bluuebunny/crossref_metadata_2025 huggingface dataset:
X-Ray Spectrochemical Determination of Potassium in Clay Minerals
Authors: Johnson Leon J.
Published: August 2006

An X-ray spectrochemical method is compared with the flame photometer determination of potassium in a series of sixty-five soil clay fractions. Two methods of preparing the clay samples for the X-ray determination were used. In one case a 20 mg sample of clay in suspension was dried onto a plastic disc as a thin film. Potassium was determined by comparing the fluorescence intensity of the unknown with a sample of known composition which was prepared for analysis by the same technique. For the second method a 100 mg sample of dried clay was pressed into a pellet using methyl cellulose as a backing. In this case a National Bureau of Standards sample (NBS-98) was prepared in an identical manner and used as a standard for determining the potassium in the unknown. The results for both techniques were highly significantly correlated with the values as determined by flame photometric analysis. The pellet technique gave a more accurate measure of the potassium content. With the thin films the same sample may be used for X-ray diffraction analysis. In either case the X-ray spectrochemical technique provides a fairly rapid and simple procedure that can be useful for handling large numbers of samples.
Surface Acidity of Smectites in Relation to Hydration, Exchangeable Cation, and Structure
Authors: Mortland M. M. , Raman K. V.
Published: August 2006

Equilibrium studies on clay films exposed to NH3 and H2O vapors demonstrate the effect of exchangeable cations on surface acidity and its relationship to hydration. At a relative humidity of 98 per cent the order of acidity on the clay surface as indicated by protonation of NH3 was Al > Mg > Ca = Li > Na = K for Wyoming bentonite and Al > Mg > Li > Ca = Na = K for nontronite. At a relative humidity of 20 per cent, however, the order was Al = Mg > Ca > Li > Na > K for the bentonite and Al = Mg > Li > Ca > Na > K for nontronite. The largest change in proton donation properties due to hydration effects was in the calcium clays. For Ca-bentonite the NH4+ formation was 16 me/100 g at 98 per cent and 80 me/100 g at 20 per cent relative humidity. In Ca-nontronite, the NH4+ formation was 14 and 64 me/100 g for the wet and dry systems respectively. The differences in proton donation between the bentonite and nontronite clays are believed to be due to charge site location and its effects on ion hydration. The NH4+ formed by the protonation process seemed to exist in different environments in the bentonite and nontronite as indicated in the i.r. absorption spectra.
Pedogenic Formation of Montmorillonite from a 2:1-2:2 Intergrade Clay Mineral
Authors: Malcolm R. L. , Nettleton W. D. , McCracken R. J.
Published: August 2006

Montmorillonite was found to be the dominant clay mineral in surface horizons of certain soils of the North Carolina Coastal Plain whereas a 2:1–2:2 intergrade clay mineral was dominant in subjacent horizons. In all soils where this clay mineral sequence was found, the surface horizon was low in pH (below 4·5) and high in organic matter content. In contrast, data from studies of other soils of this region (Weed and Nelson, 1962) show that: (1) montmorillonite occurs infrequently; (2) maximum accumulation of the 2:1–2:2 intergrade normally occurs in the surface horizon and decreases with depth in the profile; (3) organic matter contents are low; and (4) pH values are only moderately acid (pH 5–6).

It is theorized that the montmorillonite in the surface horizon of the soils studied originated by pedogenic weathering of the 2:1–2:2 intergrade clay mineral. The combined effects of low pH (below 4·5) and high organic matter content in surface horizons are believed to be the agents responsible for this mineral transformation. The protonation and solubilization (reverse of hydrolysis) of Al-polymers in the interlayer of expansible clay minerals will occur at or below pH 4·5 depending on the charge and steric effects of the interlayer. A low pH alone may cause this solubilization and thus mineral transformation, but in the soils studied the organic matter is believed to facilitate and accelerage the transformation. The intermediates of organic matter decomposition provide an acid environment, a source of protons, and a source of watersoluble mobile organic substances (principally fulvic acids) which have the ability to complex the solubilized aluminum and move it down the profile. This continuous removal of solubilized aluminum would provide for a favorable gradient for aluminum solubilization.

