Complexes of n-tetradecylammonium-beidellite with n-alkanols

${\rm{(n - }}{{\rm{C}}_{{\rm{14}}}}{{\rm{H}}_{{\rm{29}}}}{\rm{N}}{{\rm{H}}_{\rm{3}}}^{\rm{+}}{\rm{)_{{\rm{0,44}}}(n - C_{{\rm{x}}}}}{{\rm{H}}_{{\rm{2x}}}}{\rm{+}}{}_{\rm{1}}{\rm{OH) }}{}_{{\rm{1,56}}}{{\rm{\{ M}}{{\rm{g}}_{{\rm{0,28}}}}{\rm{A}}{{\rm{l}}_{{\rm{1,81}}}}{{\rm{(OH)}}_{\rm{2}}}{\rm{S}}{{\rm{i}}_{{\rm{3,56}}}}{\rm{Al}}{}_{{\rm{0,44}}}{\rm{O_{{10\}} }}}^{{\rm{0,44 - }}}}$

The compounds undergo a series of reversible phase transitions

${\beta _1} \rightleftharpoons...\rightleftharpoons{\beta_i}\rightleftharpoons...\rightleftharpoons{\beta_\omega}\rightleftharpoons{\alpha_1}...\rightleftharpoons{\alpha_j}$

The β-transitions correspond to conformational changes of the alkyl chains via rotational isomerisation, especially kink formation. The β-phases become unstable if the kink concentration exceeds 0,14 kinks/-CH2-. The β/α-transition is probably caused by a rearrangement into special gauche-block structures.

The electrical conductivity of Na-montmorillonite suspensions in various salt and clay concentrations was measured. The weight conductance of the clay suspension was found to decrease with increase in clay concentration between 0 and approximately 0·5 g clay/100 ml, then rose to a plateau at 6–10 g clay/100 ml. The weight conductance of the clay suspensions also increased with an increase in the salt solution concentration. If the model of two resistors in parallel is used in interpreting the experimental data, these changes can be attributed to an increase in the mobility of the adsorbed Na ions. It is proposed that the two resistors in series model is more realistic in describing the conductivity of the suspensions. This model predicts the observed weight conductance changes of the suspensions, while the mobility of the adsorbed ions remains constant. A constant mobility of the adsorbed Na ions in clay-water systems of low to medium salt and clay concentrations also is predicted by the diffuse double layer.

Based on X-ray powder diffraction measurements of swelling, thermodynamic analysis of adsorption and kinetics, a mechanism of interaction between xylene isomers and two organoclay complexes was derived. The work is intended to resolve the factors which make possible the chromatographic separation of the xylene isomers with organoclays. Significant differences between the behavior of fresh organoclays and xylene vapor-conditioned organoclays were noted. Only small differences were apparent between the montmorillonite and the hectorite organoclays. Force constants, enthalpy changes, entropy changes, free energy changes and two specific rate constants were derived from the information obtained from this study.

Clay (<2 μm) and fine silt (2–20 μm) fractions of twenty seven soil samples from eight tropical ferruginous profiles of the Mysore Plateau (India) were analysed for kaolinite by dehydroxylation and selective dissolution. The considerable amounts of iron extracted by the procedure and the closeness of the SiO2/R2O3 molar ratios (2·00–2·18) to the ideal value of 2·00 indicated that iron was a structural constituent of the kaolinites. The calculated unit cell cation composition of the kaolinites showed a substitution of 0·11–0·82 atoms of Fe(III) for Al in every four octahedral sites. The kaolinites in these soils appear to be products of crystallization from weathering solutions.

With the use of a BaCl2 solution containing radioactive Ba2+ ions, kinetics of cation exchange have been done on a Kenya vermiculite, natural on one hand and previously oxidized either by 50°C water or oxygenated water on the other hand. Correlatively, the quantity of ferric iron in the layer has been determined by E.P.R. These two methods have shown that during an oxidation the proportion of iron which stays in the octahedral layer depends upon the nature of the oxidizing agent. During a weak oxidation, the iron stays entirely in an octahedral layer and the exchange capacity of the vermiculite decreases; on the other hand, during an oxidation by oxygenated water, part of the iron is extracted from the octahedral layer and the exchange capacity of the vermiculite is not changed, as established by the studies of Farmer (Farmer et al., 1971). Kinetic data for Llano vermiculite also are reported and compared with those for the Kenya vermiculite.

