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Silicates

Silicates
Asbestos, Cement and Concrete, Clays, Glass, Glass Ceramics, Mica, Silica, Talc, and Zeolites are separate keywords. Gerhard Lagaly, Institute of Inorganic Chemistry, University of Kiel, Kiel, Federal Republic of Germany (Chap. 1) Werner Tufar, Department of Geosciences, Philipps University Marburg, Marburg, Federal Republic of Germany (Chaps. 1, 2) A. Minihan, Unilever Research Port Sunlight Laboratory, Bebington, Wirral, United Kingdom (Sections 3.1 3.4 and 3.10) A. Lovell, Croseld Chemicals, Warrington, Cheshire, United Kingdom (Sections 3.5 3.9) Structural Chemistry of Silicates . . Structural Classication . . . . . . . Oligo- and Cyclosilicates . . . . . . . Polysilicates . . . . . . . . . . . . . . . . Phyllosilicates . . . . . . . . . . . . . . Monophyllosilicates . . . . . . . . . . . Diphyllosilicates . . . . . . . . . . . . . Alkali Silicates . . . . . . . . . . . . . . Crystalline Silicic Acids . . . . . . . . Clay Minerals . . . . . . . . . . . . . . . Intracrystalline Reactions . . . . . . . . Tectosilicates . . . . . . . . . . . . . . . Natural Silicates . . . . . . . . . . . . . Feldspar . . . . . . . . . . . . . . . . . . Structure and Composition . . . . . . . Characterization of Individual Feldspars . . . . . . . . . . . . . . . . . . Production . . . . . . . . . . . . . . . . . Properties . . . . . . . . . . . . . . . . . . Mineral Deposits and their Extraction Processing and Quality Requirements Uses and Economic Aspects . . . . . . Nepheline and Related Compounds Leucite . . . . . . . . . . . . . . . . . . . Olivine . . . . . . . . . . . . . . . . . . . Andalusite . . . . . . . . . . . . . . . . . Kyanite . . . . . . . . . . . . . . . . . . . Sillimanite . . . . . . . . . . . . . . . . . Mullite . . . . . . . . . . . . . . . . . . . Vermiculite . . . . . . . . . . . . . . . . Perlite . . . . . . . . . . . . . . . . . . . Pumice . . . . . . . . . . . . . . . . . . . Basalt . . . . . . . . . . . . . . . . . . . . Wollastonite . . . . . . . . . . . . . . . . Toxicology . . . . . . . . . . . . . . . . . Alkali Silicates . . . . . . . . . . . . . . Introduction . . . . . . . . . . . . . . . Raw Materials . . . . . . . . . . . . . . Amorphous Anhydrous Alkali Silicates (Solid or Lump Glasses) . . . . Silicate Solutions . . . . . . . . . . . . Hydrated Water-Soluble Silicates . Crystalline Solids . . . . . . . . . . . . Uses and Applications . . . . . . . . . Economic Aspects . . . . . . . . . . . . Storage, Safety, Labelling and Transportation . . . . . . . . . . . Analysis . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . .

1. 1.1. 1.2. 1.3. 1.4. 1.4.1. 1.4.2. 1.4.3. 1.4.4. 1.4.5. 1.4.6. 1.5. 2. 2.1. 2.1.1. 2.1.2. 2.1.3. 2.1.4. 2.1.5. 2.1.6. 2.1.7. 2.2. 2.3. 2.4.

2 3 4 4 6 6 8 8 8 10 13 14 15 15 15 17 18 19 20 21 21 24 27 28

2.5. 2.6. 2.7. 2.8. 2.9. 2.10. 2.11. 2.12. 2.13. 2.14. 3. 3.1. 3.2. 3.3. 3.4. 3.5. 3.6. 3.7. 3.8. 3.9. 3.10. 4.

31 34 36 37 40 44 46 47 47 52 52 52 53 53 55 58 58 59 61 61 62 63

1. Structural Chemistry of Silicates


More than 95 vol % of the earths crust is composed of quartz and a few rock-forming silicates (plagioclase 42 vol %, potash feldspar 22 vol %, quartz 18 vol %, amphibole 5 vol %, other silicates 12 vol %). Silicon compounds are also present in the hydrosphere, mainly as dissolved silica. A large number of silicates have been identied in extraterrestrial material [1].
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a23 661

The widespread abundance of silicate minerals is accompanied by a diversity of practical uses (Table 1). Silicates are components of technical materials such as cement ( Cement and Concrete) and glass ( Glass, Glass Ceramics). Granite and sandstone are used as building materials. Quartz ( Silica) is the raw material for producing waterglass, silicon ( Silicon), and silicon compounds ( Silicon Compounds, Inorganic, Silicon Compounds,

Silicates

Figure 1. Oligosilicates and cyclosilicates A) Monosilicates (forsterite, olivine, phenakite, garnets, zircon; formulae see text); B) Disilicates (thortveitite, Sc2 [Si2 O7 ]; C) Monocyclosilicate: dreier single ring (benitoite, BaTi[Si3 O9 ]); D) Monocyclosilicate: vierer single ring (taramellite, Ba4 (Fe,Ti)4 B2 [Si4 O12 ]2 O5 Clx ); E) Monocyclosilicate: sechser single ring (beryl, Be3 Al2 [Si6 O18 ]; tourmalines XY3 Z6 B3 [Si6 O18 ]O9 (O, OH, F)4 (X = Na+ , Ca2+ ; Z = Al3+ , Mg2+ ; Y = Li+ , Mg2+ , Fe2+ , Mn2+ , Fe3+ , Al3+ ); dioptase, Cu6 [Si6 O18 ] 6 H2 O); F) Dicyclosilicate: sechser double ring (milarite, KCa2 (Be2 Al) [Si12 O30 ] 0.75 H2 O)

Organic, Silicones) and modern nonclay ceramics (SiC, Si3 N4 ) ( Silicon Carbide). Modern life is not only determined by the use of synthetic polymers but also by the widespread application of silicates and products derived from them. For example, silicon forms the basis of microelectronics.
Table 1. Practical applications of natural silicates Mineral (rock) Kaolinite (kaolin) Smectite (bentonite) Uses Production, 106 t/a

1.1. Structural Classication


Silicates comprise the largest, most extensive, and manifold class of minerals. One reason is that the bond energy of the Si O bond is higher than that of the Si Si and Si H bonds (bond energies, kJ/mol: Si O, 452; Si Si, 222; Si H, 318). Comparison with the values for carbon (C O, 358; C C, 346; C H, 413) reveals why the skeletons in silicates are Si O Si O chains instead of the C C C chains in carbon chemistry. The second reason is the ease with which silicon oxygen tetrahedra can be linked to form rings, chains, layers, or three-dimensional frameworks. Diversity is increased by isomorphous substitution of silicon by small cations (mostly Al3+ , but also other tri- and divalent cations B3+ , Fe3+ , Ga3+ , Be2+ , Zn2+ , Mg2+ ). In the 2 : 1 clay mineral sauconite Zn3 [Si4x Znx O10 (OH)2 ], Si4+ is substituted by Zn2+ . Synthetic mica phases in which Co3+ and Ni3+ replace Si4+ have been reported [1]. The common coordination number of silicon bonded to oxygen is four, but a few silicates together with the SiO2 modication stishovite contain sixfold coordinated silicon, e.g., Mg[SiO3 ] (high-temperature modication), (NH4 )2 [SiP4 O13 ], Ca3 [Si(OH)6 ][SO4 ][CO3 ] 12 H2 O (thaumasite), modications of Si[P2 O7 ]. The most comprehensive classication of silicates is presented by Liebau [13] (Table 2). The term multiplicity (M ) denotes the number of single polyhedra, rings, chains, or layers that are linked to the complex anion. Dimensional-

Talc, pyrophyllite Feldspars Micas Olivine, forsterite Perlite

paper industry, ceramics, chemical and 25 (kaolin) pharmaceutical industries foundry molding sands, iron ore 7 pelletizing, oil well drilling, building (bentonite) industry, chemical and pharmaceutical industries ller, electrical insulation, ceramics 6 3.5 2.7 2.3 2.5 0.65 0.15

glass and ceramic industry, ller ller, electrical industry refractory masses, uxes, foundry molding sands lightweight material for thermal and sound insulation Vermiculite thermal insulation, ller, lightweight material Sillimanite refractory masses Andalusite refractory masses Kyanite refractory masses Mullite refractory masses Zircon refractory material, ceramics, zirconium compounds Spodumene, production of lithium petalite Beryl production of beryllium Chrysotil (high toxicity) asbestos Including nepheline, leucite: 4.510 6 t/a.

0.005 0.1

4 (1978)

Silicates ity refers to the innite extension of the anion: D = 0, groups; D = 1, chains; D = 2, layers; D = 3, framework. A silicate that contains double tetrahedra, as in Sc2 [Si2 O7 ] (thortveitite, Fig. 1B), is called a disilicate (M = 2, D = 0). Orthoenstatite Mg2 [Si2 O6 ] (Fig. 2A) is a monopolysilicate that contains single chains of silicon oxygen tetrahedra.

materials or silicates with high levels of defects or of unknown structure. Mineralogists classify the silicates into neso-, soro-, cyclo-, ino-, phyllo-, and tectosilicates (Table 3). In classifying silicates on the basis of the way in which the silicon oxygen tetrahedra are linked to each other, it should be remembered that the real structure is determined by the interaction between the [SiO4 ] tetrahedra and the nontetrahedral cations (Section 1.3).

1.2. Oligo- and Cyclosilicates


When not specied otherwise, references concerning structure, crystallographic data, or synthesis of the silicates mentioned are found in [1]. Single [SiO4 ] tetrahedra are found in monosilicates (Fig. 1A) such as forsterite Mg2 [SiO4 ], olivine (Mg, Fe)2 [SiO4 ], phenakite Be2 [SiO4 ], garnets M12 M6 [SiO4 ]3 3 2 (M12 = Mg2+ , Fe2+ , Mn2+ ; M6 = Al3+ , Fe3+ , Cr3+ ), and zircon Zr[SiO4 ]. Because of the high charge of the [SiO4 ]4 anion, the stability of monosilicates increases in the order:
K4 [SiO4 ] < Ca2 [SiO4 ] < Ca3 Al2 [SiO4 ]3 < Zr[SiO4 ] Figure 2. Monopolysilicates A) Zweier single chains (pyroxenes); B) Dreier single chains (wollastonite, Ca3 [Si3 O9 ]

Sometimes, particularly in the technical literature, silicates of composition MO 2 SiO2 , MO 3 SiO2 (M = metal) are called di- and trisilicates, respectively. This practice is in contradiction to IUPAC rules and must be abandoned. Also, the term metasilicates for silicates M2 SiO3 , MSiO3 , M2 (SiO3 )3 should be abandoned because these silicates can be cycloor polysilicates. Connectedness of [SiO4 ] tetrahedra is a further parameter that should be mentioned in classifying silicate structures. A [SiO4 ] tetrahedron can share common oxygen ions with 0, 1, 2, 3, or 4 [SiO4 ] tetrahedra; this is indicated by Q0 , Q1 , Q2 , Q3 , or Q4 , respectively. The connectedness of silicon oxygen tetrahedra can be obtained from magic angle spinning NMR (MAS NMR) measurements. This is particularly advantageous in the study of amorphous

Examples of disilicates (Fig. 1 B) are thortveitite and barysilite MnPb8 [Si2 O7 ]3 . Synthetic Ag10 [Si4 O13 ] is a tetrasilicate. Oligosilicates with unbranched chains M = 8, 9, 10 have been synthesized. A few monocyclosilicates (with single rings, M = 1) and a dicyclosilicate are shown in Figure 1 C F. Several mono- and cyclosilicates are of practical importance. Magnesium silicate, Mg2 [SiO4 ], is used as a refractory material (forsterite products, Section 2.4). Olivine (ca. 2.3106 t/a) is mainly used as ux for slags in blast furnaces but small amounts are needed as foundry molding sands (Section 2.4). Garnets are utilized as bearings, polishing powder, abrasive products, and precious stones. (The garnets used as ferrimagnetic materials are yttrium and rare-earth iron garnets M3+ Fe5 O12 3 which consist of [FeO4 ] tetrahedra in place of [SiO4 ] tetrahedra.) Thortveitite (with scandium ions partially substituted by yttrium ions) is an important scandium mineral.

Silicates

Table 2. Classication of silicates [1] Dimensionality 1 0 0 1 2 3 Oligosilicates Cyclosilicates Polysilicates Phyllosilicates Tectosilicates monosilicates monocyclosilicates monopolysilicates monophyllosilicates tectosilicates 2 disilicates dicyclosilicates dipolysilicates diphyllosilicates Multiplicity 3 trisilicates tricyclosilicates tripolysilicates triphyllosilicates 4 tetrasilicates tetracyclosilicates tetrapolysilicates tetraphyllosilicates

Table 3. Nomenclature of silicates used by mineralogists Dimensionality 1 0 0 1 2 3 nesosubsilicates nesosilicates 2 sorosilicates cyclosilicates inosilicates phyllosilicates Multiplicity 3 4

tectosilicates

Several oligo- and cyclosilicates are valued as semiprecious or precious stones: garnets, olivine (chrysolite), zircon (hyacinth, jargon), beryl (emerald, aquamarine, heliodor, dioptas), turmaline (rubellite, schorl, indigolit). Zircon is an abundant accessory mineral, for example in glass ceramics ( Glass Ceramics). The radioactivity of rocks is often caused by the thorium and uranium content in zircon.

contain dreier single chains, for example wollastonite (Ca3 [Si3 O9 ], modications 1T, 2M, 7T, Fig. 2 B). Wollastonite is used as a ceramic material, as a ller in plastics and paints, and as a substitute for asbestos.

1.3. Polysilicates
Monopolysilicates. Polysilicates are abundant minerals, several are of practical importance. Single- chain polysilicates (dimensionality 1, multiplicity 1) are classied according to the number of silicon oxygen tetrahedra contained in the repeat unit of the chain (periodicity, P = 2, 3, etc.). Figure 2 shows polysilicate single chains with periodicities of two and three. Monopolysilicates are known with periodicities in the range 3 24 (P = 24 in synthetic Na24 Y8 [Si24 O72 ] [1]). The large group of pyroxenes (Fig. 2 A) consists of monopolysilicates with zweier single chains. Examples include enstatite (Mg2 [Si2 O6 ]), diopside (CaMg[Si2 O6 ]), and spodumene (LiAl[Si2 O6 ]). Spodumene is a source for lithium ( Lithium and Lithium Compounds, Chap. 3.1.1.) and glass ceramic production ( Glass Ceramics). Enstatite and diopside are sometimes found in ceramic masses ( Glass Ceramics). Several calcium silicates

Figure 3. Dipolysilicates A) Einer double chain (high-temperature sillimanite, Al6 [AlSiO5 ] (hT)); B) Zweier double chain (amphiboles, e.g., tremolite, Mg5 Ca2 [Si4 O11 ]2 (OH)2 ); C) Dreier double chain (xonotlite, Ca6 [Si6 O17 ](OH)2 ; D) Dreier double chain (epididymite, Na2 Be2 [Si6 O15 ] H2 O)

Dipolysilicates. The arrangement of the tetrahedra in sillimanite (high-temperature modication) is shown in Figure 3 A. However, the tetrahedral Al3+ and Si4+ ions are almost completely ordered so that sillimanite contains zweier double chains (Fig. 3 B) [1]. Zweier double chains are also the skeletons in am-

Silicates phiboles (Fig. 3 B). Xonotlite and epididymite are dipolysilicates with dreier double chains (Fig. 3 C, D).

polyanion assumes the form of a zweier single chain with the identity period distinctly smaller than in enstatite. Further examples of the adaptation of the silicate chain to edge-sharing [MO6 ] octahedra are shown for pyroxenes and pyroxenoids in Figure 5 [4].

Figure 4. Mutual adjustment of polysilicate anions and columns of [MO6 ] octahedra A) Enstatite, Mg2 [Si2 O6 ]; B) Wollastonite, Ca3 [Si3 O9 ] (low-temperature modication); C) Synthetic Ba2 [Si2 O6 ] (high-temperature modication) Na2 Be2 [Si6 O15 ] H2 O) Figure 5. Adjustment of polysilicate anions to slabs of [MoO6 ] octahedra A) Ferrosilite-III, FeSiO3 (high-temperature, medium-pressure modication) neuner single chain and [FeO6 ] octahedra; B) Pyroxmangite-type MnSiO3 (medium-pressure modication) (pyroxmangite = (Fe,Mn)7 [Si7 O21 ]), siebener single chain and [MnO6 ] octahedra; C) Rhodonitetype MnSiO3 (low-pressure modication) (rhodonite = (Mn, Ca5 )[Si5 O15 ]), single chain and [MnO6 ] octahedra

Oligopolysilicates. Synthetic oligopolysilicates are Ba4 [Si6 O16 ] (zweier triple chain), Ba5 [Si8 O21 ] (zweier fourfold chain), and Ba6 [Si10 O26 ] (zweier vefold chain). Inuence of Nontetrahedral Cations on the Structure of Polysilicates. The nontetrahedral cations exert a signicant inuence on the structure of polysilicates, in particular on their periodicity [4]. The mutual adaption of the conformation of the silicate chains to columns of [MOn ] polyhedra is shown for enstatite, wollastonite, and synthetic Ba2 [Si2 O6 ] (high-temperature modication) in Figure 4. The dimensions of two [MgO6 ] octahedra (ionic radius of Mg2+ : 0.072 nm) in enstatite (Fig. 4 A) correspond to the repeat unit (identity period; two tetrahedra) of the stretched zweier single chain. In wollastonite (Fig. 4 B) the dreier single chain ts the column of the considerably larger [CaO6 ] octahedra (two octahedra and three tetrahedra; ionic radius of Ca2+ : 0.10 nm). A further increase of the ionic radius of the octahedral cation (Ba2+ : 0.135 nm) allows the adjustment of two [SiO4 ] tetrahedra to one [BaO6 ] octahedron: the

Other factors besides the size of the nontetrahedral cations (e.g., electronegativity and valency) also control the conformation of the polysilicate anion [2, 4].

1.4. Phyllosilicates
1.4.1. Monophyllosilicates Layers of silicon oxygen tetrahedra are formed when silicate single chains are linked with each other. A simple possibility is to build up the zweier single layer (Fig. 6) by connecting zweier single chains. The term directedness indicates the way in which the apical oxygen ions of the [SiO4 ] tetrahedra are oriented. In Figure 6 A all apical oxygen ions point in the same direction.

Silicates

Figure 6. Formation of a zweier single-layer phyllosilicate by linking zweier single chains A) Unfolded layer with terminal oxygen ions pointing in the same direction; B) Folded layer with terminal oxygen ions pointing up and down: Li2 [Si2 O5 ]; C) Folded layer in petalite, Li[4] Al[4] [Si2 O5 ]2

In many other cases, however, they point in opposite directions (Fig. 6 B, C; Fig. 7).

Figure 7. Folding of tetrahedral layers in anhydrous monophyllosilicates A) Li2 [Si2 O]5 ; B) -Na2 [Si2 O5 ]; C) -Na2 [Si2 O5 ]; D) Sanbornite, Ba[Si2 O5 ] (low-temperature modication)

The layers shown in Figure 6 are highly exible, even when the terminal oxygen ions alternate between both sides. The layers can be stabilized in three ways: 1) The layers are folded 2) The layers are linked to form diphyllosilicate anions or structures with higher multiplicities 3) The layers are linked to octahedral layers of nontetrahedral cations (Section 1.4.5)

Folded zweier single layers are found in several alkali and barium phyllosilicates (Fig. 7 A D). The degree of folding depends on the cation. The layers are highly folded in Li2 [Si2 O5 ] (Fig. 7 A). The occurrence of different modications of Na2 [Si2 O5 ] (Fig. 7 B, C) reveals that the convolution (degree of folding) is not only determined by the nontetrahedral cation. A divalent cation must balance the charge of two [SiO4 ] tetrahedra. This increases the folding of the layer. The silicates Ca[Si2 O5 ] and Sr[Si2 O5 ] do not exist because the folding of the layers, which in turn is a consequence of the electrical eld of the cations, provides coordination numbers too small for calcium and strontium ions. In the presence of barium ions (Fig. 7 D), which have a larger ionic radius, the degree of folding is not as large and provides sites for barium ions with sufciently high coordination numbers (9 in sanbornite Ba[Si2 O5 ], low-temperature modication). Anhydrous, single-layer silicates containing solely trivalent cations are not known because even strong convolution cannot produce a wellbalanced charge distribution. However, Li+ and Al3+ form a very stable, anhydrous, layer silicate with highly folded layers (petalite, Li[4] Al[4] [Si2 O5 ]2 , Fig. 6 C). The stability is related to the tetrahedral coordination of Li+ and Al3+ ions which is a consequence of the high degree of layer folding induced by the trivalent aluminum ion.

Silicates Examples of monophyllosilicates with layers composed of silicate chains with P > 2 are apophyllite (Fig. 8) and gillespite BaFe[Si4 O10 ] with vierer single layers. Synthetic CaCu[Si4 O10 ], isostructural to gillespite, was used as a blue pigment in wall paintings (Egyptian Blue). The mineral name is cuprorivaite. 1.4.3. Alkali Silicates

See also Chapter 3. Among the anhydrous alkali silicates only natrosilite, Na2 [Si2 O5 ], occurs as a mineral [5]; all others are synthetic. Na4 [Si2 O6 ] is a monopolysilicate containing zweier single chains. Most of the alkali silicates are monophyllosilicates with zweier single layers: Li2 [Si2 O5 ] (Fig. 7 A); -, -Na2 [Si2 O5 ] (Fig. 7 B, C); Na4 [Si6 O14 ]; KH[Si2 O5 ] [6]; and K2 [Si4 O9 ]. Silicates with Si : O ratios < 2 : 5 contain Q4 tetrahedra besides the Q3 tetrahedra. Potassium analogues of Na2 [Si2 O5 ] are unknown [1]. Anhydrous alkali silicates are formed when quartz is melted with sodium or potassium carbonate or hydroxide (alkali silicates, waterglass). The reaction product is dissolved in water to form waterglass solutions. -Na2 [Si2 O5 ] is considered as a builder and possible substitute for zeolites in washing powders [7]. Several hydrated alkali silicates occur as minerals:
Kanemite NaH[Si2 O5 ] 3 H2 O [8] Makatite Na2 [Si4 O8 ](OH)2 4 H2 O [9] Magadiite Na2 [Si14 O29 ] 11 H2 O [10] Kenyaite Na2 [Si20 O41 ] xH2 O [10] Revdite Na2 [Si2 O5 ] 5 H2 O [11] Grumantite NaH[Si2 O5 ] 0.9 H2 O [12] Silinaite NaLi[Si2 O5 ] 2 H2 O [13] MAS NMR measurements reveal that the formula should be written as Na2 H2 Si14 O30 xH2 O, Na2 H2 Si20 O42 xH2 O [14]. Eugster [10] reported the composition Na2 Si22 O45 10 H2 O for kenyaite.

Figure 8. Vierer single layer in apophyllite, KCa4 [Si4 O10 ]2 (F, OH) 8H2 O

1.4.2. Diphyllosilicates Stabilization of zweier single layers by linkage to diphyllosilicate anions is illustrated in hexacelsian, Ba(AlSiO4 )2 (high-temperature modication, Fig. 9). Further examples are vierer double layers in naujakasite and reyerite and even neuner double layers in stilpnomelane.

Figure 9. Diphyllosilicates: zweier double layer in hexacelsian, Ba[(Al, Si)O4 ]2 high-temperature modication

The structures of sodium monosilicates Na2 H2 [SiO4 ] xH2 O (x = 1 8) [15], makatite [16], and silinaite have been determined [13]. Makatite contains vierer single layers. The zweier single layer in silinaite shows a directedness not observed previously: the slightly kinked zweier single chains alternate such that in one chain the apices point up and in the adjoining chain the apices point down. The different dimensions of the [LiO4 ] tetrahedra and [NaO2 (OH2 )4 ] octahedra which hold the layers together, impose a slight wave in the silicate layer. The natural alkali silicates and several other alkali silicates (Na2 H2 Si8 O18 xH2 O [17]; K2 H2 Si14 O30 xH2 O; K2 H2 Si20 O42 xH2 O) can be easily synthesized from dispersions of SiO2 in aqueous NaOH or KOH solutions [17 20]. A characteristic property of these sili-

Silicates

Figure 10. Preparation of crystalline silicic acids from alkali phyllosilicates by exchanging protons for the interlayer cations

Figure 11. Clay mineral structure A) Zweier single layer (tetrahedral sheets); B), C) Layers of edge-sharing [MO6 ] octahedra (octahedral sheets) Clay minerals with octahedral sheets as in (B) are called trioctahedral, those with sheets (C) are called dioctahedral.

cates is their cation exchange capacity (see Section 1.4.4). Possible practical uses include ion exchangers, adsorbents, or builders in detergents [21]. 1.4.4. Crystalline Silicic Acids Exchanging protons for the cations sandwiched between the silicate layers transforms the alkali phyllosilicates into crystalline acids (Fig. 10). In spite of the fact that the rst crystalline silicic acid was prepared from -Na2 Si2 O5 in 1924

[22], most textbooks of inorganic chemistry refer to the orthosilicic acid Si(OH)4 as the only oxo acid of silicon. The crystal structures of two H2 Si2 O5 acids prepared from -Na2 Si2 O5 were determined by Liebau [23]. Presently, more than 15 crystalline acids are known and comprise at least six modications of H2 Si2 O5 . The acids are derived from the natural and synthetic alkali silicates mentioned above, from several synthetic and natural cuprous silicates, and from a few other silicates such as apophyllite, carletonite, and gillespite [2426]. The acids derived from

Silicates Na2 H2 Si14 O30 xH2 O, K2 H2 Si14 O30 xH2 O, and K2 H2 Si20 O42 xH2 O have been considered for practical uses. These acids are interesting alternatives to various forms of silica. Practical applications may be related to adsorption properties [27] and the capability to intercalate neutral organic molecules (Section 1.4.6). A few acids even adsorb anionic surfactants (together with the gegen ions) in the interlayer space [28].

rectedness. The terms clays, kaolins and bentonites are used somewhat differently by geologists and in practical applications (see Chaps. 1, 5, 7 in [31]). A clear distinction must be made between clay (the rock) and clay mineral (the mineral) [32]. 1: 1 Clay Minerals. In kaolinite (Al2 [Si2 O5 (OH)4 ]) all terminal oxygen ions of the zweier single layer (tetrahedral sheet) point to one side and simultaneously belong to the octahedral sheet (Figs. 11 A, 12 A,13 A). Thus, the octahedra around the octahedral cations consist of these oxygen ions and additional OH ions.

