Applied Clay Science, 5 (1991) 379-395

Elsevier Science Publishers B.V., Amsterdam

379

O v e r v i e w - clay mineral applications

Haydn H. Murray
Dept. of Geology, 1005 E. Tenth St., Indiana University, Bloomington, IN47405, USA
(Received March 12, 1990; accepted after revision June 27, 1990)

ABSTRACT Murray, H.H., 1991. Overview - clay mineral applications. In: H.H. Murray (Editor), Some Applications of Selected Clay Minerals. Appl. Clay Sci., 5:379-395. The applications of the clay minerals in the various process industries engineering, petroleum discovery, recovery and refining, and others, are closely related to their structure and composition. Important characteristics relating to applications of clay minerals are particle size, surface chemistry, particle shape, surface area, and other physical and chemical properties specific to a particular application such as viscosity; color; plasticity; green, dry and fired strength; absorption and adsorption; abrasion; and others. The discussion of the applications of clay materials is organized as follows: kaolins; smectites; palygorskite (attapulgite) and sepiolite; and miscellaneous. The largest volume applications in each category are discussed in general, leaving the more specific details to be covered in the papers in this symposium that cover a particular application. The major uses of kaolins are in the paper, ceramic, paint, plastic, rubber, and cracking catalyst industries. The major uses of smectites are in drilling fluids; as a bond for foundry sands and iron ore pellets; as a sealant in many engineering applications; and as absorbents for pet litter, agriculture chemicals, and oil and water. Palygorskite and sepiolite are used as absorbents in pet litter, agricultural chemicals, water and oil sorption, and as the suspending medium in many applications such as saltwater drilling fluids, paints, pharmaceuticals, and others. Miscellaneous applications include the uses of shales and other clay materials in structural ceramic products, cement, lightweight aggregate, asphalt emulsions, and other important uses. According to U.S. Bureau of Mines figures, approximately 50 million tons of clay materials are used annually with a total value of $ I. 1 billion. This high usage and value certainly attests to the importance of clays to the economy and welfare of the United States and to industry. Clay materials perform a function in most every application and are not just an inert component in the formulation. The abundance and availability of the clay materials and their relatively low cost guarantees their continued utilization in the future. Research and development will find new applications for clays in the future which has been the pattern in the past.

INTRODUCTION

Clays and clay minerals are important geologically, industrially and agriculturally, and are important to the engineer in building foundations, tunnels, dams, etc. This overview focuses on their industrial applications and the reasons why specific clays are used in certain applications. To illustrate the im0169-1317/91/$03.50 1991 - - Elsevier Science Publishers B.V.

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portance of clays and clay minerals to industry and the economy of the United States, in 1986, according to the U.S. Bureau of Mines statistics, a total of 47.2 million tons of clay materials were marketed with a value orS1.1 billion. In most instances clays perform a function and are not just an inert component of the system. For example, ifa car body that is made out of a plastic did not contain a functional filler, the plastic would shatter like glass on impact. Therefore it is absolutely necessary that a filler such as kaolin be added to the formulation to give the plastic the necessary resilience to withstand impact and prevent shattering. Filler added to rubber improves abrasion resistance and wear. Example after example of the functionality of clays can be cited. Certain questions must be asked with regard to the utilization of clays because the kaolins, smectites, and patygorskite and sepiolite are so different in their crystal structures and their physical and chemical properties. Why are certain clays used in specific applications? What basic properties of the clays are fundamental to their use? These and other questions will be discussed and at least partially answered in this paper. There are several articles and books that discuss clay mineral applications and although many are historical, they are essential to our present understanding of how and why the clay minerals have such an extensive industrial utilization. ( A partial list of these articles and books are: Anonymous, 1955; Pask and Turner, 1955; Murray and Lyons, 1956; Grim, 1962; Clem and Doehler, 1963; Haden, 1963; Jordan, 1963; Murray, 1963, 1984; Nahin, 1963; Smoot, 1963; Ovcharenko et al., 1964; Bundy et al., 1965; Siddiqui, 1968; Grimshaw, 1971; Grim and Guven, 1978; Patterson and Murray, 1983; Robertson, 1986; and Galan, 1987. ) The fundamental physical and chemical properties and applications are discussed under the headings kaolins, smectites, palygorskite and sepiolite, and miscellaneous.

