Escolar Documentos
Profissional Documentos
Cultura Documentos
New York State Center for Advanced Ceramic Technology-Whiteware Research Center,
New York State College of Ceramics at Alfred University, Alfred, New York 14802
Porcelain represents the foundation of the ceramics discipline and one of the most complex ceramic materials. Composed primarily of clay, feldspar, and quartz, porcelains
are heat-treated to form a mixture of glass and crystalline
phases. This review focuses on raw materials, processing,
heat treatment, and mechanical behavior. Because of the
complexities of the porcelain system and despite the substantial amount of research already conducted within the
field, there remain significant opportunities for research
and study, particularly in the areas of raw material understanding, processing science, and phase and microstructure
evolution.
G. L. Messing-contributing edit01
I. Introduction
Table I.
Name
Porcelain
ASTM definition4
Maturing temnerature'
A glazed or unglazed vitreous ceramic whiteware made by the procelain process, and used
A glazed or unglazed vitreous ceramic whiteware made by the china process, and used for
nontechnical purposes, designating such products as dinnerware, sanitaryware, and
artware when they are vitreous
Stoneware
A vitreous or semivitreous ceramic ware of fine texture, made primarily from nonrefractory
&lo5
fire clay
Earthenware
06-0S6
Silica
nsioz
1713'
TRIDYMITE
\ I r
semivitreous whiteware
'
Corresponding to the increase in automation is the improvement in process control. Prior to automation, dinnerware production loss rates of up to 60% were not uncommon. Today,
loss rates within a modem dinnerware production facility are
15%-20%. This higher level of procJuctivity is accomplished
partly through improved understanding of the underlying
forces governing the rheology and plasticity of porcelain bodies. In the preautomation era, it was necessary to have relatively soft bodies with plasticity suitable for hand forming.
With the introduction of automated forming techniques, it became necessary to create stiffer bodies with more controlled
plasticity through the use of dispersants and increased particle
packing. Prior to the introduction of dispersants, casting slips
were "scooped into the mold" and the resulting casts were
uneven and difficult to handle. l 3 Dispersants-initially K2C0,
in 1844, then Na,CO,, sodium bicarbonate, and NazSi03were introduced as a means of decreasing the slip viscosity and
thus improving the drain-casting process. l 3
January 1998
Porcelain-Raw
Temperature
("C)
Cone
Temperature
("C)
Cone
Temperature
("C)
022
02 1
020
019
018
017
016
015
014
013
012
01 1
010
09
08
07
06
05 Y2
05
589
61 1
634
685
725
752
784
807
83 1
859
864
884
894
923
955
984
999
1023
1046
04
03
02
01
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1060
1101
1120
1137
1154
1162
1168
1186
1196
1222
1240
1263
1280
1305
1315
1326
1346
1366
1431
16
17
18
19
20
21
23
26
27
28
29
30
31
32
32%
33
34
35
36
1473
1485
1506
1528
1549
1569
1590
1605
1627
1633
1645
1654
1679
1717
1730
1741
1759
1784
1796
Assuming a heating rate of 150'Ch over the last few hundred degrees. If altemative heating rates are used or if a dwell is used in the firing process, the cone falls at
a temperature below that listed. Similarly, if accelerated heating rates are used, the
cone falls at a higher temperature. Cone designations continue to he commonly used
to denote the firing range of whiteware bodies.
From the firing perspective, commercial porcelain production initially relied on periodic "beehive" kilns, using coal as
the primary fuel. In small potteries, the kilns were fired infrequently, dependent on the production of sufficient ware to fill
the kiln volume, and firing cycles on the order of several days
were used.I4 As the industry progressed, so did the firing capabilities, and circular tunnel kilns designed to fit into the
footprint of the beehive kiln were de~eloped.~."
