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Porcelain—Raw Materials, Processing, Phase Evolution, and Mechanical

Behavior

Article  in  Journal of the American Ceramic Society · January 2005

DOI: 10.1111/j.1151-2916.1998.tb02290.x

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 Porcelain-Raw
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 disci-
pline and one of the most complex ceramic materials. Com-
posed 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 sub-
stantial amount of research already conducted within the
field, there remain significant opportunities for research
and study, particularly in the areas of raw material under-
standing, processing science, and phase and microstructure
evolution.
I. Introduction
C 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 mi-
crostructure and phase development. Even temperature mea-
surement of porcelain firing has required the development of its
own unique system-pyrometric cones-because thermo-
couples simply do not provide sufficient information to indi-
cate 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 world-
wide, 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
G. L. Messing-contributing edit01
Manuscript No. 190529. Received October 1, 1997; approved December 1, 1997.
Member, American Ceramic Society.
Materials, Processing, Phase Evolution, and
Mechanical Behavior
William M. Cam* and Udayan Senapati*
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
billion to $8.21 b i l l i ~ n (These
.~ numbers can be used only as
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 earth-
enware 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 por-
celains 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 de-
noted 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 insu-
lators to dinnerware; hence, the 20th-century connotation of
porcelain suggests a product more appropriately defined as “a
fine-crystalline, strong, impervious ceramic product and re-
late(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, in-
cluding chemical reactions, phase development, and micro-
structural 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 earthen-
ware bodies, as well as glazing and decorating issues.
11. Historical Perspective
The high level of intrinsic plasticity in clays and clay-based
systems and the resulting ease of forming objects precipitated
3
4 Journal of the American Ceramic Society-Carty and Senapati Vol. 81, No. 1

Table I. Traditional Definitions of Whitewares

Name ASTM definition4 Maturing temnerature'
Porcelain A glazed or unglazed vitreous ceramic whiteware made by the procelain process, and used Nepheline syenite: 2-6
for technical purposes, designating such products as electrical, chemical, mechanical, Sanitaryware: 8-1 2
structural, and thermal wares when they are vitreous Electrical: 8-1 2
Hard: 10-18'
China A glazed or unglazed vitreous ceramic whiteware made by the china process, and used for Hotel: 10-13'
nontechnical purposes, designating such products as dinnerware, sanitaryware, and
artware when they are vitreous
Stoneware A vitreous or semivitreous ceramic ware of fine texture, made primarily from nonrefractory &lo5
fire clay
Earthenware A glazed or unglazed nonvitreous ceramic whiteware 06-0S6
+Provided in pyrometric cone values.

Silica
1713'
nsioz

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 devel-
opment 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 be-
come 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 equip-
'
ment 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 improve-
ment in process control. Prior to automation, dinnerware pro-
duction 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 bod-
ies. In the preautomation era, it was necessary to have rela-
tively soft bodies with plasticity suitable for hand forming.
With the introduction of automated forming techniques, it be-
came 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 NazSi03-
were 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 5

Table 11. Temperature Equivalents for Standard-Sized and its degree of maturity. Instead, heat work recorders, such as
Orton Pyrometric Cones pyrometric cones and other similar devices (e.g., rings and
Temperature Temperature Temperature "check" keys), have been developed to follow the firing prog-
Cone ("C) Cone ("C) Cone ("C) ress as it responds to time and temperature variations, demon-
022 589 04 1060 16 1473 strating the appropriate heating rate for maturation. Pyrometric
02 1 61 1 03 1101 17 1485 cones have been the most commonly used method for thermal
020 634 02 1120 18 1506 work determinations, and, although less commonly used today
019 685 01 1137 19 1528 in industry, bodies continue to be designated by their "cone
018 725 1 1154 20 1549 value." Pyrometric cones are three-sided pyramids made from
017 752 2 1162 21 1569 mixtures of kaolin, feldspar, quartz, and other raw materials
016 784 3 1168 23 1590 resembling the body composition that function as true indica-
015 807 4 1186 26 1605 tors of chemical reaction kinetics in porcelain bodies. The first
014 83 1 5 1196 27 1627
013 859 6 1222 28 1633 standard and regularly used pyrometric cones were introduced
012 864 7 1240 29 1645 by Seger;I6 in the United States, Orton pyrometric cones17,18
01 1 884 8 1263 30 1654 are the norm. Table I1 lists the Orton pyrometric cone desig-
010 894 9 1280 31 1679 nations and their temperature equivalents. Modem commercial
09 923 10 1305 32 1717 firing processes are monitored with thermocouples and often
08 955 11 1315 32% 1730 are checked with pyrometric cones or keys for verification of
07 984 12 1326 33 1741 the heat work accomplished.
06 999 13 1346 34 1759
05 Y2 1023 14 1366 35 1784
05 1046 15 1431 36 1796 111. Raw Materials
Assuming a heating rate of 150'Ch over the last few hundred degrees. If altema-
tive heating rates are used or if a dwell is used in the firing process, the cone falls at
Because of their three-part composition of clay, feldspar, and
a temperature below that listed. Similarly, if accelerated heating rates are used, the quartz, porcelains are referred to as triaxial whitewares. Alu-
cone falls at a higher temperature. Cone designations continue to he commonly used mina can be substituted for quartz to increase the mechanical
to denote the firing range of whiteware bodies.
strength of the fired ware, and nepheline syenite can be sub-
stituted for feldspar. These primary raw materials are listed in
Table 111; less commonly used raw materials are listed as sec-
From the firing perspective, commercial porcelain produc- ondary raw materials in Table IV. (Excellent introductions to
tion initially relied on periodic "beehive" kilns, using coal as these and other common raw materials are published annu-
the primary fuel. In small potteries, the kilns were fired infre- ally. 1 9 q
quently, dependent on the production of sufficient ware to fill Another important raw material, although one less com-
the kiln volume, and firing cycles on the order of several days monly monitored or controlled within manufacturing, is the
were used.I4 As the industry progressed, so did the firing ca- process water. It is common to use tap or potable water, which
pabilities, and circular tunnel kilns designed to fit into the usually contains a wide range of cations, including Ca2', Mg2+,
footprint of the beehive kiln were de~eloped.~." Eventually, Na+, and K+. Table V provides typical tap water cation levels
linear tunnel kilns were developed that allowed significant in- from several locations. Even with well-controlled urban water
creases in production volumes. The most advanced firing ca- supplies, the level of these ions can vary, leading to substantial
pabilities are the current roller-hearth kilns, which can produce fluctuations in suspension rheology and plasticity. Also, be-
large quantities of high-quality porcelain dinnerware or vitri- cause the ionic concentration can vary dramatically with a geo-
fied tile with firing cycles as short as one hour.15 graphic location, water chemistry generalizations are difficult.
Most of the reactions occurring in porcelain bodies are ki- Although it is important to realize that water quality can impact
netically governed processes that do not reach thermodynamic the manufacturing process and substantially affect the repro-
equilibrium. Hence, measurement of temperature alone does ducibility of rheological measurements, the contribution of lo-
not provide a true indication of the heat work done on the body cal water sources is not addressed here.

