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Porcelain-Raw

Materials, Processing, Phase Evolution, and


Mechanical Behavior
William M. Cam* and Udayan Senapati*

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

fine china (13%), sanitaryware (12%), foodserviceware (1l%),


and other (19%). Between 1984 and 1993, the whitewares
industry experienced a steady net sales increase from $4.55
.~
numbers can be used only as
billion to $8.21 b i l l i ~ n (These
indicators, because the statistical accuracy is dependent on the
response to a survey by the industry.)
A (ceramic) whiteware is defined as a fired ware consisting
of a glazed or unglazed ceramic body that is commonly white
and of fine texture, designating such product classifications as
tile, china, porcelain, semivitreous ware, and earthenware.4 A
whiteware is formed from natural raw materials of which the
major portion is clay. Porcelain, stoneware, china, and earthenware bodies historically have been distinguished by their
firing temperature and compositions (Table I).5 Porcelains also
are distinguished by the lack of open porosity in the fired
b ~ d y .Compositions
~,~
for the various types of industrial porcelains are presented graphically as a portion of the
K,O-AI,O,-SiO,
phase diagram in Fig. l.x
The name porcelain is believed to have originated from
the Portuguese word Porcellana and presumably first denoted products manufactured from the shell mother-~f-pearl.~
In the 20th century, porcelain products have received wide
application in a variety of fields ranging from electrical insulators to dinnerware; hence, the 20th-century connotation of
porcelain suggests a product more appropriately defined as a
fine-crystalline, strong, impervious ceramic product and relate(d) to the structure and type of product rather than to any
particular composition. lo
This review addresses porcelains via four topical areas: raw
materials; processing, including colloidal aspects; firing, including chemical reactions, phase development, and microstructural evolution; and mechanical properties. Within each
context, the discussion of porcelain refers primarily to triaxial
blends of clay, feldspar, and a filler material (usually quartz or
alumina) and, consequently, ignores stoneware and earthenware bodies, as well as glazing and decorating issues.

Manuscript No. 190529. Received October 1, 1997; approved December 1, 1997.


Member, American Ceramic Society.

The high level of intrinsic plasticity in clays and clay-based


systems and the resulting ease of forming objects precipitated

I. Introduction

ONTEMPORARY whitewares produced worldwide represent


the foundation of much of the ceramic industry, as well as
one of the cornerstones upon which the American Ceramic
Society was founded in 1898. Porcelains comprise some of the
most complicated of all ceramics in almost all aspects of the
manufacturing process: from raw materials, processing, and
forming, to the kinetic limitations and complexities of the microstructure and phase development. Even temperature measurement of porcelain firing has required the development of its
own unique system-pyrometric
cones-because thermocouples simply do not provide sufficient information to indicate the heat work associated with the porcelain firing process.
From an economic perspective, the commercial whiteware
industry accounts for -7% of the entire ceramic market worldwide, at sales levels of $6.1 billion in 1994 and $8.5 billion in
1996., In 1994, industrial production was divided into floor
and wall tile (31%), artware and pottery (14%), dinnerware and

11. Historical Perspective

Vol. 81, No. 1

Journal of the American Ceramic Society-Carty and Senapati

Table I.

Traditional Definitions of Whitewares

Name

Porcelain

ASTM definition4

Maturing temnerature'

A glazed or unglazed vitreous ceramic whiteware made by the procelain process, and used

for technical purposes, designating such products as electrical, chemical, mechanical,


structural, and thermal wares when they are vitreous
China

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

Nepheline syenite: 2-6


Sanitaryware: 8-1 2
Electrical: 8-1 2
Hard: 10-18'
Hotel: 10-13'

&lo5

fire clay
Earthenware

A glazed or unglazed nonvitreous ceramic whiteware

06-0S6

+Provided in pyrometric cone values.

Silica

nsioz

1713'

TRIDYMITE

\ I r
semivitreous whiteware

vitreous sanitary wall


Electrical insulators

Fig. 1. Leucite-mullite-cristobalite portion of the K,O-Al,O,-SiO,


phase diagram. Metakaolin is identified on the diagram, representing the
location of the clay portion of a porcelain batch following dehydroxylation. Ranges for typical commercial porcelain compositions are identified.
Potash feldspar is incongruently melting and the eutectic liquid formation temperature is 990"C8

the development of pottery skills more than 14 centuries ago.


Whitewares were formed entirely by hand prior to the development of modem automated forming techniques early in the
20th century. The first hand jiggers were introduced around
1925: and the development of automated jiggers did not become commonplace in the dinnerware industry until the late
1940s. Roller-tool jiggers are now the most commonly used
method for forming flatware. The tile industry is by far the
most automated within whiteware manufacturing, led by equipment developments in Italy' that provide for almost entirely
automated production (other than maintenance workers); i.e.,
once the process is initiated, the only human input is in the final
inspection stages. Currently, automation continues apace
within the dinnerware industry, with movement toward dry
pressing and pressure casting. l 2 It is likely that dinnerware,
sanitaryware, and electrical insulator production will remain
second to tile production in terms of automation for some time
because of the complexity of the shapes being produced.

'

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

Materials, Processing, Phase Evolution, and Mechanical Behavior

Table 11. Temperature Equivalents for Standard-Sized


Orton Pyrometric Cones
Cone

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

and its degree of maturity. Instead, heat work recorders, such as


pyrometric cones and other similar devices (e.g., rings and
"check" keys), have been developed to follow the firing progress as it responds to time and temperature variations, demonstrating the appropriate heating rate for maturation. Pyrometric
cones have been the most commonly used method for thermal
work determinations, and, although less commonly used today
in industry, bodies continue to be designated by their "cone
value." Pyrometric cones are three-sided pyramids made from
mixtures of kaolin, feldspar, quartz, and other raw materials
resembling the body composition that function as true indicators of chemical reaction kinetics in porcelain bodies. The first
standard and regularly used pyrometric cones were introduced
by Seger;I6 in the United States, Orton pyrometric cones17,18
are the norm. Table I1 lists the Orton pyrometric cone designations and their temperature equivalents. Modem commercial
firing processes are monitored with thermocouples and often
are checked with pyrometric cones or keys for verification of
the heat work accomplished.

111. Raw Materials

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.

Because of their three-part composition of clay, feldspar, and


quartz, porcelains are referred to as triaxial whitewares. Alumina can be substituted for quartz to increase the mechanical
strength of the fired ware, and nepheline syenite can be substituted for feldspar. These primary raw materials are listed in
Table 111; less commonly used raw materials are listed as secondary raw materials in Table IV. (Excellent introductions to
these and other common raw materials are published annually. 1 9 q
Another important raw material, although one less commonly monitored or controlled within manufacturing, is the
process water. It is common to use tap or potable water, which
usually contains a wide range of cations, including Ca2', Mg2+,
Na+, and K+. Table V provides typical tap water cation levels
from several locations. Even with well-controlled urban water
supplies, the level of these ions can vary, leading to substantial
fluctuations in suspension rheology and plasticity. Also, because the ionic concentration can vary dramatically with a geographic location, water chemistry generalizations are difficult.
Although it is important to realize that water quality can impact
the manufacturing process and substantially affect the reproducibility of rheological measurements, the contribution of local water sources is not addressed here.

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

Ball (plastic) clay


Kaolin (china) clay
Soda feldspar
Potash feldspar
Nepheline syenite
A1u mina
Quartz

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

quart^,^ TiO,, Fe,O,


Montmorillonite, quartz
K,O, CaO, MgO, quartz
Na,O, CaO, MgO, quartz
CaO, MgO, quartz
Na,O
TiO,, Fe,O,

+Quartz impurity in ball clay may he as high as 35 wt%.

Table IV. Secondary Raw Materials Used in the Manufacturing of


Commerical Whitewares
Raw material

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.