Eventually,
linear tunnel kilns were developed that allowed significant increases in production volumes. The most advanced firing capabilities are the current roller-hearth kilns, which can produce
large quantities of high-quality porcelain dinnerware or vitrified tile with firing cycles as short as one hour.15
Most of the reactions occurring in porcelain bodies are kinetically governed processes that do not reach thermodynamic
equilibrium. Hence, measurement of temperature alone does
not provide a true indication of the heat work done on the body
Table 111. Primary Raw Materials Used in the Manufacturing of Commerical Whitewares
Raw material
Nominal composition
A1,0, .2Si0,.2H20
A1,0,~2Si0,~2H20
Na20~A1,0,~6Si0,
K,O~Al2O,~6SiO,
K2O~3Na,0~4A1,0,~9Si0,
'412%
SiO,
Common impurities
Bentonite/montmorillonitet
Glass frits
Petalite (lithium feldspar)
Bone ash$
Talc
Whiting
Zircon
Nominal composition
Common impurities
(M2+)(M3'),(Si,A1),O,,(OH),~nH,O
Not applicable
Not applicable
Na,O, K,O
Unknown
Chrysotile, CaO
MgCO,
Not applicable
Company specific
Li,O~Al,0,~6SiO2
Ca,(PO,),
3Mg0.2Si0,.2H20
CaCO,
ZrO,.SiO,
'This unconventional form for presenting the composition was chosen for the highly variable divalent (Mz') and trivalent
(M3') cation levels present in montmorillonites. *Bone ash is commonly used as a flux for hone china.
Ca
Distilled water
Alfred, NY
Buffalo, NY
Syracuse, NY
Victor, NY
Columbus, OH
East Liverpool, OH
York, PA
BDL
52.3
28.7
40.2
41.5
7.5
28.2
21.3
BDL
20.2
9.1
9.4
12
1.6
7.3
6.2
0.1
0.1
Dectection limit
BDL
28
12
14
21
ADL
21
9
1.
2KA1Si,08
BDL
5
ADL
BDL
1.5
ADL
1.9
2.5
1.
0.5
If the potassium is not properly removed following the weathering process, illitic clays (2:l sheet silicates) are formed instead of kaolinite.
Of primary importance for the domestic whitewares industry
are English and U.S. clays; these clays are the most widely
studied in the literature. In England, kaolins (or china clays)
and ball clays are distinguished as being primary and secondary
clays, r e ~ p e c t i v e l y .In
~ .the
~ ~ United States, however, both kaolins and ball clays usually are secondary clays, having been
deposited at a considerable distance from their place of origin.23 There are primary clay deposits within the United States
but none that are currently commercially exploited. Geographically, the major ball clay deposits are located east of the Appalachian Mountains and in western Kentucky and Tennessee;
the major kaolin deposits are located in central Georgia and
South Carolina.
Mineralogical and chemical differences between ball clays
and kaolins are minor-both are kaolinitic in nature, containing
quartz as the major impurity and iron (in the form of Fe,O,)
and titania (in the form of anatase) as minor i m p ~ r i t i e s . ~ ~ - ~ ~ , ~
The quartz is removed via wet processing of the kaolins but is
not commonly removed from the ball clays. English clays are
generally lower in titania content than U S . clays but are similar
in iron levels, leading to white bodies from English clays and
buff-colored bodies from U.S. clays.21 Table VI lists typical
chemical analyses of a Georgia kaolin, an English kaolin, and
a Kentucky ball clay. Powder X-ray diffraction (XRD) patterns
are presented in Fig. 3.
Ball clays often are referred to as plastic clays, because they
possess a finer particle size, which produces greater plasticity
Si
ADL
4
6
ADL
BDL
4
2
7
and Senapati
+Induction coupled plasma spectroscopy was used to obtain the results. BDL indicates that the cation level was below the detection limit (as specified); ADL indicates species concentration at the detection limit.
(1) CkYS
In whiteware production, the term clay refers to raw materials that provide plasticity and green strength during the
forming stages of porcelain production and that contribute substantially to the color of the fired ware.
Kaolinite, the most common clay mineral, is a 1:l sheet
silicate composed of a [Si,O,I2- layer and an [Al2(0H),l2
layer, as illustrated schematically in Fig. 2.8 The theoretical
formula for kaolinite is Si,Al,O,(OH), (frequently expressed
as A1,0,*2Si0,.2H20). Clay minerals are formed by the decomposition of feldspathic rock via geological processes; a
typical reaction sequence using potassium feldspar (microcline
or orthoclase) can be written:,l
Water
layers
dd-0
0
Water
layers
I
I
About
fI
Kaolinite
Mica
(Muscovite)
Montmorilbnite
(Hydrated)
Fig. 2. Schematic illustration of the layer structures of kaolinite, mica, and montmorillonite, showing the relative spacings between the layers (in
Angstroms). Kaolinite crystal is a 1:l sheet silicate, whereas mica and montmorillonite are 2:l sheet silicates.8
January 1998
Porcelain-Raw
Georgia kaolin2'
English kaolin"
SiO,
A1203
Fez03
TiO,
MgO
CaO
Na,O
K,O
LO1 (950C)
45.30
38.38
0.30
1.44
0.25
0.05
0.27
0.04
13.97
44.70
38.30
0.60
2.40
0.10
0.10
0.10
0.10
13.60
46.77
37.79
0.36
0.02
0.24
0.13
0.05
1.49
12.97
(2) Fluxes
Historically, potash feldspars (microcline and orthoclase)
have been the most commonly used fluxes in porcelain^.^^^^^^^
Potash feldspars rarely are pure, usually containing the minerals albite (sodium feldspar) and anorthite (calcium feldspar).