The layer structure of kaolinite from Twiggs, Georgia and fire-clay type kaolinite (Frantex B, from France), particle size separates 2–0·2 μm was studied by high resolution electron microscopy after embedment in Spurr low-viscosity Epoxy media and thin sectioning normal to the (001) planes by an ultramicrotome. Images of the (001) planes (viewed edge-on) of both kaolinites were spaced at 7 Å and generally aligned in parallel, with occasional bending into more widely spaced images of about 10 Å interval. Some of the 10 Å images converged to 7 Å at one or both ends, forming ellipse-shaped islands 80 to 130 Å thick and 300 to 500 Å long. The island areas and interleaved 10 Å layers between 7 Å layers may represent a residue of incomplete weathering of mica to kaolinite.

The proportions of micaccous occlusions were too small and the layer sequences too irregular to be detected by X-ray diffraction. The lateral continuity of the layers through the 7-10-7 Å sequence in a kaolinite particle would partially interrupt or prevent expansion in dimethyl sulfoxide (DMSO) and other kaolinite intercalating media. Discrete mica particles were also observed with parallel images at 10 Å, as impurities in both kaolinites. The small K content of the chemical analyses of the kaolinite samples is accounted for as interlayer K, not only in discrete mica particles but also in the micaceous occlusions.

Mineralogical reactions in the system Al2O3-SiO2-H2O are examined and an isothermal, isobaric cross-section of the portion of the system applicable to soil genesis, is determined. The relevance of the cross-section to soil mineralogy is discussed.

The basic salts of this system were prepared and their structures and physico-chemical properties were studies by electron microscopy, chemical analysis, X-ray powder diffraction, thermal analysis, i.r. absorption spectra, BET absorption, and acidity-basicity measurements. The salts were found to be new compounds analogous to hydrotalcite. They can be expressed by the formula; where M2+ and M3+ denote di- and trivalent cations, A− and A2− denote mono- and divalent anions, respectively, and y = z1 + 2z2; z1 ≫ z2.

The structures consist of positively charged Cd(OH)2-like basic layers and intermediate layers formed from anions and water molecules with the solid solution of divalent cation (M2+) and trivalent cation (M3+) being formed in the range of 0.6 < x/(x + y) < 0.9. The anions of Cl−, NO3− and ClO4− are easily substituted by CO32−. A large part of the NO3− makes a monodentate-type bond and the ClO4− a bridge-type bond.

The present paper presents the mineralogical composition of sediments from the Spanish Wealdian facies, selected from four stratigraphic sections of several regions in the Southern Cordillera Iberica.

Three of these sections show an irregular alternation of kaolinite rich sandy and silty-clay beds. The fourth section which contains calcareous layers, is very important from a geological point of view, because it is located where the structures of two ranges, the Iberian and the Betics, converge.

The clays of about 80 samples from these sections always consist of illite, kaolinite and interstratified clay minerals. The sandy layers also contain quartz, as well as potash and calcic-sodic felspars. The fine fraction (< 2 µm) is composed of kaolinte, between pM and T types, swelling illite and randomly interstratified clay minerals of the type (10I-14M), richer in 10 Å layers.

From the mineralogical and crystalchemical data and field observations, it is deduced that these sediments are mainly detrital. This and the layer alternation suggest, for the Upper Jurasic and Lower Cretaceous (Wealdian facies), a climate alternating from biostatic to rhexistatic. Alternating laterization and erosion might supply the materials to the Wealdian sedimentary basin.

The reaction products obtained when montmorillonites react with potassium halide at elevated temperatures, which were described in a previous publication, are further characterized. On the basis of their X-ray powder diffraction patterns, i.r. spectra, CEC and chemical composition they could be regarded as montmorillonite-illite interstratifications. Changes in morphology of various montmorillonites heated with and without K halide are related to the size, charge and position of interlayer cations. Scanning electron-micrographs of samples heated with KBr resemble those of well-crystallized illite. It is speculated that reactions of clay minerals with halides or other proton acceptors may account for some diagenetic processes in nature, e.g. the conversion of montmorillonite to illite on deep burial.

