Journal
, 82 [12] 3584–90 (1999)
Fired Porcelain Microstructures Revisited
Department of Engineering Materials, University of Sheffield, Sheffield S1 3JD, United Kingdom
The microstructure of standard commercial porcelain con-
sists of ␣-quartz grains held in a complex matrix. Quartz
grains are surrounded by amorphous silica-rich solution
rims while the matrix contains clay relicts of small (∼200
nm × 40 nm × 40 nm) primary (2Al2O3:1SiO2) mullite crys-
tals in aluminosilicate glass and feldspar relicts of acicular
(>1 µm long) secondary (3Al2O3:2SiO2) mullite in potas-
sium aluminosilicate glass. A continuous increase in mullite
crystal size from the clay–feldspar relict interface to the
feldspar relict center and their compositions indicate a
transformation from primary to secondary mullite. In alu-
minous porcelain, corundum grains are observed in addi-
tion to ␣-quartz and regions of clay and feldspar relicts.
Small (∼50 nm × 10 nm × 10 nm) tertiary mullite crystals
(formed by precipitation from Al2O3-rich glass) were de-
tected adjacent to these corundum grains.
I. Introduction
T HE microstructures and properties of porcelain bodies fab-
ricated from triaxial mixtures of clay, feldspar, and quartz
have been studied for the greater part of this century.1–3 The
purpose of the current work is to use the improved resolution
and chemical analysis capability available in modern electron
microscopes to examine porcelain microstructures. Specifi-
cally, the type and amount of mullite, the affect of alumina
additions, and the role of local glass composition are examined.
Porcelain microstructures are grain and bond type with a
large grain or filler (usually quartz) held together by a finer
bond or matrix.4 The gross microstructure of fired triaxial por-
celain consists of quartz, feldspar, and clay relicts in a glassy
matrix.1 Lundin5 and Schuller6 reported the formation of two
types of mullite crystals in porcelain bodies. Mullite crystals
coming from the clay relicts have a scaly appearance and are
referred to as primary mullite, whereas the long needle-shaped
mullite crystals crystallizing from the feldspar melt are termed
secondary mullite. Schuller6 reported no difference in the crys-
tal structure or cell dimensions of the two varieties of mullite
except that the primary mullite crystals were as small as 100 Å
in size (Lundin7 reported them to be <0.5 ␮m) and the sec-
ondary mullite crystals were large enough (>1 ␮m) to be ob-
served in the optical microscope. Mullite crystals forming in
the presence of a silica-rich glass liquid phase (such as a feld-
spar melt) are acicular whereas those forming in the absence of
a liquid phase (as in the clay relict) are uniform and equiaxed.8
At higher firing temperatures (∼1400°C), quartz and secondary
mullite are believed to partly dissolve in the glass melt whereas
primary mullite crystals are believed not to dissolve and even
to grow in size.6 The dissolution of one type but stability of the
other has been attributed to small differences in the chemistry
M. P. Harmer—contributing editor
Manuscript No. 189543. Received February 18, 1999; approved June 17, 1999.
*Member, American Ceramic Society.
3584
J. Am. Ceram. Soc.
Yaseen Iqbal and William Edward Lee*
or concentration of foreign ions in the mullite crystal lattices,
one originating from feldspar (K2O⭈Al2O3⭈6SiO2) and the
other from metakaolin (Al2O3⭈2SiO2). However, it may be that
the large, uniform aggregates of primary mullite crystals are
intrinsically less soluble than the fine, acicular secondary mul-
lite. Schuller6 showed that at 1400°C all primary mullite trans-
forms to secondary mullite and, due to the complete dissolution
of quartz, a microstructure consisting simply of glass and mul-
lite needles results.