Albite sometimes is used as the flux component in commercial
porcelains, but anorthite is not, because it does not occur in
commercially viable deposits within the United States. Figure
6 illustrates a -400 mesh (45 km) potash feldspar.
Nepheline syenite has replaced feldspars in many commercial body formulations, reducing the firing temperature and
increasing the alkali level in the glass p h a ~ e . ~ ONepheline
.~l
syenite is composed of the minerals nepheline, albite, and microcline and possesses a higher alka1i:silica ratio (4:9) than the
1 " " I " " I " " I " " I " " l " " I " " l " " l " "
28
Fig. 3. Powder XRD patterns for a domestic ball clay and kaolin, and
an English kaolin. Diffraction peaks at -6" and -8.8" 28 correspond to
Fig. 4. Powder XRD patterns for a well-crystallized and poorly crystallized kaolinite standards (Clay and Clay Minerals Society). Hinckley index evaluates the ratio of peaks in the 0,211 domain. Wellcrystallized sample contains a small amount of free quartz.
feldspars ( 1:6).28,31
(The alka1i:alumina ratio of nepheline syenite is equivalent to that of the feldspars.)
(3) Fillers
Fillers are generally the coarsest-particle-size fraction of a
porcelain body and tend to serve several functions. The coarse
particle size provides resistance to cracking during drying and
forms a skeletal network during firing to mitigate pyroplastic
IV. Processing
Depending on the industry, commercial porcelain processing
is either dry or wet.35 In many processes, dry processing is
sufficient, particularly in the consumer dinnerware market and
a portion of the tile market. In the electrical insulator and
commercial dinnerware market, wet processing is required to
obtain the mixing homogeneity necessary to maintain strength
and integrity in the finished products. Obviously, industries
that rely on slip ~ a s t i n g(such
~ ~ , as
~ the
~ sanitaryware industry)
and those that use spray-dried granulate for dry p r e ~ s i n g ~ ~ . ~ ~
(such as the low-tension electrical insulator industry and the
porcelain tile industry) must use wet processing.
January 1998
Porcelain-Raw
Specific
5Ulfdce
area (m2/g)
Typical
batch
(dry wt7c)
Surface area
(per component)
Kaolin
Ball clay
Quartz
Feldspar
25.0
27.0
0.9
1.1
25
20
25
30
6.25
5.40
0.23
0.33
51.2
44.2
1.9
2.7
12.2 m2/g
95.4% clay
Batch
Component
contribution
(a)
'As shown, the clay contributes -95% of the total specific surface area, dominating
the system. (The surface area values were obtained via nitrogen-gas adsorption.)
Material
Kaolinite
Fused silica
Quartz
~Al20,
Reference
1.8 x 10-20
0.83 x
1.7 x
5.32 x 1 0 - l ~
44
47
47
47
'The van der Waals attractive potential are greatest for alumina, least for fused
silica, and intermediate for kaolinite. Therefore, the zeta-potential necessary to disperse kaolinite is lower than that necessary to disperse alumina.
Table VII. Common Polymeric Additives and Soluble Salts Used in the Whitewares Industry to Control Suspension Behavior
and Processing Performance
Additive name
Nominal composition
Role
Common use
Na-PAA
Na-PMAA
Sodium silicate
Sodium chloride
Calcium chloride
Magnesium chloride
Magnesium sulfate
PEG
CMChIethocel
PVA
Na-poly(acry1ic acid)
Na-poly(methacry1icacid)
Na,SiO,
NaCl
CaC1,
MgC1,
MgSO4
Poly(ethy1ene glycol)
Carboxy methyl cellulose
Poly(viny1 alcohol)
Dispersant
Dispersant
Dispersant
Flocculant
Flocculant
Flocculant
Flocculant
Plasticizer
Binder
Binder
10
n .