Since 1960 asbestos production of the United States has more than tripled, a phenomenon due in large part to the development of the Coalinga asbestos deposit in western California. Although most asbestos ores contain 5–10 per cent chrysotile in the form of cross- or slip-fiber veins within massive serpentinite bodies, no such veins are to be found in the Coalinga deposit despite the fact that it contains more than 50 per cent recoverable chrysotile. The Coalinga ore consists of soft, powdery, pellet-like agglomerates of finely matted chrysotile surrounding blocks and fragments of serpentinite rock. The highly sheared and pulverized nature of the ore favors its exploitation by simple, open-pit mining, and high quality products can be prepared by either wet or dry milling processes.

Four types of serpentine material are distinguishable: (1) hard, dense blocks of serpentinite rock, ranging from fractions of an inch to several tens of feet in diameter; (2) tough, leathery sheets, resembling mountain leather, up to several square feet in size; (3) brittle blades and plates of green serpentine, a few square inches in size; and (4) friable agglomerates of soft, powdery chrysotile containing appreciable amounts of the other three. Chrysotile is the principal component of all the above materials, with the exception of the serpentinite rock which consists mainly of lizardite and/or antigorite, with small amounts of brucite, magnetite, and very short fiber chrysotile. Although chrysotile fibers up to several microns in length are present in the leathery sheets, most Coalinga chrysotile is much shorter and arranged in a swirling mesh or disoriented, tangled fibers, much like cellulose fibers in paper. Fragments of serpentinite gangue are scattered throughout the ore and contain most of the lizardite, antigorite, and brucite. Chemical, electron probe, and X-ray analyses confirm the iron-rich nature of the brucite, a critical factor in the susceptibility of this phase to oxidation in the surface weathering zone. Here brucite either dissolves, leaving behind a residue of brown, amorphous iron oxides, or transforms in situ to pyroaurite or coalingite. Dissolved magnesium precipitates as hydromagnesite immediately above the water table throughout the deposit.

The abnormally high chrysotile content of this deposit is probably a result of the intensive shearing that it underwent during or after emplacement. If the friable, chrysotile-rich ore was produced during this pulverization episode, (1) lizardite and/or antigorite in the serpentinite must have been transformed into chrysotile and (2) brucite must have been removed. It is likely that early-formed lizardite/antigorite dissolved in the ground waters which pervaded the highly sheared body and that chrysotile later precipitated from these waters, coating all available surfaces.

Glauconite-smectite and illite-smectite interlayered minerals are compared by various means in an attempt to establish the mineralogical relations between the two groups. Experiments at 2 Kb pressure and 200–350°C are reported as well as microprobe scans of pelletal glauconites. This new information is used along with published chemical data in order to establish that

(1) Illite and glauconite mixed layered phases appear to be crystallographically similar. Both series show the same relations between potassium (mica) content and the amount of smectite layers apparent in the interlayered structure.

(2) Illite and glauconite mica or mica-like phases can be separated on the basis of Fe and K contents.

(3) Probable phase relations of the two mixed layered mineral series indicate that, when the starting materials contain mixed layered mica-smectites, increasing temperature produces an iron-rich mica in the case of glauconite and an aluminous mica in the case of illite. The mixed layered phases present at intermediate temperatures are not the same for illites and glauconites.

Apparently there is no mineralogical or chemical continuity between illite and glauconite when the potassium content is 6 wt % or greater. It might be possible that the potassic interlayered minerals near montmorillonite or nontronite could form a continuous solid solution.

Hisingerite occurs as a weathering product of iron-rich saponite in rhyolitic tuff of Oya, Tochigi Prefecture. The chemical composition: SiO2, 40·68%; Al2O3, 4·44%; Fe2O3, 28·54%; MgO, 1·85%; CaO, 1·42%; Na2O, 1·50%; K2O, 0·33%; H2O+, 6·43%; H2O−, 13·70%; total 98·89%. Very broad and weak X-ray powder reflections occur at 16, 4·5, 2·5, 1·7 and 1·5 Å, which correspond to the main peaks of nontronite. It is considered that trioctahedral iron-rich saponite was altered to hisingerite, a very poorly crystalline form of nontronite, by oxidation of iron and advanced leaching of octahedral Mg ions.