Table 111. Primary Raw Materials Used in the Manufacturing of Commerical Whitewares
Raw material Nominal composition Common impurities
Ball (plastic) clay A1,0, .2Si0,.2H20 quart^,^ TiO,, Fe,O,
Kaolin (china) clay A1,0,~2Si0,~2H20 Montmorillonite, quartz
Soda feldspar Na20~A1,0,~6Si0, K,O, CaO, MgO, quartz
Potash feldspar K,O~Al2O,~6SiO, Na,O, CaO, MgO, quartz
Nepheline syenite K2O~3Na,0~4A1,0,~9Si0, CaO, MgO, quartz
A1u mina '412% Na,O
Quartz SiO, 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 Nominal composition Common impurities
Bentonite/montmorillonitet (M2+)(M3'),(Si,A1),O,,(OH),~nH,O Not applicable
Glass frits Company specific Not applicable
Petalite (lithium feldspar) Li,O~Al,0,~6SiO2 Na,O, K,O
Bone ash$ Ca,(PO,), Unknown
Talc 3Mg0.2Si0,.2H20 Chrysotile, CaO
Whiting CaCO, MgCO,
Zircon ZrO,.SiO, Not applicable
'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.
6 Journal of the American Ceramic Society-Carty and Senapati Vol. 81, No. 1

Table V. Typical Chemical Analysis of Several Tap Water 2KA1Si,08 + 3H,O + Al,Si,O,(OH), + 4Si02 + 2KOH
Samdes Showing a Broad Range of Variabilitvt
If the potassium is not properly removed following the weath-
Cation concentration (ppm)
ering process, illitic clays (2:l sheet silicates) are formed in-
Tap water site Ca Mg Na K Si
stead of kaolinite.
Distilled water BDL BDL BDL ADL BDL Of primary importance for the domestic whitewares industry
Alfred, NY 52.3 20.2 28 4 5 are English and U.S. clays; these clays are the most widely
Buffalo, NY 28.7 9.1 12 6 ADL studied in the literature. In England, kaolins (or china clays)
Syracuse, NY 40.2 9.4 14 ADL BDL and ball clays are distinguished as being primary and secondary
Victor, NY 41.5 12 21 BDL 1.5 clays, r e ~ p e c t i v e l y .In
~ .the
~ ~ United States, however, both ka-
Columbus, OH 7.5 1.6 ADL 4 ADL olins and ball clays usually are secondary clays, having been
East Liverpool, OH 28.2 7.3 21 2 1.9
York, PA 21.3 6.2 9 7 2.5 deposited at a considerable distance from their place of ori-
gin.23 There are primary clay deposits within the United States
Dectection limit 0.1 0.1 1. 1. 0.5 but none that are currently commercially exploited. Geographi-
+Induction coupled plasma spectroscopy was used to obtain the results. BDL in- cally, the major ball clay deposits are located east of the Ap-
dicates that the cation level was below the detection limit (as specified); ADL indi- palachian Mountains and in western Kentucky and Tennessee;
cates species concentration at the detection limit.
the major kaolin deposits are located in central Georgia and
South Carolina.
Mineralogical and chemical differences between ball clays
(1) CkYS and kaolins are minor-both are kaolinitic in nature, containing
In whiteware production, the term “clay” refers to raw ma- quartz as the major impurity and iron (in the form of Fe,O,)
terials that provide plasticity and green strength during the and titania (in the form of anatase) as minor i m p ~ r i t i e s . ~ ~ - ~ ~ , ~
forming stages of porcelain production and that contribute sub- The quartz is removed via wet processing of the kaolins but is
stantially to the color of the fired ware. not commonly removed from the ball clays. English clays are
Kaolinite, the most common clay mineral, is a 1:l sheet generally lower in titania content than U S . clays but are similar
silicate composed of a [Si,O,I2- layer and an [Al2(0H),l2’ in iron levels, leading to white bodies from English clays and
layer, as illustrated schematically in Fig. 2.8 The theoretical buff-colored bodies from U.S. clays.21 Table VI lists typical
formula for kaolinite is Si,Al,O,(OH), (frequently expressed chemical analyses of a Georgia kaolin, an English kaolin, and
as A1,0,*2Si0,.2H20). Clay minerals are formed by the de- a Kentucky ball clay. Powder X-ray diffraction (XRD) patterns
composition of feldspathic rock via geological processes; a are presented in Fig. 3.
typical reaction sequence using potassium feldspar (microcline Ball clays often are referred to as plastic clays, because they
or orthoclase) can be written:,l possess a finer particle size, which produces greater plasticity

