http://dx.doi.org/10.14382/epitoanyag-jsbcm.2007.

The structure of kaolinite and metakaolinite

Gabriel Varga
Constantine the Philosopher University
[email protected]

A kaolinit és a metakaolinit szerkezete vonatkozó főbb elméleteket. A kaolinit szerkezete

viszonylag jól ismert, de a kaolinitból 400 ºC fölötti
A tanulmány röviden ismerteti a kaolinit szerkeze- hőmérsékleten kialakuló metakaolinité még nincs
tét és a metakaolinit kialakulására és szerkezetére teljesen tisztázva.

1. Introduction 2. Structure of kaolinite

Building ceramics are gained by firing natural clays Kaolinite is the main constituent of kaolin. Its chemical
which contains various materials. The main and the most structure is Al2Si2O5(OH)4 (39,8 % alumina, 46,3 % silica,
used mineral is kaolin. Kaolin is a soft, lightweight, often 13,9 % water) which represents two-layer crystal (silicon-
chalk-like sedimentary rock that has an earthy odor. Besides oxygen tetrahedral layer joined to alumina octahedral layer
kaolinite, kaolin usually contains quartz and mica and also, exist alternately). The theoretical formula for kaolinite is
less frequently, feldspar, illite, montmorillonite, ilmenite, Si2Al2O5(OH)4 (other formulas are Al2O3·2SiO2·2H2O and
anastase, haematite, bauxite, zircon, rutile, kyanite, sillimi- Al2O7Si2.2H2O), which has a molecular weight of 258,071
nate, graphite, attapulgite, and halloysite. Kaolinite, the main g/mol. Kaolinite is build up from pseudohexagonal triclinic
constituent of kaolin, is formed by rock weathering. It is crystals with diameter 0,2–10 μm, with thickness 0,7 nm
white, greyish-white, or slightly colored. Kaolinite is formed and its density is 2,6 g/cm3 [5, 7 – 9].
mainly by decomposition of feldspars (potassium feldspars), Kaolinite has a 1:1 sheet structure composed of SiO4
granite, and aluminium silicates. The process of kaolin forma- tetrahedral sheets and Al(O, OH)6 octahedral sheets (or,
tion is called kaolinization. Kaolinite is a hydrous aluminium expressed in other way, [Si2O5]2- sheet and [Al2(OH)4]2
silicate. It has a stable chemical structure and good physical sheet) with pseudo-hexagonal symmetry [10].The sheets
properties for ceramic production. It is plastic, during drying are created from planes, which are occupied as follows:
phase the shrinkage is low, and its melting point is 1750 °C. O6 – Si4 – O4 – (OH)2 – Al4 – (OH)6. The morphology of
After firing it has a white color [1 – 5]. the kaolin crystals is plate-like. The c-axis of the kaolinite
crystal is perpendicular to the basal plane. A crystal system
of the kaolinite is triclinic, the space group is P1, and lattice
parameters are a = 0,515 nm, b = 0,895 nm, c = 0,740 nm,
α = 91,68°, β = 104,87°, γ = 89,9° [11]. An ideal cell of
the kaolinite is electrically neutral. Its crystalochemical
formula is Al4Si4O10(OH)8 [8].
The first model of structure was designed by Brindley
and Nakahira, see Fig. 2. and Fig. 3. The structure of
Fig. 1. – Base shape of the kaolinit crystal the lattice layers is shown in Fig. 4. Because the layers
A kaolinit kristály kiindulási alakja are close one to other, the water molecules could not get
between the sheets.
Kaolin or clays which contain kaolin are the base mate-
rials for ceramic industry, for pottery, and for building in-
dustry. Kaolinite is material for porcelain, electroporcelain,
tile, brick, and chamotte production [1 – 4]. From these
reasons, the kaolinite structure and its transformations
during heating were studied intensively for many years. A
short review of the kaolinite – metakaolinite transforma-
Fig. 2. – Structure of kaolinit designed by Brindley Nakahira,
tion was published recently in the journal Építőanyag [6]. viewed from the a-axis direction
In this paper, the structures of kaolinite and metakaolinite A kaolinit Brindley Nakahira által felvázolt szerkezete,
are presented. az a tengely irányából nézve

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 Fig. 3. – Chrystalochemical structure of kaolinit
A kaolinit kristálykémiai szerkezete

Fig. 4. – The change of the tethaedrical (light) and Fig 5. – Kaolinite crystals.
octaedhrical (dark) sheets On the right the inset depicts the elementar structure
A tetraéderes (világos) és oktaéderes (sötét) lapok váltakozása Kaolinit kristályok.
A felső kép betét-ábrája az elemi szerkezetet mutatja be.