Ethylenediamine (EDA) is adsorbed from aqueous solution on Na-, K- and Li-montmorillonite as the monoprotonated cation (EDAH+) through an ion-exchange process. On washing with distilled water the second amine function is protonated—probably through dissociation of water near the clay surface—and simultaneously formed alkali hydroxide is removed.

In air-dried clay films, prepared from unwashed suspensions, EDA is retained mainly through hydrogen-bonding with water co-ordinated to the exchangeable cation.

EDA adsorbed from the vapour phase is retained through co-ordination, either direct or indirect (i.e. through a ‘water-bridge’), depending on the hydration properties of the exchangeable cation. Indirect coordination increases the stability of the amino-clay complex against atmospheric humidity and heating in vacuum in the order K+ < Na+ < Li+.

Upon heating co-ordinated EDA is almost completely desorbed, whereas EDAH+ and EDAH22+ decompose above 160°C to form NH4+.

This review of the literature shows that there have been many attempts to modify or revise the original definition of halloysites as distinguished from kaolinites, which was based on the greater water content of the halloysites. In general, these various attempts have arrived at definitions of halloysites as distinguished from kaolinites that are based on one or more particular instrumental or chemical techniques. Further investigations with almost all of these techniques have shown the apparently clear distinctions of this kind to be misleading. All such instrumentally—or chemically—based definitions were shown to either complicate and confuse the distinction between halloysites and kaolinites or to provide only empirical and subtle distinctions. It is concluded that only the original definition, with slight adaptations, enables clear and unambiguous distinctions to be made between halloysites and kaolinites. It is noted, however, that a distinctive structure for halloysite has been postulated as a result of electron diffraction studies. Further studies of this kind could well establish such a structure as being definitive of the mineral species.

The literature also reveals a long-standing disagreement over the nomenclature of different forms of halloysite and particularly over the nomenclature of and distinction between the two forms of halloysite at the extreme ends of the hydration series. An analysis of experimental studies of the relationship between these two and other hydration states of halloysite reveals that forms of halloysite with all possible interlayer water contents between 0 and 2 molecules H2O per Al2Si2O5(OH)4 unit cell may exist and that the two end members of the hydration series may not be seen as distinct phases. The fully dehydrated halloysite is the only thermodynamically stable form of the mineral. A nomenclature system which was proposed by MacEwan in 1947 is consistent with these results. This system, amended only by the exclusion of the unnecessary term ‘metahalloysite’ should therefore be adopted in all studies of halloysites.

Possible assignments are suggested for some of the absorption bands in the 1150–400 cm−1 region of the i.r. spectra of serpentines. Polarized light was used to identify the out-of-plane vibrations in antigorites and platy lizardites and the vibrations parallel to the fibre axis in chrysotiles and fibrous lizardites. An attempt is made to correlate some known structural characteristics and the chemical composition of the serpentines with some features of the i.r. spectra.

The idealized symmetry of kaolinite-type minerals (1:1 phyllosilicates) is analysed in detail. They can be considered as OD-structures consisting of three kinds of OD-layers. Each of them, taken separately, possesses higher symmetry than their combination. This explains the well-known tendency of kaolinite-type minerals to form a wide variety of ordered and disordered polytypes as well as twins. The possible stacking sequences result from the different kinds of pairs of kaolinite layers which are derived for dioctahedral, trioctahedral as well as ‘monoctahedral’ kaolinite-type minerals, the latter being defined as those in which the three octahedral positions are occupied by three different cations or two different cations and a void. The analysis makes use of a simple symbolism and a simplified pictorial representation.

A brief summary of the most important terms and definitions of the theory of OD-structures is given in an Appendix.

This work describes the separation of alunite from natural alunitic kaolins by applying a selective flocculation procedure. In order to determine the most efficient separating procedure preliminary experiments were performed with artificial mixtures of alunite and kaolin. The same procedure was then applied to natural alunitic kaolin which enabled the preparation of kaolin of considerable purity.

A comparison is made of the ion exchange behavior, towards the cobalt ion, of five sodium montmorillonite clays. The selectivity for the bivalent ion at low cobalt loading is correlated with the average dimensions of the particles in the various clays, as characterized by several methods. The data are interpreted in terms of a higher selectivity of the bivalent ions for the broken bonds located at the edges of the clay crystals. Using a model comprising two areas of different charge densities, the experimental differences in behavior can be predicted reasonably well.