Journal of the American Ceramic Society-Carty

Table V. Typical Chemical Analysis of Several Tap Water


Samdes Showing a Broad Range of Variabilitvt
Cation concentration (ppm)
Mg
Na
K

Tap water site

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

Vol. 81, No. 1

+ 3H,O + Al,Si,O,(OH), + 4Si02 + 2KOH

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

Materials, Processing, Phase Evolution. and Mechanical Behavior

Table VI. Typical Chemical Analysis of a Georgia Kaolin,


a Kentuckv Ball Clav. and an English Kaolin
Comuosition (%I
Component

Georgia kaolin2'

Kentucky ball clayz6

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

in a whiteware body. The name "ball clay" originated from


the method of mining the clays-in large cubes or balls of clay
that were cut from the deposits.26 Processed ball clays and
kaolins have similar specific surface areas, but the quartz impurity level can be significantly higher in ball clays (up to 35%
on a dry-weight basis), requiring a much finer particle size for
the kaolinite fraction. Because ball clays frequently contain up
to several weight percent of decayed biological or organic matter, they are commonly dark in color-and sometimes blackin the raw form. The organic impurities can be removed entirely during heat treatment to produce a white body.
Kaolins commonly contain montmorillonites and smectites,
2:1 sheet silicates of variable composition (Fig. 2). Montmorillonites often incorporate water, as well as other impurity
ions, between the sheets (to compensate for ionic substitution
within the tetrahedral and octahedral layers), producing variable interlayer spacings. Smectites are particularly problematic
from a characterization perspective, because they often are present as individual layers of 2:l sheet silicates and, consequently, are undetectable via XRD. The presence of montmorillonites and smectites can have a significant impact on the
rheology and plasticity of a porcelain body, although the specific extent of their contribution is unknown. Commercially, it

is rare to have a complete mineralogical understanding of a


clay, which becomes problematic only when the impurity content varies significantly between batches.
The sheet silicate structure differentiates clays from other
common ceramic powders. The platey morphology of a clay
particle is responsible primarily for the high specific surface
areas of clays (18-30 m2/g), compared to other powders with
similar particle size. The mean diameter of ball clays and kaolins is -0.3-0.5 p,m. The high specific surface area, combined
with the platelike morphology, is believed to be responsible for
the intrinsic plasticity of clay-water systems.
From the clay mineralogy perspective, kaolinites are
grouped by their degree of Crystallinity. Standard clay samples
are available from the Clay and Clay Minerals Society, including examples of well-crystallized (KGalb) and poorly crystallized (KGa2) kaolinites. Both of these clays are Georgia kaolins; the powder XRD patterns and electron photomicrographs
are illustrated in Figs. 4 and 5. The degree of crystallinity is
determined by the "Hinkley Index," which compares the intensity of the peaks within the 0,211 domain region.27 The
greater the ratio, the greater the degree of crystallinity. It is
argued that poorer crystallinity offers greater potential plasticity and that the degree of crystallinity corresponds to a greater
degree of ionic substitution within the kaolinite lattice. However, the degree of crystallinity rarely is used as a characteristic
measurement of a clay by the ceramics industry.

(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

the interlayer spacings for mica and montmorillonite, respectively, as


illustrated in Fig. 1. Large reflection at -12.3" 28 represents the interlayer spacing for kaolinite. All three of the samples contain impurity
quartz.

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.

Journal of the American Ceramic Sociev-Gary and Senapati

Vol. 81, No. 1

deformation. Quartz and flint are the most commonly used


fillers2* in porcelain bodies and are essential to the microstructural evolution by dissolution of silica in the feldspathic glass.
The quartz grain size is important to the forming of the body;
in most modem commercial porcelain operations, a -325 mesh
(63 pm) quartz is used. However, undissolved quartz often is
responsible for a deterioration in mechanical properties as a
result of the displacive p- to a-quartz inversion at 573C during the cooling process. Figure 7 shows a photomicrograph of
a -325 mesh quartz sample.
Calcined alumina also is used as a filler in place of quartz to
circumvent the quartz inversion and thereby improve the mechanical properties of the body. The dissolution rate of alumina
is extremely slow compared to quartz because of the limited
solubility of alumina in the feldspathic glass. The significantly
greater cost of alumina compared to quartz is the major drawback to its use.
Fluxes and the fillers are termed nonplastics, because, by
themselves, they possess no intrinsic plasticity. The nonplastics
have a significantly larger particle size than the clays and,
consequently, provide networklike support for the body; they
also significantly reduce the viscosity of the slip.33 The nonplastics also allow greater plasticity to be achieved at lower
water contents, probably because of the reduction in specific
surface area within the
Also, the larger particle size
allows for a substantial increase in packing density in the green
body, resulting in increased strength and reduced shrinkage.
In industrial practice, it is common to characterize raw materials to obtain the specific surface area, particle size distribution, chemistry, mineralogy, and other data using a variety of
test methods. These results then are compiled and tracked with
the material in the process, but the correlations with manufacturing loss rates, process performance, and ware quality are
generally weak. Consequently, additional tools and more rigorous observation are needed to predict more accurately process behaviors within industry.
Fig. 5. SEM photomicrographs of (a) well-crystallized and (b)
poorly crystallized kaolinite samples used to generate the XRD patterns in Fig. 4. Well-formed faces and clay booklets are evident in the
well-crystallized sample.

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.

(1) Dry-Processing Route


Conceptually, dry processing is the simplest processing
route, by which the clay, feldspar, and quartz are mixed directly with tap water.35.39,40The amount of water varies with
the specific surface area of the batch and with the impurity and
dispersant levels (in the less-common case of dispersant use).
The amount of water is usually -18 wt% but can be as high as
21 wt%. Mixing is accomplished using a muller-mixer machine that imparts large amounts of shear to the powder-water
mixture, breaking down agglomerates and producing a homogeneous body suitable for plastic formng. (The dry-processing
route is closest to that used by the porcelain industry prior to
automation and by artisans for hand throwing and building.)

(2) Wet-Processing Route

Fig. 6. SEM photomicrograph of a -400 mesh potash feldspar


sample.

In the wet-processing route, the clays are slurried together


using local tap water as the dispersion medium; sometimes the
water contains dispersants. In some cases, the clay slurries are
allowed to age (usually on the order of 24 h) before the introduction of the nonplastics (i.e., the feldspar or nepheline syenite and the quartz or alumina). After the addition of the

January 1998

Porcelain-Raw

Materials, Processing, Phase Evolution, and Mechanical Behavior

Table VIII. Comparison of the Specific Surface Areas of


the Different Components of a Typical Whiteware Batch'
Raw material

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.)

Table IX. Effective Hamaker Constants for Kaolinite,


Silica, and Aluminat
Fig. 7. SEM photomicrograph of a -325 mesh quartz sample.

nonplastics, the suspensions sometimes are allowed to age


again, during which time the viscosity is adjusted through the
addition of polymeric additives or soluble salts. Table VII contains a list of the commonly used polymeric41 and soluble salt
additives. Mixing of the raw materials in the slurry form generally yields a more-consistent batch. A detailed discussion of
the behavior of clays within the suspension process and within
a whiteware batch is given below. Also, as noted in Table VIII,
clays contribute -95% of the surface area of a typical batch;
consequently, the colloidal behavior of the clays dominates the
rheology of the porcelain batch.

(3) Colloidal Behavior of Clays


The effective Hamaker constant (Aeff) of a particle suspended in a liquid dictates the magnitude of the van der Waals
attractive forces between the particles.4247 In the case of kaolinite, A,, is almost an order of magnitude larger than that of
silica and a factor of 7 lower than that of alumina (see Table
IX).44,47Therefore, kaolinite particles inherently are easier to
disperse than alumina; i.e., a lower zeta-potential is required
for suspension stability, allowing a broad pH range for suspension ~ t a b i l i t y . 4 ~Kaolinite
3~~
particles have zeta-potentials that
are negative over a broad pH range,48-50 and the zeta-potential
presumably lies between that of alumina and s i l i ~ a . ~ ' , ~ ~
It is well established that clays are negatively charged over
a broad pH range, and much research has been conducted to
understand the dispersion process for clays. Johnson and Norton12 are considered by many as the architects of a majority of
the dispersion science currently applied to clay systems. They
have conducted an extensive series of studies to determine the
effect of different salts-including
LiOH, NaOH, KOH,
Ba(OH),, Sr(OH),, Na,SiO,, and Na,CO,-on the dispersion
of kaolinite. Their conclusions are that ". . . (a) the charge on
the kaolinite particles controls the degree of deflocculation and
is governed by the type of cation and (b) the stability of the
system is controlled by the anion of the medium and is gov-

Material

Effective Hamaker constant (J)

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.