Figure 12. Linking of zweier single layers to octahedral sheets (dotted areas) in clay minerals A) Kaolinite, Al2 [Si2 O5 (OH)4 ]; B) Antigorite, idealized Mg3 [Si2 O5 (OH)4 ]

Figure 13. Linking of tetrahedral and octahedral sheets in clay minerals A) 1 : 1 clay minerals (kaolinite, serpentines); B) 2 : 1 clay minerals (micas, vermiculites, smectites)

1.4.5. Clay Minerals See also Chapter 2. In clay minerals (Table 4) zweier single layers (Fig. 11 A) are linked to octahedral sheets (Fig. 11 B, C). (In clay mineralogy the single tetrahedral and octahedral layers are called tetrahedral and octahedral sheets; the assembly of these sheets is called a layer [29].) The structures provide a good example of different types of di-

As the dimensions of the octahedral and the tetrahedral sheets do not match exactly (boct = btetr , Fig. 11), mechanical stress arises between both sheets (for details see [1, 29]). This causes curling of the crystals when their thickness decreases below a certain value [33]. Halloysite crystals are composed of kaolinite-type layers separated by a water layer, and often assume a tubular morphology. The mist between both types of sheets in the serpentine minerals (chrysotile, antigorite, lizardite), which are the trioctahedral counterparts of kaolinite (idealized formula Mg3 [Si2 O5 (OH)4 ]), also leads to the curling of

10

Silicates

Table 4. Classication of 1 : 1 and 2 : 1 clay minerals [30] a Layer type 1: 1 kaolin serpentine Layer type 2: 1 0 0.2 0.6 tri di tri di tri Group Octahedral character b Predominant octahedral cation c Mg2+ Al3+ Mg2+ Al3+ Mg2+ Zn2+ Mg2+ , Li+ Al3+ Fe3+ Cr3+ Mg2+ Al3+ Al3+ Mg2+ Mg2+ , Fe2+ , Fe3+ Li+ , Al3+ Al3+ Fe3+ , Al3+ Fe3+ , Al3+ , Mg2+ , Fe2+ Mg2+ , Al3+ Al3+ Al3+ , Mg2+ Species

lizardite, chrysotile d , antigorite d kaolinite, halloysite d talc, willemseite pyrophyllite stevensite, saponite sauconite hectorite montmorillonite, beidellite nontronite volkonskite (trioctahedral) vermiculite dioctahedral vermiculite

talc pyrophyllite smectite

di

0.6 0.9 0.6 0.9 0.6 1

vermiculite illites mica

tri di di tri( ?) tri

di

phlogopite biotite lepidolite muscovite, illite glauconite celadonite clintonite margarite clinochlore donbasseite sudoite

ca. 1.8 2 Variable

brittle mica chlorite

tri di tri di di tri e

Layer charge (equivalents/unit), see general formula in page 11; Tri- or dioctahedral; c Exact compositions see [31, Chap. 2]; d Nonplanar phyllosilicates; e Interlayer: dioctahedral, 2: 1 layer: trioctahedral.
b

the chrysotile crystals. This results in the formation of tubes (tubular morphology of asbestos) or in the alternation of the terminal oxygen ions in a bandlike manner as in antigorite (Fig. 12 B). The major mineral of this group is kaolinite, the most important mineral in kaolins. Total world production was ca. 25106 t in 1992 (US Bureau of Mines, 1992) ( Clays). It is used in the ceramic industry (ca. 20 %) and as a ller and coating pigment in paper production (ca. 50 %) [31,34]. Kaolin is also needed for the production of zeolites ( Zeolites) and ultramarines ( Pigments, Inorganic, Chap. 3.5.). 2: 1 Clay Minerals. 2 : 1 clay minerals consist of two zweier single layers (tetrahedral sheets) which enclose a central octahedral sheet (Fig. 13 B). The diversity of this group of phyllosilicates (Table 4) results from:

1) The occurrence of di- and trioctahedral layers (Fig. 11 B, C) 2) Isomorphous substitutions in the octahedral sheet 3) Isomorphous substitutions in the tetrahedral sheet, mainly Al3+ for Si4+ In addition, cationic sites can be vacant, and protons may dissociate from OH ions or associate to them or to O2 ions. Depending on the type and concentration of the substitutions and defects, the layers can assume negative charges. The number of charges per formula unit ([(Si,Al)4 O10 ] unit) is the most essential parameter used to characterize the 2 : 1 clay minerals. The chemical composition of the 2 : 1 clay minerals is represented by:

Silicates
M + / (H2 O)n Interlayer space {(M3+ , M2+ , M+ )(6 x 23 [Si4 y Aly O10 (OH)2 ]} Layer
)+

11

where is the valency of the interlayer cation and is the layer charge. The general formula indicates that the number of octahedral cations (M3+ , M2+ , M+ ) varies between 2 and 3. Mostly, the occupancy is near 2 (dioctahedral minerals) or 3 (trioctahedral minerals). An extensive survey of chemical compositions is given in [31].

Figure 14. Structural relations between some silicates A) Talc, Mg3 [Si2 O5 ]2 (OH)2 ; B) Palygorskite, idealized Mg5 [Si2 O5 ]4 (OH)2 (OH2 )4 4 H2 O, for exact formula see [29]; C) Sepiolite, idealized Mg4 [Si2 O5 ]3 (OH)2 4 H2 O, for exact formula see [29]

In Table 4, the clay minerals are classied according to their layer charge and their di- or trioctahedral character. The silicates with uncharged layers are pyrophyllite (idealized Al2 [Si4 O10 (OH)2 ]) and talc (Mg3 [Si4 O10 (OH)2 ]). Talc (Fig. 14 A) is a raw material in the ceramic industry ( Talc). It

is used in the production of insulating materials ( Insulation, Electric, Chap. 3.1.2.2.), as a ller (paper, paints, cosmetics, elastomers, thermoplastics), and as a carrier material for pesticides. Pyrophyllite nds similar uses [31]. Montmorillonite is the most important smectitic mineral (Table 4) of the bentonite rocks ( Clays). The various applications of bentonites (production ca. 8106 t in 1992; US Bureau of Mines, 1992) are based on the special properties of montmorillonite, in particular its ne particle size (< 2 m), intracrystalline reactivity (swelling in water and organic liquids, ionexchange properties, see Section 1.4.6), binding of organic materials and colloidal behavior [31]. Only a few of the many hundreds of applications ( Clays, Chap. 5.2.) [31, 35] are mentioned here. The special rheological properties of bentonites are exploited in the application as a foundry sand binder, for oil well drilling, iron ore pelletizing, in the building industry (in particular for subterranean curtains), in geotechnics, and as sealing materials; for pelletizing animal feed, as llers and adsorbents (e.g., in clarifying and decolorizing mineral, animal and vegetable oils, beer, and fruit juices) and as a carrier material for pesticides. The protable use as pet litter should not be overlooked. Synthetic smectites are hectorite-type materials which are produced more easily than montmorillonites under mild hydrothermal conditions. Hectorite is a very low- charged smectite ( 0.20 0.25 eq/unit) that contains Li+ ions in the octahedral sheet. It has similar uses to bentonite [36]. The synthetic materials are used in the pharmaceutical industry (e.g., as thickeners, thixotropic agents, gel-forming materials) and seem to provide suitable properties as components in muds for drilling very deep wells [31, 35]. The largest amounts of vermiculite (production about 0.65106 t/a) are used in the form of light, expanded aggregates consisting of exfoliated crystals (see Section 2.9). Illites are very ne, mica-type minerals, and essential components of soils. Mica is used in the form of sheets, ground powders, or micronized and is described in detail elsewhere ( Mica). Most synthetic products are uorinated micas. Formation of uorophlogopite in glass ceramics gives this mate-

12

Silicates 1.4.6. Intracrystalline Reactions Kaolinite, 2 : 1 clay minerals, and alkali phyllosilicates are intracrystalline-reactive, layered materials [38]. The interlayer space is accessible to guest molecules or ions (Fig. 15).

rial a precision machinability with conventional metal-working tools ( Glass Ceramics) [37]. Chlorites. Chlorites are composed of silicate layers (similar to the 2 : 1 clay minerals mentioned above) that are separated by metal hydroxide layers M(OH)2 or M(OH)3 [29]. Chlorites are not used on an industrial scale but are abundant in soils and are found in clays. Mixed-Layer Minerals. Mixed-layer minerals are very abundant in common clays and soils. The crystals are composed of layers which either differ in the composition and layer charge or are of different structural types. In most cases, the sequence of the layers is random. Typical combinations are [31] illite smectite, mica vermiculite, mica chlorite, smectite chlorite, chlorite vermiculite, and kaolinite smectite. Some mixed-layer minerals also have a regular sequence of layers [31]:
Rectorite Tosudite = muscovite (or paragonite) montmorillonite = dioctahedral chlorite smectite

Corrensite = chlorite vermiculite (or trioctahedral smectite)

Palygorskite and Sepiolite. Palygorskite (Fig. 14 B) and sepiolite (Fig. 14 C) provide further examples of phyllosilicates with single layers of different directedness. The twodimensional octahedral sheet is split into onedimensional bands comprising eight or ve octahedra. In the tetrahedral sheet some of the tetrahedra are inverted. Bands of three zweier single chains with different directedness alternate in sepiolite whereas the bands in palygorskite are composed of two zweier single chains. Channels are therefore formed in the structure which contain water molecules and exchangeable cations. The cations are bound as a consequence of isomorphous substitutions in the tetrahedral and octahedral sheets. The minerals have zeolitic properties and show a certain cation-exchange capacity. Sepiolite crystallizes as bers with diameters of 5 30 nm and a length of 10 nm 4 m. Fibers of palygorskite are 15 30 nm thick and 0.5 4.5 m long. Sepiolite and palygorskite are being increasingly used as thickeners, thixotropic agents, adsorbents, supports of pesticides and catalysts, and pet litter [31].

Figure 15. Intracrystalline reactions of phyllosilicates A) Phyllosilicates with uncharged layers (kaolinite, crystalline silicic acids); B) Phyllosilicates with charged layers (2 : 1 clay minerals, hydrated alkali silicates)

Kaolinite takes up various organic compounds (urea, hydrazine, dimethyl sulfoxide, short- chain acid amides, potassium and ammonium acetate) between the layers so that they are separated by a mono- or bilayer of neutral guest molecules (Fig. 15 A). In most cases, these molecules can be displaced by other molecules [31]. Intercalation of organic compounds promotes delamination of kaolinite particles and can improve the mechanical stability of porcelain. Kaolin modied by intercalation of urea was used in China (mainly in the Sung period, 960 1280) in the production of very thin porcelain (egg-shell porcelain) [39]. The most striking difference between the behavior of di- and trioctahedral minerals is that the

Silicates trioctahedral 1 : 1 clay minerals such as antigorite do not intercalate guest molecules. Pronounced intercalation capability is observed for the crystalline silicic acids [28, 38]. Intracrystalline-reactive phyllosilicates with charged layers can undergo various reactions (Fig. 15 B) [31]. Most important for technical applications is the intracrystalline swelling of smectites by interlamellar adsorption of water. The layer separation of calcium smectites does not normally exceed 1 nm. In the presence of sodium ions, however, the layers separate completely and form colloidal dispersions [31]. This process and the related changes in ow behavior are of great importance in many practical applications (building industry, subterranean curtains, foundry sand binder, oil well drilling uids etc. [31]). A further essential reaction is the exchange of the interlayer cations [31]. Soda activation is an important technical process in which interlayer calcium ions are displaced by sodium ions. Fixation of potassium ions by more highly charged 2 : 1 clay minerals plays an important role in soils. Clay minerals are considered as useful adsorbents in environmental technology because of their ability to bind heavy metal ions by cation exchange [31, 40, 41]. Radioactive nuclides may be removed by clay adsorbents, for instance cesium ions by vermiculites and shales [42]. Even radioactive iodide ions can be adsorbed by modied clay minerals [43]. The third reaction of technical importance is the binding of organic cations. Organo-modied bentonites are used in many applications, mainly as adsorbents, thickeners, or thixotropic agents in organic systems (lubricants, greases, paints, or asphalt). In environmental technology, organic derivatives of clay minerals adsorb toxic substances [31, 40, 41, 44].

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a tridymite structure (Section 2.2). The feldspars (Section 2.1) have loop-branched dreier frameworks (Fig. 16 B) based on a branched dreier single chain. The black tetrahedra in Figure 16 B form a dreier single chain and additional tetrahedra (stippled) bridge two tetrahedra of this chain [3]. Cordierite, Mg2 [(Al4 Si5 )O18 ], has an openbranched vierer framework.

1.5. Tectosilicates
Almost all tectosilicates (framework silicates) contain quaternary tetrahedra such that the ratio of tetrahedral cations to oxygen is 1 : 2. The fundamental chain periodicities are P = 2, 3, 4, 6: cristobalite, tridymite P = 2 (Fig. 16 A); quartz, keatite P = 3; zeolites: laumontite, gismondine, harmotone P = 4; chabazite, silicalite1 P = 6. Nephelines, (Na1x Kx )[AlSiO4 ], have
Figure 16. Framework silicates A) Zweier framework of tridymite [SiO2 ]; B) Loopbranched dreier framework of feldspars, e.g., orthoclase K[AlSi3 O8 ]

In Figure 16 the tetrahedral framework is thought to be composed of chains of a certain multiplicity. Another more common view is to

14

Silicates The most important synthetic tectosilicates are the zeolites ( Zeolites) [49, 50]. Their Si/Al ratio varies considerably. The most startling development was the synthesis of the almost Al3+ free end members of silica-rich zeolites (ZSM5 = silicalite-1, ZSM-11 = silicalite-2).

look at the polyhedra which form the framework, and the voids or polyhedral cavities generated between the framework oxygen ions. The notation [512 ], for example, indicates a polyhedron composed of 12 pentagonal faces (a pentagondodecahedron); [512 62 ] is a polyhedron with 12 pentagons and two hexagons (see Fig. 17). According to the nature of the voids and polyhedral cavities tectosilicates can be divided into three groups [4547]: 1) Pyknosiles. Tectosilicates which have no polyhedral cavities but small interstices between the framework oxygen ions; these voids can be occupied by cations and sometimes water: quartz, cristobalite, tridymite, feldspars. 2) Clathrasils. Tectosilicates with polyhedral cavities. The windows of the cages are small and the encaged ions, molecules, or their decomposition products cannot diffuse through them: melanophlogite, dodecasils, sodalite ( Silica, Chap. 8.2.2.). 3) Zeolites. The polyhedral cavities are interconnected by large windows or tunnels, and the enclosed ions or molecules can diffuse through the crystal: analcime, mordenite, faujasite, zeolite A, silicalite (ZSM-5) ( Zeolites). Under hydrothermal conditions silica crystallizes from aqueous solutions as quartz, cristobalite, keatite, or coesite ( Silica) [47, 48]. In the presence of inorganic or organic guest compounds, clathrasils are formed. The neutral molecules become enclosed in the polyhedral cavities during synthesis. The guest compounds act as templates for the formation of the polyhedra, thus determining the type of clathrasil [46, 48]. Figure 17 shows polyhedra of melanophlogite and dodecasils occupied by guest molecules. The orientation of the molecules in the cages was derived from single- crystal X-ray diffraction [48]. Minerals of technical importance are the feldspars orthoclase K[AlSi3 O8 ], albite Na[AlSi3 O8 ], and anorthite Ca[Al2 Si2 O8 ] (Section 2.1). The largest amounts of feldspars (and nepheline) are used in the glass and ceramic industries, mainly as uxes. Cordierite glass ceramics have good thermal stability and shock resistance ( Glass Ceramics).

Figure 17. Guest molecules included in cages of the host framework of clathrasils A) Xenon in the [512 ] cage of melanophlogite; B) CO2 in [512 62 ] of melanophlogite; C) Piperidine in [512 64 ] of dodecasil 3C; D) Adamantylamine in [512 68 ] of dodecasil 1H

2. Natural Silicates
2.1. Feldspar
Feldspars [68476-25-5] are anhydrous alkali/alkaline-earth aluminosilicates that closely resemble each other in structure and properties. They are among the most common and important mineral groups, constituting ca. 60 65 wt % of the Earths crust. Approximately two-thirds of them occur as plagioclases. 2.1.1. Structure and Composition The feldspars are tectosilicates (framework silicates, see Chap. 1). The [(Si, Al)O4 ] tetrahedra are linked at all four vertices yielding a

Silicates framework [Si4x Alx O8 ]x . The voids within the tetrahedral framework contain alkali metal or alkaline-earth ions for charge compensation. The structure is composed of four-membered rings, [(Si, Al)4 O12 ], containing (Al Si3 ) or (Al2 Si2 ) in each ring. The rings are linked by common oxygen atoms (two on each side) in the a direction to two neighboring rings to form zigzag bands (or double crank-shaft chains) making use of three of the four common vertices. These bands are bonded in both the b and c direction by the fourth common oxygen atom of each (Si, Al) atom (see Fig. 18: in the b direction in y = 0 or 1/2, in the c direction in y = 0.14 or 0.36) to form three-dimensional tetrahedral frameworks. As a result, the (010) and (001) planes are rather weakly bonded and readily cleaved. This property is characteristic of all feldspars. The cations K+ , Na+ , and Ca2+ , and more rarely Sr2+ and Ba2+ , occupy the large spaces within the framework of tetrahedra, and are coordinated to oxygen in a fairly irregular manner.

15

3) Ca[Al2 Si2 O8 ] = calcium feldspar = anorthite (An) In nature, these three substances seldom occur in a pure state. At high formation temperature (e.g., in some volcanic rocks), a solid solution series between Or and Ab exists: the alkali feldspars. On slow cooling [i.e., in most plutonic (igneous) rocks] an immiscibility gap below 650 C leads to partial unmixing (perthitization). Albite and anorthite form an almost innite solid solution series: the plagioclases. Between orthoclase and anorthite a wide immiscibility gap exists (see Figs. 19, 20, 21).

Figure 19. Triangular phase diagram of orthoclase albite anorthite showing mixed crystal formation found in nature (at ca. 700 C)

Figure 18. Structure of orthoclase, projection parallel to b on (010) showing two crank-shaft bands along a0

Three main types of feldspar (molecules) can be distinguished: 1) K[AlSi3 O8 ] = potassium feldspar = orthoclase (Or) 2) Na[AlSi3 O8 ] = sodium feldspar = albite (Ab)
Figure 20. Phase diagram of the alkali feldspars

16

Silicates consists of microcline containing albite strings, and antiperthite consists of albite with orthoclase strings. The feldspars are very widely distributed, mainly in igneous rocks (volcanic and plutonic rocks) and metamorphic rocks (contact and regional metamorphites). They also occur in pegmatitic and hydrothermal formations, sedimentary rocks and sediments. This means that the petrographic classication of rocks is largely based on the mass ratios and compositions of the individual feldspars and quartz. If there is a deciency of SiO2 , leucite K[AlSi2 O6 ] (see Section 2.3) or nepheline Na[AlSiO4 ] (see Section 2.2) is formed instead of the alkali feldspars. 2.1.2. Characterization of Individual Feldspars The alkali feldspars can have monoclinic and triclinic crystal forms, but the plagioclases only triclinic forms. The most important feldspars follow. Potassium Feldspars. The term sanidine denotes the metastable, glass- clear monoclinic high form of K[AlSi3 O8 ] with a random distribution of (Al, Si) produced by rapid cooling in volcanic rocks (volcanites). During the very slow cooling of plutonic rocks (plutonites) an Al/Si ordering takes place to a greater (triclinic microcline) or lesser (orthoclase) extent. Orthoclase is not visibly triclinized despite prolonged cooling in plutonites. Sanidine melts incongruently with separation of leucite. Sanidine (the high-temperature form of K[AlSi3 O8 ]) forms monoclinic prismatic crystals, with space group C3 C 2/m; lat2h tice constants: a0 = 0.856 nm, b0 = 1.303 nm, c0 = 0.718 nm (a0 , b0 , and c0 are somewhat smaller when sodium is present); the axial ratio is a0 : b0 : c0 = 0.657 : 1 : 0.551; = 115 59 ; Z = 4 (number of chemical formula units per unit cell). Orthoclase (the intermediate form of K[AlSi3 O8 ]) forms monoclinic prismatic crystals, with space group C3 C 2/m; lat2h tice constants: a0 = 0.856 nm, b0 = 1.300 nm, c0 = 0.719 nm; the axial ratio is a0 : b0 : c0 = 0.659 : 1 : 0.553; = 116 01 ; Z = 4.

Pure potassium feldspar has the composition 64.8 wt % SiO2 , 18.3 wt % Al2 O3 and 16.9 wt % K2 O. Potassium can be replaced by rubidium to a small extent, with the rubidium content in orthoclases from pegmatites reaching ca. 3 wt %. In the plagioclases, the Al2 O3 content increases on going from the acidic to the basic types: from >19 wt % in albite to almost 37 wt % in anorthite with a concomitant decrease in the SiO2 content from almost 69 wt % in albite to 43 wt % in anorthite.

Figure 21. Phase diagram of plagioclases (dry mp can be lowered by 500 C in the presence of water)

All feldspars have a high- and a low-temperature form. In the high form, the distribution of [SiO4 ] and [AlO4 ] tetrahedra is at random, while in the low form there is a high degree of order. There are also intermediate types with varying degrees of Al/Si order. Ordering changes the monoclinic orthoclase to triclinic microcline. The high forms of albite and anorthite and of albite and orthoclase are completely miscible, whereas the low forms are not. On slow cooling of the (K, Na) feldspars, segregation (perthite formation) takes place due to selective migration of the small and large cations (Fig. 20). This leads to a regular intergrowth of orthoclase (or microcline), and albite, with characteristic formation of string- or worm-shaped bodies, which can be macroscopic (macroperthite), microscopic (microperthite) or submicroscopic (cryptoperthite). Microcline perthite

Silicates Orthoclase often consists of thick platelets parallel to [010], extended in the [001] direction or having columnar development in the [100] direction. Crystals may be several centimeters or even tens of centimeters in size. Twinning is very characteristic. Microcline (the low-temperature form of K[AlSi3 O8 ]) forms triclinic pinacoidal crystals, with space group C1 C 1; lattice constants: i a0 = 0.857 nm, b0 = 1.298 nm, c0 = 0.722 nm; the axial ratio is a0 : b0 : c0 = 0.660 : 1 : 0.566; = 90 41 , = 115 59 , = 87 30 ; Z = 4. Barium Feldspars. Hyalophane, (K, Ba) [Al(Al, Si)Si2 O8 ], forms monoclinic (or pseudomonoclinic?) crystals, with space group C3 2h C 2/m; lattice constants: a0 = 0.854 nm, b0 = 1.298 nm, c0 = 0.715 nm; the axial ratio is a0 : b0 : c0 = 0.658 : 1 : 0.551; = 115 35 ; Z = 4. Celsian [001302-50-7], Ba[Al2 Si2 O8 ], forms monoclinic crystals, with space group I 2/c; lattice constants: a0 = 0.865 nm, b0 = 1.313 nm, c0 = 20.730 nm; the axial ratio is a0 : b0 : c0 = 0.659 : 1 : 20.556; = 115 02 ; Z = 8. Plagioclases. The plagioclases form ca. 40 % of the solid crust of the Earth and are widely distributed. At high temperature (see Fig. 21) there is complete miscibility between the end members anorthite, Ca[Al2 Si2 O8 ] (basic) and albite, Na[AlSi3 O8 ] (acidic). At lower temperature, miscibility is incomplete. The plagioclases are usually twinned along [010], leading to lamellar replication multiple twinning, and typical striation. The plagioclases have a structure similar to that of sanidine, the replacement of K+ by the smaller Na+ and Ca2+ ions leading to some deformation with triclinic symmetry. The lowcalcium plagioclases [albite (An010 ), oligoclase (An1030 ), and andesine (An3050 )] have a cell size similar to that of sanidine, with C 1 symmetry. The high- calcium plagioclases (labradorite (An5070 ), bytownite (An7090 ), and anorthite (An90100 )) show doubling of the c0 lattice constant, so that bytownite has I 1 symmetry and anorthite P 1 symmetry. The plagioclases are usually characterized by the content (in mol %) of anorthite (An), albite (Ab), and

17

orthoclase, whereby the content of orthoclase is usually negligibly small. An important characteristic of plagioclases is the degree of order, i.e., not only of (Al, Si), but also of (Na, Ca) and of (Na, Ca, K) in high-temperature mixed crystals containing potassium. The high- and low-temperature plagioclases can be distinguished optically. In the low-temperature plagioclases, there is an ordered distribution of (Al, Si). For example, in pure anorthite, which has no high-temperature form, the [AlO4 ] and [SiO4 ] tetrahedra alternate, whereby each oxygen is neighbored by an aluminum and a silicon ion. Despite the Al/Si disorder in high-temperature plagioclases, Al O Al groupings do not occur. Also, because the (Na, Ca) ions are smaller, the triclinic form is maintained at higher temperature, unlike sanidine. The triclinic high-temperature form of albite is also known as analbite. Monalbite is a monoclinic potassium-containing high-temperature phase of albite. Albite, Na[AlSi3 O8 ], An010 or Ab100 An00 Ab90 An10 ; C 1 lattice constants: a0 = 0.814 nm, b0 = 1.2789 nm, c0 = 0.716 nm; the axial ratio is a0 : b0 : c0 = 0.636 : 1 : 0.559; = 94 19 , = 116 34 , = 87 39 ; Z = 4. Oligoclase, An1030 or Ab90 An10 Ab70 An30 ; C 1 lattice constants: a0 = 0.817 nm, b0 = 1.284 nm, c0 = 0.713 nm; the axial ratio is a0 : b0 : c0 = 0.636 : 1 : 0.556, = 93 49 , = 116 27 , = 88 59 ; Z = 4. Andesine, An3050 or Ab70 An30 Ab50 An50 ; C 1 lattice constants: a0 = 0.818 nm, b0 = 1.288 nm, c0 = 0.711 nm; the axial ratio is a0 : b0 : c0 = 0.635 : 1 : 0.552; = 93 24 , = 116 10 , = 90 24 ; Z = 4. Labradorite, An5070 or Ab50 An50 Ab30 An70 ; C 1 lattice constants; a0 = 0.816 nm, b0 = 1.286 nm, c0 = 20.710 nm; the axial ratio is a0 : b0 : c0 = 0.635 : 1 : 20.552; = 93 34 , = 116 06 , = 89 47 ; Z = 8. Bytownite, An7090 or Ab30 An70 Ab10 An90 ; I 1 lattice constants: a0 = 0.817 nm, b0 = 1.287 nm, c0 = 1.418 nm = 20.709 nm; the axial ratio is a0 : b0 : c0 = 0.635 : 1 : 1.102; = 93 22 , = 115 58 , = 90 31 ; Z = 8. Anorthite, Ca[Al2 Si2 O8 ], An90100 or Ab10 An90 Ab0 An100 ; P 1 lattice constants: a0 = 0.818 nm, b0 = 1.288 nm, c0 = 1.417 nm = 20.785 nm; the axial ratio is a0 : b0 : c0 = 0.635 : 1 : 20.550; = 93 10 , = 115 51 , = 91 13 ; Z = 8.

18

Silicates The high-temperature form of albite, Na[AlSi3 O8 ], occurs in chamottes that have been exposed to Na2 O, e.g., in tank linings and checker bricks used in furnaces for glassmaking. -Celsian, -Ba[Al2 Si2 O8 ], is the principal component of special bricks used to line the arched roofs of the ring zones in electric tunnel furnaces for glazing stoneware and sanitary ware. It is very resistant to vapors from lead and borate glazes. Other refractory materials react with these vapors to form liquid phases. 2.1.4. Properties Physical Properties. Feldspars can be glass clear, transparent, translucent, cloudy, matt, colorless, white, gray, or colored (e.g., greenish, reddish, red, or brown) due to inclusions. Labradorite and orthoclase can be iridescent (labradorescent) and are used for decorative purposes. The feldspars can have a glassy or sometimes nacreous luster. Fused feldspars, even if originally dark in color, usually solidify as a transparent, colorless glass. Cleavage in the (001) plane is very good, moderate in the (010) plane, and just observable in the (110) plane [plagioclases also cleave in the (110) plane]. Orthoclase is named from the cleavages in the mutually perpendicular (001) and (010) planes. The plagioclases form triclinic crystals and owe their name to the fact that the angle between the (001) and (010) planes deviates by a few degrees from 90 . The fracture is conchoidal, uneven, and splintered or brittle. The Mohs hardness of albite is 6 6 1/2, and of anorthite 6 7. Densities (g/cm3 ) are: orthoclase 2.53 2.56, albite ca. 2.62, and anorthite ca. 2.76. In thin sections, the feldspars show low refraction of light and birefringence (double refraction). The average specic heat (J g1 K1 ) of orthoclase between 0 and 100 C is ca. 0.79, of albite 0.82, and of anorthite 0.80. The corresponding values for the range 0 1100 C are 1.05, 1.1, and 1.12. In the crystalline state the alkali feldspars become electrically conductive at moderate temperatures. Ionization is observed above 900 C.