KAOLINS

The term kaolin is used in three ways in that it is a rock term, a clay mineral group, and an industrial mineral commodity. Kaolins are rocks that are comprised largely of one of the kaolin group of minerals which are kaolinite, halloysite, dickite and nacrite. By far the most c o m m o n kaolin mineral is kaolinite which is the mineral whose physical and chemical properties will be discussed in this section. The other members of the kaolin group are relatively rare although occurrences of halloysite (Murray et al., 1977 ), dickite (Sudo and Shimoda, 1978: p. 190) and nacrite (Hanson et al., 1981 ) are or have been mined. In this paper the industrial mineral commodity kaolin is dis-

OVERVIEW

381

cussed and the dominant physical and chemical characteristics are those of the mineral kaolinite; however impurities, if present, such as iron and titanium heavy minerals and quartz significantly affect its industrial utilization. Kaolinite has a theoretical chemical composition of 39.8% alumina, 46.3% silica and 13.9% water. Table 1 shows typical chemical analyses of industrial kaolin from Georgia and England relative to theoretical kaolinite. As can be seen from the comparative chemical analyses shown in Table I, the industrial kaolins from Georgia and England are remarkably close in composition to a theoretical kaolin. The major chemical variations in the Georgia kaolins are in the iron and titania values. Iron can range from as low as 0.2% to as high as 1.0% and titania values from as low as 1% to as high as 2.2% and still make a good quality product. The iron is largely in goethite and ilmenite and the titanium is in rutile, anatase and ilmenite. The major chemical variations in the English kaolins are potassium, iron and silica. This is because English kaolins are primary and contain mica, feldspar and quartz. The structure of the mineral kaolinite is shown on Fig. 1 and is classified as a two-layer clay; i.e., a layer of silica tetrahedra combined through oxygens and hydroxyls which are shared with an alumina octahedral layer. This structure contains limited substitutions of other elements including some Fe substituting for A1 and some A1 possibly substituting for Si. Because of the limited substitutions, the charge on the kaolinite layer is minimal so that there is very little charge on the layer. Some charges occur on the edge of the crystal due to broken bonds (Grim, 1968). Therefore, because of this very slight charge on the lattice, kaolinite has a low base exchange capacity relative to
TABLE I Typical chemical analyses Component (%) SiO2 A1203 Fe203 TiO2 MgO CaO Na20 K20 Ignition loss (950C) *~Cretaceous in age. Kaolin Georgia *j 45.30 38.38 0.30 1.44 0.25 0.05 0.27 0.04 England 46.77 37.79 0.56 0.02 0.24 0.13 0.05 1.49 46.3 39.8 Theoretical kaolinite

13.97

12.79

13.9

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Fig. 1. Structure of kaolinite.

other clay minerals (Grim, 1968 ). Absorption, which is related to the surface charge, is another property that is important in many industrial applications. Kaolinite exhibits low absorption and adsorption which is related to the low surface charge on the particle. Electron micrographs of kaolinite show that in general it has relatively sharp crystalline outlines that exhibit a pseudo-hexagonal outline; many of the coarser kaolinite particles are vermicular stacks (Fig. 2 ). Kaolinite is white or near white in color and this is another important attribute that relates to its chemical composition which is a hydrated aluminum silicate. One of the more important properties that some kaolins exhibit is that it has good flow properties at high solids content in water. This is particularly important in paper-coating applications. The reason that kaolin has good rheology is that it has little or no charge deficiencies in the structure, it has a low surface area, exhibits good crystalline morphology, and its particle size is fine. These particles must have a relatively broad particle size distribution in order to achieve low viscosity. Figure 3 shows the particle size distribution of grades of kaolin and Fig. 4 shows the relationship between particle packing and viscosity. Kaolinite is soft, with a hardness of about 1.5 on the Mohs scale, which