Mullite is the only stable phase in the Al2O3⭈SiO2 system at
atmospheric pressure. Because of its potentially favorable
properties it has a significant role in the development of tradi-
tional and advanced ceramics.9 Mullite is orthorhombic (space
group Pbam) and its composition ranges from approximately
3Al2O3:2SiO2 to 2Al2O3:1SiO2, referred to as 3:2 and 2:1 mul-
lite, respectively.10 The nonstoichiometry is accommodated by
an oxygen vacancy defect structure. Ordering of these vacan-
cies leads to domains and twins which give additional features
in diffraction patterns which have been interpreted mistakenly
as tetragonality in high-alumina mullites. An important aspect
of the present work was to quantify the chemical compositions
of primary and secondary mullite observed in porcelain bodies.
Austin et al.11 showed that incorporation of up to 20 wt%
calcined alumina into whiteware bodies for a corresponding
amount of quartz improves the mechanical properties without
appreciably affecting the production control of shrinkages, fir-
ing schedules, and maturing temperatures. When flint (which is
predominantly quartz) is replaced by alumina, the difference
between the thermal expansion coefficients (␣) of the crystal-
line and glassy phases is also reduced. As the difference in ␣
decreases, so does the possibility of cracking and, therefore, a
significant increase in the strength of electrical porcelains can
be achieved. Khandelwal and Cook12 achieved a 200% in-
crease in transverse strength by adding 40 wt% alumina to a
vitreous china body, although additions >20 wt% lengthened
the firing process, increased overall body thermal expansion,
and reduced translucency. Increasing alumina and decreasing
feldspar content increases the total crystalline content of the
fired body.12 Analysis of the microstructures reveals a higher
mullite content and decreased crystal size. This provides hard
inclusions to arrest propagation of cracks and improve the bod-
ies thermal shock resistance. Increased interlocking of the mul-
lite crystals is also thought to increase thermal shock resis-
tance.13 On the other hand, Khandelwal and Cook12 compared
the strength of two quartz-containing bodies with different
mullite contents and observed that mullite content was not the
only factor affecting porcelain strength since the body with
lower mullite content was stronger. This indicates that micro-
structure (the quantity, size, size distribution, and shape of
various constituent phases) has an important influence on por-
celain properties. Most recently, Vazquez et al.2 investigated
the effect of alumina additions on the elastic properties of
electrical porcelains. After firing 2 h at 1270°C, the highest
value of Young’s modulus (E ≈ 53 GPa) was attained for a
body containing 10 wt% alumina. After 2 h at 1320°C, E was
directly proportional to the alumina content rising to >62 GPa.
After 2 h at 1350°C, E ≈ 66 GPa for samples containing 15
wt% alumina. Vazquez et al.2 used XRD to confirm that the
quartz:mullite ratio decreased with increased alumina content.
December 1999 Fired Porcelain Microstructures Revisited
Thus the increase in E can be attributed to increased mullite
accompanied by reduced quartz content. Similarly, physical
and mechanical properties of fired porcelain bodies can be
improved by replacing quartz and feldspar with sillimanite
sand and alumina/cordierite glass-ceramic, respectively,14
since the replacement particles behave as fracture-resistant
dispersoids.
Chaudhuri and Sarkar15 gave a second heat treatment (50 h
at 1150°C) to prefired porcelain bodies (63 wt% clay–12 wt%
quartz–25 wt% feldspar) in an attempt to crystallize the glassy
phase which contained 10–30 wt% Al2O3 after initial firing
(1 h at 1400°C). Bulk aluminosilicate glasses of similar Al2O3
content are prone to crystallization of mullite on heat treat-
ment,16 but no significant crystallization of the glassy phase in
porcelain could be achieved without addition of nucleating
agents.15,17–20 Alumina substituted for quartz as in alumina-
rich porcelains may dissolve in the SiO2-rich matrix promoting
precipitation of tertiary mullite from the alumina-saturated
glass.21 The present study also examined aluminous porcelain
bodies for the presence of tertiary mullite.