Water
layers

dd-0
0

layers
Water I
I
About

fI

Kaolinite
1 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 7

Table VI. Typical Chemical Analysis of a Georgia Kaolin, is rare to have a complete mineralogical understanding of a
a Kentuckv Ball Clav. and an English Kaolin clay, which becomes problematic only when the impurity con-
tent varies significantly between batches.
Comuosition (%I
The sheet silicate structure differentiates clays from other
Component Georgia kaolin2' Kentucky ball clayz6 English kaolin" common ceramic powders. The platey morphology of a clay
SiO, 45.30 44.70 46.77 particle is responsible primarily for the high specific surface
A1203 38.38 38.30 37.79 areas of clays (18-30 m2/g), compared to other powders with
Fez03 0.30 0.60 0.36 similar particle size. The mean diameter of ball clays and ka-
TiO, 1.44 2.40 0.02 olins is -0.3-0.5 p,m. The high specific surface area, combined
MgO 0.25 0.10 0.24 with the platelike morphology, is believed to be responsible for
CaO 0.05 0.10 0.13 the intrinsic plasticity of clay-water systems.
Na,O 0.27 0.10 0.05
From the clay mineralogy perspective, kaolinites are
K,O 0.04 0.10 1.49
LO1 (950°C) 13.97 13.60 12.97 grouped by their degree of Crystallinity. Standard clay samples
are available from the Clay and Clay Minerals Society, includ-
ing examples of well-crystallized (KGalb) and poorly crystal-
lized (KGa2) kaolinites. Both of these clays are Georgia ka-
in a whiteware body. The name "ball clay" originated from olins; the powder XRD patterns and electron photomicrographs
the method of mining the clays-in large cubes or balls of clay are illustrated in Figs. 4 and 5. The degree of crystallinity is
that were cut from the deposits.26 Processed ball clays and determined by the "Hinkley Index," which compares the in-
kaolins have similar specific surface areas, but the quartz im- tensity of the peaks within the 0,211 domain region.27 The
purity level can be significantly higher in ball clays (up to 35% greater the ratio, the greater the degree of crystallinity. It is
on a dry-weight basis), requiring a much finer particle size for argued that poorer crystallinity offers greater potential plastic-
the kaolinite fraction. Because ball clays frequently contain up ity and that the degree of crystallinity corresponds to a greater
to several weight percent of decayed biological or organic mat- degree of ionic substitution within the kaolinite lattice. How-
ter, they are commonly dark in color-and sometimes black- ever, the degree of crystallinity rarely is used as a characteristic
in the raw form. The organic impurities can be removed en- measurement of a clay by the ceramics industry.
tirely during heat treatment to produce a white body.
Kaolins commonly contain montmorillonites and smectites, (2) Fluxes
2:1 sheet silicates of variable composition (Fig. 2). Montmo- Historically, potash feldspars (microcline and orthoclase)
rillonites often incorporate water, as well as other impurity have been the most commonly used fluxes in porcelain^.^^^^^^^
ions, between the sheets (to compensate for ionic substitution Potash feldspars rarely are pure, usually containing the miner-
within the tetrahedral and octahedral layers), producing vari- als albite (sodium feldspar) and anorthite (calcium feldspar).
able interlayer spacings. Smectites are particularly problematic Albite sometimes is used as the flux component in commercial
from a characterization perspective, because they often are pre- porcelains, but anorthite is not, because it does not occur in
sent as individual layers of 2:l sheet silicates and, conse- commercially viable deposits within the United States. Figure
quently, are undetectable via XRD. The presence of montmo- 6 illustrates a -400 mesh (45 km) potash feldspar.
rillonites and smectites can have a significant impact on the Nepheline syenite has replaced feldspars in many commer-
rheology and plasticity of a porcelain body, although the spe- cial body formulations, reducing the firing temperature and
cific extent of their contribution is unknown. Commercially, it increasing the alkali level in the glass p h a ~ e . ~ ONepheline
.~l
syenite is composed of the minerals nepheline, albite, and mi-
crocline 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 Fig. 4. Powder XRD patterns for a well-crystallized and poorly crys-
illustrated in Fig. 1. Large reflection at -12.3" 28 represents the in- tallized kaolinite standards (Clay and Clay Minerals Society). Hinck-
terlayer spacing for kaolinite. All three of the samples contain impurity ley index evaluates the ratio of peaks in the 0,211 domain. Well-
quartz. crystallized sample contains a small amount of free quartz.
8 Journal of the American Ceramic Sociev-Gary and Senapati
Fig. 5. SEM photomicrographs of (a) well-crystallized and (b)
poorly crystallized kaolinite samples used to generate the XRD pat-
terns 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 sy-
enite 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
Fig. 6. SEM photomicrograph of a -400 mesh potash feldspar
sample.
Vol. 81, No. 1
deformation. Quartz and flint are the most commonly used
fillers2* in porcelain bodies and are essential to the microstruc-
tural 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 573°C dur-
ing 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 me-
chanical 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 draw-
back 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 non-
plastics 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 ma-
terials to obtain the specific surface area, particle size distri-
bution, 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 manufac-
turing loss rates, process performance, and ware quality are
generally weak. Consequently, additional tools and more rig-
orous observation are needed to predict more accurately pro-
cess behaviors within industry.
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 di-
rectly 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 ma-
chine that imparts large amounts of shear to the powder-water
mixture, breaking down agglomerates and producing a homo-
geneous 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
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 intro-
duction of the nonplastics (i.e., the feldspar or nepheline sy-
enite and the quartz or alumina). After the addition of the
January 1998 Porcelain-Raw Materials, Processing, Phase Evolution, and Mechanical Behavior 9