OVERVIEW

383

Fig. 2. Electron micrograph showing kaolinite plates and stacks from Dry Branch, Georgia.
TYPICAL PARTICLE SIZE ANALYSIS
100

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means that kaolins when relatively pure are non-abrasive. This property is very important in many industrial applications because kaolin is softer than almost all materials with which it comes into contact and therefore the wear and tear on equipment is low. Relatively pure kaolins are refractory and melt or fuse at a temperature of about 1850C. In most instances except for flint clays, kaolins are plastic and fire to a white or near white color. These properties make kaolin a very important ceramic raw material.

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Kaolin is hydrophilic and, with a small amount of chemical dispersant to negate the edge charges due to broken bonds, will disperse readily in water. For this reason kaolin is used extensively in paper-coating formulations which are suspensions of kaolinite, adhesive and water, and also in water-based interior paints. The dispersion of kaolin particles in a water-based system is essential in order for the kaolin to be able to make the contribution to the coating properties that it does (Murray, 1984). The particle shape of kaolinite is an important factor in its utilization. Particles that are in the range of 2 #m and below are thin, pseudo-hexagonal plates that orient on a coated surface because of their two-dimensional nature. This orientation gives a gloss or sheen to the coated surface which is important in the case of coated paper and for semi-gloss or high-gloss paints. Although there are other specific properties that could be enumerated, it can be seen that kaolin is one of the most versatile of the industrial minerals in its industrial uses because it: ( 1 ) is chemically inert over a relatively wide pH range (pH 4 to 9); (2) is white or near white in color; ( 3 ) has good covering or hiding power when used as a pigment or extender in coating or filling; (4) is soft and non-abrasive; (5) is fine in particle size; (6) is plastic, refractory and fires to a white or near-white color; (7) has low conductivity of both heat and electricity; ( 8 ) is hydrophilic and disperses readily in water; and (9) is relatively low in cost. The major uses of kaolin are directly related to its physical and chemical properties. The largest user of kaolin by far is the paper industry where it is used as a filler in the sheet and as a coating on the surface of the sheet. Some of the properties of importance to the papermaker are dispersion, rheology, brightness and whiteness, gloss and smoothness, adhesive demand, film

OVERVIEW

385

strength, and ink receptivity. All of these properties can be related to the fact that kaolin is white or near white, soft, hydrophylic, fine in particle size, platy in shape, low in surface area, and chemically inert. Another large user of kaolins is the ceramic industry, particularly in whiteware, sanitaryware, insulators and refractories. As mentioned before, kaolin has the physical and chemical attributes that make it an excellent ceramic raw material. Other uses, as shown in Table II, are many and diverse but every use can be related to the basic fundamental chemical and physical properties of kaolinite. A review of many of these properties has been discussed previously (Murray, 1986 ) and will not be repeated here. One treatment that is used to produce special products from kaolin is calcining, where it is thermally heated to produce special grades. One grade is thermally heated to a temperature just above the dehydroxylation temperature which is normally about 650C. At this temperature the structural hydroxyl groups are driven out as water vapor. The kaolin (which is metakaolin at this point) is bulky and has properties that make it an excellent dielectric that is used as a filler in electrical wire coatings. A second grade is thermally heated to about 1050 C, which is above the point where the metakaolin is reorganized to form mullite and cristobalite. These mullite needles that appear on the surface of the former kaolin particle (Fig. 5 ) are excellent lightscattering points which gives the product a very high brightness and good opacity. This product is used as an extender for titanium dioxide in many applications in order to reduce formulation costs particularly in paper coating and filling and in paints. Another special process that is used to modify kaolins is surface treatments. As mentioned previously kaolin is hydrophilic and can be easily dispersed in water. Ionic and/or polar non ionic surfactants are generally used to chemiTABLEII Uses of kaolin Paper coating Paper filling Extender in paint Ceramic raw material Filler in rubber Filler in plastics Extender in ink Cracking catalysts Fiberglas Foundries Dessicants Cement Pencil leads Adhesives Tanning leather Pharmaceuticals Enamels Pastes and glues Insecticides Medicines Sizing Textiles Food additives Bleaching Fertilizers Plaster Filter aids Cosmetics Crayons Detergents Roofing granules Linoleum Polishing compounds

