(1995 - Konta) Clay and man.pdf

ELSEVIER Applied Clay Science 10 (1995) 275-335

Clay and man: Clay raw materials in the service of man

Jiti Konta Professor emeritus, Department of Petrology, Charles University, Albertov 6, 12843 Prague 2, Czech Republic

Received 20 October 1994; accepted 24 May 1995

Abstract

Clay has always played a major role in human life. Clay raw materials are used and their value recognized in many economic branches, agriculture, civil engineering and environmental studies. This is largely because of their wide-ranging properties, high resistance to atmospheric conditions, geochemical purity, easy access to their deposits near the earth’s surface and low price.

Clay minerals, the essential constituents of argillaceous rocks, can be classified in seven groups according, to their crystal structure and crystal chemistry. Clay raw materials are divided in the same way into seven groups. An eighth group covers clay ochres and pigments. Further classification is based on the purpose-made technological application. Some examples show relations between the crystal structure or crystal chemistry of the dominant phyllosilicate and the technological properties. The chapter “Utilization of clay raw materials in industry and other human activities” is the most extensive. It gives information on the application of clay raw materials or individual clay minerals: in the production of foods, feedstuffs, beverages, paper, rubber, plastics, artificial leather, protective coatings for interior and exterior use, pharmaceutics, cosmetics, paints, pencils, pastels, porcelain, electro-porcelain and other fine ceramics, coarse ceramics and sialon ceramics; in the foundries, various branches of the chemical, petroleum and cement industries, agriculture and forestry; in the preparation of agrochemicals and special fertilizers, lubricating oils and gels, lightweight ceramics and effective sorbents; in the manufacture of mineral wool, in briquetting and pelletizing processes; as ingredjsents in grinding and polishing pastes, in the insulations of dumps of various kinds of waste (including toxic and radioactive waste), in thermally, electrically, acoustically and chemically resistant insulations, and in filters for the treatment of industrial, agricultural and similar outflows.

The earth sciences use the clay minerals in the earth crust: ( 1) as indicators of the environment during weathering, allothi- and authigenesis in the sediments and in the study of the source areas of the detrital supply; (2) as pH indicators and indicators of processes in micro- and mega-environments and of changes in the course of diagenesis and metamorphosis. Mineralogical, petrological, geological and geochemical investigations directed to clay minerals serve as one of the correlation methods, in the recognition of processes in the petroleum-bearing sediments, coal-bearing formations, origin of riverine, lacustrine, marine and oceanic sediments and in the climatic, geodynamic, paleogeographical, stratigraphic and weathering rate interpretations.

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276 .I. Konta/Applied Clay Science 10 (1995) 275-335

1. Introduction

Human life and the existence of many organisms on this planet are connected with clay. Most people, however, do not perceive this connection; they take it for granted similarly as air or water. Clay minerals probably played a principal catalytic role in the synthesis of the primordial organic compounds that led to the origin of the primary organisms capable of reproducing (Bemal, 195 1; Cairns-Smith and Hartman, 1986; Yuasa, 1989).

The monographs by Robertson ( 1960), Grim ( 1962), Lefond ( 1975) and Konta ( 1982a) were used in the following systematic survey. However, none of the quoted books contain complete information about all species of clay raw materials. The largest gaps even exist in the information on the most common group of clay raw materials, i.e., clays and loams. Moreover, it is necessary to complete the information on some new areas such as organo-clay complexes and swelling clay minerals pillared with R( III) and R( IV) hydroxides in the interlayer space. In addition, attention is paid to the role of clay minerals in soils and the formation and protection of the environment. The importance and utilization of clay minerals in earth sciences is also stressed. Scarce data are known about ochres and pigmen- tary clays. In the following survey, they are classified in a separate group VIII.

This contribution was written on the occasion of “The Exhibition on Clay Raw Materials in the Service of Man” held in Prague from August 30 to September 14, 1994, as part of the 13th Conference on Clay Mineralogy and Petrology. Therefore, it is appropriate to quote the books on economic geology and material composition of nonmetallic raw materials by Polak ( 1972)) Zorkovsky et al. ( 1972)) and Kuivart ( 1983) published in Czechoslovakia. Ktihnel ( 1990) reported on modem trends in the application of clays.

2. Clay minerals, major constituents of clay raw materials

Clay minerals are the basic constituents of clay raw materials. Their crystal structure, with a few exceptions, consists of sheets (hence the terms sheet silicates or phyllosilicates) firmly arranged in structural layers. The individual layers are composed of two, three or four sheets. The sheets are formed either by tetrahedrons [ Si0414-, abbreviated as “T”, or by octahedrons, e.g. [ AlO,( OH),] 6-, abbreviated as “0”. The interior of tetrahedrons and octahedrons contains smaller metal cations, their apices being occupied by oxygens from which some are connected with protons (as OH). All these fundamental structural elements are arranged to form a hexagonal network in each sheet. According to the number and the ratio of sheets in a fundamental structural layer, the existing cation substitutions in the octahedrons and tetrahedrons and the resulting charge of the layers, the crystalline clay minerals are classified into seven groups.

I. The kaolinite and serpentine group, typical two-sheet phyllosilicates, where the T:O ratio = 1: 1 and the charge of the two-sheet layer = 0.

The kaolinite subgroup with examples of ideal formulas for kaolinite Al4 [ Si40nJ (OH) a and halloysite Al, [ Si4010] (OH) a .4H,O.

The serpentine subgroup with an example of an ideal formula for chrysotile MgdSi4Qol (0I-b.

J. Konta /Applied Clay Science IO (1995) 275-335 211

II. Thle group of micas, three-sheet phyllosilicates, where the T:O ratio = 2: 1 and the charge of the three-sheet layer I 2. Example of an ideal formula of the most common clay mica, i.e. illite K,*AL,[ (Si,,Al,,)O,,] (OH)4.nHz0.

III. T!he vermiculite group, the expanding three-sheet phyllosilicates, where the T:O ratio = 2: 1 and the charge of the three-sheet layer = 1.2 to 1.8. Example of an ideal formula of the trioctahedral vermiculite (Mg, Fe’+, Fe3+),[(Si>A1)8020](OH)4.nH,0.

IV. The group of smectites, strongly expanding three-sheet phyllosilicates, where the T:O ratio= 2:l and the charge of the three-sheet layer = 0.5 to 1.2. Examples of ideal formulas of the common smectites:

montmorillonite M~+Y(A1,Fe3+)4_y(Fe2+,Mg)y[Sis_,A1,020] (OH),.nH,O, beider’lite M: Al, [ Si, -xA1x020] (OH), . nH,O, nontronite MzFei+ [ Sis _ xA1x020] (OH), . nH,O, suponite M:Mg,[ Si,_.Al,O,,] (OH),*nH,O. M+ represents adsorbed alkali cations in the interlayer space (especially Na+ ) where,

however, alkaline earths ( Ca2+ , Mg2+ ) often occur, generally M$. M+ is mostly around 0.7.

V. The pyrophyllite and talc group, non-swelling three-sheet phyllosilicates, where the T:O ratio = 2: 1 and the charge of the three-sheet layer = 0. One subgroup is represented by pyrophyllite AL, [ Si8O20] (OH), and another subgroup by talc Mg, [ S&O,,] (OH),.

VI. T:he group of chlorites, four-sheet silicates, where the T:O:O ratio = 2: 1: 1 and the charge of the four-sheet layer is 1.1 to 3.3. An example of a dioctahedral chlorite is donbass:ite: Al,[ Si802,,] (OH),Al,( OH) i2.

VII. The palygorskite and sepiolite group with the layer-fibrous structure. The formulas are, respectively Mg5[S&J (OW2(0H2L*4H20 and

Mg8[%20301 (OW4(OH2),-nH20. Besidae these, the crystalline clay minerals occur as mixed-layers or interstratifications.

They are mostly composed of two different structural layers, alternating randomly or regularly stacked above each other. The randomly mixed-layers have no specific terms and occur in nature in considerable amounts of combinations. The regularly mixed-layers of phyllosilicates are named as mineral species. They are:

Rectorite ( 14 A dioctahedral smectite with 10 A dioctahedral mica) _ Corrensite ( 14 A trioctahedral chlorite either with 14 A trioctahedral smectite, which is

low-charged corrensite, or with 14 A trioctahedral vermiculite, which is high-charged corrensiee) .

Z’osua’ite ( 14 A dioctahedral smectite with 14 A dioctahedral chlorite). Alliettite (9.3 A talc with 14 A saponite). Kulkeite (9.3 a talc with 14 A trioctahedral chlorite). Various defects exist in the crystal structures of clay minerals (Drits, 1987a). Their

differentiation is a target for experts on structural crystallography to determine the polytypes of individual clay mineral species, the state of order or disorder in the distribution of isomorphous cations in the sheets, the vacant sites for cations and the distribution geometry of irregular effects in the structure. This endeavour involves the use of a series of advanced analysis methods (Fripiat, 1981; Konta, 1981; Veniale, 1992).

The amorphous clay minerals, such as allophane (Al-rich species) and hisingerite (Fe- rich species), do not occur as mineral deposits. They are known as subordinate constituents

278 J. Konta/Applied Clay Science 10 (1995) 275-335

in some soils or hydrothermal (but seldom supergene) accumulations. Both clay minerals and clay rocks are included among clay raw materials. Economic accumulations of pure clay minerals are very rare. The industry uses clay raw materials either in raw or beneficiated state. In both cases, a complete mineralogical, petrological, chemical and technological assessment is required.

On the basis of the crystal structure, it is possible to classify also the phyllosilicates of larger dimensions than usual as far as their particles in clays are concerned. The majority of clays is known for its plasticity. However, many clay raw materials are not plastic, or they are semiplastic such as claystones, clay shales, talc, pyrophyllite, vermiculite and coarser mica. It is substantial, however, that their essential minerals have crystal structure quite comparable with that of the fine phyllosilicates occurring in clays.

3. Relation between crystal structure, crystal chemistry and technological properties

Technological properties of clay raw materials mainly depend on the properties of the clay minerals present, total mineral composition, size distribution, degree of consolidation and processing conditions. Their recognition is always fundamental. Many properties of clay minerals can be largely derived from their crystal structures and crystal chemistry (Fig. 1). They also reflect the state and distribution of the electrostatic charge of the structural layers. The negative charge is a result of the ionic substitutions in the octahedral and tetrahedral sheets of clay minerals. Thus, in the three-sheet clay minerals, where the ratio of tetrahedral to octahedral sheets equals 2: 1, the resultant negative charge may vary from 0 to 2 valency units, calculated to 20 oxygens and 4 hydroxyls in a unit cell. The ionic substitutions in the structure are controlled by the chemistry of the environment and the kinetics of reactions occurring during the formation and development of clay minerals. The electrostatic negativity of structural layers is naturally compensated by cations adsorbed in the interlayer space. The most common exchangeable cations in the interlayer space are K+, Na+, Ca’+, Mg*+ and H+. A relatively simple industrial treatment enables the exchange of any of these cations by a desirable cation. Energetically more demanding is the removal of ions from the octahedral or even tetrahedral sheets and the preparation of material with a new microstructure and larger pore volume.

Kaolinite as the most common example of dioctahedral two-sheet phyllosilicates has an ideal chemical composition A1,Si,05( OH)4. Its technological properties, however, vary, depending on the structure which can be well or poorly ordered. The well ordered T kaolinite, i.e., the triclinic kaolinite, has its two-sheet layers arranged above each other in the direction of the c axis in such a manner that no shifting along the a or b axes can be found by X-ray diffraction. The crystals of T kaolinite, therefore, afford a greater number and mostly also sharper reflections in their X-ray diffraction patterns. These are the proof of three-dimensionally well ordered crystals. The poorly ordered pM kaolinite, i.e., the pseudomonoclinic kaolinite, has a poor and diffuse X-ray diffraction spectrum. This is caused by the turbostratic structure given by the random shift of individual two-sheet layers along the b axis. The greatest shifts along the a and b axes are known in halloysite. Such a crystal structure is more akin to a two-dimensionally ordered structure. All this is then demonstrated by the shape, thickness and size of the kaolinite crystals, their fragments and properties (Fig. 2).

J. Konta /Applied Clay Science 10 (1995) 275-335 279

St K H

T --i-- A I I

10

P Mi

Ch -

Fig. 1. Similarities and differences in crystal structures of clay minerals, perpendicular sections to the base plane:(A) Minerals of the kaolinite (K) and serpentine (St) group, in which two-sheet layers alternate: T = tetrahe~dral sheet, 0 = octahedral sheet. K is kaolinite, metahalloysite (dehydrated halloysite), dickite, nacrite. H is halloy;rite containing molecular water in the open interlayer space. The c, basal parameter for the fundamental unit cell of St and K minerals is about 7.2 8, and for that of halloysite is 10 A. (B) Minerals of the pyrophyllite (P), talc (Ta) , micas (Mi) including illite, vermiculite (V) and smectite (Sm) groups have their crystal structure composed of the three-sheet layers, where one octahedral sheet (0) is always closed between two tetrahedral sheets (T, oriented with the apices against each other). The c,, parameter increases from 9 8, in pyrophyllite (9.16 A) and talc (9.3 A) up to 15 A in smectites. (C) Minerals of the chlorite group (Ch) in whose crystal structure regularly alternate the three-sheet layers of the T:O:T type, of the T:O ratio = 2: 1, with one octahedral sheet (0) so that the total T:O ratio = 2:2. The c, parameter is about 14.2 8, (after Mamas, 1981, modified).


Fig. 2. Characteristically different shapes, thickness and outlines of crystals of well ordered T kaolinite in the pseudomorphs after sodium-rich feldspar, the Podlesi kaolin, Karlovy Vary area (a), poorly ordered pM kaolinite from blue bonding clay, VonSov (b, carbon replica parallel to the stratification), and tubular crystals of halloysite (least ordered) from Javorka (c). All localities in the Czech Republic. Bars are 1 pm.

The behavior of the different kaolinite varieties in water and after drying is quite diverse. T kaolinite reduces plasticity, green strength and dry strength of the raw material. The pM kaolinite is already considerably delaminated in nature, has an enlarged specific surface area and is noted for its greater ion exchange, plasticity of wet body and greater green and dry strengths. The artificial delamination of the T kaolinite under wet conditions and using shear stress shifts its physical behavior close to that of the pM kaolinite. T kaolinite is noted for its strong coating property. It is, therefore, appreciated as an essential constituent of the coating kaolin in e.g. the paper industry. The above examples of different ordering degrees of kaolinite are only a small illustration how the knowledge on existing differences in the crystal structure of phyllosilicates can be utilized.