"
-30
/O
0.05
0
a
I
Kaolin
Background Ionic Strength: 10 mM NaCl
10
12
PH
Fig. 8. Effect of Na,SiO, on the zeta-potential of a kaolin over a
range of pH values against a background ionic strength of l0mM
NaC1. Increase in the negative zeta-potential indicates the specific
adsorption of the SiOg- ion on the clay particle surface. Na,SiO, was
added at a level of 0.05 mg/m', based on the specific surface area of
the kaolin. HCI was used to adjust the pH to 2.2 prior to the test, then
NaOH was used to increase pH.
on colloidal behavior may result from the model of the kaolinite particle. Because of its crystal structure, kaolinite exhibits
unique colloidal behavior in water. When a clay particle is
dispersed in water, one surface acts similar to silica while the
other acts similar to alumina. From a pH of -2 (the isoelectric
point of silica) to a pH of -9 (the isoelectric point of alum i r ~ a ) the
, ~ ~two sides of the kaolinite particle are oppositely
charged-the silica surface is negatively charged and the alumina surface is positively charged. This observation regarding
the complex duality of kaolinite surface charge is highly con-
and Senapati
CaCI, Effect
Effect
No
10
lo-'
100
10'
lo2
103
Porcelain-Raw
January 1998
\ j+
11
2 1 Ball Clay-Kaolin
1j
a
Kaolin
0
lo-
0.0
Alumina
v
v
I
0.2
0.4
0.6
0.8
~pectively).~~
Data indicate that -50% as much dispersant is necessary
to reach the minimum in the viscosity curve for kaolin compared to
that for alumina.
The charge on a clay particle is attributed to ionic substitution in the tetrahedral layer (specifically, A13+ for Si4+) and
octahedral layer (Fez+or Mg2+for A13+).Although this substitution most certainly occurs, it is below the level necessary to
maintain the relatively large surface charges associated with
clay particles and is inconsistent with the chemical analysis
data. A majority of the surface charge on the silica surface of
kaolinite particles probably is due to the ionization of surface
silanol groups.60 The question of the colloidal nature of kaolinite and the mechanisms responsible for suspension stability
are the research areas most important for the advancement of
porcelain science.
Stability, in the colloidal sense used here, refers to creating an environment in which the interparticle potentials are
sufficiently large to prevent f l o c c ~ l a t i o nIn
. ~traditional
~~~~~~~
whiteware terminology, a stable suspension is one that remains
suspended. Because of the extremely broad particle-size distribution in a typical whiteware body, a suspension stable from
the colloidal aspect would be undesirable, because it would
lead to mass segregation of the particles because of its size. As
a result, the body suspension never is deflocculated to the
minimum in the viscosity curve during manufacture of porcelains.
Fig. 11. High-pressure shear rheology of ball clay, kaolin, 2:1 mixture of the clays, and a standard porcelain body (30% ball clay, 14%
kaolin, 33% feldspar, and 23% quartz) showing the dependence of
rheology on water content. Water contents (dry weight basis) are denoted by the values on the plot next to the data points.77
well as the limitations involved. Several theories have been
advanced to explain plasticity in clay systems, including the
presence of montmorillonites and illites (Grim65),colloidal and
physical properties of the clays (Hauser and Johnson66), water
films (Norton and Johnson67 and East68), stretched-membrane theory (Norton69),and surface tension ( S c h ~ a r t and
z~~
Kingery and Franc171). All of these theories are useful to explain a portion of the observed plastic behavior, but a unifying
theory needs to be developed.
Consequently, in many cases, the description of plasticity is
expressed in intangible terms (poor, fair, etc.); i.e., good
plasticity implies a rheological behavior that is applied easily to
a process and bad plasticity implies rheological behavior
that is nonideal. What results is only a qualitative description of
plasticity in reference to the process in which it is applied, with
terms such as workability, cohesion, and stickiness
being applied to describe the behavior of a plastic mass. Therefore, plasticity becomes a property of a material and workability a quality endowed by the process itself. Because plastic
forming places a body in shear under pressure, a better description of plasticity may be the extent and character of shear
behavior in a body under constraining pressure.