The base shape and the lamellar structure of kaolinite weight loss. The results of isothermal firing show that the
chrystals are clearly shown in Fig. 5. One lamella crystal dehydroxylation begins at ~420 °C. The chemical equati-
consists of up to 200 elementar layers [4, 12]. ons describing this process is
Real kaolinite crystals contain defects. The density of Al2O3.2SiO2.2H2O → Al2O3.2SiO2 + 2H2O (g).
defects has a significant effect on the thermal stability The result of dehydroxylation is a new phase called a
of kaolinite. A sample with lower density of defects is metakaolinite. During this reaction, as XRD showed, the
more stable, and the dehydroxylation begins at higher higher-order reflections lost their intensity and vanished in
temperatures [8]. the XRD background. This result led to the opinion, that
the metakaolinite can be amorphous, now a conception of
3. Structure of metakaolinite the short-range order crystalline structure of metakaolinite
predominates [10, 15 – 17]. The loss of high-order reflec-
Dehydroxylation is a reaction of decomposition of tions indicates that dehydroxylation results in structural
kaolinite crystals to a partially disordered structure. This disturbances through the breaking of unstable bonds. As
change is followed with a smaller shrinkage of the di- a result, the degree of ordering became lower than that
mensions of the sample and the porosity rise [3]. The first in kaolinite as dehydroxylation progressed. The meta-
present of dehydroxylation were identificated by changes kaolinite does not collapse but, rather, retains a layered
of mechanical [13], electrical [14] properties and also by structure. The first attempt to compile a crystallographic

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 model of metakaolinite was made by Brindley and Nakahira The liberation of 11 % of residual OH groups jointed into
[16, 17], who proposed ideal well-ordered lattice Fig. 6. water molecules escaping from the sample had to be clearly
Metakaolinite maintains the a and b kaolinite lattice displayed on TGA curves. For example, our measurement
parameters, but c-axis parameter disappears, leading to of three English and two Czech kaolins does not prove the
diffuse of the XRD patterns. Octahedral layer is likely to two-step dehydroxylation.
be changed more than the tetrahedral silica layer during A different view on the metakaolinite structure can
dehydroxylation process. Presumably, the remnant oxygen be found in [20]. About 22 % of the crystal volume is
and vacant anion sites rearrange as a way to lower lattice diverted by escaping H2O that theoretically decreases the
energy. The structure of metakaolinite allows the kaolinite lattice parameter c from the value 0,713 nm to 0,556 nm
to collapse to 0,63 nm in agreement with the measured (parameters a, b remain to be constant). But experimentally
densities of kaolinite and metakaolinite. Proposed struc- it was found c = 0,685 nm. This disagreement was solved
ture of the metakaolinite shows no OH groups. A recent by a new model of the metakaolinite structure with high
work [10] assumes the rearrangement of the oxygen and concentration of the polarized vacancies. That structure
vacant sites, which gives stability to the layered structure. is unstable with excess of the lattice energy. This energy
This rearrangement builds modulations along the c-axis is released during exothermic reaction at the temperature
in metakaolinite with a period of 0,14 nm. 950 °C when the structure shrinks ∼20 % and changes into
If the metakaolinite has a structure shown in Fig. 6., new phase with different structure.
that means a regular one, that should be displayed by XRD
reflection. As it was mentioned above, it is impossible to
find the metakaolinite structure by XRD analysis. Con-
sequently, the structure of metakaolinite depictured in Fig.
6. must be considered as idealized.