Table VIII. Comparison of the Specific Surface Areas of

the Different Components of a Typical Whiteware Batch'
Specific Typical Component
5Ulfdce batch Surface area contribution
Raw material area (m2/g) (dry wt7c) (per component) (a)
Kaolin 25.0 25 6.25 51.2
Ball clay 27.0 20 5.40 44.2
Quartz 0.9 25 0.23 1.9
Feldspar 1.1 30 0.33 2.7
Batch 12.2 m2/g 95.4% clay
'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,

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 con-
tains a list of the commonly used polymeric41 and soluble salt
additives. Mixing of the raw materials in the slurry form gen-
erally 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 sus-
pended in a liquid dictates the magnitude of the van der Waals
attractive forces between the particles.4247 In the case of ka-
olinite, 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 suspen-
sion ~ 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 Nor-
ton12 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-
Silica, and Aluminat
Material Effective Hamaker constant (J) Reference
Kaolinite 1.8 x 10-20 44
Fused silica 0.83 x 47
Quartz 1.7 x 47
~Al20, 5.32 x 1 0 - l ~ 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 dis-
perse 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 defloc-
culation. The adsorption of the Cog- or SiOg- ion is not rec-
ognized 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 zeta-
potential 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; in-
stead, 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 higher-
valent cations are undesirable for developing deflocculated sys-
tems, not because the lower-valent cations deflocculate the
system, but because the higher-valent cations cause floccula-
tion, 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 floc-
culation 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-poly(acry1ic acid) Dispersant Slips, plastic bodies
Na-PMAA Na-poly(methacry1icacid) Dispersant Slips, plastic bodies
Sodium silicate Na,SiO, Dispersant Slips, plastic bodies
Sodium chloride NaCl Flocculant Slips, plastic bodies
Calcium chloride CaC1, Flocculant Slips, plastic bodies
Magnesium chloride MgC1, Flocculant Slips, plastic bodies
Magnesium sulfate MgSO4 Flocculant Slips, plastic bodies
PEG Poly(ethy1ene glycol) Plasticizer Dry pressing (with PVA)
CMChIethocel Carboxy methyl cellulose Binder Improve glaze adherence
PVA Poly(viny1 alcohol) Binder Dry pressing
10 Journal of the American Ceramic Society-Car9 and Senapati Vol. 81, No. 1
n . troversial, because it opposes the commonly held opinion that
clay particles have negatively charged basal planes with posi-
tively charged
The agglomeration of negatively charged gold particles to
the edges of clay platelets, as observed via transmission elec-
tron microscopy (TEM), forms the basis for the charge distri-
" \ bution on clay particles-e.g., that the edges must be positively
/O charged.56 The lack of particles agglomerated to the faces of
-30
4 0.05 the kaolinite particles has been used to argue that the faces are,
therefore, negatively charged. However, the pH of the suspen-
0
sion used to prepare the TEM samples is unclear. The miner-
a alogy of kaolinite would dictate that one surface behaves simi-
I
lar to silica and the other behaves similar to a l ~ m i n a . ~Part
' of
Kaolin the problem may lie further in the large amount of literature
Background Ionic Strength: 10 mM NaCl
published by clay mineralogists investigating the behavior of
0 2 4 6 a 10 12 2: 1 sheet silicates, such as those in the montmorillonite family;
only a few references in the clay mineralogy literature, such as
PH G i i ~ e n , ~make
' the distinction between the basal plane surface
chemistry characteristics of kaolinite versus other sheet silicates.
Fig. 8. Effect of Na,SiO, on the zeta-potential of a kaolin over a Direct confirmation regarding the dual surface nature of ka-
range of pH values against a background ionic strength of l0mM olinite is provided via atomic force microscopy (AFM) studies
NaC1. Increase in the negative zeta-potential indicates the specific in conjunction with surface modeling. These results confirm
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 presence of silanol and hydroxide surfaces on kaolinite
the kaolin. HCI was used to adjust the pH to 2.2 prior to the test, then particles.58
NaOH was used to increase pH. 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
on colloidal behavior may result from the model of the kaolin- curve, as illustrated in Fig. 10, is -50% of the amount to
ite particle. Because of its crystal structure, kaolinite exhibits entirely coat the surface of an alumina powder.49 The amount
unique colloidal behavior in water. When a clay particle is of dispersant necessary to reach the minimum viscosity value
dispersed in water, one surface acts similar to silica while the for the alumina particles is consistent with the amount of poly-
other acts similar to alumina. From a pH of -2 (the isoelectric (methacrylic acid) (PMAA) necessary to coat the particle sur-
point of silica) to a pH of -9 (the isoelectric point of alu- face, as demonstrated by Cesarano et al.59 The observations
m i r ~ a ) the
, ~ ~two sides of the kaolinite particle are oppositely regarding PAA and PMAA are consistent with observations on
charged-the silica surface is negatively charged and the alu- Na,SiO,. The adsorption measurements of PAA on various
mina surface is positively charged. This observation regarding kaolinites indicate substantial differences in adsorbed amounts
the complex duality of kaolinite surface charge is highly con- and a strong dependence on CaCl,