The drainage class or position in a catena is believed to be less important than the chemical factors in formation of montmorillonite from 2:1–2:2 intergrade, because montmorillonite is present in all drainage classes if the surface horizon is low in pH and high in organic matter.
Properties of Vermiculites and Smectites: Expansion and Collapse
Authors: Harward M. E. , Carstea D. D. , Sayegh A. H.
Published: August 2006

Samples of smectites and vermiculites were evaluated to (1) determine the effects of source and amount of charge, (2) determine if a continuum of properties exists, and (3) improve the basis for differentiating criteria for identification.

The montmorillonites expanded to the equivalent two-layer complex upon solvation by condensation of ethylene glycol or glycerol vapor. Beidellite exhibited the one-layer complex with glycerol vapor and the two-layer complex with ethylene glycol. The vermiculite samples did not yield regular two-layer complexes regardless of saturating cation, prior moisture or solvating agent. A number of different complexes of vermiculite were obtained depending on conditions of solvation. These corresponded to spacings of approx 13·6, 14·0, 14·3, 15·0, and 15·3 Å. Two or more of the complexes may be present in the same sample.

Potassium-saturated vermiculites and smectites both exhibited collapsed layers in a dry atmosphere. Hydration of smectites occurred at humidities above 20 per cent and resulted in poorly ordered diffraction maxima of 11–12 Å. The K-saturated vermiculites tended to retain the collapsed lattice and exhibited diffraction maxima of 10–10·6 Å with integral higher orders. Some hydration occurred as evidenced by peak asymmetry or the appearance of a small 14·3 Å line at higher humidities, although the collapsed spacing predominated. The tendency of vermiculite to hydrate decreased as the exchange capacity increased.

Differences in properties can be related to both source and amount of charge. Nevertheless, a continuum in the properties of expansion and collapse between the smectites and vermiculites was not observed. The data indicate two discrete populations. These properties may be used as differentiating criteria for identification.
Cation Replacement Studies on Heteroionic Bentonitic Clay Fractions Using Specific Ion Glass Electrodes
Authors: Fertl Walter , Jessen F. W.
Published: August 2006

Centrifuged fractions, ranging in size from 2·0 to 0·05 μ of a Wyoming bentonite, Bentonita de Durango from Mexico, and Helms clay from Texas were studied. The variation in replacement of Na+, Ca2+, Mg2+, K+, and H+ from these heteroionic clay systems under specific equilibrium conditions of salt concentrations was measured.

The displacement cation distribution was monitored by using specific ion glass electrodes, such as a sodium ion electrode, a cationic glass electrode, a calcium ion electrode and a Tektite electrode. Some factors affecting the exchange reactions are discussed and application of findings to drilling and production techniques is indicated.
Formation of Halloysite from Feldspar: Low Temperature, Artificial Weathering Versus Natural Weathering
Authors: Parham Walter E.
Published: August 2006

Weathering products formed on surfaces of both potassium and plagioclase feldspar (An70), which were continuously leached in a Soxhlet extraction apparatus for 140 days with 7·21 of distilled water per day at a temperature of approximately 78°C, are morphologically identical to natural products developed on potassium feldspars weathered under conditions of good drainage in the humid tropics. The new products, which first appear as tiny bumps on the feldspar surface, start to develop mainly at exposed edges but also at apparently random sites on flat cleavage surfaces. As weathering continues, the bumps grow outward from the feldspar surface to form tapered projections, which then develop into wide-based thin films or sheets. The thin sheets of many projections merge laterally to form one continuous flame-shaped sheet. The sheets formed on potassium feldspars may then roll to form tubes that are inclined at a high angle to the feldspar surface. Etch pits of triangular outline on the artificially weathered potassium feldspars serve as sites for development of continuous, non-rolled, hollow tubes. It is inferred from its morphology that this weathering product is halloysite or its primitive form. The product of naturally weathered potassium feldspars is halloysite · 4H2O.

