Clay minerals for advanced ceramics

H. H. Murray
Abstract-New and improved beneficiation techniques
are available to allow the production of clay minerals of ex-
ceptionally high purity. This is particularly true for kaolins
and smectites. Wet processing techniques include particle
size separation, high intensity magnetic separation, chemical
leaching ,flotation, and selectivefi70cculation. The blending of
clay minerals with other minerals provides opportunites to
make special ceramic materials such as cordierite and other
minerals that have very special ceramic properties including
low heat expansion, high fired strength, low absorption, and
other desired qualities.
Introduction
The ceramic industry today is a far cry from what it was 30
years ago. It is a highly technical, sophisticated industry and
even making common brick and other structural clay products
has become more technical. Today, the industry is involved in
ceramic engines, heat exchangers, ceramics for machining,
ceramic-metal joins, glassceramic joins, superconductors,
and many other highly technical applications that are termed
advanced ceramics. Ceramic research is an interesting and
very exciting field for the individuals involved, both inbasic
or fundmental research and in the applied and engineering
research areas.
Clays and ceramics are almost synonymous terms and
certainly were in the past. Now ceramics involves some 86
elements that can be combined to produce innumerable com-
(OrrllingI
I
j p i i q
I
( Mining 1
I
) Degrltting I
I
( Storage (tanks) and blendlng (
pounds that have present or potential usage in ceramics
(Rhodes, 1988). Twenty-two of these elements have melting
points above 1600" C (291 2" F) (Sugita, 1988). Clays are still
a necessary ingredient in many ceramic products and can be
an ingredient in some of the advanced ceramics. However, the
clays that will be used in any advanced ceramic product must
be exceptionally pure and have closely controlled properties.
This paper focuses on the new and improved beneficiation
techniques that are available to the clay industry to allow them
to produce clays of very high purity. In the United States, we
are fortunate to have large deposits and reserves of kaolins,
smectites, and attapulgite that can be beneficiated. The loca-
tion of the deposits and the processing techniques that are or
can be used are described. Illites are another group of clays
that are used in ceramics, primarily in structural clay products
and stoneware. Illites rarely occur in deposits of high purity
and the illite mineral structure generally contains iron and
fires a red or brown color. Thus, illite deposits are not
beneficiated for ceramic uses.
Clays for advanced ceramics
Kaolin
Kaolin is a clay comprised essentially of the mineral
kaolinite, which has the pure theoretical oxide composition of
46.3% SiO,, 39.8% A120, and 13.9% combined H20. The
structural formula of kaol~nite is (OH),Si,Al,Ol,. In the United
States, the largest and most ex-
tensive kaolin deposits are lo-
cated in Georgia and South Caro-
lina (Murray, 1986). These de-
posits are sedimentary and con-
tain about 90% or morekaolinite
along with minor quantities of
quartz, mica, and smectite along
with trace quantities of ilmenite,
anatase, rutile, goethite, zircon,
tourmaline, and kyanite. For
Deflocculatlon
/&
I
1 Particle separation
I
I
L Ba##lng and loading
Fig. 1 -Generalized flow sheet for kaolinite wet processing.
many uses, these accessory and
minor minerals must be essen-
tially removed or greatly reduced
in amount. The most efficient
way to remove these impurities
is a wet process, the essential
steps of which are shown in Fig.
1.
Generally the quartzand mica
are present as particles that are
H.H. Murray, member SME, is pro-
fessor of geology, 000
, Bloomington, IN. SME preprint
89-1 14. SME-AIME Annual Meet-
ing, Las Vegas, NV, February-March,
1989. Manuscript November 1988.
Discussion of this paper must be
submitted, in duplicate, prior to Feb.
28, 1990.
MINING ENGINEERING NOVEMBER 1989 1123
coarser than 44 m (325 , , blend of 37.4% cal-
mesh) and can be re-
moved by gravity set-
tling and screening.
Particle size separations
are accomplished by
using continuous cen-
trifuges that can sepa-
rate the kaolin particles
into fine and coarse frac-
tions. The particle size
of the fine fractions can
be controlled between
about 70% finer than 2
ym (5000 mesh) to es-
sentially 100% finer
than 2 ym (5000 mesh).