Building on the examples from soil mechanics72 and the
work of J e ~ ~ i kOnoda
e , ~ ~and J a n n e ~and
, ~ ~Kirby,75a modified
direct shear test has been developed using an annular design.34,76*77
This test allows plastic samples to be tested over a
range of constraining pressures, over a relatively short time
frame (-1.5 h), producing results similar to the direct shear
test^.^^,^^ Adopting an annular design minimizes problems associated with nonuniform compaction and allows continuous
shearing of the sample. Another advantage of the test is that a
shear-yield stress is measured at several pressures on a single
sample, thus allowing the sample cohesion (from a soil mechanics viewpoint) and the shear dependence on pressure to be
calculated. The test is performed within the pressure range
normally observed for plastic-forming processes, such as extrusion, but is entirely independent of the forming process,
allowing a broad range of samples to be evaluated. As illustrated in Fig. 11, the data indicate that the water contents necessary to obtain the maximum cohesion strength correlate well
with the saturation of the pore space with water.77 Also, the
effect of nonplastic additions to the clay body shows that a
significantly lower moisture level is necessary for a typical
whiteware batch compared to individual clay samples.
Within the manufacturing environment, plastic forming is
accomplished primarily through ram pressing, jiggering,78 ex-
12
t r u ~ i o n ,and,
~ ~ ,to~ an
~ extent, dry pressing, although the latter
does not necessarily require that the body behaves plastically.
Common to all of these forming methods is the application of
pressure and shear to a plastic mass to form the desired product. This applied stress state causes the plastic mass to permanently deform, compact (facilitating water loss from the piece,
if required), and flow during forming.
(5) Aging
Aging is a common phenomena within porcelain bodies,
referring to the change in rheology or plasticity within the body
over time. Historically, this change has been attributed to variabacteria-over
tions in the organic le~el~~-~~--particularly
time, which would logically lead to changes in particle-particle
interactions. Several different strains of bacteria have been
identified, and their contribution to the aging of the body is
u n d i s p ~ t e d . ~However,
' ~ ~ ~ with most modern industrial processes using potable water from water-treatment plants, the
potential for bacteria growth within the body is limited, as is
the potential for biologically driven aging processes in commercial processes.
The chemistry of the suspension medium can change over
time because of the dissolution of the raw materials, particularly the clays and the fluxes, leading to increased cation levels.
Specifically, the kaolinite particles do not appear to dissolve;
however, the impurity ions present in the clays as other clay
species or as other mineral phases are the apparent source of
the cations. Chemical analysis of the water from specific dissolution studies, as illustrated in Fig. 12, and filter press effluent shows elevated cation levels, which slowly increase with
time.86 Also, systems containing montmorillonites have high
cation exchange capacities, allowing monovalent and divalent
cations to be specifically adsorbed within the clay structure,
depending on the ionic concentration of the suspension medium. Increasing cation levels cause compression of the
charged double layer, leading to coagulation of the particles
and significant changes in the rheology of the suspensions and
the plastic bodies. It is not currently understood whether it is
better to age the suspension or the plastic body.
(7) Drying
Clay-based systems tend to be the most forgiving of all
ceramics systems because of their intrinsic plasticity. Drying
can be grouped into microscopic models and macroscopic control necessities. Both of these approaches have been addressed
in detail in the literature, and excellent reviews are available
e l s e ~ h e r e .Of
~ ~potential
. ~ ~ importance for the drying of whitewares is the new, so-called airless drying, in which steam is
used to assist the drying process, eliminating meniscus formation and substantially shortening the drying ~ y c l e . ~The
' concept of airless drying has not yet been applied to the drying of
porcelains.
V. Firing
Temperature, time, and atmosphere in the kiln affect chemical reactions and microstructural development in the porcelain
body and, consequently, are important in the fired properties of
porcelain. Fast firing of porcelain bodies has gained wide recognition and application in the whiteware i n d ~ s t r y , ' ~ re,~~-~~
ducing production costs by efficient use of energy in the firing
process. The fast firing of porcelain wares requires knowledge
of chemical reactions occurring during the process and of microstructural development.
The sequence of chemical reac\ions during the firing of porcelain bodies depends on the type of raw materials in the body,
but, for a typical clay-quartz-feldspar system, the basic reaction steps-ignoring the removal of nonchemically bound species, such as water and organics-can be outlined as follows:
(1) The crystal structure of kaolinite contains hydroxyl
groups, and the dehydroxylation of these groups to form
metakaolin (A1,03.2Si0,) occurs at -550C.9"'00 The chemical equation representing this process is
-550'C
A1,03~2Si0,-2H,0 _ jAl,03.2Si0,
I
"
" "
20
"
40
"
"
60
"
"
80
'
100
120
and Senaputi
140
+ 2H,O?