The flame-shaped films or sheets formed on artificially weathered plagioclase feldspar do not develop into hollow tubes, but instead give rise to a platy mineral that is most probably boehmite. These plates form within the flame-shaped films, and with continued weathering are released as the film deteriorates. There is no indication from this experiment that platy pseudohexagonal kaolinite forms from any of these minerals under the initial stage of weathering.
Potassium Release from Muscovite as Influenced by Particle Size
Authors: von Reichenbach H. Graf , Rich C. I.
Published: August 2006

Completeness of exchange of K from muscovite by Ba2+ ions decreased with particle size below 20 μ. Accompanying K exchange at 120°C, using a repeated batch technique, was a marked loss of Si and the formation of boehmite in the finer fractions. Several possible explanations for the unexpected high K retention of fine mica fractions are discussed. The formation of a diffusion-inhibiting surface “skin” is discounted, because equilibrium was obtained more rapidly with the fine fractions than with coarser fractions. The average degree of bending of unit mica layers due to peripheral expansion is probably greater in large particles. With bending, rotation of tetrahedra and shifting of adjacent layers with respect to each other may induce greater release of K and a lower selectivity for this ion. Fault planes may induce preferential expansion of individual layers and initiate interstratification and splitting of particles. Splitting of particles may reduce bending and increase K selectivity.
Electron Microscopic Identification of Single Crystals of Wairakite, a Rare Component in Clays
Authors: Kiss Klara , Page Harold T.
Published: August 2006

Crystallites of the finest fraction of a clay mineral from Rosamund, California, which account for over 50 per cent of the total weight, are identified as wairakite single crystals of 0·1–1 μ size. High-magnification electron microscopy revealed flat, almost perfectly square-shaped lamellae, which consist of superimposed layers of approximately < 50 Å thickness. Electron diffraction patterns from a selected single crystal proved that the basal plane of the crystallite aligned perpendicular to the electron beam is the (111) plane. It is suggested on the basis of the present study and the report of previous investigators that the pseudocubic wairakite crystals cleave along their (111) and ($\bar 1$11) planes. The indices of high order reflections, unpublished or previously reported as uncertain, are determined.
A Method for Removing Titanium Dioxide Impurities from Kaolin
Authors: Maynard R. N. , Millman N. , Iannicelli J.
Published: August 2006

The removal of titanium minerals from kaolin can be accomplished by treatment with dispersing agents in an amount in excess of that required to produce maximum deflocculation of the kaolinite particles. In this reflocculated state the kaolinite particles attain a high degree of suspensional stability, and the titanium mineral particles, primarily anatase, are liberated and can be separated by sedimentation. Substantial removal of anatase impurities can be achieved by this method.
Interparticle Potential Energies in Na-Montmorillonite Clay Suspensions
Authors: Taylor T. R. , Schmidt P. W.
Published: August 2006

The small angle X-ray scattering data obtained in an earlier investigation of a series of Na-montmorillonite clay samples containing varying concentrations of sodium metaphosphate have been used to calculate the potential energy φ(x) of the interaction between two isolated parallel clay platelets separated by a distance x. All φ(x) curves have the form expected for Na-montmorillonite. In each curve there is a potential well for a platelet separation approximately equal to the most probable separation distance determined in the earlier study. Because the depth of the potential well is of the order of 0·01 eV for all samples, the attractive forces are relatively weak. While the calculated φ(x) functions are not highly accurate, in future investigations precautions can be taken to increase the reliability of the computed potential energy functions. This preliminary study suggests that determination of φ(x) from small angle X-ray scattering data can be a useful method for quantitative study of interparticle forces in Na-montmorillonite clays.
Rheological Model Studies in Clay
Authors: Christensen R. W. , Kim J. S.
Published: August 2006

The process of deformation in clays is visualized as the combination of recoverable deformation resulting from bending and rotation of individual particles and irrecoverable deformation due to relative movement between adjacent particles at their points of contact. The relative movement between particles is treated as a rate process in which interparticle bonds are continually broken and reformed as the deformation proceeds. Accordingly, the rate of deformation is governed by the activation energy associated with the rupture of interparticle bonds. Thus, in terms of a rheological model, the fundamental element consists of a spring, representing the recoverable deformation, in series with a rate process dashpot representing the irrecoverable deformation.

Owing to the heterogeneous nature of the fabric of clay soils, i.e. varying particle size, shape, orientation, surface characteristics, etc., a wide range of activation energies, elastic stiffness, and other material properties is anticipated. This is accounted for by assuming a Gaussian distribution for the model properties. Thus, the complete rheological model postulated in this study consists of a combination of spring and dashpot elements covering the complete spectrum of model properties.