In the structure of talc and pyrophyllite, a heteroionic substitution does not exist. The charge of their three-sheet layers, therefore, equals zero. The c, parameter of the corresponding basal planes of the structure is 9.3 A, respectively 9.16 A only, because no compensating

.I. Konta /Applied Clay Science 10 (1995) 275-335 281

cations are necessary in the interlayer space. The absence of hydrated cations in the interlayer space entails a strong hydrophylic reduction of the three-sheet layers. Therefore, it is not easy to wet both talc and pyrophyllite, and to prepare a plastic body from these two minerals. The surface of talc and pyrophyllite behaves in a manner similar as greasy paper towards water. As a consequence talc and pyrophyllite can hardly be dispersed in water. The shaping technology of compositions containing finely powdered talc or pyrophyllite necessarily considers these observations.

The two-sheet layers of kaolinite also have a zero charge and consequently no compensating cations in the interlayer space. The pronounced hydrophillic surface of kaolinite, however, is mediated by the protons of the outer hydroxyl plane.

The di.octahedral mica and kaolinite belong to the most resistant common minerals in the aqueous environment and the atmosphere (Konta, 1982b), as evidenced by their crystal chemistry, especially the high SiOZ + A&O3 concentration. This explains why both minerals are applied as an ideal inert filler of many materials and as a carrier with a suitable surface.

Easily hydratable cations in the interlayer space of smectites and vermiculites adsorb water. The built cationic hydration coating takes away the three-sheet layers, so that the swelling takes place. The 2:l phyllosilicates swell in the contact with water: the stronger the swelling, the lower the charge of their layer (which varies from 2 to 0.5). Swelling is zero in micas (charge I 2), but rises in vermiculites ( 1.8 to 1.2 charge) and reaches the highest values in smectites ( 1.2 to 0.5 charge). With the decreasing charge the attractive forces between the three-sheet layers and the interlayer cations sink while the total surface area increases. But the different hydration coatings and the bonding forces of the interlayer Na+ and Ca2+ cations determine the different behavior of sodium and calcium bentonite. Sodium bentonite is noted for its high dispersiveness in water, while calcium bentonite tends to coagulate. For that reason, only a slight admixture of sodium smectite in a clay body substantially enhances plasticity, dry strength, and also shrinkage. The behavior of smectiteis and vermiculites in contact with water can be modified according to the required use by a mere exchange of the interlayer cations. Similarly, it is possible to modify the dispersion degree, the viscosity of slurries or the flocculation of other hydrophilic clays (Nederlof et al., 1991).

The replacements of uni- and divalent cations by other di-, tri- or tetravalent cations in the interlayer space of the swelling clay minerals and the pillared adsorbed molecules of polyvalent hydroxides are used in the preparation of suitable catalysts in the chemical industry. The swelling phyllosilicates with the pillared hydroxides of polyvalent cations have greater and size-stable interlayer spaces. They are known for their capacity to act as molecular sieves. Similarly, the interlamellar space in palygorskite and sepiolite may also be modilied.

In clay minerals, a relatively large specific surface area is especially appreciated. Its size also depends on the crystal chemistry. Some clay minerals, such as talc, pyrophyllite, kaolinite, illite and chlorites, only have an external surface. Their adsorptive properties, therefore, are limited. The swelling clay minerals, especially smectites and to a certain extent also vermiculites, have not only an external, but also an internal surface. The latter is always substantially larger than the external surface. The large adsorption capacity is characterized by a large specific surface area, not only for the water molecules but also for different ions occurring in water. After a certain treatment of the surface of smectites or


NATURAL SMECTITE

negatively charged layers

;“:

compensating cations

ORGANOPHILIC SMECTfTE

e alkylammonium cation ??NH3C H 8 2n*l

adsorbed clusters of organic molecule, 1 I- I

Fig. 3. The interlayer space in the structure of smectite, the essential constituent of any bentonite: natural smectite swells due to the hydration shells of water molecules around the compensating cations (Ca*+ , Na+ and others) ; the organophilic smectite is artificially prepared through replacement of the natural cations by an organic cation (e.g. alkylammonium) which enables swelling by the adsorption of organic compounds (Stockmeyer, 1990).

vermiculites, these minerals can adsorb the hydrophobic molecules of organic compounds. This is possible by the pillaring of organic polycations as e.g. alkylammonium

( + bWGJ-L + 1 ) . An organophilic bentonite swells by the adsorption of organic compounds (Fig. 3). A rapid determination of the character of the organo-clay complexes and an explanation of their formation kinetics are possible using the radiometric emanation method (Balek et al., 1992). Kato and Kuroda ( 1986) have shown that hitherto known organ+ clay complexes might be classified into four categories: ( 1) with intercalated organic cations, (2) with intercalated polar organic molecules, ( 3) as clay-polymer intercalation complexes obtained in two different ways, and (4) as organo+lay complexes with organic derivatives.

Clay minerals activated in acids yield products with a high amorphous SiO, content having a new microstructure and pores of greater adsorption properties. The food industry, for example, uses bentonite activated by hydrochloric or sulphuric acid for the removal of dark pigments from edible oils.

A mere calcination of some clay minerals at temperatures between 500 and 700°C yields amorphous products which favor the adsorption capacity. Kaolinite, which is heated in this temperature range to convert it into metakaolin, which is subsequently acid activated, is an effective catalyst for the cracking of hydrocarbons (Macedo et al., 1994).

At high temperatures, above lCKKW, new crystalline phases are produced which are important in ceramic systems like e.g. SiO*-A1,03, SiO,-MgO, MgO-Al,O,( Fez03)-SiO, and Si02-Al@-K20. Beside the neoformation of phases, an amorphous glass is formed. The new phases and the composition of glass may be foreseen if the chemical and mineral composition of the starting raw material is known. The fired kaolinite material of a high refractoriness is called calcined kaolinite ( “chamotte”). It ideally, contains the highest possible amounts of mullite. Crushed “chamotte” is a preferred filler for refractory products with a high Al,O, content. Crushed quartz acts in ceramic plastic bodies also as a filler, but with an increasing SiO, content the refractoriness of the composition iu the Si02-A1203 system decreases (Konta, 1982a, p. 240). The ideal raw materials for the manufacture of “chamotte” are kaolinite claystones (Tonsteine, Schiefertone, flint clays) with low plas-

J. Konta /Applied Clay Science 10 (1995) 275-33.5 283

ticity. The kaolinite concentration in these is high and approaches 100%. The presence of clay minerals (containing alkalies, calcium and iron) like illite, montmorillonite and chlorite, and also oxide iron pigment, lowers the fusion temperature and thus also the refractoriness. Similar systems, but always with a determining CaO portion, are important in the Portland cement technology.

4. Utili:zation of clay raw materials in industry and other human activities

The following survey provides compendious information on the uses of clay raw materials in industry and other areas of human activity. The most extensive applications are naturally in industrial branches. Many applications, however, include the area actually called the “formation and protection of the environment” or other areas. It is enough to be aware of the fact that industrial products utilizing clay raw materials, such as porcelain, various ceramic goods, plastics, rubber goods, innumerable sorts of paper and other products influence the environment of mankind. In the formation of the modern human environment, all ceramic products have a substantial significance. The building ceramic parts, right manufactured bricks and roofing tiles, sanitary ceramics, easily washable tiles for exteriors and interiors in subways, airports and railway stations, shopping centres, private flats, all of them are mainly manufactured from clay raw materials.

A balanced environment in urban and rural settlements requires, among others, a color harmony of surfaces. The most suitable are chemically resistant and inexpensive inorganic pigments. Clay ochres, white and different green paints, which will be dealt with in Group VIII, provide in correctly chosen combinations the most natural color environment of house fronts and interiors. Furthermore, clay minerals are of use in various paints and varnishes where they act as a filler, stable against weathering and improve as thixotropic suspensions the flatting effect and the adhesion. The paints and varnishes filled with clay minerals also protect against corrosion and erosion.

A vast area of utilization for clay minerals in the protection of environment is their role as sorbents and retention-insulation materials. Certain clay minerals are noted for their specific adsorption properties. Kaolinite is e.g. suitable for the sorption of fluoride ions from water. Radioactive alkaline metals are most effectively sorbed by mica clay minerals, while chlorite is suitable for divalent radionuclides. A mixture of the exfoliated vermiculite with a dressed calcium bentonite and peat can be used as a deodorizing sorbent. Calcium bentonite is used as a sorbent of nutrients from the water of dams and other reservoirs. This reduces the growth of algae and other plankton during summer months. Clay minerals in rivers, both in suspension and settled in muds, are important adsorbents of toxic substances in solution (Konta, 1995). The stirring properties of clay in water (including adsorption) have been known since the days of ancient Greece and Rome.

Sodium and calcium bentonite is commonly utilized for the insulation of dumps containing health-threatening substances. Especially appreciated are the strong swelling and sealing properties of wet sodium bentonite. The organophilic bentonite is suitable for the sorption of toxic organic compounds. More attention is continuously focused on the flow and diffusion mechanism in clays in connection with the insulation of chemically contaminated waters ( Hasenpatt et al., 1989). Many other possibilities of the utilization of clay raw


@ H*ion

& M cation (e.g.: K’, Ca”, Mg’+, etc.)

“oscillation volume” /‘3b of colloid particles, C,’ rootlet and cations

Fig. 4. Schematic illustration of the cation transfer from a primary mineral to the large surface area of a negatively charged plant rootlet, mediated through negatively charged colloid bridges (clay minerals = CM) ; the rootlets yield protons (H' ) (Keller, 1957).

materials in the formation and protection of the environment can be found in the following survey.

The role of clay minerals is also fundamental in agriculture, fruit growing and forestry. The clay minerals in soils are an inportant source of nutrients and water. As negatively charged colloidal bridges, they encourage a long-term proton exchange from plant roots for necessary cations released from weathering primary minerals (Fig. 4). This reaction, necessary for the nutrition of plants, occurs between clay minerals and the primary minerals also during the vegetative rest. Clay minerals together with organic matter in soils form a humus complex (Fig. 5)) which is very significant for the life of the majority of plants. Energetically important organic substances, as well as potassium, calcium, phosphorus, iron and many other elements are bound in this complex. Transport of these elements is facilitated by the hydrolysis and chelate bonds (Fig. 6). The clay component stabilizes the soil since it enhances its bonding and thus protects trees from being uprooted by wind. The organic polymers act in the aggregation of clay minerals and ameliorate the structure of soils (Burchill et al., 1983). In soils, clay minerals of all groups can occur. Mixed-layer structures of clay minerals, especially the random ones, are also common in soils. The crystal chemistry of the identified clay and other minerals controls the use of fertilizers.

The clays, loams and claystones that do not meet the requirements for refractoriness, or less valuable bentonites are used as redevelopment or agricultural clays and as additives into compost. They regulate the supply of nutrients and humidity to plants and stabilize the strongly sandy soils. In horticulture and agriculture the application of thermally expanded clay raw materials is increasing, such as the vermiculite, polymineral clays with a low kaolinite content, slates and phyllites since they improve the structure and water supply of heavy soils. Clay minerals are the most common carriers of pesticides, insecticides and herbicides and sometimes also special fertilizers. The calciumbentonite seNes as pelletizing clay material in the manufacture of fodder compositions, as protecting and sorption coating

J. Konta/Applied Clay Science 10 (1995) 275-335 285

1. ox 3 0

I I / o-;_o-i7j_- /II

286 J. Konta/Applied Clay Science 10 (I995) 275-335

a b

CH,

Fig. 6. Some examples of the chelate complexes with a metallic cation Cu or M (metal other than Cu) (Lehman, 1963). The stability of the Cu(II) chelate complexes increases with the growing number of rings (from a to b and to c), formed by the chelate along with metallic cation. The stability constant of the methyliminodiacetate (d) is by two orders lower than that of the methyliminodiacetate acid (e)

of seeds, for the neutralization of acid wood- and farmlands and also for the redevelopment of the landscape affected by mining or constructing activity. Perhaps these examples are sufficient for a correct understanding of the significance of clay minerals for the growth of economically important plants.

In the building industries, the numerous manufacturers of structural materials and the knowledge on ground soils are closely connected with clay science. A simple but important fact underscoring the significance of clay science in the building industries is that most of the building is “from” clays or loams and “on” clays or loams. Clay minerals are the essential constituents of clays, loams and along with calcite also of the cement raw materials. Every civil engineer knows and sensibly respects these facts (Terzaghi, 1925; Rosenqvist, 1985; Mtiller-Vonmoos and Loken, 1989). In extremely difficult cases builders discuss the unforeseen behavior of clay materials with specialists, called argilologists (Lang, 1989). It does not have to be a large problem such as the Leaning Tower of Pisa whose crippled statics reached a consolidation only through the knowledge of the fabric of clay minerals in its subsoils (Veniale et al., 1992 in Veniale, 1992). Thermally expanded clay raw materials are used as lightweight granules whose use in the lightweight concrete, plasters and suspensions in the modem building industries continually rises. The exfoliated vermiculite has a similar application.

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In archaeology, clay minerals can serve as “archaeological thermometers” in the investigation of ancient ceramics. The neyly formed phases during firing crystallize in the existing systems only in certain temperature intervals (Bare3 and LiEka, 1976; Veniale, 1990; Schomburg, 1991). This well-thought-out manufacture using clay and loam is more than nine thousand years old. The use of thermal energy is for the first time applied in this type of manufacture and is actually still applied by mankind. Man discovered ceramic manufacture about four thousand years earlier than he learned to write. It was no accident that man used ideally plastic loamy plates for his first records.

The investigation of clay minerals and argillaceous rocks in geological sciences today is an extensive region of the theoretical and applied research. A mere glance into important international abstract journals (Mineralogical Abstracts, Geological Abstracts, Bulletin signaletique, Referativny zhurnal) will convince us about this being so. Hundreds of original and compiled papers on clay minerals and clay accumulations are published in numerous scientific journals including proceedings and monographs in many countries every year.