erned by the type of anion preferentially adsorbed' ' (emphasis


existing). These conclusions are mostly correct: the charge on
the kaolinite particle governs the degree of deflocculation, and,
as illustrated in their work, that charge is governed by pH; the
type and preferential adsorption of the anion controls deflocculation. The adsorption of the Cog- or SiOg- ion is not recognized or discussed, and the OH- ion is assumed to be solely
responsible for charge generation, with the Cog- or SiOZ- ions
forming weak acids in the suspension medium. Recent zetapotential data, however, show conclusively that the SiOg- ion
preferentially adsorbs on the kaolinite particle, substantially
increasing the net negative charge on the particle, as illustrated
in Fig. 8.49
The cation does not control the charge on the particle; instead, the cation causes flocculation rather than deflocculation
because of compression of the double layer as a counterion.
Johnson and Norton's observations are correct that the highervalent cations are undesirable for developing deflocculated systems, not because the lower-valent cations deflocculate the
system, but because the higher-valent cations cause flocculation, following the Schulze-Hardy rules for compression of the
double layer and the critical coagulation c ~ n c e n t r a t i o nThe
.~~
concentration of divalent counterions necessary to cause flocculation can be a factor of 50-100 lower than necessary for
monovalent counterions-the specific ratio is dictated by the
zeta-potential. The contribution of ionic strength to the stability
of clay suspensions is illustrated in Fig. 9 for different salts and
dispersant levels.54
Part of the confusion regarding the role of the ionic species

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

Slips, plastic bodies


Slips, plastic bodies
Slips, plastic bodies
Slips, plastic bodies
Slips, plastic bodies
Slips, plastic bodies
Slips, plastic bodies
Dry pressing (with PVA)
Improve glaze adherence
Dry pressing

Journal of the American Ceramic Society-Car9

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-

Vol. 81, No. 1

and Senapati

troversial, because it opposes the commonly held opinion that


clay particles have negatively charged basal planes with positively charged
The agglomeration of negatively charged gold particles to
the edges of clay platelets, as observed via transmission electron microscopy (TEM), forms the basis for the charge distribution on clay particles-e.g., that the edges must be positively
charged.56 The lack of particles agglomerated to the faces of
the kaolinite particles has been used to argue that the faces are,
therefore, negatively charged. However, the pH of the suspension used to prepare the TEM samples is unclear. The mineralogy of kaolinite would dictate that one surface behaves similar to silica and the other behaves similar to a l ~ m i n a . ~Part
' of
the problem may lie further in the large amount of literature
published by clay mineralogists investigating the behavior of
2: 1 sheet silicates, such as those in the montmorillonite family;
only a few references in the clay mineralogy literature, such as
G i i ~ e n , ~make
'
the distinction between the basal plane surface
chemistry characteristics of kaolinite versus other sheet silicates.
Direct confirmation regarding the dual surface nature of kaolinite is provided via atomic force microscopy (AFM) studies
in conjunction with surface modeling. These results confirm
the presence of silanol and hydroxide surfaces on kaolinite
particles.58
Indirect evidence occurs in the dispersant-clay interactions.
The amount of poly(acry1ic acid) (PAA) dispersant necessary
to reach the minimum in a viscosity versus dispersant level
curve, as illustrated in Fig. 10, is -50% of the amount to
entirely coat the surface of an alumina powder.49 The amount
of dispersant necessary to reach the minimum viscosity value
for the alumina particles is consistent with the amount of poly(methacrylic acid) (PMAA) necessary to coat the particle surface, as demonstrated by Cesarano et al.59 The observations
regarding PAA and PMAA are consistent with observations on
Na,SiO,. The adsorption measurements of PAA on various
kaolinites indicate substantial differences in adsorbed amounts
and a strong dependence on CaCl,

CaCI, Effect

Effect

No

10

lo-'

100

10'

lo2

103

Ionic Concentration (mM)


Fig. 9. Effect of cation levels on the viscosity of a typical whiteware batch showing that both a Na+-salt and a Ca2+-salt lead to coagulation of
the suspension and the corresponding increase in viscosity if added at a sufficient level. Effect of salt additions is evident regardless of the dispersant

Porcelain-Raw

January 1998

Materials, Processing, Phase Evolution. and Mechanical Behavior

\ 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

Dispersant Level (mg/m2)


Fig. 10. Comparison of viscosity versus Na-PAA dispersant level for
30 vol% alumina and kaolin suspensions at pH of 8.5 (+0.2),corrected
for the specific surface area of the powders (9.6 and 21.4 m2/g, re-

~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.

(4) Suspension Rheology and Plasticity


In addition to the particle-particle interactions, three other
factors contribute to the rheology and plasticity of porcelain
systems. These are, ranked in order of importance, particle
concentration, particle size and distribution, and particle morphology.61,62The characterization of suspension rheology is
now commonplace, and each whiteware industry (i.e., dinnerware, sanitaryware, etc.) has a preferred method. Historically,
the measurement of plasticity has been difficult, and more than
30 different methods for quantifying plasticity have been suggested. BlooF3 provides an overview of the various methods
that have been used. The spectrum of tests that have been
reviewed ranges from simply judging the feel of the body by
hand to methods that require sample preparation and long testing times, such as the triaxial test in soil mechanics. Furthermore, these tests fall in two basic categories: unconstrained and
constrained, of which constrained testing is most representative
of actual forming methods. Despite the many attempts that
have been made, there continues to be a need to develop a
method that universally quantifies p l a s t i ~ i t y . ~ ~ , ~ ~
Bloor also reviews some of the theories and mechanisms
used to explain why plasticity occurs in various materials as

Pressure Dependence ((kPa/kPa)xlOO)

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-

Journal of the American Ceramic Socieg-Curty

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.

(6) Plastic Body Preparation


Plastic bodies are prepared in the wet process by the dewatering of the body suspension using a filter press. The body
suspension is pumped under pressure into the filter press, and

the excess water is removed through filter membranes. The rate


of filtration is dictated by the solids loading of the suspension,
the degree of dispersion, and the particle size d i s t r i b ~ t i o n . ~ ~ , ~ ~
If the body is too well dispersed, the filter-pressing process is
lengthy, particle segregation may occur throughout the cake,
and the resulting body probably is too stiff for proper forming.
If the body is highly flocculated, the filter-pressing process is
very rapid, but the plastic body possesses too much water, and
shape retention following the forming process is problematic.
The rheology of the suspension feeding the filter press is controlled by the use of dispersants and, coagulants such as CaC1,
(Table VII). Each manufacturing facility follows unique guidelines that have been developed through years of practical experience.
The initial suspension is filter pressed in processes that rely
on slip casting for fabrication, and the filter press cakes are
redispersed to make the casting slip. This process serves two
purposes: it removes the soluble species, resulting in greater
control over the rheology, and it provides a more economical
means of storing the body prior to its use in the production
process.

(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.

( I ) Reactions throughout the Firing Process

MonovalentCations via Nepheline Syenite

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

Vol. 81, No. 1

and Senaputi

140

Aging time (hour)


Fig. 12. Combined monovalent (Na+ and K+) and divalent (Ca2+and
Mg2+) cation concentrations in solution for nepheline syenite and a
ball clay, obtained from a 25 vol% aqueous suspension over the course
of one week. Nepheline syenite represents the highest measured dissolution levels for monovalent cations, whereas the ball clay exhibits
the highest dissolution level of divalent cations. Divalent cation dissolution level for nepheline syenite was at the detection limit and, therefore, not shown.86

+ 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

Materials, Processing, Phase Evolution, and Mechanical Behavior

100

200

300

400

500

600 700

800

13

900 1000 1100

Temperature ("C)
TGA

Well Crystallized Kaolinite

Poorly Crystallized Kaolinite

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:~'