CaCI, Effect
-
I
-
A

Effect

No

10 2 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
January 1998 Porcelain-Raw Materials, Processing, Phase Evolution. and Mechanical Behavior
0 t
a
Kaolin
0
0 v
v Alumina
v v
lo-’
0.0
‘ 0.2
v
0.4 0.6 0.8
I
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 substitu-
tion in the tetrahedral layer (specifically, A13+ for Si4+) and
octahedral layer (Fez+or Mg2+for A13+).Although this substi-
tution 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 ka-
olinite 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 cre-
ating 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 distri-
bution 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 porce-
lains.
(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 mor-
phology.61,62The characterization of suspension rheology is
now commonplace, and each whiteware industry (i.e., dinner-
ware, 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 sug-
gested. 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 test-
ing times, such as the triaxial test in soil mechanics. Further-
more, 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
11
/ \ j+ 2 1 Ball Clay-Kaolin 1j
Pressure Dependence ((kPa/kPa)xlOO)
Fig. 11. High-pressure shear rheology of ball clay, kaolin, 2:1 mix-
ture 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 de-
noted 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-mem-
brane theory” (Norton69),and surface tension ( S c h ~ a r t andz~~
Kingery and Franc171). All of these theories are useful to ex-
plain 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. There-
fore, plasticity becomes a property of a material and workabil-
ity a quality endowed by the process itself. Because plastic
forming places a body in shear under pressure, a better descrip-
tion 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 de-
sign.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 as-
sociated 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 me-
chanics 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 ex-
trusion, but is entirely independent of the forming process,
allowing a broad range of samples to be evaluated. As illus-
trated in Fig. 11, the data indicate that the water contents nec-
essary to obtain the maximum cohesion strength correlate well
with the saturation of the pore space with water.77 Also, the
effect of nonplastic additions to the clay body shows that a
significantly lower moisture level is necessary for a typical
whiteware batch compared to individual clay samples.
Within the manufacturing environment, plastic forming is
accomplished primarily through ram pressing, jiggering,78 ex-
12 Journal of the American Ceramic Socieg-Curty
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 prod-
uct. This applied stress state causes the plastic mass to perma-
nently 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 varia-
tions in the organic le~el~~-~~--particularly bacteria-over
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 pro-
cesses 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 com-
mercial processes.
The chemistry of the suspension medium can change over
time because of the dissolution of the raw materials, particu-
larly 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 dis-
solution studies, as illustrated in Fig. 12, and filter press efflu-
ent 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 me-
dium. 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 dewa-
tering of the body suspension using a filter press. The body
suspension is pumped under pressure into the filter press, and
h ( I ) Reactions throughout the Firing Process
i MonovalentCations via Nepheline Syenite
I " " " " " " " " '
0 20 40 60 80 100 120 140
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 dis-
solution levels for monovalent cations, whereas the ball clay exhibits
the highest dissolution level of divalent cations. Divalent cation dis-
solution level for nepheline syenite was at the detection limit and, there-
fore, not shown.86
and Senaputi Vol. 81, No. 1
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 con-
trolled by the use of dispersants and, coagulants such as CaC1,
(Table VII). Each manufacturing facility follows unique guide-
lines that have been developed through years of practical ex-
perience.
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 con-
trol 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 white-
wares is the new, so-called airless drying, in which steam is
used to assist the drying process, eliminating meniscus forma-
tion and substantially shortening the drying ~ y c l e . ~The
' con-
cept of airless drying has not yet been applied to the drying of
porcelains.
V. Firing
Temperature, time, and atmosphere in the kiln affect chemi-
cal 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 rec-
ognition 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 mi-
crostructural development.
4 The sequence of chemical reac\ions during the firing of por-
celain bodies depends on the type of raw materials in the body,
but, for a typical clay-quartz-feldspar system, the basic reac-
tion steps-ignoring the removal of nonchemically bound spe-
cies, 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 -550°C.9"'00 The chemi-
cal equation representing this process is
-550'C
A1,03~2Si0,-2H,0 _ jAl,03.2Si0, + 2H,O?
This is observed in typical analytical studies, such as differen-
tial 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 kaolin-
ite to a mostly tetrahedrally coordinated aluminum in metaka-
olin.
January 1998 Porcelain-Raw Materials, Processing, Phase Evolution, and Mechanical Behavior 13