On the basis of knowledge in the kinetics and thermodynamics of the defined chemical systems, clay minerals in residual rocks and sediments serve as (a) the indicators of the environment during weathering and the soil-forming processes; (b) the indicators of allo- thigenes,is and authigenesis in sediments including the estimation of source areas; (c) the indicators of pH (basicity, neutrality, acidity) during different stages of the origin and evolution of a mineral association in the megaenvironment of the geological profiles as well as microenvironments in the pseudomorphs after original minerals; (d) the indicators of changes during diagenesis and metamorphism. Clay minerals can be used as sensitive geothermometers of diagenetic and metamorphic alterations of long ago. This counts also for mineral associations in the hydrothermal fillings and hydrothermally affected sediments (e.g. Konta, 1960; Schneider and Schumann, 1979; MC Murtry and Yeh, 1981; Meunier and Velsde, 1982; Boiron and Cathelineau, 1987). Some authors utilize the received knowledge on clay minerals for the requirements of the mining and dressing of clay raw materials. The others interpret the obtained data and observations on clay minerals in the reconstruction of the geological environment during weathering, erosion, transportation, deposition and diagenesis. The kaolin profiles have been a specifically suitable material for the recognition of the weathering processes. In these profiles, the different alteration stages are preserved from a fresh rock through the initial chemical alterations up to a full kaolinization in the uppermost parts of the profiles. Residual kaolins still contain preserved clay pseudomorphs after different primary minerals, especially after the sodium-rich plagioclase, potassium feldspar and biotite. These diverse pseudomorphs testify of the importance of a geochemical micromilieu during weathering processes. Tens of papers have been devoted to the investigation of kaolins and the material taken from them by the erosion which later settle under favorable conditions as refractory clays rich in kaolinite. Examples of at least some publications are represented in this monograph by the names of authors and translated titles: Konta and Mraz ( 1965) : Petrology and geochemistry of natural kaolin from Sedlec near Karlovy Vary (Czechoslovakia) ; Konta and Koscelnfk ( 1968): Petrographical types of kaolin in the Karlovy Vary granite massif; Milicky et al. ( 1968): Kaolin deposits in the environs of Podbomny; Kuivart and Konta ( 1968): Kaolin and laterite weathering crusts in Europe; Konta ( 1969) : Comparison of the proofs of hydrothermal and supergene kaolinization -in two areas of Europe; Krystkova ( 197 1) : Kaolin deposits of the Znojmo district;


Neuiil ( 1972) : Petrology of kaolin profiles on crystalline schists in the environs of Kadaii (West Bohemia); Reichelt and Neuiil ( 1973): Petrological and geochemical study of kaolinized rocks of the inner phyllites unit near Znojmo (southern Moravia) ; Kraus and Horvath ( 1978) : Mineralogy and age of Slovakian kaolins; Stbrr and Schwerdtner ( 1966) : Mineralogical and technological investigation of the kaolin from Kemmlitz in Saxony; Starr et al. ( 1977) : Kaolin deposits of Central Europe; Kroll and Borchert ( 1969a): Geological- petrographical investigation of West-German kaolin deposits; II. Kaolin deposit Lohrheim at Diez an der Lahn; Kroll and Borchert ( 1969b) : IX. Kaolin occurrence on clay shale as a source rock in Rheinland; Lippert et al. ( 1969) : Kaolin deposits of the Federal Republic of Germany; Szpila ( 1973) : Trace elements of primary kaolins from the Lower Silesian deposits, Poland; Stoch and Sikora ( 1975) : Mineralogy of kaolins of Lower Silesia; Diman- the et al. ( 1974) : The kaolin: mineralogy, deposits, uses; Moretti and Pieruccini ( 1969) : Italian kaolin deposits; Martin Vivaldi ( 1969) : Kaolin deposits of Spain; MaksimoviE and NikoliE ( 1978): The primary kaolin deposits of Yugoslavia; Jepson ( 1984): Kaolins: their properties and uses; Petrov ( 1969) : Kaolin deposits of the USSR; Rusko ( 1976) : Kaolin- ization and the kaolins of the Ukrainian Shield; Petrov and Chukhrov ( 1977): Kaolin deposits in the USSR; Murray ( 1976a) : High intensity magnetic beneficiation of industrial minerals - a survey; Murray ( 1976~) : The Georgia sedimentary kaolins; Minato ( 1977) : Kaolin deposits of Japan and surrounded East Asia; Button and Tyler ( 1979) : Precambrian paleoweathering and erosion surfaces in southern Africa: Review of their character and economic significance.

Clay minerals and quartz are omnipresent in sediments of all formations and in all rock species. Ronov (1964) has shown that on the basis of stratigraphic data, argillaceous sediments represent about 50% of the volume of known sedimentary lithosphere. On the basis of global geochemical data, the mass representation of clay material in sediments is estimated at about 75%. These numbers also underline the importance and need to study clay matter in continually greater details.

In the theoretic and applied geology, clay minerals serve to the correlation purposes. Clay minerals and argillaceous sediments play an important role in the oil geology and oil industry (Van Olphen, 1982) : ( 1) Geologists need to know the associations of clay minerals in the oil-bearing and sealing rocks for economic-geological interpretations and the recognition of diagenetic and migration processes. The retention of the oil in the source rocks can be caused by the adsorption of hydrocarbons on the natural organo-clay complexes in these rocks. The diagenetic alterations of clay minerals are in relation to the changes of organic substances in respective sediments (Eslinger and Pevear, 1988). (2) The oil production depends on the permeability of oil-bearing sediments. The low permeabilities, measured in fresh water, are usually caused by a deposition of finely dispersed clay particles in the capillary system of pores where they act as impermeable minifilters. The swelling of some clay minerals has a smaller influence. Also the preparation and use of the thixotropic suspensions in bore holes is a direct application of the clay colloid chemistry. (3) The industrial processing of the extracted oil needs big volumes of fine aluminosilicate materials, either zeolites, or bentonite with pillared hydroxides of the multivalent cations in smectite. They are of use partly as adsorbents of unwanted compounds, partly as catalysts of the cracking.

J. Konta/Applied Clay Science IO (1995) 275-335 289

Clay minerals in different coal sorts and accompanying clays or claystones have also a specific importance for the study of theoretical and practical projects. They can serve, for example, as the geochemical indicators of a sedimentation environment in the accompanying argillaceous accumulations or argillized tuffs (Senkayi et al., 1987). Clay minerals in the tectonica.lly disturbed seams are a key to the correlation because they occur as a common admixture, and in the clay interlayers they represent dominant constituents. The coal with an admixture of minerals of the kaolinite group yields after burning a fine, loose ash, easily falling through the furnace grate. The sorts of coal with the law-fusing clay minerals, e.g. with illite, yield after the burning a lump slag that blocks the grates. The extraction of high- grade clalys and claystones accompanying the coal seams can be economically more important than the extraction of the coal itself.

Two thirds of the lithosphere are and have been covered during the long geological history by marine and deep-oceanic sediments. In these, clay minerals globally predominate, yet their sources may be different. The pronounced material is that of the detrital origin, mostly transported by rivers (Lopatin, 1952; Wollast and Mackenzie, 1983)) but the material supplied by the shore erosion, by the alteration of volcanoclastic sources and basalt lavas effused on the sea bottom, by the glacial and eolian transportation participates, too. A part of clay minerals in the present-day seas and oceans and also in geological history precipitated chemically, especially during the diagenesis or even through the contribution of organisms (some glauconites) . Extensive literature exists about the present-day clay accumulations in rivers, in their suspension and in the bottom (e.g. Packham et al., 1961; Konta, 1988; Charnley, 1989 and by these quoted authors), and in the present-day seas (e.g. Parham, 1966; Griffin et al., 1968; Lisitzin, 1972; Gorbunova, 1975; MC Cave, 1975; Biscaye, 1976; Gibbs, 1977; Lisitzina and Butuzova, 1979; Bennett et al., 1981; Kumosov, 1982; Gibbs, 1983; Leinen, 1987; Charnley, 1989). The quoted works contain substantial portion of the original papers of the whole world. Great attention is paid to the diagenetic up to metamorphic alterations of clay minerals (e.g. Whitehouse and McCarter, 1958; Kubler, 1968; Dunoyer de Segonzac, 1969; Perry, 1974; Aronson and Hower, 1976; Yeh and Savin, 1977; Powell et al., 1978; Timofeev et al., 1978; Stoffers and Singer, 1979; Aoyagi and Kazama, 1980; Aoki, 1984; Pacey, 1984; Curtis, 1985; Nadeau et al., 1985; Bethke and Altaner, 1986; Frey, 1987).

Some monographs are devoted to a specific group of clay minerals or even to a single mineral. For example, Kossovskaya and Drits ( 1970), Bailey ( 1984), Srodon ( 1984), Srodon and Eberl ( 1984) write about mica minerals or only illite, while Drits and Kossov- skaya ( 1991) about micas and chlorites. Smectites in the recent oceanic sediments are investig*ated by Aoki et al. ( 1979) and Parra et al. ( 1985); Drits and Kossovskaya ( 1990) publish a remarkable study on smectites and related mixed-layer structures. Some authors investig.ate glauconite for tens years - its structure, heterogeneity, the problem of its origin including reconstruction of the genetic environment; they compare it with allied phyllosilicates and determine the absolute age of its recrystallization by means of the Rb-Sr method (Burst, 1958; Porrenga, 1967; Bell and Goodell, 1967; MC Rae, 1972; Odin and Matter, 1981; Morton and Long, 1984; Van Houten and Purucker, 1984; Odin, 1988). Tardy and Touret ( 1987) are the creators of a genetic model for glauconite, illite and corrensite during the compaction and diagenesis on the basis of the calculation of hydration energies. Others follow the questions of the origin of nontronite in the lacustrine (PCdro et al., 1978) and

290 J. Konta /Applied Clay Science 10 (1995) 275-335

deep-oceanic sediments (e.g. Singer et al., 1984). Liebling and Scherp ( 1976) study chlorite and mica as indicators of the sedimentation environment and the source areas. The sedimentation relations of the iron-rich chlorites in the Jurassic ferrolites of Luxembourg and Lotharingia are explained by Teyssen ( 1984). Also the paper on the evolution of chlorites and white micas in greywackes from the diagenesis up to the low-temperature metamorphism (Wybrecht et al., 1985) is an example of a desirable sedimentological investigation. Other original papers or monographs on palygorskite and sepiolite are devoted to the occurrence, geochemistry and processes of the origin in lakes or deep-oceanic sediments (e.g. Bowles et al., 1971; Church and Velde, 1979; Singer and Gal& 1984).

Many of the quoted papers and other studies published in numerous journals contain weighty information about clay minerals as indicators of the paleoclimate, geodynamics, paleogeography, stratigraphic questions and the weathering rate.

4.1. A survey of wide-ranging uses of clay raw materials

Clay raw materials are generally known under various trade names. The number of trade names of clays and loams in the world is estimated at 700 (Robertson, 1954; Konta, 1980; and trade names in catalogues of some companies). Our systematic classification is primarily based on the mineral, chemical and structural composition. A supplier usually defines trade names according to the key technological properties, material and granulometric composition. Experts can derive mutual relationships between the different properties.

I: Raw materials with a significant portion of two-sheet phyllosilicates

I, A,: Kaolin and beneficiated kaolin containing mainly crystalline A12Si,0,(OH),

Occurrence: Kaolin occurs as primary kaolin, i.e., residual rock, originating through the alteration of suitable silicates in a primary site and as secondary kaolin, originating through erosion and aquatic transportation of the material from a residual kaolin, under certain grain- size sorting and rapid deposition. Numerous rock-forming silicates alter into kaolinite through an intense hydrolysis, supported by natural acids. The kaolinization of sodium feldspar (albite) can serve as an example:

2NaA1Si,0s + H&O3 + H,O albite acid water

3 Na2C03 + Al,Si,O,(OH), + 4Si0, sodium carbonate in solution kaolinite silica in solution

The alteration of primary silicates of granites, syenites, gneisses, arkoses, phonolites and rhyolites into kaolinite occurs either in weathering processes or because of the impact of hydrothermal solutions. The formation of deep kaolin profiles took place in several periods of geological history. The thickest kaolin profiles were formed in the tropical forest climatic belt which moved in geological history far to the north with respect to the present equator. This is the reason why kaolins occur also in the territory of the Czech Republic and other countries now remote from the equator.


Characterization: A common raw kaolin contains kaolinite, white mica (muscovite and newly formed illite or mixed-layer structures of illite and smectite), quartz and residues of undecomposed silicates, mostly feldspars, biotite and accessory minerals. The accessory minerals can be divided in primary (e.g. tourmaline, zircon, garnet, ilmenite and rutile) and newly formed minerals (e.g. siderite, pyrite, marcasite, chlorite, goethite, akaganeite, hematite, anatase and rutile) .

Raw kaolin has few practical uses. Industrial beneficiation is necessary in order to separate non-clay minerals from the kaolin. The beneficiated product is characterized by high refractoriness and very low content of chromogenous oxides like iron.

Beneficiated kaolin is strongly enriched by kaolinite A12Si205( OH),. Its refractoriness usually varies between 1790 and 1850°C. It is an important raw material for many fields in industry. The following survey highlights various applications of beneficiated kaolin.

Application Requirements

As an industrial filling Paper industry ??in different sorts of paper 0 in coated paper (coating kaolin) (Murray, 1976b; I3undy and Ishley, 199 1)

Rubber industry 0 in tyres, soles, sealings and insulations

Plastics industry 0 in plastic covers, foils 0 in water pipes and other tubes ??in containers, boxes ??in plastic tiles and bricks for floors 0 in sealing compositions and cables 0 in phonograph records and diskette coatings. ??in thermoplastic roofings 0 airport landing and take-off strips

Manufacture of dyes and paints

0 water., oil, silicate, latex, insecticide and microbiocide paints

Constant white color and rheological properties of the suspension, ideal ink and colors receptor; a coating mixture contains e.g. 56 wt% of solid particles and 44 wt% of water whereby on 100 wt% parts of kaolin 7 parts are ethylated starch, 4 parts styrene-butadiene latex and 0.5 calcium stearate lubricant (Slepetys and Cleland, 1993; Smook, 1982). Kaolin free of Ni, Cr, i.e. rubber poisons. Kaolin is resistant to moisture, chemicals, bacteria, heat variations; it supports the stability of polymers and has favorable mechanical properties such as elasticity, low abrasivity and constant white color; especially intercalated complexes of kaolinite with different polymers that accelerate the curing process and stabilize the plastics, e.g. hydrazine, formamide, carbamide, pyridine, imidazole and other polymers; or polyacrylonitrile and others (Dannenberg, 1975; Sugahara et al., 1988; Sugahara et al., 1989b; Slonka, 1990)

Constant white color, stabilizer of dyes, mild sorption properties

292 J. Konta /Applied Clay Science IO (1995) 275-335

Manufacture of adhesives Constant white color and specific surface reactivity

Manufacture of pencils and pastels ( + graphite or dyes)

Constant bonding, whiteness, softness (absolutely without quartz) and extrusive properties

Manufacture of ink forfountain pens Constant whiteness, rheological properties, chemical resistance, nonabrasivity, easy dispersibility, softness

Manufacture of soaps, detergents, asbestos products, arttjicial leather

As an adhesive and mildly acting sorbent in the manufacture of Linoleum and other floor-cloth cement Constant rheological properties, uniform

dispersion, penetration and mild adhesiveness, stable color

Corrugated paper Felt pads for metal panels (indoor tennis court surfaces) Electric insulation coatings Art paper, wallpaper Protective coatings (textile finishes) Sorbent offluoride from water (Chaturvedi et al., 1988)

