Kaolinite


Kaolinite is a clay mineral, part of the group of industrial minerals with the chemical composition Al2Si2O54. It is a layered silicate mineral, with one tetrahedral sheet of silica linked through oxygen atoms to one octahedral sheet of alumina octahedra. Rocks that are rich in kaolinite are known as kaolin or china clay.
The name "kaolin" is derived from "Gaoling", a Chinese village near Jingdezhen in southeastern China's Jiangxi Province. The name entered English in 1727 from the French version of the word: kaolin, following François Xavier d'Entrecolles's reports on the making of Jingdezhen porcelain.
Kaolinite has a low shrink–swell capacity and a low cation-exchange capacity. It is a soft, earthy, usually white, mineral, produced by the chemical weathering of aluminium silicate minerals like feldspar. In many parts of the world it is colored pink-orange-red by iron oxide, giving it a distinct rust hue. Lighter concentrations yield white, yellow, or light orange colors. Alternating layers are sometimes found, as at Providence Canyon State Park in Georgia, United States. Commercial grades of kaolin are supplied and transported as dry powder, semi-dry noodle, or liquid slurry.

Chemistry

Notation

The chemical formula for kaolinite as used in mineralogy is, however, in ceramics applications the formula is typically written in terms of oxides, thus the formula for kaolinite is.

Structural transformations

Kaolinite group clays undergo a series of phase transformations upon thermal treatment in air at atmospheric pressure.

Drying

Below, exposure to dry air will slowly remove liquid water from the kaolin. The end-state for this transformation is referred to as "leather dry". Between 100 °C and about, any remaining liquid water is expelled from kaolinite. The end state for this transformation is referred to as "bone dry". Throughout this temperature range, the expulsion of water is reversible: if the kaolin is exposed to liquid water, it will be reabsorbed and disintegrate into its fine particulate form. Subsequent transformations are not reversible, and represent permanent chemical changes.

Metakaolin

Endothermic dehydration of kaolinite begins at 550–600 °C producing disordered metakaolin, but continuous hydroxyl loss is observed up to. Although historically there was much disagreement concerning the nature of the metakaolin phase, extensive research has led to a general consensus that metakaolin is not a simple mixture of amorphous silica and alumina, but rather a complex amorphous structure that retains some longer-range order due to stacking of its hexagonal layers.
Al2Si2O54 -> Al2Si2O7 + 2 H2O

Spinel

Further heating to 925–950 °C converts metakaolin to an aluminium-silicon spinel which is sometimes also referred to as a gamma-alumina type structure:
2 Al2Si2O7 -> Si3Al4O12 + SiO2

Platelet mullite

Upon calcination above 1050 °C, the spinel phase nucleates and transforms to platelet mullite and highly crystalline cristobalite:
3 Si3Al4O12 -> 2 + 5 SiO2

Needle mullite

Finally, at 1400 °C the "needle" form of mullite appears, offering substantial increases in structural strength and heat resistance. This is a structural but not chemical transformation. See stoneware for more information on this form.

Occurrence

Kaolinite is one of the most common minerals; it is mined, as kaolin, in Malaysia, Pakistan, Vietnam, Brazil, Bulgaria, Bangladesh, France, the United Kingdom, Iran, Germany, India, Australia, South Korea, the People's Republic of China, the Czech Republic, Spain, South Africa, and the United States.
Mantles of kaolinitic saprolite are common in Western and Northern Europe. The ages of these mantles are Mesozoic to Early Cenozoic.
Kaolinite clay occurs in abundance in soils that have formed from the chemical weathering of rocks in hot, moist climates—for example in tropical rainforest areas. Comparing soils along a gradient towards progressively cooler or drier climates, the proportion of kaolinite decreases, while the proportion of other clay minerals such as illite or smectite increases. Such climatically-related differences in clay mineral content are often used to infer changes in climates in the geological past, where ancient soils have been buried and preserved.
In the Institut National pour l'Etude Agronomique au Congo Belge classification system, soils in which the clay fraction is predominantly kaolinite are called kaolisol.
In the US, the main kaolin deposits are found in central Georgia, on a stretch of the Atlantic Seaboard fall line between Augusta and Macon. This area of thirteen counties is called the "white gold" belt; Sandersville is known as the "Kaolin Capital of the World" due to its abundance of kaolin. In the late 1800s, an active kaolin surface-mining industry existed in the extreme southeast corner of Pennsylvania, near the towns of Landenberg and Kaolin, and in what is present-day White Clay Creek Preserve. The product was brought by train to Newark, Delaware, on the Newark-Pomeroy line, along which can still be seen many open-pit clay mines. The deposits were formed between the late Cretaceous and early Paleogene, about 100 to 45 million years ago, in sediments derived from weathered igneous and metakaolin rocks. Kaolin production in the US during 2011 was 5.5 million tons.
During the Paleocene–Eocene Thermal Maximum sediments were enriched with kaolinite from a detrital source due to denudation.