This is observed in typical analytical studies, such as differential thermal analysis (DTA) and thermogravimetry (TGA).
DTA-TGA curves for kaolinite are presented in Fig. 13. These
measurements also are important in the design of fast-firing
schedules. 15,92-95Dehydroxylation kinetics, believed to be first
order, yields a dehydroxylation rate directly proportional to the
surface area of k a ~ l i n . ~Furthermore,
~,'~~
the dehydroxylation
process is an endothermic process that is accompanied by a
reorganization of octahedrally coordinated aluminum in kaolinite to a mostly tetrahedrally coordinated aluminum in metakaolin.
January 1998
Porcelain-Raw
100
200
300
400
500
600 700
800
13
Temperature ("C)
TGA
80
'
100
200
300
400
500
600 700
800
900
1000 1100
Temperature ("C)
Fig. 13. DTA-TGA curves for a well-crystallized and poorly crystallized kaolinite sample (from Figs. 4 and 5 ) . Dehydroxylation process initiates
at a slightly lower temperature in the poorly crystallized sample, compared to the well-crystallized sample. Similarly, the exothermic reaction
associated with the spinel crystallization also is shifted to a slightly lower temperature.
either phase. The details regarding the two phases are discussed
in the microstructure section. Furthermore, the exact role of the
spinel phase in the reaction sequence and the microstructure
development has not been clearly established.
(5) The amorphous silica liberated during the metakaolin
decomposition is highly reactive, possibly assisting eutectic
melt formation at -990C, as suggested by S ~ h u l l e r . ' ~ ~ . ' ~ ~
Lundin'O' suggests instead that amorphous silica transforms
directly to cristobalite at -1050"C, but the general lack of
cristobalite in modem commercial porcelain bodies suggests
that the former scenario is more plausible.
(6) As illustrated in Fig. 1, a eutectic melt of potash feld-950-1 000C
spar with silica starts appearing at -990C. The eutectic tem3(A1,03~2Si0,) A 0.282A18(A1,,,,, @2.66)032perature is dependent on the type of feldspar: for potash feld+ 6Si0,
spar, the eutectic melt forms at -990C; for soda feldspar, the
eutectic melt forms at 1050"C, according to the K,O-Al,O,or
SiO, and Na,O-Al,O,-SiO,
phase diagrams, r e s p e c t i ~ e l y . ' ~ ~
The lower liquid formation temperature in the potash feldspar
-950-1000C
3(A1,0,.2Si02) A 0.562Si8(A1,,~,, @5,33)032 systems is beneficial for reducing the porcelain firing temperature. Also, the presence of albite in potash feldspar can reduce
+ 3Si0,
the liquid formation temperature by as much as 60C.101As the
where @ represents a vacancy. A y-alumina-type phase
temperature continues to increase, porosity is eliminated via
viscous-phase sintering.
(0.282A18(A11,,,3@2~66)03~)
and an aluminosilicate spinel
(0.562Si,(A1,0,6,@,,,,)03~)are the predicted reaction products.
(7) Porcelain bodies generally contain two different mulThe silica reaction product is amorphous. The exact structure
lite evolution paths: primary and secondary. The exact source
and temperatures for the formation of these two different types
of the spinel phase continues to be controversial, and the literature presents conflicting evidence regarding the existence of
of mullites continue to be debated. However, the spinel phase,
(2) The a-to @-quartzinversion occurs at 573C. Because
of the relatively great flexibility of the packed particle network,
the quartz inversion is of little consequence during the heating
cycle.
(3) Sanidine, the homogeneous, high-temperature, mixedalkali feldspar, forms within 700-10000C.'0' The formation
temperature apparently is dependent on the sodium:potassium
ratio.