As a bonding material for Abrasive wheels ( + abrasives) Welding rod coatings ( + oxides) Well penetrable foundry sands ( + quartz sand) Cements (putties)

As a dust dispersal adsorbent for Pesticides ( + poisons) (Khandal et al., 1992)

The same and constant whiteness

Constant bonding, chemical resistance

Adsorption properties according to requirements, constant white color, chemical resistance

Pharmaceutic and cosmetic products (salves, powders) (Robertson and Ward, 1951; Hladon, 1988) Special fertilizers


As a refractory plastic and bonding material in the ceramic industry Whiteware, porcelain Constant chemical purity, white firing Sanitary ware color, rheological properties, bonding, Tiles and wall-tiles suitable shrinkage, porosity and Electra-ceramics permeability, high thermal stability Refractories (Baumgart et al., 1984; Burst, 1991) Saggars.for kilns Cordierite bodies and mullite bodies ( + quartz, feldspar, clays, bone phosphate, talc, alumina)

As a thermally resistant and chemically suitable material in the chemical industry Manufacture of catalysts of chemical Chemical purity and compositional reactions, adsorbents, foundry mould paints simplicity (e.g. for the polymerization of (after activation in H,S04 or by calcining) styrene) (Hettinger, 1991) Ultramarine pigment ( + soda + C + S) Uniform melting and homogeneity A1uminu.m sulphate (Al,O, + H2S04) Manufacture of synthetic zeolites (Murat et Thermally activated kaolinite al., 1992)

As a bonding and chemically resistant material in the manufacture of special cements Refractory cement ( + K,C03) Heat and chemical resistance Acid-resisting cement ( Na2Si03 + plastics)

As a gla:ssforming material in the glass industry Manufacture of glassfibres Optimum viscosity, strength and chemical

resistance of the aluminum-rich glass; a certain portion of organic matter in the kaolin is desirable

As a sensitive dosimeter in situ For determining the migration of radionuclides, especially in the vicinity of radioactive wastes (Muller et al., 1992)

As a basis of the manufacture of sialons Si-Al-Cl-N modern ceramic materials Constant chemical purity (Cutler et al.,

1978; Lee and Cutler, 1979; Sugahara et al., 1989a; Stoch, 1990)

Waste-free technology of the beneficiation of kaolin enables controlled separation and utilization of

294 .I. Konta /Applied Clay Science 10 (1995) 275-335

?? coarser, silty kaolin (e.g. trade name Carlsbad PK3) ?? silty fraction with grain size above 0.020 mm as a decorative paint 0 coarser silt and sand in a mixture with resin and required dye ingredient as plaster paints 0 sand and fine gravel in the building industries and for bitumen coatings, also in the

manufacture of lime-sand bricks 0 fine to medium-coarse gravel in the building industries, for road grounds and similar

constructions

I, A,: Clays (and loams) with high portion of kaolinite, and thus also A1203, and low content of iron compounds

Occurrence: Clays and loams of the I, A, category occur in nature as fillings of differently large depressions, either in the shape of layers, or lenses, together with other aquatic sediments. The clay or lutite material with possible sand admixture, deposited in water, was usually released by erosion from not too distant kaolin profiles in different time periods. Bolewski et al. ( 1991) classifies clays of the I, A2 to I, A, categories into: ( 1) refractory clays, (2) white firing clays, and (3) earthenware clays (colored firing). This broad classification is commonly recognized by ceramic experts for a long time. Our classification is based on a larger abundance of clays known from England (Holdridge, 1956), Germany (Kromer, 1978) and the Czech Republic (Konta, 1982a).

I, A,a: Superduty to high refractory kaolinite clays

Characterization: The superduty kaolinite clays are noted for their fusion temperature above 181O”C, the high refractory kaolinite clays between 1810 and 1760°C. U.S. specifi- cations are less stringent, i.e. above 1745°C and 1745 to 1690°C respectively. The majority of clays (sometimes loams) of the I, A,a category have a refractoriness between 1830 and 1760°C. Their firing color is white. Requirements are as follows:

Common mineral composition (wt%) : Chemical composition (wt%) :

Kaolinite 80 to nearly 100 Mica/illite 20-10 Somewhere It/Sm and other mixed-layer structures

Quartz several wt%, alkal. feldspars and heavy minerals as accessories

SiO* 45.3-53.0 TiOz 0.2-1.7 Al& 32.0-38.0 Fe,Os 0.8-l .2

MgG 0.0-0.54 CaO 0.10-0.7

Na,O 0.0-0.7 K,O 0.2-2.5 L.O.I. (1OOo”c) 9.1-14.2

The SiOZ content increases with an increasing quartz amount while the Al,O, content and the loss on ignition (L.O.I.) decrease. The most valuable kaolinite clays contain less than 1 wt% total Fe,O,. Kaolinite is usually well to medium ordered.

Also other technological properties are important such as particle size, plasticity, green, dry and firing strengths, thermal vitrification range, firing color after 1180,125O and 14 10°C drying and firing shrinkage, moisture at plastic limit, suction capacity and porosity of fired bodies.


Uses: Clays of the I, A,a category are used under different trade names in the manufacture Of:

earthenware (mostly top grade), sanitary earthenware, vitrified whiteware, white and colored glazed tiles, electrical insulators, as additives to porcelain mass (Konta, 1980; Bare:, 1980; Baumgart et al., 1984; Vtelensky, 1990) white wall tiles, general earthenware, as bonding clays, as a cement for interior bonding of bodlies and into abrasives (Fabri and Fiori, 1985) refractory construction bodies enamels ivory Iearthenware, ochre-brown earthenware faience

I, A,b: High refractory black clays Requirements are as follows:

Characterization: Chemical composition (wt%) :

The fusion temperature is between 1790 SiOZ 40.6-49.1 TiO, 0.16-1.97 and 175O”CThe firing color is white.They contain about k 10 wt% of the lignite Al@, 29.0-37.4 Fe& 0.4-2.8 portion, the remaining clay matter MgO 0.0-0.5 CaO 0.1-0.5 corresponding by its mineral composition to the preceding clay group.

Na,O 0.0-0.7 K,O 0.1-2.7 L.O.I. ( 1000°C) 12.3-25.0 and more (Konta, 1980; Bare& 1980)

Uses: small admixture improves the casting and suspending properties of industrial suspensions in the manufacture of general and sanitary earthenware or porcelain (Vtelensky, 1990) enhance the strength and bonding in the manufacture of white or colored wall tiles as an ingredient in enamel, where they improve adhesion and formation of thin continual films

I, A,c: Moderate to high refractory kaolinite clays to loams, with slight to moderate silt or sand admixture (mostly quartz and mica), often bonding

Characterization: The fusion temperature is between 1790 and 1650°C. The firing color is white to light beige. Requirements are as follows:


Common mineral composition ( wt%) :

Kaolinite 55-80 Mica/illite 35-10 ( +It/Sm) Quartz x.0 Feldspar x.0 Anatase and other HM, somewhere Opal 0.x Organic matter 0.5

Chemical composition ( wt%) :

SiOZ 47.2-58.0 TiO,

Al,03 28.3-35.1 Fez03 MgO 0.01-1.4 CaO Na,O 0.0-1.1 K,O L.O.I. (1000°C) 7.7-13.1

0.7-l .8 0.62.4 0.1-1.5 0.63.6

Uses: mostly as bonding clays for ivory earthenware, electrical porcelain as bonding clays commonly termed “ball clays’ ’ in different manufactures, e.g. foundry industry, the varieties without silt and sand in pencil industry off-white dust pressed tiles as bonding material in the press-molding of SIC or corundum saggars and other kiln furniture manufacture of plasticine and plastic clays or loams utilized by sculptors and manufacture of silicate cements (putties)

I, A2d: Moderate to low refractory siliceous clays or loams (with higher amount of silt or sand and thus also quartz), bonding, in the refractoriness range between 1750 and 1470°C

Characterization: Kaolinite is a substantial constituent. The mica/illite content mostly varies between 10 and 33 wt%. The kaolinite portion sinks with the increasing content of quartz and mica. The Si02 content varies in the range between 58 and 8 1 wt%, while A&O3 from 28 up to only about 10 wt%.

0

0

0

0

0

0

0

0

0

0

0

Uses for the manufacture of (or as) : ivory earthenware faience buff tiles enamelling clay bonding for abrasives general earthenware of different brown shades (Fabri and Fiori, 1985) colored wall tiles, floor tiles and fireplaces (Fabri and Fiori, 1985) electrical porcelain and electrical refractories fire clay sanitary kiln bodies and furniture substitution for SiOZ in pottery bodies

I, A,: Halloysite clays or residues with halloysite

Characterization: They usually contain as major mineral the rod-like crystals of halloysite, A12Si205( OH),.nH,O, or metahalloysite, Al,Si,O,( OH)+ The refractoriness of these


minerals is comparable to that of the beneficiated kaolin and high refractory clays. The halloysitse residues are similarly beneficiated as the kaolin residues. A minor admixture of halloysit’e in a porcelain mass enhances the green and dry strengths.

Uses: 0 manufacture of thin-wall porcelain, especially chemical porcelain 0 manufacture of electrical porcelain 0 in the cosmetics industry into skin powders (absolutely without quartz) 0 a catalyst for the polymerization of styrene (Njopwouo et al., 1987) 0 trimethylsilylated halloysite as a catalyst with very homogeneous pores of 1.7 nm diam-

eter (Oya et al., 1988)

I, A,: Kaolinite claystones (“Schiefertone’ ‘,jint clays)

Characterization: Semiconsolidated, nonplastic or slightly plastic sediments, mostly of conchoidal fracture, with a high content of usually well ordered kaolinite. The mineral and chemical composition is very similar to that of the I, A2 clay raw materials. Some varieties contain larger admixture of lignite or coal. Enhanced Al,O, content may be usually caused by an admixture of gibbsite or boehmite. The firing color of kaolinite claystones varies from white to light ochreous.

Uses: 0 manufacture of calcined flint clays or “chamotte”, extensively used as an indispensable

refractory raw material in the manufacture of colorless coarse and fine ceramic products

I, B: Raw materials with the two-sheet phyllosilicate Mg,Si,O,(OH),, antigorite or chrysotile

Occurrence: Raw materials with antigorite or chrysotile occur in serpentinites. They are formed during the late or postmagmatic hydrothermal alteration of ultrabasic igneous rocks containing olivine and pyroxene, i.e. pyroxenite, peridotite and dunite. A majority of serpentinites contains flaky antigorite developed under stress conditions. Fibrous chrysotile crystallizes under static conditions.

Characterization: Antigorite is a flaky and chrysotile a fibrous variety of serpentine. Chemical composition of both varieties is the same, i.e. Mg,Si,05(OH)4. The greenish color of serpentinites is caused by an admixture of ferrous iron. The accompanying minerals are talc, chlorite and carbonates.

Uses: The excellent thermal and electrical insulating properties, heat and chemical resistance of antigorite and chrysotile determine their uses in many production and civil engineering applications. The demand for this raw material dropped considerably or its use was disbarred in most countries when it was established that inhaling minute particles, especially the fibrous chrysotile asbestos during extraction, processing and prolonged contact, causes fibrosis -- an incurable disease of the respiratory tract. The group of asbestos, industrial materials of analogous thermal insulating properties, also includes fibrous amphiboles and their varieties: anthophyllite, actinolite, crocidolite, tremolite.

Contemporary most frequent uses: As a thermal-insulatingfillerfor


?? asbestos thermal insulating products, mostly as a mixture with MgO for the insulation of turbines, furnaces, ovens and drying rooms

0 manufacture of thermal insulating plates, flat handles and stands, boards, roofings, pipes, boiler cabinets, drains in foundries and safety curtains for movie theaters

?? protective synthetic, and rubber suits, aprons, gloves and boots 0 fire-proof paints ?? insulations slowing the cooling of steel and iron parts 0 building fire walls

As an electrical-insulating materialfor (or in) 0 electrical insulating shelters, fabrics, plates, cables and wire insulation ??manufacture of battery boxes

As a chemical-resistant material for ?? acid-resistant tubes and tubs ?? caulking sulphuric acid vats ??manufacture of brushes for corrosive liquids 0 manufacture of packing and sealing compounds to resist chemical agents and acid fumes,

high temperature and pressurized steam

As a sorbent with fair capillary transferfor 0 steam and acid filtration 0 manufacture of thin to thick filters for pharmaceutical use, chemicals, wines, fruit juices,

plant and animal extracts, lubricants 0 manufacture of fire-proof wicks and torches 0 lubricant mixtures

As a pigmenting material ?? finely dispersed serpentine minerals (around 20 wt%) in glazes cause green-grey color

with a dull effect (Schomburg, 1993)

II: Raw materials, often polymineral, with significant portion of three-sheet mica phyllosilicate, especially K < ,Al,[(SiAI, ,),O,,](OH),- nH,O

II, A: Clays and loams without requirement of a refractoriness

Characterization: Less valuable but very important plastic raw materials are the polymineral clays and loams. Above all they contain mica/illite, then kaolinite, chlorite, sometimes vermiculite, various mixed-layer structures of phyllosilicates, quartz, alkaline feldspars, accessory heavy minerals, oxide iron pigment, and possibly also carbonates (calcite) and organic matter. The chemical composition considerably varies. The Fe,O, content is substantially higher than in the previous clay and loam categories.

Two categories of these clays and loams are especially notable: II, Al - pottery clays and loams; II, A2 - brick clays and loams including loess and shale.

II, A,: Pottery clays and loams


They are especially important in the manufacture of: red or ochre firing pottery products, i.e. “terra cotta”, insulators and garden pottery ( Muiioz de La Nava et al., 1990; Dell' Anna and Laviano, 199 1) deeply colored ceramic tiles and plates (Dell’ Anna and Laviano, 199 1) bricks and fireplace tiles colore’d vitrified ware and earthenware majolica some lirefighting applications

More detailed information can be found in Konta ( 1982a). So-called pottery stones are polymineral associations containing mainly quartz, sericite

and kaolinite with admixture of dickite, rectorite, tosudite, smectite or mixed-layer structures It/Sm, plagioclase, K-feldspar, calcite, siderite and pyrite. They have been formed through hydrothermal alteration of various rocks. They are mostly used in Japan (Kaji et al., 1986; Nakagawa, 1988; Miyaji and Tsuzuki, 1988). The clay accumulations of variable composition oftlen fill not only hydrothermally altered spaces but also bulky tectonic faults.

