira 1986; Weiss and
Rieder 1997).
Rieder and Weiss (1991) have extended the method to XRD. In this case, however,
because of the large curvature of the Ewald sphere (wavelength 1 ) the reflections are
no longer on ellipses and concentrated at low diffraction angles. Presumably, a
synchrotron source could provide sufficiently short wavelengths to make XRD closer to
OTED.
ACKNOWLEDGMENTS
Discussions with M. Nespolo (University of Nancy) greatly influenced this chapter.
Useful suggestions came from S. V. Soboleva (IGEM, Moscow). Constructive comments
have been provided by the referees, S. Guggenheim and M. Rieder. Research was
financially supported by MURST (Layer silicates: Crystal chemical, structural and
petrologic aspects project) and CNR (Igneous and metamorphic micas project).

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Zvyagin BB, Zhukhlistov AP, Plotnikov VP (1996) Advances in electron diffraction of minerals. In VI
Simonov Structural studies of minerals. Nauka, Moscow, 225-234 p (in Russian)
4 Crystallographic basis of Polytypism and Twinning in Micas
Massimo Nespolo
LCM3B, UMR, CNRS 7036
Universit Henri Poincar Nancy 1, BP 239
F54506 Vandoeuvre-les-Nancy cedex, France
nespolo@lcm3b.uhp-nancy.fr

Slavomil urovi
Slovak Academy of Sciences
Institute of Inorganic Chemistry; Department of Theoretical Chemistry
Dbravsk cesta, 9; SK-842 36 Bratislava, Slovakia
uachduro@savba.sk

INTRODUCTION
Although the investigation of micas dates back to the pre-scientific era (see Cipriani,
this volume), the idea of polytypism (originally not distinguished from polymorphism)
in the micas did not ensue until 1934, when Pauling proposed it in a private conversation
quoted by Hendricks and Jefferson (1939). The existence of several structural types was
however known from goniometric measurements and morphological analysis performed
in the 19th century (e.g., Marignac 1847; Baumhauer 1900) and collected in the 4th
volume of the Atlas der Krystallformen (Goldschmidt 1918; for a comparative review and
later measurements see Peacock and Ferguson 1943) and appears also in the different
axial settings introduced to describe the unit cell of micas (e.g., Brooke and Miller 1852;
Des Cloizeaux 1862; Koksharov 1875; Tschermak 1878).
The systematic investigation by X-ray diffraction (XRD) started with Mauguin (1927,
1928), who pointed out that the c axis of phlogopite was half that of muscovite. Pauling
(1930) was the first to solve the structure of a mica, a fuchsite (now termed chromian
muscovite, according to Rieder et al. 1998), by visual comparison of a subset of intensities
from photographs, and introduced the first model of the structure of phyllosilicates on the
basis of the coordination theory. Jackson and West (1931) were the first to perform a
complete structure determination, investigating a muscovite-2M1. Hendricks and Jefferson
(1939) investigated one hundred samples of micas and discovered several polymorphs,
many of which were however twins of simpler structural types (shorter-period polytypes).
The symmetry of the 2:1 mica layer was not fully recognized until Pabst (1955) showed
that the correct space-group type of 1M polytype was C2/m instead than Cm, as previously
assumed by Hendricks and Jefferson (1939) and reported also by Peacock and Ferguson
(1943). Since the accomplishment of such an apparently easy task as the determination of
the structure of the single-layer polytype took so long time and so much effort, it is not
surprising that the whole phenomenon of polytypism in micas occupied several researchers
from different countries for a long run of time, and still keeps undisclosed some of its most
interesting and challenging points.
Although the causes of the complexity of the phenomenon of polytypism in micas
are multifaceted, they can be simplified to magic words, local (partial) symmetry, and a
magic number, 3. As shown hereafter, each atomic plane in mica has an ideal
symmetry of at least trigonal, which is preserved in each of the two kinds of sheets
(tetrahedral and octahedral), but it is reduced to monoclinic when considering the layer as
1529-6466/02/0046-0004$15.00 DOI:10.2138/rmg.2002.46.04
156 Nespolo&urovi

a unit. The two T sheets of a layer are staggered along c and the amount of the stagger in
the (001) projection is ideally |a|/3. For each non-orthogonal polytype an ideally
orthogonal multiple cell can always be chosen, with 3-times the periodicity of the
polytype in the stacking direction. In the real structure, some of the atoms move slightly
from the positions corresponding to the ideal symmetry, but each atomic plane still
preserves a trigonal pseudo-symmetry. Then, the (001) projection of the layer stagger
deviates more or less from |a|/3, and the multiple cell is close to, but not exactly
orthogonal. The magic words and magic number can be traced also in reciprocal space,
where the reflections with k = 0(mod 3) reveal the symmetry principle on which a
polytype is built, and the reflections with k 0(mod 3) permit the identification of the
stacking sequence.
The existence of a multiple cell with a metric pseudo-symmetry higher than the
structural symmetry, together with the trigonal pseudo-symmetry of the planes of the basal
oxygen atoms, is also the geometrical reason of the extensive occurrence of twinning in
micas. Although polytypism and twinning can be reduced to relatively simple common
geometrical bases, the development of general criteria to recognize the presence of
twinning from the diffraction pattern took a long time, and still many questions remain
open.
The purpose of this chapter is to give a general overview of the factors, in terms of
lattice geometry and of symmetry, which are responsible for polytypism and twinning in
micas, and to provide general and simple criteria to be applied in the experimental
practice of polytype and twin identification. For this reason, micas are hereafter regarded
as built by layer archetypes, i.e. idealized layers where most of the structural distortions
are not taken into account. The true atomic structure of the mica layer influences mainly
the intensities but not the geometry of the diffraction pattern, and is discussed in detail in
Ferraris and Ivaldi (this volume) and in Brigatti and Guggenheim (this volume).
Rigorous mathematical demonstrations are not given here: readers wishing to
acquire a deeper knowledge are invited to consult the original publications, quoted
hereinafter, where those demonstrations are given in detail. The crystallographic
terminology follows Wondratschek (2002).

NOTATION AND DEFINITIONS


The geometrical description of mica polytypes is given in terms of the OD theory
developed by Dornberger-Schiff (e.g., 1964) and her successors. OD stands for Order-
Disorder and indicates that the stacking of layers may produce both periodic (ordered)
and non-periodic (disordered) structures. It has no relation with the chemical order-
disorder phenomena. The OD theory emphasizes particularly the role of polytypes which
involve pairs, triples, quadruples etc. of geometrically equivalent layers, or, when this is
not possible, the smallest number of kinds of triples, quadruples etc. of layers. These
polytypes are termed Maximum Degree of Order (MDO) polytypes. The layer-group
notation adopted here is the one developed by Dornberger-Schiff (1959), in which the
direction of missing periodicity is indicated by parentheses. For example, C12/m(1)
indicates a monoclinic holohedral C-centered layer, having (a,b) as the layer plane (for
details see Merlino 1990).
The indicative symbols for polytypes were introduced by Ramsdell (1947) and are
written as NSn, where N is the number of layers, S indicates the symmetry and n is a
sequence number, often (but not always) indicating the order in which polytypes have
been discovered. Ramsdells symbolism is actually a mixed symbolism, since S
(nowadays given with a single uppercase letter according to the IUCr Ad-Hoc committee
CrystallographicBasisofPolytypismandTwinninginMicas 157

recommendations: Guinier et al. 1984) is used to indicate the six crystal families, the
trigonal syngony (syngony = crystal system) and the rhombohedral Bravais system: A =
anorthic (triclinic), M = monoclinic, O = orthorhombic, Q = quadratic (tetragonal), T =
trigonal, R = rhombohedral, H = hexagonal, C = cubic. This mixed symbolism is
nowadays preserved for historical reasons and its use is accepted only for indicating
polytypes. Q, R and C cannot appear in micas (Takeda 1971).
To classify, but also to identify experimentally, mica polytypes, the relations
between a lattice and its derivative lattices (superlattices, sublattices) are of fundamental
importance. Different authors have given contrasting definitions. Here, we adopt the
definition in terms of the group-subgroup relations, in agreement with the International
Tables for Crystallography, Vol. A, 5th ed., in press (Th. Hahn, pers. comm..). Sublattice
is termed a derivative lattice obtained from an original lattice by taking a subgroup of
translations: its unit cell is larger than that of the original lattice. In contrast, superlattice
is termed a lattice obtained from an original lattice by taking a supergroup of translations:
its unit cell is smaller than that of the original lattice. Because the derivative lattice
obtained from the original one by taking a subgroup (supergroup) of translations has a
larger (smaller) unit cell, in some publications the terms superlattice and sublattice are
defined in the opposite way. The superlattice-sublattice character of a derivative lattice is
inverted when going from one space to its dual (i.e. from direct to reciprocal, or vice
versa).
The notations most often used in the following are summarized here for ease of
consultation:
The mica layer and its constituents
T: tetrahedral sheet = Ob-Z-Oa or Oa-Z-Ob
O: octahedral sheet = Oa-Y-Oa
I: plane of the interlayer cations (also: these cations as such).
Ob: plane of the basal oxygen atoms of the tetrahedra
Oa: plane of the apical oxygen atoms of the tetrahedra; this plane, contains
approximately also OH groups and, depending on the kind of mica, F and, less
frequently, Cl and S.
T1,T2: the two translationally independent tetrahedral sites within a T sheet
M1,M2,M3: the three translationally independent octahedral sites within an O sheet
Ma,Me,Mi: average cations occupying the three translationally independent octahedral
sites (Ma = Maximal; Me = Medium; Mi = Minimal, with reference to their
scattering power)
(Ma), (Me), (Mi): X-ray scattering power of the (average) cations Ma,Me,Mi
Z: plane of the tetrahedral cations
Y: plane of the octahedral cations (whose coordination polyhedra are however not
regular octahedra but rather trigonal antiprisms).
Tet: tetrahedral OD layer = Oau-Z-Ob-I-Ob-Z-Oal (l = lower, u = upper; see text)
Oc: octahedral OD layer = Oal-Y-Oau
p2j: OD packet pointing up = Tet2j/2 + Oc2j+1/2
q2j+1: OD packet pointing down = Oc2j+1/2 + Tet2j+2/2
M: the entire mica layer (T-O-T). There are two types: M1 and M2 depending on the
location (M1 vs. M2/M3) of the origin of the O sheet. Standard character M
indicates layer, italics M indicates cation sites.
158 Nespolo&urovi

Axial settings, indices and lattice parameters


a, b, c: monoclinic crystallographic axes in the space-fixed reference (in italics)
a1~6, b1~6, c: monoclinic crystallographic axes in the crystal-fixed reference (in italics)
A1, A2, A3, c: hexagonal crystallographic axes (in italics)
AF1, AF2, AF3, CF: hexagonal crystallographic axes of the family structure (in italics)
a, b, c / a1~6, b1~6, c / A1, A2, A3, c / AF1, AF2, AF3, CF: crystallographic basis vectors
(in bold)
C1, C2, C3: the three orthohexagonal cells (Fig. 1; cf. Arnold 2002)
cn : the (001) projection of the of the c basis vector
c0: vertical distance between two interlayer cations on the opposite sides of an M
layer (c0 = c1cos*)
c*1 : parameter along c* of the simplest polytype (1M): it corresponds to about 0.1-1
HK.L: diffraction indices expressed in hexagonal axes
hkl: diffraction indices expressed in orthohexagonal axes
lC1: l index in the C1 setting
lT: l index in the twin setting
: obliquity of the twin, divided into a component within the (001) plane (||) and a
component normal to the (001) plane ()
: angular deviation from orthohexagonality of the (001) plane
: linear deviation from orthohexagonality of the (001) plane
t(hkl): trace of the plane (hkl) onto the (001) plane
n
t(hkl): normal to t(hkl) in the (001) plane

Figure 1. Relation between the hexagonal


cell P and the three orthohexagonal cells C1,
C2, C3 (cf. Arnold 2002).

Symbols
N: number of layers in the conventional cell
N: number of layers in the unit cell of the (pseudo)-orthohexagonal setting: N = N
for orthogonal polytypes, N = 3N for non-orthogonal polytypes
Ti: character (0~5) indicating the mica OD packet orientation
CrystallographicBasisofPolytypismandTwinninginMicas 159

v2j,2j+1: character (0~5) indicating the displacement between two adjacent mica
OD packets p2j and q2j+1
v: the vector assigned to the character v
v: character (0~5, *, +, ) indicating vector sum of v2j,2j+1 over a
complete polytype period and corresponding to the projection of the c axis onto
the (001) plane
RSiP: i-th Rotational Sequence of the polytype P
Ri: i-th translationally independent reciprocal lattice row parallel to c* of the
single individual (1 i 9).
Ci: i-th composite row: translationally independent reciprocal lattice row parallel
to c* of the twin (1 i 9).
I j: symbol identifying the node features of a row of the reciprocal lattice parallel
to c*. I is the number of reflections in the c*1 repeat, j a sequence number.
Symmetry and symmetry operations
-symmetry: the symmetry proper of an individual layer (-operation: a symmetry
operation transforming a layer into itself; the set of -operations constitute
a layer-group)
-symmetry: the symmetry of a layer pair (-operation: a coincidence operation
transforming a layer into the adjacent one)
-operations: symmetry or coincidence operations which do not change the sign of the
coordinate in the layer stacking direction. They are labeled - or - if
they refer to - or -operations, respectively
-operations: symmetry or coincidence operations which change the sign of the
coordinate in the layer stacking direction and thus turn a layer or a stack of
layers upside down. They are labeled - or - if they refer to - or -
operations, respectively. Evidently, . = , . = , . = and . = .

THE UNIT LAYERS OF MICA


The conventional layer of mica is described in details in Ferraris and Ivaldi (this
volume). Here we recall only those definitions that are referred to in the following.
The conventional layer (also termed TOT layer or 2:1 layer) is constructed of seven
atomic planes: Obl, Zl, Oal, Y, Oau, Zu, Obu, where l and u stand for lower and
upper respectively. Interlayer cations occurr between two successive layers in the I
plane. This layer is referred as the M layer and is subdivided into two kinds of sheets: T
(Tl: Obl, Zl, Oal, and Tu: Oau, Zu, Obu) , and O (Oal, Y, Oau). On the basis of the occupation
of the three octahedral sites, three families of micas exist: homo-octahedral (all three sites
are occupied by one type of cation), meso-octahedral (one site is occupied differently
from the other two), and hetero-octahedral (all three sites are occupied differently). In
these three families the idealized -symmetry of the O sheet is H(3)1m, P(3)1m, and
P312 respectively (Dornberger-Schiff et al. 1982). Two models were introduced to
describe the -symmetry of the T sheet: the Pauling model (Pauling 1930), which
neglects all the distortions and assumes -symmetry P(6)mm; and the Trigonal model,
which considers only the ditrigonal rotation of tetrahedra and assumes -symmetry
P(3)1m. Both these models neglect the distortions occurring in the O sheet. Although the
Trigonal model may seem still rather abstract, it is sufficient to describe the diffraction
features useful for polytype and twin identification, whereas the Pauling model is too
abstract. In fact, the main influence on the conditions for a reflection comes from the
ditrigonal rotation of the tetrahedra. The other distortions, not taken into account by the
Trigonal model, are quantitatively less relevant; they influence mainly the diffraction
160 Nespolo&urovi

intensities, and to a much lesser degree the geometry of the diffraction pattern; for this
reason they can be neglected, in the first approximation.
The stagger of the two T sheets reduces the -symmetry of the M layer to
monoclinic. Depending on whether the origin of the O sheet (which must be taken at the
site with the point symmetry corresponding to the -symmetry of the sheet) is in M1
(trans) or in M2/M3 (cis), the layer itself is termed M1 or M2 respectively, and the
highest -symmetry for these two layers is C12/m(1) and C12(1) respectively (for details
see Ferraris and Ivaldi, this volume). The preliminary stage of the experimental study of a
mica sample, such as the identification of the polytypic stacking sequence, is normally
performed by assuming that the structure is homo-octahedral, and thus in the hypothesis
of all M1 layers. For this assumption Nespolo et al (1999d), following a suggestion by S.
urovi (pers. comm.), introduced the term homo-octahedral approximation.
Alternative unit layers
Besides the M layer, other unit layers were introduced, in most cases to simplify the
description of some features, such as the diffraction pattern.
Amelincks-Dekeysers unit layer . Amelinckx and Dekeyser (1953) pioneered the
study of the spiral growth of micas. They also introduced the first vectorial and symbolic
representation of the stacking sequence of layers in mica polytypes. These authors used a
unit cell having the apical oxygen atoms and (OH/F) groups at the boundaries (Fig. 2). In
this way, the unit cell is orthogonal and the monoclinic symmetry is achieved by stacking
successive cells along three directions making 120. Although this cell has nowadays no
practical importance, it represents the first description alternative to Paulings (1930)
model and the precursor of the TS unit layers described below.
Franzini and Schiaffinos A and B layers . Franzini and Schiaffino (1963a,b)
assumed that the ditrigonal rotation of the tetrahedra was mainly not related to the misfit
of the a and b parameters of the tetrahedral and octahedral sheets, but to an intrinsic
tendency of the potassium to assume an octahedral (actually antiprismatic) coordination.
Those authors concluded that, with a single type of layer, rotations of (2n+1)60 were
not possible for K-micas. To explain polymorphs and twins in which such rotations
appear, Franzini and Schiaffino (1963a) introduced two kinds of monolayers, called A
and B, in which the antiprismatic coordination for the interlayer cation is preserved for all
the six rotations. These two layers differ for the orientation of the octahedral sheet with
respect to the tetrahedral sheets: in practice, the slant of the octahedra is reversed in the
two layers1. The ordered repetition of layers of the same kind (both A or both B)
produces 1M, 2M1 and 3T polymorphs, while the alternate repetition of both A and B
layers produces 2O, 2M2 and 6H polymorphs, however preserving the antiprismatic
coordination for the interlayer cation. The co-existence of A and B layers was however
regarded as highly improbable (Franzini 1966; 1969). The starting assumption of this
theory, namely the impossibility of trigonal prismatic coordination for the interlayer
cation, is not correct (Sartori et al. 1973), and the Franzini and Schiaffino theory lost its
importance.
Despite that, the terms Franzini-type A and B have found their way into the
literature. As Franzini (1969) noted, owing to ditrigonalization, the basal-oxygen atoms
in the type A approach the cations in the adjacent octahedral sheet, whereas they move

1 Griffen (1992) described the direction of the ditrigonalization of the T sheets with respect to the
triangular bases of the octahedra in terms of the rotations O (opposite, corresponding to Franzini-type A
of layer) and S (same, corresponding to Franzini-type B of layer). This terminology, borrowed from
pyroxenes, is commonly not adopted for micas.
CrystallographicBasisofPolytypismandTwinninginMicas 161

Figure 2. Schematic representation of a slab b/4 thick, showing three layers of the 1M
polytype. Four different unit cells are shown: the M layer (solid lines), the U layer
(dashed lines), the TS D layer (dotted lines) and the cell used by Amelinckx and
Dekeyser (1953) (dotted-dashed lines). The OD layers and packets are indicated
directly in the figure.

apart in type B layers, if compared with the Pauling model. This holds also for
phyllosilicates other than micas. Whereas in mica structures refined to date only the type
A has been found, the type B has been encountered in some 1:1 phyllosilicates and in
some chlorites, where the energetic handicap of the type B is balanced by a more
favorable arrangement of hydrogen bonds elsewhere in the structure.
The U layer. The origin of the entire M layer is in the I plane. By shifting the origin
into the O sheet, the U-layer (Fig. 2) is obtained and, inside it, a smaller portion, called
the u-layer, which does not represent a unit layer but consists of two tetrahedral sheets
and the interlayer cations between. These layers were used as a tentative interpretation of
the crystallographic transformation of biotites by means either of crystallographic slips
(CS) of cation or oxygen planes corresponding to cation-to-cation or oxygen-to-coplane-
oxygen distance (CS of the first sort) or of co-operative slip movements of two atomic
planes (oxygen-oxygen or oxygen-cation) in a single octahedral sheet (CS of the second
162 Nespolo&urovi

sort) (Takuchi 1971; Takuchi and Haga 1971). A CS of the first sort probably occurs
during polytype formation when a strengthening of the interlayer bonding is accompanied
by a destabilization of the O sheet (Nespolo 2001).
The TS layers. Similarly to the choice of Amelinckx and Dekeyser (1953), Sadanaga
and Takeda (1969) and Takeda and Sadanaga (1969) described the structure of micas by
means of orthogonal unit layers. Whereas Amelinckx and Dekeyser (1953) had chosen
the origin in the Oa / OH / F plane, Sadanaga and Takeda (1969) and Takeda and
Sadanaga (1969) defined their TS unit layers between two octahedral sheets of successive
M layers and preserved the origin in the plane of the I cations (Fig. 2). TS unit layers are
defined within the Trigonal model and consist of four layers, labeled D, D*, T and T*,
with -symmetry P (3)1m (D and D*) and P(6)2m (T and T*). D is related to D* and T
to T* by an 180 rotation about c* (see Fig. 2,3). Because of their trigonal -symmetry,
which is higher than the monoclinic -symmetry of the M layer, four kinds of unit layers
are necessary to describe all possible polytypes. These layers are related by only
translations, without rotations, and next layers are staggered a/3 along one of the three
hexagonal axes A1, A2, A3 in the plane of the layer. As shown by Nespolo et al (1999d),
the TS unit layers represent the most suitable geometrical description for a simple
computation of the PID function (see below). The letters D and T indicate a ditrigonal
or trigonal coordination of the I cation respectively for the two kinds of layer. Actually,
D/D* layers have the I cation in antiprismatic coordination, whereas in the T/T* layers
the I cation is in prismatic coordination. In both cases, the coordination polyhedron is
trigonal where only the nearest-neighbor oxygen atoms are considered, whereas it
becomes ditrigonal by considering also the next-nearest-neighbor oxygen atoms. A
symbolism like A/A* (for antiprismatic) and P/P* (for prismatic) instead of D/D*
and T/T* respectively would perhaps had been more appropriate. The TS layers are
constructed by half-pairs of M1 layers in the homo-octahedral approximation and, as
shown hereafter, their use is in the calculation of the Periodic Intensity Distribution
function to solve an unknown stacking sequence.
The OD layers and the OD ap ckets . The OD interpretation presupposes that any
polytype of a given polytypic substance may be considered as consisting of disjunct parts
periodic in two dimensions, called OD layers, whose pairs remain geometrically
equivalent in any polytype of the same family. The OD layers do not necessarily coincide
with the layers commonly chosen on the basis of the chemical identity and/or cleavage
properties. In other words, the layers by which a polytypic substance is most commonly
described from the crystal-chemical point of view are not always the most suitable layers
to describe the geometrical equivalence of layer pairs. Furthermore, the choice of the OD
layers in general is not absolute (Grell 1984); their purpose is not to explain but to
describe and/or predict polytypism of a substance based on symmetry.
Micas are considered to consist of two kinds of OD layers. The octahedral OD layer
(Oc) corresponds to the sequence Oal-Y-Oau, and the tetrahedral OD layer (Tet) to the
sequence Oau-Z-Ob-I-Ob-Z-Oal, with the Oal and the Oau planes (au = apical upper; al =
apical lower) half belonging to neighboring OD layers (Fig. 2). By denoting an OD layer
with the general letter L, Tet and Oc OD layers are L2j and L2j+1 respectively, where j is a
running integer. Another useful unit is the OD packet, which corresponds to half of the M
layer plus half the plane of the I cations, and constitutes the smallest continuous part,
periodic in two dimensions, representing fully the chemical composition of a polytype
(urovi 1974). OD packets are by definition polar and lie within one side or the other
pointing alternatively along +c and c: they are indicated with the letters p and q: p2j =
Tet2j/2 + Oc2j+1/2; q2j+1 = Oc2j+1/2 + Tet2j+2/2 (Fig. 2). All mica packets within the same
family are geometrically equivalent and their symmetry is P(3)1m (homo-octahedral
CrystallographicBasisofPolytypismandTwinninginMicas 163

Figure 3. The four TS unit layers. a, b: orthohexagonal axes. Black and open small circles
represent M1 and M2 sites respectively. Double circles represent interlayer cations and
OH/F groups, which are overlapped in the (001) projection. u and l indicate octahedral
cations with z = +1/2 and z = -1/2 respectively, overlapped in (001) projection for T and T*
layers (modified after Nespolo et al. 1999d).

family), C1m(1) (meso-octahedral family) or C1 (hetero-octahedral family) (Dornberger-


Schiff et al. 1982; Backhaus and urovi 1984; urovi, et al. 1984). This reduces the
problem of handling two kinds of OD layers to that of one kind of OD packet and this
facilitates, among others, also the systematic derivation of MDO polytypes (see below).
164 Nespolo&urovi

Furthermore, both M1 and M2 mica layers within the same family consist of the same
kind of OD packet.