2.1.3. Production Feldspar can be synthesized by solid-state or liquid-phase reactions: 1) Albite is formed by heating a mixture of 1 mol Al2 O3 , 6 mol SiO2 , an excess of Na2 O, and sodium tungstate as a mineralizer at 900 1000 C with a long reaction time (days). 2) Orthoclase is formed by heating a mixture of 1 mol Al2 O3 , 6 mol SiO2 , and a large excess of K2 O, with tungstic acid for mineralization at 900 1000 C, or by heating a mixture of Al2 O3 , SiO2 and acidic potassium tungstate at 900 C. Crystals are obtained on treatment with boiling water. 3) Anorthite is obtained by fusing a mixture of Al2 O3 , SiO2 and CaCO3 . The temperature is maintained slightly below the melting point ( 1500 C), and the mixture is slowly cooled. Four modications (, , , and ) are known. Preparative methods using hydrothermal reactions in autoclaves or high-pressure reactors are also known: 1) Albite is synthesized by heating precipitated aluminum silicate and excess sodium silicate at ca. 500 C 2) Orthoclase is synthesized by heating a mixture of Al2 O3 , SiO2 and KOH with water in a ratio corresponding to K2 O Al2 O3 6 SiO2 at 400 C, or from an aqueous slurry of potassium aluminate or Al(OH)3 with potassium silicate in the presence of CO2 at 360 400 C 3) Anorthite is synthesized by heating a mixture of aqueous slurries of SiO2 , Al2 O3 , and CaO in the presence of CaCl2 as a mineralizer at 470 C All synthetic feldspars are Al/Si disordered. Ordering requires geologic periods of time. Feldspars also occur in industrial products (ceramics). In synthetic feldspars, Si4+ can be completely replaced by Ge4+ , and Al3+ by Ga3+ or Fe3+ . This gives new end members that are only found as synthetic compounds. For example, anorthite, -Ca[Al2 Si2 O8 ], which corresponds to natural anorthite, occurs in y ash and sometimes in blast-furnace slags. It is formed when CaO- containing slags attack the chamotte (re bricks) in blast furnaces and lime kilns.

Silicates In the liquid phase, albite is one of the most strongly dissociated silicates. The rate of crystallization in alkali feldspar melts is extremely small due to their high melt viscosity. The fusion range of natural orthoclase is 1140 1300 C (incongruent melting, see also Section 2.3). Fused anorthite has a comparatively low viscosity, however, and crystallizes readily and rapidly on cooling to form large, well-formed crystals. The maximum crystallization rate occurs 20 25 C below the temperature at which melting starts. A glass is formed only if the cooling rate is very rapid. Chemical Properties. Chemical attack, including weathering, readily decomposes or changes the feldspars. The prolonged action of water on pulverized feldspar leads to preferential dissolution of the alkali ions, but also dissolves CaO and Al2 O3 , eventually giving a residue of polysilicic acids. Water containing dissolved CO2 is more aggressive; alkali metals and Al2 O3 are dissolved preferentially, and the reaction proceeds with formation of kaolinite (Al2 O3 2 SiO2 2 H2 O). Strong mineral acids decompose alkali feldspars slowly, producing a residue of polysilicic acids. However, powdered anorthite dissolves completely in hydrochloric acid at 100 C. Under high pressure (i.e., in autoclaves at ca. 200 bar) potassium feldspars are converted to kaolinite by 5 % hydrouoric acid at 225 C or by 0.5 1 mol/L HCl at 320 330 C. This rst causes complete hydrolysis of the starting material, followed by the formation of kaolinite and silicic acid. At lower temperatures, the reaction only produces a residue with a high silicic acid content. Anorthite is almost completely converted into kaolinite by treatment with 0.5 mol/L HCl at 340 C. Concentrated solutions of alkali hydroxide decompose the alkali feldspars completely above 110 C. Reaction with 1 2 % solutions of alkali hydroxide leads to the formation of soluble products. 2.1.5. Mineral Deposits and their Extraction The most important raw materials are the potassium feldspars (orthoclase, microcline), followed by sodium feldspar (albite). The other

19

members of the plagioclase group are of very little value, although rocks with a high plagioclase content has been tested as a raw material for aluminum production. Nepheline syenite is industrially important (see Section 2.2), as are other rocks and sediments rich in feldspar (e.g., granites, syenites, and porphyries). Feldspar also occurs in some apatite deposits (e.g., in the Kola Peninsula, Russia). Furthermore, feldspar is extracted from sedimentary rocks (e.g., arkoses). Economically useful deposits of high-grade feldspars are of limited occurrence. They are mostly plutonic rocks, pegmatites, and volcanic rocks with feldspar inclusions. When exposed, feldspathic rocks are often partially or completely kaolinized. Feldspar often arises as a byproduct during the processing of kaolin or mica. World production of feldspar is ca. 6.7106 t/a (all weights specied are in metric tons). The demands of European industry can be met from European deposits, the most important being in Italy, Turkey, Germany, France, Spain, the Czech Republic, Portugal, Russia, Norway, Sweden, Poland, Hungary, Finland and Greece. The most important producers are Germany: Amberger Kaolinwerke, Hirschau; Birkenfelder Feldspatwerke Schweyer & Vollmer, Ellweiler; Gebr der Dorfner, Hirschau; Kaliu Chemie, Hannover; Keramische Rohstoffwerke Bauscher-Mandt, Weiden; Villeroy & Boch, Keramische Werke, Mettlach; Italy: Gruppo Maffei SpA., Milano; Minerali Industriali SpA.; France: Denain Anzin Min raux (Feldspaths e du Midi, Feldspaths du Morvan, Feldspaths Baux); Norway: Noroat A/S; Spain: Unimin; Finland: Partek; Sweden: Svenska Forshammar AB, Gothenburg; Spain: Industrias del Cuarzo and Lansa; Turkey: Esan; Elginkam; former Soviet Union; United States: The Feldspar Corp., Spruce Pine/NC.; IMC Chemical Group Inc., Industrial Minerals Div., Boston/Mass.; Foote Minerals Co., Exton/Pa., Kings Mountain; Mica Co. Inc., Kings Mountain/NC.; Pacer Corp., Custer/SD.; San Antonio Mica Mine, Ajo/Ariz.; Mexico: Materias Primas Monterrey SA, Monterrey/N.L.; Argentina: Piedra Grande SA, San Luis; Japan: Kinsei Kogyo Co Ltd., Osaka; Morimura Bros. Inc., Tokyo; Nissho-Iwai Co. Ltd., Tokyo; Sumitomo Corp., Tokyo; India: Golecha Palawat & Co., Rajastan; Shree Modi Levigated Kaolin Pvt. Ltd., Rajastan; South Africa: Ceramic Minerals (Pty.) Ltd.,

20

Silicates lectors, and foaming agents) and adjustment of the pH. Albite and potassium feldspar can also be separated from each other if necessary. Feldspar also arises as a byproduct in the wet processing of kaolin. Quartz is rst removed from an aqueous suspension of the crude ore. Kaolinite and feldspar are then separated in hydrocyclones, dewatered, and dried with rotary or tray dryers ( Clays, Chap. 4.1.2.). The degree of separation (feldspar : quartz ratio) is ca. 9 %. In another process, the kaolinite and accompanying clay minerals are slurried, and the feldspar quartz concentrate (particle size 0.1 0.5 mm) is separated into feldspar and quartz by an electric eld of 40 kV. The degree of separation (feldspar : quartz ratio) is ca. 96 %. Highintensity magnetic separators are used to remove paramagnetic impurities. Grinding is performed in nonferrous equipment and is followed by air elutriation, giving products with a maximum grain size of 40 150 m. Quality requirements vary considerably and depend on the end product consumer. High-quality products generally require highpurity raw materials of dened composition. For white glasses, light- colored ceramics, glazes and enamels, the content of heavy metal ions must be extremely small ( 0.08 wt %). Contents of Na2 O and/or K2 O and Al2 O3 must be specied to ensure satisfactory physical and chemical properties, especially strengths of glasses. When the products are used as uxes, the alkali oxide content must be increased to bring about the desired reduction of the melting point. Important quality criteria for some applications are the particle size, the particle size distribution, and the tolerance range for the fractions of over- and undersized particles. Chemical and physical data of some feldspar grades are given in Table 5; some particle size distributions for feldspar sands and powders are given in Tables 6. 2.1.7. Uses and Economic Aspects The glass and ceramic industries are the main consumers of sodium and potassium feldspars and also of related minerals of lower quality

Dunswart/Transvaal; General Overseas Traders S.A. (Pty.) Ltd., Johannesburg; Martin & Robson (Pty.) Ltd., Germiston; Otavi Mining Co. (Pty.) Ltd., Johannesburg; Rand London Corp. Ltd., Johannesburg; Rondebult Clayworks (Pty.) Ltd., Boksburg. Opencast mining is used to extract sedimentary and pegmatitic deposits, although pegmatite is also obtained by underground mining. The usual methods such as drilling, explosives or cutting are used for massive rock deposits. Scrapers and front loaders are used for sedimentary deposits (loose rock), working in stepped faces. 2.1.6. Processing and Quality Requirements Processing. Usually, processing of feldspar consists of crushing and/or grinding with subsequent classication, but some feldspar is also processed by otation (e.g., feldspar in granitic rocks). The methods used to process the massive or loose rock depend on the end product, the mineral composition and the available equipment. In the simplest case, the feldspathic rock is progressively broken down by jaw crushers, ball mills, roller mills or pin mills; classied by vibratory sieves; washed if necessary; and dried. It is then ground using impact mills or ball mills to produce a coarse powder and classied by air elutriation. The nal product contains not only feldspar, but also accompanying minerals (e.g., quartz or mica). Marketable products should have a favorable mineral composition with a high feldspar content. A quartz content of the product is not detrimental, since quartz is needed in any case for many applications (e.g., production of porcelain, glass and enamel). Any mica can be removed by air classication after breakdown of the rock. Accompanying minerals with a high magnetic susceptibility can be removed by magnetic separation. The content of heavy metal ions in the end product can be reduced to a safe level by this method. The otation process was introduced for processing feldspar in 1960 by the Finnish company Lohja Oy. The rock is rst crushed, sometimes washed and dried and then ground. Mica, quartz, other accompanying minerals and feldspars are obtained in the froth or as a sediment in a series of otation stages. Selectivity depends on the choice and dosage of reagents (activators, col-

Silicates
Table 5. Chemical composition and physical data for selected feldspar grades Theoretical Feldspar sand, AKW a FS 800 S FS 900 L Total feldspar 100 content, wt % K feldspar, wt % 100 Na feldspar, wt % Ca feldspar, wt % Quartz, wt % Other silicates 64.8 SiO2 , wt % Al2 O3 , wt % 18.2 Na2 O K2 O, wt % 16.9 CaO, wt % MgO, wt % Fe2 O3 , wt % TiO2 , wt % Loss on ignition, wt % Hardness (Mohs) Density, g/cm3 Begin of sintering, C End of sintering, C Sintering interval, K Begin of uxing, C Softening interval, K Half-sphere point, C End of uxing, C Fluxing interval, K
a c

21

Glass

Noroat c Na 86.5 16.5 61 9 12 1 69.2 18.7 7.20 2.80 1.82 0.11 0.19

Forshammar d Maffei ed F5 67 41 25 1 29 4 75.5 14.7 4.85 4.25 0.20 0.10 0.13 0.45 80 F 7 SE 90

FS 960 L 92 43 43 6 2 67.7 18.2 5.00 7.20 1.2 0.03 0.08 0.03 0.20

FFF b K 90 45 42 3 5 2 67.5 18.5 5.00 8.12 0.56 0.10 96.5 65.5 28.5 2.5 3 0.5 65.4 18.7 3.36 11.10 0.51 0.06 0.29

100

81 76 5 12 7 67.5 17.0 0.60 12.70 0.02 0.04 0.12 0.50 1.0

94 87 7 4 2 65.8 17.8 0.80 14.65 0.04 0.02 0.042 0.044 0.25

100

80 12 - 15 5-8 70.9 17.52 9.30 0.65 0.60 0.10 0.30 0.03 0.75 61 2 2.65

90 5 5 70.10 18.20 10.20 0.30 0.60 0.10 0.10 0.05 0.50 61 2 2.65 1135 1270 135 1300 30 1365 1500 200

68.7 19.4 11.8

6 2.6 1130 1340 210 1430 90 1560 1630 200

6 2.6 1175 1365 190 1440 75 1570 1600 160

6 2.6 1150 1250 100 1330 80 1420 1580 250

1140

6 2.6 1140 1270 130 1290 20 1330 1410 120

1460

AKW Amberger Kaolinwerke, Hirschau, Germany. b Glass-grade feldspar, oated, Lohja Oy, Virkkala, Finland. H. Bj rum, K/S Noroat, Oslo, Norway. d Svenska Forshammars AB, Gothenburg, Sweden. e Gruppo Maffei o S.p.A., Monte Orno, Milan, Italy.

Table 6. Typical particle size distributions (in %) for selected feldspar sand grades Screen analysis DIN 66 165, mm > 1.0 0.5 1.0 0.1 0.5 0.063 0.1 0.040 0.063 < 0.04 Dry screen residue DIN 53 734, m > 125 > 100 > 90 > 71 > 63 > 40 3 6 12 18 25 34 48 6 FS 800 S 0.05 18 25 22 35 FS 900 SF 0.05 21 29 23 27 FS 900S 0.20 85 11 3 1 Grind number 8 10 Grading FS 900L 0.10 30 70 0.10 0305 0.20 65 35

5 10 18 35

3 8 20

3 10

22

Silicates fractive indices of many paint resins, plasticizers and polymers are almost the same as those of the feldspars (n 1.55). Feldspathic rocks that can be dressed are also used as building stone, as hard core in roads, and as bright, reective chippings in bitumenbonded road surfaces. In Western Europe, the approximated total consumption of feldspar is ca. 3.7106 t/a and is divided as follows:
Ceramics Glazes and enamels Glass Abrasives Fillers Others 57 % 4.5 % 34 % 1.5 % 0.4 % 2.6 %

with respect to heavy metal ions and accompanying minerals (i.e., feldspathic pegmatites, aplites, phenolites and Cornish stone). See also Glass, Chap. 5.1., Ceramics, General Survey, Chap. 2.4. The alkali feldspars have a uxing action due to their alkali-metal oxide content. They reduce the temperature at which melting begins (i.e., the sintering point of the raw material mixture) and thus shorten the time required for melting or ring. This reduces energy consumption and increases production capacity and the life of the refractory linings. On cooling the melt, the oxidic components of the feldspar form a glassy structure, which provides the glassy matrix in ceramic products. Al2 O3 increases melt viscosity, facilitating mechanical forming of the glass. It also increases hardness and impact strength (toughness) and prevents crystallization (devitrication). In ceramic masses, the Al2 O3 in the glassy matrix reduces the tendency to re cracking and increases impact strength. Sodium feldspar is usually added at a level of 0.2 17 wt % as a raw material for glass. Potassium feldspar is generally employed for ceramic products, although sometimes calcium or calcium/sodium feldspar is also used. Feldspar (admixtures of 4 20 wt %) is used in the coating for arc-welding electrodes to improve the ow of the molten slag. In blast furnaces, the addition of feldspar also improves slag ow during tapping. Powdered feldspar is used as a mild abrasive due to its hardness, conchoidal fracture and platelet-shaped particles. Light- colored alkali feldspars, anorthite and plagioclase are added to coatings in the form of ne sands or coarse powders to give antiskid properties to oor coverings and surfaces intended for vehicles and pedestrians. Finely ground feldspar grades are good llers for exterior paints because of their chemical inertness, lack of photoreactivity and good dry brightness. As a ller feldpsar competes with other, often cheaper, raw materials such as calcite and dolomite. They are also used as llers for pigments, adhesives, rubber (especially foam rubber), thermoplasts and thermosets. They can be used as llers in large amounts approaching the critical pigment volume concentration (CPVC), giving transparent or nearly transparent paints and polymer products, because the re-

Alkali feldspars can be replaced completely or partially by leucite (Section 2.3), nepheline or nepheline syenite (Section 2.2), thereby increasing the alkali oxide and Al2 O3 content and reducing the SiO2 content. If low levels of accompanying minerals and heavy metal ions are unnecessary, other substitutes can be used: feldspathic pegmatites, aplites, phonolites and porphyries; and to a limited extent plagioclase, anorthosite (plutonic rocks containing ca. 90 % plagioclases), Cornish stone (though this can liberate uorine on thermal decomposition of the melts) and the blast furnace slags Carolina stone and Calumite (both consisting of kaolinite, feldspar, quartz and some uorspar). Worldwide extraction of feldspars is estimated at > 6.7106 t/a. Together with nepheline, nepheline syenite, and leucite, total production exceeds 7.5106 t. In 1990, 247 000 t feldspar and 135 000 t pegmatite were produced in the Federal Republic of Germany. The production gures of pegmatite in 1988 1993 in the United States are ca. 670 000 t/a, in the CIS 310 000 t/a, in Italy ca. 295 000 t/a, in France ca. 195 000 t/a, in Mexico ca. 127 000 t/a, in Brazil ca. 110 000 t/a, in Spain ca. 90 000 t/a, in Turkey ca. 73 000 t/a, in Norway ca. 71 000 t/a, in Venezuela ca. 70 000 t/a, in Finland ca. 68 000 t/a, in Rumania ca. 60 000 t/a, in Sweden ca. 52 000 t/a, in India ca. 50 000 t/a, in Argentina and in the Republic of South Africa ca. 47 000 t/a, respectively. The total feldspar mining production in 1994 amounted to 1 806 935 t in Italy, 765 202 t in the United States, 528 027 t in Thailand, 500 000 in Turkey, 385 000 t in France, 379 427 t in Ger-

Silicates many, 319 658 t in South Korea, 274 789 t in Venezuela, 250 000 t in Spain, 170 000 t in the Czech Republic, 140 000 t in Brazil, 133 400 t in Mexico, 92 440 t in Portugal, 79 000 in Iran, 76 188 t in Colombia, 70 000 t in Russia, 70 000 t in India, 62 905 t in Norway, 55 000 t in Sweden, 53 503 t in Japan, 50 000 in Argentina, 46 000 t in Poland, 43 805 t in the Philippines, 43 600 t in Hungary, 41 389 t in Finland, 40 000 t in Cuba, 39 745 t in Egypt, 37 156 t in the Republic of South Africa, and 35 000 t in Greece. Furthermore, the feldspar mining production amounted in 1994 e.g., to 23 500 t in Australia, to 8000 t in the United Kingdom, and 4883 t in Austria.

23

2.2. Nepheline and Related Compounds


The alkali aluminosilicate nepheline, KNa3 [AlSiO4 ]4 , a feldspathoid, belongs to the nepheline group of tectosilicates without nontetrahedral anions. The aluminum : silicon ratio is 1 : 1. Structure and Mineralogy. As in all tectosilicates, the oxygen ions at the vertices of the [AlO4 ] and [SiO4 ] tetrahedra in nepheline are linked to the four neighboring tetrahedra. This produces a three-dimensional open framework in which the relatively large Na+ and K+ cations are located in the spaces between the tetrahedra. In tectosilicates, these spaces can be occupied by alkaline-earth ions, nontetrahedral anions (e.g., in the feldspathoids sodalite and scapolite), or water (in zeolites). In minerals of the nepheline group the tetrahedra exhibit a hexagonal or pseudohexagonal arrangement. In nepheline (Fig. 22), alternating [AlO4 ] and [SiO4 ] tetrahedra are linked together at common vertices to form an easily distorted hightridymite structure with six-membered rings. The apices of the [AlO4 ] tetrahedra point parallel to the c axis, and those of the [SiO4 ] tetrahedra point in the opposite direction. Unlike the high-tridymite structure, Si4+ ions in nepheline are replaced by Al3+ ions in half of the tetrahedral positions. In order to maintain charge neutrality, 3 Na+ ions and 1 K+ ion are found per formula unit in the centers of the channels parallel to the c axis.

Figure 22. Idealized structure of nepheline, KNa3 [AlSiO4 ]4 , with [(Si, Al)O4 ] tetrahedra linked to form six-membered rings Projection parallel to c on (001)

In natural nepheline, the ratio of K+ to Na+ can vary considerably, and Ca2+ can also be incorporated in the lattice. There is often an excess of SiO2 , i.e., less than half the Si4+ is replaced by Al3+ , so that less Na+ is required to maintain charge neutrality. Nepheline [012251-27-3], KNa3 [AlSiO4 ]4 , crystallizes in the hexagonal pyramidal system with space group C6 P 63 and has the 6 following lattice constants: a0 = 1.001 nm, c0 = 0.841 nm; the axial ratio is c0 /a0 = 0.840; Z = 2. = 2.65 g/cm3 (also potassium-free with a0 = 0.996 nm, c0 = 0.836 nm). The following minerals of the nepheline group have properties similar to those of nepheline: Kalsilite, K[AlSiO4 ] (Fig. 23), crystallizes in the hexagonal pyramidal system with space group D6 P 63 ; lattice constants: a0 = 6 0.518 nm, c0 = 0.869 nm; the axial ratio is c0 /a0 = 1.678; Z = 2. Trikalsilite, (Na, K)[AlSiO4 ], crystallizes in the hexagonal system, probably with space group C6 P 63 ; lattice constants: a0 = 1.54 nm, 6 c0 = 0.86 nm; the axial ratio is c0 /a0 = 0.559; Z = 18. Kaliophilite, K[AlSiO4 ], crystallizes in the hexagonal trapezohedral system with space group D6 P 63 22; lattice constants: 6 a0 = 2.706 nm, c0 = 0.861 nm; the axial ratio is c0 /a0 = 0.318; Z = 54; pseudocell: a0 = 1.562 nm = a0 /3, c0 = 0.861 nm, c0 /a0 = 0.551; Z = 18.

24

Silicates magmatic rocks, and at about the same time as alkali feldspars in plutonic rocks. In hypabyssal and effusive rocks, nepheline occurs as phenocryst and in the matrix. The ratio potassium : (potassium + sodium) in nepheline varies between 7 % and 37 % in effusive rocks and also in plutonic rocks, in which nepheline was formed in the presence of anorthoclase or sanidine. In plutonic rocks containing orthoclase and albite, nepheline contains 14 23 atom % potassium. Igneous nepheline (slow cooling) has a cloudy or greasy luster and is known as elaeolite. On rapid cooling (effusive rock), the crystals remain clear. Albite can form isomorphous mixtures with nepheline in sodium-rich solid solutions with a maximum albite content of ca. 20 mol % at 700 C; the albite is often irregularly distributed, i.e., in zones. As with feldspar (see Section 2.1.2), the order/disorder behavior of Al/ Si in the nepheline is temperature dependent.

Figure 23. Structure of kalsilite, K[AlSiO4 ]. The structure of nepheline, KNa3 [AlSiO4 ]4 , is obtained by replacement of K4 by KNa3

Occurrence in Industrial Products. In refractory technology nepheline occurs in four modications that do not contain potassium, NaAlSiO4 :

High eucryptite, Li[AlSiO4 ], only exists as a synthetic product, and is obtained by heating natural eucryptite (low eucryptite), LiAl[SiO4 ]; it is stable above 962 C. It crystallizes in the hexagonal trapezohedral system with a superlattice structure, with space group D4 P 62 22 6 or D5 P 64 22; lattice constants: a0 = 0.528 nm, 6 c0 = 1.127 nm; the axial ratio is c0 /a0 = 2.134; Z = 3. Nepheline is a feldspathoid and occurs only in rocks with a low SiO2 content (< 50 wt % SiO2 ); it has a lower SiO2 content than the alkali feldspars. It is formed in alkaline rocks in place of albite if the magma is sufciently unsaturated with SiO2 . It is often associated with other feldspathoids such as sodalite, cancrinite, or leucite, or less often with kalsilite. Nepheline is a typical main constituent of the Atlantictype igneous rocks, plutonic rocks (e.g., foyaites, theralites and essexites), hypabyssal and volcanic rocks (e.g., phonolites, tephrites and nephelinites). In the Mediterranean suite, minor amounts of nepheline are usually found with the common leucite (see Section 2.3). Nepheline crystallizes immediately after mac minerals in

High carnegieite [001302-34-7], Na[AlSiO4 ], crystallizes in the cubic system, with space group T4 P 21 3; lattice constants: a0 = ca. 0.74 nm, Z = 4. It has the cubic high cristobalite-type lattice with additional sodium, and can form mixed crystals with cristobalite to a limited extent. High carnegieite occurs only as a synthetic product; in mineralogy it is often termed -carnegieite. High nepheline [012251-27-3], Na[AlSiO4 ], is orthorhombic. Low nepheline [012251-27-3], -Na[AlSiO4 ], is hexagonal pyramidal. It occurs, for example, in chamotte and SiO2 - containing corundum bricks. It is converted into mullite in the walls of blast furnaces, glass-melting furnaces and checker bricks by the attack of Na2 SO4 and Na2 O. Low carnegieite, -Na[AlSiO4 ], is triclinic.