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Fig. 5. Electron micrograph of calcined kaolin showing small mullite crystals (bar is 1/~m in Icngth ).

caUy modify the kaolinite surfaces to produce a particle which has hydrophobic or organophilic characteristics. These surface-modified kaolins are used in paper, paint, plastics, rubber, ink and other, more specialized processes.
SMECTITES

Smectite is the name given to a group of sodium, calcium, magnesium, iron, and lithium aluminum silicates. The individual mineral names for these are sodium montmorillonite, calcium montmoriUonite, saponite, nontronite and hectorite. The rocks in which these smectite minerals are dominant is bentonite. The name bentonite was first used by Knight ( 1898 ) and is the term commonly used to describe the industrial mineral. The term bentonite was defined by Ross and Shannon (1926) as a clay material altered from a glassy igneous material, usually a tuffor volcanic ash. Grim and Guven ( 1978 ) used the term bentonite for any clay predominantly comprised of a smectite mineral without regard to origin. Bentonites which are used industrially are predominantly comprised of either sodium montmorillonite or calcium montmorillonite, and to a much lesser extent hectorite. These smectite minerals have significantly different physical and chemical properties which dictate to a large degree their industrial utilization. Smectite is a three-layer clay mineral (Fig. 6) in contrast with kaolinite

OVERVIEW

387

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Exchangeable Cations n H20

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Aluminum. iron, magnesium

oe Silicon, occasionallyaluminum

Fig. 6. Structure ofsmectite.

which is a two-layer clay. This three-layer clay has two silica tetrahedral sheets joined to a central octahedral sheet. There is considerable substitution in the octahedral sheet of Fe and Mg for Al, which creates a charge deficiency in the layer. Also, there is some substitution of silicon by aluminum in the tetrahedral sheets which again creates a charge imbalance. Grim (1962) points out that many analyses have shown that this charge imbalance is about - 0 . 6 6 / unit cell. This net positive charge deficiency is balanced by exchangeable cations adsorbed between the unit layers and around the edges. Thus, if the exchangeable cation is sodium the specific mineral is sodium montmorillonite if it is calcium it is a calcium montmorillonite. Sodium and calcium are hydrated in the interlayer position. Sodium montmorillonites generally have one water layer in the interlayer position and calcium montmorillonites generally have two water layers.

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The high charge on the smectite layer is satisfied by water layers containing cations such as sodium, calcium, magnesium, iron and lithium. Smectites have a high base exchange capacity that generally is of the order of 60-100 m E q / 100 grams of clay. The cations and the associated water layers can be replaced by polar organic molecules such as ethylene glycol, quaternary amine, polyalcohols, and others. This is an important property which can be translated into useful products. Smectites are normally very thin flakes of extremely small particle size (Fig. 7 ), which gives the material a high surface area. These characteristics give smectites a high degree of absorbency for many materials and when mixed with water the high charge and fine particle size give the fluid a very. high viscosity. Thus these basic properties of the mineral relate to the many industrial uses which are described in the following paragraphs. The color of smectites can vary from white to tan to brown or brownish green or blue-green in color. Color also controls the use in some instances. In 1985 the bentonite production in the United States was 3,750,000 tons and for the world the production was estimated to be about 7,000,000 tons. The primary uses of bentonite are in drilling muds, as a foundry bond clay,

Fig. 7. Electronmicrographof sodium montmorillonitefrom Kaycee,Wyoming.