MICA POLYTYPES AND THEIR CHARACTERIZATION


The crystal chemical reason for polytypism is that adjacent layers (two-
dimensionally-periodic units) can be linked to each other in many translationally non-
equivalent ways. However, the nearest-neighbor relationships remain preserved.
Translated into the language of symmetry, this means that the pairs of adjacent layers
remain geometrically equivalent in all polytypes of the same family.
The geometrical equivalence must be fulfilled not necessarily by the real layers, but
by their archetypes, i.e. the (partially) idealized layers to which the real layers can be
reduced by neglecting some distortions occurring in the true structure. The notion of
polytypism becomes thus unequivocal only when it is used in an abstract sense to
indicate a structural type with specific geometrical properties. In micas, these archetypes
are the layers described by the Trigonal model. Of the several kinds of layers presented in
the previous section, the OD layers, and the OD packets, are the most suitable ones to
both show and exploit the geometrical equivalence.
Micas as OD structures
If the position of a layer is uniquely defined by the position of the adjacent layers
and by the so-called vicinity condition (VC)2, which states the geometrical equivalence of
layer pairs, the resulting structure is fully ordered. If, on the other hand, more than one
position is possible that obeys the VC, the resulting structure is an OD structure and the
layers are OD layers. VC structures may thus be either fully ordered structures or OD
structures (Dornberger-Schiff 1964, 1966, 1979; see also urovi 1999). All OD
structures are polytypic; the reverse may or may not be true (see the arguments in
Zvyagin 1993). Equivalency depends on the choice of OD layers and also on the
definition of polytypism (see below).
In each of the three mica families, the packet pairs p2jq2j+1 and q2j+1p2j+2 are
geometrically equivalent through a -operation of the Oc2j+1 OD layer and of the Tet2j+2
OD layer, respectively. These operations are denoted as 2j,2j+1[(i)] and
(j)
2j+1,2j+2[ ] respectively .The resulting polytype depends on the kind of these operations
(they follow from the -symmetry of Oc or Tet) and on their sequence in the polytype.
Since . = and, particularly for OD structures, a product like kl[(i)]mn[(j)]is allowed
only if l=m, each even number of such products, e.g.,
(1)
01[ ]12[ (2)] 23[ (3) ] 34[ (4) ] . 2n-1,2n [ (2n)]
yields a 0,2n[]-operation. This operation can be either a translation, a glide operation or a
screw rotation, whose translation component is the so-called repeat unit. The -operation
can be continued, i.e. continuously repeated, and then it generates a periodic polytype.
The operation is thus global (total) for the polytype obtained. Of special importance are
the 02[]-operations which play a decisive role in the derivation of MDO polytypes, as
shown below. If the distribution of subsequent operations is completely random so that
no generating -operation can be found, the polytype is disordered. Disordered polytypes
have been reported as 2n60 rotations only (e.g., Ross et al. 1966; let us indicate them as
1Md-A, where A stands for subfamily A) and with both 2n60 and (2n+1)60
rotations (Kogure and Nespolo 1999a; let us indicate them as 1Md-M, where M stands

2 The vicinity condition (e.g., Dornberger-Schiff 1979) consists of three parts. VC : VC layers are
either geometrically equivalent or, if not, they are relatively few in kind; VC : translation groups of all VC
layers are either identical or they have a common subgroup; VC : equivalent sides of equivalent layers are
faced by equivalent sides of adjacent layers so that the resulting pairs are equivalent.
CrystallographicBasisofPolytypismandTwinninginMicas 165

for mixed-rotation), whereas no examples with (2n+1)60 rotations only (let us


indicate them as 1Md-B, where B stands for subfamily B) have been reported to date.
Note that in periodic polytypes some -operations also become global, whereas the
remaining ones are valid only in a subspace of the crystal space. Note also that, alone, a
-operation could not be used to construct a polytype, because its repeated application
leads back to the area of the starting layer or packet. For more details concerning the OD
interpretation of mica structures, see Dornberger-Schiff et al (1982); for the derivation of
MDO mica polytypes see Backhaus and urovi (1984); for the classification and
abundance of MDO mica polytypes see urovi et al (1984).
The set of all the operations valid in the whole crystal space and in a subspace of the
crystal space constitutes a space groupoid (Dornberger-Schiff 1964; Fichtner 1965, 1977,
1980). The theory of groupoids was introduced in mathematics by Brandt (1927) and
applied in crystallography in Germany by the OD school (Dornberger-Schiff 1964, 1966),
and in Japan by the school of Ito and Sadanaga, with special emphasis on those groupoids,
termed twinned space groups, which are necessary to explain the existence of polysynthetic
structures (e.g., Ito 1935, 1938, 1950; Ito and Sadanaga 1976; Sadanaga 1978; Sadanaga et
al. 1980). The OD school used the terms total for a space-group operation, local or partial
(as synonyms) for a symmetry operation valid in a subspace of the crystal space, and
coincidence operation, represented by a single transformation matrix, for a non-symmetry
operation that corresponds approximately to a one-way movement in the structure, i.e.
an operation without the corresponding inverse operation. Sadanaga and Ohsumi (1979)
and Sadanaga et al (1980) used instead global, local and partial in the same way the OD
school used total, local/partial and coincidence respectively. To avoid any possible
confusion, hereafter the word partial is not adopted, and the term local is used to
indicate a symmetry operation valid in a subspace of the crystal space.
Within the Pauling model, an isolated Tet layer has -symmetry P(6/m)mm, with 12
-operations and 12 -operations. Within a group, the three axial and the three inter-axial
directions are symmetry-related and thus one entry for each of these two sets in the
conventional Hermann-Mauguin symbol suffices to characterize the corresponding
symmetry operations. However, in the OD structures, any of these operations can play a
specific role and this is why Dornberger-Schiff (1964 p. 44 ff; 1966 p. 54) introduced
extended Hermann-Mauguin symbols consisting of seven entries: . . . (.) . . . where the
unique direction is in parentheses, the three entries to the left refer to the three axial
directions A1, A2, A3 (Fig. 1; cf. Fig. 4) and the three entries to the right refer to the three
inter-axial directions B1,B2,B3 where BiAi. Such an extended Hermann-Mauguin symbol
for the layer-group P(6/m)mm reads: P 2/m 2/m 2/m (6/m) 2/m 2/m 2/m
Within the Trigonal model, this -symmetry reduces to trigonal. The extended
Hermann-Mauguin symbols, depending on which of the two maximal non-isomorphic
subgroups is preserved (either P (3)1m or P(6)2 m , become: P 1 1 1 (3) 2/m 2/m 2/m
and P 2 2 2 (6) m m m.
The individual operations in each of these two groups can be characterized either by
the extended Hermann-Mauguin (H-M) symbols (as usual in the OD literature), or with
reference to the orthogonal (ORT) axes. Although indexing in the orthohexagonal setting
in unequivocal, the correspondence between H-M symbols and ORT symbols depends on
which cell is adopted (C1 vs. C2: see Fig. 1). In Table 1, all correspondences are shown.
The two -symmetries of the Tet layer correspond to 2n60 and (2n+1)60
rotations, respectively, of successive M layers about c*. Each family of polytypes is
defined in terms of the -symmetry of the Oc layer, which is the same as that of the O
166 Nespolo&urovi

Table 1. Extended Hermann-Mauguin (H-M) symbols and corresponding


operations indexed in orthogonal (ORT) axes for the two -symmetries of the
Tet layer within the Trigonal model. The extended H-M symbols consist of
seven entries: . . . (.) . . . where the unique direction is in parentheses, the three
entries to the left refer to the three axial directions A1, A2, A3 and the three
entries to the right refer to the three inter-axial directions B1,B2,B3 (BiAi).
The corresponding orthogonal indices are given with reference to both the C1
and the C2 cells.

P(3)1m

-operations -operations

H-M ORT (C1) ORT (C2) H-M ORT (C1) ORT (C2)

1 1 1 1 1 1
-1 -1 -1 1
(3) 3 [001] 3 [001] (3) 3-1[001] 3-1[001]
(3)1 31[001] 31[001] (3)1 31[001] 31[001]
[. . . (.) m . .] m (010) m (110) [. . . (.) 2 . .] 2[010] 2[310]
[. . . (.) . m .] m (110) m (110) [. . . (.) . 2 .] 2[310] 2[310]
[. . . (.) . . m] m (110) m (010) [. . . (.) . . 2] 2[310] 2[010]

P(6)2m

-operations -operations

H-M ORT (C1) ORT (C2) H-M ORT (C1) ORT (C2)

1 1 1 (2)1 m(001) m(001)


(3)-1 3-1[001] 3-1[001] (6)1 6-1[001] 6-1[001]
(3)1 31[001] 31[001] (6)1 61[001] 61[001]
[m . . (.). . .] m (100) m (130) [2 . . (.) . . .] 2[100] 2[110]
[.m . (.) . . .] m (130) m (130) [. 2 . (.) . . .] 2[110] 2[110]
[. . m (.) . . .] m (130) m (100) [. . 2 (.) . . .] 2[110] 2[100]

sheet (see Table 2 in Ferraris and Ivaldi, this volume), and is then divided into two
subfamilies on the basis of the Tet -symmetry: subfamily A for P(3)1m, and subfamily B
for P(6)2 m . We suggest for the polytypes where Tet layers with both P(3)1m and
P(6)2m -symmetries co-exist, the term mixed-rotation polytypes (see also Nespolo
1999). Both subfamily A and subfamily B polytypes are OD structures, because the layer
stacking obeys the VC. However, the layer stacking in the mixed-rotation polytypes with
the geometry of the Trigonal model violates the VC: these polytypes are OD structures
only within the Pauling model, i.e. for a null ditrigonal rotation of the tetrahedra
(Backhaus and urovi 1984).
CrystallographicBasisofPolytypismandTwinninginMicas 167

Figure 4. The nine possible displacements in the structure of polytypes of phyllosilicates. Left: the
OD symbols and corresponding vectors, within the primitive hexagonal unit cell (modified after
Durovic 1999). The sum of any two vectors is indicated, and the result of the summation of any
number of vectors should be taken modulo primitive hexagonal cell. The individual vectors are
designated by their conventional numerical characters and signs + and , whereas the zero
displacement * is not indicated. The + and vectors do not explicitly occur in micas.
However, in Class b polytypes the total displacement, obtained as vector sum of the packet-to-
packet displacements (v2j,2j+1, second line of the full OD symbol) corresponds to , namely cn =
(0,1/3). Right: the corresponding Z vectors (modified after Zvyagin et al.1979) (cf. Table 4). In
the publications by Zvyagin and his school, the coordinate system is oriented so that the
orthogonal a axis points up and the b axis to the left. Here we follow instead the conventions of
the International Tables for Crystallography: the space-fixed references, and consequently the Z
vectors, are rotated by 180 with respect to their orientation in the original publications.

Figure 5. An isolated hetero-octahedral Oc layer, with the three two-fold axes in the
plane of the layer (-operations).

In Figure 5 an isolated Oc layer is shown. Depending on whether Ma, Mi and Me are


all equal, two different or all different the Oc layer is homo-, meso- or hetero-octahedral
respectively, and the -symmetry is H(3)1m, P(3)1m and P(3)12 respectively. In the
168 Nespolo&urovi

Figure 6. The hetero-octahedral Oc layer shown in Figure 5 after substitution of 2/3 of the OH/F
groups with Oa from the upper and lower tetrahedra. Only one of the three -operations remains,
defining the relation between the type of site (M1, M2, M3) and its occupation (Ma, Me, Mi). (a)
-operation 2[010], Mi cation in the M1 site, layer type M1. (b) -operation 2[310], Me cation in the
M1 site, layer type M2. (c) -operation 2[310], Ma cation in the M1 site, layer type M2.

meso-octahedral family Oc includes six -operations (1, 3+[001], 3-[001], m(010), m(110), m(110))
and six -operations (2[010], 2[310], 2[310],1, 3+[001],3-[001]); these numbers in the homo-
octahedral family have, in fact, to be multiplied by three, owing to the H centering,
whereas for the hetero-octahedral family Oc includes three and three -operations (the
first three of each set). In Figure 6 the same projection is given, but with the positions of
the OH/F groups remaining after the substitution with Oa are indicated. This substitution
destroys two-thirds of the -operations, leaving one (hetero-octahedral) or two (homo-
and meso-octahedral) -operations (the identity and one m reflection) and one or two -
operations (one of the two-fold rotations in the plane of the layer, and the inversion). For
meso- and hetero-octahedral Oc layer, for the sake of simplicity and without loss of
generality, let us assume that (Mi) < [(Ma), (Me)]. The origin of the Oc layer is then,
according to the convention described in Ferraris and Ivaldi (this volume), at the Mi
average cation. In Figure 6a, one of the -operations (the only one for hetero-octahedral
Oc layer) is the two-fold rotation along [010], and the M1 (trans) site contains the Mi
average cation. The M layer is thus of the type M1. Instead, in Figure 6b and 6c the -
operation is the two-fold rotation along [310] and [310] respectively: the M1 site contains
the Me or the Mi cation respectively, and in both cases the M layer is of type M2.
MDO op lytypes . Polytypes in which not only the pairs of layers, but also the triples,
CrystallographicBasisofPolytypismandTwinninginMicas 169

quadruples etc. are geometrically equivalent, or, when this is not possible, contain the
smallest number of kinds of triples, quadruples etc., are termed Maximum Degree of
Order (MDO) polytypes. This definition originates in a simple philosophy: if a certain
configuration (say a triple of layers) is energetically favorable, it will be repeated again
and again and will not be intermixed with other, less favorable configurations.

Figure 7. The (001) projections of a Tet layer (the I cation, not shown, takes place in the hole
between the two rings of tetrahedra). The two-fold axes in the plane of the layer (half of the -
operations of the Tet layer) are indicated. (a) The configuration corresponding to the Pauling
model, with zero ditrigonal rotation. The symmetry of the Tet layer is P(6/m)mm. (b) The
configuration corresponding to subfamily A in the Trigonal model. The symmetry of the Tet layer
is P(3)1m. (c) The configuration corresponding to subfamily B in the Trigonal model. The
symmetry of the Tet layer is P(6)2m.

MDO polytypes of the subfamily A [P(3)1m -symmetry of the Tet layer] are more
favorable then MDO polytypes of the subfamily B [P(6)2m -symmetry of the Tet layer],
probably because of the different (staggered vs. eclipsed) configuration of the facing Ob
atoms (Fig. 7). The most common polytypes are indeed MDO subfamily A. Of the MDO
subfamily B, only 2M2 is relatively common in Li-rich trioctahedral micas, where an
important structural role of the fluorine atoms has been proposed (Takeda et al. 1971). 2O
has been found in its ideal space group in a fluor-phlogopite (Ferraris et al. 2001) and in
the brittle mica anandite (Giuseppetti and Tadini 1972; Filut et al. 1985): the structure
refinement of anandite indicates that it cannot be described in terms of an orthohexagonal
C-centered cell, its space-group type being Pnmn. 2O was also obtained synthetically in
fluor-phlogopite (Sunagawa et al. 1968; Endo 1968), and identified from direct
170 Nespolo&urovi

observation of the growth spirals on the surface, but no diffraction study has been
performed. Several non-MDO subfamily A polytypes have been reported, as well as
some mixed-rotation polytypes, but their number is far smaller than MDO polytypes. The
abundance of MDO subfamily A polytypes shows that the geometrical equivalence of
OD layers is an important factor even when considering the real structures. The
occurrence of non-MDO polytypes is easily understood when considering that the MDO
concept specifically refers to a layer-by-layer growth. In all the environments where
crystals grow in a fluid phase, the spiral-growth mechanism, to which the MDO criteria
apply less strictly, becomes dominant as soon as the supersaturation decreases below a
certain critical value (Sunagawa 1984). As a matter of fact, the appearance of long-period
polytypes in micas has precise structural reasons. In polytypes based on the close-packed
arrangement of atoms, such as SiC, CdI2 etc., the layer thickness is only a few and the
long-range interactions are not negligible. In micas the layer is about 10 thick and the
long-range interactions are thus less relevant. The probability of the occurrence of non-
MDO polytypes, as well as of non-periodic (disordered) polytypes, depends in general on
how close are the layers to their archetypes (i.e. how close is the real symmetry to the
ideal OD symmetry). The more a layer deviates from its archetype, the less valid are the
equivalencies between adjacent layers. The consequence is that when the pairs of
adjacent layers are not geometrically equivalent, they are also not energetically
equivalent and the ambiguity in the stacking of layers is lost.
The first derivation of the predecessors of the MDO polytypes dates back to Smith
and Yoder (1956), who theoretically described the six non-equivalent polytypes (termed
simple polymorphs by them) that can be obtained by stacking the M1 layer with the
same rotation (in the two possible directions) between adjacent layers. All other
polytypes were collectively termed complex polymorphs. The term polymorphism was
also used by Zvyagin (1962) and by Franzini and Schiaffino (1963a,b), whereas the word
polytypism when referring to micas was used for the first time probably by Amelinckx
and Dekeyser (1953). The adjectives simple and complex used by Smith and Yoder
(1956) represent a qualitative description, as well as the word standard used by Bailey
(1980a). Zvyagin et al (1979) (see also Zvyagin 1988) introduced the notion of
condition of homogeneity3, which identifies polytypes in which the position of any
layer relative to the others and the transition from it to the adjacent ones, are the same or
equivalent for all layers. These polytypes are called homogeneous polytypes; the
remaining ones are called inhomogeneous polytypes. The condition of homogeneity is
similar to the condition of the Maximum Degree of Order, but with less emphasis on
chemical variations, and thus also on the symmetry distinguishing the three families. The
main difference is that Zvyagin applies his condition to the entire crystal-chemical layer,
whereas the algorithms for the derivation of MDO polytypes (Dornberger-Schiff et al.
1982, Dornberger-Schiff and Grell 1982) apply to OD layers or OD packets: the latter in
micas roughly correspond to half-layers. Within the homo-octahedral approximation in
micas, the procedures for the derivation of simple, standard, homogeneous,
MDO, yield identical results (Table 2): this is however, in general, not true for other
compounds, because the algorithms for the derivation of MDO polytypes are
considerably different from those employed to derive homogeneous or simple
polytypes. The difference becomes evident when considering that there are only 6
simple or standard polytypes (that become 8 when considering the non-congruent
polytypes, i.e. counting separately each member of an enantiomorphous pair), but they
simply correspond to homo-octahedral MDO polytypes. There are then 14 non-equivalent

3 In some texts, the Russian term is translated as uniformity instead of


homogeneity. Here we adopt the latter translation, closer to the original meaning.
Table 2. Comparative classification of mica polytypes in the homo-octahedral approximation.

Relative rotations between successive M layers

1M: 0; 2M1: 120 and 2O: 180; 2M2: 60 and 2nu60 (2n+1)u60 Both 2nu60
240; 3T: 120 or 240 300; 6H: 60 or 300 and (2n+1)u60

Subfamily A MDOa Subfamily B MDOa Subfamily A non-MDOa Subfamily B non-MDOa Mixed-rotationb

All triples of OD packets within More than one type of triple of OD packets More than one type of triple
a given polytype equivalent within a given polytype of OD packets within a
given polytype

OD structures Non OD structures1

Homogeneous with all Homogeneous with Inhomogeneous with all Inhomogeneous with octahedra Inhomogeneous with mixed
octahedra parallelc octa-hedra parallel and octahedra parallelc parallel and antiparallel (parallel and antiparallel)
anti-parallel regularly regularly alternatingc and randomly alternating
alternatingc orientation of octahedra c

All triples of M layers within a given polytype More than one kind of triples of M layers within a given >1 kind of triples of M layers
equivalent polytype within a given polytype

Standard, group Id Standard, groups I & II Non-standard, group Id Non-standard, groups I & II Non-standard, groups I & II
alternating alternating mixed, non-alternating

Simplee Complexe
Crystallographic Basis of Polytypism and Twinning in Micas

Ternaryf Senaryf Ternaryf Senaryf


1
These are OD structures if the ditrigonal rotation of the tetrahedra is zero.
a
Durovic et al (1984); bNespolo (1999); cZvyagin et al (1979) and Zvyagin (1988); dBailey (1980a); eSmith and Yoder (1956); f Ross et al (1966).
MDO stands for Maximum Degree of Order.
171
172 Nespolo&urovi

(22 non-congruent) polytypes in the meso-octahedral family, and 36 non-equivalent (60


non-congruent) polytypes in the hetero-octahedral family, which obey the condition of
Maximum Degree of Order. Zvyagins condition of homogeneity applies to homo- and
meso-octahedral polytypes, but not to the hetero-octahedral family.
The reason for the derivation of the polytypes mentioned above is to single out, from
the theoretically infinite number of periodic polytypes within a given family, those with
relatively short periods in the stacking direction, which are most likely to be encountered
in investigated specimens. To calculate theoretical single-crystal diffraction patterns is
easy, provided that the structure of the single layer is known, and the distribution of
intensities can then be used for their identification by simple visual comparison with
patterns obtained experimentally (Weiss and Wiewira 1986). Thus, it is irrelevant which
set of polytypes as derived by different authors/schools is used, provided it fulfils its
purpose, namely it allows the identification of the polytype. Identification of long-period
(non-MDO) polytypes requires special algorithms exploiting the periodicity of the
intensity distribution, and this is treated at the end of this chapter.

SYMBOLIC DESCRIPTION OF MICA POLYTYPES


The indicative symbolism developed by Ramsdell (1947) is not sufficiently
informative for polytypes with more than 2-3 layers in the repeat unit. Because of the
rapid increase of the number of possible polytypes with the number of layers in the repeat
unit (Mogami et al. 1978; McLarnan 1981) the Ramsdell notation needs augmentation
with another, descriptive symbolism, from which the structure, including its symmetry,
can be reconstructed when the structure of the individual layer is known. Note that a
symbol, which describes the stacking mode in an individual polytype, consists of a string
of characters. Symbolism is a set of rules governing the construction of symbols. The
symbols introduced to describe the stacking mode in mica polytypes can be broadly
divided into two types, orientational (giving the absolute orientation of layers with
respect to a space-fixed reference) and rotational (giving the relative rotations between
pairs of layers).
1) Orientational symbols
1A) DA symbols. The first symbolic description is from Dekeyser and Amelinckx
(1953), who used a set of vectors and numerical symbols to indicate the complete
stagger of the layer, defined as the (001) projection of the vector connecting two
(OH/F) sites on the two sides of the octahedral sheet. Six characters n = 1,2,3,1,2,3
represent the stagger of the layer with respect to a space-fixed reference (Fig. 8).
These symbols apply to the homo-octahedral approximation only and therefore
cannot correctly describe polytypes containing M2 layers.
Figure 8. Symbols used by Dekeyser and Amelinckx
(1953) to indicate the orientation of a whole M layer.
These symbols can be considered the predecessors of
OD and Z symbols (cf. Fig. 4). With respect to the
original figure in Dekeyser and Amelinckx (1953), the
b and c axes have been taken in the opposite direction
(b left instead of right, and c coming out from the plane
instead of into) in accordance with the conventions of
the International Tables for Crystallography.