(4) Metakaolin transforms to a spinel-type structure and
amorphous free silica at -950"-1000"C,'0~-106 as shown by the
following chemical eq~ation:~'
14
and Senapati
. " I _
Porcelain-Raw
January 1998
' \
I \
o=AL
o=0
0 =OH
'
*+-.4
Oxygen i o n s , v a r i o u s p o s i t i o n s
Aluminum
Silicon
= Si
o=o
16
and Senapati
Fig. 17. SEM photomicrograph of a polished and HF-etched commercial dinnerware sample illustrating the apparent dissolution of alumina grains (denoted A) and mullite formation around the particles
with mullite needles growing into the glassy matrix.131
Fig. 15. Replica illustrating a kaolinite particle fired to 1200C with
preferred orientation of mullite crystals on the particle surface. I3O This
represents primary mullite formed during the firing of a porcelain.
AaAT
1 -
l+um
+-
1-2vp
Ep
2Em
where Aa is the difference in expansion coefficients between
the glassy matrix and the particle, AT the cooling range of the
matrix-particle system, vm and up the Poisson's ratios; Emand
Epthe elastic moduli, and the subscripts m and p the matrix and
the particle, respectively.
The nature of cracks in porcelain bodies is dependent on the
expansion coefficients of the matrix and the particle. If the
particles contract more than the matrix, P is negative, resulting
in circumferential cracking around the particles. This is true for
quartz particles in the feldspathic glass matrix of the porcelain
body. The stress generation and associated cracking due to the
presence of quartz particles tend to be severe because of the
rapid displacive phase tradsformation of quartz during cooling.
January 1998
Porcelain-Raw
17
VII. Conclusions
Vol. 15.02. American Society for Testing and Materials, Philadelphia, PA.
5F. H. Norton, Fine Ceramics, Technology and Applications; pp. 1-19, 2768, 78-95, 130-54. R. E. Krieger, Malabar, FL, 1978.
6F. H. Norton, Elements of Ceramics; pp. xi-xiv, 1 4 5 , 94-105. AddisonWesley, Cambridge, MA, 1952.
7R. A. Haher and P. A. Smith, Overview of Traditional Ceramics; pp.
3-15 in Ceramics and Glasses, Vol. 4, Engineered Materials Handbook. ASM
International, Metals Park, OH, 1991.
8W. D. Kingery, Introduction to Ceramics; pp. 78-79, 5 3 2 4 0 . Wiley, New
York, 1976.
E. Rosenthal, Pottery and Ceramics; pp. 22654. Penguin Books, Middlesex, U.K., 1949.
OL. H. Milligan, Refractory Whitewares of the Porcelain Type, Am. Ceram. Soc. Bull., 29 [4] 1 5 4 5 7 (1950).
(a)Whitewares Technology at the Turn of the Millenium, Interceram, 45
[2] 71-74 (1996). (h)Whitewares Technology at the Turn of the Millenium,
Znterceram, 45 [3] 147-51 (1996). (c)Whitewares Technology at the Turn of
the Millenium, Interceram, 45 [4] 2 3 5 4 0 (1996).
I2R. C. P. Cubbon, Preparation of Whiteware Bodies, Interceram, 43 [4]
1 4 (1994).
13A.L. Johnson and F. H. Norton, Fundamental Study of Clay: 11, Mechanisms of Deflocculation in the Clay-Water System, J. Am. Ceram. Soc., 24 [6]
189-203 (1941).
I4J, Cochran, An Investigation of the 19th Century Pot Shops of Ohios
Hocking and Vinton Counties, Am. Ceram. Soc. Bull., 21 [9] 188-89 (1942).
15T.Manfredini and L. Pennisi, Recent Innovations in Fast Firing Process;
pp. 213-23 in Science of Whitewares. Edited by V. Henkes, G. Onoda, and W.
Carty. American Ceramic Society, Westerville, OH, 1996.
I6H. Seger, Gesammelte Schriften, 2nd ed., 1908, as referenced in F. Singer
and S. S. Singer, Industrial Ceramics. Chapman and Hall, London, U.K., 1963.
I
.
I7C. 0.Fairchild and M. F. Peters, Characteristics of Pyrometric Cones, .
Am. Ceram. Soc., 9 [I I] 701-42 (1926).
18
and Senapati
January 1998
Porcelain-Raw
19
20
and Senapati
Dr. Senapati is currently a postdoctoral fellow in the New York State Center for Advanced Ceramic Technology-Whiteware Research Center at Alfred University. He
received his Bachelors of Technology in ceramic engineering from Banaras Hindu
University, India, in 1992 and M.S. and Ph.D. degrees in glass science from Alfred
University in 1994 and 1997, respectively. Dr. Senapati is a member of the American
Ceramic Society and has been actively involved in glass and ceramics research.