Synthesis and genesis

Difficulties are encountered when trying to explain kaolinite formation under atmospheric conditions by extrapolation of thermodynamic data from the more successful high-temperature syntheses. La Iglesia and Van Oosterwijk-Gastuche thought that the conditions under which kaolinite will nucleate can be deduced from stability diagrams, based as they are on dissolution data. Because of a lack of convincing results in their own experiments, La Iglesia and Van Oosterwijk-Gastuche had to conclude, however, that there were other, still unknown, factors involved in the low-temperature nucleation of kaolinite. Because of the observed very slow crystallization rates of kaolinite from solution at room temperature Fripiat and Herbillon postulated the existence of high activation energies in the low-temperature nucleation of kaolinite.
At high temperatures, equilibrium thermodynamic models appear to be satisfactory for the description of kaolinite dissolution and nucleation, because the thermal energy suffices to overcome the energy barriers involved in the nucleation process. The importance of syntheses at ambient temperature and atmospheric pressure towards the understanding of the mechanism involved in the nucleation of clay minerals lies in overcoming these energy barriers. As indicated by Caillère and Hénin the processes involved will have to be studied in well-defined experiments, because it is virtually impossible to isolate the factors involved by mere deduction from complex natural physico-chemical systems such as the soil environment.
Fripiat and Herbillon, in a review on the formation of kaolinite, raised the fundamental question how a disordered material could ever be transformed into a corresponding ordered structure. This transformation seems to take place in soils without major changes in the environment, in a relatively short period of time, and at ambient temperature.
Low-temperature synthesis of clay minerals has several aspects. In the first place the silicic acid to be supplied to the growing crystal must be in a monomeric form, i.e., silica should be present in very dilute solution. In order to prevent the formation of amorphous silica gels precipitating from supersaturated solutions without reacting with the aluminium or magnesium cations to form crystalline silicates, the silicic acid must be present in concentrations below the maximum solubility of amorphous silica. The principle behind this prerequisite can be found in structural chemistry: "Since the polysilicate ions are not of uniform size, they cannot arrange themselves along with the metal ions into a regular crystal lattice."
The second aspect of the low-temperature synthesis of kaolinite is that the aluminium cations must be hexacoordinated with respect to oxygen. Gastuche et al., as well as Caillère and Hénin have concluded, that only in those instances when the aluminium hydroxide is in the form of gibbsite, kaolinite can ever be formed. If not, the precipitate formed will be a "mixed alumino-silicic gel". If it were the only requirement, large amounts of kaolinite could be harvested simply by adding gibbsite powder to a silica solution. Undoubtedly a marked degree of adsorption of the silica in solution by the gibbsite surfaces will take place, but, as stated before, mere adsorption does not create the layer lattice typical of kaolinite crystals.
The third aspect is that these two initial components must be incorporated into one and the same mixed crystal with a layer structure. From the following equation for kaolinite formation
2Al3 + 2H4SiO4 -> Si2O5. 2Al3 + 5H2O
it can be seen, that five molecules of water must be removed from the reaction for every molecule of kaolinite formed. Field evidence illustrating the importance of the removal of water from the kaolinite reaction has been supplied by Gastuche and DeKimpe. While studying soil formation on a basaltic rock in Kivu, they noted how the occurrence of kaolinite depended on the "degrée de drainage" of the area involved. A clear distinction was found between areas with good drainage and those areas with poor drainage. Only in the areas with distinct seasonal alternations between wet and dry was kaolinite found. The possible significance of alternating wet and dry conditions on the transition of allophane into kaolinite has been stressed by Tamura and Jackson. The role of alternations between wetting and drying on the formation of kaolinite has also been noted by Moore.

Laboratory syntheses

Syntheses of kaolinite at high temperatures are relatively well known. There are for example the syntheses of Van Nieuwenberg and Pieters ; Noll ; Noll ; Norton ; Roy and Osborn ; Roy ; Hawkins and Roy ; Tomura et al. ; Satokawa et al. and Huertas et al..
Relatively few low-temperature syntheses have become known ; DeKimpe ; Bogatyrev et al. ).
Laboratory syntheses of kaolinite at room temperature and atmospheric pressure have been described by DeKimpe et al.. From those tests the role of periodicity becomes convincingly clear. DeKimpe et al. had used daily additions of alumina and silica during at least two months. In addition, adjustments of the pH took place every day by way of adding either hydrochloric acid or sodium hydroxide. Such daily additions of Si and Al to the solution in combination with the daily titrations with hydrochloric acid or sodium hydroxide during at least 60 days will have introduced the necessary element of periodicity.
Only now the actual role of what has been described as the "aging" of amorphous alumino-silicates can be fully understood. Time as such is not bringing about any change in a closed system at equilibrium; but a series of alternations, of periodically changing conditions, will bring about the low-temperature formation of more and more of the stable phase kaolinite instead of amorphous alumino-silicates.

Uses

The main use of the mineral kaolinite is the production of paper; its use ensures the gloss on some grades of coated paper.
Kaolin is also known for its capabilities to induce and accelerate blood clotting. In April 2008 the US Naval Medical Research Institute announced the successful use of a kaolinite-derived aluminosilicate infusion in traditional gauze, known commercially as QuikClot Combat Gauze, which is still the hemostat of choice for all branches of the US military.
Kaolin is used :
Humans sometimes eat kaolin for health or to suppress hunger, a practice known as geophagy. Consumption is greater among women, especially during pregnancy. This practice has also been observed within a small population of African-American women in the Southern United States, especially Georgia. There, the kaolin is called white dirt, chalk, or white clay.

Safety

People can be exposed to kaolin in the workplace by breathing in the powder or from skin or eye contact.

United States

The Occupational Safety and Health Administration has set the legal limit for kaolin exposure in the workplace as 15 mg/m3 total exposure and 5 mg/m3 respiratory exposure over an 8-hour workday. The National Institute for Occupational Safety and Health has set a recommended exposure limit of 10 mg/m3 total exposure TWA 5 mg/m3 respiratory exposure over an 8-hour workday.

Citations

General references

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