A large volume of a high-viscosity glass increases the
strength of porcelain bodies, although the accompanying de-
crease in body flexibility reduces thermal shock resistance. The
dissolution of quartz upon firing influences the chemical com-
position of the glass phase. Dissolution rate is a strong function
of grain size and is much slower for coarse, low-surface-area,
quartz. Quartz crystals observed in standard porcelain (50 wt%
clay–25 wt% feldspar–25 wt% quartz) are usually rounded in
shape, showing evidence of attack by the feldspar melt.22
Variations in local glass composition were also investigated in
the present study.
II. Experimental Procedure
Standard and aluminous porcelain samples were provided by
Allied Insulators (Leek New Road, Stoke-on-Trent, England).
The compositions of standard and aluminous porcelain in wt%
are given in Table I.
For X-ray diffraction (XRD), powder (sieved <325 mesh) of
standard (Por-S) and aluminous (Por-H) porcelain were
scanned from 2␪ ⳱ 10°→60°, at a scanning speed of 0.5°/min,
using a Philips diffractometer (with CuK␣ radiation, ␭ ⳱
0.1541838 nm) at 50 kV and 30 mA. The diffractometer was
calibrated with an ␣-quartz standard before use. JCPDS Cards
5-490 (␣-quartz), 15-776 (mullite), and 10-173 (corundum)
were used to identify crystal phases. The volume percents of
␣-quartz, corundum, and mullite were determined by compar-
ing the areas under the XRD peaks of these phases in porcelain
samples to the same peaks in standards (i.e., ␣-quartz, ␣-alu-
mina, and molochite) using Sietronics XRD Trace Processing
Software version 2.0 (1993). The volume percent of glass pres-
ent was estimated by subtracting the sum of the volume per-
cents of crystalline phases from 100.
Optical and scanning electron microscopy specimens were
polished using 6, 3, and 1/4 ␮m diamond pastes after grinding
with silicon carbide powders and water. The polished surfaces
were etched for 3 min in 5% HF solution and then gold/carbon
coated. A Polyvar optical microscope and JEOL 6400 SEM
(operating at 20 kV) were used. Secondary electron images
(SEI) were used predominantly and SEM energy dispersive
spectroscopy (EDS) using a Link eXL detector was used to
distinguish corundum from quartz.
Table I. Compositions of Porcelain-S and Porcelain-H
Standard porcelain Aluminous porcelain
Body recipes (Por-S) (wt%) (Por-H) (wt%)
Dorset ball clay 30 30
China clay 20 10
Potash feldspar 25 20
Silica sand 25 20
Calcined alumina 20
3585
Standard TEM specimen preparation techniques were used,
involving grinding, polishing, dimpling, Ar+ ion beam thin-
ning, and carbon coating. A Philips 420 TEM operating at 120
kV was used for bright-field (BF) imaging and selected area
diffraction (SAD). A JEOL 3010 TEM operating at 300 kV
was used for high-resolution electron microscopy (HREM).
␣-Quartz crystals present in most of the samples or a single-
crystal Si sample was used as a standard for the camera con-
stant (␭L) calibration, where ␭ is the electron wavelength and
L the camera length. At least three selected area electron dif-
fractions (SADPs) from single crystals were indexed and in-
terzonal angles calculated with an in-house computer program.
To simulate diffraction patterns and confirm pattern indexing,
the structure factor based computer package “DIFFRACT” was
used.23
The chemical compositions of crystals and matrix glass were
analyzed using EDS (JEM 3010 eXL) in the TEM. Semiquan-
titative data were obtained by comparing experimental traces to
standards. EDS was performed on approximately 100 mullite
crystals and 50 glassy regions. To minimize error due to sili-
ca-rich glass covering mullite crystals, mullite crystals on
the edges of samples with little or no overlapping glass were
analyzed.