The response of the rheological model is analyzed for creep and constant strain-rate loading. The analysis is accomplished numerically using a digital computer since no closed form solution exists for the non-linear systems of equations that result from this model. Experimental data for a number of triaxial tests on clays under various conditions of loading are presented for comparison with the model behavior.
Specific Co-Absorption of Purines and Pyrimidines by Montmorillonite (Clay-Organic Studies XV)
Authors: Lailach G. E. , Brindley G. W.
Published: August 2006

The co-absorptions of various purines and pyrimidines from aqueous solutions by Na- and Ca-montmorillonite are studied in the range of pH 1–6. The pyrimidines, thymine and uracil, which are not absorbed from solutions of these Compounds alone, are appreciably absorbed from solutions containing also adenine or 2,6-diaminopurine, are weakly absorbed from solutions containing hypo-xanthine, and are not absorbed from solutions containing purine, cytosine, and caffeine. The specific co-absorption is tentatively attributed to hydrogen-bond formation between the molecules in solution rather than to an overlapping of the molecular configurations (vertical stacking). The montmorillonite-organic associations have a basal spacing of about 12-5 Å which permits only a single molecular layer between successive silicate layers.
Lithium and Potassium Absorption, Dehydroxylation Temperature, and Structural Water Content of Aluminous Smectites
Authors: Schultz Leonard G.
Published: August 2006

X-ray analysis of Li+- and K+-saturated samples, differential thermal analysis (DTA), thermal gravimetric analysis (TGA), and chemical analysis of 83 samples enable a distinction to be made between Wyoming, Tatatilla, Otay, Chambers, and non-ideal types of montmorillonite, and between ideal and non-ideal types of beidellite. The Greene-Kelly Li+-test differentiates between the montmorillonites and beidellites. Re-expansion with ethylene glycol after K+-saturation and heating at 300°C depends upon total net layer charge and not upon location of the charge. Wyoming-type montmorillonites characteristically have low net layer charge and re-expand to 17 Å, whereas most other montmorillonites and beidellites have a higher net layer charge and re-expand to less than 17 Å.

Major differences in dehydroxylation temperatures cannot be related consistently to the amount of Al3+-for-Si1+ substitution, nor to the amount of Mg, Fe, type of interlayer cations, or particle size. The major factor controlling temperature of dehydroxylation seems to be the amount of structural (OH). Of 19 samples analyzed by TGA, montmorillonites and the one ideal beidellite that give dehydroxylation endotherms on their DTA curves between 650° and 760°C all contain nearly the ideal amount of 4(OH) per unit cell, but the non-ideal montmorillonites and beidellites that give dehydroxylation peaks between 550° and 600°C do not. Non-ideal beidellites contain more than the ideal amount of structural (OH) and non-ideal montmorillonites seem to contain less, although the low temperature of dehydroxylation of the latter could also be due to other structural defects. Change in X-ray diffraction intensity of the 001 reflection during dehydroxylation suggests that the extra (OH) of beidellite occurs at the apex of SiO4 or AlO4 tetrahedrons with the H+ of the (OH)− polarized toward vacant cation sites in the octahedral sheet.
Soil Minerals in the Al2O3-SiO2-H2O System and a Theory of Their Formation
Authors: Kittrick J. A.
Published: August 2006

An attempt has been made to assemble the best thermodynamic information currently available for soil minerals in the Al2O3-SiO2-H2O system at 25°C and 1 atm. Montmorillonite is included by considering its aluminum silicate phase. Diagrams are presented so that the stability of the minerals can be visualized in relation to the ionic environment. Although the Al2O3-SiO2-H2O system is a very simple one compared to soils and sediments, the stability diagrams depict a mineral stability sequence and mineral pair associations that are in good agreement with natural relations.

According to the stability diagram, mineral pairs that can form in intimate association are gibbsite-kaolinite, kaolinite-montmorillonite, and montmorillonite-amorphous silica. Forbidden pairs are amorphous silica-kaolinite, amorphous silica-gibbsite, and montmorillonite-gibbsite. The formation of intimate mixtures of three or more of these minerals is also forbidden. The stability diagrams predict ion activity relationships that are in reasonable agreement with those obtained from soils and sediments.