II, A,: Brick clays and loams including loess, shale

Characterization: They contain a high portion of the silt fraction (0.004-0.063 mm) besides clay particles (below 0.004 mm or 0.002 mm according to other authors) and possible admixture of sand grains (0.063-2 mm). In the silt fraction, mainly quartz, mica and other common rockforming minerals occur. The amount of rock fragments, including the carbonate rocks, increases with the rising grain size. As a common admixture, the iron oxide pigment occurs, fairly uniformly distributed, which dyes the raw material in different ochreous shades.

Clay fraction is always polymineral: illite Chemical composition is characterized by and fragrnents of micas, kaolinite, chlorite, highSiO,, total Fe203 and often also CaO vermiculite, smectite and their mixed-layer andK,O + Na,O contents which reduce the structures. firing temperature

Uses: ??manufacture of kiln wares, such as bricks, ceiling bricks, roofing bricks, roofing tiles and

drainpipes (Winkler, 1954; Kreimeyer, 1987; Dunham, 1992) 0 tiles and related products including ornamental tiles (Gonzalez-Garcia et al., 1990) ?? in earthen- and loam-glazes, especially containing 1 to 3 wt% rutile

In all categories and species of clays and loams of the group II, the mentioned technological properties (see I, AZ) are also followed. Among them, the most extended vitrification range is especially appraised.

II, B: Redevelopment and agricultural clays, loams and claystones

Occurrence and characterization: These polymineral argillaceous sediments contain mica/illite, smectite, chlorite, also their possible mixed-layer structures, but to a lesser


extent kaolinite, fragments of feldspars, quartz, carbonates and organic matter (with still preserved proteins, sugars and other energetically important substances). Accessory minerals must be innocuous. The extraction of these clays, loams or claystones may be useful if they have to be removed as overlying or accompanying material of more valuable raw materials, such as e.g. coal, kaolins and refractory clays.

Uses: ?? redevelopment of open pit mines and quarries (land reclamation) 0 additives into composts (in order to enhance the content of potassium, calcium, phos-

phorus, organic matter and other nutrients)

II, C: Clays, claystones to shales for the manufacture of thermally expanded granules

Characterization: They mainly contain illite or sericite, fragments of micas, kaolinite, chlorite, smectite (in unconsolidated clays and claystones), various other random mixed- layer phyllosilicates, quartz and numerous accessory minerals. During a hard firing between 1000 and 12OO”C, they bloat under the pressure of the gaseous phase escaped from the sintered material. An enhanced kaolinite and primary mica amount acts unfavourably. The ideal chemical composition is preferably plotted in ternary diagram (Riley, 195 1; White, 1960; Babtiek and Bare& 1969; Bylova et al., 1981; Decleer and Viaene, 1993).

Uses: 0 to obtain expanded granules of required sizes (keramsite) for lightweight concrete, in

loose non-inflammable insulations, in soil reclamation projects and related purposes

II, D: Roojing slates and phyllites

Occurrence and characterization: Slates and phyllites occur in the uppermost zone of metamorphic rocks. They are formed by low-grade regional metamorphism of clay to lutite (below 0.063 mm) elastic sediments. The Czech-extracted grey slates of Proterozoic age, greenish phyllites of probably Cambro-Ordovician age and deeply grey shales of Culm age are known for their desirable, fine-grained texture, perfect fissility along the planar schistosity, minimum porosity and imbibition capacity, high compressive strength perpendicular to schistosity and resistance to frost and hailstones.

The essential minerals in roofing slates and phyllites are sericite (fine-flaky potassium mica rich in aluminum) and fine-grained quartz; the auxiliary minerals are chlorite, then albite, somewhere graphitoid substance and accessory apatite, tourmaline and ore minerals (Fediuk, 1984). The SiO, content mostly varies in wt% between 56 and 58, Al,O, between 20 and 24, Fe,O, 1.3 and 3.6, Fe0 2.5 and 6.5, MgO 1.0 and 2.3, K20 3.0 and 4.7, H,O+ 3.4 and 4.6, and other components occur in lower amounts.

Uses of bulky lumps: 0 manufacture of pickling vats for the food industry 0 electrical insulation boards 0 tombstones ??window sills ?? smooth house veneer


0

0

0

0

0

0

0

0

0

0

0

0

0

0

Uses as variously sized slabs: roofing slates floorings and walls of interiors, corridors and bricking of fireplaces slabs for tables including laboratory and billiards table tops (when polished)

Uses of slate waste: manufacture of expandite (in the kiln bloated slate as lightweight aggregate not necessarily in granules, dry crushed material in size between 2 to 15 mm)Finely milled, wet: as aluminosilicate ingredient into milled limestone in the cement factories as essential material (together with sand) in the manufacture of bricksFinely milled, dry: as ing,redient in concrete and similar bricks as major filler for bitumen and asphalt products applied on roads, damp proof courses, roofing felts and bitumen paints (the optimum fine size distribution is important in all cases ) inert tiller in plastics and rubber inert tiller in priming paints (to preserve metals), and in varnishes inert tiller for sealing compounds in the furniture industry carrier for fertilizers and insecticides filler for jointless flooring compounds filler :n battery boxes and electrical insulators

II, E: Micas

Occurrence and characterization: The big crystals of micas occur in pegmatites and their aureoles. Small to quite fine flakes are common in some metamorphites (mica schists and phyllites,) and magmatites. However, easily extractable mica fragments especially occur in mica-rich sediments, where material and size sorting took place during aquatic transportation.

Three particular micas are industrially the most important: Muscov:ite (whitish) KA12(AlSi3)O10(OH,F)2, Phlogopite (brownish) KMg,( AlSi,)O,& F,OH),, Biotite (brown-black) K(Mg,Fe2+,Mn),(Al,Si,)O10(OH,F),

Uses: The big chipping plates are used in special cases. The majority of industry-grade micas is delivered either in the form of finely to coarsely ground powder (dry or wet), or in finely sorted size fractions.

Insulation electrical and thermal properties are utilized in: manufacture of electrical ceramics: condensers and commutators (phlogopite) in auto and alero engines, telephones, radio, sparking plugs for piston aircraft engines (phlogopite), industrial and domestic heaters with wires coiled round mica pressed bodies, in the manufacture of electrical insulators; phlogopite has higher thermal resistance manufacture of heat insulation materials manufacture of joint cements for final wall coating, where mica prevents cracking and shrinking


??manufacture of asphalt rolled paper and artificial roofing tiles, where all micas including biotite may be used; the micas have a decorative effect, and enhance resistance against weathering

0 manufacture of insulation coatings for cables and wires, antioxidation paints for steel (Hayashi et al., 1989, 1991a)

0 manufacture of some wallpapers, where mica creates a silky effect and subtly reflects light (Davis, 1992)

@ manufacture of windows for ovens, heating pipes, oil and gas lamps, where big chipping plates are used and where transparency and thermal stability are required

Chemical and mechanical resistance,jlaky shape and sorption properties are utilized by the following industrial branches: ??manufacture of paints, where mica, in optimum size fraction, improves the flatting effect,

acts as anti-sagging and anti-penetration material, and enhances the heat resistance of paints

?? in emulsion paints, where finely milled mica enhances the slip and brushability (Davis, 1992)

0 manufacture of vinyl coatings where mica enhances adhesion and reduces moisture penetration

?? as additives into varnish insulation coatings ?? in the anti-corrosive coatings, because muscovite is one of few common minerals ultrast-

able against the weathering ?? in traffic paints for road-signs, airports etc., where mica filler acts by its durability and

enhances reflectance 0 in exterior house paints, where optimum milled mica acts against the formation of cracks

and prevents chalking 0 extending aluminum flake 0 suspending red lead ( Pb304) 0 in decorating paints finishing stucco, cement coatings and artificial stone and blocks 0 manufacture of plastics, where mica enhances a glittering sheen (not only muscovite but

also biotite) and stabilizes plastics (Hayashi et al., 1991b; Chand, 1992; Davis, 1992) 0 illite in marl is an excellent adsorbent of Cs+ (also radioactive Cs) (Cornell, 1992)

Special use of muscouite: 0 in optical instruments, as mica compensator plates with high optical transparency

Biotite: 0 pigment in ceramic glazes with a low CaO content (Schomburg, 1993)

III: Vermiculite, M~(AI,Si).,010(OH),M~.35 - 4.5H20

Occurrence: Economically important vermiculite deposits occur in rocks originally rich in biotite, where a hydrothermal or supergene alteration of biotite to vermiculite took place. Vermiculite is mainly extracted from such altered basic pegmatites, alkaline pyroxenite, syenite, minettes and especially carbonatite complexes.


Characterization: The ideal composition of vermiculite is given by the above formula. Its platy ~crystals are very well fissile along the basal plane, the color being light grey, greenish with nacreous lustre.

Uses:

III, A,: Fresh vermiculite serves

0 for the purification of water, e.g. for the sorption of some toxic metals like Pb, Zn and Cd

III, A,: Thermally exfoliated vermiculite

may be applied in some industrial branches, building industries, agriculture and protection of the environment. A multiple volume expansion is reached by sharp firing at around 800°C. Its use depends on the degree of mechanical disintegration or grinding, and the size classification to several fractions:

12.5-6.25 mm 0 for byre and piggery floors as a strong adsorbent, for application in compost mixtures,

and for improving the structure of heavy soils 0 as incubators, safe and vault linings, and pipeline protection 0 in expansion joints on concrete pavements ??as resistant crating material for exotic fruits and fragile, inflammable goods including

glass 0 in horticulture and agriculture as hydroponics for seed germination and root development

6.25-3.36 mm 0 as insulation in the transport of hot ingots 0 as heat and refractory insulation of furnaces, kilns, cookers, water heaters, tanks and

other containers, pipe covering and boiler laggins

3.36-2 mm ??in house, factory and agricultural insulations, e.g. loose fill of cavity walls, between

joists, ispaces behind refractory bricks in fireplaces, floor and roof screens 0 in protlecting steel girders and anti-sweat coatings 0 in insulating plasters (thermal and acoustic) 0 in lightweight concrete (similarly as keramsite but with stronger insulating effects) 0 in decorative stuccos (coarse structure and marble effect)

2-I mm ??for soundproofing in schools, public halls, telephone booths, film, TV and broadcasting

studios

l-O.42 mm 0 as infla.mmable acoustic, heat resistant and/or lightweight insulations for motor vehicles,

aeroplanes, refrigerated trucks, passenger cars, and cold stores 0 in the manufacture of prefabricated insulating wall boards 0 in filters for purification of water and beverages

304 J. Konia /Applied Clay Science 10 (1995) 275-335

?? in filters for purification of industrial, agricultural and other outflows 0 in fire-resistant coating of roofing felts ?? as an oil rig sealing compound 0 in deodorizing compositions (together with peat and specifically beneficiated bentonite) 0 in horticulture and agriculture for improving the structure and water economy of soils

0.42-O. I25 mm 0 as filler in the manufacture of linoleum shingles 0 in cornice boards 0 in dielectric switchboards ?? as catalyst, e.g. for isomerization of alpha-pinene ?? as catalyst carrier in chemical industry 0 in explosives for reducing incendivity (similarly as diatomite powder)

0.125-0.074 mm 0 in lubricating grease for reducing friction and increasing thermally resistance 0 as filler for tyres and other rubber goods 0 as filler for plastic products, especially shellac and rezyls, for floor coverings, crown-cap

seals of plastic bottles and gaskets 0 in insecticide dusts and sprays

< 0.074 mm 0 as filler for paints ?? as filler for rubber goods with smooth surface 0 as asphalt filler 0 for controlling the release of fertilizers in soils 0 for plugging drill holes ?? in textile finish (coating) 0 as catalyst carrier ?? as filter aid

0.074-O. 053 mm ?? in wallpaper, to enhance color stability 0 on outdoor billboards (enhances durability) 0 in fireproof inorganic paints 0 for the manufacture of fireproof film boxes 0 for building up viscosity in oil 0 in foundry mould facing, core wash and sand binder

< 0.053 mm ?? as extender for aluminum paint 0 as extender for gold and bronze printing, inks and paints

< 0.044 mm up to micronized ?? in dyes, e.g. ultramarine ?? as filler for craft paper (from sulphate cellulose) 0 as insecticide carrier ?? in lubricating oil additive for sealing worn pistons

J. KontaIApplied Clay Science 10 (1995) 275-335 305

0 in outdoor paints for traffic and other public signs 0 as scouring powders for purification of different containers 0 as filler of battery boxes, plastics and crayons 0 in dusting decals

III, A,: Axid-activated vermiculite

is an effective catalyst for the cracking of heavy fuels to obtain the highest gasoline portion ( Suquet et al., 1994).

IV: Bentonite

Occurrence and characterization: Bentonite occurs in the form of lenses in other sediments, mostly as a weathering product after volcanoclastic material settled in water. It also commonly occurs as a product of supergene or hydrothermal alteration of some volcanic rocks, e.g. rhyolites, porphyres, phonolites, dacites, andesites and basalts. Smectites are especially formed through the decomposition of volcanic glass.

The chemical composition of smectite, the dominant mineral of bentonites, is variable. It varies between: Montmorillonite Al,,,,(Mg,Fe2+),~,,Si,0,,(OH),0.5C~,,, .nH,O, Beidellite Al,( A10.33Si3.67) 010( OH) 20.5Ca,,,3. nH,O.

In the interlayer space of both smectites different cations are adsorbed, especially alkalies and alkaline earths.

As accompanying or accessory minerals, illite, kaolinite, vermiculite, chlorite, zeolites, some milxed-layer structures of phyllosilicates, residues of undecomposed silicates, e.g. feldspar:;, biotite, amphibole and quartz can occur. Accessory heavy minerals are common. Carbonates, especially calcite, have been found in some bentonites.

Uses:

IV. A: Bentonite with calcium smectite

The raw or activated Ca-bentonite is appreciated for its strong adsorptive properties (Robertson, 1986).