Silicates In refractory technology, ve modications of the polymorphic substance KAlSiO4 are known: hexagonal trapezohedric kalsilite, orthorhombic (high) kaliophilite, hexagonal kaliophilite (kalinepheline), natural hexagonal kaliophilite and anomalous kaliophilite. A characteristic feature of kalsilite is that it polymerizes: trikalsilite and tetrakalsilite are known. Kalsilite occurs in incrustations on the chamotte walls of blast furnaces and in the chamotte checker bricks of Siemens Martin furnaces. Potassium nepheline is formed at < 1540 C in chamotte bricks of industrial furnaces that are exposed to K2 O vapors (e.g., in the brick linings of blast furnaces and tuyeres). High kaliophilite is stable above 1540 C. It also occurs in the chamotte linings of blast furnaces and tuyeres, as well as in the chamotte checker bricks in Siemens Martin furnaces and glass furnaces used to melt optical K2 O glasses. Properties and Composition of Industrial Products. The following physical properties are important for industrial applications. Density: Nepheline: 2.56 2.665 g/cm3 Kalsilite: 2.59 2.625 g/cm3 -Carnegieite: 2.513 g/cm3 -Carnegieite: 2.343 g/cm3 Mohs hardness: Nepheline: 5 1/2 6 Kalsilite: 6 Specic heat at 20 100 C: Crystalline: 0.77 J g1 K1 Amorphous glass: 0.804 J g1 K1 Melting point: Sodium nepheline + albite, 100 70 % NaAlSiO4 : 1526 1410 C Kalsilite (0 20 % NaAlSiO4 ): 1300 1350 C -Carnegieite (ca. 100 % NaAlSiO4 ): 1526 C Eutectic in the system nepheline albite: 1068 C Transformation temperature: Nepheline - carnegieite: 1248 5 C -Carnegieite - carnegieite: 687 692 C Nepheline + 30 % kalsilite - carnegieite: 1400 C Nepheline + 35 % anorthite - carnegieite: 900 C

25

Nepheline shows piezoelectric properties in a high-frequency eld. Compositions of commercially mined nephelines are given in Table 7. Nepheline has a markedly alkaline reaction in water. Dilute acids, especially HCl, decompose nepheline, producing gelatinous silicic acid. Deposits. Only a small number of workable nepheline syenite deposits are known, the most important of which are in Canada, Norway and Russia. The rock in a certain Canadian deposit consists of ca. 54 % albite, 18 % microcline, 18 % nepheline, < 4 % biotite, 6 % muscovite and magnetite. In the Western world, only four companies extract and process nepheline-containing rocks (only nepheline syenite), the combined output being ca. 1.2106 t/a. Extraction. The rock is usually extracted by open- cast mining using explosives. Adhering impurities are removed by sieve grates (grizzlies) prior to size reduction. Ferromagnetic impurities (e.g., biotite) are removed by means of rotary magnets or high-intensity magnetic separation. Quality Specications. The quality required depends on the use, e.g., Grade A (Table 8) for the glass industry, Grade B for glass wool manufacture, ceramic grade for the ceramic industry and a lower grade for use as a ller. The grades differ in iron content (Grade A 0.08 % Fe2 O3 , Grade B: 0.4 % Fe2 O3 ) and in color, which varies with heavy metal content and mean particle size (in some applications). Uses. The most important consumer is the glass industry, which accounts for ca. 70 % of the nepheline marketed. Here, the silicate acts not only as a source of SiO2 and Al2 O3 , but also as a ux. Mixtures of raw materials for bottle manufacture can contain 5 15 % nepheline. Nepheline can replace feldspars in most ceramic and glass-making applications (see Section 2.1.7) with only small adjustments to batch chemistry being necessary. The choice between feldspar and nepheline (nepheline syenite) is often a question of cost. The ceramic industry consumes ca. 15 % of the total nepheline output. The nepheline content in sanitary and whiteware ceramics can be

26

Silicates

Table 7. Analyses of natural nephelines and kalsilites (in wt %) A SiO2 TiO2 Al2 O3 Fe2 O3 MgO CaO Na2 O K2 O H2 O (105 C) H2 O (105 1000 C) Total nE n0 Nepheline Kalsilite Others 44.65 0.00 32.03 0.59 0.00 0.71 17.25 3.66 0.21 0.96 100.06 1.535 1.531 81.9 12.9 5.2 B 41.88 0.03 32.99 0.74 0.00 0.78 16.11 6.82 0.03 0.71 100.16 C 40.20 0.05 32.51 1.82 0.10 1.44 10.86 12.22 0.00 0.20 99.77 1.543 1.539 54.7 45.3 D 38.47 0.00 30.81 1.63 0.63 0.20 2.09 25.65 0.00 0.20 99.94 1.543 1.537 9.9 88.9 1.2 E 38.48 0.05 31.01 1.12 0.00 0.03 0.30 28.33 0.67 100.00 1.539 1.533 1.4 96.8 1.8 99.50 99.57 99.66 1.53 1.53 F 63.36 22.05 0.09 5.80 5.77 2.43 G 60.20 23.30 0.07 0.30 10.60 5.10 H 60.8 23.0 0.08 0.03 0.05 10.4 4.6 0.7

76.1 23.6 0.3

A) Nepheline phonolite, New Zealand. B) Nepheline foyaite Transvaal. C) Nepheline potassium ankaratrite, Angola. D) Kalsilite, venanzite, Italy. E) Kalsilite, complex granular intergrowth of kalsilite and nepheline, Angola. F) Nepheline aplite (whole rock), Feldspar Corp., USA. G) Nepheline syenite (whole rock), Sobin Chem. Inc., Canada. H) Nepheline Senite (Treminex 958), Quarzwerke GmbH, Frechen, Germany. Table 8. Composition (wt %) of Canadian nepheline syenite products (Grade A) Company Indusmin IMC Loss on ignition. SiO2 59.8 60.2 Al2 O3 23.6 23.3 K2 O 5.0 5.1 Na2 O 10.2 10.6 CaO 0.6 0.3 Fe2 O3 0.07 0.08 LOI 0.6 0.4

25 30 %, in industrial chemical porcelain and translucent porcelain china 15 30 %, and in oor and wall tiles 15 55 %. Finely ground nepheline and feldspar (see Section 2.1.7) are becoming increasingly important as llers for plastics [especially unsaturated polyester resins, poly(methyl methacrylate), and thermoplastic polyurethanes], rubber, adhesives, paints and pigments (Table 9). Since the refractive indices of nepheline and the matrix are almost the same, e.g., in nepheline/poly(vinyl chloride) compositions, transparency is maintained, even at high pigment volume concentrations. The high surface and volume resistance of nepheline mean that it can also be used as a ller in insulating paints, casting resins for electrical applications and other products. In Russia, nepheline syenite is an important raw material for aluminum production. In a multistage process, the Al2 O3 is extracted and then treated by melt electrolysis. High activity silica gels can be produced from nepheline by decomposition with hot 22 % sulfuric acid.

2.3. Leucite
The potassium aluminum silicate leucite, a feldspathoid, belongs to the analcime leucite group of tectosilicates without nontetrahedral anions. The aluminum : silicon ratio is 1 : 2. Structure and Mineralogy. As with all the tectosilicates, the oxygen ions at the vertices of the [AlO4 ] and [SiO4 ] tetrahedra are linked to four neighboring tetrahedra. This produces a three-dimensional open framework in which K+ ions are located in the spaces within the framework. Whereas in the nepheline group the arrangement of tetrahedra is hexagonal or pseudohexagonal, the minerals of the analcime leucite group have a cubic or pseudocubic arrangement. Leucite [001302-34-7], K[AlSi2 O6 ], is dimorphous. Below 605 C, it exists as low leucite (-leucite) and above 605 C as high leucite (leucite). Low leucite crystallizes in the tetragonal pseudocubic system, with the space group C6 I 41 /a; lattice constants: a0 = 1.304 nm, 4h

Silicates
Table 9. Physical data for nepheline llers Product Particle diameter, m D50 value Minex 4 Apex 400 Minex 7 Apex 700 Minex 10 10.8 9.1 3.9 5.9 2.7 Upper limit 30 32 20 25 15 Brightness (555 nm) 90 90.5 90 92 90 Density, g/cm3 2.6 2.6 2.6 2.6 2.6

27

Trade names: Minex is produced by Indusmin and Apex by IMC.

c0 = 1.385 nm; the axial ratio is c0 /a0 = 1.062; Z = 16. High leucite crystallizes in the cubic hexakis-octrahedral system, with the space group O10 Ia 3 d; a0 = 1.343 nm; Z = 16. h Leucite is isotypical with analcime, Na[AlSi2 O6 ] H2 O; pollucite, (Cs, Na)[AlSi2 O6 ] H2 O, and synthetic Cs[FeSi2 O6 ]; it is homeotypic with wairakite, Ca[AlSi2 O6 ]2 H2 O. In leucite, K+ can be replaced to a small extent by Na+ , rarely by Rb+ , and very rarely by Ca2+ ; these minor substituents sometimes appear as enriched isomorphous layers. The pseudocubic, pale green iron(III) leucite, K[FeSi2 O6 ], also known as a synthetic material, can occur in very small quantities with the rock-forming leucite. The apparently cubic crystals of leucite are anisotropic and consist of numerous twin lamellae, which are arranged parallel to the surfaces of the apparent rhombic dodecahedron. In thin sections, leucite shows a complex twinning on {110} under crossed polarizers. On raising the temperature to 605 C, leucite becomes isotropic and is then genuinely cubic (high leucite). The transformation is reversible. Leucite is the most characteristic component of SiO2 -unsaturated magmatites with a preponderance of potassium (Mediterranean rocks) and is typical of magmatic regions (e.g., the Rome region in Central Italy). It is found in many foyaitic and theralitic volcanic rocks. Leucite occurs in refractory products, e.g., in chamotte bricks from blast furnaces and tuyeres. High leucite melts congruently at 1686 C. When potassium feldspar is heated, it melts incongruently above 1150 C forming a mixture of leucite crystals in a SiO2 -rich melt. At 1150 C, the melt contains 57.8 wt % leucite crystals, and at 1530 C all the leucite becomes molten. On cooling, leucite crystallizes rst, and the melt therefore becomes richer in SiO2 . The

leucite crystallization is completed at 1150 C and potassium feldspar is then formed. Properties. Leucite crystals are usually white or gray, glassy, translucent, but very seldom clear. Cleavage is poor parallel to (110), the fracture being conchoidal and brittle. The following physical properties are important for the use of leucite as a raw material for glass: Density: leucite 2.47 2.50 g/cm3 , molten glass produced from leucite 2.41 g/cm3 . Mohs hardness: 5 1/2 6. Melting point: pure leucite 1686 C, impure leucite 1298 1430 C. Heat of crystallization: 47.65 kJ/mol. The tendency to crystallize is very low, and the melt therefore usually solidies as a glass. Volume increase on solidication of the melt: 2.9 %. Specic heat (10 100 C): natural mineral 0.8 J g1 K1 , in the amorphous state 0.733 J g1 K1 . Leucite can contain up to 1.5 wt % Na2 O and 0.8 wt % CaO. It is decomposed by concentrated hydrochloric acid with precipitation of SiO2 . Deposits and Processing. Leucite deposits occur in the United States (Montana and Wyoming) and in Italy (Mount Vesuvius). Processing and classication of the leucite grades are very similar to that of feldspar and nepheline (see Sections 2.1.6 and 2.2). Uses. Leucite, like feldspar, is mainly used as a raw material in glass manufacture. Other applications include the production of potassium fertilizers, alum and potassium nitrate.

2.4. Olivine
Olivine (peridot, chrysolite) [1317-71-1] is a rock-forming nesosilicate (an orthosilicate, i.e.,

28

Silicates Olivine (Fig. 24) can include small amounts of other substituent elements (e.g., nickel). Weathering removes MgO and SiO2 , forming the important nickel serpentine ore mineral garnierite (nickel deposits of the New Caledonia type). Olivine occurs as intergrown, loose, prismatic or thick tabular crystals and as granular aggregates. Cleavage in the (001) plane is good, and also takes place imperfectly in the (010) plane, the fracture being conchoidal. Olivine crystallizes at an early stage from a magma. It is found typically as the main mineral constituent in ultrabasic igneous rocks (peridotites and dunites), and as a residual material in the serpentinites formed from them. In the ultrabasics, olivine is accompanied by pyroxene, etc. Olivine is often found in basic magmatites both in plutonic and volcanic rocks (e.g., gabbros, diabases, basalts and melaphyres). It also occurs in meteorites. Olivine is a main constituent of the upper earth mantle. Olivine of jewelry quality is known as chrysolite, and forms clear, pale green stones that can be polished. In the presence of water, olivine readily forms other silicates, e.g., serpentine (serpentinization antigorite, chrysotile). Olivine often then becomes pseudomorphosed to form serpentine, Mg6 [(OH)8 /Si4 O10 ], and talc, Mg3 [(OH)2 /Si4 O10 ]. The magnesium removed during serpentinization occurs as brucite, Mg(OH)2 , magnesite, MgCO3 , and cryptocrystalline magnesite of the Kraubath type (Styria, Austria). The iron present in olivine forms secondary magnetite Fe3 O4 [Fe3+ (Fe2+ Fe3+ )O4 ] during serpentinization. Synthesis. Synthetic olivine is produced by calcination of chrysotile tailings from the asbestos mines in the Thetford Mines area of Canada. The tailings are calcined at 850 C in a rotary kiln to give a mixture of forsterite and silica. A purer forsterite can be synthesized by adding magnesite during calcination. The pelletization of magnesite and the tailings is followed by calcination in a rotary kiln at 800 C and further heating to a temperature of 1350 C in a static furnace, whereby magnesite combines with the silica to form forsterite.

a silicate with isolated [SiO4 ]4 tetrahedra held together by metallic ions) belonging to the olivine series of minerals (Mg, Fe)2 [SiO4 ]. There is an innite series of solid solutions of the end members forsterite (Fo) [015118-03-3], Mg2 [SiO4 ], and fayalite (Fa), Fe2 [SiO4 ]. The intermediate members are olivine (Mg9070 , Fe1030 )2 [SiO4 ], hyalosiderite (Mg7050 , Fe3050 )2 [SiO4 ], hortonolite (Mg5030 , Fe5070 )2 [SiO4 ], and ferrohortonolite (Mg3010 , Fe7090 )2 [SiO4 ]. Other members of the olivine series include tephroite Mn2 [SiO4 ], knebelite, (Mn, Fe)2 [SiO4 ], and iron knebelite (Fe, Mn)2 [SiO4 ].

Figure 24. Structure of olivine, projection parallel to b on (010) The [SiO4 ]4 tetrahedra point alternately upward and downward

Structure and Mineralogy. The minerals of the olivine series form orthorhombic crystals, space group D16 Pmcn, Z = 4, with the follow2h ing lattice constants (in nm):
Forsterite a0 0.600 b0 0.478 c0 1.028 Olivine 0.601 0.478 1.030 Hortonolite 0.607 0.479 1.034 Fayalite 0.617 0.481 1.061

Silicates Forsterite in Industrial Products. Forsterite is a common component of refractory magnesia products (especially chrome magnesite bricks), and is the principal component of refractory forsterite bricks ( Glass, Chap. 5.7.). It is used in high-frequency insulators and also occurs in special metallurgical slags and upon reaction of refractory magnesia products with acidic slags. Properties. Olivine has a glassy luster and is transparent or translucent, but seldom colorless (i.e., iron-free). The yellowish to green color (which gives it its name) varies from light to dark and may be opaque or even black with high iron content. The double refraction (birefringence) indices are usually high and depend on the magnesium : iron ratio. The following physical properties are important for industrial applications: Density: forsterite (Fo) 3.21 g/cm3 , Fo90 /Fa10 (90 mol Fo/10 mol Fa) 3.25 g/cm3 , fayalite (Fa) 4.34 g/cm3 . Mohs hardness: forsterite 6 1/2 7, fayalite 6 1/2. Melting point: forsterite (no decomposition) 1885 C (volume change 3 %), fayalite 1205 C. Temperature stability limit for magnesiumrich olivine in an oxidizing atmosphere 1750 C; softening temperature under a load of 2 kg/cm2 1600 1700 C; thermal shock resistance moderate. Heat of fusion of forsterite 3.444 kJ/mol; specic heat (21 51 C) 0.791 kJ/g; thermal conductivity (kJ m1 h1 K1 ) at 100 C 19.3, at 500 C 11.3, and at 1000 C 8.8; mean coefcient of thermal expansion over the range 0 500 C 8.3106 K1 , 0 1000 C 9.5106 K1 , 0 1500 C 11.0106 K1 . Free energy of formation: forsterite 1922 kJ/mol, fayalite 1337.5 kJ/mol. Electrical resistivity: at 800 C 2106 cm, at 1200 C 104 cm, at 1400 C 103 cm. Ideal chemical compositions: forsterite (2 MgO SiO2 ): 57.3 wt % MgO, 42.7 wt % SiO2 ; fayalite (2 FeO SiO2 ): 70.5 wt % FeO, 29.5 wt % SiO2 . Olivine is insoluble in water, even at elevated temperature and pressure (620 C, 30.4 MPa). It is stable towards cold acid, but complete decomposition takes place on heating in dilute acid

29

(0.2 mol/L HCl), forming silica gel. Olivine reacts similarly with HNO3 and H2 SO4 , but dissolves only slowly in 20 % H2 F2 . Solutions of the alkali metal sulfates readily decompose it. Olivine is resistant to alkaline solutions. The chemical resistance of olivine in refractory materials is good towards reducing atmospheres, moderate toward carbon, poor toward acidic ux, good toward basic ux, and good toward molten metals. The following data are characteristic of commercial olivines: Density: 3.1 3.3 g/cm3 Bulk density (dry sand): 1.4 1.7 g/cm3 Tamped density (dry sand): 1.7 1.9 g/cm3 Bulk density (molding sand): 1.7 2.1 g/cm3 Moisture content (max.): 0.5 % Softening point: > 1700 C Specic heat: 0.84 1.38 J g1 K1 Coefcient of thermal expansion (20 1200 C): 11.6106 K1 FeO content (max.): 8 wt % pH: 9 The most useful properties of forsterite-rich olivines are their high softening point, low and nearly linear thermal expansion, low thermal conductivity, high density, low abrasivity and (unlike silica) lack of toxicity. Deposits and Commercial Products. An important economic factor in the extraction of olivine is the fact that olivine-rich ultrabasics or olivine rocks and the serpentinites derived from them are associated with chromite, platinum, and nickel deposits. The principal olivine deposits extracted today are in Norway, Japan, Austria, the United States, Italy, Spain and Pakistan. Smaller producers are Mexico, Sweden, India and Brazil. Japan has a large production of olivine and a production of serpentine which is several times higer than that of olivine. 6 t. The rst deposit was extracted in 1948 in Aaheim (Norway). World production of forsterite-rich olivine and dunite is ca. 6.8106 t/a, of which ca. 2.1106 t/a are in Europe. Commercial olivines usually contain at least 85 % forsterite. Their chemical composition is MgO ca. 45 50 %, SiO2 ca. 40 43 %, FeO ca. 5 7 %. Loss on ignition is ca. 1 2 %.

30

Silicates ( Glass, Chap. 5.7.). The added MgO combines with excess SiO2 to form forsterite. The addition of chrome ore improves thermal shock resistance and reduces the modulus of distortion (V modulus). The most important advantage compared with magnesia bricks is that scale and slags with a high iron oxide content do not adhere to the wall surfaces below 1400 C because the MgO is bonded. Also, forsterite bricks are less liable to sulfate attack in the temperature range 800 1100 C. However, olivine can be attacked by Al2 O3 , CaO, SiO2 and alkali due to the formation of lower melting eutectics. For refractory-grade olivine an Mg-rich composition closer to that of forsterite is required. Refractory olivine is used in the steel industry and in the manufacture of precast refractory linings for incinerators, where its heatstorage properties can result in more complete combustion, and its low expansion rate allows heat cycling without spalling of the lining. Highly refractory cements (particle size range 0 0.2 or 0 1 mm). These are formulated as for forsterite bricks, but with a higher content of uxing materials. Highly refractory ramming mixtures with similar compositions to those of bricks. These are incorporated into furnace linings by manual or compressed-air ramming. Sand-blasting material which does not involve a silicosis hazard (unlike silica). Olivine is used to some extent as a blasting abrasive and as a grit in water-jet cutting. Together with other minerals, it is used in cleaning buildings and occasionally for etching structural steel. Olivine bricks as heat reservoirs in electrical night storage heaters.

Rocks that contain higher proportions of derived minerals such as serpentine and talc are known as dunite. The chemical composition is MgO ca. 36 42 %, SiO2 ca. 36 39 %, with a correspondingly higher loss on ignition. Extraction and Processing. Olivine is extracted by both open- cast and underground mining. The rock is usually broken up by explosives. The mined rock is processed by multistage size reduction (jaw crushers, cone crushers, and hammer mills), and classied by multiple-deck vibratory screens, with intermediate washing to remove any soft accompanying minerals (e.g., pyroxene, serpentine, chlorite or talc) in the form of a slurry. After washing, the material is mechanically dewatered by continuous centrifuges and dried by rotary or belt dryers (residual moisture content < 0.5 %). Powdered olivine is produced by impact or hammer mills, giving products with narrow particle size ranges and low dust contents. Uses. Important uses for magnesium-rich olivines are: 1) Ore additive in steel blast furnaces to condition the slag and improve its ow. Here, olivine replaces dolomite and silica and enables the ratio (CaO + MgO) : (SiO2 + Al2 O3 ) to be adjusted to ca. 0.8 1.2 %. Also, less heat is required to melt the slag components. 2) Olivine is well suited for the slag conditioning of furnace slag and for basicity control in blast and electric arc furnaces. Olivine is added in the form of lumps (10 40 mm), sinter (3 6 mm) and pellets. 3) Olivine sand is used in foundry sands for casting manganese steel, high-alloy steels, brass, bronze and aluminum and in the production of gray iron and alloy steel, which usually require a ne nish. Olivine sands have several advantages over silica sands: the casting surfaces are smoother, fettling and cleaning are easier. Olivine sands can be reused many times, and there is no danger of silicosis. However, the basicity of olivine prevents its use in many applications, for example, with acid-catalyzed furan and phenolic no-bake binders. 4) Highly refractory forsterite bricks containing magnesia binders and possibly chrome ore 5)

6)

7)

8)

2.5. Andalusite
Andalusite [12183-86-1] belongs to the nesosubsilicates (orthosilicates that contain isolated [SiO4 ] tetrahedra and additional nontetrahedral anions), and, like kyanite (Section 2.6) and sillimanite (Section 2.7), is a mineral of the Al2 SiO5 group.

Silicates Structure and Mineralogy. Al2 SiO5 can form three different crystal structures, i.e., Al2 SiO5 exhibits polymorphism in the form of andalusite, sillimanite and kyanite. In all three phases one aluminum atom (AlI , Fig. 25) always has the coordination number six, i.e., it is surrounded octahedrally by six oxygen ions. The [AlI O6 ] octahedra are linked by common edges to form chains parallel to the c axis. The c0 dimension in all three minerals is therefore approximately the same (ca. 0.55 nm). The other aluminum atom (AlII , Fig. 25) in andalusite has the coordination number ve, in sillimanite four, and in kyanite six. The chains of octahedra in andalusite are held together by [AlO5 ] and [SiO4 ] groups. In andalusite none of the bonds break preferentially, so that andalusite has a higher Mohs hardness (7 1/2) than sillimanite or kyanite. Libethenite Cu2 [OH/PO4 ], adamine Zn2 [OH/AsO4 ] and eveite Mn2 [OH/AsO4 ] are isotypical with andalusite. The formula of andalusite is Al[6] Al[5] [O/SiO4 ]. It forms orthorhombic dipyramidal crystals with space group D12 Pnnm; lattice constants: 2h a0 = 0.778 nm, b0 = 0.792 nm; c0 = 0.557 nm; the axial ratio is a0 : b0 : c0 = 0.982 : 1 : 0.703; Z = 4. Some Mn3+ and Fe3+ and a small amount of Cr3+ and Ti4+ always replace the aluminum in andalusite (usually 2 3 atom % in total). Viridinite is a variety that contains several percent of Mn2 O3 and Fe2 O3 (a0 = 0.7808 nm, b0 = 0.5929 nm, c0 = 0.5567 nm). Manganese andalusite is also known. Andalusite has a greater potential for ionic substitution (diadochy) than kyanite and sillimanite. Andalusite occurs rather widely as intergrown, fairly large, thick columnar crystals. It can also occur in aggregates that may be granular, in the form of bunches or tufts, as radially arranged columns, and as coarsely tangled masses and lenses. Andalusite also occurs as chiastolite in argillaceous and spotted slates (Knotenschiefer), forming yellowish-white crystals containing a gray to black carbonaceous impurities in a regular manner. Andalusite usually has a matt, cloudy, translucent, or opaque appearance and can be red, green or reddish-gray with a vitreous luster. It shows a variable degree of cleavage parallel to {110}. Transparent crystals of gem quality are rare (California, Brazil).

31

Andalusite represents a typical example of a mineral formed by contact metamorphism (hornfels, etc.). Typically, it often occurs in argillaceous rocks with a low lime content in contact aureoles around igneous intrusions. In places, andalusite is found in granite when the magma resorbed aluminum-rich sedimentary rocks. This mineral is also found in pegmatites and in accidental blocks (volcanic ejecta). Furthermore, andalusite is observed in mesozonal, aluminum-rich mica schists along with sillimanite, muscovite, biotite, almandine, and in some places also with cordierite and staurolite, although never with microcline. Properties. The following physical properties are important for industrial applications: Density: 3.09 3.16 g/cm3 Mohs hardness: 7 1/2 Phase changes: > 1350 C: decomposition to mullite and vitreous SiO2 ; on cooling, volume increases by 3 6 % with respect to the starting material 1840 C: incongruent melting point, conversion to corundum and vitreous SiO2 1920 C: complete fusion Specic heat capacity (0 100 C): 0.705 J g1 K1 Thermal conductivity: at 0 C 2.26 kJ m1 h1 K1 , at 189 C 4.08 kJ m1 h1 K1 The ideal chemical composition is the same as that of kyanite and sillimanite: 62.93 wt % Al2 O3 , 37.07 wt % SiO2 . Andalusite is not attacked by mineral acids apart from hydrouoric acid, which attacks it very slowly in the cold, but readily when hot. Andalusite is stable towards dry HCl and Cl2 . Fused KOH strongly attacks andalusite, as does a solution of CO2 in water at 160 C and 0.6 0.7 MPa. Deposits and Extraction. Andalusite deposits are mined in France (C tes du Nord), Poro tugal (Porto), the Republic of South Africa (in three areas of the Transvaal: Groot Marico, Lydenburg, Thabazimbi), the Peoples Republic of China and the United States (White Mountains; Hawthorne, Nevada). The overlying rocks above the andalusitebearing schists and sands are not usually very

32

Silicates

Figure 25. Structure of andalusite, Al[6] Al[5] [O/SiO4 ] A) Projection parallel to c on (001); B) [AlO6 ] octahedra along the c axis

thick. Therefore, extraction is mainly by opencast mining using explosives, compressed air hammers and front loaders. The French deposits contain schists in which the andalusite content, which is coarsely crystalline, is ca. 15 %. The andalusite crystals are up to several centimeters long in the direction of the c axis and 1 4 mm wide in the direction of the a and b axes. Accompanying minerals are biotite, iron-rich chlorite, and quartz. The material is processed to give two grades of andalusite concentrate: 59 % Al2 O3 with 1 % Fe2 O3 , and 53 % Al2 O3 with 1 % Fe2 O3 . Processed andalusite sand has a particle size of 0.3 1.6 mm and is slightly colored. In the Republic of South Africa, the andalusite is interbedded with schists. The primary deposits consist of andalusite-bearing schists in which the average content of extractable andalusite is 7 10 %. The secondary deposits are alluvial andalusite sands (placer deposits), in which the content of extractable andalusite is 10 50 %, reaching 50 60 % in the Burgersfort mine (Zimro). In the White Mountains area of the United States 3 20 m thick deposits containing 70 80 % andalusite occur. In Hawthorne, Nevada, the vein-like deposits are 0.5 1.5 m thick and 1000 m long. They are extracted to a depth of 30 m. Recently, a promising deposit was found near Tomduff in the Republic of Ireland. It consists of a series of andalusite schists and quartz-biotite schists, is 200 m thick, and continues for 3000 m along the strike.

Ore Treatment and Commercial Products. The broken schists and sands are crushed to a grain size of 0.3 1.6 mm (or to 0.6 3.35 mm by Weedons Minerals). Biotite, chlorite and other ferromagnetic minerals are removed by high-intensity magnetic separators. Quartz and other low-density minerals are removed by a wet process using settling tanks. These processes are described in detail elsewhere ( Magnetic Separation; Gravity Concentration). The dried andalusite concentrate is the commercial product. Commercial grades, with the amounts of major impurities, are listed in Table 10. The refractory properties of the mullite vitreous SiO2 matrix (that is formed from the andalusite concentrate by reaction at high temperature) improve with increasing Al2 O3 content (ideally 62.93 %). They also improve with decreasing TiO2 content (max. 2 %), decreasing Fe2 O3 content (< 1 % if possible) and decreasing alkali-metal content (uxing effect). Uses. Andalusite, like sillimanite, kyanite and synthetic mullite, is an important raw material for the production of highly refractory materials and is marketed with sillimanite and kyanite as sillimanite minerals. The increase in volume when andalusite is red above 1350 C is small (3 6 %), whereas the corresponding increase for kyanite is considerably greater. Andalusite of the proper neness is suitable for use as a ller in coatings and plastics subjected to great mechanical or chemical stress, due to its crystal chemical properties and mor-

Silicates
Table 10. Grades of andalusite concentrates Company Denain Anzin Mineraux Cullinan Andalusite Export minerals Marico Minerals Zimro Lager Mining Hoogenoog Andalusite Grade keraphalite KB standard premium normal upgraded Al2 O3 , wt % 59 53 52.5 54.3 56 58.8 61.6 59 57 59.9 60 Fe2 O3 , wt % 1.531 1 2 1.6 <1 1.3 0.6 1.2 1.2 2 <1

33

Denain Anzin Mineraux is located in Paris, all other companies are in the Republic of South Africa.

phology. The length : width ratio of the crystals is 10 : 1 50 : 1. However, the energy required for grinding is considerable owing to the hardness of the mineral. Economic Aspects. The annual consumption of crude rock by the Federal Republic of Germany, including material red to > 1350 C, is ca. 51 000 t. In France the annual consumption of sillimanite minerals is ca. 30 000 t and in the Republic of South Africa ca. 135 000 t. The Western countries have a consumption of ca. 170 000 t and the worldwide consumption of sillimanite minerals is ca. 300 000 350 000 t/a in the last few years.

direction [001], giving them a ruler-like appearance and, on the other hand, complete cleavage along (100) and the anisotropic hardness, i.e., 4 4 1/2 Mohs in the c [001] direction, and 6 7 Mohs perpendicular to this in the b [010] direction.