Any quartz and mica
particles that are finer
than 44 ym (325 mesh)
will be contained in the
coarse fraction.
High intensity mag-
netic separators are a
standard processing
technique used in the
kaolin industry (Ian-
nicelli, 1976). This
process uses a canister
filled with fine stainless
steel wool that when
magnetized willremove
iron and titanium con-
taining minerals from
C
MAGNET COIL
I
TOP VlEW
I MAGNET STEEL ,
SLURRY IN I I
=+
SIDE VlEW
SECTION THROUQH MAQNET
Fig. 2-Diagrammatic sketch of a high gradient magnetic separator.
the kiolin slurry as it passes through the canister (Fig. 2,
following page). A new superconducting magnet has been
developed and is in continuous operation in a kaolin plant. It
has reduced power costs and improved the removal of fine
paramagnetic mineral particles ( ~b mh a r n and Falconer, 1985).
Other processes used to remove iron and titanium mineral
impurities are flotation (Greene and Duke, 1962) and selec-
tive flocculation (Bundy and Berberich, 1969; Maynard,
Skipper, and Millman, 1968; Mercade, 1972; and Shi, 1986).
Chemical leaching is a standard beneficiation technique that
is used to remove soluble iron. In this process the kaolin slurry
is acidified with sulfuric acid to a DH of about 3 to solublize
the iron. Sodium hydrosulfide, a strong reducing agent, is
added to reduce ferric iron to ferrous iron, which then com-
bines with the sulfate iron to form a soluble ferrous sulfate ~ ~
compound that is removed during the dewatering process. The
result of this wet process, used by the kaolin industry, is a very
pure kaolinite product. Some of these kaolin products can be
iailored to special ceramic applications.
An example of the blending of kaolin with other minerals
to make a special ceramic material is in the ceramic support for
the automobile catalytic converter. A material was needed
that had a reasonable firing temperature and a very low
thermal expansion. The continual heating and cooling of the
ceramic support unit caused severe thermal stresses that
caused rapid failure of the monolith unit. From phase dia-
grams, it was determined that the mineral cordierite might
have the requisite properties needed for the ceramic support.
The firing temperature was about 1300" C (2372" F) and the
thermal expansion was 9.8 x l o7. Cordierite has the structural
formula of Mg2A1,Si,0,, and an oxide composition of 13.7%
MgO, 34.9% A1,0, and 5 1.4% SiO,. It was determined that a
cined talc (magnesium
silicate), 5 1.7% cal-
cined kaolin (alumi-
num silicate) and
10.9% alumina(a1umi-
num oxide) would pro-
duce a composition
that, when fired, would
produce cordierite.
This cordierite ceramic
support unit for the
automobile catalytic
converter unit is now
used extensively on
American and foreign
made automobiles.
Some ceramic prop-
erties and physical
constants of relatively
pure kaolin taken from
published ceramic data
are as follows:
Dry shrinkage,
4.0 - 7.5%;
Compressive
green strength (with
50% flint), 2 MPa (300
psi);
Fired shrinkage
(1300" C or 2372" F),
6%- 15%;
Fusion tempera-
ture, 1850" C (3362"
F);
Specific gravity, 2.60;
Hardness (Mohs scale), 2; and
Pyrometric cone equivalent (PCE), Cone 33 to 36.
The above values are representative of values obtained
from relatively pure kaolins.
When kaolin is heated the structural water is lost at about
550" C (1022" F) and metakaolin, which is amorphous to X-
rays, is formed (Brindley and Nakahira, 1959). At a tempera-
ture of about 950" C (1742" F), the metakaolin transforms to
gamma alumina and cristobalite. Further heating transforms
the silica carrying gamma alumina to mullite and cristobalite.
Smectite
Smectite is the name for a group of sodium, calcium,
magnesium, iron, lithium, aluminum silicates that include the
minerals sodium montmorillorite, calcium mont-morillonite,
saponite, nontronite, and hectorite. These smectite minerals
are usually dominant in bentonite.