As a sorbent, both for removing undesirable substances in various operations, and as an additive sorbent in different products ?? in the recovery of used lubricating oil from motor cars, aeroplanes, turbines, transformers

and other power plants ?? as a dry, powder detergent for the sorption of impurities ?? in food industry, for the removal of impurities from edible oils, fats and waxes; e.g. palm,

soya, rapeseed, maize, linseed, poppy, sunflower and other oils, bone and fish fat, tallow, l&d (incl. deodorizing), castor oil, cod liver and beeswax

?? for the removal or substantial reduction of invertase from yeast suspensions ?? for the removal of alkaloids and insecticides from vegetable extracts 0 in the manufacture of livestock fodder compositions

306 J. Konra /Applied Clay Science 10 (1995) 275-335

?? in pharmacy as anti-irritant for eczema, part of industrial protective creames (Robertson and Ward, 195 1) ? ?for manufacture of intercalated organic medicaments with a prolonged effect

?? in cosmetics for manufacture of mud packs, baby powder, face powder and creames 0 as an additive sorbent in soaps, rubber, artificial leather, in materials coating roads and

building grounds 0 in wool processing (fuller’s earth), for fulling coarse blankets and finishing indigo dyed

cloth ?? in the water-supply industry and closed spaces for the sorption of metallic and other ions

from water, and insulation of radioactive fission products (for which highly compacted bentonite is required, sometimes with addition of other materials) (Bucher and Miiller- Vonmoos, 1989; Proust et al., 1990; Bard and Czurda, 1991; Beziat et al., 1992); for the sorption of sulphur, nicotine and pesticides from the atmosphere, and the most important sorbent for the abiotic transformation and detoxication of agrochemicals (Mortland, 1976; Ristori et al., 1987; Pusino et al., 1993)

?? for the coagulation of humic substances in water (Tombacz et al., 1990) 0 as a sorbent for purification of water in dam lakes and similar reservoirs where it removes

nutrients promoting the reproduction of algae and other unwelcome plankton (Konta, 1995)

As a bonding material 0 in pencil industry as bonding cement for graphite and dyes ?? in agriculture as a protecting and sorption coating of seeds ?? in foundry industry as a bonding cement of foundry sands (e.g. in iron works)

As a catalyst 0 in fuel refineries for the conversion of hydrocarbons (petroleum oil cracking) (Hettinger,

1991) ?? for the dehydration of oils (e.g. castor oil) 0 for the manufacture of polystyrene and similar compounds ?? in the synthesis of terpenes ?? after saturation with Ni-ions or other metals for purification and hydrogenation of edible

fats

As a retention and neutralizing material ?? for additives in composts to retain water and essential nutrients in soils for a long time 0 for the neutralization of acid wood- and farmlands ?? in artificial fog in film studios ?? as an insulating material for waste dumps (Weiss, 1989)

As a stabilizer of reclaimed soil and storage source of nutrients and humidity ?? for redevelopment of regions affected by mining or building activities

IV, B: Bentonite with sodium smectite

Bentonite either in its natural form or artificially activated with Na’ ions is especially appreciated for its strong swelling in polar liquids. A small admixture of sodium bentonite


already enhances the plasticity, green compression strength and dry compression strength of other (clay raw materials or aggregates. It rapidly forms a dispersion in water and other polar liquids to ultrafine particles.

The green compression strength is utilized ?? in foundries as moulding material for quartz sands in steel, iron and non-ferrous foundries,

where Na-bentonite cement is added in amounts of 5 to 7 wt% ?? in different applications for the regeneration of floor sands ?? in the manufacture of refractories where sodium bentonite in slight addition is a bonding

agent in silica refractories, quartzite bricks, zircon refractories and refractory cements ?? as addlition in glazes for the manufacture of insulators and pottery goods ?? as addlition in the manufacture of mineral wool, asbestos and vermiculite insulations ?? as addlition in briquetting or pelletizing applications (e.g. aggregation of coal, industrial

dust, graphite and ores) 0 in the textile industry: for the impregnation of textiles and other materials requiring a

thin inorganic film (slight crustification) 0 in the pencil industry: slight addition strongly enhances the green and dry compression

strengths ?? for the insulation of dumps containing hazardous waste including radioactive materials

with sodium bentonite as a sealing material (Weiss, 1989; Meunier et al., 1992; Pusch, 1992; Tessier et al., 1992)

Dispervion ability, long-standing suspension and its thixotropy is utilized ?? in mineral, silica and water paints (with thixotropic effects) 0 as additive in polishing and grinding pastes ?? in agriculture and horticulture as a carrier of fungicides and insecticides and as addition

in animal dips ?? in the drilling industry where thixotropic Na-bentonite suspension is used for the grouting

of weakly cohesive bore hole walls ?? in cosmetics for mud packs, face creames and sun-tan preparations 0 in pharmacy as addition to calamine lotion, colloidal iodine preparations, wet compresses,

mercury and zinc pastes and salves (Robertson and Ward, 1951) and as artificial muds in pelotherapy of rheumatic diseases (Ferrand and Yvon, 1991)

0 in the manufacture of aeroengine lubricants where sodium bentonite enhances their thermal stability

0 in dry cleaning as laundry detergents for heavily soiled fabrics 0 in industrial, building, agricultural and forestry activities as major component of liquid

hand cleansers ?? in the building industries as addition into insulating barium-sulphate plasters in X-ray

laboraltories and works ?? in environment protection: insulation of dumps containing hazardous materials where

especially the swelling and sealing properties of Na-bentonite under humid conditions are appreciated

Required and readily controlled viscosity and plasticity is utilized

308 .I. Konta/Applied Clay Science 10 (1995) 275-335

0 in civil engineering for the preparation of portland cement slurry and mortar in the mixture with milled blast-furnace slag and water, where addition of sodium bentonite gives a mobile, self-hardening slurry suitable for the quick construction of impervious, under- ground earth-retaining walls ( Kita, 1989)

?? in the manufacure of bituminous emulsion paints 0 in the construction of roads, parking lots and airports: in tar and bitumen emulsions

coating these surfaces ?? in the industrial manufacture of oil pesticides

Specific mild adsorptive and absorptive properties are utilized 0 in breweries, wine-making, sugar factories and by bee-keepers, where sodium bentonite

acts as a readily dispersible inorganic sorbent without any toxic elements ?? in water purification in some water-supply stations ?? in removing oxidation products from lubricating oils where the efficiency is inversely

proportional to the amount of water adsorbed in bentonite (Shanshool et al., 1990) ?? in the adsorption and deamination of some amino acids (Siffert and Naidja, 1992) 0 in pharmacy as a carrier of active substances, e.g. codeine phosphate or quinine hydro-

chloride (Hladon, 1988)

IV, C: Bentonite with other exchangeable cations

Bentonite with an artificially incorporated cation in the interlayer space acts in a desirable specific way: 0 synthetic Zn-smectite as catalyst of alkylation reactions (Luca et al., 1992) ??Ni-bentonite as catalyst in the manufacture of hydrogenated vegetable oils (Bond, 1987) 0 Al-montmorillonite as catalyst for ethylene hydration (Atkins et al., 1983; Ballantine et

al., 1983) or carrier of thioamides and herbicides (Ristori et al., 1987) ??Cr( III) and Fe( III) interlayer cations in montmorillonite are the most active source of

protons (solid acids) in selective catalytic reactions, especially for carbocation of hydrocarbons (Adams et al., 1983)

. cu2+ in montmorillonite catalyses non-biological degradation of oxamide (CONH,) 2 which is a very effective nitrogen fertilizer for some highly valuable crops (Ristori et al., 1991)

??Ag + -montmorillonite intercalated with acrylonitrile and subsequently polymerized is an effective antimicrobial and antifungal material (Oya et al., 1992; Oya et al., 1994)

??with different cations (Li+, Na+, Mg2+, Zn2+ ) saturated montmorillonite as a carrier of the pesticide aminotriazole (Morillo et al., 1991)

?? yttrium-montmorillonite is applied in the preparation of silicon oxynitride ceramic powders for the manufacture of nitride ceramics called SIALON or SIMGON (Kooli et al., 1992)

IV, D: Acid-activated bentonite

Characterization: Activation in HCl or H2S04 (with different molar concentrations) leads to a dissolution or removal of the octahedral sheets and interlayer cations, resulting in an increase of the pore volume and pore diameter, an enrichment of residual amorphous


SiOz and an increase of sorption properties (Adams, 1987; JovanoviE and JanaEkoviE, 1991).

Uses: ??removal of pigments from fats, especially edible oils (Srasra et al., 1989) 0 acid-treated montmorillonite with intercalated long-chain alkylammonium ions is of great

importance in the manufacture of paints for its thixotropic and thickening effect (Fahn and Buckl, 1968)

??with adsorbed dye as a filler of carbonless copying papers (Fahn and Fenderl, 1983)

IV, E: Pillared bentonite with incorporated inorganic R(M) and R(N) hydroxides in smectite

Preparation and characterization: Pure bentonite, usually 2-3 wt% of the < 2 pm fraction in a water suspension, with addition of R( III) or (IV) hydroxide (from chlorohydrate or chloride solution) is stirred for a few hours at room temperature. The reaction is also possible by a direct addition of the pillaring solution to dry bentonite. The resulting product is washed with deionized water and filtered. It is subsequently dried under a stream of dry air at slightly increased temperature (about 30°C).

The SiOz sol is prepared from tetraethylorthosilicate, [ Si( OC,H,),] , in ethanol and HCl under continual stirring. Beside this, a thick white slurry of Ti( IV) isopropoxide, [ Ti( OCHI CH,/,),] , is mixed with ethanol and stirred some minutes. This is then added to the above silica sol. The resulting mixture is stirred for a longer period, giving rise to a yellowish sol. Finally, the resulting SiO,-TiO, sol is mixed with the thin bentonite suspension and stirred at 50°C for several hours. The interlayer SiO*-TiO, pillared smectite is washed several times with deionized water and finally gently dried (Malla and Komameni, 1993).

Catalytic activity and selectivity of R( III) and/or R( IV) pillared smectites calcined at 300-500°C arises from the newly incorporated and thus enlarged constant interlayer space, unique polarity and large surface area. By this change it approaches the zeolite-like structures (Raman and Raman, 1989). For these purposes, beidellite is more suitable than montmorillonite due to the origin of Si-OH acid sites in the beidellite structure (Schutz et al., 1987).

Actually, a series of R( III) and (IV) hydroxides, exceptionally also (II), has been applied ‘to the incorporation into the interlayer space of different smectites including saponite: Al( III) Zr( IV) Cr( III) Ti( IV) Al( III)--SiO1 SiO*-Ti (IV) Ga( III) SiO,-Mg( II) La( III)-Al( III) Al( III)--Ga( III) Fe( III)--Al( III)

(Brindley and Sempels, 1977; Plee et al., 1987; Figueras et al., 1990) (Yamanaka and Brindley, 1979) (Pinnavaia et al., 1985) (Sterte, 1986; Yamanaka et al., 1987) (Occelli, 1987; Sterte and Shabtai, 1987) (Yamanaka et al., 1988; Malla and Komarneni, 1993) (Bellaoui et al., 1990) (Iwasaki, 1991) (Sterte, 1991) (Gonzalez et al., 1992) (Zhao et al., 1993)

310 J. Konra /Applied Clay Science 10 (1995) 275-335

Uses: 0 intercalation of large organic ions and, after heating, the removal of organic compounds 0 as catalysts of required pore size (Lagaly, 1987) ??Al (III) hydroxide pillared into saponite is a new catalyst for high temperature conversion

of heavy oil fractions into gasoline (Chevalier et al., 1992) ?? as catalyst carriers ?? as molecular sieves 0 as effective adsorbents (because of their strong hydration strength of trivalent and tet-

ravalent cations pillared in the interlayer space) ?? as sensors (responding to a physical stimulus) 0 as strong and selective adsorbents of many organic compounds including poisons endan-

gering the environment (Zielke and Pinnavaia, 1988) 0 as effective sorbent of phosphate anions from water (Al-smectite) (Peinemann and

Helmy, 1992) 0 in liquid-column chromatography (Nakamura et al., 1988) where also pure montmoril-

lonite with Ru( phen) :’ is applied (Tsvetkov et al., 1990).

IV, F: Organophilic bentonite

Manufacture and characterization: The washed bentonite, free of coarser, non-clay minerals, represents a suspension of the purest smectite (Sm) with original exchangeable cations (mostly NaC, Ca*+ and Mg*+ ). Addition of 90 to 110 meq/ 100 g of the quartemary ammonium salt to the smectite suspension leads to a rapid and almost complete exchange for original cations according to the equation (Jones, 1983) :

Sm- -Na+ + R,R2R3R4NfC11 +Sm-N+R,R,R,R, + NaCl

The resultant flocculated hydrophobic product is filtered and finally dried at 30-50°C. The most commonly used organic cations contain one or more octadecyl groups, which

are derived from hydrogenated animal fat tallow. Examples are di(C18H37) dimethylammonium, di ( C,aH3,) benzyl methylammonium and (C, aH3,) benzyl dimethylammonium and also tetramethylammonium. Other organic compounds intercalated into smectite are e.g. polyacrylamide, cethylpyridinium, trimethylphenylammonium, various insecticides and herbicides, and drugs. The surveys on the research of organo-clay complexes have been published by Weiss ( 1963), Theng ( 1974) and Lagaly ( 198 1) .

Uses: 0 as catalysts of chemical reactions (Comelis et al., 1983; Gregory et al., 1983; Adams,

1987; Lagaly, 1987; Ghosh and Mishra, 1989) ?? in a dispersion of hydrophilic polymers in oils supports formation of gel with thixotropic

properties ?? for the manufacture of thixotropic paints, where the organophilic bentonite prevents

pigment settling, reduces separation of liquid phase and enhances application properties including coating (Jones, 1983)

?? in drilling oil-based suspensions stable at higher temperatures (corresponding to depths of more than 4 km) (Jones, 1983)


0 in greases with increased thermal resistance, where it strengthens the influence of anti- oxidants and chemicals, esp. rust inhibitors (Jones, 1983; Iwasaki et al., 1989)

0 in fibreglass resin where it supports their thixotropic behavior and prevents the separation of fiberglass from the resin (Jones, 1983)

0 as a sorbent of toxic organic substances in waste waters and for the insulation of industrial and municipal dumps (Weiss, 1989; Lee et al., 1990; Stockmeyer, 1990, Stockmeyer, 199 1) and with the additional advantage that it can be re-used after calcination at 500°C (Michot and Pinnavaia, 199 1)

0 as a carrier of organic pesticides and herbicides (Mortland, 1970; Margulies et al., 1988; Ghosh. and Mishra, 1989; Bansal, 1990)

??as org,ano-mineral complexes in fertilizers 0 as large hydrophobic organic cations (e.g. pentachlorophenol) in organo-clay complexes

enhance the sorptive properties of soils (Boyd et al., 1988) ??as smectites saturated with the small, hydrophobic organic cation (trimethylphenylam-

monium) which effectively adsorbs aromatic hydrocarbons from water (Jaynes and Boyd, 1991)

0 in cosmetic preparations, suntan creames and emulsions (Vicente et al., 1989) ??in inks for retaining stable suspension 0 in pohshing pastes and emulsions 0 as bentonite complex with phenol or diethylketone is a strong adsorbent for Zn and Ni

from water; other organwclay complexes adsorb further metals (Stockmeyer and Kruse, 1991)

0 for the: preparation of a complex clay mineral/carbon layer with unique absorption effects of active carbon

0 as a possible cementing material preventing the erosion of sand dunes and similar loose accumulations (Tazaki et al., 1989)

V: Pyrolphyllite and talc raw materials

Occurrence: Pyrophyllite and talc crystallize during metamorphic or hydrothermal processes. Pyrophyllite commonly occurs in mixtures with sericite, as e.g. in the Lukavice deposit, .Bohemia (Jiranek et al., 1993). In such cases its industrial application is limited. The largest pyrophyllite deposits are known in Japan where they are extensively used. Zaykov ;and Udakhin ( 1994) described some types of pyrophyllite mineralization in the Urals and have shown that pyrophyllite rocks with quartz and sericite are most suitable in ceramic manufacture because of their sintering range between 1100 and 1200°C. Talc commonly occurs with an admixture of tremolite, chlorite, dolomite, mica and magnesite. Its deposits are connected with basic or ultrabasic magmatites and magnesium-rich carbonate rocks.