2.6. Kyanite
Kyanite [1302-76-7] (cyanite, disthene) belongs to the nesosubsilicates (orthosilicates that contain isolated [SiO4 ] tetrahedra and additional nontetrahedral anions) and, like andalusite (Section 2.5) and sillimanite (Section 2.7), is a mineral of the Al2 SiO5 group. Structure and Mineralogy. One aluminum atom (AlI , Fig. 26) always has the coordination number six, the [AlI O6 ] octahedra being linked by common edges to form chains parallel to the c axis. The other aluminum atom (AlII , Fig. 26) in kyanite also has the coordination number six. The chains of [AlI O6 ] octahedra are joined to other [AlII O6 ] octahedra, which are attached alternately to the right and left and are also linked via isolated [SiO4 ] tetrahedra to form stable planar structures parallel to [100]. Vacant octahedra form open channels parallel to (001). This accounts for the extension of the crystals in the c
Figure 26. Structure of kyanite, Al[6] Al[6] [O/SiO4 ], projection parallel to c on (001) Due to the low degree of symmetry, there are four different types of aluminum atoms, all with six- coordination. AlI and AlII in kyanite correspond to AlI in sillimanite (see Fig. 27) and andalusite (see Fig. 25) and form chains of octahedra.

The mineralogical formula of kyanite is Al[6] Al[6] [O/SiO4 ]. It forms triclinic pinacoidal crystals with space group C1 P 1; lattice constants: a0 = 0.710 nm, i b0 = 0.774 nm, c0 = 0.557 nm; the axial ratio is a0 : b0 : c0 = 0.917 : 1 : 0.720; = 90 051 /2 , = 101 02 , = 105 441 /2 ; Z = 4. The oxygen ions in kyanite are approximately in cubic close packing, yielding the highest density (3.53 3.65) of the Al2 SiO5 polymorphs. Ionic substitution is possible to a somewhat larger extent with kyanite than with sillimanite (Section 2.7), but is appreciably less than with andalusite (Section 2.5). Fe3+ can replace alu-

34

Silicates creases by 14 16 % with respect to the original mineral 1830 C: incongruent melting, forming corundum and vitreous SiO2 1920 C: complete fusion The ideal chemical composition is 62.93 wt % Al2 O3 , 37.07 wt % SiO2 . Kyanite is stable towards strong mineral acids. Attack by chlorine and dry HCl is only slight at red heat. Hydrouoric acid decomposes ca. 84 % of the material. Molten KOH strongly attacks kyanite. However, there is little attack by aqueous solutions of alkali hydroxides. Deposits and Extraction. Kyanite is a common constituent of crystalline schists. Few deposits can be extracted economically, and these consist mainly of schists that contain kyanite in crystal aggregates or as small coarse masses. Kyanite can also occur in lenses in pegmatites and in similar formations or nest-like masses in quartz veins. The worlds largest reserves are in the United States and stretch from northeast Georgia to South and North Carolina and Virginia in the Appalachians. Other large deposits are found in Canada and the Republic of South Africa. Deposits in the United States, Brazil, the Republic of South Africa, Zimbabwe, Spain and India are exploited commercially. In the United States, kyanite- containing quartzite is extracted using explosives and excavation, followed by grinding and otation. The otation concentrate contains 91 % kyanite and 2 5 % iron oxides, with silica making up the balance. The Fe2 O3 content of the dried concentrate is reduced to 0.16 0.94 % by highintensity magnetic separation. The commercial product contains 59.5 61.8 % Al2 O3 . A kyanite sillimanite concentrate is produced as a byproduct of the treatment of zirconium sands in Australia. In Spain, alluvial deposits of kyanite- containing gravel are dug by front-loading equipment. After washing and wet tumbling, the kyanite is picked out by hand, calcined at 1480 C, crushed and classied into grain sizes of 0 1, 1 3 and 3 5 mm. Its composition is Al2 O3 58 63 %, Fe2 O3 0.5 1.5 %, TiO2 0.15 0.5 % and alkali metals ca. 0.7 %.

minum in the lattice to a small extent, as can Cr3+ in rare cases, which leads to an increase in the refractive indices. Low levels of alkali metals and hydroxide have also been found in completely transparent kyanite crystals. Kyanite occurs mainly as radially arranged lamellar aggregates that may be tangled together. The crystals are intergrown, shaped like broad stalks or rulers that extend in the direction of the c (001) axis, and are frequently bent into a slightly waved shape and transversely striated due to translational movement. Kyanite is translucent to transparent and is usually blue, but is often ecked and irregularly colored. It can also be white or yellowish-white (rhatizite), pink or pinkish, with a nacreous or vitreous luster. Cleavage parallel to {100} is fully developed, is well-marked parallel to {010} and is poor or brous parallel to {001}. Cleavage parallel to {001} has the character of a brous fracture, since {100} also represents a slip plane with [001] as the slip direction. Kyanite is a typical mineral of (aluminumrich) metamorphic rocks, especially of mesozonal crystalline rocks, in which it is mainly associated with rutile, staurolite, almandine, hornblende, micas and corundum. It is occasionally found in gneisses, micaceous schists, granulites and eclogites. In catazonal rocks, kyanite only occurs in high-pressure formations because sillimanite is stable at lower pressures. Kyanite is the high-pressure form of Al2 SiO5 ; andalusite and sillimanite both crystallize at lower pressures, with sillimanite being the high-temperature form. On heating at atmospheric pressure, both kyanite and andalusite are converted monotropically to sillimanite. The conversion of kyanite to mullite and vitreous SiO2 is of industrial importance, because these reactions take place above ca. 1200 C. Properties. The following physical properties of kyanite are important for industrial applications: Density: 3.53 3.65 g/cm3 Mohs hardness: 4 1 7 2 Phase changes: < 1300 C: unstable with respect to sillimanite 1335 C: decomposition to mullite and vitreous SiO2 , on cooling, volume in-

Silicates Uses. Kyanite is an important raw material for refractory products (ceramics) and is marketed with sillimanite and andalusite as an industrial mineral. Unlike sillimanite, andalusite and mullite, kyanite undergoes a large volume increase (16 18 %) when heated above 1325 C. Powdered kyanite is therefore used in mixtures for ceramic and refractory products to compensate for shrinkage on ring. The refractory properties of the matrix of mullite and vitreous SiO2 formed from kyanite concentrates at high temperature are a function of its chemical composition.

35

b0 = 0.760 nm, c0 = 5.75 nm; the axial ratio is a0 : b0 : c0 = 0.979 : 1 : 0.757; Z = 4.

2.7. Sillimanite
Sillimanite (brolite) belongs to the nesosubsilicates (orthosilicates that contain isolated [SiO4 ] tetrahedra and additional nontetrahedral anions) and, like andalusite (Section 2.5), kyanite (Section 2.6) and mullite, is a mineral of the Al2 SiO5 group. Structure and Mineralogy. One aluminum atom (AlI , Fig. 27) always has the coordination number six. The [AlI O6 ] octahedra are linked by common edges to form chains parallel to the c axis. The other aluminum atom (AlII , Fig. 27) in sillimanite has the coordination number four. The chains of octahedra in sillimanite are laterally bonded by [AlII O4 ] and isolated [SiO4 ] tetrahedra which form bands of [Al2 Si2 O10 ] tetrahedra from two linked chains of [AlSiO6 ] (see Fig. 27). The four- coordinated aluminum in sillimanite cannot be substituted by silicon. Parallel to b (010), very strongly bonded layers are formed from the [AlO6 ] chains and [Al2 Si2 O10 ] bands. These can easily be cleaved from the neighboring layers by separation at the apices of the [AlO6 ] octahedra. This explains the perfect cleavage of sillimanite parallel to {010}. The chain structure also accounts for the generally brous structure of sillimanite crystals (brolite). As sillimanite has chains of tetrahedra, it is classied as an inosilicate (chain silicates, i.e., silicates with innite chains of [SiO4 ]4 tetrahedra). The mineralogical formula of sillimanite is Al[6] Al[4] [O/SiO4 ]. It forms orthorhombic dipyramidal crystals with space group D16 Pbnm; lattice constants: a0 = 0.744 nm, 2h

Figure 27. Structure of sillimanite, Al[6] Al[4] [O/SiO4 ], projection parallel to c on (001)

Sillimanite has low tolerance to ionic substitution, the aluminum atoms in the lattice being replaceable only by some Fe3+ and a small amount of titanium. Although alkali metals and hydroxide are often reported, they either occupy the spaces in the lattice or are impurities in the mineral. Sillimanite usually forms columnar, brous or matted aggregates. Single crystals are rare, but large crystals (about the size of a st) are produced synthetically. Dense masses intergrown with quartz are known as brous quartz. Sillimanite is yellowish gray, gray, brownish or grayish-green in color, is transparent to translucent and has a vitreous luster or a silky luster when in brous form. Sillimanite is usually a common minor constituent of ortho- and paragneisses (e.g., feldspar quartz cordierite gneisses), micaceous schists, granulites, eclogites, and of pegmatites and quartz veins that occur in these rocks. It also occurs in contact-metamorphic rocks, sometimes in the form of very ne bers. At high temperature (> 650 C theoretical, ca. 1480 C in practice), kyanite and andalusite are converted to sillimanite. At even higher temperature (1545 C), sillimanite is converted to mullite, which has a lower SiO2 content, and vitreous SiO2 . Accompanying minerals include feldspars, quartz, cordierite, muscovite, biotite, almandine, staurolite, corundum, andalusite, kyanite, rutile and ore minerals such as magnetite and ilmenite.

36

Silicates Republic of South Africa). World production is ca. 30 000 t/a. The deposits are mainly extracted by opencast mining. Due to the hardness of the rock, drilling and blasting are necessary. The rock is crushed and classied with screening equipment. Quality Specications (see Table 11). Sillimanite used in the production of clay- containing refractory products of group 1 ( Refractory Ceramics and ISO R 1109) must contain at least 56 % Al2 O3 (ISO R 1109). Uses. The most important use for sillimanite is in refractory materials. It is normally precalcined to ca. 1550 C to convert the sillimanite to sinter-mullite (see Section 2.8), which has a high thermal shock resistance and a very low coefcient of thermal expansion (5.6106 K1 at 20 1000 C). Sillimanite with a high corundum content is more resistant to slags with a high iron oxide content. Mechanically cut natural rock and bonded bricks are only used for lining blast furnaces, glass melting furnaces and roasting furnaces. Coarsely ground material is used for highly refractory mortars and ramming compounds. Finely ground material is used in the production of architecturally applied ceramics (e.g., sanitary ware or wall and oor tiles). Sillimanite is used as a ller in paints, coatings, adhesives and plastics, especially in systems cross-linked by polyaddition due to the nature of its surface (functional SiOH groups for polyaddition and polycondensation), high hardness, and ability to reinforce the matrix due to its acicular (i.e., needle-like) or brous structure.

Properties. Sillimanite is the modication of Al2 [O/SiO4 ] that is stable at high temperature and low pressure. Cleavage on (010) is fully developed, but the fracture is uneven. The following physical properties are important for industrial applications: Density: 3.23 3.25 g/cm3 (2.95 g/cm3 after heating at 1545 C) Mohs hardness: 6 7 Phase changes: 1545 C: decomposition to mullite and a vitreous matrix containing ca. 95 % SiO2 1810 C: liquid phase reaction to form corundum and a vitreous phase 1860 C: complete fusion > 1860 C: boiling of the melt, producing a vapor phase with a high SiO2 content and a liquid phase with a high Al2 O3 content Temperature stability limit in an oxidizing atmosphere: 1600 C Softening temperature under a load of 2 kg/cm2 : 1550 1650 C Thermal coefcient of expansion: at 20 100 C 2.8106 K1 , at 300 C 4.1106 K1 , at 800 C 4.3106 K1 , and at 1200 C 4.6106 K1 . Specic heat capacity: at 300 C 0.92 kJ kg1 K1 , at 1200 C 1.0 kJ kg1 K1 Thermal conductivity: at 300 C 5.4 5.9 kJ m1 h1 K1 , at 1200 C 4.6 5.0 kJ m1 h1 K1 Sillimanite (Al2 O3 SiO2 ) has the ideal chemical composition 62.93 wt % Al2 O3 , 37.07 wt % SiO2 . It is insoluble in water, is decomposed by ammonium uoride on heating and is resistant to weathering. Like the other Al2 [O/SiO4 ] modications, sillimanite is very difcult to melt and highly resistant to acids. Its chemical resistance when used as a refractory material is as follows:
Toward reducing atmospheres Toward carbon Toward acidic uxes Toward basic uxes Toward molten metals moderate moderate good moderate good

2.8. Mullite
Mullite [1302-93-8] belongs to the nesosubsilicates (orthosilicates that contain isolated [SiO4 ] tetrahedra and additional nontetrahedral anions) and is very similar to sillimanite (Section 2.7) in its structure and properties. Structure and Mineralogy. Mullite has a sillimanite structure, but differs from sillimanite in having a deciency of oxygen. Since some of

Deposits and Extraction. Sillimanite deposits occur in Australia, India, Namibia, the Republic of South Africa, Brazil and Sri Lanka. The sillimanite is usually associated with quartz and kaolin (Australia) or with corundum (India,

Silicates
Table 11. Sillimanite specications (wt %) Al2 O3 Highly enriched With a high corundum content 59 65 65 78 SiO2 39 33 33 20 Fe2 O3 <1 <1 TiO2 max. 2 max. 2 Na2 O/K2 O max. 0.1 max. 0.1

37

the silicon atoms in the [SiO4 ] tetrahedra are replaced by Al3+ , some of the positions normally occupied by oxygen atoms are left unoccupied to maintain charge balance. Therefore, mullite has a higher aluminum content than sillimanite and has a chemical composition between 3 Al2 O3 2 SiO2 and 2 Al2 O3 SiO2 . The mineralogical formula of mul[6] [4] lite is Al4 Al4 [O3 (O0.5 , OH, F)/Si3 AlO16 ] [6] [4] or Al4 Al4 [O4x/2 /Si4x Alx O16 ], where x = 1.0 1.6. It forms orthorhombic dipyramidal crystals, with space group D9 2h Pbam; lattice constants: a0 = 0.7566 nm, b0 = 0.7682 nm, c0 = 0.2884 nm (i.e., half of c0 for sillimanite); the axial ratio is a0 : b0 : c0 = 0.985 : 1 : 0.375; Z = 1. Synthetic mullite, 3 Al2 O3 2 SiO2 , has lattice constants a0 = 0.7576 nm, b0 = 0.7688 nm, c0 = 0.2884 nm; the axial ratio is a0 : b0 : c0 = 0.981 : 1 : 0.375. Synthetic mullite, with the composition 2 Al2 O3 SiO2 , has lattice constants a0 = 0.7576 nm, b0 = 0.7687 nm, c0 = 0.2883 nm; the axial ratio is a0 : b0 : c0 = 0.986 : 1 : 0.375. Another modication of Al2 SiO5 appears to be a newly discovered phase in the system Al2 O3 SiO2 H2 O, crystallizing in the orthorhombic dipyramidal system, with space group D9 Pbam; lattice constants: 2h a0 = 0.755 nm, b0 = 0.827 nm, c0 = 0.283 nm; the axial ratio is a0 : b0 : c0 = 0.913 : 1 : 0.342. These cells of mullite are subcells (i.e., the ordering effects of the oxygen defects and of the silicon and aluminum ions are neglected). There are always six (silicon + aluminum) ions per subcell in mullite and twelve (silicon + aluminum) ions with doubled c lattice constants in sillimanite. In a few cases, ordering is found, and additional superlattice reexes are observed corresponding to a larger unit cell, e.g., a0 = 3a0 , b0 = 8b0 , and c0 = 6c0 , and a0 = 0.74 nm, b0 = 0.76 nm and c0 = 0.29 nm. Sillimanite is ordered, with c0 = 2c0 , and the same must also be true for pr gite, 2 Al2 O3 SiO2 , which is a only known as a synthetic product.

In naturally-occurring mullite, Fe3+ or Ti4+ can replace Al3+ to a small extent (up to 1 wt % Fe2 O3 and up to 2 wt % TiO2 ). Natural mullite forms small pseudotetragonal colorless, white, yellowish or reddish crystals with columnar or needle-like development in the c [001] direction. Cleavage is well developed on (010), but is difcult to observe due to the normally small size of the crystals. Synthetic mullite is colorless, but green when Al3+ is substituted by Cr3+ . In synthetic products (e.g., chamottes and porcelain bodies), mullite has extremely ne crystals (< 1 m). When these crystals come into contact with slags, larger prismatic crystals often form at the reaction interface. Melt-mullite products contain even larger crystals. Occurrence and Formation. Mullite is not very often found in natural rocks. It greatly resembles sillimanite, with which it can easily be confused. It occurs almost entirely in contactmetamorphosed formations in primary argillaceous sandstones and phyllites contained as inclusions in basalts and also in a narrow exogenous contact zone (buchite) with anatexis at the edge of basalt pipes. The name mullite stems from its occurrence in sintered lumps of sedimented clay in the basalt of the island of Mull in Scotland. The formation of mullite in synthetic products, such as chamotte products, porcelain and high-aluminum slags (e.g., from coal and coke) is of great industrial importance. It is formed when kaolinite is strongly heated or calcined to 1200 1600 C and is also produced when kyanite, andalusite, sillimanite or other aluminosilicates are strongly heated, decomposing them into mullite and vitreous SiO2 . At 1810 C, mullite dissociates into an equilibrium mixture of corundum and molten SiO2 . However, some investigations have shown that mullite can have a congruent melting point. In silicate slags, mullite only crystallizes if minor amounts of basic oxide components are present. Very small amounts of Na2 O, etc., signicantly reduce the dissociation temperature of mullite.

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Silicates
Toward reducing atmospheres Toward carbon Toward acidic uxes Toward basic uxes Toward molten metals moderate moderate good moderate moderate

Properties. The following physical properties are important for industrial applications: Density: 3.10 3.16 g/cm3 Mohs hardness: 6 7 Phase changes: 1810 C: incongruent melting with decomposition to corundum and a vitreous phase 1920 C: complete melting Crystallization: Occurs readily from the melt, welldeveloped crystals (usually nely matted together) are formed, even on very rapid cooling Temperature stability limit in an oxidizing atmosphere: 1850 C Thermal expansion coefcient: at 500 C 4.0106 K1 , at 1000 C 4.5106 K1 , at 1500 C 5.3106 K1 Specic heat capacity: at 25 C: 0.633 Jg1 K1 Thermal conductivity: at 100 C 22.2 kJ m1 h1 K1 at 500 C 15.5 kJ m1 h1 K1 at 1000 C 14.2 kJ m1 h1 K1 Electrical resistivity: at 500 C 3105 cm, at 1000 C 7103 cm, at 1500 C 5102 cm The ideal composition of mullite is 71.8 wt % Al2 O3 , 28.2 wt % SiO2 . Both natural and synthetic mullite often deviate from the composition 3 Al2 O3 2 SiO2 (60 mol % Al2 O3 ), and an Al2 O3 content of 63 mol % is not uncommon. Mullite is obtained as a solid crystalline mass by sintering a mixture of Al2 O3 and SiO2 in the molar ratio 3 : 2 at 1775 C. Water and strong mineral acids do not attack mullite even when heated. Mullite also resists concentrated hydrouoric acid at room temperature for long periods, although rapid decomposition takes place on heating to 70 100 C. Resistance to molten metals and basic compounds is moderate. To achieve complete breakdown, mullite must be fused with sodium peroxide or a mixture of sodium carbonate and borax glass. The chemical resistance of mullite in refractory materials is:

Deposits. Natural mullite is mined from only one signicant deposit in northern Transvaal in the Republic of South Africa (Otavi Mining Company). The production rate is ca. 5000 t/a. Synthesis. Synthetic mullite is of considerable economic importance. Outputs are as follows: United States ca. 27 000 t/a , United Kingdom: > 12 000 t/a. Producers in Germany Vereinigte Aluminiumwerke and H lst AG; in the u United Kingdom Keith Ceramic Materials Ltd.; in Hungary Hungary Motim Alumina and Electrocorundum Factory; in the United States Washington Mills Electro Minerals Corp.; in Brazil Elfus Ltda.; in Japan Showa Denko KK. For the very great demands placed on refractory materials, mullite is superior to the sillimanite minerals (sillimanite, andalusite, kyanite), which can be converted into crystalline mullite and a vitreous SiO2 matrix only after calcination. Two main grades of synthetic mullite are produced: fused mullite (electromullite) and sinter mullite. Fused zirconia mullite is also produced. In general, sintered mullite is manufactured in a rotary kiln, whereas fused mullite is produced either in a Higgins furnace or using a tilt-pour electric arc furnace. Electromullite. A mixture of kaolinite and calcined aluminum oxide in a precisely controlled ratio is melted in an electric arc furnace. The product is crushed and classied into various grain sizes. In the selection of the raw materials, careful attention must be paid to levels of impurities, especially iron, other heavy metal ions and alkali metals. Metallic contaminants generated by abrasion of the crushing and classifying equipment are removed by magnetic separators. The reaction product contains up to 95 % mullite and 76.4 75.2 % Al2 O3 . The following composition is given for an English grade: mullite 95 %, vitreous matrix and corundum 5 %, SiO2 23 %, Al2 O3 76.2 %, Fe2 O3 0.1 %, CaO 0.2 %, MgO 0.1 %, K2 O + Na2 O 0.4 %. The melting point (Seger cones) is ca. 1900 C, and the material withstands long-term loading at 1750 C.

Silicates Sinter mullite. The purity of this material is somewhat lower than that of electromullite. Briquettes of kaolinite, aluminum hydroxide and some water for bonding are sintered in tunnel furnaces at 1750 C and are then crushed and classied into size fractions. The product contains ca. 86 % mullite (i.e., 72.9 % Al2 O3 ), ca. 0.7 % Fe2 O3 and small amounts of other impurities. It withstands long-term loading at 1700 C. The sinter mullite produced by the Vereinigte Aluminiumwerke (Germany) has the following specication: Al2 O3 72 %, SiO2 16 %, density 3.1 g/cm3 , mean particle diameter 30 m, maximum particle size 100 m, color white. Uses. The main area of use for mullite is in highly refractory materials for lining metallurgical melting furnaces and glass melting tanks, along with other applications where strongly acidic attack takes place at high temperatures. Mullite is also used as a raw material for porcelain for electrical insulation, as an opacier for high-quality enamels, as a polishing medium (due to its great hardness), as a ller in plastics and paints, and as an abrasion-resistant reinforcing ller in coatings for surfaces and roadways that are subject to severe mechanical stress. Some of the synthetic mullites distinguishing attributes (e.g., excellent thermal shock resistance, good hot strength under load, volume stability at high temperatures, low shrinkage, high resistance to aggressive melts and slags, good abrasion resistance, and additionally high creep resistance of fused mullite) also permit its wide use. Refractories for the steel and glass industries are the most important market for sintered and fused mullite and fused zirconia mullite. Synthetic mullite is also used in the ceramic industry.