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389

for pelletizing iron ores, and as a sealant in irrigation ditches, farm ponds, earthen dams, etc. Sodium montmorillonite, which is the major constituent of the Wyoming or Western bentonite is a high-swelling clay which will expand up to 10 or more times its dry volume when placed in water. This unique swelling property makes it a necessary ingredient in freshwater drilling muds throughout the world, and commonly the Wyoming or Western bentonite yields 100 barrels of mud per ton (203/T) (Grim and Guven, 1978). Only 5% of this highswelling bentonite is required to produce the high viscosity, thixotropic fluid with low filter cake permeability that is necessary to meet the American Petroleum Institute (API) drilling fluid specifications. Hectorite also makes an excellent drilling mud but only limited quantities are available because its occurrence is relatively rare. It is used for special applications where highviscosity suspensions are required. Some calcium montmorillonites can be treated with a sodium salt such as soda ash to make a drilling mud but neither the viscosity nor the water loss properties are as good as that of the natural sodium Wyoming bentonites. The molding sands used in foundries are comprised of high-silica sand and bentonite. The bentonite provides bonding strength and plasticity. A small amount of tempering water is added to the mixture to make it plastic. This mixture of sand, clay and water can then be molded around a pattern and be cohesive enough to maintain the proper shape after the pattern is removed and while molten metal is poured into it. The important foundry properties are green compression strength, dry compression strength, hot strength, flowability, permeability and durability. These properties vary greatly with the amount of tempering water (Grim and Guven, 1978 ). Both sodium and calcium bentonites (montmorillonites) are used as bonding clays. Calcium bentonite has a higher green strength, lower dry strength, lower hot strength, and better flowability than sodium bentonite. Blends of sodium and calcium bentonites are commonly used to gain the optimum properties from each. Bentonites are used extensively to pelletize iron ores (DeVaney, 1956). Finely pulverized ore concentrates are pelletized into marble-size balls about 1 inch (2.5 cm) in diameter for ease of shipping and to produce a superior blast furnace feed. Bentonite constitutes about 0.5 wt.% of the ore. Because of its superior dry strength, sodium bentonite is preferred for pelletizing ores. Because of their high swelling capacity, sodium bentonites are used for water impedance. The bentonite is used to impede the movement of water through earthen structures such as dams, to prevent seepage of water from ponds and irrigation ditches, and to stop water from entering basements of homes. Another use of high-swelling sodium bentonite is in the slurry-trench or diaphragm-wall method of excavation in construction in areas of unconsolidated rocks or soils (Lang, 1971 ). In this method the trench being excavated is filled with bentonite slurry and the earth material being excavated is re-

39o "FABLE 111 Special industrial uses of smectites Crayons Cement Dessicants Cosmetics Paint Fillers Ceramics Catalysts Detergents Aerosols Adhesives Pharmaceuticals Food additives De-inking in paper Tape joints compounds Emulsion stabilizers Animal feed bonds Bleaching clays Industrial oil absorbents Agricultural carriers Cat box absorbents Beer and wine clarification Medical formulations Polishing and cleaning agents

H H M(IRRAY

moved through it. A thin filter cake on the walls of the excavation prevents loss of fluid, and the hydrostatic head of the slurry prevents caving and running of loose soil, which makes costly shoring unnecessary. Other uses of smectite are shown in Table III. Two special treatments are used to produce special smectite products. These are acid activation and organic cladding. Certain smectites, particularly calcium montmorillonite, are treated with either sulfuric or hydrochloric acid to remove ions from the octahedral layer to increase the charge on the particle. These highly charged particles are widely used to decolorize mineral, vegetable and animal oils. Sodium montmorillonite is processed so that the inorganic exchangeable ions are replaced with alkylamine cations to produce a hydrophobic surface (Jordan, 1950). These organic-clad sodium montmorillonites are used as thickeners in paints, greases, oil-base drilling muds, and to gel various organic liquids.
PALYGORSKITE A N D SEPIOLITE