1B) Z symbols. Zvyagin (1962) introduced a numerical/vectorial description giving the


stacking of half-layers, as defined by the interlayer cations and the origin of the O
sheet. This choice made Zvyagins symbols more general than the symbols
introduced previously and also suitable for some other phyllosilicates. However,
CrystallographicBasisofPolytypismandTwinninginMicas 173

Zvyagin changed the notation three times. At first (Zvyagin 1962) he adopted the
letters A, B, C, A,B,C to indicate the absolute orientation of the entire layer. He
then adopted the characters i and i to indicate the intra- and inter-layers
displacement of half-layers (Zvyagin 1967). Later (Zvyagin et al. 1979) the Greek
letters were abandoned in favor of the corresponding Roman (si and ti) and with a
sign inversion between i and ti, to make homogeneous the definitions of si and ti.
Finally, the s and t letters were dropped, leaving only their numerical subscripts
as orientation characters (Zhukhlistov et al. 1990). These most recent symbols, and
the vectors they represent, are here termed Z symbols and Z vectors. As for DA
symbols, Z symbols are oriented symbols linked to a space-fixed, orthohexagonal
reference with (a, b) axes in (001) plane (see also Zvyagin 1985). For non-
orthogonal N-layer polytypes, the period along the c axis of this reference
corresponds to 3N layers (Fig. 9). The vector connecting the origin of the octahedral
sheet with the nearest interlayer site and vice versa, always looking at the sequence
of layers in the same direction, is called intralayer displacement: its projection on the
(001) plane has length |a|/3 and corresponds to the vector T2j-2 (or T2j-1, depending on
which of the two half-layers is considered) in Figure 2. There are six possible
orientations for each half layer, indicated by the six layer-fixed ai axes (i = 1~6). The
projection of the intralayer displacement is indicated by the character i = 1,2,6
when the ai axis is parallel to the space-fixed axis a (Fig. 4). The interlayer
displacement is the vector giving the relative displacement between two adjacent
layers: it can take any of the six orientations 1~6 described for the intralayer vector,
and in some other phyllosilicates, also two independent orientations corresponding to
b/3 (indicated as + and respectively), but it can also be a zero vector
(indicated as 0). In micas, owing to the presence of interlayer cations, only the 0
interlayer displacement occurs. The (a, b) components (sx, sy) of Z vectors are given

Figure 9. The conventional monoclinic cell (dashed lines), the (pseudo)-orthohexagonal cell (solid
lines), and the (pseudo)hexagonal cell [(001) base shaded] built overlapping three conventional
cells. The scale along c is compressed (modified after Nespolo et al. 2000a).
174 Nespolo&urovi

Table 3. OD symbols and Z symbols and the (a, b)


components of the corresponding orientation vectors.

OD symbol Z symbol (sx, sy)


3 3 (1/3, 0)
2 4 (1/6, 1/6)
1 5 (-1/6, 1/6)
0 6 (-1/3, 0)
5 1 (-1/6, -1/6)
4 2 (1/6, -1/6)
+ + (0, 1/3)
(0, -1/3)
0 * (0, 0)

in Table 3. The complete symbolism, giving the stacking sequence of half layers, is
ij0kl0mn0. For micas containing only M1 layers, i=j, k=l, m=n etc.; the character
0 can be omitted and a shortened symbol IKM is obtained (Zhukhlistov et al.
1990). M2 layers always correspond to intralayer displacement of the same parity;
opposite parity would in fact produce a trigonal prismatic coordination for the Y
cations. The Z vector for each layer corresponds to the (001) projection of a pair of
intralayer displacement vectors and it is obtained by summing their (sx, sy)
components. For micas built by M1 layers only, this is equivalent to twice the
components, namely (2sx, 2sy) (Table 3). Z vectors are thus twice as long as DA
stacking vectors (and also SY vectors, described below), and directed in the opposite
way. Since 2/3 is translationally equivalent to 1/3, in practice the (a, b)
components of the Z vectors are the same as those of the intralayer displacements,
but with the signs interchanged. The DA and SY stacking vectors are the (001)
projections of vectors not passing through a cationic site in the O sheet. On the other
hand, Z vectors are the (001) projections of vectors passing through that cationic site.
As a consequence, Z vectors can distinguish between M1 and M2 layers, whereas the
other two cannot. The latter simply correspond to the vector sum of Z vectors.
The fundamental merit of Z symbols is that they can describe also meso-
octahedral polytypes. Their shortcoming is that the symbols describing homo-
octahedral mica polytypes are identical with those describing meso-octahedral
polytypes consisting of M1 layers, and additional information must be given also.
Moreover, in their present form, they cannot handle hetero-octahedral polytypes.
1C) OD symbols. The OD school, inspired by Z symbols, derived the most general
symbols to describe mica polytypes (urovi and Dornberger-Schiff 1979;
Dornberger-Schiff et al. 1982; Backhaus and urovi 1984; urovi et al. 1984;
Weiss and Wiewira 1986). These symbols consist of a sequence of characters
referring to one period, placed between vertical bars; two lines of characters are
used; the first line indicates the packet orientations, and the second line the packet-
to-packet displacements. A dot . separating the orientational characters for packets
p2j and q2j+1 indicates the position of Oc layer. The OD symbols are thus expressed:

T0 T1 T2 T3
v0,1 * v 2,3 *
CrystallographicBasisofPolytypismandTwinninginMicas 175

where Tj = 0~5, v2j,2j+1 = T2j+T2j+1 (v, T are the vectors corresponding to v and T
characters, and the vector sum is taken modulo primitive hexagonal cell), and *
indicates null vector (no displacement) (Fig. 4). Note that the parity of the
orientational characters is necessarily opposite to that of the displacement characters.
The vector sum of v2j,2j+1 over a complete polytype period (hereafter indicated as v,
for shortness) corresponds to the cn projection of the c axis onto the (001) plane and
gives the total displacement, which can correspond to the characters 0~5, *,
+ and (see Tables 3 and 4). In the meso-octahedral family, the v2j,2j+1
characters in the second line are redundant because they follow unequivocally from
the T2jT2j+1 characters in the first line: simplified symbols |T0 T1 T2 T3 | can
also be used. In the hetero-octahedral family the chirality of the packets is taken into
account: right- and left-handed packets are indicated by a prime () or double prime
(), respectively, substituting the dot, where the chirality is conventionally
determined by the direction connecting Ma to Mi (Fig. 10) (urovi et al. 1984).
Also in this case the v2j,2j+1 characters in the second line are redundant, and
simplified symbols T2j T2j+1 or T2j T2j+1 for the individual packet pairs can be used.
Although the v2j,2j+1 displacement characters are redundant in both these families,
their vector sum v, as shown in the next section, allows the classification of mica
polytypes in terms of their reticular features: the complete two-line symbols yield
thus additional information. Finally, in the homo-octahedral family, there are only
two distinguishable orientations of the packets. This follows from the fact that the Oc
layer here is H centered and it can be attached to the Tet layer so that its three
equivalent origins can be reached simultaneously by the three T vectors with even-
or odd (uneven)- numbered characters, respectively. These two orientations of a
packet, differing by a 1800 rotation, are indicated by orientational characters e and u,
respectively. In this case, the first line of characters is redundant and simplified
symbols consisting just of the line of displacement v2j,2j+1 characters may be
sufficient (Dornberger-Schiff et al. 1982).
The OD symbols for the packet orientations were defined with respect to
hexagonal axes A1, A2, A3 as indicated in Figure 4. In Table 3 they are described in
terms of the (a, b) orthohexagonal identity periods. The orthohexagonal cell used in
the OD literature corresponds to the C2 setting (Fig. 1). In practice, for the meso-
octahedral family, the OD symbols correspond to (6-Z)(mod 6), where Z are
Zvyagins characters. For the hetero-octahedral family the same numerical relation
holds, but the chirality of the packets is considered. For the homo-octahedral family,
Zvyagin uses one of the three e- or u-vectors as representative: 6 or 3, respectively.
Going from 0 to 5 instead than from 1 to 6, the OD symbols obey the closure
property of the mod function. The corresponding OD vectors are disposed in a
clockwise sequence, whereas Z vectors are defined counter-clockwise (Fig. 4), but
their crystal chemical basis is the same.
1D) TS symbols (Sadanaga and Takeda 1969; Takeda and Sadanaga 1969) give the
relative positions of the TS unit layers and are written as a sequence of N symbols
Lj(Xj, Yj), j = 1-N, where Lj is the type of layer and N is the number of layers in
the polytype period. Considering two successive repeats of N layers, (Xj, Yj) are
the (a, b) components of the vector connecting the origin of the last (N-th) layer of a
repeat and the origin of the j-th layer of the next repeat (Fig. 2). These symbols
respect only the homo-octahedral approximation.
2) Rotational symbols
2A) SY vectors. Smith and Yoder (1956) described the stacking sequence in a way
similar to Dekeyser and Amelinck (1953). The stacking vectors are defined as the
(001) projection of the vector connecting two nearest interlayer cations on the two
176

Table 4. Table of vector sums for the nine possible displacement vectors appearing in the structure of most common
phyllosilicates. The individual vectors v are represented by their respective characters v and the result of summation should
be taken modulo primitive hexagonal cell (cf. Fig. 4). These nine vectors form a translation group with vector addition as the
group operation.

OD Z

0 1 2 3 4 5 * + 6 5 4 3 2 5 0 +
0 3 1 * 5 + 0 2 4 6 3 5 0 1 + 6 4 2
1 4 + 2 * 0 1 3 5 1 2 + 4 0 6 5 3 1
2 1 + 5 3 * 2 0 4 2 5 + 1 3 0 4 6 2
3 * 2 0 + 4 3 5 1 3 0 4 6 + 2 3 1 5
4 5 * 3 + 1 4 2 0 4 1 0 3 + 5 2 4 6
5 + 0 * 4 2 5 1 3 5 + 6 0 2 4 1 5 3
Nespolo & urovi

* 0 1 2 3 4 5 * + 0 6 5 4 3 2 1 0 +
+ 4 3 0 5 2 1 + * + 2 3 6 1 4 5 + 0
2 5 4 1 0 3 * + 4 1 2 5 6 3 0 +

CrystallographicBasisofPolytypismandTwinninginMicas

Figure 10. Construction of the stacking symbol for hetero-octahedral mica polytypes demonstrated on two one-layer (two-packet) polytypes, through the (001)
projection of the Oc layer. Gray squares indicate the position of OH groups (coinciding in the projection to the interlayer cations). Shaded octahedra contain M1
(trans) sites. Thick hexagons are drawn through the lower and upper apical oxygen atoms, as in Durovic et al. (1984, Fig. 5). Thick solid arrows are orientational
vectors T2j and T2j+1, thick dotted arrows are displacement vectors v2j,2j+1. The chirality (enantiomorphous hand) is determined by the curved arrow leading from
Mi to Ma around the upper OH group: clockwise = right-handed, counter-clockwise = left-handed. Mi and Ma stand for octahedral sites with (Mi)nimal and
(Ma)ximal average X-ray scattering power, respectively (modified after Durovic et al.1984).
177
178 Nespolo&urovi

sides of a layer. Becuase interlayer cations and (OH, F) groups overlap in the (001)
projection, in practice the methods of Dekeyser and Amelinckx (1953) and of Smith
and Yoder (1956) are equivalent; however, Smith and Yoder (1956) did not adopt a
symbolic notation. Also these vectors are correct only in the homo-octahedral
approximation and cannot thus describe correctly polytypes containing M2 layers.
2B) RTW symbols. Ross et al (1966) introduced a numerical description (RTW
symbols) giving the relative rotations between successive stacking vectors
representing a sequence of M1 layers. This description is the most immediate,
although not the most general (it applies to the homo-octahedral approximation
only), to describe the mica-polytype stacking mode and to derive all possible mica
polytypes with a given number of M1 layers (Takeda 1971; Mogami et al. 1978;
McLarnan 1981). However, the method cannot distinguish between M1 and M2
layers. RTW symbols are orientation-free, rotational symbols written as a sequence
on N characters Aj = 0,1,2,3, the j-th character giving the rotation angle between j-
th and (j+1)-th layers as integer multiple of 60. A RTW symbol corresponds to the
difference, with sign inverted, between pairs of displacement OD characters [Aj =
(v2j,2j+1- v2j-2,2j-1)] or to the difference between pairs of Z characters corresponding to
successive M1 layers [Aj = +(Z2j+1-Z2j-1)]. The opposite sign between OD and Z
symbols originates from the fact that Z and RTW symbols are defined counter-
clockwise, whereas OD symbols are defined clockwise. The closure of the
periodicity after N layers is expressed by the condition (Takeda 1971):

Aj = 0 ( mod 6 )
N
j =1
(1)

2C) Thompsons symbols. Thompson (1981) introduced an operatorial description of


mica stacking, in which operators N1 and N-1 (N = 1,6) produce 2/N
counterclockwise (N1) or clockwise (N-1) rotation of the M layer. These operators are
divided into dot [N = 1(mod 2)] and cross operators [N = 0(mod 2)].
Bailey (1980a,b) gave an alternative description of the polytypism of the micas, by
classifying the six possible directions of the stagger of the tetrahedral sheets within a
layer (positive and negative directions of the three hexagonal axes in the plane of the
layer). The six possible positions of octahedral cations with respect to a space-fixed
reference were divided into two groups, labeled I (negative stagger) and II (positive
stagger). The first layer of each polytype was kept with tetrahedral stagger along a1
(octahedral cation positions I): as a consequence, the axial setting used to derive the
polytypes was not the most suitable to identify polytypes from their diffraction pattern,
and a final axial transformation is necessary. Subfamily A, subfamily B and mixed-
rotation polytypes correspond to sequences of octahedral cations belonging to group I
only, to groups I and II alternating, and to groups I and II mixed non-alternating. Baileys
notation cannot distinguish between M1 and M2 layers and is not adopted here. We
instead make reference to OD and Z (collectively termed orientational symbols when
referring to both, for shortness) and to RTW symbols.

RETICULAR CLASSIFICATION OF POLYTYPES:


SPACE ORIENTATION AND SYMBOL DEFINITION
Mica polytypes can belong to five symmetries: H, T, O, M and A (Takeda 1971). In
both the Pauling and the Trigonal models, the lattice of triclinic polytypes is metrically
monoclinic, and the (001) projection of the c axis, labeled cn, can take three values: 0, |a|/3,
|b|/3, on the basis of which mica polytypes are classified into orthogonal, Class a and Class
b respectively. The number N of layers building a polytype can be expressed as:
CrystallographicBasisofPolytypismandTwinninginMicas 179

N = 3n(3K+L) (K and n non-negative integers; L=1 or 2) (2)


where n defines the Series and L the Subclass; K is a constant entering in the
transformation matrices relating axial settings (Nespolo et al. 1998).
The structural model of each polytype, as described by the stacking vectors, has six
possible orientations with respect to the space-fixed (a, b) axes, each 60 apart. These
orientations correspond to one sequence of characters in the RTW symbols, but to six
different sequences of orientational symbols, and are in general non-equivalent. The cn
projection may correspond to v = * (orthogonal polytypes), v = 0~5 (Class a
polytypes), or to v = + or (Class b polytypes), i.e. to cn = (0, 0), (1/3, [0, 1/3])
and (0, 1/3) respectively. For non-orthogonal polytypes, cn can be reduced to (1/3, 0)
(Class a) or (0,1/3) (Class b) by means of the C-centering vectors and by rotating the
structural model around c*. These six orientations can be grouped in the following way
(Nespolo et al. 1999d).
1. Class a polytypes. Each orientation corresponds to a different cn projection, i.e. to a
different character of v, from 0 to 5. Among these, there is only one that
corresponds to the b-unique setting with an obtuse angle: that with v = 0, i.e. cn
= (1/3, 0).
2. Class b polytypes. Three orientations correspond to v = +, i.e. cn = (0, 1/3) (acute
angle) and three others to v = , i.e. cn = (0,1/3) (obtuse angle). The three
orientations with the same v (cn) are equivalent for triclinic polytypes, but not for
monoclinic cases. The symmetry elements are oriented according to an a-unique
setting with obtuse. Only one of the three orientations leading to v = agrees
with such a requirement.
3. Orthogonal polytypes. The six orientations correspond to v = *, i.e. cn = (0, 0), and
they are equivalent for hexagonal, trigonal and triclinic polytypes, whereas for
orthorhombic and monoclinic polytypes only two orientations, related by 180
rotation around c = c* axis, lead to the correct orientation of the symmetry elements.
Because both the reticular features and the OD character are based on the geometry
of the layer stacking in polytypes, some relations between the OD and the reticular
classifications can be established (Backhaus and urovi 1984; Nespolo 1999).
1. Subfamily A. These polytypes are described by orientational symbols with characters
of the same parity, i.e. by all-even characters in the RTW symbol. They include the
three most common MDO polytypes (1M, 2M1, 3T) and the great majority of non-
MDO polytypes found so far. Successive layers are related by 2n60 rotations; the x
component of the stacking vector of each packet (half-layer) is either always +1/3
(odd orientational parity of characters in the orientational symbols) or always -1/3
(even orientational parity of characters in the orientational symbols). As a
consequence, in Series 0 [n = 0 in Equation (2), i.e. polytypes with the number of
layers not a multiple of 3] the x component of cn cannot be 0 and these polytypes
belong to Class a. In Series higher than 0, the number of layers building the polytypes
is a multiple of 3 and thus v is *, + or (the x component of cn is always 0).
Therefore, these polytypes cannot belong to Class a.
2. Subfamily B. These polytypes are described by orientational symbols with characters
of alternating parity, i.e. by all-odd characters in the RTW symbol. Successive layers
are related by (2n+1)60 rotations. Only polytypes with an even number of layers
appear in this subfamily. In addition, because layers with different orientational parity
have an opposite x component of the stacking vector, v is *, + or and it is not
possible to have a Class a polytype.
3. Mixed-rotation polytypes. These polytypes correspond to orientational symbols with
180 Nespolo&urovi

character of different, non-alternating parity and to mixed parity of the characters in


the RTW symbol. Because there is no definite rule for the layer orientational parity
sequence, the three kinds of polytypes (orthogonal, Class a, Class b) are possible.

LOCAL AND GLOBAL SYMMETRY OF MICA POLYTYPES


FROM THEIR STACKING SYMBOLS
The main purposes of descriptive stacking symbols are: 1) to uniquely identify a
polytype; 2) to enable the reconstruction of the structure of the polytype once the
structure of the layer is known; 3) to enable a symmetry analysis of the polytype, not only
for the systematic derivation of MDO polytypes but also to determine the symmetry
(local and global) of a polytype from its symbol in a purely analytical way without the
need to draw auxiliary pictures (although these may be quite useful to visualize the
stacking sequence); and 4) to calculate the Fourier transform of the polytype. It is thus
necessary to know how the individual point operations influence the individual characters
in the symbol. For mica polytypes, there are 24 point operations constituting the point
group 6/mmm. The effect of each of them on the six vectors corresponding to the
orientational symbols can be expressed in a general form, e.g., a 60 clockwise rotation
converts an OD vector j into j+1, or a Z vector j into j-1, but as a working tool it
is more convenient to compile a table of conversions to give the results explicitly. Note
that the vectors given in Figure 2 and 4 are actually the (001) projections of the intralayer
stacking vectors that give the absolute orientations of packets (half-layers in Zvyagins
concept). The transformation of these projections is almost trivial for -operations,
whereas it must be combined with an inversion for -operations because the stacking
vector must always to point in the same direction, namely along +c. For example, a 180
rotation around the b axis (H-M: [. . . (.) . . 2], ORT : 2[010] in Table 5a) converts a vector
0 into vector 3 but such a vector would point along -c. The corresponding vector
directed along +c is 0. It follows that the 2[010] rotation applied to a packet p2j = 0
yields a packet q2j+1 = 0. Tables 5a and 5b give the conversion rules for OD symbols
and Z symbols, respectively. Moreover, a -operation leaves unchanged the order of the
sequence of characters in the orientational symbol, whereas a -operation inverts it. The
effect of the 24 point operations of the point group 6/mmm on the entire orientational
symbol is given in Table 6.
Derivation of MDO polytypes
The derivation of MDO polytypes for homo-, meso-, and hetero-octahedral micas
were described in detail by Backhaus and urovi (1984). Therefore, only basic ideas are
given here.
The first step is to construct all packet triples compatible with the crystal chemistry.
The use of meso-octahedral micas demonstrates the procedure. Let us take an M1 layer and
begin with the packet p0 in the orientation 0 (any other initial orientation could be used).
The packet q1 must then be also in the orientation 0 to preserve M1 layer. The packet-
pair is then 0 . 0 because the sum of the two orientational vectors 0 + 0 = 3, where
3
3 is the displacement vector (cf. Fig. 4). A single meso-octahedral packet has the
symmetry C1m(1) but in the following we shall not consider the translations of the layer
group. The point group m has the order 2 and consists of two operations: the identity (an
operation of the first sort, whose transformation matrix has determinant +1) and the
reflection (an operation of the second sort, whose transformation matrix has determinant
1). Therefore, any transformation of such a packet consists always of two operations with
CrystallographicBasisofPolytypismandTwinninginMicas 181

Table 5a. Conversion of characters appearing in the OD symbols of mica polytypes. The individual
operations are characterized by their extended Hermann-Mauguin (H-M) symbols and by the
corresponding operations indexed in orthogonal (ORT) C2 setting axes. Cf. Table 1 and Backhaus and
Durovic (1984).
-point operations Character conversion by point operation -point operations
H-M ORT j: 012345 eu* H-M ORT
1 1 j: 012345 eu* 1 1
(6)-1 (6)-1 1+j: 123450 ue* (6)-1 (6)-1
(3)-1 (3)-1 2+j: 234501 eu* (3)-1 (3)-1
(2)1 (2)1 3+j: 345012 ue* (2)1 = m(001) (2)1 = m(001)
(3)1 (3)1 4+j: 450123 eu* (3)1 (3)1
(6)1 (6)1 5+j: 501234 ue* (6)1 (6)1


-point operations Character conversion by point operation -point operations
H-M ORT j: 012345 eu* H-M ORT
[m . . (.) . . .] m(130) 5-j : 543210 ue* [2 . . (.) . . .] 2[110]
[. . . (.) . m .] m(110) 4-j : 432105 eu* [. . . (.) . 2 .] 2[310]
[. . m (.) . . .] m(100) 3-j : 321054 ue* [. . 2 (.) . . .] 2[100]
[. . . (.) m . .] m(110) 2-j : 210543 eu* [. . . (.) 2 . .] 2[310]
[. m . (.) . . .] m(130) 1-j : 105432 ue* [. 2 . (.) . . .] 2[110]
[. . . (.) . . m] m(010) -j : 054321 eu* [. . . (.) . . 2] 2[010]

Table 5b. Conversion of characters appearing in the Zvyagin symbols of mica polytypes. The individual
operations are characterized by their extended Hermann-Mauguin (H-M) symbols and by the
corresponding operations indexed in orthogonal (ORT) C2setting axes. Cf. Table 1 and Zvyagin (1997).