The theoretical formula without considering lattice substi-
tutions is (OH),A1,Si,02,~N H20 (interlayer). The theoretical
composition without the interlayer material is 66.7% SiO,,
28.3% A120,, and 5% H,O. Smectite always differs from the
theoretical formulabecause of substitutions within the lattice.
Common substitutions are aluminum for silicon in the silica
tetrahedral sheet, which appears tobe limited to less than 15%,
and magnesium and iron for aluminum in the octahedral sheet.
Substitutions in the octahedral sheet range from a small
percentage to almost complete. Nearly total replacement of
aluminum by magnesium results in the mineral saponite and
by iron yields the mineral nontronite. When lithium substi-
tutes for sodium or calcium, the mineral is called hectorite.
1124 NOVEMBER 19B9
MINING ENGINEERING
MINING ENGINEERING
Table 1-Chemical Analyses of Some Smectite Minerals
Na Montmorlllonlta Ca Montmorlllonlte Saponlte Nontronite ~wtorlte
SiO, 61.12 61.77 50.01 39.92 55.17
A'>0, 23.10 19.85
3.89 5.37 0.33
TiO, - 0.24 0.04 0.08
0.21 29.46
0.12
Fe,O, 4.37 1.95
-
FeO -
- - 0.28 -
MgO 2.50 5.56 25.61 0.93
CaO 0.24 1 89 1.31 2.46 :
Na, O 2.90 0.07 -
- 2.20
K2 0.04 0.09
0.08
H,O* 6.45 7.72 12.02 7.00
Li,O 1.14
NOVEMBER 1989 1125
there is some substitution of aluminum for
silicon and substitution of magnesium,
manganese, and iron for aluminum.
The mineral form is elongate, which gives
this clay mineral some unusual properties. A
small amount (4% or less) added to porce-
lain material improves the molding charac-
teristics and improves the strength (Ovchar-
enko, et al., 1964). Elongate fine particle
size attapulgite improves the plasticity
(Grimshaw, 197 1) of a ceramic body.
The mean chemical analyses taken from averaging 101
Attapulgite loses the internal pore water between 250' and
samples (Weaver and Pollard, 1973) gives the following 350" C (482" and 662" F). Hydroxyl water is lost between
percentages: SiO,, 59.49%; A 1,0,21.93%; Fe,O 3.77%; FeO,
400" and 600" C (752" and 11 12" F). At 800' to 1000" C
0.2%; MgO, 3.55%; CaO, 1.18%; Na20, 0.82%; K20, 0.34%;
(1472" and 1832" F), enstatite, mullite, and cristobalite form.
Ti 0 0.25%; and H20+, 8.38%. Typical analyses of sodium Attapulgite can be purified by using wet process beneficia-
moritmorillonite, calcium montmorillonite, saponite, non-
tion techniques so that major, nonclay impurities such as
tronite, and hectorite are shown in Table 1.
quartz, calcite, and dolomite can be removed. A pure fine
The smectite minerals are very fine in particle size, usually particle size attapulgite can be produced that has potential
of the order of less than 1 pm (12,000 mesh). Most smectites applications in ceramics for its binding properties and chemi-
are dry processed for use as drilling muds, foundry bond clays, cal content. Attapulgite fuses at about 1500" C (2732" F).
ore pelletizing, and sealants. However, some are wet proc- Attapulgite clays are sometimes referred to as sorptive
essed to produce very pure and uniform products for use as clays because they have a large surface area and can absorb
suspending agents, in cosmetics, special ceramics, pencil and adsorb many materials. The term fuller's earth is more or
leads, detergents, catalysts, and other specialty applications. less a catch-all term for clays or other fine-grained, earthy
Fine particle size, relatively pure smectites are excellent materials suitable for sorbent uses. Attapulgite is produced in
plasticizers and bonding agents even in very small percentage the southeastern United States near the Georgia-Florida bor-
additions. Montmorillonite (Grimshaw, 1971) has a cross- der in the vicinity of Quincy, FL and Attapulgus, GA.
breaking strength ranging from 1500 to 2500 g/cm2 (3070 to
5 120 psf) , which is the highest of the clay materials. Summary
One of the important properties of smectite is its high
exchange capacity particularly for cations. Thus, special clays
Clay minerals including kaolinite, sodium and calcium
can be produced with a particular cation on the exchange
montmorillonites, and attapulgite have useful ceramic proper-
position. The range of cation exchange milliequivalents per
ties. As they occur in nature, most have impurities associated
I00 g (3.5 oz) for sodium montmorillonite is 75 to 150. This
with them and, therefore, must be beneficiated to produce a
is referred to as cation exchange capacity (CEC).
uniform, fine particle size clay with a high degree of purity.