Palygorskite and attapulgite are names for the same hydrated magnesium aluminum silicate mineral. The preferred name according to the International Nomenclature Committee is palygorskite, although in trade circles the name attapulgite is better known. Sepiolite is structurally similar to palygorskite except it has a slightly larger unit cell. Both minerals consist of double silica tetrahedral chains linked together by octahedral oxygen and hydroxyl groups containing aluminum and magnesium ions in a chain-like structure (Fig. 8 ). Both minerals occur as fibrous lath-like particles similar to the electron micrograph of palygorskite (Fig. 9 ). The term fuller's earth is a catchall term for clays or other fine-grained earthy materials suitable for bleaching and sorbent uses. It has no compositional or mineralogical meaning. The term was first applied to earthy materials used in cleansing and fulling wool which removed lanolin and dirt, thus the name

OVERVIEW

391

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Fig. 8. Structureof p~ilygorskite(attapulgite). fuller's earth. Therefore the term fuller's earth is quite often used for palygorskite (attapulgite), sepiolite and smectite clays that have sorptive qualities. Palygorskite and sepiolite are normally light tan or cream to brown in color although some have a blue-green tint. They are classed as a three-layer inverted structure (Fig. 8 ) and iron commonly substitutes for aluminum and magnesium in the octahedral layer, thus producing a moderate charge on the structure. This charge causes these minerals to have a base exchange capacity that is intermediate between kaolin and smectites usually of the order of 40 meq/100 g. Because of the inversions of the silica tetrahedral layers the structure has parallel channels or holes throughout, which, along with the elongate nature of the particles and the fine particle size, gives a high surface area. The charge on the particles, the channels in the structure, and the high surface area give palygorskite and sepiolite a high capacity to absorb and adsorb various materials which makes it useful in many industrial applications. Also the elongate lath-like particles cause high viscosity when it is added to any liquid.

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Fig. 9. Electron micrograph ofpalygorskite (attapulgite) from Quincy. Florida.

It is a physical and not a chemical viscosity so is very stable as a suspending medium in many applications such as in saltwater drilling fluids. The statistics for the production of palygorskite and sepiolite are difficult to separate from fuller's earth production. According to the U.S. Bureau of Mines the United States fuller's earth production in 1985 was 2 000 000 tons and attapulgite was 1 000 000 tons. For the world, it is estimated that the fuller's earth production is about 3 000 000 tons of which 1 800 000 tons is palygorskite and sepiolite. The applications of palygorskite (attapulgite) and sepiolite are many and diverse (Table IV ). One of the larger uses is as a viscosity builder in saltwater or high electrolyte-content drilling muds. The viscosity and gel strength of the mud are not affected by variations in electrolyte concentration and thus can be used with saltwater or when formation brines become a serious problem and with oil base drilling fluids. Because palygorskite and sepiolite are not easily flocculated, these clay minerals are used as suspending agents in paints, suspension fertilizers, medicines, pharmaceuticals and cosmetics. In paint, these minerals improve the thickening and thixotropic properties.

OVERVIEW TABLE IV Industrial uses of palygorskite (attapulgite) and sepiolite Paint Paper Ceramics Asphalt Adhesives Pharmaceuticals Catalyst supports Animal feed Petroleum refining Cat box absorbents Drilling fluids Suspension fertilizers Agricultural carriers Industrial floor absorbents Mineral and vegetable oil refining