-point operations Character conversion by point operation -point operations


H-M ORT j: 654321 0 H-M ORT
1 1 j: 654321 0 1 1
(6)-1 (6)-1 5+j : 543216 0 (6)-1 (6)-1
(3)-1 (3)-1 4+j : 432165 0 (3)-1 (3)-1
(2)1 (2)1 3+j : 321654 0 1
(2) = m(001) 1
(2) = m(001)
(3)1 (3)1 2+j : 216543 0 (3)1 (3)1
(6)1 (6)1 1+j : 165432 0 (6)1 (6)1
[m . . (.) . . .] m(130) 1-j : 123456 0 [2 . . (.) . . .] 2[110]
[. . . (.) . m .] m(110) 2-j : 234561 0 [. . . (.) . 2 .] 2[310]
[. . m (.) . . .] m(100) 3-j : 345612 0 [. . 2 (.) . . .] 2[100]
[. . . (.) m . .] m(110) 4-j : 456123 0 [. . . (.) 2 . .] 2[310]
[. m . (.) . . .] m(130) 5-j : 561234 0 [. 2 . (.) . . .] 2[110]
[. . . (.) . . m] m(010) -j : 612345 0 [. . . (.) . . 2] 2[010]
182 Nespolo&urovi

Table 6. Transformation rules for OD and Z symbol under the effect of the -
symmetry operations of the hexagonal syngony. i,j,., p (OD symbols)
and i,j,.,p (Z symbols) are the original symbols. The individual operations
are characterized by their extended Hermann-Mauguin (H-M) symbols and by
the corresponding operations indexed in orthogonal (ORT) C2 setting axes. Cf.
Table 1 (modified after Nespolo et al. 1999).

-point operation effect on OD symbol effect on Z-symbol


H-M ORT sequence sequence
1 1 i,j,.,p i,j,. p
(6)-1 (6)-1 1+i,1+j,.,1+p 5+i,5+j,.,5+p
(3)-1 (3)-1 2+i,2+j,.,2+p 4+i,4+j,.,4+p
(2)1 (2)1 3+i,3+j,.,3+p 3+i,3+j,.,3+p
(3)1 (3)1 4+i,4+j,.,4+p 2+i,2+j,.,2+p
(6)1 (6)1 5+i,5+j,.,5+p 1+i,1+j,.,1+p
[m . . (.) . . .] m(130) 5-i,5-j,.,5-p 1-i,1-j,.,1-p
[. . . (.) . m .] m(110) 4-i,4-j,.,4-p 2-i,2-j,.,2-p
[. . m (.) . . .] m(100) 3-i,3-j,.,3-p 3-i,3-j,.,3-p
[. . . (.) m . .] m(110) 2-i,2-j,.,2-p 4-i,4-j,.,4-p
[. m . (.) . . .] m(130) 1-i,1-j,.,1-p 5-i,5-j,.,5-p
[. . . (.) . . m] m(010) -i,-j,.,-p -i,-j,.,-p

-point operation effect on OD symbol Effect on Z-symbol


H-M ORT sequence sequence
1 1 p,., j,i p.,j,i
(6)-1 (6)-1 1+p,,1+j,1+i 5+p,.,5+j,5+i
(3)-1 (3)-1 2+p,,2+j,2+i 4+p,.,4+j,4+i
(2)1=
(2)1 = m(001) 3+p,,3+j,3+i 3+p,.,3+j,3+i
m(001)
(3)1 (3)1 4+p,,4+j,4+i 2+p,.,2+j,2+i
(6)1 (6)1 5+p,,5+j,5+i 1+p,.,1+j,1+i
[2 . . (.) . . .] 2[110] 5-p,.,5-j,5-i 1-p,.,1-j,1-i
[. . . (.) . 2 .] 2[310] 4-p,.,4-j,4-i 2-p,.,2-j,2-i
[. . 2 (.) . . .] 2[100] 3-p,...,3-j,3-i 3-p,.,3-j,3-i
[. . . (.) 2 . .] 2[310] 2-p,,2-j,2-i 4-p,.,4-j,4-i
[. 2 . (.) . . .] 2[110] 1-p,.,1-j,1-i 5-p,.,5-j,5-i
[. . . (.) . . 2] 2[010] -p,.,-j,-i -p,.,-j,-i
CrystallographicBasisofPolytypismandTwinninginMicas 183

the above properties. Accordingly, in the packet pair . 03. 0 the two packets are related
simultaneously with two operations, and a look at Table . 5a shows that these,
converting 0. into .0 and 3 into itself are [. . .(.) . . 2] 2[010] and an inversion. The packet
pair has thus the point symmetry 2/m.
The packet triples p0q1p2 compatible with the Trigonal model in the subfamily A are
02-operations converting p0 into p2
0 . 0 0 , 0 . 0 2 plus its enantiomorphous 0 . 0 4 . The two
3 * 3 * 3 *
are in the first case (Table 5a) a translation (isogonal with the identity) and a glide
operation (isogonal with [(.)..m(010)]). A continuation of any of these -operations leads
to the same string . 03. 0*03. 0*03. 0* because any of them converts also displacement
characters 3 in the same way. This string has modulus 03. 0 , the vector 3 is the interlayer
vector of this one-layer monoclinic polytype. However, because 3 = +a/3 (acute
angle), it must be re-oriented by a rotation of 180o around c* to bring it into the standard,
second setting (obtuse angle). Evidently, this can be made (Table 5a) by adding 3 to all
characters, thus 30. 3 is obtained. The basis vectors of this 1M polytype with symmetry
C12/m1, are a, b, c0-a/3, where c0 is a vector perpendicular to the layer planes with length
corresponding to the layer width (e.g., a distance between two closest planes of
interlayer cations).
The two 02-operations for the triple 03. 0*2 are (Table 5a) a clockwise three-fold screw
rotation (first sort operation, isogonal with (3)-1 3[001]) and a glide operation (second sort
operation, isogonal with [. . . (.) m . .] m(110)). A continuation of the (3)-1, through a
step-by step application onto the characters in the starting triple, converts 02, then
24 and 40 but also 35, 51 and 13, which closes the period. The resulting
symbol 03. 0*25. 2*4.4
1 *
characterizes a three-layer, trigonal 3T polytype with symmetry P3212
and basis vectors a1, a2, 3c0. A continuation of [. . . (.) m . .] m(110) converts 02 but
then 20, and 35, 53 which closes the period. The symbol 03. 0*25. 2* describes a two-
layer monoclinic polytype (glide operation is the global operation here) with an interlayer
vector equal to the sum of the two displacement vectors 3 + 5 = 4 (cf. Fig. 4). Also
this polytype must be clockwise rotated by 120o, by adding 2 to all characters, to bring it
into the standard setting. The final form is 25. 2*4.4 1 *
, the 2M1 polytype with symmetry
C12/c1 and basis vectors a, b, 2c0-a/3.
The packet triple 03. 0*4 , enantiomorphous to the previous example, yields analogous
results. The continuation of the (3)1 gives string 03. 0*4.4 2 . 2 , a 3T polytype with symmetry
1 * 5 *
P3112, the enantiomorphous counterpart to P3212. The continuation of [. . . (.) . m .] m
(110)) gives a preliminary symbol 3 * 1 * and, after re-orientation by an anti-clockwise
0 . 0 4.4

rotation by 120, 4.4 2 . 2 , which is the same 2M polytype, just with another choice of
1 * 5 * 1
origin on the glide plane.
This example is instructive: from a pair of packet triples which are enantiomorphous
to each other, we obtain, in general, three non-congruent MDO polytypes. Two of them,
generated by first-sort operations, contain only packet triples of the one or of the other
kind, and these two polytypes form an enantiomorphous pair. The third polytype,
generated by second-sort operations, contains both kinds of packet triples, regularly
alternating, and it is thus obtained twice in the process of the derivation of MDO
184 Nespolo&urovi

polytypes. Thus, for the meso-octahedral micas of the subfamily A we have obtained the
three known MDO polytypes constructed by M1 layers: 1M, 2M1 and 3T. The subfamily
B is handled in the same way, yielding MDO polytypes 2O, 2M2 and 6H containing M1
layers.
The derivation of MDO polytypes containing M2 layers is in principle the same;
there is just a circumstance that not all the 02-operations constructed mechanically are
suitable as MDO-generating operations. These details, however, are outside the scope of
this paper and the reader should consult Backhaus and urovi (1984). The list of all
homo-, meso- and hetero-octahedral MDO polytypes can be found in Table 7, in context
with relations of homomorphy described below.
As shown above, whereas monoclinic and orthorhombic polytypes have to be
oriented according to the crystallographic conventions, this is irrelevant for orthogonal
polytypes of the triclinic, trigonal and hexagonal syngonies. Thus, e.g., the symbol for the
3T polytype is equally good in any of the six possible orientations. In general: any of
the mutually congruent strings of characters describe the same polytype.
The symmetry analysis from a polytype symbol
The two meso-octahedral MDO polytypes derived in the previous section is now
used to demonstrate a reverse procedure: to read-out the local and global symmetry
from the descriptive symbol. The permanent use of Table 5a (or Table 5b, if Z symbols
are to be analyzed) is not emphasized at every step. Before starting such a task, we must
check the formal correctness of a symbol: the parity of any displacement character must
be opposite to that of the two orientational characters above it which, in turn, must have
the same parity. Also the rule T2j + T2j+1 = v2j,2j+1 must be observed. Otherwise, the
symbol is wrong.
Let us take an extended (more than one identity period) string of characters
corresponding to the 3T polytype, which has six packets within the identity period:
...2 . 2 4.4 0 . 0 2 . 2 4.4 0 . 0 2 . 2...
5 * 1 * 3 * 5 * 1 * 3 * 5

-operations. Evidently, 02[3-1] is the only global non-trivial -operation because it


converts any packet p or q into p+2 or q+2. In addition, there is a trivial 06-operation: a
translation by the identity period (and its multiples, of course). The global 04[31] is a
consequence. Other -operations are only local. The three packet pairs 03. 0 , 25. 2 and 4.4 1
have [. . . (.) . . m], [. . . (.) . m .] and [. . . (.) m . .] respectively as local operations
converting each of the packet pair into itself, but these operations do not hold for the
neighboring packets. There are also other local -operations. For example, the 02-glide
reflection isogonal with [. . . (.) m . .], which is the MDO-generating (global) operation
for the polytype 2M1 (see above), has only local character in the 3T polytype.
operations. Within the packet pair 03. 0 there are two operations 01[1] and
01[. . . (.) . . 2]. The latter converts not only 00, 24, and 42 (i.e. it mutually
converts the two neighboring packet pairs), but also the entire string of characters into
itself. Thus, this two-fold rotation is global. Similar statements hold for all two-fold
rotations converting any p2j into q2j+1. And analogous results are obtained also for all two-
fold rotations converting q2j+1 into p2j+2, i.e. those, operating across the interlayer e.g.,
12[. . . (.) 2 . .] converts 02, 20, 44, etc., for the entire string. All of the two-fold
axes are in the inter-axial directions so that the space-group type is P3212.
CrystallographicBasisofPolytypismandTwinninginMicas 185

The inversions valid for each packet pair p2j q2j+1 are only local operations. If a string
of characters corresponds to a centrosymmetric polytype, then this string, starting and
ending with the same character(s), read forwards and backwards, must remain the same.
This is not the case in polytype 3T.
Let us now consider the meso-octahedral MDO polytype 2M1 derived above, already
in the standard orientation 4.4 2 . 2 . The only non-trivial -operation here is the glide
1 * 5 *
operation isogonal with [. . . (.) . . m], the local mirror reflections hold only for individual
M1 layers as in the previous case, and also other -operations are local. On the other
hand, this polytype is centrosymmetric. This becomes evident if we write down an
extended string of characters so that it will contain an odd number of packet pairs pq.

... 4.4 2 . 2 4.4 2 . 2 4.4 2 . 2 4.4 ...


1 * 5 * 1 * 5 * 1 * 5 * 1

This symbolism remains the same when read forwards and backwards. In a way
similar to the above, also all the two-fold rotations [. . . (.) . . 2] can convert any q2j+1 into
p2j+2 and are global: 24, 42 51, 15. The other two-fold rotations, converting any
p2j into q2j+1, remain local. The space-group type of this polytype is thus C12/c1, taking
into account the C-centering with respect to the orthogonal axes a, b.
As an example of a polytype containing also M2 layers, we consider the meso-
octahedral polytype identified by the OD symbol |2.4 0.0| (Z symbol 420660). The
extended string of characters containing an odd number of packet pairs is:
... 2 . 4 0 . 0 2 . 4 0 . 0 2 . 4 0 . 0 2 . 4 ...
3 * 3 * 3 * 3 * 3 * 3 * 3

from which it clearly appears that the polytype is non-centrosymmetric. The only global
-operation is the trivial 04 translation (and its multiples) corresponding to the identity
2.4
period. The packet pair 3 has no local -operations, but 01[(.)..2] 2[010] as a local -
operation. The -symmetry is C12(1) and the pair of packets corresponds to an M2 layer.
0.0
Instead, as seen in the example of 3T, the packet pair 3 has [(.)..m] m(010) as a local
-operation, and 23[1] and 23[. . . (.) . . 2] 2[010] as local -operations. The -symmetry is
C12/m(1) and the pair of packets corresponds to a M1 layer. The only global -operation
for the polytype is [. . .(.) . . 2] 2[010] located at both the Oc layers. The space-group type
is C2.
The complete analysis for the 8 meso-octahedral polytypes of Class a with period up
to 2 layers is given in Table 8.
186

Table 7. Relation of homomorphy between MDO polytypes of micas. Shortened (non-redundant) OD symbols are given for hetero-octahedral polytypes only: for
enantiomorphous polytypes, they are shown in parentheses [the packet pair ij is enantiomorphous of (-i)(-j), where the orientational characters are expressed
mod 6]. Modified after Durovic et al (1984).
subfamily A subfamily B
Homomorphous
Ramsdell OD symbol Ramsdell OD symbol
MDO group
symbol Homo Meso Hetero symbol Homo Meso Hetero
3.3 |33| (|33|) 3.3 0.0 |33 00|
0 * |00 00| 0 * 3 * |33 00| (|33 00|)
u.u 5.1 1.5 |51| (|15|) u.u e.e 1.5 2.4 |15 24|
I 1M 0 * 0 * 2O 0 * 3 * 0 * 3 *
0 * |51| (|15|) |15 24|
2.4 4.2
|24 42| 5.1 2.4 1.5 4.2 |51 24| (|15 42|)
3 * 3 * |24 42| 0 * 3 * 0 * 3 * |51 24| (|15 42|)

4.4 2.2
1 * 5 *
|44 22|
e.e e.e
II 2M1
1 * 5 * |02 04|
Non-MDO
|02 04|
2.2 1.1
5 * 4 *
|22 11|
e.e u.u
III 2M2 5 * 4 *
|40 53|
Non-MDO
|40 43|
0. 0 4.4 2 . 2 |00 44 22| (|00 22 44|)
3 * 1 * 5 * |00 44 22| (|00 22 44|)
Nespolo & urovi

0. 0 2. 2 4.4 |00 22 44 00 22 22 44|


3 * 5 * 1 * (|00 44 22 00 44 22|)

4. 2 2.0 0. 4 |42 20 04| (|24 40 02|)
e. e e.e e. e 3 * 1 * 5 *

3 * 1 * 5 * 2. 4 4. 0 0.2 |42 20 04| (|24 40 02|)


3 * 5 * 1 *
IV 3T
e. e e. e e.e
2. 4 0.2 4. 0 |24 02 40| (|42 04 20|)
3 * 5 * 1 *
3 * 1 * 5 *

4. 2 0. 4 2.0 |24 02 40| (|42 04 20|)


3 * 5 * 1 *

|42 40 20 24 04 02|
(|24 20 40 42 02 04|)
Non-MDO
|24 04 02 42 40 20|
(|42 02 04 24 20 40|)
Table 7 (continued).
subfamily A subfamily B
Homomorphic
Ramsdell OD symbol Ramsdell OD symbol
MDO group
symbol Homo Meso Hetero symbol Homo Meso Hetero
|00 55 44 33 22 11|
0 . 0 5 . 5 4.4 3 . 3 2 . 2 1 . 1 (|00 11 22 33 44 55|
3 * 2 * 1 * 0 * 5 * 4 *
|00 55 44 33 22 11|
0 . 0 1 . 1 2 . 2 3 . 3 4.4 5 . 5 (|00 11 22 33 44 55|)
3 * 4 * 5 * 0 * 1 * 2 * |00 55 44 33 22 11|

(|00 11 22 33 44 55|
4 . 2 3 . 1 2.0 1 . 5 0 . 4 5 . 3 |42 31 20 15 04 53|
3 * 2 * 1 * 0 * 5 * 4 * (|24 35 40 51 02 13|)
e . e u . u e.e u .u e . e u . u
3 * 2 * 1 * 0 * 5 * 4 * 2 . 4 3 . 5 4 . 0 5 . 1 0.2 1 . 3 |42 31 20 15 04 53|
V 6H 3 * 4 * 5 * 0 * 1 * 2 * (|24 35 40 51 02 13|)
e . e u . u e . e u . u e.e u . u
3 * 4 * 5 * 0 * 1 * 2 * |24 13 02 51 40 35|
2 . 4 1 . 3 0.2 5 . 1 4 . 0 3 . 5
3 * 2 * 1 * 0 * 5 * 4 * (|42 53 04 15 20 31|)
4 . 2 5 . 3 0 . 4 1 . 5 2.0 3 . 1 |24 13 02 51 40 35|
3 * 4 * 5 * 0 * 1 * 2 * (|42 53 04 15 20 31|)

|42 13 20 51 04 35|
(|24 53 40 15 02 31|)
Non-MDO
|24 31 02 15 40 53|
(|42 35 04 51 20 13|)
Crystallographic Basis of Polytypism and Twinning in Micas
187
Table 8. The analysis of the local (see Tables 5a and 5b) and global (see Table 6) symmetry of the eight Class a meso-octahedral polytypes with
188

period up to two layers. For the derivation of the independent polytypes see Backhaus and Durovic (1984) and Zvyagin (1997). The corresponding
Ramsdell symbols apply to the homo-octahedral polytypes obtainable from the relation of homomorphy. The layer groups and space-group types
are given in the Trigonal model: the possibility of symmetry reduction to a subgroup in the real structures should always be taken into account.

OD-Symbol 3 . 3 (#) 5 . 1 (#) 2 . 4 4 . 2 (#) 2.4 0.0 4.4 2 . 2 (#) 0.2 4 . 0 4 . 0 2.0 2.0 2 . 2
(#) = MDO 0 * 0 * 3 * 3 * 3 * 3 * 1 * 5 * 1 * 5 * 5 * 1 * 1 * 5 *
Z-Symbol 330 150 420240 420660 220440 640260 260460 460440
p2nq2n+1 VU-operation 2[010],C1 2[010],C3-1(a) 2[010], 3-1(a) 2[010],C3-1 (a) 2[310],C1 2[310],C3-1(a) 2[C310],C3-1(a) 2[310],C31(a)
p2n W-operation m(010) m(C110) m(C110) m(C110) m(110) m(010) m(110) m(C110)
q2n+1 W-operation m(010) m(110) m(110) m(110) m(110) m(C110) m(010) m(010)
p2nq2n+1 type of layer M1 M2 M2 M2 M1 M2 M2 M2
p2nq2n+1 O-symmetry C12/m(1) C12(1) C12(1) C12(1) C12/m(1) C12(1) C12(1) C12(1)
p2n+2q2n+3 VU-operation 2[010],C31 (a) 2[010],C1 2[C310],C1 2[C310],C3-1(a) 2[310],C31(a) 2[C310],C1
p2n+2 W-operation m(110) m(010) m(C110) m(110) m(C110) m(C110)
q2n+3 W-operation m(C110) m(010) m(C110) m(010) m(010) m(C110)
p2n+2q2n+3 type of layer M2 M1 M1 M2 M2 M1
p2nq2n+1 O-symmetry C12(1) C12/m(1) C12/m(1) C12(1) C12(1) C12/m(1)
Nespolo & urovi

Global U-operation 2[010],C1 2[010] 2[010]C1 2[010] 2[010],C1 2[010] ----- -----
Location p2nq2n+1 p2nq2n+1 p2nq2n+1 (2[010]) p2nq2n+1 q2n-1p2n q2n-1p2n
q2n+1p2n+2 q2n+1p2n+2 p2n+2q2n+3(2[010]) p2n+2q2n+3 q2n+1p2n+2 q2n+1p2n+2
----- -----
q2n-1p2n C(1)
q2n+1p2n+3 C(1)
Global W-operations m(010), 02t 02t c(010), 04t 04t c(010), 04t 04t c(010), 04t 04t

Space-group type C2/m C2 C2/c C2 C2/c C2 Cc C1


(b)
RTW symbol 0 22
C
Ramsdell symbol(b) 1M 2M1
(a)
These V-U operations are coincidence operations (one-way movement) and not local symmetry operations.
(b)
Symbols for the homo-octahedral polytypes homomorphic to the meso-octahedral polytypes listed in this table.
CrystallographicBasisofPolytypismandTwinninginMicas 189

RELATIONS OF HOMOMORPHY AND


CLASSIFICATION OF MDO POLYTYPES

Polytypes are usefully classified not only within the same family, but also between
different families. On the basis of the number of layers and of the parity of the
corresponding characters in the orientational symbols, several meso-octahedral polytypes
can be related to one homo-octahedral polytype; similarly, taking into account the
chirality of the packets, several hetero-octahedral polytypes can be related to one meso-
octahedral polytype. In mathematics, a n 1 relation is a homomorphism, of which the 1
1 relation (isomorphism) is a special case: the n 1 relation of polytypes of different
families is hence termed relations of homomorphy.
The recognition of such relations is also of practical importance. For instance, if
during the refinement of a mica structure the homo-octahedral model fails, only the
choice between the related meso- or hetero-octahedral models has to be made. All such
polytypes have the same framework of all atoms except those octahedrally coordinated.
Therefore, they have identical or very similar basis vectors, and the space-group type of
the homo-octahedral polytype is their common supergroup. Also their diffraction patterns
are closer to one another than to those of other polytypes: the geometry in reciprocal
space is virtually the same and also the distribution of intensities is very similar owing to
the fact that the framework of non-octahedral atoms in an average mica represents
about 70 % of the total diffraction power.
The relations of homomorphy can be easily revealed by analyzing the OD symbols
(urovi et al. 1984):
1) by substituting the primes () or double primes () in the symbols of hetero-
octahedral polytypes with dots (.), the corresponding meso-octahedral polytypes are
obtained;
2) by substituting the Tj orientational characters in the symbols of meso-octahedral
polytypes with e (for even) or u (for uneven), the corresponding homo-
octahedral polytypes are obtained;
3) the relation of homomorphy between hetero- and homo-octahedral polytypes is
obtained by combining steps 1) and 2);
4) some of the hetero-octahedral MDO polytypes are in relation of homomorphy with
non-MDO meso-octahedral polytypes, but the further homomorphy to the homo-
octahedral family yields again MDO polytypes (for details, see urovi et al. 1984).
Note that the relations of homomorphy can, in some cases, make two or more sub-
periods identical although they are different in the original polytype: as a result,
polytypes with a different periodicity can be in homomorphy. As an example, let us
consider the meso-octahedral polytypes of Class a given in Table 8. Of the six 2-layer
polytypes, the following four are homomorphous with the homo-octahedral 2M1
polytype.
4.4 2 . 2 0.2 4 . 0 4 . 0 2.0 2.0 2 . 2
1 * 5 *, 1 * 5 *, 5 * 1 *, 1 * 5 *
In fact, the relation of homomorphy gives for each: e.e e . e , for which the shortened
1* 5 *
symbol is |15|. The other two polytypes ( 23. 4*43. 2* and 23. 4*03. 0* ), however, are
190 Nespolo&urovi

homomorphous with e3. e*e3. e* . In the homo-octahedral family, this polytype has 1-layer
periodicity, with a shortened symbol |3|, and this corresponds to 1M rotated by 180 about
c* (Fig. 11). This apparent reduction of periodicity occurs whenever: 1) the sequence of
v2j,2j+1 displacement vectors of a meso-octahedral polytype contains two or more identical
sub-periods, which are different for T2j.T2j+1 orientations of the packets; 2) the sequence
of T2j.T2j+1 orientation vectors of a hetero-octahedral polytype contains two or more sub-
periods which differ only in the chirality of the packets.
The relations of homomorphy in mica structures are summarized in Table 7. Full
symbols are given for homo-and meso-octahedral polytypes, shortened symbols (the line
of orientational characters) for hetero-octahedral polytypes. The reason for the
somewhat unusual layout of this table is related to the fact that two out of the six homo-
octahedral MDO polytypes, 1M and 2O, have the same projection normal to [010] (YZ
projection). Thus, for the framework of the non-octahedral atoms in the homo-octahedral
MDO polytypes (and also for the corresponding homo-octahedral approximations), there
exist five different YZ projections labeled by Roman numbers I to V in the first column
of Table 7. The significance of the YZ projections will be explained below in the section
Identification of MDO polytypes.
As an example for the relations of homomorphy, let us take the hetero-octahedral
polytype 23' 4*01'2*45' 0* (subfamily A). This polytype is homomorphous to the meso-
octahedral polytype 23. 4*0.2 4 . 0 and this, in turn, is homomorphous to the homo-octahedral
1 * 5 *
polytype 3T e3. e*e1. e*e5. e* : all belong to the MDO group I. The two polytypes in the hetero-
and meso-octahedral families are constructed of M2 layers. However, in the homo-
octahedral family, the distinction between M1 and M2 layers becomes meaningless: the
information about the type of layer is thus lost when applying the relation of
homomorphy down to the homo-octahedral family.
From the examples above it is evident that: 1) the homo-octahedral approximation
corresponds to applying to a polytype the relation of homomorphy; 2) in micas, the
classical Ramsdell notation rigorously applies to homo-octahedral polytypes only.