Amorphous silica probably limits high silica levels, with montmorillonite also forming at high silica levels. Kaolinite forms at intermediate and gibbsite at low silica levels. These minerals in turn probably control the activity of aluminum ions at a level appropriate to the pH. The formation of gibbsite, kaolinite, montmorillonite and amorphous silica appears to be controlled by a combination of kinetics and equilibria. That is, the kinetic dissolution of unstable silicates appears to control the H4SiO4 level. The new mineral(s) most stable at that H4SiO4 level appear to precipitate in response to solution equilibria.
Refinement of the Crystal Structure of Nacrite
Authors: Blount Alice M. , Threadgold I. M. , Bailey S. W.
Published: August 2006

The crystal structure of nacrite from Pike’s Peak district, Colorado, has been refined by least squares and electron density difference maps utilizing ten levels of data. Complete refinement was inhibited by thick domains involving a/3 interlayer shifts in the “wrong direction”. The ideal structure is based on a 6R stacking sequence of kaolin layers, in which each successive layer is shifted relative to the layer below by −1/3 of the 8·9 Å lateral repeat. This direction is X in nacrite, contrary to the usual convention for layer silicates, because of the positioning of the (010) symmetry planes normal to the 5·1 Å repeat direction. Alternate layers are also rotated by 180°. The pattern of vacant octahedral sites reduces the symmetry to Cc and permits description of the structure as a 2-layer form with an inclined Z axis.

Adjacent tetrahedra are twisted by 7·3° in opposite directions so that the basal oxygens approach more closely both the Al cations in the same layer and the surface hydroxyls of the layer below. Interlocking corrugations in the oxygen and hydroxyl surfaces of adjacent layers run alternately parallel to the [110] and [11̄0] zones in successive layers. The upper and lower anion triads in each Al-octahedron are rotated by 5·4° and 7·0° in opposite directions as a result of shared edge shortening. Nacrite has a greater interlayer separation and smaller lateral dimensions than dickite and kaolinite, and the observed β angle deviates by 1½° from the ideal value. These features, as well as its overall lesser stability, are believed due to the less favorable positioning in nacrite of the basal oxygens relative to the directed interlayer hydrogen bonds.
Montmorillonite-Organic Complexes - Gas Chromatographic Determination of Energies of Interactions
Authors: Bissada K. K. , Johns W. D.
Published: August 2006

Gas-solid chromatographic measurements of interaction energies were made for the systems ethanol and acetone with K-, Na-, Ba-, and Ca-montmorillonites. The results revealed an increased interaction energy in the order

K-mont. < Na-mont. < Ba-mont. < Ca-mont.

Interaction energies ranged from about 14 kcal/mole for K-montmorillonite to about 30 kcal/mole for Ca-montmorillonite. A very good agreement was observed between experimental heats of adsorption values and theoretical values for the electrostatic attractive energy between the respective cations and polar molecules.

These results confirm our earlier suggestions that complex formation takes place through cation-dipole interactions and that the polar molecules solvate the exchange cations in a manner similar to the hydration of cations in aqueous solutions.
Surface Conductance and Electrokinetic Properties of Kaolinite Beds
Authors: Lorenz Philip B.
Published: August 2006

A technique was developed for forming clay beds of uniform porosity between 48 and 62 per cent. The surface conductance and streaming potential of sodium kaolinite were determined over a range of values. Zeta potential as calculated from the classical formula was about - 30 mV at neutral pH and changed sign at pH 4. The surface conductivity of the sodium clay at various pH values was directly proportional to the zeta potential and from 12 to more than 30 times as large as the calculated electrokinetic surface conductivity. Similar measurements were made on kaolinite in the acid (hydrogen-aluminum) and calcium forms. The acid clay fitted the experimental correlation found for the sodium series, but the calcium clay, with less than one-tenth of the zeta potential of the sodium clay at neutral pH, had half its surface conductance. The results are interpreted as showing that exchangeable ions on kaolinite are mostly in a condensed layer on the surface where the mobility determines surface conductance. The surface mobilities for Na, Ca and H-Al are 20, 8 and 0 per cent of normal, respectively. Apparently hydrogen ion from the solution is very effective in replacing sodium, which exhibits its electrokinetic and conductive properties in proportion to its concentration on the surface.
Transformation of Montmorillonite to Nickel-Chlorite
Authors: Gupta G. C. , Malik W. U.
Published: August 2006

Nickel-chlorite has been obtained by the co-precipitation of nickelous hydrous oxide and montmorillonite at an OH/Ni ratio of 2.0. Chemical analysis shows that 16 me of Ni is fixed per gram of clay. System without any free nickelous hydrous oxide is quite stable up to an investigated period of 6 months, shows impedence to collapse on heating to 550°C, and no expansion of 001 spacing on glycerol treatment.