393

Another major use of these minerals is as floor sweep compounds, for absorbing oil and grease spills on factory and service station floors. Granular particles of these minerals are the most effective floor absorbent. Palygorskite (attapulgite) and sepiolite are used extensively in agriculture as absorbents and adsorbents for chemicals. The fertilizer chemical, pesticide, or herbicide is mixed onto the granular clay particles which are placed in the ground with the seeds. The chemical is slowly released to provide the necessary plant food or protection for the growing plant. Finely pulverized palygorskite and sepiolite clays or fuller's earth are also used to absorb and adsorb chemicals which can be dusted or sprayed on the plant or on the surface of the ground. Another large use for fuller's earth materials which includes palygorskite and sepiolite is for pet litter. Granular clay particles are an effective litter for absorbing animal waste particularly for domestic cats. The clay materials can be effectively treated with chemicals which will prevent odors and bacterial degradation for several days. The cat litter market is very large and continues to grow particularly in North America and Europe. Palygorskite and sepiolite are also used to decolorize and clarify mineral, vegetable and animal oils. In this process, the color bodies are absorbed by the clay particles which are then filtered out of the particular oil. An important property is that the clay must not have a high oil retention capacity. Haden ( 1963 ) described several uses of palygorskite (attapulgite) including use as a foundry sand binder, metal-drawing lubricants, anti-caking agents, catalyst carbon-free duplicating paper, wax emulsions, and catalyst carriers. In Turkey, sepiolite is used for various special ceramic and refractory applications (Anonymous, 1978).
MISCELLANEOUSCLAYS

Common clays and shales are important raw materials in many parts of the world, particularly for ceramic structural clay products. These include drain tile, bricks, sewer pipe, conduit tile, structural tile, flue linings, and others. No world figures are available, but the United States produces about 16 106 tons annually at an average value of $3.50/ton. The properties that are important are plasticity, shrinkage, dry and fired strength, fired color, and vitri-

394

H.H MURRAY

fication range. Clays and shales that are associated with coals and lignites are a common raw material for structural clay products. These clays are commonly a mixture of kaolinite and illite and the shales are largely comprised of the clay minerals illite and chlorite along with quartz. Some of the underclays are classified as fireclays as they are refractory in that they will withstand high temperatures. Some of these clays are called flint clays, which are almost pure kaolinite. Flint clays are a refractory raw material in many parts of the world. Some shales and slates are used as a raw material to produce lightweight aggregate. These shales must contain a material that will produce a gas at the vitrification temperature of the shale so that small gas vesicles will form and cause the shale to bloat (Murray and Smith, 1958 ).
SUMMARY

The application of kaolins, smectites, palygorskite and sepiolite, and miscellaneous clays and shales are diverse. The fundamental properties of each clay mineral determines to a large extent the applications of that particular clay. The physical and chemical properties such as particle shape, charge on the particle, color, surface area, exchange capacity and viscosity are all related to the structure and composition of the clay minerals. As processing techniques become more sophisticated the uses for these fine-particle materials will expand and the values become higher.

REFERENCES Anonymous, 1955. Kaolin Clays and their Industrial Uses. J.M. Huber Corp., New York, NY, 214 pp. Anonymous, 1978. Bentonite, sepiolite, attapulgite, etc. - swelling markets for active clays. Ind. Miner. Mag., 126: 49-91. Bundy, W.M., Johns, W.D. and Murray, H.H., 1965. Physico-chemical properties of kaolinite and relationship to paper coating quality. Tappi, 48: 688-696. Clem, Arthur, G. and Doehler, R.W., 1963. Industrial applications of bentonite. In: Proc. Conf. Clays and Clay Minerals, 10th Pergamon, Oxford, U.K., pp. 272-283. DeVaney, F.D., 1956. U.S. Pat. 2743172. Galan, E., 1987. Industrial applications of sepiolite from Vallacas-Vicalvaro, Spain: a review. In: Proc. Int. Clay Conf. (Denver, Colo., 1985), pp. 400-404. Grim, R.E., 1962. Applied Clay Mineralogy. McGraw Hill, New York, NY, 422 pp. Grim, R.E., 1968. Clay Mineralogy. McGraw Hill, New York, NY, 2nd ed., 596 pp. Grim, R.E. and Guven, N., 1978. Bentonites - geology, mineralogy, properties, and uses. (Developments in Sedimentology, 24. ) Elsevier, NY, 256 pp. Grimshaw, R.W., 1971. The Chemistry and Physics of Clays. Wiley Interscience, New York, 4th ed., 1024 pp. Haden, W.L., Jr., 1963. Attapulgite: properties and uses. In: Proc. Conf. Clays and Clay Miner. 10th. Pergamon, Oxford, U.K., pp. 284-290.

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