BASIC STRUCTURES AND POLYTYPOIDS. SIZE LIMIT FOR THE


DEFINITION OF POLYTYPE
The term polytype implies that there is a family of structures to which the polytype
belongs. The original idea of Baumhauer (1912, 1915), who introduced the term
polytypism, was that the individual members of a family consist of identical layers and
differ only in their stacking mode.
Since that time, different views concerning the notion of polytypism were expressed,
but the present official definition recommended by the Ad-hoc Committee on the
Nomenclature of Disordered, Modulated and Polytype Structures (Guinier et al. 1984) is
very close to the original concept of Baumhauer. According to this definition, an
element or compound is polytypic if it occurs in several structural modifications, each of
which can be regarded as built up by stacking layers of (nearly) identical structure and
composition, and if the modifications differ only in their stacking sequence. Polytypism
is a special case of polymorphism: the two-dimensional translations within the layers are
essentially preserved. The Ad-hoc Committee, however, admitted that this definition is
CrystallographicBasisofPolytypismandTwinninginMicas 191

Figure 11. Relation of homomorphy between the two-layer meso-octahedral


2 . 4 4 . 2 polytype (left) and the one-layer homo-octahedral e . e polytype (right),
3 * 3 * 3

illustrated by showing separately the two Oc layers. Solid vectors: packet orientation; dotted
vectors: packet-to-packet displacements. Solid circles and open squares represent two different
average cations. In the meso-octahedral polytype (left), the two Oc layers have the origin in either
of the two cis-sites, where the different average cation is located: they correspond to M2 layers.
The packet orientations, given by the vectors connecting the interlayer/OH sites (overlapped in
projection) to the origin of the Oc layer, are 2 (packets p0 and q3) and 4 (packets q1 and p2). For
both packet pairs, the vector sum (packet-to-packet displacement) is in orientation 3. By applying
the relation of homomorphy, i.e., by making identical the content of the three octahedral cation
sites, and obtaining the corresponding homo-octahedral polytype (right), both layers are
transformed into the type M1, and the packet orientations change into e for both packets. The
packet-to-packet displacements do not change. As a consequence, the two layers in the homo-
octahedral polytype have the same orientational vectors, but the periodicity is halved. The v, now
coinciding with v0,1, corresponds to 3 (acute angle), but can be transformed into 0 (obtuse
angle) by rotating the polytype by 180 about the normal to the layer.
192 Nespolo&urovi

too wide because except for the two-dimensional periodicity of layers it imposes no
restrictions on the sequence and stacking mode of layers.
The fact that the definition is not sufficiently geometric prompted urovi (1999) to
suggest that the layers and their stacking must be limited by the vicinity condition (VC,
see the section Micas as OD structures), and that a family can encompass only those
polytypes which are built on the same structural and symmetry principle, i.e. only those
which belong to the same OD groupoid family. This idea was in principle supported also
by Makovicky (1997) who, at the same time, proposed to distinguish between proper
polytypes, belonging to the same OD groupoid family, and improper polytypes, which
cannot be interpreted as such. Recently, Christiansen et al. (1999) suggested a more
detailed classification concept related to this subject. Makovicky also accepted the term
polytypoids for polytypic substances in which more than 0.25 atoms per formula unit
differ in at least one component as proposed by the IMA-IUCr Joint Committee on
Nomenclature (Bailey et al. 1977). This term was applied also by Bailey (1980b) for the
specific case of micas, and recommended also by the Ad-hoc Committee, as discussed
above.
Abstract polytypes
The experience gathered over years with refined periodic structures of polytypic
substances indicate that, sensu stricto, each such polytype is an individual polymorph
with its own stability field, although the energy differences between polytypes of the
same compounds are very small. This is caused by desymmetrization, i.e. by changes in
the atomic coordinates of individual layers imposed by the influence of the neighboring
layers and it is different for different stacking modes. Thus, even layers in different
polytypes of the same substance are not identical. A prominent example in micas (1M
and 2M1 polytypes of biotite with the same composition) was given by Takeda and Ross
(1975), who not only found significant differences in the constituent layers of the
polytypes but also postulated that these differences are "directly related to the atomic and
geometric constraints imposed by the adjacent unit layers varying with the relative
orientation of the adjacent layers". Desymmetrization occurs even in such less pliable
structures as SiC, as convincingly reported by researchers at the former Leningrad
Electrotechnical Institute (Sorokin et al. 1982a,b; Tsvetkov 1982; see also Tairov and
Tsvetkov 1983) who showed that also the chemical composition (the ratio of Si/C) varies
from polytype to polytype grown under (nearly) the same conditions. If these facts were
taken absolutely at the face value, the notion of polytypism would loose its unifying
significance. In order to overcome these difficulties, the concept of a polytype is often
considered an abstract notion referring to a structural type with relevant geometric
properties, belonging to an abstract family whose members consist of layers with
identical structure and with identical bulk compositions. Such an abstract notion lies at
the root of all systematization and classification schemes of polytypes.
In micas (as well as in many other phyllosilicates) the Pauling model and also the
homo-octahedral approximation are abstractions which are very useful, among others, for
didactic purposes to gain first knowledge, but also for the calculation of identification
diagrams of MDO polytypes, and for the calculation of PID functions, described in
sections about experimental identification of mica polytypes below. A better
approximation, but still an abstraction, is the Trigonal model, which is important for the
explanation of subfamilies and for some features in the diffraction patterns. Also, when
speaking of a specific polytype, a characteristic sequence of abstract mica layers is
intended rather than deviations from stoichiometry, distribution of cations within
octahedral sheets, distortion of coordination polyhedra, etc.
CrystallographicBasisofPolytypismandTwinninginMicas 193

Basic structures
Owing to the fact that the energy difference between polytypes of the same
substance is very small, the occurrence of different polytypes should be influenced
mostly by the kinetics of crystal growth, and the frequency of occurrence of different
polytypes is, in principle, directly related to the number of layers in the period. However,
this statement is contradicted by the existence of a certain degree of structural control
(Smith and Yoder 1956; Gven 1971) that governs the frequency of occurrence of
polytypes as a function of the crystallization environment and of the crystal chemistry. As
firstly noted by Ross et al (1966), a portion of the stacking sequence of the non-MDO
mica polytypes coincides with the stacking sequence of one of the MDO subfamily A
polytypes, similarly to what happens in SiC polytypes. The remaining portion represents
a deviation from the sequence. For this reason, Baronnet and Kang (1989) introduced the
term basic structures to indicate these three MDO polytypes, as well as 2M2 and 1Md-A.
The non-MDO polytypes are thus said to belong to one structural series: the three
structural series 1M, 2M1 and 3T were defined (Ross et al. 1966; Baronnet 1978; Takeda
and Ross 1995). A structural series based on 2M2 has not been found, but its existence
cannot be excluded in principle. The causes of the existence of a stacking memory in the
basic structures are not well understood. Energy differences between two polytypes of the
same family are small. However, the real structures are constructed not by layer
archetypes, but by, more or less, desymmetrized layers: the corresponding energy
differences may be sufficient to control the original stacking sequence.
However, also when the crystal chemistry is practically identical, a certain degree of
structural control exists, as shown by the fact that a few polytypes are clearly dominant,
with the others appearing with much lower frequency. A general trend towards a relation
between the formation environment, the crystal chemistry and the polytype frequency
exists also (Nespolo 2001). The three basic structures may thus be not truly polytypic,
even when the crystal chemistry is identical.
HTREM observations and some implications
The application of the High Resolution Transmission Electron Microscopy
(HRTEM) (Iijima and Buseck 1978) has made possible the observation of several
stacking sequences that would not be revealed by other techniques. At the same time,
HRTEM has raised the question of the limits within which an observed stacking sequence
should be considered a polytype. Kogure and Nespolo (1999b) stated that the stacking
sequences revealed by HRTEM observation can be defined as a polytype only when they
are repeated sufficiently to reveal the presence of a memory mechanism reproducing with
regularity the stacking sequence; otherwise, they should rather be considered defects. It is
questionable whether a sequence repeated only three times, like the 22-layer biotite
reported by Konishi and Akai (1990), may be rigorously termed a polytype. In such
cases it is recommended to speak of a sequence corresponding to a certain polytype. In
such cases, we described the form as a sequence corresponding to the polytype XY.
The problem is similar to that of nanocrystals where it is also questionable how many
unit cells are necessary to determine a phase.

IDEAL SPACE-GROUP TYPES OF MICA POLYTYPES AND


DESYMMETRIZATION OF LAYERS IN POLYTYPES
The ideal space-group type of a given polytype can be derived from the stacking
sequence, as described above. However, three kinds of symmetries are required:
194 Nespolo&urovi

1) the stacking symmetry, deduced from the sequence of packet orientations and
displacements, which gives the space-group type in the Trigonal model;
2) the structural symmetry, which may be lower than the stacking symmetry because of
structural distortions not taken into account by the Trigonal model;
3) the diffractional symmetry, which may be higher than the structural symmetry. This
phenomenon is termed diffraction enhancement of symmetry (Ito 1950) and occurs
when a crystal is constructed by substructures whose symmetry is higher than that of
the crystal itself (e.g., Iwasaki 1972; Matsumoto et al. 1974). In micas, diffraction
enhancement of symmetry was observed in the oxybiotite-10A1 from Ruiz Peak,
which gave a monoclinic diffraction pattern, despite both the stacking symmetry and
the structural symmetry were triclinic (Sadanaga and Takeda 1968).
The validity of the local symmetry operations is often only approximate, and the
atomic coordinates can deviate more or less from the values demanded by the
corresponding space groupoid, depending on the stacking of the packets in the
investigated crystal, and this is phenomenon known as desymmetrization (urovi 1979).
The -symmetry of the M layers can thus be lower than the -symmetry of the layer
archetypes described by the Trigonal model (see Table 2 in Ferraris and Ivaldi, this
volume). The space-group type corresponding to the stacking symmetry in general does
not require the highest -symmetry compatible with the family (homo-, meso- or hetero-
octahedral) and the type of layer (M1 vs. M2). The layer is thus allowed, although not
required, to attain a layer-subgroup. The general trend that results from the structure
refinements performed on mica polytypes can be summarized as follows (see Table 9,
and Tables 1-3 in Brigatti and Guggenheim, this volume):
1) 1M polytype has been refined only in the highest space-group types and layer-groups
compatible with the type of layer: C2/m and C12/m(1) for the M1 layer; C2 and
C12(1) for the M2 layer.
2) The highest space-group type for the 2M1 polytype is C2/c. All but one example of
2M1 polytypes refined so far belong to the meso-octahedral family and are
constructed by M1 layers. Most of these polytypes have been refined in C2/c. This
space-group type allows a desymmetrization of the layer-group to C1, which
corresponds to the -symmetry normally obtained in 2M1 polytypes (Gven 1971;
Zussman 1979; Takeda and Ross 1975). An important exception is oxybiotite-2M1
refined by Ohta et al (1982), where the highest -symmetry C12/m(1) was observed
within experimental erro; this was also the -symmetry of coexisting oxybiotite-1M
(Ohta et al. 1982). Three studies of meso-octahedral margarite-2M1 refined in the
space-group type Cc have been reported (Guggenheim and Bailey 1975, 1978;
Joswig et al 1983; Kassner et al. 1993), where the reduction of symmetry was related
to the Si-Al ordering, that made the two T sheets no longer equivalent. The layer
group is only C1, because of the destruction of the center of symmetry. A further
reduction of symmetry was observed in the ephesite-2M1 reported by Slade et al.

Table 9 (next nine ap ges ). Relevant properties of the MDO polytypes. Only polytypes for which
the ccupancies of the octahedral sites were given in the original papers are reported. Following
Durovic et al (1984), the effective scattering amplitude is taken directly from the original papers,
when reported; otherwise it has been calculated assuming half-ionized atoms, even where the
structure was refined using electron or neutron diffraction data. Polytypes built by M2 layers are in
bold characters. References are given according to the sequence numbers in the tables of the Brigatti
and Guggenheim chapter. For polytypes not reported there, the complete reference is given. (e) =
electron diffraction data; (n) = neutron diffraction data; otherwise X-ray diffraction data.
Crystallographic Basis of Polytypism and Twinning in Micas 195

Reference Type of mica R factor Space- G(M1) G(M2) G(M3) Full


group polytype
type symbol

Subfamily A 1M polytype
Homo-trioctahedral
u .u
1-95 Phlogopite 13.1 C2/m 11.0 11.0 11.0 0 *
u .u
1-61 Synthetic iron mica 9.3 C2/m 25.0 25.0 25.0 0 *
Synthetic lithian u .u
1-97 7.3 C2/m 10.4 10.4 10.4 0 *
flourphlogopite
u .u
3-15 Barium mica 7.1 C2/m 8.8 8.8 8.8 0 *
u .u
1-70 Phlogopite (n) 2.0 C2/m 11.7 11.7 11.7 0 *
u .u
1-97 Phlogopite 4.1 C2/m 11.0 11.0 11.0 0 *
u .u
1-72 Fluorophlogopite 6.1 C2/m 11.0 11.0 11.0 0 *
u .u
1-86 Phlogopite (n) 6.6 C2/m 11.9 11.9 11.9 0 *
u .u
1-98 Fluro phlogopite 4.3 C2/m 11.0 11.0 11.0 0 *
u .u
1-104 Synthethic fluormica 3.8 C2/m 9.4 9.4 9.4 0 *
u .u
1-94 Tetraferriphlogopite 4.2 C2/m 10.5 10.5 10.5 0 *
u .u
1-108 Fluoro phlogopite 2.9 C2/m 10.2 10.2 10.2 0 *
Tetra germanatian u .u
1.108 3.7 C2/m 11.0 11.0 11.0 0 *
fluoro phlogopite
Silica- and
u .u
1-69 alkali-rich 3.0 C2/m 10.6 10.6 10.6 0 *
trioctahedral mica
u .u
1-103 Germanate mica 3.9 C2/m 14.0 14.0 14.0 0 *
u .u
1-102 Germanate mica 5.0 C2/m 19.5 19.5 19.5 0 *
u .u
1-110 Fluoro phlogopite 4.3 C2/m 10.8 10.8 10.8 0 *
Knurr and Bailey u .u
Phlogopite 3.1 C2/m 12.1 12.1 12.1 0 *
(1986)
Potassium u .u
3-7 2.5 C2/m 13.4 13.4 13.4 0 *
Kinoshitalite (27)
u .u
1-82 Cs-ferriannite 5.5 C2/m 25.0 25.0 25.0 0 *
Magnesian annite u .u
1-45 3.9 C2/m 19.9 19.9 19.9 0 *
(WA8E)
u .u
1-60 Cs-tetra-ferri-annite 3.9 C2/m 25.0 25.0 25.0 0 *
196 Nespolo & urovi

u .u
1-87/92 Ferroan phologopite 3.9 C2/m 17.2 17.2 17.2 0 *
u .u
3-9 Ferrokinoshitalite 3.2 C2/m 20.0 20.0 20.0 0 *
u .u
3-8 Kinoshitalite 3.35 C2/m 12.0 12.0 12.0 0 *
Meso-trioctahedral
Takuchi and 3.3
Xantophyllite 10.8 C2/m 11.3 11.0 11.0 0 *
Sadanaga (1966)
Synthethic 3.3
1-96 5.1 C2/m 3.5 6.6 6.6 0 *
fluor-polylithionite
3.3
1-66 Annite 4.4 C2/m 22.6 22.7 22.7 0 *
3.3
1-100 Synthetic MgIV mica 9.2 C2/m 10.7 10.1 10.1 0 *
3.3
1-99 Biotite 4.4 C2/m 16.2 16.0 16.0 0 *
3.3
1-93 Lepidolite 6.7 C2/m 3.0 8.2 8.2 0 *
3.3
1-105 Taeniolite 2.4 C2/m 8.5 8.1 8.1 0 *
3.3
1-107 Germanate mica 3.8 C2/m 7.9 8.3 8.3 0 *
3.3
1-106 Germanate mica 5.5 C2/m 6.6 10.5 10.5 0 *
Sokolova et al 3.3
Ephesite 11.5 C2/m 3.2 11.4 11.4 0 *
(1979)
3.3
1-62 Lepidolite 3.5 C2/m 3.6 8.2 8.2 0 *
5.1
1-128 Lepidolite 6.2 C2 4.7 10.1 4.7 0 *
3.3
1-85 Oxybiotite 4.4 C2/m 12.6 15.2 15.2 0 *
Manganoan 3.3
1-63 5.4 C2/m 15.2 16.1 16.1 0 *
phlogopite (1)
Barian manganoan 3.3
1-64 3.8 C2/m 12.6 14.9 14.9 0 *
phlogopite (5)
3.3
3-10 Clintonite (n) 2.0 C2/m 11.8 11.2 11.2 0 *
3.3
3-12 Clintonite (1782/5) 2.1 C2/m 12.1 11.2 11.2 0 *
3.3
3-13 Clintonite (94594) 3.9 C2/m 11.6+ 11.6- 11.6- 0 *
3.3
3-14 Clintonite (105455) 2.1 C2/m 11.5 11.2 11.2 0 *
Ferroan phologopite 3.3
1-8 3.3 C2/m 18.6 17.8 17.8 0 *
(M14)
Ferroan phologopite 3.3
1-9 2.4 C2/m 17.9 17.1 17.1 0 *
(M32)
Ferroan phologopite 3.3
1-12 6.2 C2/m 20.4 19.8 19.8 0 *
(M13)
Crystallographic Basis of Polytypism and Twinning in Micas 197

Ferroan phologopite 3.3


1-11 2.1 C2/m 19.0 18.2 18.2 0 *
(M73)
Ferroan phologopite 3.3
1-10 3.5 C2/m 20.4 19.6 19.6 0 *
(M62)
3.3
1-111 Norrishite 7.8 C2/m 2.5 23.3 23.3 0 *
Ferroan phlogopite 3.3
1-21 2.5 C2/m 13.9 15.1 15.1 0 *
(8)
3.3
1-22 Phlogopite (9) 2.2 C2/m 13.7 14.0 14.0 0 *
Ferroan phlogopite 3.3
1-23 2.2 C2/m 16.3 16.5 16.5 0 *
(10)
Ferroan phlogopite 3.3
1-24 1.9 C2/m 14.7 16.8 16.8 0 *
(11)
Ferroan phlogopite 3.3
1-25 2.1 C2/m 14.5 16.1 16.1 0 *
(12)
Ferroan phlogopite 3.3
1-26 2.3 C2/m 17.5 17.0 17.0 0 *
(15)
Ferroan phlogopite 3.3
1-27 3.0 C2/m 19.0 18.4 18.4 0 *
(16)
Magnesian annite 3.3
1-28 2.6 C2/m 18.6 18.4 18.4 0 *
(17)
3.3
1-112 Protolithionite 3.8 C2/m 20.2 19.4 19.4 0 *
Magnesian annite 3.3
1-7 3.1 C2/m 18.7 20.2 20.2 0 *
(MP9)
Titanian phlogopite 3.3
1-13 2.0 C2/m 12.9 15.4 15.4 0 *
(18)
Ferroan phlogopite 3.3
1-17 3.2 C2/m 17.6 18.1 18.1 0 *
(19)
Aluminian 3.3
1-14 2.7 C2/m 16.1 16.9 16.9 0 *
phlogopite (20)
Ferrian phlogopite 3.3
1-15 2.3 C2/m 15.3 16.1 16.1 0 *
(21)
Ferroan phlogopite 3.3
1-16 3.3 C2/m 16.3 17.1 17.1 0 *
(22)
Ferrian phlogopite 3.3
1-18 3.4 C2/m 16.2 16.8 16.8 0 *
(23)
Ferrian phlogopite 3.3
1-19 2.7 C2/m 17.1 17.5 17.5 0 *
(24)
Ferroan phlogopite 3.3
1-20 2.2 C2/m 16.6 17.7 17.7 0 *
(25)
Brigatti & Poppi Potassium 3.3
2.6 C2/m 14.3 13.3 13.3 0 *
(1993) kinoshitalite (26)
3.3
1-6 Biotite 3.33 C2/m 19.0 18.1 18.1 0 *
3.3
1-1 Phlogopite (1a) 2.9 C2/m 13.2 12.9 12.9 0 *
3.3
1-2 Phlogopite (1b) 2.8 C2/m 13.4 12.9 12.9 0 *
3.3
1-3 Phlogopite (2a) 2.9 C2/m 13.2 12.9 12.9 0 *
198 Nespolo & urovi

Aluminian 3.3
1-4 3.0 C2/m 13.3(1) 13.2(1) 13.2(1) 0 *
phlogopite (3a)
3.3
1-5 Phlogopite (4a) 2.5 C2/m 13.0 12.7 12.7 0 *
Phlogopite 3.3
1-36 2.8 C2/m 14.0 13.1 13.0 0 *
(Tas27-2Ba)
Phlogopite 3.3
1-37 2.5 C2/m 13.7 13.3 13.3 0 *
(Tas27-2Bb)
Ferroan phlogopite 3.3
1-38 2.8 C2/m 15.7 15.6 15.6 0 *
(Tag15-4)
Phlogopite 3.3
1-39 2.8 C2/m 14.9 14.8 14.8 0 *
(Tag15-3)
Ferroan phlogopite 3.3
1-32 2.3 C2/m 16.8 16.5 16.5 0 *
(Tpg63-2B)
Phlogopite 3.3
1-29 2.7 C2/m 13.4 13.3 13.3 0 *
(Tae23-1a)
Phlogopite 3.3
1-30 2.7 C2/m 13.5 13.5 13.5 0 *
(Tae23-1b)
Phlogopite 3.3
1-31 3.0 C2/m 14.0 13.7 13.7 0 *
(Tae23-1c)
Phlogopite 3.3
1-40 2.8 C2/m 13.8 13.6 13.6 0 *
(Tpq16-4A)
Phlogopite 3.3
1-35 2.8 C2/m 13.8 13.4 13.4 0 *
(Tpt17-1)
Tetra-ferri
3.3
1-33 phlogopite 3.2 C2/m 12.9 12.8 12.8 0 *
(Tas22-1a)
Tetra-ferri
3.3
1-34 phlogopite 3.3 C2/m 13.9 13.1 13.1 0 *
(Tas22-1b)
Tetra-ferri
3.3
1-41 phlogopite 3.1 C2/m 14.6 13.8 13.8 0 *
(Tpq16-6B)
Tetra-ferri 3.3
1-42 3.1 C2/m 13.5 13.1 13.1 0 *
phlogopite (S1)
1-43 Tetra-ferri 3.3
2.5 C2/m 13.8 13.5 13.5 0 *
phlogopite (S2)
Brigatti et al Ferroan phlogopite 3.3
2.8 C2/m 15.7 15.6 15.6 0 *
(1997) (Tag15-4a)
1-48 Ferroan phlogopite 3.3
2.8 C2/m 15.2 15.4 15.4 0 *
(Tag15-4b)
Ferroan phlogopite 3.3
1-49 2.8 C2/m 13.8 13.6 13.6 0 *
(Tpq16-4Aa)
1-50 Ferroan phlogopite 3.3
2.4 C2/m 13.7 13.4 13.4 0 *
(Tpq16-4Ab)
Brigatti et al Ferroan phlogopite 3.3
3.0 C2/m 15.9 15.3 15.3 0 *
(1997) (Tpq16-4Ac)
Brigatti et al Ferroan phlogopite 3.3
3.1 C2/m 13.5 13.1 13.1 0 *
(1997) (Tas22-1c)
3.3
3-1 Clintonite (5a) 3.49 C2/m 13.0 12.6 12.6 0 *
3.3
3-2 Clintonite (7c) 3.73 C2/m 13.4 13.3 13.3 0 *
Crystallographic Basis of Polytypism and Twinning in Micas 199