Journal of the American Ceramic Society-Carty

14

and Senapati

Vol. 81, No. 1

a fully satisfactory metakaolin structure should account for the


presence of 11%-12% residual hydroxyl groups (based on the
initial kaolinite hydroxyl level), the cell parameters should be
consistent with spectroscopy data, and the model should not
-1075C
contravene bonding rules. The BN model shows no hydroxyl
3A120,.2Si02 + 4Si0,
0.282A1,(All,,,, @2.66)032
groups, whereas the MacKenzie model, shown in Fig. 14(b),
does incorporate hydroxyl groups in the A1-0 layers and sator
isfies most of the deficiencies of the other models. In the current
authors' opinion, controversies such as the coordination of
0.562Si8(A1,,~,, $5,33)032
3A120,.2Si02 + 4Si0,
aluminum (more specifically, the ratio of fourfold to sixfold
coordinated aluminum), the exact dimensions of the c paramEarly studies on the aluminosilicate crystal structures indicate
eter, and the amount of hydroxyl groups in the A1-0 layers
the mullite structure to be identical to the sillimanite structure,
continue to be far from resolved, and further characterization
with each having orthorhombic crystal lattices.102Later studand structural modeling is necessary.
ies, however, indicate that the stable form of aluminosilicates
The structure of the spinel phase that forms at -980C by the
formed at higher temperatures (>lOOO"C) and atmospheric
decomposition of metakaolinite also is controversial. Some repressure is mullite, but the literature also presents unresolved
s e a r c h e r ~ ~ believe
~ ~ , ' ~it ~to*be~ an
~ ~aluminum silicon spinel,
issues as to the nature of the melting of mullite, i.e., whether it
whereas ~ t h e r ~believe
~ ~ that
~ Jit ~is a~ y-alumina
, ~ ~ ~
phase.
' Furthermore, addimelts congruently or incongruently.
Okada et aZ.Io5 suggest that the decomposition product of
tional work on mullitel'o has indicated that chemical homogemetakaolin is a y-alumina phase, but containing silica accordneity is essential to the formation of mullite at lower temperaing to chemical analysis. In summary, the structure of the
tures. On the atomic level, mullite formation can start at 980C,
spinel phase remains unclear.
but homogeneity on the nanometer scale can delay mullite
formation to temperatures as high as 1300C.
(3) Mullite Formation
(8) At -1200"C, the melt becomes saturated with silicaUnresolved questions regarding the structure and identity of
quartz dissolution ends, and quartz-to-cristobalite transformathe spinel phase also have led to difficulties in understanding
tion begins.
the formation of mullite in porcelain bodies. LundinIo1 has
(9) Above 12OO0C,mullite crystals grow as prismatic crysconcluded through electron microscopy studies of porcelain
tals into the remains of the feldspar grains (referred to as feldbodies that the concentration gradients and diffusion rates of
spar relicts by Lundin'O').
alkalis are the two most important factors affecting mullite
(10) As the body starts to cool, pyroplastic deformation
formation. Comer'30 has demonstrated that mullite can preferand relaxation within the glass phase prevent the development
entially orient on the surface of kaolinite relicts (presented in
of residual stresses until the glass transition temperature is
Fig. 15), and Lundin has proposed that the mullite in the clay
reached. As the body cools below the glass transition temperarelicts serves as a seed for the crystallization of the mullite
ture, residual stresses are developed because of thermal expanneedles in the feldspar relicts. The mullite formed in the clay
sion mismatch between the glass and the included crystalline
relicts is generally termed the primary m ~ l l i t e ,because
~ ~ ~ ,it~ ~ ~
phases (i.e., mullite and quartz, and in some cases, alumina and
forms at a lower temperature and is a product of the clay
cristobalite).
minerals. As alkali diffuses out of feldspar at higher tempera(1 1) Cooling through the quartz inversion (573C) results
tures, secondary mullite nucleates and grows. An electron miin a quartz particle volume decrease of 2%,29,102which can
crograph of secondary mullite in a feldspar relict is shown in
produce sufficient strain to cause cracking of the glassy matrix
Fig. 16.131Studies on the morphology of mullite have indicated
and the quartz grains. The cracking severity is dictated by the
that primary mullite occurs mostly in the form of scaly crysquartz particle size and the cooling rate. The effect of free
tals,112.113whereas secondary mullites are mostly needlequartz on the porcelain strength is discussed below.
shaped crystal^.^^^^^^^ It is believed that the secondary mullites
(12) Finally, the p- to a-cristobalite inversion at 225"are formed from the recrystallization and dissolution of alumi250C is similar to the quartz inversion, but it produces a larger
nosilicates in the melt.
volumetric change (-5%); with a higher activation energy barJohnson and P a ~ k ' ,have
~ suggested that impurities, such as
rier, the transformation is less severe than that of q ~ a r t z . ~ ~ , ' Fe,03
~ ~ and TiO,, affect the kinetics and morphology of mullite
formation and that the exsolution of silica facilitates mullite
(2) Metakaolinite Formation
formation in kaolin. In another study, Pask and T ~ m s i ahave
'~~
The microstructure development in any clay-based product
postulated that the heating rate is crucial to the crystal structure
is triggered by the conversion of kaolin to metakaolin. One of
of mullite. Slow heating rates lead to formation of spinel at
the earliest works in this field by LeChatlier114concluded, on
lower temperatures, which then reacts with silica by a diffuthe basis of thermal analysis and acid dissolution tests, that the
sion-nucleation mechanism to form orthorhombic mullite. Fast
free alumina on dissolution comes from the molecular transheating rates lead to tetragonal mullite formation, with the
formation of kaolinite. Several researchers have shown that
aluminum ion in sixfold coordination at temperatures as low as
kaolin transforms to metakaolin at -50O"-55O0C, but previous
980C. The tetragonal mullite then converts to the desirable
studies115-119have suggested a noncrystalline or amorphous
orthorhombic mullite at higher temperatures. Further studies
structure for metakaolin. Brindley and Nakahira (BN),96,97on
involving high-temperature dynamic XRD are required to unbasis of XRD studies, first proposed a crystal structure for
derstand the mullite formation kinetics,
morphology, and crys'
metakaolin. The BN model for metakaolin maintains the a and
tal structures in porcelain bodies.
b kaolinite lattice parameters in metakaolin, but the c-axis peAnother source for mullite may be from the dissolution of
riodicity disappears, leading to diffuse XRD patterns. BN also
alumina that has been substituted for quartz within a porcelain
have indicated that the octahedral aluminum hydroxide layer of
body. Figure 17 shows the appearance of mullite surrounding
kaolinite is likely to be changed more than the tetrahedral silica
alumina grains and the formation of mullite needles into the
layer during the dehydroxylation process and that the structure
glass phase in a commercial dinnerware body fired at cone
of metakaolin allows the kaolinite layers to collapse to -0.63
9.I3l TEM is necessary to verify that the surrounding phase is
nm, in agreement with the measured densities of kaolin and
mullite and that alumina particle dissolution is the basis for
metakaolin. The proposed BN metakaolin structure is illusadditional mullite formation.
trated in Fig. 14(a). Most of the metakaolin models published
(4)
Cristobalite Formation
since the BN mode1120-126have been modifications of it. On
Lundinlol has indicated that, in a porcelain body with excess
the basis of computer simulation and nuclear magnetic resonance (NMR) studies, MacKenzie et d.lo4 have proposed that
quartz, the cristobalite phase begins to form when the rate of
being a nonequilibrium unstable phase, certainly transforms to
mullite above 1075C. The chemical reactions describing the
conversion to mullite are97

. " I _

Porcelain-Raw

January 1998

Materials, Processing, Phase Evolution. and Mechanical Behavior

' \

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

Fig. 14. Meta-kaolin models from (a) Bnndley and Nakahira96,97


and (b) Mackenzie et

transition of quartz to cristobalite exceeds the rate of quartz


dissolution. The transformation of quartz to cristobalite is a
solid-state reaction starting from the surface of the quartz grain.
Schneider et al. 134 have shown that the transformation of
quartz to cristobalite can be accelerated by high crystal defect
density and small particles. It also is probable that the cristobalite may form as a devitrification product from the glass
phase as the melt becomes saturated with silica. The potential
for cristobalite formation becomes less likely, however, under
the modem trend to shorter firing schedules and lower firing
temperatures.

VI. Mechanical Properties


There are three major theories that have been developed to
explain the strength of porcelains.

(1) Mullite Hypothesis


One of the oldest theories on the strength of porcelain, the
mullite hypothesis, first proposed by Zoellner, 135 posits the
strength of a porcelain body as solely dependent on the feltlike
interlocking of fine mullite needles. Later versions of this hypotheses have indicated that the strength increases with in-

creasing mullite ~ o n t e n t . ' ~ ~At


- ' ~higher
~
temperatures, the
mullite needles coarsen, leading to a smaller number of larger
needles. The larger needles do not interlock as efficiently as the
smaller ones, resulting in decreased strength. Hence, firing
temperature and generating the correct amount of properly
sized mullite needles are vital in achieving the desired strength.
Furthermore, secondary mullite, because of its acicular morphology and smaller needle diameter, might increase strength
more than primary mullite.

(2) Matrix Reinforcement Hypothesis


The difference in thermal expansion coefficients between the
matrix (glassy phase, in the case of porcelain) and dispersed
particles (such as quartz and alumina) or crystalline phases
formed during firing (such as mullite and cristobalite) produces
strong compressive stresses on the glassy phase. Such induced
"thermal" compressive stresses due to thermal expansion m i s match lead to strength improvements in the porcelain bodies.
This idea of matrix reinforcement, widely referenced in the
literature as the prestressed theory of strength improvement in
porcelain,139is discussed most often in regard to quartz particles in a glassy matrix. For a single spherical particle in an
isotropic medium, the differences in thermal expansion coef-

Journal of the American Ceramic Society-Car9

16

and Senapati

Vol. 81, No. 1

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.