III. Results
XRD was used to compare Por-S and Por-H. Por-S con-
tained ∼22 vol% ␣-quartz, ∼16 vol% mullite, and ∼62 vol%
glass. Por-H contained ∼17 vol% ␣-quartz, ∼12 vol% mullite,
∼25 vol% corundum, and ∼46 vol% glass.
Reflected-light microscopy of Por-H revealed quartz grains
“Q”, dark pores “O”, regions of clay “P”, and feldspar “S”
relicts (Fig. 1(a)). Note that larger (>30 ␮m) quartz grains are
cracked but smaller ones are not. The pores and quartz grains
can be more clearly seen in the SEI of Por-S (Fig. 1(b)) and the
dark quartz grains “Q” (surrounded by darker silica-rich solu-
tion rims “R”), pores “O”, regions of clay “P”, and feldspar “S”
relicts in a glass matrix are shown in Figs. 2(a,b). Note the
variation in mullite crystal size at the clay–feldspar relict in-
terfaces labeled “I” and columnar crystal growth from the clay
relict “P” into the feldspar relict “S”. It was not possible to
measure the exact size of individual crystals due to aggregation
of primary mullite and interlocking of secondary mullite from
SEM micrographs. From TEM individual primary mullite crys-
tals in clay relicts were often elongated approximately ⱕ200
nm × 40 nm × 40 nm or cuboidal although they occurred in
large (several micrometers diameter) aggregated clumps
whereas the acicular secondary mullite crystals in feldspar
relicts had similar width and thickness but were up to several
micrometers long.
␣-Quartz grains could be distinguished from corundum be-
cause the former were always surrounded by amorphous silica-
rich solution rims, whereas the corundum grains labeled “A”
were not (Figs. 3(a,b)). Corundum grains were located adjacent
to the clay or feldspar relicts (Fig. 3) whereas quartz grains
were completely isolated from the remaining body constituents
by the solution rim. Figure 4 is from a region containing small
(ⱕ0.2 ␮m long) mullite crystals observed in the clay relict of
Por-S. Figures 5(a–c) show a cuboidal mullite crystal (∼0.2
␮m) and corresponding [001] SADP observed in the clay relict
of Por-S. This crystal contained 83.3 wt% Al2O3 and 16.7 wt%
SiO2 (i.e., 74.6:25.4 mol%), which is close to 2:1 mullite. The
light region ∼50 nm within the crystal may be amorphous.
Figure 6 shows a region of acicular secondary mullite crystals
in a feldspar relict of Por-S. Figure 7 is a BF-TEM image of an
elongated (∼1.2 ␮m long) mullite crystal and a corresponding
[1 1 1] SADP from a similar feldspar relict in Por-S. This crys-
tal contained 70.4 wt% Al2O3 and 29.6 wt% SiO2 (i.e., 58.3:
41.7 mol%), which is close to 3:2 mullite. Figure 8 is a BF-
TEM image of a mullite crystal (∼0.7 ␮m long) and a
corresponding [1 1 2] SADP observed in the aluminous porce-
lain. This crystal had the elongated morphology of a secondary
3586 Journal of the American Ceramic Society—Iqbal and Lee
Fig. 1. (a) Reflected-light micrograph of etched (gold-coated) Por-H
showing quartz grains “Q”, dark pores “O”, clay relicts “P”, and re-
gions of secondary mullite “S” in a glass matrix. (b) Secondary elec-
tron image (SEI) of etched Por-S showing quartz grains, pores, regions
of clay, and feldspar relicts.
mullite crystal but its composition (77.3 wt% Al, 15.5 wt% Si,
5.4 wt% Fe, and 1.8 wt% Ti) gave the Al2O3:SiO2 weight
percent ratio of 81.5:18.5 (i.e., 72:28 mol%), which is close to
2:1 mullite. This may be a crystal at the interface of clay and
feldspar relicts which has not transformed to secondary mullite
but may have grown in length (>0.5 ␮m) due to the lower
viscosity of the matrix. The presence of Fe and Ti in the EDS
spectrum (not shown) indicates that there is some contribution
from glass as well.