100 200 300 400 500 600 700 800 900 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.

(2) The a-to @-quartzinversion occurs at 573°C. Because either phase. The details regarding the two phases are discussed
in the microstructure section. Furthermore, the exact role of the
of the relatively great flexibility of the packed particle network,
the quartz inversion is of little consequence during the heating spinel phase in the reaction sequence and the microstructure
cycle. development has not been clearly established.
(3) Sanidine, the homogeneous, high-temperature, mixed- (5) The amorphous silica liberated during the metakaolin
alkali feldspar, forms within 700°-10000C.'0' The formation decomposition is highly reactive, possibly assisting eutectic
temperature apparently is dependent on the sodium:potassium melt formation at -990°C, as suggested by S ~ h u l l e r . ' ~ ~ . ' ~ ~
ratio. Lundin'O' suggests instead that amorphous silica transforms
(4) Metakaolin transforms to a spinel-type structure and directly to cristobalite at -1050"C, but the general lack of
amorphous free silica at -950"-1000"C,'0~-106 as shown by the cristobalite in modem commercial porcelain bodies suggests
following chemical eq~ation:~' that the former scenario is more plausible.
(6) As illustrated in Fig. 1, a eutectic melt of potash feld-
-950-1 000°C spar with silica starts appearing at -990°C. The eutectic tem-
3(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 -990°C; 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 . ' ~ ~
-950-1000°C
The lower liquid formation temperature in the potash feldspar
3(A1,0,.2Si02) A 0.562Si8(A1,,~,, @5,33)032 systems is beneficial for reducing the porcelain firing tempera-
+ 3Si0, ture. Also, the presence of albite in potash feldspar can reduce
the liquid formation temperature by as much as 60°C.101As the
where @ represents a vacancy. A y-alumina-type phase temperature continues to increase, porosity is eliminated via
(0.282A18(A11,,,3@2~66)03~) and an aluminosilicate spinel viscous-phase sintering.
(0.562Si,(A1,0,6,@,,,,)03~)are the predicted reaction products. (7) Porcelain bodies generally contain two different mul-
The silica reaction product is amorphous. The exact structure lite evolution paths: primary and secondary. The exact source
of the spinel phase continues to be controversial, and the lit- and temperatures for the formation of these two different types
erature presents conflicting evidence regarding the existence of of mullites continue to be debated. However, the spinel phase,
14 Journal of the American Ceramic Society-Carty
being a nonequilibrium unstable phase, certainly transforms to
-
mullite above 1075°C. The chemical reactions describing the
conversion to mullite are97
-1075°C
0.282A1,(All,,,, @2.66)032 3A120,.2Si02 + 4Si0,
-
or
- rent authors' opinion, controversies such as the coordination of
3A120,.2Si02 + 4Si0,
. " I _
0.562Si8(A1,,~,, $5,33)032
Early studies on the aluminosilicate crystal structures indicate
the mullite structure to be identical to the sillimanite structure,
with each having orthorhombic crystal lattices.102Later stud-
ies, however, indicate that the stable form of aluminosilicates
formed at higher temperatures (>lOOO"C) and atmospheric
pressure is mullite, but the literature also presents unresolved
issues as to the nature of the melting of mullite, i.e., whether it
melts congruently or incongruently. ' Furthermore, addi-
tional work on mullitel'o has indicated that chemical homoge-
neity is essential to the formation of mullite at lower tempera-
tures. On the atomic level, mullite formation can start at 980°C,
but homogeneity on the nanometer scale can delay mullite
formation to temperatures as high as 1300°C.
(8) At -1200"C, the melt becomes saturated with silica-
quartz dissolution ends, and quartz-to-cristobalite transforma-
tion begins.
(9) Above 12OO0C,mullite crystals grow as prismatic crys-
tals into the remains of the feldspar grains (referred to as feld-
spar relicts by Lundin'O').
(10) As the body starts to cool, pyroplastic deformation
and relaxation within the glass phase prevent the development
of residual stresses until the glass transition temperature is
reached. As the body cools below the glass transition tempera-
ture, residual stresses are developed because of thermal expan-
sion mismatch between the glass and the included crystalline
phases (i.e., mullite and quartz, and in some cases, alumina and
cristobalite).
(1 1) Cooling through the quartz inversion (573°C) results
in a quartz particle volume decrease of 2%,29,102which can
produce sufficient strain to cause cracking of the glassy matrix
and the quartz grains. The cracking severity is dictated by the
quartz particle size and the cooling rate. The effect of free
quartz on the porcelain strength is discussed below.
(12) Finally, the p- to a-cristobalite inversion at 225"-
250°C is similar to the quartz inversion, but it produces a larger
volumetric change (-5%); with a higher activation energy bar-
rier, the transformation is less severe than that of q ~ a r t z . ~ ~ , ' Fe,03
(2) Metakaolinite Formation
The microstructure development in any clay-based product
is triggered by the conversion of kaolin to metakaolin. One of
the earliest works in this field by LeChatlier114concluded, on