Different properties studied (X-ray diffraction analysis, thermal [D.T.A. and T.G.A.] data, i.r. absorption analysis, Polarographic reduction behavior and cation exchange capacity measurements) confirm the complete transformation of montmorillonite to nickel-chlorite.

“Seeding” of the hydroxide out of the “fixed” interlayer positions takes place on ageing the sample with free nickelous hydrous oxide. No montmorillonite could be detected by X-ray diffraction analysis in spite of this backward reaction.
Anauxite and Kaolinite Structures Identical
Authors: Bailey S. W. , Langston R. B.
Published: August 2006

Single crystal X-ray diffraction patterns reveal that the structure of selected anauxite crystals is the same as the structure of macroscopic kaolinite crystals. Anauxite and kaolinite crystals are intergrowths on a domain scale of units in pseudotwin orientations. Individual domains in anauxite have the triclinic geometry of kaolinite, and give X-ray reflections that compare closely in intensity with those calculated from the atomic parameters of kaolinite. Large crushed crystals of anauxite give powder patterns identical with that of kaolinite. Because it has been shown recently that the chemical composition of anauxite is also identical with that of kaolinite, it is recommended that the term “anauxite” no longer be used.
A Purple-Colored 1M Mica Clay From Silverton, Colorado
Authors: Tien Pei-Lin
Published: August 2006

A purple-colored clay of 1M mica polymorph in association with lead-zinc ore was collected from an abandoned mine dump near Silverton. Colorado. Electron micrographs show that the crystallites of the clay are less than 2μ in size and have poorly developed hexagonal outlines. Differential thermal and i.r. absorption analyses indicate similarity with those of muscovite. The structural formula of the 1M mica polymorph is (K1.45 Na0.02) (Al3.75 Mg0.19) (Si6.90 Al1·10) O20 (OH)4. The purple color may be related to trace amounts of manganese in the clay.
Deferration Effect on Structural Ferrous-Ferric Iron Ratio and CEC of Vermiculites and Soils
Authors: Roth C. B. , Jackson M. L. , Syers J. K.
Published: August 2006

Deferration by reduction of free Fe2O3 with Na2S2O4 in the presence of Na citrate and NaHCO3 caused a change in valence state of 10 to 35 per cent of the total structural iron in micaceous vermiculites, soils, nontronite, and muscovite. An increase in Fe2+ on deferration was accompanied by an equivalent decrease in Fe3+. Subsequent treatment with H2O2 reoxidized the structural Fe2+ previously formed.

Sesquioxide coatings on micaceous vermiculites were examined electron microscopically. These coatings were composed predominantly of Fe2O3 with approximately 10 per cent by weight of Al2O3 and small amounts of SiO2, as determined by chemical analysis of the deferration extracts.

The cation exchange capacity (CEC) increased 10–60 per cent as a result of deferration of micaceous vermiculites and soils. Treatment of the deferrated sample with H2O2 restored the Fe3+ content to approximately the original value but the CEC was not affected. Consequently, the increase in CEC on deferration was attributed to the removal of the positively charged sesquioxide coating. The reversible change in valence of structural iron without an equivalent change in CEC was attributed to deprotonation-protonation of the structure (OH− ⇄ O2−) simultaneous with the oxidation-reduction of iron (Fe2+ ⇄ Fe3+) in the phyllosilicate layer.
Intermolecular Interaction in Montmorillonites: NH-Co Systems
Authors: Doner H. E. , Mortland M. M.
Published: August 2006

The mechanism of interaction between cationic organic molecules satisfying exchange sites in montmorillonite and organic molecules with carbonyl groups was investigated. Dialkyl amides adsorbed on trimethyl-ammonium- and tetramethylammonium-montmorillonite were studied by i.r. spectroscopy. The electronegativity or basicity of the amides, expressed as a summation of the Taft polar factors (Σσ*), was found to be linearly related to the C-O stretching frequency after adsorption on trimethyl-ammonium-montmorillonite. Furthermore, the changes in the C—O and N—H stretching frequencies of the amides and trimethylammonium ion respectively, exhibited a direct linear relationship. Thus, the dialkyl amides were shown to be hydrogen bonded through the oxygen of the carbonyl group to the hydrogen of the trimethylammonium. The (001) spacing of trimethyl-ammonium-montmorillonite was 12·9 Å Only after the adsorption of amide molecules of the size of N,N-diethylacetamide or larger did this spacing change. Dialkyl amides were adsorbed on tetramethylammonium-montmorillonite, but less energetically than on trimethylammonium-clay. The (001) spacing of tetramethylammonium-montmorillonite was 13·8 Å and remained the same after adsorption of the dialkyl amides. Evidence of hydrogen bonding between the hydrogen of trimethylammonium-ion and some other carbonyl compounds was also noted.
Structural Organization in Amorphous Silico-Aluminas
Authors: Cloos P. , Léonard A. J. , Moreau J. P. , Herbillon A. , Fripiat J. J.
Published: August 2006