3.3
3-3 Clintonite (8a) 3.11 C2/m 13.2 12.9 12.9 0 *
3.3
3-4 Clintonite (8d) 3.18 C2/m 12.7 13.0 13.0 0 *
3.3
3-5 Clintonite (9a) 3.29 C2/m 13.0 13.1 13.1 0 *
3.3
3-6 Clintonite (9b) 2.70 C2/m 12.6 13.0 13.0 0 *
rubidian cesian 3.3
1-65 4.5 C2/m 16.0 15.8 15.8 0 *
phlogopite
Ferroan phlogopite 3.3
1-44 2.9 C2/m 18.3 18.2 18.2 0 *
(WA3H)
Magnesian annite 3.3
1-46 3.3 C2/m 19.6 19.3 19.3 0 *
(WA8H)
Ferroan phlogopite 3.3
1-47 2.8 C2/m 18.8 18.6 18.6 0 *
(WA23E)
3.3
1-51 Magnesian annite 3.2 C2/m 19.6 18.9 18.9 0 *
3.3
1-55 Magnesian annite 3.6 C2/m 19.1 18.2 18.2 0 *
3.3
1-56 Magnesian annite 3.2 C2/m 19.6 18.8 18.8 0 *
3.3
1-54 Magnesian annite 3.2 C2/m 19.4 18.5 18.5 0 *
3.3
1-53 Magnesian annite 3.1 C2/m 19.9 19.6 19.6 0 *
3.3
1-52 Magnesian annite 3.7 C2/m 19.8 19.2 19.2 0 *
3.3
1-58 Fe-Li rich mica 26 3.3 C2/m 19.6 22.3 22.3 0 *
3.3
1-59 Fe-Li rich mica 33 3.6 C2/m 23.5 239 23.9 0 *
3.3
1-57 Fe-Li rich mica 120 2.6 C2/m 24.7 24.4 24.4 0 *
Fe-Li rich mica 5.1
1-118 3.86 C2 12.7 13.0 12.7 0 *
130(2)
Hetero-trioctahedral
5'1
1-129 Zinnwaldite 5.7 C2 15.0 11.5 13.5 0 *
3'3
1-113 Lepidolite 7.3 C2 3.7 11.4 11.5 0 *
Zhukhlistov et al 3"3
Li-Fe phengite (e) 10.2 C2 8.0 15.1 14.8 0 *
(1983)
1'5
1-130 Masutomilite 4.6 C2 8.5 11.1 8.1 0 *
Fe-Li rich mica 5'1
1-117 2.96 C2 13.5 12.6 12.8 0 *
130(1)
Fe-Li rich mica 5'1
1-123 2.89 C2 13.8 13.0 13.6 0 *
140(1)
Fe-Li rich mica 5"1
1-124 2.73 C2 13.3 12.4 13.7 0 *
140(2)
200 Nespolo & urovi

1'5
1-120 Fe-Li rich mica 104 3.34 C2 12.0 12.1 11.8 0 *
1'5
1-119 Fe-Li rich mica 137 3.63 C2 13.0 13.0 11.3 0 *
5'1
1-122 Fe-Li rich mica 177 3.39 C2 13.8 12.7 12.8 0 *
5"1
1-121 Fe-Li rich mica 54b 3.78 C2 11.9 11.6 13.0 0 *
5'1
1-125 Fe-Li rich mica 24 3.72 C2 14.2 12.3 13.0 0 *
1'5
1-115 Fe-Li rich mica 55a 3.74 C2 11.3 12.0 9.4 0 *
1'5
1-116 Fe-Li rich mica 55b 3.21 C2 11.3 13.0 9.9 0 *
5"1
1-126 Fe-Li rich mica 47 3.31 C2 19.2 15.8 19.4 0 *
5"1
1-127 Fe-Li rich mica 103 3.63 C2 16.0 14.3 17.6 0 *
5"1
1-114 Fe-Li rich mica 114 3.35 C2 10.2 8.5 12.2 0 *
Meso-dioctahedral
Ferrous celadonite 3.3
2-3 10.8 C2/m --- 21.4 21.4 0 *
(e)
3.3
2-2 Paragonite (e) 12.1 C2/m --- 10.8 10.8 0 *
3.3
4-1 Boromuscovite 3.8 C2/m --- 12.5 12.5 0 *
Hetero-dioctahedral
Dioctahedral mica 3"3
2-1 10.9 C2 --- 12.8 11.5 0 *
(e)
Subfamily B 2O polytype
Homo-trioctahedral
Ferraris et al u .u e.e
Fluor-phlogopite 4.5 Ccmm 12.8 12.8 12.8 0 * 3 *
(2000)
Meso-trioctahedral
3.3 0.0
3-17 Anandite* 6.1 Pnmn 0 * 3 *
3.3 0.0
3-18 Anandite* 6.4 Pnmn 0 * 3 *
Subfamily A 2M1 polytype
Meso-trioctahedral
4.4 2 . 2
1-139 Biotite 5.6 C2/c 15.8 16.3 16.3 1 * 5 *
4.4 2 . 2
Sartori (1977) Lepidolite 11.3 C2/c 2.3 8.7 8.7 1 * 5 *
Sokolova et al 4.4 2 . 2
Bityite (e) 11.5 C2/c 2.3 8.7 8.7 1 * 5 *
(1979)
4.4 2 . 2
1-135 Magnesian annite 4.2 C2/c 19.4 18.6 18.6 1 * 5 *
4.4 2 . 2
1-138 Lepidolite 9.1 C2/c 3.6 7.5 7.5 1 * 5 *
Crystallographic Basis of Polytypism and Twinning in Micas 201

4.4 2 . 2
1-137 Oxybiotite 3.9 C2/c 12.6 15.2 15.2 1 * 5 *
4.4 2 . 2
3-76 Li-Be rich mica 3.0 Cc 1.1 11.5 11.5 1 * 5 *
4.4 2 . 2
1-141 Ephesite 4.7 C1 2.9 11.5 11.5 1 * 5 *
Magnesian annite 4.4 2 . 2
1-132 3.7 C2/c 20.8 20.1 20.1 1 * 5 *
(MP16)
Magnesian annite 4.4 2 . 2
1-133 2.7 C2/c 17.5 16.8 16.8 1 * 5 *
(MP17a)
Magnesian annite 4.4 2 . 2
1-134 3.4 C2/c 17.2 16.6 16.6 1 * 5 *
(MP17b)
4.4 2 . 2
1-131 Biotite 2.72 C2/c 18.8 18.3 18.3 1 * 5 *
4.4 2 . 2
1-136 Magnesian annite 2.8 C2/c 19.4 18.4 18.4 1 * 5 *
Hetero-trioctahedral
0"2 0 ' 4
1-140 Zinnwaldite 5.8 Cc 16.2 14.3 17.4 1 * 5 *
Meso-dioctahedral
Radoslovich 4.4 2 . 2
Muscovite 17.0 C2/c --- 12.3 12.3 1 * 5 *
(1960)
4.4 2 . 2
Takuchi (1965) Margarite 16.8 C2/c --- 11.5 11.5 1 * 5 *
4.4 2 . 2
2-4 Muscovite 12.8 C2/c --- 12.3 12.3 1 * 5 *
4.4 2 . 2
2-36 Muscovite 3.5 C2/c --- 11.8 11.8 1 * 5 *
4.4 2 . 2
2-37 Phengite 4.5 C2/c --- 12.3 12.3 1 * 5 *
4.4 2 . 2
2-46 Muscovite (n) 2.7 C2/c --- 12.3 12.3 1 * 5 *
Udagawa et al 4.4 2 . 2
Muscovite 14.2 C2/c --- 12.3 12.3 1 * 5 *
(1974)
4.4 2 . 2
3-19 Margarite 4.0 Cc --- 11.5 11.5 1 * 5 *
Sidorenko et al 4.4 2 . 2
Paragonite (e) 11.1 C2/c --- 11.6 11.6 1 * 5 *
(1977a)
4.4 2 . 2
2-39 Paragonite 4.5 C2/c --- 11.9 11.9 1 * 5 *
4.4 2 . 2
2-47 Phengite 3.3 C2/c --- 13.2 13.2 1 * 5 *
4.4 2 . 2
2-38 Muscovite 2.7 C2/c --- 12.7 12.7 1 * 5 *
4.8 (LT) 4.4 2 . 2
2-19/20 Muscovite C2/c --- 12.1 12.1 1 * 5 *
6.0 (HT)
4.4 2 . 2
2-21 Muscovite (n) 4.0 C2/c --- 13.4 13.4 1 * 5 *
4.4 2 . 2
4-2 Boromuscovite 3.8 C2/c --- 12.5 12.5 1 * 5 *
4.4 2 . 2
2-30 Chromphyllite 4.8 C2/c --- 19.9 19.9 1 * 5 *
202 Nespolo & urovi

Mg-, Fe-bearing 4.4 2 . 2


2-5 2.54 C2/c 0.64 15.5 15.5 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-6 2.96 C2/c 0.97 13.9 13.9 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-7 3.58 C2/c 0.46 13.5 13.5 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-8 2.92 C2/c 0.44 13.7 13.7 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-9 3.93 C2/c 0.84 15.0 15.0 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-10 2.89 C2/c 0.32 13.8 13.8 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-11 2.78 C2/c 0.49 13.7 13.7 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-12 2.11 C2/c 0.38 13.7 13.7 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-13 3.87 C2/c 1.73 14.0 14.0 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-14 3.12 C2/c 0.88 13.6 13.6 1 * 5 *
muscovite
Mg-, Fe-bearing 4.4 2 . 2
2-15 2.80 C2/c 0.39 13.8 13.8 1 * 5 *
muscovite
4.4 2 . 2
Smyth et al (2000) Phengite 1.3 C2/c --- 11.6 11.6 1 * 5 *
Cr-containing 4.4 2 . 2
2-16 2.5 C2/c 0.1 13.8 13.8 1 * 5 *
muscovite
Cr-containing 4.4 2 . 2
2-17 3.1 C2/c --- 13.8 13.8 1 * 5 *
muscovite
Cr-containing 4.4 2 . 2
2-18 3.3 C2/c 2.1 14.5 14.5 1 * 5 *
muscovite
Subfamily B 2M2 polytype
Meso-trioctahedral
2.2 1.1
1-144 Lepidolite 7.2 C2/c 2.0 8.4 8.4 5 * 4 *
2.2 1.1
1-143 Lepidolite 9.6 C2/c 3.0 8.2 8.2 5 * 4 *
2.2 1.1
1-142 Lepidolite 4.8 C2/c 2.5 8.6 8.6 5 * 4 *
Meso-dioctahedral
Dioctahedral mica 2.2 1.1
2-50 11.7 C2/c --- 11.2 11.2 5 * 4 *
(e)
2.2 1.1
2-49 Nanpingite 5.8 C2/c --- 12.9 12.9 5 * 4 *
Subfamily A 3T polytype
Hetero-trioctahedral
4 ' 2 2 '0 0 ' 4
1-145 Lepidolite 4.7 P3112 5.2 3.4 10.3 3 * 1 * 5 *
Pavlishin et al 2 ' 4 0'2 4 ' 0
Protolithionite 3.8 P3112 18.7 14.3 15.6 3 * 1 * 5 *
(1981)
2"4 0"2 4"0
1-146 Protolithionite 3.0 P3112 16.1 14.4 17.6 3 * 1 * 5 *
Crystallographic Basis of Polytypism and Twinning in Micas 203
Hetero-dioctahedral
0 ' 0 4 '4 2 ' 2
2-53 Muscovite 2.4 P3112 --- 11.5 12.5 3 * 1 * 5 *
0 ' 0 4 '4 2 ' 2
2-54 Paragonite (e) 13.0 P3112 3.4 9.2 10.3 3 * 1 * 5 *
0 ' 0 4 '4 2 ' 2
2-51 Phengite (KZ) 3.6 P3112 --- 13.4 13.7 3 * 1 * 5 *
0 ' 0 4 '4 2 ' 2
2-52 Phengite (DM) 4.5 P3112 --- 12.5 13.0 3 * 1 * 5 *
11.1
Pavese et al 7.0 (LT) (LT) 0"0 4"4 2"2
Phengite (n) P3112 --- 11.5 3 * 1 * 5 *
(1997) 5.0 (HT) 11.2
(HT)
0 ' 0 4 '4 2 ' 2
Smyth et al (2000) Phengite 0.9 P3112 --- 12.7 13.0 3 * 1 * 5 *

*The structure of anandite-2O cannot be described using an orthohexagonal C-centered cell and contains four
independent octahedral positions. The symbol of this polytype is therefore only an approximation.

(1987), where a different Si-Al ordering in the four tetrahedral sites reduced the
space-group type to C1. Only one example of hetero-octahedral 2M1 polytype is
known so far: the zinnwaldite refined by Rieder et al (1996). In the
hetero-octahedral family, the highest layer-group for both M1 and M2 layers is
C12(1): correspondingly, the highest space-group type for 2M1 is Cc, which is
realized in this zinnwaldite-2M1. This mica is built up by M2 layers, with local V-U
operations 2[310] and 2[C310] for the two layers respectively, as can be easily confirmed
by analyzing the OD symbols (Table 9) on the basis of the conversion rules given in
Table 5a.
3) The highest space-group type for the 3T polytype is P31,212, which is compatible
with the highest layer groups in all the three families, namely C12/m(1) (homo- and
meso-octahedral) and C12(1) (hetero-octahedral). We are aware of nine structure
refinements of 3T polytypes in which the composition of the O sheet was given. All
belong to the hetero-octahedral family, and three of them wereconstructed up by M2
layers. Refinement of meso-octahedral 3T polytypes is desirable to investigate (a)
the desymmetrization of the layer group in this polytype; (b) the frequency of
occurrence of M2 layers that, at least in Li-rich micas, seems higher than in other
polytypes.
4) The highest space-group type for the 2M2 polytype is C2/c, the same as 2M1.
All the polytypes refined so far have this symmetry.
5) The polytype 2O has ideal space-group type Ccmm, which was reported only
recently in a fluor-phlogopite from the Khibiny massif (Kola Peninsula, Russia)
(Ferraris et al 2000). Previously, two examples were reported in anandite
(Giuseppetti and Tadini 1972; Filut et al. 1985), where however an unusual crystal
chemistry, including tetrahedral Fe3+ and octahedral S2- and Cl-, reduced the
space-group type to Pnmn, with some indications of further reduction to P21. The
anandite-2O cannot be described with the orthohexagonal C-centered cell and
contains four independent octahedral positions, two of which are on mirror planes.
The symbols given in Table 9 for anandite-2O are thus only a rough approximation.

In C2/c and P31,212 space-group types there are two independent T sites and the two
independent M2/M3 sites. The possibility of cation ordering exists in these groups, and it
is often verified in the O sheet, but more rarely in the T sheets (Bailey 1975; 1984;
Amisano-Canesi et al. 1994; see also the examples of margarite and ephesite given
above). If the O-symmetry C12/m(1) is maintained no ordering occurs, although it is not
204 Nespolo&urovi

prevented by the space-group type. Thus, this is an example of local symmetry being
higher than that required by the global symmetry. As shown by Gven (1971) and by
Zussman (1979), the symmetry in the interlayer is different also, which is 1 in C12/m(1)
-symmetry and 2[010] in C1 and C12(1) -symmetries (for details see Ferraris and Ivaldi,
this volume).

CHOICE OF THE AXIAL SETTING


A non-orthogonal mica polytype forms, besides the conventional (double)
monoclinic C-centered cell, both a pseudo-orthorhombic C-centered sextuple cell and a
pseudo-hexagonal P triple cell. For hexagonal and trigonal polytypes (|| = = 0) the
triple cell is rigorously hexagonal. For all others, the orthohexagonal relation b = a31/2 is
obeyed only approximately, the deviation being measured either by an angular parameter
(Donnay et al. 1964) or by a linear parameter (Zvyagin and Drits 1996), which is a
function of || (Fig. 12). For metrically monoclinic polytypes, (Class a) or (Class b)
of the sextuple and triple cells are in general only close to 90.

Figure 12. A small portion of the (001) two-dimensional hp lattice of micas. and
(exaggerated) are the angular and linear deviations from hexagonality. A1, A2: hexagonal
axes ( = 0. = 0); aH, bH: orthohexagonal axes ( = 0. = 0) of the C1 cell (bH = aH31/2);
a, b: pseudo-orthohexagonal axes ( 0. 0). The figure is drawn for the case b > bH.
Black circles: lattice nodes of the crystal lattice; dashed lines: H cell of the twin lattice;
dotted lines: C1 cell built on the hexagonal and pseudo-hexagonal meshes (modified after
Nespolo et al. 2000a).

The monoclinic setting in which, within the Trigonal model, cn is constant and the
value of the monoclinic angle changes with the number of layers is labeled aS [Class a: cn
= (1/3, 0); S stands for Standard] and bT [Class b: cn = (0,1/3); T stands for
Transitional]. The corresponding monoclinic l indices are labeled laS and lbT (Nespolo et
al. 1997a). The metric equations in both direct and reciprocal space and the relations
between l and h, k indices are given in Table 10. The bT setting is monoclinic a-unique
CrystallographicBasisofPolytypismandTwinninginMicas 205

and does not correspond to any of the settings commonly adopted to describe monoclinic
crystals. Nevertheless, it facilitates the comparison of the atomic coordinates with other
polytypes (Backhaus and urovi 1984) and is thus the preferred setting to derive the
family structure from a single polytype or vice versa. From bT a monoclinic b-unique
setting is obtained through the exchange of axes by a -b; b -a; c -c, so that a > b
and > 90, as in the Smith and Yoder (1956) definition: this setting is labeled bS (Fig.
13). The exchange of axes is adopted when indexing the diffraction pattern (Nespolo et
al. 1998; see also Takeda and Ross 1995).

Figure 13. Definition of the aS, bT and bS axial settings of mica polytypes.
a
S and bS settings have a < b, bT setting has b < a [used by permission of
the editor of Mineralogical Journal, from Nespolo (1999) Fig. 2, p. 56].

For each Series and each Class, K = 0 of the Subclass 1, see Equation (2), determines
the axial setting of the first polytype of the Series, which is termed the Basic axial setting.
All the polytypes belonging to the same Series and the same Class can be indexed in a
setting whose axes are parallel to the axes of the Basic axial setting but whose period
along c is 3K+L [Eqn. (2)] times the corresponding period of the Basic axial setting. For
each Series the angle is constant, within the Trigonal model, and the value of cn, non-
translationally reduced, changes with the number of layers: this nsetting is ntermed Fixed-
angle setting. For the two Classes this setting is symbolized by 3 ,aF and 3 ,bF, which for
206 Nespolo&urovi

Series 0 are shortened in aF and bF (Nespolo et al. 1997a; 1998) (Fig. 14). This setting is
obtained from aS and bS by means of the transformation:

Tables - 21
( 1) L 1 0 ( 1) ( K + L 1)
L


( a b c ) 3n ,a ;3n ,b S 0 ( 1) = ( a b c ) 3n ,a ;3n ,b F
L 1
0 (3)

0 0 1

Table 10. Metric equation in direct and reciprocal space and relation between Miller indices orthogonal and monoclinic settings for the

relation between orthogonal and

where L (Subclass) and K are defined in Equation (2). The


monoclinic l indices

choice of a common setting for polytypes belonging to


laS. = (lC1 h)/3

lbT = (lC1 k)/3

different Series is instead geometrically not possible,


because these polytypes are not based on the same Basic
axial setting (Fig. 14).

GEOMETRICAL CLASSIFICATION OF
RECIPROCAL LATTICE ROWS
By considering the lC1 (mod 3) index of reciprocal
lattice nodes (Table 10) on rows related by n60 rotations
(0 n 5), Nespolo et al (1997b, 2000a) have shown that
relation between lC1 and h, k indices

there are only nine translationally independent rows


parallel to c* (Fig. 15) indicated as Ri, 1 i 9. In each Ri
the same distribution of "present" and "absent" reflections
lC1 = h(mod 3)

lC1 = k(mod 3)

is repeated along a* and b* with 3p and 3q translations (p


and q are integers of the same parity). Ri are defined in
terms of h and k as: [hi(mod 3), ki(mod 3), l] and are
distributed along the edges and diagonals of a rhombus-
shaped unit, termed tessellation rhombus (Fig. 15, solid
lines), which can tessellate the entire reciprocal space by
(3p, 3q) translations. A smaller unit, termed minimal
rhombus, can be drawn (Fig. 15, dotted lines), defined by
the same Ri each taken only once. Opposite edges are
different and, contrary to the tessellation rhombus, the
Metric equations in
reciprocal space

b*cos = c*/3
a*cos = c*/3

minimal rhombus does not represent a translational unit.


The two rhombi have six possible orientations, which
represent equivalent descriptions of the same reciprocal
lattice: they simply differ in the distribution of the Ri. Six
equivalent rhombi are obtained by applying the five
rotations (besides the identity) to the hi, ki indices of each
two Classes (after Nespolo 1999).

of the nine Ri of the original rhombus and bringing the


Metric equations in

resulting Ri within the area spanned by the original


ccos = -b/3
ccos = -a/3
direct space

rhombus through a (3p, 3q) translation between equivalent


rows. The rows that can be obtained by rotating the original
rhombus are within a star-polygon constructed by the six
rhombi with the common origin (Fig. 15). The values of p
and q to be considered are those connecting rows internal to
the star-polygon but external to the original rhombus with
rows internal to the original rhombus, i.e. (0, 2), (1, 1)
Class

and (2, 2).


a

b
CrystallographicBasisofPolytypismandTwinninginMicas 207

Figure 14. Schematic view of the axial settings of mica polytypes. Black circles:
direct lattice nodes. The number below each node indicates the number of layers
of the polytype to which that node belongs. Horizontal axis is a or b
depending on the Class and on the setting used. The c axes of S and F settings
are shown as solid and dotted lines respectively. In all settings, the reference is
right-handed. The superscript a or b in the S and F symbols is omitted, since the
figure is drawn for both Classes (they differ in the label of the horizontal axis).
The figure shows that in cases of polytypes with a number of layers multiple of
3, the c axis of the corresponding F setting does not pass on any lattice node: the
F setting of the next Series has thus to be used.
208 Nespolo&urovi

Figure 15. Minimal rhombus (dotted lines; in


the foreground) and tessellation rhombus
(solid lines) in the six orientations defining
the star polygon. The nine translationally
independent rows are distinguished by
sequence numbers (R1 R9) (modified after
Nespolo et al. 2000a).