Fig. 18. Polished, but unetched, porcelain sample showing cracking


associated with quartz grains (denoted Q). Also visible in the photomicrograph are alumina particles (denoted A).131
Fig. 16. SEM photomicrograph of secondary mullite formed within
a feldspar relict in a commercial dinnerware porcelain sample. Sample
was polished, then etched using a 10% HF solution for 20 s.l3I

ficients can lead to radial and tangential stresses. The total


stress, P, on the particle can be given by140

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.

If the matrix contracts more than the particle, then P is positive,


resulting in radial cracks emapating from the particles, which
could easily connect and cause deleterious strength. There is no
evidence of particles or crystalline phases having lower expansion than the glassy phase in porcelain bodies; hence, the second effect can be ignored.
Warshaw and SeiderI4l have demonstrated that particle size
is crucial to crack development in the porcelain body. The
electron micrographs of larger quartz grains (50-150 pm) exhibit continuous peripheral fracture at or near the grain boundaries and interconnected matrix fractures: those between 25 and
50 pm exhibit less-severe pgipheral fracture and rare matrix
fractures, and those <10 pm exhibit only occasional peripheral
fracture with total absence of matrix fracture. Figure 18 illustrates cracking associated with a quartz grain in a commercial
dinnerware body. The maximum strength was observed for 25
pm quartz particles. The decrease in strength with smaller
particles is due to dissolution of quartz in the melt, leading to
fewer particles and, hence, less prestress, resulting in lower
strength. The larger particles result in interconnected matrix
fractures, similar to those for radial cracks, leading to poor
strength. An effect that can lead to artifacts in microstructural
evaluation is the release of induced stresses during specimen
preparation; e.g., grinding and polishing of samples might lead

January 1998

Porcelain-Raw

Materials, Processing, Phase Evolution, and Mechanical Behavior

to some observed cracks on surfaces because of stress release.


Warshaw and Seider also have shown that alumina particles in
porcelain bodies increase strength. The current authors support
the idea, suggested first by Hasselman and F ~ l r a t h , that
~ ~this
is due to dispersion strengthening of the matrix and not to
matrix reinforcement.
There is an increasing trend among porcelain manufacturers
to use nepheline syenite instead of feldspar as a flux. Holm~ t r o m ~ ~has
. ~attributed

this trend to several factors. First,


nepheline syenite contains less free quartz than feldspar. Second, nepheline syenite results in a glassy matrix whose thermal
expansion is closer to that of the residual quartz crystals, thus
reducing the potential for cracking due to the quartz inversion.
Kristoffersson et al. 44 have noted similar effects of nepheline
syenite on strength increase of porcelain bodies.

17

grains because of being crystallized either from the glass phase


or by the direct conversion of quartz; the cristobalite is formed
at the expense of quartz, consequently reducing the quartz content of the body; and the cristobalite inversion temperature is
lower, 225-25OoC, compared to 573C for the quartz inversion, leading to lower strain development during the cooling
process. The lower inversion temperature, however, also may
pose a potential cyclic fatigue problem for porcelains that may
be heated and cooled during use (such as commercial dinnerware).

VII. Conclusions

Because of the complex interplay between raw materials,


processing routes and approaches, and the kinetics of the firing
process, porcelains represent some of the most complicated
(3) Dispersion-Strengthening Hypothesis
ceramic systems. The introduction of automated processing
The dispersion-strengthening hypothesis proposes that the
schemes has required the development of fundamental underdispersed particles limit the size of Griffith flaws, leading to
standing, but, despite the immense amount of existing and
increased strength. Hasselman and Fulrath also have studied
ongoing research, this understanding remains limited. Major
the effect of alumina spheres in glass on the strength of glasschallenges to the development of porcelains and the improveceramic composites, with the expansion coefficient of the glass
ment of commercial manufacturing processes remain, includmatched to that of alumina. The results of strength and fracture
ing in-depth understanding of the colloidal nature of the raw
studies indicate that the strength of the glass-ceramic composmaterials necessary for improved control; a reliable means of
ite is a function of the volume fraction of the dispersed phase
quickly quantifying and understanding plasticity in clay sysat low volume fractions; at high volume fractions of the distems; the means to reliably predict the microstructure and
persed phase, the strength is dependent on the volume fraction
phase evolution in porcelain systems, whether composed of
and the particle size of the dispersed phase. Maity et
three primary components or several raw materials; and theohave shown that the replacement of some of the quartz by
retical explanations regarding the roles of the crystalline phases
sillimanite and some of the feldspar by cordierite increases
on firing, consistent with the observed mechanical properties.
strength. They have hypothesized that strength increase is a
From a research perspective, the study of porcelains continues
dispersion-strengthening effect, because sillimanite and cordito present multiple, complex research challenges, offering sigerite act as dispersant solids in the glassy matrix. B l ~ d g e t t ~ ~ nificant opportunities for growth and development well into the
and Harada et aZ.148also have indicated strength increase in
foreseeable future.
porcelain bodies with the addition of alumina particles. Likewise, they support a strengthening mechanism because of
Acknowledgments: The authors would like to thank J. Howles, M.
stronger particles, as observed when zircon is added to porceTindale, and C. Perry for their assistance with the XRD patterns and for their
help preparing several of the figures.
lain bodies.
In porcelain bodies, the thermal expansion coefficients of the
glass matrix rarely match those of the dispersed particles;
References
hence, there is always a strengthening effect because of matrix
Giants in Whitewares, Ceram. Ind., 145 [3] 4 3 4 5 (1995).
reinforcement. Furthermore, interlocking mullite needles al*Giants: A lO-year Summary, Ceram. Ind., 145 [3] 55-57 (1995).
Imports Remain Threat to Tile Industry, Ceram. Ind., 147 [9] 1 6 1 8
ways are formed because of the firing temperature and kinetics.
(1997).
Hence, a universal theory of strength in porcelain bodies
4Standard Definition of Terms Related to Ceramic Whitewares and Related
should account for all the above mechanisms for strengthening.
Products, ASTM Designation C 242. I996 Annual Book of ASTM Standards,
~

(4) Overall Strength Considerations


Intrinsic flaw size is perhaps the predominant factor affecting the strength of porcelain bodies and depends very much on
the microstructure. Although the simplest intrinsic flaw in a
ceramic can be a pore, the presence of a glassy phase tends to
generate nearly spherical pores in a highly dense matrix, thus
improving the strength of porcelains. In the absence of pores,
strength is dictated mostly by the presence of preexisting
cracks. The typical strength-controlling factors in multiphase
polycrystalline ceramics are thermal expansion coefficients of
the phases, elastic properties of the phases, volume fraction of
different phases, particle size of the crystalline phase, and
phase transformations. All of these factors are present in porcelain systems and are dependent on the extent of the firing
process. In terms of strength reduction, phase transformation is
probably the most important because of the presence of quartz
and cristobalite.
(5) Effect of Quartz and Cristobalite on Strength
The presence of cristobalite, instead of quartz, in the porcelain body often produces an increase in strength, despite the
fact that cristobalite experiences a larger displacive transformation than quartz during cooling. The increase in strength of
cristobalite porcelains can be explained via three perspectives:
the cristobalite grains tend to be much smaller than the quartz