Fig. 6. - Lattice of metakaolinite supposed by Brindley and Nakahira

A metakaolinit kristályrácsa Brindley and Nakahira
feltételezése szerint
Oxigén ionok különböző pozíciókban (alumínium, szilícium)

A revisited structural model of metakaolinite was pro-

posed by MacKenzie by computer simulation and nuclear
magnetic resonance studies [19]. This structure accounts
the presence of 11–12 % residual OH groups, which are
incorporated in the Al-O layers. This structure is shown
on Fig. 7. MacKenzie assumes that homogeneous and
inhomogeneous mechanisms of the dehydroxylation are
possible. Water is lost from the first regions, which became
micropores, and the structural continuity is preserved in
the second regions, which became metakaolinite. From
the model of MacKenzie it could be excepted that the Fig. 7. – Structure by MacKenzie
residual OH groups will liberate at higher temperatures. A metakaolinit szerkezete MacKenzie szerint

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 4. Conclusion [7] http://europa.eu.int/eur-lex/sk/dd/docs/2001/32001L0030-SK.doc
[8] Číčel, B. – Novák, I. – Horváth, I.: Mineralogy and crystalloche-
mistry of clays. SAV, Bratislava 1981.
Nowadays the structure of kaolinite is well known. [9] http://webmineral.com/data/Kaolinite.shtml
It is build up by octahedrical layers of Al(O, OH)6 and [10] Sujeong Lee – Youn-Joong Kim – Hi-Soo Moon: Energy-filtering
tetrahedrical layers of SiO4, which varies in 1:1. The electron microscopy (EF-TEM) study of a modulated structure in
structure of metakaolinite, created from kaolinite at the metakaolinite represented by a 14 { modulation. J. Amer. Ceram.
Soc., 86, 2003., N1, 174–176.
temperatures higher than 400 °C is still not clear. This is
[11] Iqbal, Y. – Lee, W.E.: Microstructural evolution in triaxial porcelain.
caused by the absence of XRD reflections, which could J. Amer. Ceram. Soc., 83, 2000., N12, 3121–3127.
show exactly the metakaolinite structure. What is generally [12] http://www.arenisca.com/kaolnite.gif
known in the present time, it is double layer structure of [13] Kozík, T. – Šubňa, I.: Mechanical strength of the ceramic material
the metakaolinite taken from the kaolinite crystal. The in the dehydroxylation temperature region. Silikáty, 25, 1981., N3,
237–241.
most commonly spread imagination of the structure of
[14] Kozík, T. et al.: The temperature dependence of the electric conduc-
metakaolinite presents a metakaolinite crystal as a crystal tivity of unfired porcelain mixture. Ceramics-Silikáty, 36, 1992.,
with high concentration of defects. N2, 69–72.
[15] Chin-Yi Chen – Wei-Hsing Tuan: Evolution of mullite texture on
Acknowledgements firing tape-cast kaolin bodies. J. Amer. Ceram. Soc., 85, 2002.,
This work was supported by grant VEGA 1/3179/06. The author N5, 1121–1126.
thanks to Dr. I. Štubňa for his help. [16] Brindley, G.W. – Nakahira, M.: The kaolinite-mullite reaction
series: I, A survay of outstanding problems. J. Amer. Ceram. Soc.,
References 42, 1959., N7, 311–314.
[17] Brindley, G.W. – Nakahira, M.: The kaolinite-mullite reaction series:
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[2] http://www.georgiamining.org/Kaolin/kaolin.htm [18] Brindley, G.W. – Nakahira, M.: Kinetics of dehydroxylation of
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[4] http://www.nanomineral.info/MH_eng.htm [19] MacKenzie, K.J.D.: Feats of clay, or mineral chemistry revisited.
[5] http://www.chemicalland21.com/industrialchem/inorganic/KAO- Chemistry in New Zealand, 1978., N3, 8–12.
LIN.htm [20] Freund, F.: Kaolinite-metakaolinite, a model of a solid with extre-
[6] Štubňa, I. – Varga, G. – Trník, A.: Investigation of kaolinite dehydroxy- mely high lattice defect concentration. Ber. Deutsche Keram. Ges.,
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