Figure 9 is a BF-TEM image of a crystal in Por-H which
EDS and SAD confirmed was corundum. The small (∼50 nm ×
10 nm × 10 nm) crystallites adjoining the corundum contained
38.4 wt% Al2O3 and 58.6 wt% SiO2, (41:59 mol%), suggesting
that they are tertiary mullite crystals in a silica-rich matrix.
Here again the contribution of glass to EDS peaks from tertiary
mullite made composition measurements unreliable and it
was not possible to ascertain whether the tertiary mullite was
2:1 or 3:2.
The local composition of the glassy phase was determined
for more than 50 regions adjacent to different crystalline
phases. Although the glass close to ␣-quartz and in regions
away from mullite was silica-rich, the composition of glass
close to mullite crystals varied. The Al2O3 and K2O content of
the glass close to mullite crystals varied from 0 to 12 wt% (i.e.,
0 to 13 mol% Al2O3) and 0 to 5 wt% (i.e., 0 to 4 mol% K2O),
respectively. Similarly, the K2O content of the glassy phase in
the vicinity of quartz crystals varied from 0 to 5 wt% (4 mol%)
and, in most cases, no Al2O3 was detected in similar regions.
Precise chemical analysis of glass in regions containing mullite
was not possible because of the small/interlocking mullite crys-
tals contributing to the EDS peaks from glass. Figure 10(a) is
Vol. 82, No. 12
Fig. 2. (a) SEI of Por-S showing quartz grains “Q” surrounded by
solution rims “R”, pores “O”, regions of clay “P”, and feldspar “S”
relicts in a glass matrix. Note the variation in crystal size at the clay–
feldspar relict interface “I”. (b) SEI of Por-S showing quartz grains
“Q” (surrounded by solution rims “R”), pores “O”, regions of clay“P”,
and feldspar “S” relicts. Note the direction of crystal growth from the
outer surface of the clay relict toward feldspar relict.
a BF-TEM image of Por-H, showing glass between an ␣-quartz
crystal (Q) and mullite crystals. EDS from the ␣-quartz crystal
and three spots labeled 1, 2, and 3 in crystal-free glass detected
100% SiO2. However, spot 4 contained 12.8 mol% Al2O3 and
87.2 mol% SiO2 and spot 5 42.9 mol% and 57.1 mol% SiO2
although spots 4 and 5 overlap mullite crystals and are embed-
ded in the glass. Another ␣-quartz crystal labeled “Q” sur-
rounded by a silica-rich solution rim (R) is shown in Fig. 10(b).
The primary mullite (P) with “scaly” appearance formed in the
clay relicts is also apparent in this micrograph.
IV. Discussion
Porcelains are heterogeneous with crystalline phases and
pores dispersed in a glass matrix. The major phases (Figs. 1 and
2) in standard triaxial porcelain bodies are mullite, ␣-quartz,
glass and pores.7 Aluminous porcelain (Por-H) contains corun-
dum (␣-Al2O3) because 20 wt% calcined alumina is added
(Fig. 3). Bodies with a high percentage of quartz may also
contain cristobalite,5 although no cristobalite peaks were iden-
tified in this study. Optical micrographs revealed pores as dark
regions and secondary mullite crystals growing in to the feld-
spar relicts. Cracks were seen within some quartz grains (Fig.
1). These cracks formed by release of microstresses within the
quartz grains and the surrounding glass phase from the large
thermal expansion coefficient difference between the crystal-
line quartz (␣ ≈ 23 × 10−6 K−1) and glassy phase (␣ ≈ 3 × 10−6
K−1) in the temperature range 20 –750°C.24 This stress is mani-
December 1999 Fired Porcelain Microstructures Revisited 3587

Fig. 4. Bright-field (BF) TEM image of a general area containing

small primary mullite crystals in Por-S. The compositions (wt%) cal-
culated from the semiquantitative EDS data for crystals 1, 2, 3, and 4
were 57.5Al2O3:42.5SiO2, 67.5Al2O3:32.5SiO2, 41.3Al2O3:58.7SiO2,
and 42.8Al2O3:57.2SiO2, respectively. Note the higher than expected
SiO2 content due to overlapping glass.