the basis of thermal analysis and acid dissolution tests, that the
free alumina on dissolution comes from the molecular trans-
formation of kaolinite. Several researchers have shown that
kaolin transforms to metakaolin at -50O"-55O0C, but previous
studies115-119have suggested a noncrystalline or amorphous
structure for metakaolin. Brindley and Nakahira (BN),96,97on
basis of XRD studies, first proposed a crystal structure for
metakaolin. The BN model for metakaolin maintains the a and
b kaolinite lattice parameters in metakaolin, but the c-axis pe-
riodicity disappears, leading to diffuse XRD patterns. BN also
have indicated that the octahedral aluminum hydroxide layer of
kaolinite is likely to be changed more than the tetrahedral silica
layer during the dehydroxylation process and that the structure
of metakaolin allows the kaolinite layers to collapse to -0.63
nm, in agreement with the measured densities of kaolin and
metakaolin. The proposed BN metakaolin structure is illus-
trated in Fig. 14(a). Most of the metakaolin models published
since the BN mode1120-126have been modifications of it. On
the basis of computer simulation and nuclear magnetic reso-
nance (NMR) studies, MacKenzie et d.lo4 have proposed that
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
contravene bonding rules. The BN model shows no hydroxyl
groups, whereas the MacKenzie model, shown in Fig. 14(b),
does incorporate hydroxyl groups in the A1-0 layers and sat-
isfies most of the deficiencies of the other models. In the cur-
aluminum (more specifically, the ratio of fourfold to sixfold
coordinated aluminum), the exact dimensions of the c param-
eter, and the amount of hydroxyl groups in the A1-0 layers
continue to be far from resolved, and further characterization
and structural modeling is necessary.
The structure of the spinel phase that forms at -980°C by the
decomposition of metakaolinite also is controversial. Some re-
s e a r c h e r ~ ~ believe
~ ~ , ' ~it ~to*be~ an
~ ~aluminum silicon spinel,
whereas ~ t h e r ~believe ~ ~ that ~ Jit ~is a~ y-alumina
, ~ ~ ~ phase.
Okada et aZ.Io5 suggest that the decomposition product of
metakaolin is a y-alumina phase, but containing silica accord-
ing to chemical analysis. In summary, the structure of the
spinel phase remains unclear.
(3) Mullite Formation
Unresolved questions regarding the structure and identity of
the spinel phase also have led to difficulties in understanding
the formation of mullite in porcelain bodies. LundinIo1 has
concluded through electron microscopy studies of porcelain
bodies that the concentration gradients and diffusion rates of
alkalis are the two most important factors affecting mullite
formation. Comer'30 has demonstrated that mullite can prefer-
entially orient on the surface of kaolinite relicts (presented in
Fig. 15), and Lundin has proposed that the mullite in the clay
relicts serves as a seed for the crystallization of the mullite
needles in the feldspar relicts. The mullite formed in the clay
relicts is generally termed the primary m ~ l l i t e ,because~ ~ ~ ,it~ ~ ~
forms at a lower temperature and is a product of the clay
minerals. As alkali diffuses out of feldspar at higher tempera-
tures, secondary mullite nucleates and grows. An electron mi-
crograph of secondary mullite in a feldspar relict is shown in
Fig. 16.131Studies on the morphology of mullite have indicated
that primary mullite occurs mostly in the form of scaly crys-
tals,112.113whereas secondary mullites are mostly needle-
shaped crystal^.^^^^^^^ It is believed that the secondary mullites
are formed from the recrystallization and dissolution of alumi-
nosilicates in the melt.
Johnson and P a ~ k ' ,have
~ suggested that impurities, such as
~ ~ and TiO,, affect the kinetics and morphology of mullite
formation and that the exsolution of silica facilitates mullite
formation in kaolin. In another study, Pask and T ~ m s i ahave '~~
postulated that the heating rate is crucial to the crystal structure
of mullite. Slow heating rates lead to formation of spinel at
lower temperatures, which then reacts with silica by a diffu-
sion-nucleation mechanism to form orthorhombic mullite. Fast
heating rates lead to tetragonal mullite formation, with the
aluminum ion in sixfold coordination at temperatures as low as
980°C. The tetragonal mullite then converts to the desirable
orthorhombic mullite at higher temperatures. Further studies
involving high-temperature dynamic XRD are required to un-
derstand the mullite formation kinetics, morphology, and crys-
'
tal structures in porcelain bodies.
Another source for mullite may be from the dissolution of
alumina that has been substituted for quartz within a porcelain
body. Figure 17 shows the appearance of mullite surrounding
alumina grains and the formation of mullite needles into the
glass phase in a commercial dinnerware body fired at cone
9.I3l TEM is necessary to verify that the surrounding phase is
mullite and that alumina particle dissolution is the basis for
additional mullite formation.
(4) Cristobalite Formation
Lundinlol has indicated that, in a porcelain body with excess
quartz, the cristobalite phase begins to form when the rate of
January 1998 Porcelain-Raw Materials, Processing, Phase Evolution. and Mechanical Behavior