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2.9. Vermiculite
Structure and Mineralogy. Vermiculite belongs to the phyllosilicates (sheet or layer silicates) and has a mica-like foliated structure. It displays the typical properties of the montmorillonite saponite group to a pronounced degree: the layers have a greater excess charge and a greater capacity for cation exchange than talc or pyrophyllite layers. The structure contains

layers similar to those found in talc, pyrophyllite ( Talc), biotite, and muscovite ( Mica, Chap. 2.). It comprises innite, two-dimensional double silicate layers 2 [Si4 O10 ]4 (Fig. 28). Part of the Si4+ is substituted by Al3+ , and the terminal oxygen ions of the [(Si, Al)O4 ] tetrahedra are always on the same side (Fig. 28 A). The hexagons formed by these oxygen ions have hydroxyl groups at their centers. In this double layer, the oxygen layers formed from O (bound to one Si) and OH groups face each other directly, forming octahedral voids. These voids are occupied mainly by Mg2+ , but also by Fe3+ and Al3+ (Fig. 28 B), which hold together the two Si2 O5 /OH sheets. The octahedral voids are formed by four oxygen atoms and two hydroxyl groups. Due to the partial replacement of Si4+ by Al3+ , the double layer pocket Mg3 [(SiAl)4 O10 /(OH)2 ] has a slight excess negative charge, which is compensated by additional cations, e.g., Mg. These cations, together with water molecules, are interlayered between the layer pockets, usually Mg2+ or, less frequently, Ca2+ . This interlayer (intermediate layer) has a positive excess charge and consists of a double layer of H2 O Mg2+ H2 O, in which the H2 O locations may be only partially occupied. Each H2 O in this interlayer is linked to an oxygen atom in the neighboring silicate double layer by a hydrogen bond. Thus, vermiculite structurally resembles a kind of talc expanded by H2 O that has been formed from (hydrous) mica by potassium depletion. The swelling capacity (ability to be hydrated) of vermiculite is due to the fact that the silicate layers have a slight excess negative charge and thus repel each other; this facilitates the penetration of water into the interlayer with its small positive excess charge. Unbonded water can be removed from the vermiculite by heating to < 110 C, but the water xed by cations in the interlayer is only released at > 300 C. On heating, the water in the interlayer is released either gradually or, on sudden heating, with expansion and formation of worm-shaped structures. Exfoliation causes unidirectional expansion perpendicular to the cleavage plane (001) and the volume increases greatly (from 8- to 50-fold). If the trapped water is driven off slowly, even at 250 C vermiculite shows no exfoliation. Exfoliation of vermiculite can also be caused by treatment with hydrogen peroxide, which leads

40

Silicates

Figure 28. Structure of vermicullite A) The two-dimensional innite silicate layer [(Si, Al)4 O10 ]x , projection parallel to c on (001); B) Intermediate H2 O Mg2+ H2 O layer between two silicate double layers, projection perpendicular to the a axis

to release of oxygen by reaction with interlayer magnesium ions. The mineralogical formula of vermiculite is:
(Mg, Fe3+, Al)3 [(OH)2 /Al1.25 Si2.75 O10 ] Mg0.33 (H2 O)4

or
Mg2.36 Fe3+ Al0.16 [(OH)2 /Al1.28 Si2.72 O10 ]0.64 0.48 Mg0.32 (H2 O)4

Vermiculite forms monoclinic crystals, with the following lattice constants: a0 = 0.533 nm, b0 = 0.918 nm, c0 = 21.436 nm; = 97 ; the distance between the layers, d002 = 1/2c sin , is ca. 1.425 nm. Batavite and protovermiculite are related to vermiculite and have similar compositions and lattice constants. In nickel vermiculite, a high proportion (10 25 atom %) of the Mg2+ ions is substituted by Ni2+ . The alkali metal content of vermiculite is always very small, and high contents are due to replacement of layers of vermiculite by layers of biotite. An increase in the number of these biotite layers can eventually lead to the formation of hydrobiotite. Another mixed-layer mineral is formed by interlayering of the vermiculite with chlorite; when there

is a high iron content, this is known as jefferisite, and when the interlayering is regular, with a 1 : 1 ratio, it is known as corrensite. Crystals of vermiculite can reach a size of several centimeters and are then easily confused with biotite. However, they are usually much smaller (2 m) and can be of the size of clay particles when they occur in sediments. Vermiculite forms monoclinic pseudohexagonal, short, columnar platelets and mainly occurs in aggregates, which can be bent into worm-like shapes. Fibrous formations can also occur, but are very rare. Vermiculite is brown, bronzecolored, yellow, green, or colorless. Cleavage on (001) is perfect and mica-like, but the platelets are not elastic as in micas. Deposits of vermiculite often occur in ultrabasic and basic rocks (e.g., pyroxenites, hornblendites, peridotites and their metamorphic equivalents) that have undergone hydrothermal potassium metasomatism and alteration to actinolite biotite formations. These in turn can be altered in the nal stages potassium of this metasomatism or by anhydrous processes to formations of vermiculite and hydrobiotite with relicts of phlogopite, biotite, tremolite and actinolite. The alteration of biotite to vermiculite takes

Silicates place by leaching of K+ from between the silicate layers by hydrothermal activity, percolating ground water or supergene weathering. Vermiculite found as an alteration product of biotite in other metamorphic rocks, such as schists and gneisses, is of similar origin. Vermiculite is only rarely found as an alteration product of mica in marine sediments. In places, vermiculite is found in these sediments as an alteration product of, e.g., chlorite and amphibole. Vermiculite occurs occasionally in marble and in carbonatites. Of some economic importance are vermiculite deposits in the contact zones between ultrabasic and basic rocks and acid intrusives. Vermiculite is transformed into enstatite and talc on heating to 650 C. Under increasingly severe hydrothermal conditions (< 200 C, 70 MPa) it is converted into pseudochlorite, which is itself converted to chlorite and montmorillonite at ca. 550 C. Vermiculite is easily altered into biotite by potassium metasomatism, although this process is only rarely observed in nature. Properties. The following physical properties are of interest for industrial applications: Density: 2.3 2.75 g/cm Mohs hardness: 1 1/2 2 Sintering temperature: ca. 1260 C Fusion point: 2000 2400 C mp: 1315 C Specic heat capacity: 0.84 kJ kg1 K1 Thermal conductivity: 0.062 0.065 W m1 h1 K1 Deposits and Extraction. Deposits of economic importance are found in northern Transvaal (Republic of South Africa), at Libby in Montana, at Louise in Virginia, and at Encoree in Laurens County in South Carolina (USA). Further deposits occur in Brazil, Zimbabwe, Kenya, Australia, India, China, Russia and Japan. The vermiculite in these deposits has been formed from phlogopite and biotite by weathering (leaching of K) and hydrothermal alteration. The vermiculite at Encoree in South Carolina occurs in metamorphic rocks in contact with acidic intrusions interspersed with pegmatites. Accompanying minerals include corundum, apatite, serpentine, chlorite, talc and mica. At Palabora in the Transvaal (Republic of South Africa), the Archean contains a Protero-

41

zoic intrusive alkali rock complex that consists of, e.g., pyroxenite, syenite, ultrabasic pegmatoids and carbonatite. This intrusive complex is not only well known for its large copper deposit, but also has an outstanding vermiculite deposit. The vermiculite is an alteration product of phlogopite and is free of asbestos. The vermiculite bearing zones are selectively extracted by open-cast mining, The ore is loosened by blasting and removed by front loaders. The vermiculite ore is beneciated by screening, jigging and classication. Processing has three aims: 1) To separate the vermiculite from the accompanying rock, including rudimentary biotite and phlogopite 2) To delaminate the books formed from the vermiculite layers and to split the leaves (thickness > ca. 0.8 mm) into akes 3) To classify the akes into commercial particle size fractions In the rst stage, the rock is usually broken into < 20 mm or < 16 mm granules, and the adhering ne material is removed by washing and screening. Further size reduction separates the vermiculite from the accompanying rock. In a process operated by Palabora Mining (RSA), the vermiculite akes are separated from the accompanying rock, including mica, by multistage screening in a horizontal stream of air using various suspension techniques. The products from both the United States and South Africa are separated into ve or six size grades in the millimeter range. The chemical compositions are listed in Table 12. Compared with the North American material, South African vermiculite has undergone a higher degree of physical transformation, gives a higher yield on thermal expansion, and therefore has a higher market value. The difference can also be seen from the chemical composition. Expansion. Vermiculite, similar to perlite (exhibiting three-dimensinal expansion), expands when heated., but only in one direction (one-dimensional) showing the unique phenomenon of exfoliation by sudden heating to ca. 300 C or higher. Responsible for this exfoliation is a double layer of water (i.e., an

42

Silicates

Table 12. Chemical composition of raw vermiculite (average values, wt %) Component SiO2 MgO Al2 O3 Fe2 O3 K2 O Na2 O CaO Cr2 O3 MnO P2 O5 S Cl H2 O Total Libby, Montana 38.64 22.68 14.94 9.29 7.84 1.23 0.29 0.10 Trace Trace 0.28 5.29 100.58 Encoree, South Carolina 38.66 20.04 17.36 8.45 5.24 0.75 0.50 0.11 Trace Trace 0.52 8.71 100.34 Palabora (RSA) 39.37 23.37 12.08 5.45 2.46 0.80 1.46 0.30 0.15 0.18 0.02 14.24 99.88

H2 O Mg2+ interlayer) trapped between the silicate double layers and liberated upon heating, whereby the rapidly generated vapor cannot be set free without buckling and separating the structural layers. The low thermal conductivity and low density of expanded vermiculite lead to its widespread use in thermal and acoustic insulation applications, as well as in refrigeration engineering. Expansion occurs prerpendicular to the cleavage plane (001). The suitability of a particular vermiculite for conversion to expanded aggregates can be assessed by differential thermal analysis. However, the temperature time prole of the furnace used for expansion can only be established with certainty by a laboratory-scale expansion test. For the expansion and exfoliation of vermiculite various furnaces (e.g., rotary, cascade, vibrating tray, injection tray) can be used. The vermiculite concentrate is heated to between 430 and 1100 C. The water in the vermiculite is liberated in three stages in 0.25 8 s, beginning with a reversible reaction at ca. 150 C, followed by the onset of exfoliation above 500 C and vaporization of the residual water at 870 C. The bulk density is reduced from about 640 1040 to 64 176 kg/m3 . In some industrial processes, the vermiculite akes are expanded in 5 8 s at 1250 1500 C and then cooled immediately to 400 C. Since exfoliated vermiculite shows a huge increase in bulk, only shipping of the vermiculite ore or concentrate is economic. Plants for expansion of the vermiculite are therefore generally located close to the consumers.

Uses. In its most important applications, vermiculite is used in its expanded state to exploit its low density, good thermal and acoustic insulating properties and high absorption capacity for liquids. Vermiculite is utilized in the construction industry for thermal and acoustic insulation. Thermal insulation is the largest market. Loose lling is widely used in the construction industry and in industrial applications for insulating hollow spaces (e.g., cavity walls), ceilings, walls and roofs. Loose-ll vermiculite is commonly a coarse grade with a particle size up to 16 mm and a bulk density of 56 72 kg/m3 . At cryogenic temperatures perlite is a better insulator, but vermiculite is also used in limited quantities for such purposes. Vermiculite is also utilized in the manufacture of castable insulation products. For producing high-alumina vermiculite cement, a fasthardening cement, alumina and lime are heated in a furnace to a high temperature. The product is ground to a powder, and vermiculite is added. Vermiculite cement can also be manufactured by combining it with Portland cement. Vermiculite cement is used in the production of ultralightweight aggregates for the construction industry (Table 13) and as lightweight insulation. Vermiculite is utilized as a constituent in the manufacture of refractory blocks and re bricks for use in furnaces up to 1200 C. In packaging technology, vermiculite is used to cushion impacts, for thermal insulation and to absorb liquids in case of breakage of the container.

Silicates
Table 13. Physical properties of vermiculite lightweight concrete Vermiculite/ cement ratio 8:1 6:1 4:1 Density, kg/m3 400 480 560 Compression strength, N/mm2 0.70 0.95 1.23 Thermal conductivity, Wm1 h1 K1 0.094 to 0.158 Shrinkage on drying, % 0.35 to 0.45

43

In metallurgy, it is used to cover molten metal for thermal insulation during intermediate storage prior to casting. Expanded vermiculite is also used with garden and house plants to store water and plant nutrients (hydroculture), as a lter for swimming pools and for absorbing spilled liquids. Economic Aspects. Total world production of crude vermiculite is ca. 512 500 t/a. Because of the short resources the production declined in the United States to ca. 177 000 t/a. Vermiculite is invariably expanded at a location close to the consumer to facilitate transport. The largest consumer country is the United States. European consumption is modest, most being imported from the Republic of South Africa. Although the total consumption of silicates used for thermal and acoustic insulation (including expanded perlite, hydrated and expanded broken glass, glass wool and rock wool) continues to increase, that of vermiculite is decreasing due to its comparatively high price.

Composition varies according to the type of deposit:


SiO2 Al2 O3 K2 O Na2 O CaO MgO Fe2 O3 TiO2 MnO2 SO3 H2 O, chemically bound Density Softening temperature Melting temperature Specic heat Bulk density, broken, classied 72.0 76.0 wt % 11.0 17.0 wt % 4.0 5.0 wt % 2.9 4.0 wt % 0.5 2.0 wt % 0.1 0.5 wt % 0.5 1.5 wt % 0.03 0.2 wt % 0.03 0.1 wt % 0 0.2 wt % 2 7 wt % 2.2 2.4 g/cm3 810 1090 C 1260 1340 C 831 J g1 K1 1.45 kg/L

The most signicant variations are in water content, which has an important inuence on the physical properties after expansion. Deposits and Processing. The most important European deposits are found in Greece (Milos, Kos), Italy (Sardinia), Slovakia, Hungary, Bulgaria and Iceland. Further important deposits are located in Turkey (Cumaovasi, Izmir), Canada, Australia, Japan and the United States (New Mexico). Perlite is commonly extracted by open-cast mining. It is then crushed (usually by cone crushers) and classied using vibratory screens into several grain sizes with closely specied tolerances. The industrial value of the classied ore depends on the temperature and time necessary for expansion, relative volume increase, ratio of closed to open bubbles (cells), nonexpandable fraction and compression strength of the product. Expansion. Like vermiculite, perlite expands when heated, but in three dimensions. Expanded perlite has excellent insulation properties, comparable to those of vermiculite, which it can substitute to some extent. Expansion is performed in two types of furnace: (1) tilted

2.10. Perlite
Perlite of rhyolitic composition is a natural, volcanic glass that is usually black or gray, but sometimes brownish red. It has curved shrinkage cracks and therefore breaks up into spheroidal granules. It is usually produced by rapid cooling of rhyolitic melts (rhyolite being the volcanic equivalent of granite). Being a volcanic glass, perlite contains few crystals and only a small amount of water (2 6 % combined water). Naturally-occurring glasses containing 3 8 % water are known as pitchstone (hydrated glass). Perlite was rst mined and expanded in 1946 in the United States. It has since been put to a wide range of uses in Europe. Thermally expanded perlite is increasing in importance as a lightweight ller in constructional units for thermal and noise insulation.

44

Silicates Milos) after expanding and grinding to 98 % < 40 m are given below:
Refractive index Brightness index Ry (according to DIN 53 163) Bulk density Tamped density Oil absorption number (standard grade) Water absorption number (standard grade) Water absorption number (hydrophobic grade) pH Thermal expansion coefcient (0 100 C) Thermal conductivity (25 C) Bulk density 0.04 kg/L 0.09 kg/L 0.13 kg/L Thermal conductivity (bulk density 0.09 kg/L) 20 C 400 C 800 C 1.49 82 85 0.080 kg/L 0.240 kg/L 500 600 g/100 g 400 500 g/100 g 20 25 g/100 g 89 0.007 K1

horizontal rotary furnaces through which the feed material passes in countercurrent ow to the combustion gas and (2) vertical rotary or blast furnaces through which the expanding grains and hot gases pass in cocurrent ow. Vertical expanders are more common. The expansion results from shock heating the grains to a temperature in the softening range (727 1127 C), which results in bursting. Then the water bound in the perlite vaporizes and the heatsoftened grains expand into light, cellular particles with up to 15 30 times the original volume. The cellular structure consists of numerous tiny, closed, thin-walled, glass-sealed air bubbles, which account for the excellent insulating properties of the expanded perlite. The optimum temperature time prole must be closely followed. Longer heating times lead to shrinkage of the heated aggregates, and higher temperatures cause shrinkage and/or melting. The expanded material is classied in cyclones. In some cases, the expanded perlite is ground by pendulum or roller mills. If the product is to be used as a ller or additive, it is treated to make it hydrophobic; it may be silanized with dilute aqueous silane suspensions, or coated with dilute, aqueous silicone oil emulsions. Quality. Important quality criteria for the expanded material include bulk density, ratio of closed to open air bubbles (cells), unexpanded fraction, and, if used as a ller, compression strength of the bulk material and binder requirement or water absorption properties. The bulk density of expanded perlite depends on the amount of chemically bonded water in the unexpanded material and on the temperature time prole used for expansion and can be 0.03 0.2 kg/L. The fraction of the material with open cells and the fraction of nonexpanded grains should not exceed 5 %. These parameters are both determined by a water-immersion test using material that has not been rendered hydrophobic. Properties. The most important properties for the diverse applications of expanded perlite are its extremely low density, low thermal conductivity, low thermal expansion, good sound absorption, adequate compression strength at a bulk density of > 0.1 kg/L, and resistance to acids, weathering, and microbial attack. The average properties of industrial perlite (from

0.04 W m1 h1 K1 0.05 W m1 h1 K1 0.06 W m1 h1 K1 0.05 W m1 h1 K1 0.11 W m1 h1 K1 0.22 W m1 h1 K1

When perlite is used as a ller and as an additive to lightweight concrete, very high compression strength and resistance to abrasion are required during mixing. These grades have higher densities (0.12 0.14 g/L) and are produced from rhyolitic rock. Uses. Expanded perlite is used as an ultralightweight aggregate in the construction industry and as lightweight insulation. The most important uses of expanded perlite (normally treated to render it hydrophobic) include loose-ll insulation, lled plaster board and wall elements, insulating silicate-bonded boards for thermal and ame protection, insulating bitumen-bonded boards for back facing, insulating boards and coating materials with polymer binders, mortar (bonded with cement, plaster, or silicate), polymer dispersion mortars and plasters for thermal insulation and prevention of condensation on walls and ceilings (e.g., in swimming pools and high humidity rooms). Coarse-grade expanded perlite (2 5 mm) is used in metallurgy to limit the loss of heat from molten metal surfaces. A ne grade (0.15 1.8 mm) is used as a thermal insulator in cryogenic applications. In cryogenic applications, expanded perlite is normally uses unfer vaccum conditions.

Silicates Expanded perlite, with a bulk density of 0.04 0.06 kg/L, is used as an adsorptive ltering aid in precoated lters (e.g., for drinking water or medicinal products). Economic Aspects. Next to the United States, Western Europe is now the largest consumer of perlite. World annual production of raw perlite is estimated to be ca. 1.8106 t. In Germany ca. 100 000 t/a perlite is expanded, of which ca. 70 000 t (corresponding to ca. 580 000 m3 ) is used as a raw material for the building industry. The amount of perlite (from Italy, Greece and Iceland) expanded in the United Kingdom is > 120 000 t/a. The total for France is ca. 90 000 t/a.

45

2.11. Pumice
Pumice [001332-09-8] is not a crystalline silicate mineral, but a light-colored, highly vesiculated, foamed volcanic glass of mainly acid character (> 66 % SiO2 , rhyolite), with a high melt viscosity, high pore volume (> 50 %) and variable water content. Rhyolite itself is an acid volcanic rock consisting of feldspar, quartz, biotite, etc. and glassy groundmass. By rapid undercooling (quenching) of rhyolitic magma, volcanic rocks are produced which consist completely or almost completely of volcanic glass, named obsidian (containing less than 1 wt % H2 O and composed of more than 80 wt % of volcanic glass including mostly very negligible amounts of minute inclusions of quartz, tridymite, feldspar, fayalite, etc.) or pumice, the latter highly vesiculated. Volcanic lava of rhyolitic composition releases enclosed gases (water vapor, carbon dioxide, nitrogen, sulfur dioxide, chlorine, etc.) at ca. 1000 C explosively as a result of an abrupt pressure drop forming bubbly pumice. Due to its high porosity, pumice is very light and oats on water. The specic heat capacity of pumice is 1.00 J g1 K1 and its thermal conductivity at 50 C is 0.274 W m1 h1 K1 . Crushed and classied pumice is employed as an additive in light insulating concrete used to make constructional units. Due to its limited compression strength, this building material can only be used for one- or two-storey buildings or for cladding load-bearing frameworks.

The specic heat capacity of pumice concrete is 1.005 kJ kg1 K1 and its thermal conductivity is 0.457 W m1 K1 for a density of ca. 1.1 kg/L. Building blocks (e.g., Bisotherm, Bisothermwerke Carl Riffer, Urmitz) consist of pure, natural pumice granules treated to remove organic and inorganic impurities. Denser inorganic impurities such as fragments of obsidian and lavastone are removed by air separation and organic impurities by calcining at ca. 400 C in rotary kiln (DIN 18 151, 18 152). They are mainly used to build houses. Pumice in different industrial grades has a wide range of applications: stonewashing of denim and cotton, in agriculture (soil substitute, additive), paint manufacture (non-skid coatings, acoustic insulating ceiling paints, llers for textured paint), chemical industry (ltration media, chemical carriers, pesticide carriers), cleaning and polishing of metals and plastics, compounders (powdered hand soaps, glass cleaners), dental and cosmetic (polishing natural teeth and dentures, smoothing rough skin), rubber (erasers, mold-release agents), glasses and mirrors (TV tube processing, glass bufng and polishing), furniture (hand-rubbed satin nishing, piano keys, picture frame gold leang), leather (bufng), electronics (cleaning circuit boards) and pottery (ller). Powdered pumice is used as an abrasive, as a polishing medium, as an antiskid material and as an additive to pumice soap. It is also used as an absorption medium due to its large surface area (e.g., in packages carrying breakable liquid containers). As an insulator, pumice competes with expanded perlite (see Section 2.10) and expanded, exfoliated vermiculite (see Section 2.9). The output of pumice in Germany is ca. 2.4106 t/a, worldwide ca. 6.5 7106 t/a. Important commercially exploited pumice deposits occur in Germany (Koblenz-Neuwied district), in Italy (isle of Lipari northeast to Sicily, and around Naples), on volcanic Greek islands (Dodecanese group: islands of Yali and Nisyros, Cyclades group: Thera Island), in Spain (Province of Ciudad Real, Canadas area on isle of Tenerife), Portugal (on the volcanic island of Sao Miguel in the Azores), the United States (in central New Mexico in the area of Santa Fe, at Gate in Oklahoma, and in Idaho and California),

46

Silicates 4000 kg/cm2 , with a maximum of 5800 kg/cm2 ) and transverse strength (150 250 kg/cm2 , DIN 52 100). It should be as homogeneous as possible and should be resistant to frost, acids and waste gases (e.g., ue gas). The shapes of the naturallyoccurring blocks of material also inuence possible uses, e.g., columnar masses with polygonal cross sections, having 4 7 sides (feldspar basalts). The density of basalt varies between 3.00 and 3.15 g/cm3 , the bulk density between 2.95 and 3.00 g/cm3 and the bulk density of basalt lava between 2.20 and 2.35 g/cm3 . The porosity of basalt varies between 0.2 and 0.9 vol %, and of basalt lava between 20 and 25 vol %. Thus, the water absorption of basalt varies between 0.1 and 0.3 wt %, and of basalt lava between 4 and 10 wt %. The specic heat capacity (0 770 C) is ca. 1.09 J g1 K1 , and the thermal conductivity (0 100 C) is ca. 0.028 W cm1 K1 . The linear expansion coefcient is ca. 9106 K1 . Anhydrous basalt begins to melt at ca. 1280 C, but at only ca. 1100 C if it contains 1 % water. Basalt wool is stable up to 900 C. Sunburnt basalt is unsuitable for many applications. It is affected by weathering very soon after it is mined, especially by the heat of strong sunlight in the presence of moisture. Characteristic white spots are formed, and the rock crumbles. This phenomenon is not limited to basalts alone, but can also occur with other effusive rocks (e.g., phonolite). The sunburning disease of basalt is probably mainly due to the conversion of nepheline into analcime (Na[AlSi2 O6 ] H2 O), which is accompanied by a volume increase of ca. 5.5 %.

on Caribbean islands (Dominicana, Martinique), on volcanic islands of Japan (southern parts of Hokkaido and Kyushu), and in New Zealand (North Island).

2.12. Basalt
Basalt is the most common volcanic rock, occupying large areas of the Earths surface (e.g., plateau basalt). It contains < 52 % SiO2 and is the volcanic equivalent of the gabbro rock family. Basalt has a dense, compact, sometimes granular or porphyric structure and is dark to black in color. The main constituents of the matrix are plagioclase (anorthite 50 75 %) and pyroxene (mainly augite). Accessory minerals include olivine, magnetite, ilmenite, alkali feldspar, alkali pyroxene, alkali amphibole, feldspathoids and volcanic glass. Basalts are worldwide by far the most extensive exposed crustal igneous rocks, and their formation can be observed even now (e.g., numerous volcanoes in Asia, the United States, Europe and at the mid-ocean ridges). The most important types are the tholeiitic basalts (often associated with some olivine and, when supersaturated with SiO2 , even quartz) and the alkali basalts (feldspathoids, alkali pyroxene, alkali amphibole and olivine). Mediumto coarse-grained basalts are known as dolerites, while olivine basalts (which contain feldspathoids as well as plagioclases) are known as basanites, and anchimetamorphic basalts of the Permian/Carboniferous era are known as melaphyres, diabases and greenstones. The largest single basalt mass in Europe is in the Vogelsberg region of Germany. Other large deposits are in Hegau, the Eifel, the Westerwald and the Rh n mountains. Another deposit exo tends from the Oberpfalz (Bavaria), through the Erzgebirge and as far as the Lausitz region. Some basalts have high strengths and are therefore used in the construction industry, e.g., as hard core, paving stones and building materials. In another important application, molten basalt is converted into refractory bers (mineral wool for insulation and re protection) ( Fibers, 5. Synthetic Inorganic, Chap. 2.2.). The physical properties required depend on the use intended for the basalt. These include high compression strength (2500

2.13. Wollastonite
Wollastonite [013983-17-0], Ca3 [Si3 O9 ], is polymorphic. Three modications occur naturally, the commonest being low wollastonite which has two polytypical structural modications: triclinic wollastonite (-1T) and monoclinic wollastonite (-2M, parawollastonite). Structure and Mineralogy. In monoclinic wollastonite, the [SiO4 ] tetrahedra are linked to form innite one-dimensional dreier single chains of [Si3 O9 ]6 units (Fig. 29). These are bonded together by Ca2+ ions (which balance

Silicates the electrical charge), and the chains lie parallel to b [010]. This explains why the crystals are always extended in the direction of b [010]. The monoclinic structure is derived from the triclinic by inner twinning on the (100) plane. Wollastonite (-1T) and wollastonite (-2M) are therefore inosilicates (silicates containing [SiO4 ] tetrahedra in innite chains).

47

Figure 29. Basic conguration of [SiO4 ] tetrahedra in the innite one-dimensional dreier single chains [Si3 O9 ]6 of wollastonite, Ca3 [Si3 O9 ]

Cyclowollastonite (high wollastonite or pseudowollastonite) is a cyclosilicate and is stable above 1126 C. The [SiO4 ] tetrahedra are arranged in three-membered rings [Si3 O9 ]6 , which are linked together and neutralized by Ca2+ ions (Fig. 30). High-pressure Ca3 [Si3 O9 ] also contains rings of tetrahedra.