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

Journal of the American Ceramic Society-Carty

I8W. J. McCaughey and J. M. Neff, Notes on Constitution of Pyrometric


Cones, Am. Cerum. Soc. Bull., 23 [lo] 373-75 (1944).
L9AnnualMinerals Review, Am. Ceram. Soc. Bull., 76 [6] 65-144 (1997).
,Materials Handbook, Ceram. Ind., 146 [ I ] 41-178 (1997).
21H.H. Murray and W. D. Keller, Kaolins, Kaolins, and Kaolins; pp. 1-24
in Kaolin Genesis and Utilization. Edited by H. Murray, W. Bundy, and C.
Harvey. Clay Minerals Society, CO, 1993.
22R,W. Grimshaw, The Chemistry and Physics of Clays; pp. 366-439.
Wiley-Interscience, New York, 1971.
23T,Dombrowski, Theories of Origin for the Georgia Kaolins: A Review;
see Ref. 21, pp. 75-98.
24D.M. Moore and R. C. Reynolds, X-ray Diffraction and the Ident@cation
and Analysis of Clay Minerals, 2nd ed.; pp. 227-60. Oxford University Press,
New York, 1997.
25S, W. Bailey, Review of the Structural Relationships of the Kaolin Minerals; see Ref. 21, pp. 2 5 4 2 .
26P. S. Powell, Ball Clay Basics, Am. Ceram. Soc. Bull., 75 [6] 74-76 (1996).
27D,N. Hinkley, Variability in Crystallinity Values Among the Kaolin
Deposits of the Coastal Plain of Georgia and South Carolina; pp. 229-35 in
Proceedings of the 1 Ith National Conference on Clays and Clay Minerals (Ottawa, Ontario, Canada, 1962).
*%. T. Lundin, Studies on Triaxial Whiteware Bodies. Almqvist and Wiksell,
Stockholm, Sweden, 1959.
29F. Singer and S. S. Singer, Industrial Ceramics; pp. 9-12, 167-69,23644,
393-99, 430-78. Chapman and Hall, London, U.K., 1963.
,OL. E. Oberschmidt, The Use of Nepheline Syenite in Electrical Porcelain
Bodies, Am. Ceram. Soc. Bull., 36 [I21 4 6 4 4 5 (1957).
,C. J. Koenig, Nepheline Syenite in Hotel Chinaware Bodies, J. Am.
Ceram. Soc., 25 131 90-93 (1942).
V.E. Gontmakhler, I. P. Nesterenko, and V. A. Kopeikin, Phase Transformations in Firing Nepheline Containing Ceramic Masses, Steklo Keram., 4,
26-27 (1976).
33S.S. Kocatopcu, Fundamental Study of Clay: VII, Effect of Particle Size
on Properties of Casting Slips, J. Am. Ceram. Soc., 29 [4] 99-107 (1946).
34C.Lee, The Characterization of Plasticity in Clay-Based Systems; M.S.
Thesis. Alfred University, Alfred, NY, 1995.
35J,S . Reed, Introduction to the Principles of Ceramic Processing, 2nd ed.;
pp. 395474. Wiley, New York, 1993.
36W,H. Earhart, Use of North Carolina Kaolin in Casting Bodies, Am.
Ceram. Soc. Bull., 19 [5] 163-68 (1940).
37N. Staneva and I. Kasabov, The Influence of Electrolytes on the Casting
Properties of Porcelain Slips, Interceram, 45 [ l ] 12-14 (1996).
38J.R. Fisher and J. F. Potter, Factors Affecting the Physical Structure of
Dry-Pressed Steatite, Am. Ceram. Soc. Bull., 34 161 177-81 (1955).
39C. H. Rapp, Factors Affecting Physical Properties of a Dry-Mixed
Body, Am. Ceram. Soc. Bull., 19 [3] 87-89 (1940).
40R.A. Snyder and J. D. Hamish, Dry Mixing in the Electrical Porcelain
Industry, Am. Ceram. Soc. Bull., 19 [7] 258-59 (1940).
41D.J. Shanefield, Organic Additives and Ceramic Processing; pp. 21 1-79.
Kluwer, Dordrecht, The Netherlands, 1995.
4ZH.C. Hamaker, The London-van der Waals Attraction Between Spherical Particles, Physica, 4, 1058-72 (1937).
43L. Bergstrom, A. Meurk, H. Arwin, and D. J. Rowcliffe, Estimation of
Hamaker Constants of Ceramic Materials from Optical Data Using Lifshitz
Theory, J. Am. Ceram. Soc., 79 [2] 3 3 9 4 8 (1996).
44L. Bergstrom, M. Sjoberg, and L. Jiimstrom, Concentrated Kaolinite Suspensions-Polymer Adsorption and Rheological Properties; see Ref. 15, pp.
65-77.
4sJ. E. Funk and D. R. Dinger, Flocculation by van der Waals Energy/
Particle Size Distribution, Am. Ceram. Soc. Bull., 74 [ l ] 48-52 (1995).
46R.J. Hunter, Introduction to Modem Colloid Science; pp. 17-20, 227-98.
Oxford Science, Oxford, U.K., 1993.
47W. B. Russel, D. A. Saville, and W. R. Schowalter, Colloidal Dispersions;
p. 148. Cambridge University Press, Cambridge, U.K., 1989.
48D.J. Williams and K. P. Williams, Electrophoresis and Zeta-Potential of
Kaolinite, J. Colloid Interface Sci., 65 [I] 79-87 (1978).
49K. Rossington, U. Senapati, and W. Carty, A Critical Evaluation of Dispersants for Clay-Based Systems, presented at the American Ceramic Society
Whitewares Division Meeting (San Antonio, TX, Nov. 1997); manuscript in
preparation.
sOM.Tschapek, L. Tcheichvili, and C. Wasowski, The Point of Zero Charge
of Kaolinite and Si02-A1,0, Mixtures, Clay Miner., 10, 219-29 (1974).
51M. Hashiba, H. Okamoto, Y. Nurishi, and K. Hiramatsu, The ZetaPotential Measurement for Concentrated Aqueous Suspension by Improved
Electrophoretic Mass Transport Apparatus-Application to A1,0,, ZrO,, and
SIC Suspensions, J. Muter. Sci., 23, 2893-96 (1988).
52L.Bergstrom, Rheology of Concentrated Suspensions; pp. 193-244 in
Surface and Colloid Chemistry in Advanced Ceramics Processing. Edited by
R. J. Pugh and L. Bergstrom. Marcel Dekker, New York, 1994.
53D.J. Shaw, Introduction to Colloid and Interface Science, 4th ed.; pp.
210-34. Butterworth-Heinemann, Oxford, U.K., 1992.
54K.Rossington, U. Senapati, and W. Carty, The Effect of Ionic Strength on
Clay and Whiteware Body Suspension Rheology, manuscript in preparation.
55R.0. James, Characterization of Colloids in Aqueous Systems; pp 349410 in Advances in Ceramics, Vol. 21, Ceramic Powder Science. Edited by
G. L. Messing, K. S. Mazdiyasni, J. W. McCauley, and R. A. Haber. American
Ceramic Society, Westerville, OH, 1987.
56P. A. Thiessen, Wechselseitige Adsorption von Kolloiden, Ztachr.
Elektrochem, 48 [12] 675-81 (1942).