I \ ' \ \

o=AL
o=0
0 =OH
' *+-.4

A Y
I

Y
I
B

0 @ Oxygen i o n s , v a r i o u s p o s i t i o n s

Aluminum Silicon 0 = 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 cristo-
balite 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 hy-
potheses 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 mor-
phology 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 par-
ticles in a glassy matrix. For a single spherical particle in an
isotropic medium, the differences in thermal expansion coef-
16 Journal of the American Ceramic Society-Car9
Fig. 15. Replica illustrating a kaolinite particle fired to 1200°C with
preferred orientation of mullite crystals on the particle surface. I3O This
represents primary mullite formed during the firing of a porcelain.
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
+-
2Em Ep
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.
and Senapati Vol. 81, No. 1
Fig. 17. SEM photomicrograph of a polished and HF-etched com-
mercial dinnerware sample illustrating the apparent dissolution of alu-
mina grains (denoted A) and mullite formation around the particles
with mullite needles growing into the glassy matrix.131
Fig. 18. Polished, but unetched, porcelain sample showing cracking
associated with quartz grains (denoted Q). Also visible in the photo-
micrograph are alumina particles (denoted A).131
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 expan-
sion than the glassy phase in porcelain bodies; hence, the sec-
ond 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) ex-
hibit continuous peripheral fracture at or near the grain bound-
aries 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 illus-
trates 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. Sec-
ond, 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.
(3) Dispersion-Strengthening Hypothesis
The dispersion-strengthening hypothesis proposes that the
dispersed particles limit the size of Griffith flaws, leading to
increased strength. Hasselman and Fulrath also have studied
the effect of alumina spheres in glass on the strength of glass-
ceramic composites, with the expansion coefficient of the glass
matched to that of alumina. The results of strength and fracture
studies indicate that the strength of the glass-ceramic compos-
ite is a function of the volume fraction of the dispersed phase
at low volume fractions; at high volume fractions of the dis-
persed phase, the strength is dependent on the volume fraction
and the particle size of the dispersed phase. Maity et ~ 1
have shown that the replacement of some of the quartz by
sillimanite and some of the feldspar by cordierite increases
strength. They have hypothesized that strength increase is a
dispersion-strengthening effect, because sillimanite and cordi-
erite 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
porcelain bodies with the addition of alumina particles. Like-
wise, they support a strengthening mechanism because of
stronger particles, as observed when zircon is added to porce-
lain bodies.
In porcelain bodies, the thermal expansion coefficients of the
glass matrix rarely match those of the dispersed particles;
hence, there is always a strengthening effect because of matrix
reinforcement. Furthermore, interlocking mullite needles al-
ways are formed because of the firing temperature and kinetics.
Hence, a universal theory of strength in porcelain bodies
should account for all the above mechanisms for strengthening.
(4) Overall Strength Considerations
Intrinsic flaw size is perhaps the predominant factor affect-
ing 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 por-
celain 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 porce-
lain body often produces an increase in strength, despite the
fact that cristobalite experiences a larger displacive transfor-
mation 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
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 con-
tent of the body; and the cristobalite inversion temperature is
lower, 225“-25OoC, compared to 573°C for the quartz inver-
sion, 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 dinner-
ware).
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
ceramic systems. The introduction of automated processing
schemes has required the development of fundamental under-
standing, but, despite the immense amount of existing and
ongoing research, this understanding remains limited. Major
challenges to the development of porcelains and the improve-
ment of commercial manufacturing processes remain, includ-
ing in-depth understanding of the colloidal nature of the raw
materials necessary for improved control; a reliable means of
quickly quantifying and understanding plasticity in clay sys-
tems; the means to reliably predict the microstructure and
phase evolution in porcelain systems, whether composed of
.
three primary components or several raw materials; and theo-
~ ~ ~ 3 ~ ~ ~
retical explanations regarding the roles of the crystalline phases
on firing, consistent with the observed mechanical properties.
From a research perspective, the study of porcelains continues
to present multiple, complex research challenges, offering sig-
foreseeable future.
Acknowledgments: The authors would like to thank J. Howles, M.
Tindale, and C. Perry for their assistance with the XRD patterns and for their
help preparing several of the figures.
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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 Missouri-
Rolla 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, Amster-
dam, 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 Technol-
ogy-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 Ad-
vanced 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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