Figure 30. Basic conguration of [SiO4 ] tetrahedra in the dreier single rings of [Si3 O9 ]6 of cyclowollastonite, Ca3 [Si3 O9 ]

Wollastonite (-1T), Ca3 [Si3 O9 ], forms triclinic pinacoidal crystals, with space group C1 P 1, and has the following lattice constants: i

a0 = 0.794 nm, b0 = 0.732 nm, c0 = 0.707 nm; the axial ratio is a0 : b0 : c0 = 1.084 : 1 : 0.966; = 90 02 , = 95 22 , = 103 26 ; Z = 2. Wollastonite (-2M), (parawollastonite), Ca3 [Si3 O9 ], forms monoclinic prismatic crystals, with space group C5 2h P 21 /a; lattice constants: a0 = 1.536 nm, b0 = 0.729 nm, c0 = 0.708 nm; the axial ratio is a0 : b0 : c0 = 2.107 : 1 : 0.971; = 95 241 /2 ; Z = 4. Cyclowollastonite (high wollastonite, pseudowollastonite), Ca[Si3 O9 ], forms triclinic pseudohexagonal crystals (b:a= 1.707 3); lattice constants: a0 = 0.690 nm, b0 = 1.178 nm, c0 = 1.965 nm; the axial ratio is a0 : b0 : c0 = 0.586 : 1 : 1.668; = = 90 , = 90 48 ; Z = 8. High-pressure Ca3 [Si3 O9 ] forms triclinic crystals with lattice constants a0 = 0.6695 nm, b0 = 0.9257 nm, c0 = 0.6666 nm; the axial ratio is a0 : b0 : c0 = 0.723 : 1 : 0.720, = 86 38 , = 76 08 , = 70 23 . In natural wollastonite, Ca2+ can only be substituted to a very small extent (ca. 1 2 atom %) by Mg2+ , Fe2+ and Mn2+ . Alternatively, it can be substituted by 2 wt % Al2 O3 . In the wollastonite (-1T) found in industrial products, (-Ca3 [Si3 O9 ]), Ca2+ can be substituted by Fe2+ up to 70 wt % FeSiO3 . In industrial cyclowollastonite, (-Ca3 [Si3 O9 ]), Ca2+ cannot be substituted by Fe2+ , but can be substituted by Mn2+ up to 1 2 atom % and by Sr2+ over the entire concentration range. Wollastonite is usually intergrown and wellformed crystals are very rare. It occurs mostly in the form of thick plates parallel to {100} and {001} and is always extended on the b axis [010]. It is often found in coarse masses, in at, thin, divergently radiating masses, or in stalked, spiky, tabular, lamellar or nely brous aggregates and masses. Magmatic formation of wollastonite is possible where the magma resorbed calcium while in contact with limestones. This mineral is found in some alkaline igneous rocks and in phonolites, andesites, etc. Wollastonite is commonly a product of contact metamorphism, and sometimes also of regional metamorphism. Under the conditions of contact metamorphism, wollastonite is formed at high temperatures from quartz and calcite in siliceous limestones and by SiO2 metasomatism in pure limestones. Cyclowollas-

48

Silicates The reaction is accelerated by the addition of mineralizers (e.g., 1 wt % NaCl, Na2 WO4 or CaF2 ). The solid-state reaction between CaO and SiO2 is also accelerated in the presence of water vapor. Finely ground CaO and SiO2 are melted together in the molar ratio 1 : 1, the melt is then rapidly cooled to form a glass, and the vitreous product is then heated to 800 1000 C. Deposits and Processing. Although wollastonite (-1T) and wollastonite (-2M), which is somewhat rarer, are widely distributed, in the past only a few deposits were extracted economically up to the 1980s, when the demand for wollastonite and its production increased and doubled in less than 10 years. The most important deposits are in the United States (Willsboro and Harrisville in the State of New York, Riverside in California, Tonopah in Nevada), China (Meiyaoshan and Tiengongshan in Jilin province, Fulapu and Shijianfang, near Faku in Liaoning province, Xinyu in Jiangxi province, Daye in Hubei province, Changxing in Zhejiang province, Qinghai province), India (Belka in the Sirohi District, Kheratarala in Udaipur District), Finland (Lappeenranta), along with Mexico (La Blanca and Panllo Natera in Zacatecas State), Chile, Namibia (Usakos), Kenya (Kajiado), Turkey, Pakistan, North Korea, Russia, Canada, Spain, Greece, Morocco, New Zealand and Cuba. In the Willsboro mines, the rock contains ca. 60 % wollastonite (-1T) and (-2M), ca. 40 % almandine, and some diopside. It is crushed in three stages to < 16 mesh (1.2 mm). The almandine is then removed by magnetic separators. The wollastonite concentrate is nally ground and classied by air elutriation. The rock from Lappeenranta contains an average of 20 % wollastonite (-1T) and (-2M) and accompanying minerals: calcite, dolomite, and quartz. Treatment consists of wet grinding (rod mills), classication (hydrocyclones), otation (the wollastonite becomes concentrated at the bottom of the otation cell), magnetic separation of the wollastonite concentrate, ltration and drying. The nished product consists of 90 % wollastonite, 4 % quartz, 4 % calcite and 2 % other silicates. Table 15 gives the chemical composition of commercial wollastonite products. Table 14

tonite is only rarely found in metamorphic rocks (e.g., south-west Iran, Kropfm hl near Passau in u Bavaria). Cyclowollastonite is formed when wollastonite is heated to > 1126 C. It melts congruently at 1544 C. In industrial products, cyclowollastonite is the modication that is most often formed, e.g., in silicate bricks, in blast furnace slags and their reaction products with silicate bricks, in slightly basic open-hearth slags, or as a devitrication product in high-calcium bottle glasses. Properties. The physical properties of interest for industrial applications are given in Table 14. Wollastonite is usually white, translucent and sometimes pale greenish, bluish or brownish. It has a vitreous luster, a nacreous luster on fractured surfaces and coarse masses, and a silky luster in brous aggregates. Cleavage is perfect on (100) and (001) and well developed but variable on (101) and (201). The Mohs hardness is 4 1/2 5 and the density 2.8 2.9 g/cm3 . Cyclowollastonite usually forms irregular grains and is colorless, with cleavage on (001). The Mohs hardness is 5 and the density 2.91 g/cm3 . The lower limit of transparency to UV light is at = 290 nm. Wollastonite shows a yellowish thermoluminescence at moderate light intensities. The phosphorescence is yellowishwhite and is intensied by doping with 0.5 wt % Nd2 O3 . Cathodic luminescence is inuenced by vacuum, temperature and additives. The electrical conductivity at 1300 C is 0.18 1 cm1 and the dielectric constant at 20 C is 6.17. The ideal chemical composition for CaO SiO2 is 48.29 wt % CaO, 51.71 wt % SiO2 . Aqueous mineral acids decompose wollastonite and pseudowollastonite, producing gelatinous SiO2 . Alkaline solutions do not attack it. It is resistant to weathering and industrial atmospheres. Production. Pseudowollastonite (cyclowollastonite) is produced industrially as a sintered phase by a diffusion reaction:

Silicates
Table 14. Physical properties of wollastonite Property Density, g/cm3 Mohs hardness Temperature of phase change, C Enthalpy of phase change, kJ/mol mp, C Heat capacity at 1400 C, kJ kg1 Melt viscosity, kg m1 s1 at 1550 C at 1600 C at 1650 C Specic heat capacity, J g1 K1 at 1100 C at 0 700 C (-1T) and (-2M). Table 15. Chemical composition of commercial grades of wollastonite (-1T) and (-2M) Component SiO2 CaO Al2 O3 Fe2 O3 MnO TiO2 MgO Na2 O K2 O Loss on ignition Finland 51.80 44.50 0.44 0.22 0.3 max. 0.01 max. 0.05 0.56 0.10 0.01 2.20 United States 50.90 46.90 0.25 0.55 0.10 0.05 0.10 India 52.00 47.00 0.14 0.31 Theoretical 51.79 48.29 Wollastonite 1.8 2.9 4 1/2 5 1190 7.42 Pseudowollastonite 2.91 5 Vitreous CaO SiO2 2.9

49

1512 1434 2.73103 2.40103 2.38103 1.09 1.08 0.99

0.90

0.55

gives the physical properties of Finnish wollastonite (-1T) and (-2M). Uses. Wollastonite is widely used in ceramics, plastics, asbestos substitution, metallurgy, paints and glass manufacturing. Wollastonite is classifed into high aspect ratio wollastonite and milled or powdered wollastonite. High aspect ratio wollastonite has an aspect ratio of 1:10 to 1:20 and is well suited as a reinforcing functional ller in plastics, rubber, paints, and coatings and as an asbestos substitute. In these applications, wollastonite is characterized by enhanced hardness, exural strength, and impact resistance, and also improves the electrical properties and the thermal and dimensional stability of plastics. Milled or powdered wollastonite is used as a ller in ceramics and in metallurgy. The milled wollastonite grades are cheaper than the high aspect ratio grades. The highest volume use of high-grade wollastonite, i.e., modications (-1T) and (-2M), is as a raw material for ceramic products (see Tables 15 and 16). Teh considerable increase in

use o wollastonite can be attributed to the spread of fast-ring techniques, signicantly reducing the consumption of energy and improving productivity. Its important advantages include its lack of chemically bonded water (which could break down the structure and even cause explosions during ring), the ease of water removal on drying via the capillaries associated with its acicular (i.e., needle-like) crystal structure, the low shrinkage on drying and ring, the very low coefcient of expansion, the fairly low melting point, the mechanical strengthening of the green molded articles due to the acicular structure present until ring and the high breaking strength and thermal shock resistance of the nished product. The high lightness value (see Table 16), which is maintained after ring, enables wollastonite (-1T) and (-2M) to be used in the production of neutral, white ceramic products (e.g., white tableware). The raw material mixture should contain 20 50 % wollastonite. Other uses include wall and oor tile bodies and glazes, sanitary ware, earthenware, frits, frit

50

Silicates coated grades. Wollastonite is used in both thermoplastics (polyamides, polyesters, liquid crystal polymers and engineering resins) and thermosets (phenolic molding compounds, epoxies, polyurethanes, polyurea and unsaturated polyesters). Typical loadings of wollastonite in plastics are: nylon 50 %, low-density polyethylene 40 %, polypropylene 23 28 % and polystyrene 30 %. A further important market for wollastonite is automotive plastics, in which it acts chiey as a reinforcement, e.g., in reinforced reaction injection molded components. In paints and coatings high aspect ratio wollastonite is used as a reinforcing ller. In paint lms, wollastonite improves the mechanical strength, durability and resistance to weathering, cracking and other ageing effects. Wollastonite has a pH of 9.9 in water and hence functions as an effective alkaline buffer in latex paints, preventing destabilization due to pH drift, particularly when acidic pigments and extenders such as kaolin and aluminum silicate are utilized. Acicular wollastonite can be mixed with mineral ller materials exhibiting platelet-shaped, lamellar particle shapes (kaolinite, mica, talc, and pyrophyllite) to give ller mixtures with desirable rheological working properties (e.g., adjustable thixotropy). Wollastonite is an important substitute for short-ber asbestos and is used widely in reinforcement applications, in re-resistant wall board and cement products and friction products (brake pistons, brake linings, clutches etc.). In metallurgical applications the low temperature uxing of wollastonite imparts better surface nish in continuously cast steel and inhibits sparking in welding. Due to its luminescent properties, wollastonite, especially the synthetic variety, is the base material of many phosphors, whose characteristics can be varied by doping with heavy metal and rare earth ions. Synthetic wollastonite is used in synthetic bone implants, to replace bone loss and as a vertebral prosthesis in medical cases requiring loadbearing capacity. Synthetic wollastonite quickly forms strong, biologically safe bonds with osseous tissue. The favorable electrical properties of wollastonite (high volume resistance and surface resistance, low dielectric loss angle) lead to its use

glazes, and porcelain enamels and specialized applications.


Table 16. Physical properties of Finnish wollastonite (-1T) and (-2M) Property Density, g/cm Mohs hardness Refractive index mp, C Coefcient of thermal expansion, K1 pH of 10 % aqueous suspension Particle size (<74 m), % Specic surface area, cm2 /g Oil number, g oil/100 g substance Brightness value FMY/C, % Solubility in water (5 min, 100 C), mg/100 mL Particle shape
3

FW 200

FW 325 2.9 4.5 5 1.63 1394 1410 1.5106 9.0 98.9 3040 35 86

96.5 2980 27 86

0.0071 0.0076 Columnar to needleshaped

Tristimulus value Y measured with standard illuminant according to DIN 5033, color temperature 2856 K, ca. 546.1 nm using ELREPHO equipment.

The addition of wollastonite to frits for ceramic glazes and enamels reduces the ring temperature and the formation of hairline cracks and helps stop cracking, crazing, breaking and glaze defects. It also improves surface hardness and luster. Blister formation due to outgassing of volatile constituents is also reduced. Wollastonite added in amounts of 1 3 % to int and/or ux reinforces semivitreous products and decreases shrinkage and moisture expansion. In some other ceramic applications, feldspar and quartz are substituted by 2 5 % wollastonite in vitried bodies to lower vitrication temperatures and to decrease shrinkage. The (-1T) and (-2M) modications are preferred for use as llers in industrial chemical products and plastics. The chain structure of the lattice leads to the formation of acicular crystals and short bers, which impart structural viscosity both to molten thermoplastics and to coating materials (paints, plastisols, etc.) and improve the mechanical properties of the solid matrix. In polymer emulsion paints, texture paints, plasters and putties, addition of wollastonite improves abrasion resistance and weathering resistance and reduces shrinkage cracking. The plastics industry is a major consumer of wollastonite. In plastics most grades of wollastonite can be utilized, but most signicant are those with high aspect ratio, ne and surface-

Silicates as an additive to electrical insulating paints and casting materials. Acicular wollastonite particles can be mixed with ller materials with platelet-shaped particles (kaolinite, mica, talc and pyrophyllite) to give ller mixtures with desirable rheological working properties (e.g., thixotropy that can be adjusted). The most important producers and suppliers of natural and synthetic wollastonite are the NYCO Minerals Corporation (Willsboro, New York, United States) and the Partek Industrial Minerals Oy (Lappeenranta, Finland). World production of natural wollastonite is estimated at 365 000 t/a. Of the 120 000 t/a of wollastonite that is expected to be produced in the United States, some 90 000 t is consumed by the domestic market and the surplus is exported mainly to Europe. The production of natural wollastonite by Mexican producers is estimated to be 30 000 t/a, by Indian ca. 60 000 t/a, by China 120 000 t/a, and by Finnish producers ca. 30 000 t/a. The European consumption is estimated to be well over 70 000 t/a, of which ca. 65 % is used in the ceramics industry.

51

pirable wollastonite (-1T) and (-2M) dusts are suspected to be carcinogenic.

3. Alkali Silicates
3.1. Introduction
Historical Aspects. The solubility in water of a fused mixture of int pebbles with potash was rst described by the Brussels physician Jean Baptiste van Helmont (1577 1644) in his posthumous work Ortus medicinae, Amsterdam 1648. Independently, Johann Rudolph Glauber (1604 1670) studied the properties of a thick solution that he obtained from a fused mixture of sand, int pebbles, or crystalline quartz with potash, and named Liquor Silicum. He recommended its use as a curative agent, for the production of liquid uxes in metal smelting, and for glazing earthenware vessels (Furni Novi Philosophici, Amsterdam 1648 1650). In 1768, during the course of his alchemical studies, Goethe became interested in potassium silicate [116]. Although there were many later reports, the water-soluble silicates were seldom put to practical use until about 1825 when Johann Nepomuk von Fuchs in Munich investigated the industrial production of water-soluble potassium and sodium silicates, which he named waterglasses (i.e., water-soluble glasses), and proposed that their solutions might be used as adhesives, for sealing porous stone, and as binders for fresco painting [117]. He exchanged ideas with Justus von Liebig and C. F. Kuhlmann. The latter rst produced waterglass in France in 1841 [118, 119]. Soon afterwards, similar work was undertaken in England by W. Gossage, and in various parts of the United States [120]. Waterglass was more widely used during the course of the American Civil War (1861 1865), when the northern states utilized it in soap manufacture as a replacement for rosin formerly obtained from the southern states. Denitions. Commercial alkali silicates are generally specied according to: 1) Source of alkali (soda, potash, lithia).

2.14. Toxicology
Most of the silicates described in Chapter 2 are not known to be toxic or carcinogenic. However, the inhalation of ne particles (< 5 m, brogenic dusts) of silicates and hydrated silicates which have an acicular or brous morphology and are insoluble in the environment inside the lungs (pH < 7) should be ltered out by means of effective industrial dust-removal equipment or respiratory protection masks. The MAK values for inert granular and platelet-shaped silicate dusts is set at 6.0 mg/m3 in view of possible effects on the respiratory organs. This gure applies to exposure to the dust for one year, or, if each individual exposure to dust is known and documented, for a total exposure time of one year spread over a period of ve years. In the case of exposure to ne wollastonite dust (respirable dust < 5 m), respiratory protection is recommended. It is not yet known whether there is a health hazard from the inhalation of cyclowollastonite dust. However, res-

52

Silicates Aerosil) is recommended. The alkali-metal oxides are provided in the form of their carbonates or hydroxides. The purity of the starting materials is dictated by the purity requirements for the end products. An appropriate sulfate may also be used as a cheap source of alkali in silicate production, but requires the presence of a reducing agent (normally coal dust). Very little sulfate-derived glass is produced because the melting process is longer and this, together with the presence of sulfur oxide gases, increases corrosion of the furnace walls. In addition, residual alkali sulfate and ash from the coal result in a relatively impure product.

2) Ratio of silica to alkali-metal oxide. The usual ratio given is the weight (wt %) ratio or modulus, RW . The equivalent molar ratio, RM , can be more useful, particularly when comparing ratios of potassium and sodium silicates. For sodium silicates, the conversion factor is RM = 1.032 RW , while for potassium silicates, RM = 1.568 RW . 3) Water content of the silicate. For solid, crystalline silicates, this corresponds to the water of crystallization. For example,sodium metasilicate, Na2 O SiO2 , can be prepared in anhydrous form, or as the pentahydrate or nonahydrate [121]. Amorphous alkali silicate glasses are essentially anhydrous. The water content of silicate solutions is customarily dened indirectly by giving the density of the solution, which together with the silica to alkali-metal oxide ratio, denes a unique composition for the silicate solution. Solid alkali-metal silicates used in industry are divided into two groups: 1) Water-soluble silicates solidied as a glass from a melt, normally containing ca. 1.5 4 mol SiO2 /mol M2 O (Section 3.3). These silicates and their aqueous solutions are commonly referred to as waterglass (solid glass or liquid glass). The most common commercial products are concentrated waterglass solutions, which are usually produced by dissolution of silicate glasses in water or by direct dissolution of sand in sodium hydroxide (see Section 3.4). 2) Solid, crystalline sodium silicates, often with water of crystallization. Commercial products of this type are known for Na2 O n SiO2 , where n = 0.5 (orthosilicate), 1.0 (metasilicate), and 2.0 (disilicate) (see Section 3.6).

3.3. Amorphous Anhydrous Alkali Silicates (Solid or Lump Glasses)


Properties. Sodium and potassium silicate glasses are prepared commercially as glass lumps or powders. They are normally colored owing to the presence of impurities, the most usual colors being blue to green or yellow-brown caused by the presence of di- or trivalent iron, respectively. Alkali silicate glasses with compositions close to those of stoichiometric compounds (e.g., Na2 O 2 SiO2 , K2 O 2 SiO2 , K2 O 4 SiO2 ) can be made to crystallize by holding them just below their melting points for long periods. In general, however, commercial alkali silicates are not stoichiometric compounds. Instead, their molar ratio, SiO2 /M2 O, usually uctuates around average values at which stable solutions can be obtained (Table 17). The vast majority of commercially produced alkali silicate glass is sodium silicate. Furthermore, sodium silicate liquors with a wide range of RW values may be produced by blending two different liquors with each other or with alkali hydroxide. Virtually all commercial glass production is of sodium silicate of RW = 2.0 (alkaline glass) or RW = 3.3 (neutral glass) [122]. A smaller amount of potassium silicate glass is manufactured and is normally restricted to the ratios RW = 2.5 and RW = 2.0 2.1. Lithium silicate glasses are not readily watersoluble and hence are not produced on a commercial scale [123].

3.2. Raw Materials


The dominant silica component used in industry is quartz sand (grain size 0.1 0.5 mm) which has been washed to remove clays and other impurities. The most problematic impurity in such sands is iron, normally present to the extent of ca. 300 ppm. To obtain extremely pure alkali silicates, mainly for scientic use, very nely divided, very pure silica (e.g., fume silica such as

Silicates
Table 17. Typical, commercially available alkali silicate glasses Product name Pyramid AL Pyramid NL HK40 HK28/30 Na2 O, wt % 33.2 22.9 32 28 K2 O, wt % SiO2 , wt % 66.3 76.7 68 72 Weight ratio 2.00 3.35 2.1 2.5 Mol ratio 2.06 3.46 3.3 3.9

53

Table 18. Physical properties of commercial silicate solutions Commercial name Density at 20 C, kg/m3 1150 1260 1400 1500 1500 1260 1330 1600 SiO2 , wt % 17.50 22.2 29.2 31.2 28.1 21.3 23.3 30.8 Li2 O, wt % 1.55 5.8 8.9 12.5 14.0 8.6 11.4 21.6 Na2 O, wt % K2 O, wt % Total solids, wt % 19.0 28.0 38.1 43.6 42.1 29.9 34.8 52.4 Weight ratio 11.3 3.85 3.30 2.50 2.00 2.48 2.05 1.43 Mol ratio Viscosity at 20 C, cP 5.6 3.97 3.41 2.58 2.06 3.89 3.21 2.24 < 10 20 250 500 400 200 180 30 200 pH at 20 C 10.7 10.5 10.8 11.2 11.4 10.9 11.8 12.6

Crystal L29 Crystal 52 Crystal 79 Crystal 100S Crystal 100A Pyramid K53 Pyramid K66 Pyramid K120

Figure 31. SiO2 Na2 O system

54

Silicates silica, causing dissolution. Solid silicates can be dissolved at temperatures in the region of the boiling point in concentrated circulating solution, but silicate solutions are almost invariably produced by operating at pressure. Production. Mixtures of pure silica sand (glass sand) and alkali carbonate in the required ratio are continuously fed by a cooled screw conveyor into furnaces that are regeneratively heated by oil or gas. The raw material ratio must allow for losses of alkali carbonate due to vaporization and attack on the material of the furnace. The temperature of the gas space is ca. 1600 C, the nal melt temperature being 1300 1500 C. The carbon dioxide is driven off by reaction of the metal carbonate with the silica:
M2 CO3 + nSiO2 M2 O nSiO2 + CO2

The structure of silicate glasses is based on tetrahedral SiO4 groups that are associated as polysilicate anions by sharing corners of the tetrahedra. The environment of a single Si atom is referred to as Qn , where n is the number of shared corners for the tetrahedron [124]. The structures of the glasses are discontinuous, with SiO2 -rich domains separated by clusters of M+ ions.

Figure 32. SiO2 K2 O system

The melting points of the solid silicates may be obtained from the liquidus diagrams of the systems SiO2 Na2 O and SiO2 K2 O (Figs. 31 and 32). Sodium silicates with RW 3 are only slightly attacked by water at room temperature. Sodium silicates with RW = 2 are hygroscopic and cake on storage in moist air. At equivalent molar ratios, potassium silicate glasses are more hygroscopic than their sodium counterparts potassium silicate of RW = 2.0 (RM = 3.1) also cakes in contact with moist air. Addition of a large excess of hot water to silicate glass causes hydrolysis and leaches out some of the alkali [125]. This alkali then attacks the residual

The furnaces are all of similar construction and size (capacity 150 t) to those used in the glass industry ( Glass, Chap. 5.2.). They must be lined with high-quality refractory bricks (e.g., sillimanite) since the alkaline melts are very aggressive. The melt ows through the furnace and leaves continuously via an overow into small molds which are moved along in an endless chain. The cast pieces (diameter ca. 8 cm, thickness 1 2 cm) cool as they are transported and often shatter. Silicates are also produced in a batch process in small furnaces or continuously in rotary furnaces. The cast blocks of silicate glass are dissolved in water while still warm or after intermediate storage (see Section 3.4). For some applications, they are ground and sieved.

3.4. Silicate Solutions


Properties. Solutions of sodium and potassium silicates with SiO2 /M2 O 1.5 are colorless, water white, and viscous. The viscosity increases with concentration and, for a given constant silica content, with the SiO2 /M2 O ratio. When a critical concentration is reached, it rises very rapidly with further concentration (see Fig. 33). For a given ratio there is a limiting concentration above which the solution becomes either too viscous or too unstable for industrial use.

Silicates

55

Figure 33. Change of viscosity with density at constant SiO2 : Na2 O ratios

The structures of the silicate solutions have been probed by a wide variety of techniques such as IR/Raman spectroscopy, light scattering, and chromatography [126130]. The most valuable techniques are, however, trimethylsililation and 29 Si-NMR [129, 131133]. Alkali silicate solutions contain, in addition to Me+ , OH , and ) orthosilicate (Hx SiO(4x 4 ) ions, a wide variety of linear, cyclic, and highly cross-linked polysilicate ions. The degree of polymerization of the silicate ions increases with increasing concentration and increasing ratio of the solution. Relatively small polysilicates ( 8 Si atoms) can be identied by comparing their silylated derivatives with derivatives of known structures from silicate minerals [134]. In addition, 29 Si-NMRalso allows identication of oligomeric silicate ions in dilute solutions [131 133]. In more concentrated solutions, however, and particularly at high ratios, NMR signals of individual species cannot be observed, peaks in the NMR spectrum then correspond to the Qn species (see Section 3.3) [135]. This is illustrated in Figure 34, which shows 29 Si-NMR spectra for sodium silicates of RW = 2.0 and 3.3 at typical commercial concentrations. The spectrum of the material with RW = 2.0 is dominated by silicons of the Q2 type, indicating a preponderance of small cyclic or linear silicate ions; in the material with RW = 3.3, on the other hand, more than 50 % of the silicon atoms are present as Q3 or Q4 species, indicating a higher

level of three-dimensional, branched polysilicates. These large polysilicate anions are mainly responsible for the high viscosity of silicate solutions. The silicate anions are in dynamic equilibrium and addition of alkali hydroxide (tantamount to reducing the ratio) causes hydrolysis of the polysilicates, thus reducing the viscosity, although even highly alkaline silicate solutions still contain polysilicates. Extensive dilution with CO2 -free water also depolymerizes the polysilicate anions. A wide variety of silicate solutions are available commercially. Sodium silicates are marketed with RW ranging from 1.5 to 3.85, while potassium silicates are available with RW from 1.43 to 2.48. Lithium silicates are also available commercially. Table 18 gives physical data for a few typical commercial silicate solutions, while Table 19 lists typical composition ranges for a commercial sodium silicate (RW = 3.3). All silicate solutions are highly alkaline. Dilution reduces the pH, but less than might be anticipated owing to the buffering action of the silicate. For example, dilution of Crystal 79 (RW = 3.3, 25 wt % silica) to a 1 wt % solution reduces the pH from 11.6 to 10.8. Addition of acids and acid salts (including carbon dioxide and bicarbonates) to silicates liberates silica. This is the basis of the industrial preparation of silica sols, silica gels, and precipitated silicas, the type of silica being formed depending on the concentration, temperature and

56

Silicates

Figure 34. 29 Si-NMR spectra for sodium silicates A) Crystal 100 A; B) Crystal 79

salt content of the solution ( Silica) [122, 136]. Salts of polyvalent cations yield mixtures of silica gel with metal hydroxide [123]. Welldened silicates are usually formed only after prolonged heating of the solution, sometimes under pressure. Under these conditions, industrially valuable crystalline silicates such as zeolites ( Zeolites) or clays (e.g., kaolin) may be formed [136]. The addition of saturated sodium chloride or sodium nitrate solutions to silicate solutions precipitates alkali- containing silica gels which redissolve on dilution [121]. Saturated sodium sulfate and sodium carbonate solutions can be mixed with silicate solutions at room temperature without causing precipitation, as can strongly alkaline salts such as trisodium phosphate and sodium metaborate. Most organic compounds are incompatible with soluble silicate solutions. Some polyhydric alcohols (e.g., glycerol) are compatible with sodium silicates and yield stable single-phase solutions. Other organics, such as polyol esters, produce a homogeneous system with silicate solutions but slowly react to give a solid mass [137]. Such systems have found use as setting systems (e.g., in the foundry industry and soil consolidation). Heating of sodium and potassium silicates in the absence of carbon dioxide initially produces very viscous solutions; as

water loss continues, solid foams are formed that still contain signicant amounts of water. Lithium silicates are stable at and around room temperature, but precipitate on heating to > ca. 60 C. The effect is reversible upon cooling [138].
Table 19. Composition range of typical commercial sodium silicate solution (RW = 3.3) Assay SiO2 Na2 O Li K Mg Ca Sr Ba Al P S Ti V Cr Mn Fe Co Ni Cu Zn La Ce Zr W ppm unless otherwise stated. Content 29.2 wt % 8.9 wt % 0.2 0.5 20 50 5 20 1 80 15 <15 50 200 < 1 10 10 30 30 80 0.1 0.8 <1 < 0.5 1 25 100 <1 < 0.5 < 0.1 0.2 < 0.2 1.0 0.2 1.0 < 0.3 2.0 5 20 < 1 25

Silicates Production. Cold or warm lump glass (the latter to improve heat conservation) is usually dissolved at 5 bar and ca. 150 C. Stationary systems may be used, but rotating vessels or circulation of the liquor accelerate dissolution rates. Direct steam heating is usually employed in large ( 15 m3 ) vessels. High glass : water ratios are used to give a satisfactory dissolution rate. Since the alkali silicates do not have a definite solubility in water, prolonged heating can lead to setting of the glass liquid mix into an intractable elastic mass [122]. An excess of solid glass is heated with water until the required concentration is reached. The silicate solution, containing solid impurities (silicates of, for example, iron, titanium, alkaline earths) is removed from the residual excess glass. The solutions are then claried by settling at elevated temperatures or by ltration. Some commercial silicate solutions are too viscous to be handled in this way, and are produced in a more dilute form, followed by evaporation of water under reduced pressure. A variety of molar ratios and concentrations can be produced by appropriate mixing of a small number of silicate solutions produced directly from glass, either with each other or with the appropriate alkali hydroxide. Sodium silicate solutions of molar ratio 2.5 can be prepared by direct dissolution of quartz sand in sodium hydroxide solution under pressure at ca. 150 C. Even higher ratios can be obtained by this method if a more soluble form of silica is substituted for the quartz sand. Sodium silicates with RW up to 3.3 may be obtained by this method using silica sources such as amorphous silica, diatomite, or cristobalite [123, 139]. Processes of this kind are likely to increase in importance because they require less energy than glass formation followed by dissolution. As lithium silicate glasses are insoluble, lithium silicate solutions are prepared commercially by dissolution of amorphous silica in lithium hydroxide. Owing to the temperature instability of lithium silicate solutions, this process is carried out at or near room temperature.