Characterization: Although pyrophyllite, Al,Si~O,,( OH);?, differs chemically from talc, Mg,Si,Cr,O(OH),, their crystal structures are analogous. This is also why their physical properties are so close to each other. The hardness of talc according to Mohs scale is 1 and that of pyrophyllite between 1 and 2. The wettability of both minerals is the lowest among all phyllosilicates.

Pyrophyllite aggregates are ( 1) fine-grained flaky with a distinct structural foliation, (2) massive spherulitic, or (3) radially needle-like.


Talc aggregates are either very finely crystalline, massive (steatite), or fine-grained platy, exhibiting a high degree of lubricity (soapstone).

Uses of pyrophyllite (always infine-powdered state) : 0 as filler for rubber and plastics 0 as filler for paints 0 as filler in roofings and wallpaper ?? as insecticide carrier 0 in the manufacture of refractory constructive bodies ?? in alumosiliceous ceramic products 0 as a gentle and neutral sorbent for bleaching textiles and ropes 0 in neutral cosmetic products

Uses of talc in massive lumps: 0 as oven and furnace hearths 0 in acid-proof pickling vats ?? in sanitary wares 0 in laboratory table tops 0 in fuel application elements ?? as ornamental objects ?? in french chalk used by tailors

in granulated fragments (2-4 mm) : 0 for bituminous roofing felt and paper

finely powdered 0 as coating for the manufacture of art or glazed paper and wallpaper ?? as filler in blotting and printing paper ?? as filler for transparent tracing paper ?? as filler for textiles and oilcloth 0 a filler for paints (especially distempers) 0 in plasters ?? as a thin water suspension for washing plasters 0 as filler for asbestos products ?? as filler for gentle lens-grinder’s mastics ?? as filler for rubber, linoleum and plastics 0 as filler for soaps 0 as filler for pencils ?? in alkaline cements ?? for ropes and strings where talc supports smooth surface ?? in magnesium coatings of floors 0 as filler for insulating coverings for boilers and steam-pipes 0 as pesticide carrier 0 in polishes (with constant holding of grain-size) ?? as lubricant in medical and cosmetic powders and salves (for sensitive skin) and in baby

powders ?? as dry lubricant for surfaces


0 as homogeneous film for packing parachutes to prevent moisture-rotting 0 for the insides of rubber gloves 0 on the surface of inner tyres ?? in ceramic products (especially cordierite bodies) ( Hubner, 199 1) 0 in the manufacture of electrical porcelain 0 in the manufacture of table ware with lower tension ?? in the manufacture of tiles 0 in the manufacture of saggars for kilns 0 in the manufacture of grinding balls ?? in the manufacture of refractories based on forsterite and enstatite

VI: Chlorite raw materials

Occurrence: Rocks with desirable high concentration of iron-poor chlorite occur in the uppermost zone of the regionally or hydrothermally altered silicate rocks, which are partly affected by stress. The common accompanying minerals are sericite and fine-grained quartz. One of these rocks is extracted in Austria, e.g. at Aspang (Lower Austria) or at Kleinfeistritz (Steyer) under the name leucophyllite (Holzer and Prochaska, 1990).

iron-rich chlorites, especially chamosite and thuringite, occur in some iron ores of sedimentary origin (Teyssen, 1984).

Characterization: Chlorites are four-sheet phyllosilicates with a rather variable chemical compodtion. From about fifteen mineral species belonging to the chlorite group, the most abundant constituent of chlorite-rich rocks ’ clinochlore (Mg,Al)&,AlO,a( OH),.Mg(OH),. The leucophyllite is a sericite+hrLrite schist rich in clinochlore. Its sintering range varies between 900 and 1040°C and the material can thus be used in ceramic industry. Leucophyllite reduces the green dilatation of porous compositions and clay materials fired at low temperatures. Most chlorites are colored in green shades but clinochlore is whitish.

Uses: ?? raw chlorite poor in iron is a very suitable sorbent of bivalent radionuclides, especially

radioactive barium ( 14’Ba) contaminating the environment (Eylem et al., 1989)

Leucophyllite is used: 0 in the manufacture of earthenware, majolica and wall tiles 0 as an ingredient for glazes and compositions similar to cordierite 0 in the manufacture of fireproof table earthenware and stove tiles

Nickel-bearing chlorites (and vermiculites) are used: ?? as brilliant green color of glazes (&homburg, 1993)

VII: Palygorskite and sepiolite

Occurrence: Both magnesium hydrosilicates occur in some sediments and as hydrothermal fill:ings. The sediments of lacustrine and marine origin containing palygorskite or sepiolite reflect an aquatic, magnesium-rich environment and a terrigenous or through halmyrolysis formed clay material. Common accompanying minerals are montmorillonite,


clinoptilolite, gypsum and/or pyrite. This corresponds to conditions close to a saline environment (Singer and Galan, 1984). Some authors presume that palygorskite and sepiolite in sediments originate through the alteration of montmorillonite under increased activity of Mg*+ ions (Kukovsky and Ostrovskaya, 1961; Bonatti and Joensun, 1968; Stoch, 1974).

Characterization: Palygorskite Mg,Si,02,(OH),( 0H2),.4H20 is a magnesium hydro- silicate with a possible slight substitution of magnesium by aluminum. The crystal structure is layer-fibrous, with double silica tetrahedral chains running parallel to the c axis. The octahedral sheets are similar to those in the sheet clay minerals, but are continuous only in one direction. The magnesiums in the octahedral sheet are shielded by the oxygen and hydroxyl planes ending with water of crystallization (OH,). In their vicinity, further molecules of so-called zeolite water (H,O) occur in free interlamellar channel.

Sepiolite Mg,Si,,O,,( OH),( OH,),.nH,O has a crystal structure very similar to that of palygorskite. The substitution of magnesium by other ions is still limited. The layer-fibrous structure of both minerals also determines the lath-shaped to fibrous forms of their crystals. They are only visible under the (electron) microscope.

Uses of palygorskite:

Adsorption properties are utilized ?? in the manufacture of pesticides 0 in bedding for small domestic animals 0 as cleaning material for the removal of oil and grease (also from water) 0 for the sorption of excessive water vapor 0 in manufacture of pigments for wallpapers 0 as sorbent for purification of dyehouse effluents ?? as sorbent for purification of liquid sugar (i.e. ionic adsorption at certain pH) 0 in purification of animal fats, vegetable oils and waxes ?? in purification of liquid fraction from oil shales ?? in decolorization and purification of petroleum, wax, paraffin and lubricating oils (includ-

ing used ones)

It serves as a molecular sieve ?? in separation of hydrocarbons and other organic substances of similar chemical compo-

sitions

Catalytic effects are utilized 0 in industrial pyrolysis and cracking of petroleum oils 0 in catalytic isomerization to obtain hydrocarbons with a high octane number ?? in catalytic polymerization (e.g. pinene to polyterpenes) or in manufacturing of perfumes

and essences ?? to enhance acidity and catalytic effects by rhodium incorporation in the interlamellar

space of palygorskite and amorphous Si02 enhance acidity and catalytic effects ?? in the hydrogenation of vegetable oil (esp. Ni-palygorskite)

Rheological properties and thixotropy are applied 0 in palygorskite suspensions of drilling muds

Uses of sepiolite


Adsoqotion properties are utilized 0 in purifying petroleum products, lubricating oils, transformer oils, liquid fraction from

oil shales and used lubricant oils ?? in the refining glucose, liquid sugar, wine and cider, vinegar, gelatine and glycerine ?? in the manufacture of packages protecting against moisture and in laboratory desiccators 0 in the sorption of organic vapors ?? in the manufacture of white copying paper ?? in the treatment of domestic and municipal liquid sewage, where sepiolite supports

growing of methanobacteria as a source of biogas and methane (Perez-Rodriguez et al., 1989)

?? in chromatographic experiments

Sepiol’ite serves as a molecular sieve 0 for the separation of gases and vapors including hydrocarbons and ions from a solution 0 for the filtration and removal of pigments and nickel from oils

Catalytic effects are utilized 0 in the isomerization of cyclohexene 0 sepiolite with Al, Cr or H+ substituting Mg is a hydrothermally stable catalyst (Perez

Pariente et al., 1988)

Thermal and chemical resistance is utilized 0 in the manufacture of refractory and ceramic elements, electrical insulators

Rheological properties such as toughening, suspending and gelling are applied 0 in the manufacture of greases 0 in pharmaceutical and cosmetic products, paints, inks and polishes ?? in oil-well drilling (to resist salt solutions) 0 in ceramic suspensions and the subsequent formation of ceramic bodies (Simonton et

al., 1988)

A suitable light color enables the application 0 in the manufacture of paints and wax polishes

VII, A: Axid-activatedpalygorskite

The microstructure similarly changes to that of smectites. The enlarged micropores and newly developed texture in the residual amorphous SiOZ enhance decolorating effects (Gonzalez et al., 1989a,b).

VII, B: s’epiolite with incorporated metal cations

Sepiolite with incorporated Cu(I1) in interlamellar space strongly catalyses e.g. the conversion of alcohols.

VIII: Clay ochres and pigments

The eighth group includes color clay materials of very different structural and chemical compositions. They represent a separate region although they can be classified in some of

316 J. KontalApplied Clay Science 10 (1995) 275-335

the foregoing groups according to their respective crystal structures. The application of clay ochres and pigments is, however, so specific that they deserve to be classified separately.

The proper color is given either by the presence of some non-clay pigment, such as in ochres, or by the presence of any chromogenous element in the crystal structure (especially Fe, Ni, Cr) . The natural color hue can be modified by the drying intensity and even more under constant heating at higher temperatures.

The most common samples cover: Clay ochres in which illite and kaolinite predominate. The red or ochreous hue is caused

by a slight admixture of limonite (goethite or another cryptocrystalline form of a trivalent iron hydroxide) or hematite (Tessier and Triat, 1973).

Benefciated kaolin with a high concentration of kaolinite Al,Si,O,( OH), whose white color has the corresponding pigmentation effect.

Lizardite (an iron-containing chrysotile variety) (Mg > Fe > Al),Si,O,( OH), is green to yellow-green.

Celudonite K( R:.GR:.i ) Si40i0( OH), where R2+ represents Fe’+ and Mg’+, while R3+ are Al3 + and Fe3 + ; it is a green three-sheet phyllosilicate of the clay micas group.

Glauconite K( R2 + <o.8R:T.2) Si40,0( OH), is a three-sheet phyllosilicate crystallographi- tally very near to celadonite. It occurs in green to yellow-green hues.

Nontronite (or ferrismectite) Fe,( Si 3.67A10,33)010(OH),.nH,0 is green to yellow-green. Pimelite (a nickel-bearing smectite) Ni3Si,010( OH) *.nH,O, is intensively green.

Mixtures of pimelite with other minerals are called “gamierite”, “nepouite” and “nou- meaite” .

Vokhonskoite (a chromiferous smectite) (Al > Fe > Cr),( Si,,,,Ab.,,) OiO( OH) ,.nH,O has a permanent green color. It was used by the makers of art oil paints already in Renaissance Italy.

Uses: 0 as coatings of interior and exterior walls some, especially clay ochres, beneficiated kaolin

or its silt waste and celadonite or glauconite 0 in the manufacture of oil and other paints

5. Essential manuals and monographs in clay science from the middle of the 20th century

The global and national state of any science is illustrated in basic manuals essential monographs for a certain time period. In the past fifty years the world of clay scientists has been influenced by more than a hundred books and monographs. The language in which the books were written, was of great significance as far as their influence was concerned. In the given extent of this monograph, it is possible to acknowledge in chronological order at least the names of authors and titles of their works (Table 1) . They are given in their original wordings in the references section.

Equally important are the books and monographs on the investigation methods of clay minerals and argillaceous rocks (Table 2). Some original papers in Germany and the USA have a pioneering start, e.g. “X-ray and colloidal chemical investigation about clay”

_I. Konta/Applied Clay Science 10 (1995) 275-335 317

Table 1 Essential manuals and monographs in clay science from the middle of the 20th century

Country (b’ut published in) Author (and year) Title

USA France

Germany Russia

USA

Russia USA Czechoslovakia Japan USA USA France

France

France Ukraine

Russia Norway

Russia France

Czechoslovakia

USA (a paper)

Australia Russia

Russia

Poland

UK

Russia

USA

USA (Netherlands)

Poland Germany Germany

France (Netherlands)

Marshall ( 1949) Millot ( 1949)

Jasmund (1951) Ginzburg and Rukavishnikova (1951) Grim (1953) (2nd edition 1968) Chukhrov (1955) Keller ( 1957) Konta (1957) Sudo(1959) Garrels ( 1960) Grim (1962) Caillere and H&in (1963) Millot ( 1964)

Pedro ( 1965) Kukovsky (1966)

Zkhus ( 1966) Gjems (1967)

Petrov (1967) Dunoyer de Segonzac ( 1969) Gregor and &Eel ( 1969) Helgeson et al. (1969) Loughnan (1969) Vasilev ( 1969)

Chukhrov et al. ( 1970) Kozydra and Wyrwicki ( 1970) Grimshaw (1971)

Vikulova et al. (1973) Weaver and Pollard (1973) Rieke and Chilingarian (1974) Stoch (1974) Gieseking ( 1975) stijrr (1975)

Velde (1977)

The Colloid Chemistry of the Silicate Minerals. Relations between the Composition and the Genesis of the Sedimentary Argillaceous Rocks. The Silicate Clay Minerals. The Minerals of an Old Weathering Crust of the Urals.

Clay Mineralogy.

The Colloids in the Earth Crust. The Principles of Weathering. Clay Minerals of Czechoslovakia. Mineralogical Study on Clays of Japan. Mineral Equilibria at Low Temperature and Pressure. Applied Clay Mineralogy. Mineralogy of Clays.

Geology of Clays. Translated in Moscow into Russian (1968) and at Springer into English (1970). The Classification of Clay Minerals. The Pecularities of the Structure and Physical-chemical Properties of Clay Minerals. Clay Minerals and their Paleogeographic Importance. Studies on Clay Minerals and Clay-Mineral Formation in Soil Profiles in Scandinavia. Scientific Principles of the Old Weathering Crusts. Clay Minerals during the Diagenesis. Passing into Metamosphism. Bentonite and its Application.