The geometrical characteristics of the reciprocal lattice rows parallel to c*, each
taken as a whole, are termed "row features". In the Trigonal model all mica polytypes
have the same row features, described by the regular tessellation {3,6} (Takeda and
Donnay 1965; see the section Tessellation of the hp lattice), and the nine Ri were
classified into three types (Fig. 16):
1. S (Single) rows [h = 0(mod 3) and k = 0(mod 3)].
2. D (Double) rows [h 0(mod 3) and k = 0(mod 3)]. There are two translationally
independent D rows, labeled Di: i = 1,2; h = i(mod 3); k = 0(mod 3).
3. X (seXtuple) rows [k 0(mod 3)]. There are six translationally independent X rows,
labeled Xi: 1 i 6; h = i(mod 3); k = 2(-1)i(mod 3).
The nine Ri rows are thus classified as: R1 = S; R2-3 = D1-2; R4-9 = X1-6. This
classification of Ri corresponds exactly to the classification in three types of rows
introduced by urovi (1982), who did not adopt specific names for each type of rows.
Each of the three types lies on non-intersecting circular orbits centered on c*, of radius
3h2 + k2 (cf. Table 4 and Fig. 19 in Ferraris and Ivaldi, this volume). Each of these orbits
contains only one type of rows (an n60 rotation overlaps rows belonging to the same
type only) and becomes an ellipsis when the incident beam is inclined by a general angle
to the sample. This is the principle on which the oblique-texture electron diffraction
method (OTED, see Zvyagin 1967) is based, and has been recently applied also to XRD
(Rieder and Weiss 1991; for details, see Ferraris and Ivaldi, this volume). Figure 16
shows the orbits of S (solid lines), D (dashed lines), and X (dotted lines). For D and X
CrystallographicBasisofPolytypismandTwinninginMicas 209

Figure 16. Rotational relation between reciprocal lattice rows parallel to c*.
Because of the pseudo-hexagonal symmetry of the 001 r.p., each type of row (S,
D, X) lies on a circular orbit around c* with radius 3h + k. Solid, dashed and dotted
orbits contain S, D and X rows respectively. D and X orbits are further subdivided
into those containing only one set of six rows (DI and XI, thick orbits) and those
containing two sets of six rows (DII and XII, thin orbits). The n 60 rotations,
which correspond to the relative orientation of twinned mica individuals, relate
only rows of the same type and same set (S, DI, DII, XI, XII), whereas the non-
crystallographic rotations typical of plesiotwins relate rows of the same type but of
different sets (DI and DII; XI and XII) (modified after Nespolo et al. 2000a).

rows, two types of orbits exist: type I (DI and XI orbits, thick lines) connects one set of
six D or X rows, whereas type II (DII and XII orbits, thin lines) connects two sets of six D
or X rows. The n60 rotations about c* lead to an alternate exchange of the two D-type
Ri located on the long diagonal of the minimal rhombus, and they exchange the six X-
type Ri on the edges of the minimal rhombus in six different ways.

SUPERPOSITION STRUCTURES, FAMILY


STRUCTURE AND FAMILY REFLECTIONS
By superposing two or more identical copies of the same polytype translated by a
superposition vector (i.e. a vector corresponding to a submultiple of a translation period)
a fictitious structure is obtained, which is termed a superposition structure. Among the
infinitely possible superposition structures, that structure having all the possible positions
of each OD layers is termed a family structure: it exists only if the shifts between
210 Nespolo&urovi

adjacent layers are rational, i.e. if they correspond to a submultiple of lattice translations.
The family structure is common to all polytypes of the same family (Dornberger-Schiff
1964; urovi 1994). From a group-theoretical viewpoint, building the family structure
corresponds to transforming (completing) all the local symmetry operations of a space
groupoid into the global symmetry operations of a space-group (Fichtner 1977, 1980).
Additional virtual atoms are created by the completed operations, and the resulting
model may have physically unrealistic interatomic distances: they appear in the
superposition structure, which is a purely mathematical construction, as a consequence of
the group-theoretical process of completing the local symmetry operations. The group of
translations of the polytype reciprocal lattice can be decomposed into a subgroup of
translations, which corresponds to the Fourier transform of the family structure (family
sublattice), and one or more cosets. The family sublattice is again common to all
polytypes of the same family. This means that all polytypes of the same family,
normalized to the same volume of scattering matter, have a weighted sublattice in
common. The diffractions that correspond to the family sublattice are termed family
diffractions (or, more commonly, family reflections). As discussed below, when indexed
with respect to the basis vectors of any of the polytypes of the same family, the family
sublattice shows several non-space-group absences, which indicate the existence of local
symmetry operations. Clearly, the family reflections convey important information,
because they reveal the symmetry of the family structure. The family reflections are
always sharp, including the case of non-periodic (disordered) polytypes. In fact, the
disorder of the stacking concerns the distribution of subsequent -operations. If this
distribution is periodic, after a finite even number of steps a period is closed and the
product of those -operations is the generating -operation (remember that the product of
an even number of -operations is a -operation). If instead the distribution of subsequent
-operations is not periodic, no generating -operation can be found, and the polytype is
disordered. In the family structure the -operations are completed to global operations:
the family structure and its Fourier transform, which consists in the family reciprocal
sublattice, are thus common to both periodic and non-periodic polytypes of the same
family4 (urovi and Weiss 1986; urovi 1997, 1999).
Because the family structure can be deduced from the symmetry principle of the
polytype family, it is possible to illustrate its derivation by means of a very simple,
hypothetical example, in which the actual atomic arrangement is not taken into account,
and geometrical figures with the appropriate -symmetry are used instead. Let us
consider the three hypothetical polytypes (urovi 1999) and their geometric diffraction
patterns in Figure 17. The polytypes are constructed by stacking equivalent layers
perpendicular to the plane of the drawing, with -symmetry P(1)m1. The stacking
direction is a, and the distance between adjacent layers is |a0|. The -symmetry is
indicated by isosceles triangles with a mirror plane [.m.]. The three polytypes can be
related to a common orthogonal four-layer cell with a = 4a0, inside which the cell of the
polytype is shown by bold lines (Fig. 17). The first polytype (1A, MDO) has basis vectors
a1 = a0 + b/4; b1= b; c1 = c and space-group P111. The only global -operation is the
translation a0 + b/4. The second polytype (2M, MDO) has basis vectors a2 = 2a0; b2= b;
c2 = c and space-group P1a1. The global -operations are the translation a = 2a0 and an a-
glide plane at y = 1/8 and 7/8. The third polytype (4M, non-MDO) has basis vectors a3 =
4a0; b3= b; c3 = c and space-group P1a1. The global -operations are the translation a =

4 The remaining diffractions, which correspond to the cosets of the weighted reciprocal lattice with
respect to the family sublattice, are termed non-family reflections and are instead typical of each polytype:
they can be sharp or diffuse, depending on whether the polytype is ordered or not, i.e. on whether the
distribution of subsequent -operations is ordered or random.
CrystallographicBasisofPolytypismandTwinninginMicas 211

Figure 17. Schematic representation of three hypothetical structures belonging to the same
family. The layers are perpendicular to the plane of the drawing, and their constituent atomic
configurations are represented by isosceles triangles with -symmetry [.m.]. All structures are
related to a common, orthogonal four-layer cell with a = 4a0. The family structure is obtained by
superposing two identical copies of the same polytype, translated by b/4, the superposition
vector. The diffraction indices refer also to the common cell. Family diffractions correspond to k
= 2k (open circles), and the non-family diffractions, characteristic for individual polytypes, to k
= 2k+1 (close circles) (modified after Durovic and Weiss (1986).
212 Nespolo&urovi

4a0 and an a-glide plane at y = 0 and y = 1/2. The geometric diffraction pattern of each of
these polytypes can be divided into two parts: k = 2k (open circles) and k = 2k+1 (full
circles). The k = 2k are the family reflections, which define the family reciprocal
sublattice, common to all the three polytypes. The Fourier transform of this subgroup of
diffraction gives the family structure, with space-group C1m1, a = 2a0, b = b/2: the
superposition vector is b/2. The non-family reflections are those for which k = 2k+1: the
number of reflections along each row in the four-layer reciprocal cell is the same as the
number of layers in the period of the polytype.
Family structure and family reflections of mica polytypes
For micas, the family structure of the Pauling model is nine-fold (the supergroup of
translation in direct space has the order nine) and the superposition vectors are a/3 and
b/3; its symmetry is P6/mmm (Dornberger-Schiff et al. 1982). To any of the atoms in the
layer, eight additional atoms are generated in the family structure, with coordinates (x1/3,
y); (x, y1/3) and (x1/3, y1/3). The family reflections are those with h = 0(mod 3) and k
= 0(mod 3), and correspond to S rows. The subgroup of translations in reciprocal space has
the order nine. Because the layer stagger is |a|/3, the family vectors of the Pauling model
complete the local symmetry operations of space groupoids to global symmetry operations
of space groups after one single layer. Therefore, the period along the c axis of the family
structure is c0 = 1/c*1 = c1Msin1M and thus corresponds to the vertical distance between
two closest interlayer cations. The basis vectors of the family structure are AF1 = A1/3, AF2 =
A2/3, CF = c0. (Backhaus and urovi 1984; urovi et al. 1984; urovi 1994).
In the Trigonal model each of the three families (homo-, meso- and hetero-
octahedral) splits into two subfamilies, A and B. For both subfamilies the family structure
is three-fold and the superposition vectors are b/3. To any of the atoms in the layer, two
additional atoms are generated in the family structure, with coordinates (x, y1/3). The
family reflections are those with k = 0(mod 3) and correspond to S and D rows. The
subgroup of translation in reciprocal space has the order three. The family vectors
complete the local symmetry operations of space groupoids to global symmetry
operations of space groups after three layers for subfamily A, but after two layers for
subfamily B. The basis vectors for the family structure are thus AF1 = (A1+2A2), AF2 = -
(2A1+A2), CF. For subfamily A, CF = 3c0; for subfamily B, CF = 2c0. The symmetry of the
family structure is HR31m (where the subscript R indicates that the smaller cell is
rhombohedral) for subfamily A, and H63/mcm for subfamily B (urovi 1994). The
adoption of the H-centered cell allows the description of the family structures and the real
structures in the same axes, but additional absences appear in the diffraction pattern (cf.
Smrok et al. 1994, Appendix, for cronstedtite-3T). Mixed-rotation polytypes are OD
structures only when the ditrigonal rotation of the tetrahedra is zero. Their family
structure and family reflections are those of the Pauling model (S rows).
From the practical viewpoint, as noted by urovi (1982), the family reflections of
the nine-fold family structure (S rows) are common to all members of a family and are
thus not useful for the purpose of distinguishing individual polytypes. D rows instead are
characteristic of all members of a subfamily (A or B, in case of micas), permit to
distinguish the kind of polytype (subfamily A, subfamily B or mixed-rotation).
The real layers building micas deviate from their archetypes by several distortions,
and the shifts between successive layers are in general not exactly rational. The
intensities, but not the geometry, of the family reflections differ from polytype to
polytype of the same family, and the divergence increases with the deviation of the real
layers from their archetypes. Notwithstanding, the concepts of family structure and
family reflections are useful in the identification of twins and polytypes, as shown below.
CrystallographicBasisofPolytypismandTwinninginMicas 213

REFLECTION CONDITIONS
In the diffraction pattern of mica polytypes, systematic non-space-group absences
extensively appear. The International Tables for Crystallography term this kind of
absences additional reflection conditions (Hahn and Vos 2002). This definition does not
provide anything about the kind of information one can get from these absences. As seen
above, the absences along S and D rows derive from the existence of local symmetry
operations that relate pairs of packets. These local symmetry operations are not accounted
for in the space-group type. In the Trigonal model, any mica polytype of a given family is
constructed from layer archetypes in which the atoms in each plane are distributed
according to a hexagonal pattern. These atoms are either on special positions, or on
positions that, without corresponding to any translation-free symmetry operation of the
space-group type, have higher translational symmetry. These positions, under the symmetry
operations of a space-group type, define sets of points (crystallographic orbits) the
eigensymmetry group of which includes additional translations, and are known as
extraordinary orbits of space-groups (Wondratschek 1976; Matsumoto and Wondratschek;
1979). The corresponding lattice of translation vectors is a proper superlattice of the
polytype lattice. In reciprocal space, these vectors correspond to a sublattice, which shows
systematic non-space-group absences when indexed with respect to the basis vectors of the
polytype. The OD description is based on the existence of local symmetry operations,
whereas the description in terms of crystallographic orbits is based on the points on which
those local symmetry operations act. In spite of the different languages, the concepts are
basically the same. The approach involving crystallographic orbits is not specifically
related to VC structures but it is more general. The possible superlattices were however
derived for all space-group types within the same syngony (Engel et al. 1984). There are no
derivations yet for the cases in which the superlattice belongs to a Bravais system higher
than that of the entire lattice. The superlattice common to all polytypes of a family (family
superlattice, i.e. the lattice of the family structure) corresponds to this latter case (with the
exception of trigonal-hexagonal polytypes, of which only 3T has been reported so far). A
general symmetry analysis of mica polytypism in terms of crystallographic orbits is
nowadays a completely open task, but the non-space-group absences along S and D rows
are interpretable in terms of extraordinary orbits as well. The deviations of layers from their
archetypes correspond to the movement of part of the atoms slightly away from the
positions of higher translational symmetry, towards general positions. As a consequence,
violations of the non-space-group absences appear as faint reflections between pairs of
family reflections. These faint reflections can be recorded in dioctahedral micas (Rieder
1968) and, with longer exposure times, in Li-rich trioctahedral micas (Rieder 1970), but
they are almost undetectable in Li-poor trioctahedral micas. This sequence is in accordance
with the extent of the structural distortions, which decreases in the same order.
The reflection conditions in the two subfamilies were derived by Nespolo (1999).
The number and positions of reflections along the D rows reveal the symmetry of the
family structure (HR31m: subfamily A; H63/mcm: subfamily B; P6/mmm: mixed-
rotation). In addition, they are particularly useful in evaluating the possible presence of
twins. Taking into account that for non-orthogonal polytypes only one out of three of the
orthogonal l indices corresponds to integer monoclinic indices, and that subfamily B
polytypes necessarily contain an even number of layers, the reflection conditions are (N
and N are the number of layers in the conventional and orthogonal cell respectively):
1. S rows (family reflections of the nine-fold family structure): one reflection out of N
always occurs, with presence criterion lC1= 0(mod N).
2. D rows: one reflection (family reflection) out of N occurs for subfamily A polytypes
[presence criterion lC1 = (Nh/3)(mod N), + for the obverse setting of the family
214 Nespolo&urovi

structure, for the reverse setting], two (family reflections) for subfamily B [equally
spaced, at lC1 = 0(mod N/2)], and N (non-family reflections) for mixed-rotation
polytypes.
3. X rows: N reflections appear in the c*1 repeat (non-family reflections for all
polytypes).
One or more of the N reflections along X rows (and for mixed-rotation polytypes
also along D rows) may be very weak or absent. This non-space-group absence is related
not to the symmetry of the family structure, as for family reflections, but to the stacking
mode within the polytype.
The family structure of subfamily A polytypes admits a primitive rhombohedral cell,
and its lattice (family sublattice) can be overlapped for all polytypes belonging to
subfamily A only if it is rotated by 180 around the normal to the layer when comparing
polytypes built by layers of opposite orientational parity. This is because the
rhombohedral primitive cell of the family structure for subfamily A polytypes is in the
obverse setting for one orientational parity of the layers (odd orientational parity of the
symbols), but in the reverse setting for the other (even orientational parity of the
symbols). In Series 0, all polytypes belonging to subfamily A are Class a polytypes.
Polytypes belonging to a different Subclass have opposite orientational parity. The aF
setting alternates the directions of (a, b) and (a*, b*) axes with the Subclass (Fig. 14) and
is exactly the axial setting leading to the overlap of the sublattice built on family
reflections. In higher Series, polytypes belonging to subfamily A can be orthogonal or
Class b polytypes and there is no longer a 1:1 correspondence.
Subfamily B polytypes show two reflections along D rows. However, polytypes of
this subfamily either are orthogonal or belong to Class b, for which the non-right angle is
(before the axes interchange) and the lC1 index of the superlattice nodes does not
depend on h. The reciprocal sublattice in this case matches for all polytypes, which is
consistent with the fact that the primitive cell of the family structure is hexagonal.
In mixed-rotation polytypes, the family reflections are only those of the nine-fold
family structure and appear along S rows. D rows convey important information, because
the different number of reflections along the rows, or their diffuseness, unambiguously
reveals the mixed-rotation character of the polytype.

NON-FAMILY REFLECTIONS AND ORTHOGONAL PLANES


Reciprocal central planes, which have c* in common, can be usefully classified, on
the basis of the rows they contain, into SD and SX. Here we consider the six densest
central planes, which are sufficient for a twin/polytype analysis. The three densest central
reciprocal planes (r.p., hereafter) are of type SX: 0k*, hhl andhhl. These planes have the
shortest separation between pairs of reciprocal lattice rows parallel to c* (about 0.22-1),
and are followed by the three densest SD central r.p. h0l, h.3h.l and h.3h.l (about 0.38-
1
). These six central planes are shown in Figure 18, projected onto the (a*, b*) plane. The
three SD central planes are 60 apart each, and the same holds for the three central SX
planes. The two kinds of planes are each 30 apart. The SD central planes show the
symmetry of the family structure. Then, from the intensities measured along one or more
X rows, the stacking sequence can be determined. However, the presence of twinning
must be excluded before analyzing the intensity distribution, and for this purpose the
analysis of the geometry of the diffraction pattern, in particular the number and type of
orthogonal planes, is of primary importance. A plane is orthogonal if the direction r*
corresponding to the line perpendicular to c* and passing through the origin (a direction
that belongs to the orthohexagonal cell) contains a node for each row parallel to c*.
CrystallographicBasisofPolytypismandTwinninginMicas 215

Figure 18. (001) projection of mica reciprocal lattice. Open circles: S rows;
open triangles: D rows; close circles: X rows. The six central planes (three SD
and three SX) that can commonly be recorded by a photographic technique such
as precession camera are indicated (modified after Nespolo et al.1999d). Cf.
Figure 4 in Sadanaga and Takeda (1969) and Figure 1 in Durovic (1982).,
In case of a non-orthogonal plane, no nodes are present on r* along the X rows, and
the node closest to r* is at a height c*1/3N, where N is the number of layers in the
conventional cell. If the node on r* or closest to it corresponds to an absent reflection, the
orthogonality of the plane must be judged from the position of the two adjacent
reflections, whose height is either c*1/N (orthogonal plane) or 2c*1/3N (non-
orthogonal plane). For D rows the family character of the reflections should be
considered. In subfamily A polytypes, reflections appear at c*1/3 (non-orthogonal SD
plane); in subfamily B polytypes, reflections appear at 0 and c*1/2 (orthogonal SD plane);
in mixed-rotation polytypes, the D rows correspond to non-family rows and the same
criteria given for X rows hold. Finally, S rows always contain a node on r*.
The number and features of the orthogonal planes (as defined above) depend both on
the Class (lattice features) and on the subfamily (OD character). These are easily
obtained by taking into account that polytypes in subfamily B and in subfamily A Series
> 0 never belong to Class a, whereas polytypes in subfamily A Series 0 always belong to
Class a.
1. Orthogonal polytypes. In case of subfamily A polytypes, only the three SX central
planes are orthogonal, according to the above definition. For subfamily B and
mixed-rotation polytypes, all the six central planes are orthogonal.
2. Class a polytypes. One SX central r.p. is orthogonal: 0kl.
3. Class b polytypes. None of the three SX central planes are orthogonal. In subfamily
A polytypes (Series > 0) the SD central planes are non-orthogonal and thus none of
the six densest central planes is orthogonal. In subfamily B, the three densest SD
216 Nespolo&urovi

central planes are orthogonal. In mixed-rotation polytypes, D rows correspond to


non-family reflections and on these rows, in general, N reflections occur. On the
basis of the relation between l indices in bT and in C1 settings (lbT and lC1; Table 10),
the three SD densest central planes are orthogonal also.

HIDDEN SYMMETRY OF THE MICAS: THE RHOMBOHEDRAL LATTICE


Takeda (1971) analyzed the symmetry properties of the RTW symbols and showed
that the stacking of the mica layers can produce polytypes belonging to five kinds of
symmetries: A, M, O, T, H; it is thus not possible to obtain a polytype belonging to the
rhombohedral Bravais system. Notwithstanding, the rhombohedral lattice appears in the
geometry of the diffraction pattern and plays an important role in the twinning of the
micas. Here the first aspect is briefly analyzed, whereas the effect on twinning is
considered below. There are two categories of polytypes in which the rhombohedral
lattice represents a kind of hidden symmetry for micas.
1) Subfamily A polytypes. As shown in the section dealing with the family structure, the
family structure of subfamily A polytypes has symmetry HR(3)1m, admitting a
primitive rhombohedral cell. Within the Trigonal model the family reciprocal
sublattice is rhombohedral both in its geometry and intensity distribution. In the real
diffraction pattern the intensity distribution deviates from rhombohedral symmetry
proportionally to the deviations of the layer from their archetypes described by the
Trigonal model, but the geometry remains rhombohedral.
2) Class b polytypes. Successive lattice planes parallel to (001) are shifted by 1/3 of the
short (Class a) or the long (Class b) diagonal of the two-dimensional pseudo-
hexagonal mesh built on (A1, A2) axes. For Class b polytypes a pseudo-rhombohedral
primitive cell can be chosen, having (almost) the same volume of the reduced cell
(Fig. 19). The primitive cell is closer to rhombohedral when the layers are closer to

Figure 19. Projection onto the (001) plane of the primitive,


conventional (double, monoclinic), pseudo-hexagonal (triple), C1
(sextuple, pseudo-orthohexagonal) and pseudoto c axis of the
orthogonal cell-rhombohedral (primitive) cells of Class b polytypes.
Black, white and gray circles represent lattice nodes at z = 0, 1/3
and 2/3 (z is referred to c axis of the orthogonal cells). Thick lines:
and borders
2/3 (z isofreferred
the C1 cell
to c and
axisofofthethepseudo-hexagonal
orthogonal cells). cell.
Thick Dashed
lines:
lines: borders of the upper plane of the conventional and primitiveb d cellsf (the
h lower
C llplaned is fin hcommon d with
h C1 celll and ll pseudo-
D h d
hexagonal cell respectively). The pseudo-rhombohedral cell (dotted lines) is best viewed by means of the pseudo-rhombohedral axes
aR. a, b: (pseudo)-orthohexagonal axes. A1, A2: (pseudo)-hexagonal axes (modified after Nespolo 1999).
CrystallographicBasisofPolytypismandTwinninginMicas 217

their archetypes as described by the Trigonal model. The general reflection


conditions for the rhombohedral lattice in hexagonal axes, -h+k+l = 3n, expressed in
the C1 setting become: -3h+k+2l = 6n. Taking into account the C centering
condition, the latter equation corresponds to l(mod 3) = k(mod 3), which is simply an
alternative expression of the condition that monoclinic indices are integers, given in
Table 10 for the bT setting (Nespolo 1999).
Because non-orthogonal polytypes of subfamily A Series > 0 belong to Class b, in
this case the hidden rhombohedral symmetry appears both in the family sublattice and
in the entire polytype lattice.

TWINNING OF MICAS: THEORY


The definition and classification of twinning is given in Appendix A. The pseudo-
symmetries typical of micas made the recognition of the twin laws difficult, and Friedel
initially classified mica twins among the macles aberrantes (Friedel 1904, p. 222), i.e.
oriented crystal associations without either twin plane or twin axis stricto sensu. The
derivation of the twin laws for mica polytypes must consider the point groups of the twin
lattice and of the lattice of the individual, and the point group of the syngony of the
individual. The twin operators are the point symmetry operators of the twin lattice not
belonging to the point group of the individual and can be obtained by coset
decomposition. The decomposition of the twin lattice point group (order m) yields one
subgroup (the point group of the individual, order m < m) and n = m/m-1 cosets
corresponding to the twin laws. Hereafter the subgroup corresponding to the point group
of the individual is always given first, and the twin laws follow as cosets No. 1 to n. All
merohedral polytypes, in any syngony, may undergo twinning by syngonic merohedry:
the twin laws depend on the point group of the polytype and should thus be derived case
by case (see the example for 3T below). Instead, twins other than by syngonic merohedry
can be derived with a general procedure. Hereafter, indexing is given in the
(pseudo)orthohexagonal setting of the twin lattice.
1) Polytypes of the orthorhombic syngony with a hP lattice may undergo twinning by
metric merohedry, the twin lattice coinciding with the lattice of the individual. The
coset decomposition gives two twin laws:

{
6 / mmm = 1, 2[010] , 2[001] , 2[100] , 1, m( 010) , m( 001) , m(100) }
{
6[+001] ,6[001] , 2[110] , 2 1 10 , 6[+001] , 6[001] , m(130) , m(130)

} (4)

{3 + +
[001] ,3[001] , 2[310] , 2 3 10 , 3[001] , 3[001] , m(110 ) , m(1 10 ) }.