Fig. 3. (a) SEI of Por-H showing quartz grains surrounded by solu-

tion rims, pores, regions of clay, and feldspar relicts along with the
corundum grains labeled “A”. Note the difference between the
␣-quartz and corundum grains. The former are surrounded by solution
rims whereas the latter are not. (b) SEI of Por-H showing quartz grains
surrounded by solution rims, pores, regions of clay, and feldspar relicts
and corundum grains labeled “A”. Note the presence of corundum
grains inside clay and feldspar relicts.

fest in TEM images as bend contours in the quartz crystals

(Fig. 10(b)). The cracking of, or in the vicinity of, larger (>30
␮m) quartz grains indicated that cracking is directly related to
quartz grain size.25 Previous SEM studies revealed mullite
grains, a glass phase and SiO2 grains.5,25,26 In the present
study, SEM revealed an uneven distribution of crystalline
phases in a glass matrix (Figs. 1–3). A schematic of the ob-
served microstructure is shown in Fig. 11. The wide solution
rims around quartz grains showed their extensive dissolution.
Primary mullite was present in the form of compact aggregates
of small crystals (<0.5 ␮m long) in the clay relicts and sec-
ondary mullite crystals in the form of characteristic prismatic
needles (>1 ␮m long) in feldspar relicts.7 Because of different
formation conditions in the clay- and feldspar-rich environ- Fig. 5. (a) BF-TEM image of a primary mullite crystal and (b) a
ments, these two types of mullite have different size, shape, corresponding [001] SADP solved in (c) in a clay relict of Por-S. This
and degree of aggregation7 as will now be described. crystal contained 83.3 wt% Al2O3 and 16.7 wt% SiO2.
The kaolinite–mullite reaction series was studied by Come-
foro et al.,27 Brindley and Nakahira,28 and Chakravorty and
Ghosh.29 For porcelain the reaction series for formation of were observed after firing to 800°C and spinel phase formation
mullite has been described by Carty and Senapati21 as follows: was seen above 900°C. Dark nanometer scale features were
(1) metakaolin forms by the dehydroxylation of clay at 500– observed in samples fired to 1000°C. The authors speculate this
500°C; (2) metakaolin transforms to a spinel-type structure and may be preliminary mullite crystallization. It is likely that these
amorphous free silica at 950–1000°C; (3) the spinel transforms features are primary mullite crystals, although their composi-
to primary mullite and silica at temperatures above 1075°C; tion was not determined. Secondary mullite crystals were ob-
and (4) secondary mullite forms by the reaction of the clay served after firing to 1200°C. Lundin7 demonstrated that mul-
relicts with feldspar relicts at ∼1200°C.6 lite crystals grow from the outer surface of the clay relict into
McConville et al.30 studied the microstructural evolution in the feldspar relict, showing that primary mullite relict serves as
kaolinite using TEM. Dehydroxylated metakaolin platelets a seed for nucleation of secondary mullite. The present obser-
3588 Journal of the American Ceramic Society—Iqbal and Lee
Fig. 6. BF-TEM image of a region of secondary mullite needles in a
feldspar relict of Por-S.