“Evaluation of irreversible reactions in geochemical processes involving minerals and aqueous solutions”. Chemical Weathering of the Silicate Minerals. Old Weathering Crusts of the Cristalline Basement of the Southern Baltic Region. Clays, their Mineralogy, Properties and Practical Importance. Clay Raw Materials of Poland.

The Chemistry and Physics of Clays and Allied Ceramic Materials. Facial Types of Argillaceous Rocks.

The Chemistry of Clay Minerals.

Compaction of Argillaceous Sediments.

Clay Minerals. Soil Components. Kaolin Deposits of the GDR in the Northern Region of the Bohemian Massif Clays and Clay Minerals in Natural and Synthetic Systems.

318 J. Konta /Applied Clay Science 10 (I 995) 275-335

Country (but published in) Author (and year) Title

USA (Netherlands)

New Zealand (Netherlands) Israel (Germany)

Hungary Czechoslovakia Netherlands Poland

Czechoslovakia Germany

USA UK

USA

Israel and Spain (Netherlands)

USA USA

France (Netherlands)

USA (Netherlands) USA

USA

UK USA

Canada (Netherlands) UK USA Netherlands USA

France USA

Czechoslovakia USA (Netherlands) Slovenia USA UK (Italy)

UK

USA (Germany)

USA

France (UK)

Japan UK

Grim and Giiven (1978) Theng ( 1979) Yariv and Cross (1979) Q Nemecz ( 198 1) &Eel et al. (1981) Bolt (1982) Kozlowski (1982)

Konta ( l982a) Baumgart et al. ( 1984) Bailey ( 1984) Barrer and Tinker (1984) Bowers et al. (1984) Singer and Galan ( 1984) Sposito (1984) Weaver et al. (1984) Velde (1985)

Drever (1985) Bennett and Hulbert (1986) Colman and Dethier ( 1986) Robertson ( 1986) Chapman and McKinley (1987) Gillott (1987) Newman (1987) Bailey (1988) Burch (1988) Eslinger and Pevear (1988) Charnley ( 1989) Dixon and Weed (1989) Kraus(1989) Weaver (1989) Driaj ( 1990) Hochella (1990) Mackenzie (1990)

Mitchell (1990)

O’Brien and Slatt ( 1990) Houseknecht and Pittman ( 1992) Velde ( 1992)

Nagasawa ( 1992) Manning et al. (1993)

Bentonites. Geology, Mineralogy, Properties and Uses.

Formation and Properties of Clay-Polymer Complexes. Geochemistry of Colloidal Systems.

Clay Minerals. Mineralogy and Crystal Chemistry of Clays. Soil Chemistry: Physico-chemical Models. Kaolin Raw Materials. A Monograph on Mineral Raw Materials of Poland. Ceramic and Glass Raw Materials. Process Mineralogy of Ceramic Materials.

Micas. Reviews in Mineralogy. Clay Minerals: their Structure, Behaviour and Use.

Equilibrium Activity Diagrams.

Palygorskite-Sepiolite: Occurrences, Genesis and Uses.

The Surface Chemistry of Soils. Shale-Slate Metamorphism in Southern Appalachians.

Clay Minerals: A Physico-Chemical Explanation of their Occurrence. The Chemistry of Weathering. Clay Microstructure.

Rates of Chemical Weathering of Rocks and Minerals.

Fuller’s Earth: A History of Calcium Montmorillonite. The Geological Disposal of Nuclear Waste.

Clay in Engineering Geology. Chemistry of Clays and Clay Minerals. Hydrous Phyllosilicates (other than Micas). Pillared Clays. Clay Minerals for Petroleum Geologists and Engineers.

Clay Sedimentology. Minerals in Soil Environments.

Kaolins and Kaolinite Clays of Western Carpathians. Clays, Muds and Shales. Bentonites in Slovenia. Mineral-Water Interface Geochemistry. The Importance of Soil Clay Mineralogy in Determining Soil Properties and Fertility. Pillared Layered Structures: Current Trends and Appli- cations. Argillaceous Rock Atlas.

Origin, Diagenesis, and Petrophysics of Clay Minerals in Sandstone. Introduction to Clay Minerals. Chemistry, origins, uses and environmental significance. Clay Minerals - Their Natural Resources and Uses. Geochemistry of Clay-Pore Fluid Interactions.


Table 2 Methodical manuals and monographs that influenced the research of clay minerals and argillaceous rocks

Country (‘but published in) Author (and year) Title

UK

Russia

UK

Ukraine Russia

UK

Czechoslovakia

Poland USA

Netherlanrls

USA

UK

UK

UK Russia

Belgium Netherlands

USA

Benelux (UK)

Brindley ( 195 1)

Kitaigorodsky (1952)

Mackenzie (1957)

Bobrovnik et al. (1958) Vikulova and Zvyagin ( 1958)

Brown (1961)

Konta ( 1962)

Langier-Kuzniarowa ( 1967) Zvyagin ( 1967)

Beutelspacher and Van der Mare1 ( 1968) Jackson ( 1969) (supplemented edition from 1956) Mackenzie (1970, 1972)

Gard (1971)

Farmer (1974) Drits and Sakharov (1976)

Thorez ( 1976) Van der Mare1 and Beutelspacher ( 1976) Carroll ( 1979)

Van Olphen and Fripiat (1979)

X-Ray Identijcation and Crystal Structures of Clay Minerals. X-Ray Structure Analysis of Fine Crystalline and Amorphous Substances. The Differential Thermal Investigation of Clays. The Investigation and Utilization of Clays. Methodical Manual to the Petrographic- mineralogical Investigation of Clays. The X-Ray Identification and Crystal Structures of Clay Minerals. Imbibometry. The Investigation of Argillaceous Rocks on Ground Sections. Thermograms of Clay Minerals. Electron Diffraction Analysis of Clay Mineral Structures. Translated from the Russian into English. Atlas of Electron Microscopy of Clay Minerals and their Admixtures. Soil Chemical Analysis. Advanced Course.

Differential Thermal Analysis of Clays. Vol. 1, Fundamental Aspects; Vol. 2, Applications. The Electron-Optical Investigation of Clays. The Infrared Spectra of Minerals. X-Ray Diffraction Analysis of Mixed-layer Sheet Silicates. Practical Identtj?cation of Clay Minerals. Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures. Clay Minerals, a Guide to their X-ray Identijcation. Data Handbook for Clay Materials and Other Non-metallic Minerals.

UK

USA

Benelux

The book contains results achieved by means of at least ten different methods on referent samples from known world localities. Brindley and Brown (1980) Crystal Structures of Clay Minerals and

their X-Ray Identification. Stucki and Banwart (1980) Advanced Chemical Methods for Soil and

Clay Minerals Research. Fripiat (1981) Advanced Techniques for Clay Mineral

Analysis.

UK

It informs about the principles and application of the thermoanalytical methods, high resolution electron-microscopy, neutron scattering techniques (NST), nuclear magnetic resonance (NMR) , Mijssbauer spectroscopy, electron spin resonance (ESR) , ultraviolet and visible light spectroscopy, infrared spectroscopy and electron spectroscopy for chemical analysis (ESCA) Smart and Tovey (1981) Electron Microscopy of Soils and

Sediments: Examples.

320 .I. Konta /Applied Clay Science IO (1995) 275-335

Country (but published in)

USA (a paper)

Germany

Canada (a paper)

Author (and year)

Sudo et al. (1981) Ferraro (1982)

Smart and Tovey (1982)

White et al. ( 1982)

Schomburg and St&r ( 1984)

Kodama (1985)

Title

Japan (Netherlands) UK

UK

Electron Micrographs of Clay Minerals. The Sadtler Infrared Spectra Handbook of Minerals and Clays. Electron Microscopy of Soils and Sediments: Techniques. “Thin-film analysis of clay particles using energy dispersive X-ray analysis”. Atlas of Dilatometric Curves of Clay Mineral Raw Materials. “Infrared spectra of minerals. Reference guide to identification and characterization of minerals for the study of soils”. Electron Micrographs (TEM, SEM) of Clays and Clay Minerals. A Handbook of Determinative Methods in Clay Mineralogy. Electron Dt$fraction and High-Resolution Electron Microscopy of Mineral Structures.

Germany

UK

Russia (Germany)

Poland

USA

France

Russia and France (Germany)

USA

USA

USA USA

Mackinnon and Mumpton ( 1990)

Stucki et al. ( 1990) Gtiven and Pollastro ( 1992)

USA Reynolds and Walker ( 1993)

UK Syvitski (1991)

Henning and St& ( 1986)

Wilson (1987)

Drits (1987b)

Wytwicki (1988)

Moore and Reynolds (1989)

Eberhatt (1989)

Drits and Tchoubar ( 1990)

Pevear and Mumpton ( 1989)

Derivatographic Analysis of Argillaceous Rocks. X-Ray Diffraction and the Identijication and Analysis of Clay Minerals. Structural and Chemical Analysis of Materials. X-ray Diffraction by Disordered L.amellar Structures. Theory and Applications to Microdivided Silicates and Carbons. The U.S. Clay Minerals Society Workshop Lectures: Vol. 1. Quantitative Mineral Analysis of Clays. Vol. 2. Electron-Optical Methods in Clay Science. Vol. 3. Thermal Analysis in Clay Science. Vol. 4. Clay-Water Interface and its Rheological Implications. Vol. 5. Computer Applications to X-ray Diffraction Analysis of Clay Minerals. Principles, Methods, and Applications of Particle Size Analysis.

(Hofmann et al., 1934), “Electron micrographs of clay minerals” (Shaw and Humbert, 1941) or “Diagnostic criteria for clay minerals” (Bradley, 1945)) predominantly by means of X-ray diffraction. In the middle of the 20th century, the very important paper, “Some notes on the recording and interpretation of X-ray diagrams of soil clays”, was published in Great Britain by Mac Ewan ( 1949).

Useful information on clay minerals and clay accumulations is also presented in hand- books and monographs on sedimentary rocks and soils. Their mere listing, however, would considerably expand this chapter. Hundreds and thousands of original papers have appeared

J. Konra /Applied Clay Science 10 (1995) 275-335 321

in specialized journals, proceedings of clay conferences or symposia and are scattered in other scientific journals all over the world. Number of the theoretic papers highly predom- inates over that of the original applied results. The most important results are usually soon incorporated into current manuals and monographs.

6. Conclusion

In ordler to implement the described and other ways of utilization of clay raw materials, it is necessary to gather as much information as possible from the basic and applied research. Argilology or clay science enables a reliable determination of the material and structural composition of clay minerals and rocks, in addition to the recognition of their diverse properties and the history of their origin. Even though the roots of clay science can be traced back as far as in the 19th century, it has been recognized as a useful, progressive, interdisciplinary natural and also technical science only since the middle of the 20th century. In fact, an exact differentiation of specific clay minerals did not occur until the 1920’s and 1930’s when X-ray diffraction method was introduced. Since then the study of clay minerals and clay raw materials has been developed in an impressive manner. Also technological studies of new materials on the basis of phyllosilicates have decisively contributed to the development of clay science.

At present there is hardly a prestigious university which would ignore clay science. This is partly due to the extraordinarily widespread application of clay raw materials in practice and also due to the role and significance of clay minerals in geological sciences.

The interdisciplinary character of clay science follows from the fact that it draws information from the methodology and theory of other natural and technical sciences. These include physics, physical chemistry, colloid chemistry, inorganic, organic and analytical chemistry, mineralogy, crystallography, petrology, geology, sedimentology, geochemistry, soil science, soil mechanics and technology of silicates. Although clay science today is an extensive and interdisciplinary science, it is primarily one of geological sciences.

At a university level registration and discussion of the most significant facts, data, their interpretation and research methods are covered. Naturally, this includes also the transmis- sion of foreign scientific literature. This incessant, cumulative process of gathering knowledge and experience from experimental and literary work is an integral part of the technological progress and economic development in every country.

Acknowledgements

I am well aware of the fact that the development of any scientific discipline or branch is connected with the names of certain personalities. This is true also in the case of applied clay science. Therefore, my special thanks go, above all, to my friend of many years, Mr. R.H.S. IRobertson, from Dunmore, PitIochry in Scotland, whose monographs ( 1960,1986) inspired the writing of some parts of this paper and the idea of the clay raw material exhibition. My thanks belong also to all other authors cited who significantly contributed

322 J. Konta /Applied Clay Science IO (I 995) 275-335

to the development of theoretical or applied clay science. Many of the works cited suggest tremendous possibilities in research and modem technologies.

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Adams, J.M., Clapp, T.V. and Clement, D.E., 1983. Catalysis by montmorillonites. Clay Miner., 18: 411-421. Aoki, S., 1984. The vertical change of the clay mineral composition in some deep-sea cores raised from the

northern part of the Central Pacific Basin. Geol. Sure. Jpn. Cruise Rep., 20: 193-197. Aoki, S., Kohyama, N. and Sudo, T., 1979. Mineralogical and chemical properties of smectites in a sediment core

from the Southeastern Pacific. Deep-Sea Res., 26: 893-902. Aoyagi, K. and Kazama, T., 1980. Transformational changes of clay minerals, zeolites and silica minerals during

diagenesis. Sedimentology, 27: 179-188. Aronson, J.L. and Hower, J., 1976. Mechanism of burial metamorphism of argillaceous sediment, 2: Radiogenic

carbon evidence. Geol. Sot. Am. Bull., 87: 738-744. Atkins, M.P., Smith, D.J.H. and Westlake, D.J., 1983. Montmorillonite catalysts for ethylene hydration. Clay

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Ballantine, J.A., Pumell, J.H. andThomas, J.M., 1983. Organic reactions in a clay microenvironment. Clay Miner., 18: 347-356.

Bansal, O.P., 1990. Sorption of oxamyl on clay minerals. Clay Res., 9: 25-33. Bare& M., 1980. Technological properties of plastic ceramic raw materials from the deposits Nova Ves I and II

in the Cheb Basin. (In Czech with German abstract.) Acta Univ. Carol., Geologica, Praha, Nos. 3/4: 297- 321.

BareS, M. and LiEka, M., 1976. K exaktnfmu studiu stare keramiky (K otazkam vztahu vypichane lengyelske kultury) (To an exact investigation of the ancient ceramics). Sbomfk N&r. muzea v Praze, Acta Musei Nationalis Pragae, Series A - Historia, vol. KKK, Nos. 3/4: 137-244 + 8 tables.

Barrer, R.M. and Tinker, P.B., 1984. Clay Minerals: Their Structure, Behaviour and Use. Proc. R. Sot., Lond., 432 pp.

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