All the operators corresponding to the same twin law are equivalent under the action
of the symmetry operators of the orthorhombic syngony. If the lattice is only oC,
twinning is by pseudo-merohedry. The twin lattice (hP) does not coincide exactly
with the lattice of the individual, because for the latter the orthohexagonal relation b =
a31/2 is only approximated. However, the two lattices have the three orthohexagonal
axes parallel. The coset decomposition is the same as given in Equation (4), but the
non-zero obliquity ( = || 0, = 0) makes the operators in each of the two cosets
not equivalent, as described in detail below.
218 Nespolo&urovi

2) Polytypes of the monoclinic and triclinic syngony with an hP lattice may undergo
twinning by metric merohedry. For the monoclinic syngony the coset decomposition
gives five twin laws, each with four equivalent twin operators:

{ } {
6 / mmm = 1, 2[010] , 1, m( 010) 2[001] , 2[100] , m( 001) , m(100) }
{3[
001] } {
, 2[310] , 3[001] , m(110) 6[001] , 2[110] , 6[001] , m(130) } (5)

{
} {
3[+001] , 2 3 10 , 3[+001] , m(1 10) 6[+001] , 2 1 10 , 6[+001] , m(130)

}
whereas for the triclinic syngony the coset decomposition gives eleven twin laws,
each with two equivalent twin operators:

{ } {
6 / mmm = {1, 1} 2[010] , m( 010) 2[001] , m( 001) 2[100] , m(100) } { }
{ } { } {
3[001] , 3[001] 2[310] , m(110) 6[001] , 6[001] 2[110] , m(130) } { } (6)

{3[ ] } {2 ) } {6[ ] } {2 }
+
001]
, 3[+001 , m(1 10 +
001]
, 6[+001 , m(130) .
3 10 1 10

If the lattice of the individual is oC, the first two cosets in Equation (5) and the first
four cosets [Eqn. (6)] correspond to metric merohedry, whereas the others correspond
to pseudo-merohedry ( = || 0, = 0). If the lattice of the individual is mC Class
a, the twin laws in Equations (5) and (6) correspond to reticular pseudo-merohedry.
The hP twin lattice is a sublattice for the individual, with subgroup of translation 3:
the twin index is thus 3.
3) Monoclinic and triclinic Class b polytypes with a two-dimensional hexagonal mesh in
the (001) plane and a cn projection of exactly |b|/3 has a hR lattice. Twin elements
belonging to the hR lattice but not to the monoclinic or triclinic syngony correspond
to the twinning by metric merohedry, whereas twin elements belonging to the hP
sublattice but not to the hR lattice correspond to twinning by reticular merohedry. The
subgroup of translation defining the hP sublattice is 3, and thus the twin index is 3
also. The coset decomposition gives five (monoclinic syngony) or eleven (triclinic
syngony) twin laws:
monoclinic syngony:
{ } {
6 / mmm = 1, 2[100] , 1, m(100) 3[001] , 2[110] , 3[001] , m(130) }
{ } {
3[+001] , 2 1 10 , 3[+001] , m(130) 2[001] , 2[100] , m( 001) , m(100)

} (7)

{
6[001] , 2[310] , 6[001] , m(110) } {6 + +
[001] , 2 3 10 , 6[001] , m(1 10 ) }.
triclinic syngony:
{ } {
6 / mmm = {1, 1} 2[100] , m(100) 3[001] , 3[001] 2[110] , m(130) } { }
{ } { } {
2 1 10 , m(130) 3[+001] , 3[+001] 2[001] , m( 001) 6[001] , 6[001]

} { } (8)

{ } {
6[+001] , 6[+001] 2[310] , m(110 ) } {2[ 010]
, m( 010 ) } {2 3 10
, m(1 10) . }
CrystallographicBasisofPolytypismandTwinninginMicas 219

The first two [Eqn. (7)] or four [Eqn. (8)] cosets give the twin laws by metric
merohedry, the others give the twin laws by reticular merohedry. Twin operators in
each coset are equivalent by the action of the symmetry elements of the syngony.
If the two-dimensional mesh in the (001) plane is not rigorously hexagonal (||
0), or if the cn projection is not exactly |b|/3 ( 0), the hR lattice does not coincide
exactly with the lattice of the individual; moreover, the hP sublattice is only an
approximate sublattice for the individual. The twin laws derived in Equations (7) and
(8) do not change, but they correspond to pseudo-merohedry and reticular pseudo-
merohedry instead of metric merohedry and reticular merohedry respectively. The
operators in each coset are no longer equivalent.
Choice of the twin elements
The twin element that relates a pair of individuals occurs in the morphology of the
twin. Micas show two kinds of twin morphologies: rotation twins, with composition
plane (001), and reflection twins, with composition plane (almost) normal to (001). As
noted by Friedel (1904), the twin axis for rotation twins is within the composition plane,
whereas the twin plane for reflection twins coincides with the composition plane.
Whereas the morphological twin operation is unique, the geometrical operations
bringing the twin lattice into self-coincidence are in general more numerous, as shown in
the previous section. For zero obliquity, the operations within each coset corresponding
to a twin law are equivalent, when considering only the lattice, by the action of the
symmetry elements of the individual. The morphological twin operation is termed the
representative operation of the coset (Nespolo and Ferraris 2000). For non-zero
obliquity, however, they are no longer equivalent and the correct twin operations are
those obeying the law of Mallard, which requires that the twin operations are
crystallographic operations. As an example, let us consider the decomposition of the
point group of the hP twin lattice with respect to the point group of the monoclinic
syngony in Equation (5). If the monoclinic polytype has a hP lattice (twinning by metric
merohedry) or sublattice (twinning by reticular merohedry) the six two-fold axes in the
(001) plane are exactly 30 each apart and each of them is perpendicular to a plane (hk0):
the four operations in each coset are truly equivalent, when considering only the lattice.
Instead, if the lattice or sublattice of the individual is not exactly hexagonal (twinning by
pseudo-merohedry and reticular pseudo-merohedry), either || or (in general both) is
non-zero. For || 0 the 2[310], 2[310], 2[110] and 2[110] are (2n+1)30 apart from 2[010] /
2[100] and they are no longer perpendicular to the (hk0) planes (Fig. 20). Twin axes and
twin planes deviate thus from mutual perpendicularity: rotation twins and reflection twins
are no longer equivalent, even for centrosymmetric crystals, and are called reciprocal
twins (Mgge 1898) or corresponding twins (Friedel 1904, 1926). For = 0 the
equivalence relations become:

2[310] 2[010] = 3[001] 2 m(110) m( 010) = 3[001] 2


2 3 10 2[010] = 3[+001] 2 m(1 10) m( 010) = 3[+001] 2

2[110] 2[010] = 6[001] 2 m(130) m( 010) = 6[001] 2


2 1 10 2[010] = 6[+001] 2 m(130) m( 010) = 6[+001] 2

2[100] 2[010] = 2[001] m(100) m( 010) = 2[001]


220 Nespolo&urovi

Figure 20. Component of the obliquity within the (001) plane of the pseudo-hp
lattice of micas. The six directions [hk0] (including the a and b axes) in the
(001) plane (solid lines) would be equivalent in a hexagonal lattice. The dashed
thick line is t(130), i.e., the intersection of the (130) plane with the (001) plane,
which is almost but not exactly normal to [110] direction (it would be normal to
it in a truly hp lattice). The trace of the t(010) and t(100) coincide with a and b axes
respectively ( = 90). To improve the clearness of the figure, the t(hkl) of the
other three planes that would be equivalent in a truly hp lattice are not shown,
but they can be easily traced (modified after Nespolo and Ferraris 2000).

Only the two-fold rotation about c of the twin lattice is a correct twin operation, in
the sense that it restores the lattice, or a sublattice, of the individuals. If however 0,
the c axis of the twin lattice is no longer exactly perpendicular to the (001) plane and the
above rotations are defined only with respect to c* and not to c: none of them is thus a
correct twin operation. The rotations about c* give simply the (approximate) relative
rotations between pairs of twinned mica individuals, but are not true twin operations.
Similar considerations apply also to the rotoinversion operations. depends upon the
obliquity of the twin but, at least in Li-poor trioctahedral micas, is sufficiently small to be
neglected for practical purposes (Donnay et al. 1964; Nespolo et al. 1997a,b, 2000a).
In Table 11 the complete scheme developed above is summarized for ease of
consultation.
Effect of twinning by selective merohedry on the diffraction pattern
The above analysis does not consider the case of selective merohedry, which does
not appear in the morphology of the twin but influences the diffraction pattern by relating
lattice nodes corresponding to present reflections from one individual to nodes
corresponding to non-space-group absences from another individual. Twinning by either
syngonic or metric merohedry (for the definitions, see Appendix A) does not modify the
geometry of the diffraction pattern. Instead, twinning by selective merohedry, i.e. when
the twin operation belongs to the point group of the twin lattice but not to the point group
of the family structure, produces an unusual diffraction pattern. The typical case is that of
the 3T polytype orthogonal Series 1 subfamily A, space-group type P31,212, which has an
hP lattice. As shown above, the family structure is rhombohedral and the family
reflections (S and D rows) obey the presence criterion l = Nh/3(mod N). With respect to
Table 11. Kind of twinning and twin laws for mica polytypes classified on the basis of the polytype syngony, polytype lattice and twin lattice.
Syngony of Lattice of the Twin Kind of twinning Twin laws Twin Rotation between Polytypes
the individual individual lattice index pairs of individuals
H/T hP hP syngonic merohedry # 1 # merohedral polytypes
O hP hP metric merohedry [310] (110); [C310] (C110) 1 (120) all polytypes
oC hP pseudo-merohedry [310] (110); [C310] (C110) 1 (1202H) all polytypes
oC syngonic merohedry # 1 # merohedral polytypes
A/M hP hP metric merohedry [310] (110); [C310] (C110) (120) all polytypes
[110] (130); [C110] (C130) 1 (60)
[100] (100) (180)
oC hP pseudo-merohedry [310] (110); [C310] (C110) (1202H) all polytypes
1
[110] (130); [C110] (C130) (602H)
oC metric merohedry [100] (010) 1 (180) all polytypes
hR hR metric merohedry [110] (130); [C110] (C130) 1 (60) all polytypes
(Class b hP reticular merohedry [310] (110); [C310] (C110) (60) all polytypes
3
polytypes) [100] (100) (180)
aC/mC Class b hR pseudo-merohedry [110] (130); [C110] (C130) 1 (1202H) all polytypes
hP reticular [310] (110); [C310] (C110) (602H) all polytypes
3
pseudo-merohedry [010] (010) (180)

aC /mC Class a hP reticular [310] (110); [C310] (C110) (1202H) all polytypes
pseudo-merohedry [110] (130); [C110] (C130) 3 (602H)
[100] (100) (180)
M mC Class b mC syngonic merohedry [100](100) 1 (180) merohedral polytypes
mC Class a mC syngonic merohedry [010](010) 1 (180) merohedral polytypes
A mC Class b mC metric merohedry [100](100) 1 (180) all polytypes
mC Class a mC metric merohedry [010](010) 1 (180) all polytypes
Crystallographic Basis of Polytypism and Twinning in Micas

aC Class b mC pseudo-merohedry [100](100) 1 (1802H) all polytypes


aC Class a mC pseudo-merohedry [010](010) 1 (1802H) all polytypes

aC aC syngonic merohedry C1 1 0 merohedral polytypes

The unconventional C centring of triclinic polytypes is adopted to preserve the same pseudo-orthohexagonal axes (a, b) used for polytypes of
the other Bravais systems. Rotations about c*. #Symmetry elements and relative rotations depend on the point group of the individual
221
222 Nespolo&urovi

the period of the family sublattice, 1/3c0, one reflection appears in the 1/c0 repeat, with
presence criterion l = h(mod 3). The coset decomposition gives three twin laws:
{ } {
6 mmm = 1,3[+001] ,3[001] ,2 [010 ] ,2 [310 ] ,2 [3 1 0 ] 2 [100 ] ,2 [1 1 0 ] ,2 [110] ,2 [001] ,6 [001] ,6 [+001] }
(9)
{m( 100 ) } {
, m(130 ) , m(1 3 0 ) , m(001) , 6[001] , 6[+001] m(010 ) , m(110 ) , m(1 1 0 ) , i, 3[001] , 3[+001] }
By expressing the twin laws through the Shubnikovs two-color group notation (in
which the twin elements are dashed: Curien and Le Corre 1958), the three twin laws are:
622; 6m2; 312/m. The complete twin [i.e. twin by merohedry or reticular
merohedry, in which the number of individuals generated from the original individual is
equal to the number of possible twin laws (Curien and Donnay 1959)] contains four
individuals and has symmetry 6/m 2/m 2/m. The 622 and6m2 twin laws
correspond to syngonic selective merohedry class IIA, whereas the312/m twin law
corresponds to syngonic complete merohedry class I (Table A1). In the twins by syngonic
selective merohedry, the twin operations do not belong to the point group of the family
structure, and the two individuals in the twin are rotated by (2n+1)60, whereas layer
rotations of subfamily A polytypes are 2n60. These twin operations produce the
complete overlap of the reflections along X rows and S rows, but not of those along D
rows. For example, theh0l family row of one individual is overlapped to the
symmetrically independent h0l family row of the other individual. Because of the
presence criterion given above, the two reflections from the two individuals in the 1/c0
repeat along D rows are not overlapped, but are separated by 1/3c0 (Fig. 21). The 622
and6m2 twin laws, although being twin laws by merohedry according to the classical
definition, produce the overlap of only one third of the family reflections (those along S
rows), behaving thus as twin laws by reticular merohedry with respect to the family
structure.

Figure 21. h0l r.p. (SD family plane) of the 3T polytype twinned by selective merohedry. Black
circles: family reflections overlapped by the twin operation (common to both individuals). Gray and
white circles: family reflections from two individuals rotated by (2n+1) 60, not overlapped by the
twin operation (modified after Nespolo et al.1999a).
CrystallographicBasisofPolytypismandTwinninginMicas 223

Diffraction patterns from twins


The twin reciprocal lattice results from the overlap of the reciprocal lattices of the
individuals. From each individual, lattice rows of the same type (S, D or X) overlap into a
single composite row. The reflections along a composite row are perfectly aligned for cn =
|a|/3 or |b|/3, but slightly deviate from alignment where cn departs from those ideal values.
Because of the physical (non-zero) dimension of the reflections, which for micas are
commonly broad and oval-shaped, a zigzag disposition of reflections from different
individuals can in practice be observed only for significant deviations of cn, typical of
dioctahedral micas and, to a minor extent, for Li-rich trioctahedral micas (Rieder 1970).
The zigzag disposition of the reflections along rows parallel to c* is indicative of twinning,
but it is normally not noticeable in Li-poor trioctahedral micas. The presence of twinning
has thus to be evaluated, in general, from the geometry of the SD and SX central planes.
For non-orthogonal polytypes the metric relations lC1 = h (mod 3) (Class a) and lC1 = k
(mod 3) (Class b) hold (see Table 10). Depending upon the twin law(s) (and thus the
relative orientation of twinned individuals), non-family reflections from different
individuals may either overlap or occur at positions separated by c*1/3N, where N is the
number of layers in the repeat unit (Table 10). Where two of the three positions in a c*1/N
repeat are occupied, the presence of twinning should be suspected. In contrast, where each
of the three positions are occupied, the number of reflections in a c*1 repeat of a non-
orthogonal twinned N-layer polytype is the same as that of an untwinned 3N-layer
polytype. This phenomenon is known as apparent polytypism (Takano and Takano
1958). However, twinning in some cases modifies the appearance of the D rows, which, for
subfamily A polytypes, may show two reflections at 1/3 and 2/3 of the c*1 repeat, as in case
of selective merohedry. The number and the position of reflections along D rows, as well as
the number of orthogonal planes, in most cases allows the presence of twinning to be
distinguished.
1. Twinning of subfamily A polytypes in which individuals are rotated by (2n+1)60
corresponds to twinning by reticular pseudo-merohedry. This twinning produces a
separation of the single reflection on D rows from each individual into two
reflections, corresponding to l(c*1) = 1(mod 3) and l(c*1) = 2(mod 3); no reflection
appears corresponding to l(c*1) = 0(mod 3); this pattern is clearly different from that
of a subfamily B polytypes, where two equally spaced reflections appear. In
addition, if rotation is by 60, for Series 0 polytypes (Class a) the orthogonal plane
of one individual necessarily overlaps a non-orthogonal plane of another individual.
The composite diffraction pattern has thus two or three SX orthogonal central planes.
2. Twinning of subfamily A polytypes in which individuals are rotated by 2n60
corresponds to twinning by reticular pseudo-merohedry for Class a (Series 0), but to
pseudo-merohedry for Class b (Series > 0). Twinning produces overlap of the single
reflection on D rows from each individual; no reflection appears corresponding to
l(c*1) = 0(mod 3). However, for polytypes of Series 0 (Class a) two or three SX
planes are orthogonal, depending on the number of individuals. When three such
planes appear (three or more twinned individuals), the geometrical features of the
diffraction pattern are the same as for orthogonal Series 1 polytypes. This situation
corresponds to the 3T polytype vs. twinned 1M. For dioctahedral micas it is
distinguished by careful examination of the appearance of weak reflections violating
the reflection conditions (e.g., Nespolo and Kogure 1998), whereas for trioctahedral
micas different techniques, such as microscopic observation of the crystal surface,
may be necessary (e.g., Nespolo and Kuwahara 2001). If the twin involves only two
224 Nespolo&urovi

individuals, successive reflections along X are unequally separated (1/3 and 2/3) and
two SX planes are orthogonal: the presence of twinning is thus easily recognized.
3. Subfamily B polytypes either are orthogonal or belong to Class b. In the latter case
only three of the five pairs of twin laws correspond to twinning by reticular pseudo-
merohedry. However, the corresponding twin operations lead to the overlap of the
two reflections on D rows from each individual; no SX plane is orthogonal, whereas
the three SD planes are orthogonal. The presence of twinning is not evident.
4. For mixed-rotation polytypes D rows are non-family rows. For Class a polytypes, two
individuals rotated by 180 share one orthogonal r.p. 0kl, but reflections are unequally
spaced. The presence of twinning is thus evident. In other cases, two or more SX
planes are orthogonal, as for subfamily A polytypes of the same Class, but no SD
plane is orthogonal. The presence of twinning is again evident. For Class b polytypes
the three SD planes are orthogonal and the presence of twinning is not evident.
In Tables 12a-12c the complete scheme of the identification process is shown. The
approximated relative rotations between twinned individuals are given: the corresponding
twin laws are easily obtained from Table 11. For Class a polytypes (which represent most
of the polytypes reported to date) the presence of twinning can be confirmed or excluded
by simple inspection of the geometry of the diffraction pattern. Special attention is
however needed to distinguish a 3N-layer orthogonal polytype from the spiral twinning of
three non-orthogonal N-layer Class a polytypes in which the individuals are rotated by
2n60. For polytypes of Class b subfamily A Series 1 the presence of reticular pseudo-
merohedry twinning is also evident. In the other cases the presence of twinning cannot be
confirmed or excluded by analyzing the geometry of the diffraction pattern.
Allotwinning
The oriented association of two or more crystals differing only in their polytypic
character is termed allotwinning, from the Greek , different, with reference to
the individuals (Nespolo et al. 1999c). Allotwinning differs from twinning in that the
individuals are not identical but have a different stacking sequence. Allotwinning differs
also from oriented overgrowth (epitaxy: Royer 1928, 1954) and oriented intergrowth
(syntaxy: Ungemach 1935) because the chemical composition is (ideally) identical and,
because the building layer(s) are the same, at least two of the three parameters those in
the plane of the layer are identical also. A cell common to the two individuals can
always be found, which in general is a multiple cell for both crystals: the parameter not in
the plane of the layer is the shortest one common to the cells of both individuals. As in
case of triperiodic epitaxy, a three-dimensional common lattice exists (allotwin lattice): it
may coincide with the lattice of one or more individuals or be a sublattice of it. Whereas
a triperiodic epitaxy in general may or may not occur, depending on the degree of misfit
of the lattice parameters of the individuals, there is no similar condition in allotwinning,
because the individuals have a common mesh in the plane of the layer(s) even in
polytypes with a different space-group type.
The allotwin operation is a symmetry operation for the allotwin lattice, which may
belong to the point group of one or more individuals also. The allotwin of N individuals
is characterized by N allotwin indices: the allotwin index of the j-th individual is the
order of the subgroup of translation in direct space defining the allotwin lattice with
respect to the lattice of the j-th individual.
Tessellation of the hp lattice
Assuming the mica two-dimensional lattice in the (001) plane is hp [|| = 0], the
lattice can be described through a regular tessellation {3,6}, i.e. an assemblage of equal
Table 12a. Classification of diffraction patterns for N = 3K+L. For the correspondence between the relative rotations of twinned individuals and the
twin laws see Table 11 (after Nespolo 1999).

Number of reflections in the c*1 repeat along reciprocal lattice rows corresponding to family reflections
Number of planes 1 2
with orthogonal N
appearance [lC1 z 0(mod 3)] lC1 = 1(mod 3) and 2(mod 3) [lC1 = 0(mod N) and N/2(mod N)]

Subfamily A Series 0 Class a ------------- Mixed-rotation Series 0 Class a


1 (SX) -------------
untwinned polytype untwinned polytype
Subfamily A Series 0 orthogonal
Subfamily A Series 0 orthogonal
3 (SX) polytype untwinned or ------------- -------------
(60 / 180)-twinned polytype
120-twinned
Subfamily B Series 0 Class b Mixed-rotation Series 0 Class b
3 (SD) ------------- ------------- polytype untwinned or polytype untwinned or 120
120-twinned -twinned
Subfamily B Series 0 orthogonal Mixed-rotation Series 0
6 (SX and SD) ------------- -------------
polytype orthogonal polytype
.
Crystallographic Basis of Polytypism and Twinning in Micas
225
226

Table 12b. Classification of diffraction patterns for N = 3(3K+L).

Number of reflections in the c*1 repeat along reciprocal lattice rows corresponding to family reflections
Number of 2
planes with 1
N
orthogonal [lC1 z 0(mod 3)] lC1 = 1(mod 3) and 2(mod 3) lC1 = 0(mod N) and N/2(mod N)
appearance
Subfamily A Series 1 Class b
0 polytype untwinned or --------- --------- ---------
120-twinned
Mixed-rotation Class a:
Subfamily A Series 0 Class a
1 (SX) --------- --------- Series 1 untwinned polytype
polytype 180-twinned
Series 0 polytype 180-twinned
Subfamily A Series 0 Class a Subfamily A Series 0 Class a
Mixed-rotation Series 0 Class a polytype
2 (SX) polytype 120-twinned (two polytype 60-twinned (two ---------
(60 / 120)-twinned (two individuals)
individuals) individuals)
Subfamily A Series 0 Class a Subfamily A Series 0 Class a
polytype 120-twinned polytype 60-twinned (three
Mixed-rotation Series 0 Class a polytype
Nespolo & urovi

(three individuals) individuals)


3 (SX) --------- (60 / 120)-twinned (three
S