and Senapati

Vol. 81, No. 1

57N. Giiven, Molecular Aspects of Clay-Water Interactions; pp. 2-79 in


Clay-Water Interface and Its Rheological Implications, CMS Workshop Lectures, Vol. 4. Edited by N. Giiven and R. Pollastro. The Clay Minerals Society,
Boulder, CO, 1992.
58M. Baba, H. Ishii, T. Okuno, H. Miyake, and S. Kakitani, AFM Observation and Analysis for Atomic Arrangement on the Surface of Layer Silicates
by a Novel Procedure of Image Processing, Poster Presentation at The 11th
International Clay Conference, Ottawa, Canada, 1997.
59J.Cesarano 111, I. A. Aksay, and A. Bleier, Stability of Aqueous a-Al,O,
Susuensions with PoMmethacrvlic acid), Polvelectrolvte.
J. Am. Ceram. Suc.,
,
71 +I 250-55 (19ssj.
60R. K. Iler, The Chemistry ofSilica; pp. 355-60,659-65. Wiley, New York,
1979.
6H, A. Barnes, J. F. Hutton, and K. Walters, An Introduction to Rheology;
pp. 115-37. Elsevier Science Publishers, Amsterdam, The Netherlands, 1989.
62L. Bergstrom, Rheology of Concentrated Suspensions; pp. 193-244 in
Surface and Colloid Chemistry in Advanced Ceramics Processing. Edited by
R. J. Pugh and L. Bergstrom, Marcel Dekker, New York, 1994.
63E.C. Bloor, Plasticity: A Critical Survey, Trans. Br. Ceram. Soc., 56,
423-81 (1957).
64E. 0. Wilson, Plasticity of Finely Ground Minerals with Water, J. Am.
Ceram. Soc., 19 141 115-20 (1936).
65R.E. Grim, Relation of the Composition to the Properties of Clays, J.
Am. Ceram. Soc., 22 151 141-51 (1939).
66E.A. Hauser and A. L. Johnson, Plasticity of Clays, J. Am. Ceram. Soc.,
25 [9] 223-27 (1942).
67F.H. Norton and A. L. Johnson, Fundamental Study of Clay: V, Nature of
Water Film in Plastic Clay, J. Am. Cerum. Soc., 27 [3] 77-80 (1944).
68W.H. East, Fundamental Study of Clay: X, Water Films in Monodisperse
Kaolinite Fractions, J. Am. Cerum. Soc., 33 [7] 211-18 (1950).
h9F,H. Norton, Fundamental Study of Clay: VIII, A New Theory for the
Plasticity of Clay-Water Masses, J. Am. Ceram. Soc., 31 181 2 3 W 0 (1948).
70B.Schwartz, Fundamental Study of Clay: XII, A Note on the Effect of the
Surface Tension of Water on the Plasticity of Clay, J. Am. Ceram. Soc., 35 121
4 1 4 3 (1952).
71W.D. Kingery and J. Francl, Fundamental Study of Clay: XIII, Drying
Behavior and Plastic Properties, J. Am. Ceram. Soc., 37 [12] 596-602 (1954).
72T.W. Lambe and R. V. Wbitman, Soil Mechanics; pp. 52-70, 97-161.
Wiley, New York, 1969.
73A,W. Jenike, Storage and Flow of Bulk Solids, Bulletin No. 123, Utah
Engineering Experimental Station, University of Utah, Salt Lake City, UT,
1964.
74G. Y. Onoda and M. A. Janney, Application of Soil Mechanics Concepts
to Ceramic Particulate Processing; pp. 53-74 in Advances in Powder Technology. Edited by G. Y. Chin. ASM, Metals Park, OH, 1982.
7sJ. M. Kirby, Rheological Characteristics of Sewage Sludge, Rheol. Acta,
27, 3 2 6 3 4 (1988).
76P. Nowak, Correlations of Extrusion Behavior with High-pressure Shear
Rheometry; M.S. Thesis. Alfred University, Alfred, NY, 1995.
77W.Carty and C. Lee, The Characterization of Plasticity; see Ref. 15, pp.
89-101.
78R. E. Gould and J. Lux, Some Experiences with the Control of Plastic
Bodies for Automatic Jiggering; pp. 171-88 in Ceramic Fabrication Processes. Edited by w. D. Kingery. MIT Press, Cambridge, MA, 1968.
79G. C. Robinson, Extrusion Defects; pp. 391-407 in Ceramic Processing
before Firing. Edited by G. Y. Onoda and L. L. Hench. Wiley, New York, 1978.
sOJ.S. Reed, T. J. Martin, and W. G. Carlson, Mechanics of Extrusion; see
Ref. 15, pp. 157-68.
sH. Spurrier, The Why of Aging Clays, J. Am. Ceram. Soc., 4, 113-18
(1921).
8ZD.Glick, I. The Microbiology of Aging Clays, J. Am. Ceram. Soc., 19
[6] 169-75 (1936).
83D. R. Baker and D. Glick, 11. Sterilization Effects on Properties of
Clays, J. Am. Ceram. Soc., 19 [7] 209-12 (1936).
84D. Glick, 111. The Effects of Various Treatments Upon the Aging of a
Ceramic Body, J. Am. Ceram. Soc., 19 [8] 2 4 0 4 2 (1936).
ssA. L. Johnson, D. E. Postlewaite, and S. C. Rittenberg, Bacteria, A Factor
in Slip Control, J. Am. Ceram. Soc., 32 [ l l ] 347-50 (1949).
86H. Lee, The Effect of Mixing Intensity on the Properties of Clay Suspensions; M.S. Thesis in preparation. Alfred University, Alfred, NY.
871.A. Aksay and C. H. Schilling, Mechanics of Colloidal Filtration; pp.
85-93 in Advances in Ceramics, Vol. 9, Forming of Ceramics. Edited by J. A.
Mangels and G. L. Messing. American Ceramic Society, Columbus, OH, 1984.
ssB. J. Kellett and D. Znidarcic, Applications of Granular Mechanics to Slip
Casting, Filter Pressing, and Drying; 5ee Ref. 15, pp. 13346.
89G. W. Scherer, Fundamentals of brying and Shrinkage, see Ref. 15, pp.
199-2 12.
90J.E. Funk, Psychometric Drying; pp. 77-95 in Technical Innovations in
Whitewares. Edited by J. S. Reed, J. E. Funk, P. F. Johnson, and J. R. Varner.
Alfred University Press, Alfred, NY, 1981.
91N.W. Wager, Airless Drying, The New Technology Being Used in England, presented at CMC 1996 Manufacturing Workshop and Exposition,
Charlotte, NC, 1996 (Workshop 6A, Basics of Drying).
92N,G. Holmstrom, Fast-Firing of Triaxial Porcelain, Am. Ceram. Soc.
Bull., 60 [4] 470-73 (1981).
93J.E. Funk, Designing the Optimum Firing Curve for Porcelains, Am.
Ceram. Soc. Bull., 62 [6] 632-35 (1982).
94L.Pennisi, The Firing Process; pp. 255-59 in Ceramics and Glasses, Vol.
4 Engineered Materials Handbook. ASM International, Metals Park, OH, 1991.

January 1998

Porcelain-Raw

Materials, Processing, Phase Evolution, and Mechanical Behavior

95G.C. Robinson, Designing Firing Schedules with Thermal Analysis; see


Ref. 15, pp. 249-64.
9hG, W. Brindley and M. Nakahira, The Kaolinite-Mullite Reaction Series:
I, A Survey of Outstanding Problems, J . Am. Ceram. Soc., 42 [7] 311-14
(1959).
y7G,W. Brindley and M. Nakahira, The Kaolinite-Mullite Reaction Series:
11, Metakaolin, J. Am. Ceram. Soc., 42 [7] 314-18 (1959).
y8H.Schneider, K. Okada, and J. Pask, Mullite and Mullite Ceramics; p. 106.
Wiley, New York, 1994.
99G. W. Brindley and M. Nakahira, Kinetics of Dehydroxylation of Kaolinite and Halloysite, J. Am. Ceram. Soc., 40 [lo] 34650 (1957).
looH. B. Johnson and F. Kessler, Kaolinite Dehydroxylation Kinetics, J.
Am. Ceram. Soc., 52 [4] 199-204 (1969).
T. Lundin, Microstructure of Porcelain (in Microstructure of Ceramic Materials), NBS M i x . Publ., 257, 93-106 (1964).
,A. B. Searle, Refractory Materials, 3rd ed.; pp. 158-65. Charles Griffin,
London, U.K., 1940.
Io3G.W. Brindley and M. Nakahira, The Kaolinite-Mullite Reaction Series: 111, The High-Temperature Phases, J. Am. Ceram. Soc., 42 [7] 319-23
(1959).
IM(a)K. J. D. MacKenzie, I. W. Brown, R. H. Meinhold, and M. E. Bowden,
Outstanding Problems in Kaolinite-Mullite Reaction Sequence Investigated
by Si and 27A1Solid-state Nuclear Magnetic Resonance: I, Metakaolinite, J.
Am. Ceram. Soc., 68 [6] 293-97 (1985). (b)K. J. D. MacKenzie, I. W. Brown,
R. H. Meinhold, and M. E. Bowden, Outstanding Problems in KaoliniteMullite Reaction Sequence Investigated by 2ySi and
Solid-state Nuclear
Magnetic Resonance: 11, High-Temperature Transformations of Metakaolinite,
J. Am. Ceram. Soc., 68 [6] 298-301 (1985).
Io5K, Okada, N. Otsuka, and J. Ossaka, Characterization of Spinel Phase
Formed in the Kaolin-Mullite Thermal Sequence, J. Am. Ceram. Soc., 69 [lo]
C-251-C-253 (1986).
IohB. Sonuparlak, M. Sarikaya, and I. A. Aksay, Spinel Phase Formation
during 980C Exothermic Reaction in the Kaolinite-to-Mullite Reaction Series, J. Am. Ceram. Soc., 70 [ I l l 8 3 7 4 2 (1987).
Io7K.H. Schuller, Reactions between Mullite and Glassy Phase in Porcelains, Trans. Br. Ceram. Soc., 63, 102-17 (1964).
Io8K.H. Schuller, Process Mineralogy of Ceramic Materials; Ch. I. Edited
by W. Baumgart. Ferdinand Enke, Stuttgart, Germany, 1984.
lo9E. M. Levin, C. R. Robbins, and H. F. McMurdie; Fig. 407 (p. 156,
K,O-AI,O,-SO,)
and Fig. 501 (p. 181, Na,O-Al,O,-SiO,)
in Phase Diagrams for Ceramists. Edited by M. K. Reser. American Ceramic Society, Columbus, OH, 1964.
I. A. Aksay, D. M. Dabbs, and M. Sarikaya, Mullite for Structural, Electronic, and Optical Applications, J. Am. Ceram. Soc., 74 [lo] 2343 (1991).
II1I. A. Aksay and J. A. Pask, Stable and Metastable Equilibria in the System Si0,-A1,03, J. Am. Ceram. Soc., 58 [11-12] 507-12 (1975).
l12F. J. Klug, S. Prochazka, and R. H. Doremus, A1,03-Si0, System in the
Mullite Region, J. Am. Ceram. Soc., 70 [lo] 750-59 (1987).
Il3F. J. Klug, S. Prochazka, and R. H. Doremus, A1,03-Si0,
Phase Diagram in the Mullite Region; pp. 1 5 4 3 in Ceramic Transactions, Vol. 6,
Mullite and Mullite Matrix Composites. Edited by R. F. Davis, J. A. Pask, and
S. Somiya. American Ceramic Society, Westerville, OH, 1990.
I14H. Le Chatlier, De 1Action de la Chaleur sur les Argiles (Concerning
the Action of Heat on Clays), Bull. SOC. Fr. Mineral., 10, 204-11 (1887).
lIsJ. F. Hyslop and H. B. Rooksby, Effect of Heat on Crystalline Break Up
of Kaolin, Trans. Br. Ceram. Soc., 27 [4] 93-96 (1928).
I l 6 J . F. Hyslop and H. B. Rooksby, Further Note on Crystalline Break Up
of Kaolin, Trans. Br. Ceram. Soc., 27 [4] 299-302 (1928).
I1H. Insley and R. H. Ewell, Thermal Behavior of the Kaolin Minerals,
J. Res. Natl. Bur. Stand., 14 [ S ] 615-27 (1935).
l18A. L. Roberts, Refractory Clays I, Trans. Br. Ceram. Soc., 44, 69-75
( 1945).
IL9R.W. Grimshaw, E. Heaton, and R. L. Roberts, Refractory Clays 11,
Trans. Br. Ceram. Soc., 44,76-92 (1945).
IZoR. Pampuch, Infrared Study of Thermal Transformations of Kaolinite
and the Structure of Metakaolinite, Pr. Mineral, 6, 53-70 (1965).
I2lS. Iwai, M. Tagai, and T. Shimamnne, Procedure for Dickite Structure