Smectites lose their hydroxyl water in the range of 400" to
These resultant high purity clay products have some very
700" C (752" to 1292" F). At temperatures of about 900" C
desirable ceramic properties that can be used in some of the
(1 652" F), several phases form including cristobalite, cordier-
more advanced ceramic products. +
ite, mullite, spinel, enstatite, and anorthite depending on the
composition of the smectite. Smectites fuse at temperatures
References
between 1200" and 1400" C (2192" and 2552" F), again
depending On their composition.
Brindley,G. W., and Nakahira. M., 1959, TheKaolinite-Mullite Reaction Series, Journalolrhe
The largest and highest quality sodium bentonite deposits
American Ceramics Sociely. Voi. 42. pp. 311-324.
in the world are located in South Dakota, Wyoming, and Bundyy, W. M., and Berberich, J. P., 1969, US patent 3477809.
Montana. The major nonclay minerals in this sodium montmo-
Greew E. W.. and Duke. J. 8. . 1962, "Selective froth flotation of ultrafine minerals or slimes."
rillonite are quartz, cristobalite, feldspar, mica, and some
Trans. SME-AIME, 223, pp. 389-395.
Grimshaw, R.W., 1971. The Chemistry and Physicsof Clays, Wiley-Interscience, NewYork,
zeolite. Most all of these nonclay minerals can be separated by
,,, pp.
wet processing provide an pure sodium lannicell,, J,, 1976, "New Developmentsin Magnel~cSeparation;'lEEE Trans. Magn. Mag-12,
montmorillonite. pp. 436-443.
Bentonites in which calcium montmoril~onites are the Maynard, R. N., Skipper, 8. R., and Millman, N. , 1968. US patent 3371988.
major mineral constituent are found in Arizona, Texas, and Mercade. V. v.. 1972. US patent3701417.
Mississippi. The nonclay minerals are essentially the same as Murray. H.H.. 1986. Clays. Ullmanns En c y c l o p e d i a o l l n d ~ ~ ~ ~ i a ~ c h e ~ i ~ r ~ ~ VOI. ~ 7 , pp. 109-
those in the sodium montmorillonite or western bentonite.
136.
These calcium montmorillonites can be purified by wet proc-
Ovcharenkoo. F. D.. 1964, "TheColioidChemistryof Palvorskite."lsraelProgram torscienttfic
ess beneficiation methods.
Translations, Jerusalem, 101 pp.
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Vol 67. No. 8, pp. 1267.
Attapulgite
Shi, J.. 1986, US patent 4604369.
Sugita, K , 1988. "The Current Status and Future Technological Problems Associated with
The term attapulgite and palygorskite are synonymous. structural Fine Ceramicsfrom a Japanese Industrial Viewpoint:' International Forum on Fine
Most mineralogists use the term palygorskite but attapulgite
'88) Nagoya, Japan.
is the preferred industrial term. Some use the term attapulgite
Weaver, C E., and pollard. L.D.. 1973, The Chernlsrry ol Clay Minerals. Developments In
Sed~mentology. Vo1.15, Elsevier, Amsterdam. Netherlands, 213 pp.
when the length is (less than about ratio of wer"harn . A . and Falconer, T , . , 1985, The Eriez Commerctai Superconductiq ~ i ~ h
length to diameter). The structural formula of attapulgite is
Gradient Separator;. (Abstract) Conference on Superconducting Magnetic Separation,
(OH,) (OH), Mg, Si, 0,,*4H,O. In the structure of attapulgite,
lm~erial College. London, PP. 2.