Fig. 7. (a) BF-TEM image of a secondary mullite crystal (∼1.2 ␮m
long) and (b) a corresponding [1 1 1] SAD solved in (c) in a feldspar
relict of Por-S. Its chemical composition was 70.4 wt% Al2O3 and 29.6
wt% SiO2.
vations (Fig. 2) clearly demonstrate that secondary mullite
crystals originate from the outer surface of the clay and grow
into the less viscous feldspar relict. The higher viscosity of the
glassy phase in the clay relict than that in feldspar (which is
more fluid because of its higher alkali content) favors growth
of mullite crystals from clay to feldspar relicts. The continuous
increase (from ∼0.2 to >1 ␮m) in the size of mullite crystals
toward the feldspar relict (Figs. 2–3) indicates the possible
transformation of primary into secondary mullite.6
Consider the composition of primary and secondary mullite.
Vol. 82, No. 12
Fig. 8. (a) BF-TEM image of a primary mullite crystal and (b) a
corresponding [1 1 2] SADP solved in (c) in Por-H. EDS detected 77.3
wt% Al, 15.5 wt% Si, 5.4 wt% Fe, and 1.8 wt% Ti. The Al2O3:SiO2
wt% ratio was thus 81.5:18.5 in this crystal.
Fig. 9. (a) BF-TEM image of a corundum crystal In Por-H with
tertiary mullite crystals at its edge (arrowed).
Primary mullite forms from the metakaolin (composition
Al2O3 2SiO2) and secondary mullite is observed in the feldspar
melt (composition K2O⭈Al2O3⭈6SiO2). 2:1 and 3:2 mullite con-
tain 77.2 wt% Al2O3 and 22.8 wt% SiO2, and 71.8 wt% Al2O3
and 28.2 wt% SiO2, respectively. Mullite forming in the clay
relict is consequently more alumina-rich (2:1) than that in the
feldspar, which is 3:2 secondary mullite. The average weight
percent compositions determined by EDS in the present study
for primary (81.5Al2O3:18.5SiO2) and secondary mullite crys-
tals (70.4Al2O3:29.6SiO2) are in agreement with the above ar-
gument. The reason for the variation in chemical composition
may be the different glassy environments (in clay and feldspar
relicts) in which the crystals are embedded. The 2:1 composi-
tion observed for the elongated crystals which are assumed
(from their morphology) to be secondary (Fig. 8) may be pri-
mary mullite crystals transforming to secondary mullite or pri-
mary mullite grown larger due to the less viscous matrix at the
December 1999 Fired Porcelain Microstructures Revisited
Fig. 10. (a) BF-TEM image of a general area observed in por-H,
showing glass between an ␣-quartz crystal and primary mullite crys-
tals. EDS from the ␣-quartz crystal and three spots labeled 1, 2, and 3
detected 100 wt% Si whereas spots 4 contained 19.9 wt% Al2O3 and
80.1 wt% SiO2 (i.e., 12.8 mol% Al2O3 and 87.2 mol% SiO2) and spot
5 contained 39.9 wt% Al2O3 and 61 wt% SiO2 (i.e., 42.9 mol% Al2O3
and 57.1 mol% SiO2). (b) BF-TEM image of an ␣-quartz crystal
surrounded by a silica-rich solution rim. Note the primary mullite with
scaly appearance in the clay relicts around the solution rim.
clay–feldspar relicts interface. Therefore, mullite crystals with
Al2O3:SiO2 weight percent ratio close to 70:30 and often
longer than 1 ␮m are secondary whereas crystals with
Al2O3:SiO2 weight percent ratio close to 80:20 usually shorter
than 0.5 ␮m are primary.
The ∼50 nm white transparent region observed within the
primary mullite crystal (Fig. 5) may be amorphous silica
trapped inside the crystal. A similar amorphous region within
mullite crystals in alumina–silica glasses with 70 wt% alumina
was reported by Risbud.31
Porcelain contains >60 vol% of a high-viscosity glass. Its
properties are critically dependent on the continuous glassy
phase. In general, silicate melts consist of three types of cat-
ions, namely glass formers (e.g., Si4+ and P5+), modifiers (such
as K+, Na+, and Ca2+), and amphoterics (e.g., Al3+ and Fe3+)
which may act either as glass formers or as modifiers.32 Ad-
dition of modifiers to complex oxide glasses decreases the
viscosity, whereas addition of silica or alumina increases it. In
porcelain, glass forms at ∼1100°C in the contact zone between
feldspar crystals and clay. Amorphous silica discarded from
clay relicts during metakaolin formation may assist eutectic
melt formation at ∼900°C.6 The glassy phase increases in vol-
ume with temperature because of quartz dissolution. Conclu-
sions regarding the homogeneity of glass phases have histori-
3589
Fig. 11. Schematic of the observed microstructure of triaxial porce-
lain: (s) secondary mullite, (P) primary mullite, (Q) ␣-quartz, (R)
solution rim.