19

Modification by Dehydration, Acta Cqstallogr., Sect. B: Struct. Crystallogr.


Crysr. Chem.. [27] 248-50 (1971).
I2F. Freund, The Defect Structure of Metakaolinite; pp. 13-25 in Proceedings of the International Clay Conference (Madrid, Spain, 1972).
IZ3T.Wataname, H. Shimizu, K. Nagasawa, A. Masuda, and H. Saito, 29Si
and 27Al Mas/NMR Study of the Thermal Transformations of Kaolinite, Clay
Miner., 22, 3 7 4 8 (1987).
IZ4T.W. Davies and R. M. Hooper, Structural Changes in Kaolinite Caused
by Rapid Dehydroxylation, J. Mater. Sci. Lett., 4, 3 9 4 2 (1985).
Komarneni, C. A. Fyfe, and G. J. Kennedy, Order-Disorder in I : ]
Type Clay Minerals by Solid-state 27Al and 29Si Magic-Angle-Spinning NMR
Spectroscopy, Clay Miner., 20, 327-34 (1985).
Iz6A. K. Chakraborty and D. K. Ghosh, Reexamination of Kaolinite-toMullite Reaction Series, J . Am. Ceram. Soc., 61, 170-73 (1978).
Iz7K. Srikrishna, G. Thomas, R. Martinez, M. P. Corral, S. De Aza, and J. S.
Maya, Kaolinite-Mullite Reaction Series: A TEM Study, J. Mater. Sci., 25,
607-12 (1990).
**M.J. Hyatt and N. P. Bansal, Phase Transformations in Xerogels of
Mullite Composition, J. Mater. Sci., 25, 2815-21 (1990).
lz9W. Ch. Wei and J. W. Halloran, Phase Transformation of Diphasic Alnminosilicate Gels, J. Am. Ceram. Soc., 71, 166-72 (1988).
I3OJ. J. Comer, Electron Microscopy Studies of Mullite Development in
Fired Kaolinites, J. Am. Ceram. Soc., 43 [7] 378-84 (1960).
I3lC. Perry, Microstructural Evolution in Alumina Porcelains; B.S. Thesis. New York State College of Ceramics at Alfred University, Alfred, NY,
1997.
I3,S. M. Johnson and J. A. Pask, Role of Impurities on Formation of Mullite
from Kaolinite and AI,O,-SiO, Mixtures, Am. Ceram. Soc. Bull., 61, 838-42
(1982).
3J. A. Pask and A. P. Tomsia, Formation of Mullite from Sol-Gel Mixtures and Kaolinite, J. Am. Ceram. Soc., 74, 2367-73 (1991).
134H.Schneider. A. Maidic. and R. Vasudevan. Kinetics of the OnartzCristobalite Transformation in Refractory-Grade Silica Materials, Mater. Sci.
Forum, 7, 91-102 (1986).
135A.Zoellner, Zur Frage der Chemischem und Physikalischen Natur der
Porzellans (Some Chemical and Physical Properties of Porcelains), Sprechsaal, 41, 471-73 (1908).
13%. C. Sane and R. L. Cook, Effect of Grinding and Firing Treatment on
the Crystalline and Glass Content and the Physical Properties of Whiteware
Bodies, J. Am. Ceram. Soc., 34, 145 (1951).
137J.E. Schroeder, Inexpensive High-Strength Electrical Porcelain, Am.
Ceram. Soc. Bull., 57, 526 (1978).
138L.Mattyasovszky-Zsolnay, Mechanical Strength of Porcelain, J. Am.
Ceram. Soc., 40, 299-306 (1957).
139P.Rado, The Strange Case of Hard Porcelain, Trans. Br. Ceram. Soc.,
71 [4] 131-39 (1971).
140Davidge,Mechanical Properties of Ceramics; p. 86. Cambridge University Press, Cambridge, U.K., 1979.
l4lS. I. Warshaw and R. Seider, Comparison of Strength of Triaxial Porcelains
Containing Alumina and Silica, J. Am. Ceram. Soc., 50, 33743 (1967).
I4D. P. H. Hasselman and R. M. Fulrath, Proposed Fracture Theory of a
Dispersion-Strengthened Glass Matrix, J. Am. Ceram. Soc., 49.68-72 (1966).
143N.G. Holmstrom, Fast Firing of Triaxial Porcelain, Eng. Sci. Proc., 1
[lo] 780-87 (1980).
144A.Kristoffersson, I. L. Ekberg, H. Leandersson, and R. Carlson, HighStrength Triaxial Porcelain by an Improved Glassy Phase, Third Euro Cerum.,
2, 1059-84 (1993).
t45S. Maity and B. K. Sarkar, Development of High-Strength Whiteware
Bodies, J. Eur. Ceram. Soc., 16, 1083-88 (1996).
14%.
Maity, T. K. Mukhopadhyay, and B. K. Sarkar, Sillimanite SandFeldspar Porcelains: I. Vitrification Behavior and Mechanical Properties, Interceram, 45, 305-12 (1996).
14W. E. Blodgett, High-Strength Alumina Porcelains, Am. Ceram. SOC.
Bull., 40, 74-77 (1961).
148R.Harada, N. Sugiyama, and H. Ishida, Al,03-Strengthened Feldspathic
Porcelain Bodies: Effects of the Amount and Particle Size of Alumina, Ceram.
Eng. Sci. Proc., 17, 88-98 (1996).
0

20

Journal of the American Ceramic Society-Carty

and Senapati

Vol. 81, No. 1

Dr. Carty is an assistant professor in the Department of Ceramic Engineering and


Materials Science at the New York State College of Ceramics at Alfred University. He
received B.S. and M.S. degrees in ceramic engineering from the University of MissouriRolla in 1985 and 1987, respectively, and a Ph.D. in materials science and engineering
from the University of Washington in 1992. After graduate studies, Dr. Carty spent one
year as a postdoctoral research scientist with Koninklijke/Shell-Laboratorium, Amsterdam, The Netherlands. He joined the faculty at Alfred University in 1993. Dr. Carty is
currently the Director of the New York State Center for Advanced Ceramic Technology-Whiteware Research Center, an industry-university research consortium. He is
affiliated with the Whitewares Division and the Basic Science Division of the American
Ceramic Society.

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.

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