57

able as ne powders or as granules. In general they are prepared by evaporating silicate solutions to the point where solids are formed which are sufciently stable to allow commercial handling but which retain adequate solubility. Typically this occurs at water contents of ca. 20 %. In principle a wide range of products with different ratios can be made, although in practice the ratio tends to be restricted to the range RW = 2.0 3.3 where the products are amorphous. Unlike nely divided silicate glasses, these materials dissolve in water under normal conditions to give silicate solutions; the rate of dissolution is a function of ratio, water content, and particle size. Thus at low ratios (RW = 2.0), materials in the size range 100 200 m dissolve completely at room temperature in a few minutes, whereas a similar product with a higher ratio (RW = 3.3) requires a higher temperature ( 50 C) to achieve the same dissolution rate. These are, however, both considerably faster than the anhydrous glass analogues, for which dissolution takes many hours and may not go fully to completion. In dissolving hydrated water soluble silicates, too large an excess of water should be avoided since rapid leaching of the alkali hydroxide can give a solution pH that is too low to attack the residual silicic acid, thus leaving it as an insoluble residue. Examples of commercial materials are listed in Table 20. The manufacturing processes employed include spray or drum drying of silicate solutions followed by sieving to the required size. Granular materials are formed by mechanical compaction of the spray dried powders to give products which are more easily handled and are less dusty.

3.6. Crystalline Solids


Numerous crystalline alkali silicates have been reported both in anhydrous and hydrated forms [121]. The ratios vary typically from RW = 0.5 to RW = 2.0 and they are often referred to by the more traditional names:
Common name orthosilicate (SiO2 2Na2 O) sesquisilicate (2SiO2 3Na2 O) metasilicate (SiO2 Na2 O) disilicate (2SiO2 Na2 O) RW 0.5 0.67 1.0 2.0

3.5. Hydrated Water-Soluble Silicates


Hydrated water-soluble silicates are normally manufactured in the sodium form and are avail-

58

Silicates

Table 20. Hydrated, water soluble sodium silicates Commercial name Pyramid P 40 Pyramid P 60 Pyramid P 10 Pyramid G 80 Pyramid G 90 Na2 O, wt % 26.7 18.5 28.0 26.0 26.0 SiO2 , wt % 53.3 61.5 56.0 52.0 52.0 Weight ratio 2.00 3.30 2.00 2.00 2.00 Molar ratio 2.06 3.41 2.06 2.06 2.06 Water, wt % 20.0 20.0 16.0 22.0 22.0 Bulk density, g/L 400 500 550 650 80 120 750 850 800 950

In addition, several higher ratio silicates have been discovered and synthesized with ratios such as 4 : 1, 8 : 1, 9.4 : 1, 14 : 1, and 22 : 1 [140, 141]. Many of the latter are complex layered structures, often occurring naturally and having some cation exchange properties. The structured principles of all of these crystalline silicate species have been reviewed [142]. The only crystalline silicates which are presently of any commercial signicance are the metasilicate family represented by the general formula Na2 O SiO2 nH2 O. Products are available with n = 0, 5, 8 and 9, and within this range the anhydrous silicate (n = 0) and the pentahydrate (n = 5) are the most important. Metasilicate and its hydrates differ in structure. Whereas the anhydrous material contains innite chains of general formula Na2 SiO3 , the hydrates, more properly represented by the formula Na2 [SiO2 (OH)2 ](n 1)H2 O, contain the [SiO2 (OH)2 ]2 ion as a discrete entity. The metasilicates crystallize well and are readily soluble in water. Anhydrous sodium metasilicate melts congruently above 1018 C, and above 70 C it is the solid phase in equilibrium with aqueous solutions. Below this temperature, the hydrolyzed ion [SiO2 (OH)2 ]2 is formed and the various hydrates can be crystallized. Although potassium metasilicates behave similarly, they are not commercial products. Production. Anhydrous metasilicate is produced by two general methods: 1) It can be prepared in a furnace by direct fusion of sand and sodium carbonate at temperatures above the melting point of metasilicate (1088 C), followed by solidication, grinding, and sieving. In some cases a solidstate reaction has been used above the melting point of sodium carbonate (850 C) but below that of the metasilicate in rotary or tunnel kilns. The corrosive nature of metasilicate

melts on furnace refractories makes this a less attractive route. 2) Alternatively, it can be obtained by drying solutions at the metasilicate composition in a uidized bed [143] or a drum granulator [144]. In the latter case the hot liquor is sprayed on to the powder bed whose particles grow and dry uniformly in a current of hot air. At the end of the drum the beaded product is screened and the nes recycled to provide powder for further growth. Metasilicate hydrates can be obtained by direct hydration of anhydrous metasilicate or by crystallization of a solution of metasilicate with the appropriate composition. In the case of metasilicate pentahydrate for example the heated solution of composition Na2 O SiO2 5H2 O is kept above 72.2 C (its melting point) and is crystallized by spraying on to a bed of particles cooled to below this temperature in a rotary drum granulator using a similar procedure to that described above for the anhydrous metasilicate. Typical products and properties of metasilicates are shown in Table 21. Of particular interest lately has been the preparation of synthetic layered silicate structure [145]. These materials of general composition Na2 O 2 SiO2 have ion-exchange properties.

3.7. Uses and Applications


The uses of alkali metal silicates fall into two broad categories: 1) As raw materials from which further important industrial products can be derived. This application utilizes the silicate anions as building blocks for the formation of a range of silica- containing materials and represents the single largest use of soluble silicates. These derived products include silica

Silicates
Table 21. Typical properties of metasilicate products Commercial name Metso A 100 Metso 510 Metso 520 Metso 950 Chemical formula Na2 O SiO2 Na2 O SiO2 5 H2 O Na2 O SiO2 5 H2 O Na2 O SiO2 9 H2 O Water content, wt % 43 43 57 Bulk density, g/L 1200 1000 1000 800 Average particle size, mm 0.8 0.8 1.0 0.6

59

sols, silica gels, precipitated silicas, zeolites, aluminosilicates, magnesium silicates, synthetic clays, ceramics, and catalysts. 2) As functional additives in a wide range of applications exploiting the varied properties of the silicates. These properties include: a source of buffered alkalinity; an inorganic polymeric system with adhesive, binder, and lm-forming capabilities; nontoxic, nonammable and environmentally benign; wide range of available compositions; capable of forming hybrid systems with organics (e.g., polymers) and other inorganics (phosphates, borates); complexation or precipitation of ions in solution; intumescent properties on heating; low cost. Detergents represent the largest functional use of silicates. In broad terms use is made of the alkalinity and buffering capacity to aid in soil removal, assist in the suspension of soil particles, enhance the effectiveness of surfactants by sequestering calcium and magnesium ions, and inhibit corrosion of metal surfaces. In fabric washing powders [146] liquid silicates have traditionally been incorporated into the spray dried powders at levels of 5 15 %, whereby the silicate also provides crisp and easily handled detergent granules. The levels of incorporation of liquid silicates have been decreasing with the change to zeolite-based powders and more use is now being made of powdered soluble silicates added after spray drying. In industrial cleansing agents and dishwasher detergents the silicate product of choice has been metasilicate, either anhydrous or pentahydrate. There are now some concerns about the high alkalinity of such materials in domestic products and a move to granular soluble powders with higher ratio (RW 2.0) is likely to occur. Foundries. Large quantities of liquid silicate (typically with RW = 2) are used in the foundry

industry to bind together sand molds and cores prior to pouring the molten metal. The silicate is set by reaction with CO2 [147] blown through the silicate sand mixture, or by incorporation of glycerol esters which hydrolyze and cause the setting reaction by release of organic acids [148]. Adhesives. Silicate liquors are used widely as adhesives. The largest consumer is the paper and board industry for such duties as spiral tube winding, corrugated boxboard, and ber drums. Silicates are also used to bind insulating materials such as vermiculite in building panels, coal dust briquettes, roong tiles, bricks and ceramics, refractory cements, and in the manufacture of welding rods. In the latter case, lithium silicate has proven to be particularly effective since it not only provides the necessary strength and degree of water resistance, it also reduces signicantly the amount of CrVI evolved during the welding, thus providing safety benets [149, 150]. Surface Coatings. Silicate liquors are used in a variety of surface coating applications. Examples include the sealing of porous surfaces such as concrete; as a vehicle for the preparation of paints for masonry and glass surfaces and for general re proong duties; and as a component in spray coating systems based on concrete and glass ber. Silicates are also used to coat TiO2 pigment particles to improve stability. Paper Deinking and Bleaching. Sodium silicate liquors are used in the paper industry to promote deinking of recycled newsprint and also to act as a promoter to achieve enhanced bleaching with hydrogen peroxide. Both of these are environmentally driven applications, and demand is expected to grow as pressure increases to recycle more paper and to switch from chlorine to peroxide- containing bleaches. Water Treatment. Silicates are added to water, including potable water, in concentrations

60

Silicates Table 22 shows the breakdown of the total volume by application for Western Europe and the United States.
Table 22. Silicate usage by industry application (in percent) Application Detergents Paper TiO2 Water treatment Civil engineering Miscellaneous Total Derivatives (silica, zeolites etc) Total Western Europe 28.1 7.3 4.6 2.9 7.7 6.4 57 43 100 United States 32.6 7.5 4.6 3.5 5.8 54 46 100

of a few ppm to prevent discoloration due to dissolved iron. The precise mechanism is not fully understood, but it appears that the silicate forms a soluble iron hydroxide silicate complex which prevents the formation of visible iron ocs. An additional benet of such water treatment with silicate is the corrosion protection afforded to metal pipes, presumably by similar complex formation at the metal surface. Other water treatment uses have included a coagulation aid in alum occulation processes and for boiler water treatment. Civil Engineering. Silicates are used to stabilize soils in many civil engineering projects involving drilling, tunneling, and mining. Silicate solutions mixed with appropriate setting agents are pumped into the ground where they harden the soil [151]. An interesting application of this technology is the Sanipor process for repairing sewers without the need to dig up city roads and streets [152154]. Other similar uses include sealing around landll sites, waste xation, and coastline stabilization. Enhanced Oil Recovery. Use of silicates with considerable growth potential is in enhanced or tertiary oil recovery, particularly in offshore locations. Flooding the oil eld with silicate solutions promotes the formation in situ of soaps and surfactants which improve the oil ow from the porous rock [155, 156].

3.9. Storage, Safety, Labelling and Transportation


The CAS und EINECS numbers are shown in Table 23 for various soluble silicates. A comprehensive review of the health and safety aspects of silicates has been published [157, 158]. The primary hazard of all soluble silicates is their alkalinity. Contact effects range from irritation to corrosion. Ingested or inhaled silicates are rapidly eliminated in the urine. Quoted LD50 (oral, rat) values are 1280 mg/kg for sodium metasilicate, 1300 mg/kg for sodium silicates with RW = 2.0, and 1600 mg/kg for RW = 3.0 according to the Registry of Toxic Effects of Chemical Substances 1981 1982. There are no exposure limits quoted for sodium or potassium silicates by any regulatory body. A limit of 2 mg/m3 is given for caustic soda and caustic potash by both ACGIH and the HSE (under the EH40/92 exposure regulations) and exposure to silicate should therefore be limited, according to its composition, to remain in line with the caustic soda and potash gures. For lithium silicates a similar situation prevails, but the exposure limit for lithium hydroxide is 1 mg/m3 . Alkali silicates are not ammable or explosive. Due to their alkalinity, solutions attack aluminum, tin, and zinc, with evolution of hydrogen, at concentrations above ca. 10 %. Powdered silicates tend to be hygroscopic and packaging must therefore provide adequate protection against water vapor ingress to avoid caking. Avoidance of prolonged contact with CO2

3.8. Economic Aspects


Estimated 1990 world silicate consumption (expressed as dry glass) is ca. 4106 t (including captive use). The approximate geographic split is United States, Japan and Western Europe 20 % each with the remaining 40 % for the rest of the world. The latter gure is speculative since it does not include Eastern Europe and China. The sales value of the noncaptive volume is ca. $1.5109 . Consumption is estimated at 65 75 % of installed capacity. The volume of silicate supplied to the merchant market, expressed as 100 % solids, is estimated to be:
United States Western Europe Japan 470 000 t 500 000 t 500 000 t

Silicates
Table 23. CAS and EINECS numbers for various soluble silicates Product Sodium silicate solutions, glasses, or solids Sodium metasilicate and hydrate Sodium orthosilicate Sodium sesquisilicate Potassium silicates Lithium silicate solutions Formula Na2 O(SiO2 )x x > 1.6 Na2 O SiO2 (H2 O)y y = 0, 5, 9 2Na2 O SiO2 3Na2 O 2SiO2 K2 O(SiO2 )x x > 1.6 Li2 O(SiO2 )x 6 x 12 CAS registry no. [1344-09-8] [6834-92-0] [13472-30-5] [15593-82-5] [1312-76-1] [12627-14-4] EINECS no. 2 156 874 2 299 129 2 367 413 2 396 711 2 151 991 2 357 300

61

is also necessary since both solids and solutions will readily absorb this from the air to form alkali metal carbonates. Under the rules of the EEC Dangerous Substances Directive 67/548/EEC as amended by 92/32/EEC all silicates with RW 1.6 are classied as irritant. However, the labeling classication for sodium silicates is under review in Europe and a new set of safety phrases will be agreed taking into account both RW and concentration. In the environment, commercial silicates rapidly depolymerize on dilution to give molecular species indistinguishable from natural dissolved silica in ground waters. The pH of most silicate solutions is however above the acceptable limit for direct discharge to rivers and sewers, and dilution or neutralization must be carried out rst. For disposal to landll, the classication of silicates varies according to composition and also by countries. In general the more alkaline the products the more likely it is to be classied as hazardous or special waste although concentration is also important. Thus in the United Kingdom metasilicates above 0.1 % and all silicate solutions above 10 % qualify as special waste [159].

ltered, washed, calcined, and then weighed. If very great accuracy is required, the silica is volatilized by fuming with hydrouoric and sulfuric acids. The sesquioxides remaining after this are accounted for in the calcination. Potassium silicate glasses are dissolved and fumed with hydrochloric acid to give silica-free ltrates whose sodium content is determined by ame photometry. The potassium content of sodium silicate glasses is determined analogously. The silica content of aqueous silicate solutions can be determined more conveniently by titration. The solution is neutralized using methyl red as indicator, an excess of pure sodium uoride is then added, and the alkali that is liberated according to the equation
SiO2 + 6 F + 2 H2 O SiF2 + 4 OH 6

3.10. Analysis
The alkali-metal content of soluble silicates is determined by titration in dilute solution with hydrochloric or sulfuric acid using methyl orange as indicator. The silica is determined gravimetrically. Alkali metals are removed as the chlorides by fuming the diluted silicate solution several times with hydrochloric acid in a at porcelain dish. The insoluble silica is then

is backtitrated with hydrochloric acid. Chloride is titrated by the argentometric method in a dilute aqueous solution of the silicate. Sulfate is determined by precipitation as barium sulfate from the ltrate from which the silica has been removed. Other possible impurities (CO2 , Al2 O3 , Fe2 O3 , TiO2 , CaO, MgO) are determined by the methods used for analyzing ordinary glass. Spectrophotometry is recommended, particularly for iron and titanium. Alkali silicates that are normally insoluble in water are dissolved by pressure dissolution and investigated as for soluble silicates. Remaining insoluble matter is weighed and may be analyzed as for water-insoluble silicates. Since 1972, the following ISO specications for alkali silicate analysis were published, 1686: general, 1687: density of silicate solutions, 1688: density of the dry substance, 1689:

62

Silicates
11. M. Fleischer: Revdite, Am. Mineral. 67 (1982) 1076. 12. J. Puziewicz: Grumantite, Am. Mineral. 73 (1988) 440. 13. G. Y. Chao, J. D. Grice, R. A. Gault: Silinaite, a new Sodium Lithium Silicate Hydrate Mineral from Mont Saint-Hilaire, Quebec, Can. Mineral. 29 (1991) 359 362; J. D. Grice: The Crystal Structure of Silinaite, NaLiSi2 O5 2H2 O: a Monophyllosilicate, Can. Mineral. 29 (1991) 363 367; K. Benneke, P. Thiessen, G. Lagaly: Synthesis and properties of sodium lithium silicate slinaite, Inorg. Chem. 34 (1995) 900 907. 14. G. Scholzen, K. Beneke, G. Lagaly: Diversity of Magadiite, Z. Anorg. Allg. Chem. 597 (1991) 183 196. 15. L. S. Dent Glasser, P. B. Jamieson: Sodium Silicate Hydrates. The Structure of Na2 O SiO2 8H2 O, Acta Crystallogr. Sect. B 32 (1976) 705 710. 16. H. Annehed, L. F lth, F. J. Lincoln: Crystal a Structure of Synthetic Makatite Na2 Si4 O8 (OH)2 4H2 O, Z. Kristallogr. 159 (1982) 203 210. 17. G. Berg ly et al.: Chemical Characterization, e Structural Features, and Thermal Behavior of Sodium Hydrogen Octosilicate, Clays Clay Miner. 39 (1991) 490 497. 18. K. Beneke, G. Lagaly: Kanemite Intracrystalline Reactivity and Relations to Other Sodium Silicates, Am. Mineral. 62 (1977) 763 771; Kenyaite Synthesis and Properties, Am. Mineral. 68 (1983) 818 826; A Hydrated Potassium Layer Silicate and its Crystalline Silicic Acid, Am. Mineral. 74 (1989) 224 229. 19. W. Schwieger, W. Heyer, F. Wolf, K.-H. Bergk: Zur Synthese von kristallinen Metallsilicathydraten mit Schichtstruktur, Z. Anorg. Allg. Chem. 548 (1987) 204 216. 20. K. H. Bergk, P. Grabner, W. Schwieger: Die hydrothermale Kristallisation des Magadiits, Z. Anorg. Allg. Chem. 600 (1991) 139 144. 21. K.-H. Bergk, W. Schwieger, M. Porsch: Aluminiumfreie Schichtsilicathydrate Synthese und Eigenschafts-Anwendungs-Beziehungen, Chem. Tech. (Leipzig) 39 (1987) 459 466, 508 514; K.-H. Bergk, D. Kaufmann, M. Porsch, W. Schwieger: Herstellung und Verwendung von Magadiit als Phosphatsubstitut in Waschmitteln, Seifen ole Fette Wachse 113 (1987) 555 561.

determination of ratio, 1690: gravimetric determination of SiO2 content, 1691: gas volumetric determination of CO2 content, 1692: titration of alkalinity, 2122: preparation of solutions of solid alkali silicates and determination of insoluble components, 2123: determination of dynamic viscosity of silicate solutions, 2124: titrimetric determination of SiO2 content, 3200: gravimetric determination of SO 2 content of alkali sil4 icates, 3201: photometric determination of iron content of alkali silicates.

4. References
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22. R. Schwarz, E. Menner: Zur Kenntnis der Kiesels uren, Ber. Dtsch. Chem. Ges. 57 a (1924) 1477 1481. 23. F. Liebau: ber Kristallstrukturen zweier u Phyllokiesels uren, H2 Si2 O5 , Z. Kristallogr. a 120 (1964) 427 449. 24. J.-L. Guth et al.: Un nouveau type de silice hydrat e cristallis e, C.R. Hebd. Seances e e Acad. Sci. Ser. D 286 (1978) 5 8. 25. C. Frondel: Crystalline Silica Hydrates from Leached Silicates, Am. Mineral. 64 (1979) 799 804. 26. G. Lagaly, R. Matouschek: Die kristallinen Kiesels uren aus Apophyllit, Carletonit und a Gillespit, Neues Jahrbuch Miner. Abh. 138 (1980) 81 93. 27. H.-H. Kruse, K. Beneke, G. Lagaly: Gas Adsorption by a Crystalline Silicic Acid, Colloid Polymer Sci. 267 (1989) 844 852. 28. J. D ring, K. Beneke, G. Lagaly: Adsorption o Properties of Crystalline Silicas: II. Adsorption of Anionic Surfactants and Delamination, Colloid Polym. Sci. 270 (1992) 609 616. 29. G. W. Brindley, G. Brown: Crystal Structures of Clay Minerals and their X-ray Identication, Mineralogical Society, London 1980. 30. Report of the Clay Minerals Soc. Nomencalture Commitee, Clays Clay Miner. 39 (1991) 333 335; 45 (1997) 298 300. 31. G. Lagaly, K. Jasmund (eds.): Tonminerale und Tone. Struktur, Eigenschaften, Anwendungen und Einsatz in Industrie und Umwelt, Steinkopff Verlag, Darmstadt 1993. 32. Denition of Clay and Clay Minerals, Clays Clay Miner. 43 (1995) 255 256. 33. A. Weiss, J. Russow: Uber das Einrollen von Kaolinkristallen, in I. Th. Rosenqvist, P. Graff-Petersen (eds.): Proc. Int. Clay Conf., Stockholm 1963, v. 1, 69 74. 34. W. B. Jepson: Kaolins: their Properties and Uses, Philos. Trans. R. Soc. London Ser. A 311 (1984) 411 432. 35. I. E. Odom: Smectite Clay Minerals: Properties and Uses, Philos. Trans. R. Soc. London Ser. A 311 (1984) 391 409. 36. K.-H. Bergk, D. Wolf, W. Schwieger, M. Porsch: Hectorit ein kristallines Magnesiumsilicat mit Zukunft, Chem. Tech. (Leipzig) 41 (1989) 245 251. 37. W. Vogel, W. H land: Zur Entwicklung von o Bioglaskeramiken f r die Medizin, Angew. u Chem. 99 (1987) 541 558. 38. G. Lagaly, K. Beneke: Intercalation and Exchange Reactions of Clay Minerals and

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General References 51. H. U. Bambauer, F. Taborszky, H. D. Trochim in W. E. Tr ger (ed.): Bestimmungstabellen, o

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Silicates
Optische Bestimmung der gesteinsbildenden Minerale, Part 1, 4th ed., E. Schweizerbartsche Verlagsbuchhandlung, Stuttgart 1971. H.-R. Bosse et al.: Untersuchungen uber Angebot und Nachfrage mineralischer Rohstoffe, XIX Industrieminerale, Bundesanstalt f r Geowissenschaften und u Rohstoffe, Hannover; Prognos AG Europ isches Zentrum f r Angewandte a u Wirtschaftsforschung Basel 1986. W. E. Tr ger, H. U. Bambauer, F. Taborszky, o H. D. Trochim in O. Braitsch (ed.): Optische Bestimmung der gesteinsbildenden Minerale, Part 2, E. Schweizerbartsche Verlagsbuchhandlung, Stuttgart 1967. B. Coope et al.: Industr. Minerals Directory, Metal Bulletin Books Ltd., Surrey 1977, p. 601. DAns-Lax, Springer-Verlag, Heidelberg 1967, pp. 1 - 217, 1 - 662, 1-681, 1-757, 3-493. DAns-Lax, Springer-Verlag, Heidelberg 1970, pp. 1 - 216, 1 - 341, 1 - 420, 1 - 754, 1 - 1289, 3 - 492. W. A. Deer, R. A. Howie, J. Zussman: Orthoand Ring Silicates, Rock-Forming Minerals, vol. 1, Longmans, Green and Co., London 1962. W. A. Deer, R. A. Howie, J. Zussman: Sheet Silicates, Rock-Forming Minerals, vol. 3, Longmans, Green and Co., London 1962. W. A. Deer, R. A. Howie, J. Zussman: Framework Silicates, Rock-Forming Minerals, vol. 4, Longmans, Green and Co., London 1963. W. A. Deer, R. A. Howie, J. Zussman: Disilicates, Rock-Forming Minerals, vol. 1A, Longman Scientic and Technical, London 1997. W. A. Deer, R. A. Howie, J. Zussman: Orthosilicates, Rock-Forming Minerals, vol. 1A, Longman Scientic and Technical, London 1997. W. A. Deer, R. A. Howie, J. Zussman: Disilicates, Rock-Forming Minerals, vol. 1B, Longman Scientic and Technical, London 1997. W. A. Deer, R. A. Howie, J. Zussman: Single-chain Silicates, Rock-Forming Minerals, vol. 2A, Longman Scientic and Technical, London 1997. W. A. Deer, R. A. Howie, J. Zussman: Double-chain Silicates, Rock-Forming Minerals, vol. 2B, Longman Scientic and Technical, London 1997. 65. W. A. Deer, R. A. Howie, J. Zussman: An Introduction to the Rock-Forming Minerals, 2nd ed., Longman Scientic and Technical Group, London 1992. 66. H. Freund: Handbuch der Mikroskopie in der Technik vol. 4, Umschau Verlag, Frankfurt/Main 1974. 67. Gmelin, System-Nr. 35, Al, [A], 35, 41, 47, 57, 69. 68. Gmelin, System-Nr. 35, Al, [B], 312, 390, 492. 69. Gmelin, System-Nr. 27, Mg, [A], Lief. 1, 92. 70. Gmelin, System-Nr. 35, Al, [A], 41. 71. Gmelin, System-Nr. 35, Al, [B], 313. 72. Gmelin, System-Nr. 27, Mg, [B], 351. 73. Gmelin, System-Nr. 1 5, Si, [8], 482. 74. Ind. Miner. (London) 1970, 2, 11. 75. Ind. Miner. (London) 1975, 7, 15. 76. Ind. Miner. (London) 1975, 11, 9. 77. Ind. Miner. (London) 1975, 12, 47. 78. Ind. Miner. (London) 1976, 1, 22. 79. Ind. Miner. (London) 1976, 9, 71. 80. Ind. Miner. (London) 1977, 4, 17. 81. Ind. Miner. (London) 1977, 5, 39. 82. Ind. Miner. (London) 1977, 6, 41. 83. Industrial Minerals Directory, 1st ed., Metal Bulletin Books, Surrey 1977, pp. 374, 565, 591, 620. 84. T. Hahn, M. J. Buerger: The Detailed Structure of Nepheline, KNa3 Al4 Si4 O16 , Z. Kristallogr. Kristallgeom. Kristallphys. Kristallchem. 106 (1955) 308. 85. H. Kittel in W. A. Colomb (ed.): Lehrbuch der Lacke und Beschichtungen, vol. 2, Heenemann, Berlin 1974, p. 379. 86. O. L ckert: Pigment + F llstoff Tabellen, M. u u u. O. L ckert, Laatzen 1980. u 87. Landolt-B rnstein, 5th ed., p. 1259. o 88. F. Machatschki: Spezielle Mineralogie auf geochemischer Grundlage, Springer Verlag, Wien 1953. 89. St. v. Naray-Szabo: Die Struktur des Pollucits CsAlSi2 O6 x H2 O, Z. Kristallogr. Kristallgeom. Kristallphys. Kristallchem. 99 (1938) no. 4, 277. 90. W. P. Pearson: Structure Reports for 1969, vol. 34 A, Oosthoek, Scheltma & Holkema, Utrecht 1975, p. 366. 91. P. Ramdohr, H. Strunz: Klockmanns Lehrbuch der Mineralogie, 16th ed., Enke Verlag, Stuttgart 1978. 92. Rheinisch Westf lisches Elektrizit tswerk a a Aktiengesellschaft (RWE): Bau-Handbuch Technischer Ausbau, 10th ed., Essen 1990.

52.

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