cally been drawn from values of index of refraction measured
on thin sections using optical microscopy.7 Since mullite crys-
tals cannot be resolved from glass phase in the optical micro-
scope, the data were obtained from two phases (mullite + glass)
rather than single-phase glass. Such unreliable data gave rise to
the opinion that the glass phase in fired porcelain was inho-
mogeneous. In contrast, conclusions drawn from a combination
of quantitative phase determinations, rate measurements, and
electron microscopic observations of phase distribution reveal
that while the composition of the glass is regulated by the
presence of mullite, it is not so inhomogeneous as had previ-
ously been believed.7 The dissolution of quartz grains causes
the greatest inhomogeneity of the glassy phase, and, according
to Lundin,7 “the rate-determining step is assumed to be alumina
diffusion from the adjacent mullite crystals, causing the essen-
tial part of the concentration gradient to fall within the crystal-
free solution rims around the quartz grains.” This concentration
gradient disappears in porcelains in which cristobalite forms.
Thus, the most homogeneous glass is seen in porcelains either
with no quartz content or with such high quartz content that it
saturates the melt and forms cristobalite. After examining the
glassy phase in 30 whitewares, Hermansson and Carlsson20
found that the composition of glass was consistently the same
(76 wt% SiO2, 16 wt% Al2O3, 7 wt% K2O, 1 wt% CaO).
Klykova et al.33 reported glass compositions with varying
Al2O3:SiO2. In the present study, the composition of glassy
phase close to ␣-quartz grains and crystal-free region was
SiO2-rich (>80 wt% SiO2). In the vicinity of corundum grains,
the composition of glass phase is expected to be Al2O3-rich,
but here again the formation of tertiary mullite left the com-
position SiO2-rich. Away from the crystal phases, K2O and
Al2O3 contents were also inhomogeneous, illustrating the local
heterogeneity of glass composition in porcelain bodies.
The small tertiary mullite size (∼50 nm × 10 nm × 10 nm,
even smaller than primary mullite) indicates their formation at
a late stage in the microstructural evolution. They are believed
to form from dissolution of corundum giving alumina-rich
glass which leads to precipitation of tertiary mullite.34
V. Conclusions
The microstructure of standard porcelain bodies consists of
␣-quartz and mullite in a glassy matrix, whereas aluminous
porcelain contains corundum as well. The growth of mullite
crystals from the clay–feldspar interface to feldspar relicts in-
dicates the transformation of primary mullite into secondary
mullite. Small (<0.5 ␮m long) primary mullite crystals (2:1
mullite) in the clay relict can be distinguished from the acicular
(>1 ␮m long) secondary mullite crystals (3:2 mullite) in the
3590 Journal of the American Ceramic Society—Iqbal and Lee
feldspar relict by their size and composition. Mullite crystals
forming at the edges of corundum crystals are tertiary mullite.
In general, the glass phase close to ␣-quartz crystals and in
crystal-free regions is silica-rich. K2O and Al2O3 contents vary,
indicating the local heterogeneity of glass composition in por-
celain bodies. In clay and feldspar relicts, mullite crystals con-
tribute to EDS peaks from glass, and therefore, it is not possible
to determine the exact glass composition, particularly in re-
gions containing primary/tertiary mullite.
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