A structure model for amorphous hydrated or dehydrated silico-aluminas with composition varying between 0 < Al: Al + Si < 1 is presented. A central core made from a tetrahedral network in which silicon is partially substituted by aluminium carries a net negative electrical charge. This charge is balanced by more or less polymerized hydroxyaluminium cations forming a coating around the core.

As Al: Al + Si increases, the number of substitutions in the core increases as well as the complexity of the hydroxyaluminium cations in the coating.

For Al: Al + Si ≳ 0·8, a demixing is observed, leading to the formation of a crystalline pseudo-boehmite and bayerite.

Upon heating, the coating as well as the demixed phases are transformed into a spinel structure containing tetrahedral aluminium, while the core structure remains unaffected.

This model could explain the solubility features, the phosphate reaction and the catalytic properties of amorphous silico-aluminas.
Layering Phenomena in Colloidal Suspensions
Authors: Merchant S. R. , Rosauer E. A.
Published: August 2006

Aged suspensions of microspheres and two kaolinites exhibit several horizontal layers. Particle concentration is greater at the top of a layer; lower layer tops have increasing particle concentrations. Lower layers also settle more rapidly than upper layers; however, an increase in original suspension concentration results in a proportional increase in the particle concentration of comparable layers and causes comparable layers to settle at a slower rate. The average equivalent diameter of particles within and between kaolinite layers is identical. The maximum measured diameters are also identical. Microsphere layers show similar uniformity of average and maximum diameters. Ultimate settling of layers in suspension does not result in observable layers in the sediment. Data are interpreted as indicating that, in a colloidal suspension, particles interact to become observable as definite horizontal layers. A sequence of mechanisms is proposed for layer formation.
Effect of Acidity in Montmorillonite Interlayers on the Sorption of Aniline Derivatives
Authors: Yariv S. , Heller L. , Kaufherr N.
Published: August 2006

Sorption of aniline and its derivatives by montmorillonite substituted by cations of widely different acidity depends upon the polarizing power of the interlayer cations. Infra-red spectra indicate that the anilines are mostly bound to the interlayer cations through water molecules, except in Cs montmorillonite, where bonding to the oxygen surfaces of the alumino-silicate sheets seems to predominate. Anilines are weak bases, which compete with the oxygen surfaces for protons of acidic interlayer water. Consequently, the tendency of anilines to act as proton donors in the clay interlayers increases with the polarizing power of the exchangeable cation. The concept of ‘basic’ water is introduced to account for some of the features of the spectra of Cs montmorillonite treated with the organic ligands.
Electrochemical Alteration of Clay Soils
Authors: Gray D. H. , Schlocker J.
Published: August 2006

The composition and physical properties of three clay soils were altered by introducing aluminum under an electro-chemical gradient in order to evaluate the role of pH in controlling changes in soil composition and the feasibility of pH buffering during electrochemical treatment.

Both X-ray diffraction and selective chemical extraction methods were used to determine the distribution and mode of occurrence of aluminum in the treated samples. Aluminum was detected in the treated samples in both exchangeable form and as a hydroxy-aluminum interlayer. Aluminum oxide minerals such as gibbsite were not detected in any of the treated samples. Mineralization by aluminum ions was speeded and intensified in bentonite soils by buffering the catholyte with carbon dioxide.

Plasticity of bentonite soil samples from South Dakota was reduced markedly by electrochemical treatment, whereas the plasticity of an illite soil from Illinois and an illite-montmorillonite soil from Mississippi were relatively unaffected. Nearly all treated samples exhibited some degree of electrochemical induration or mineralization. Induration was most pronounced in bentonite soil samples with high water contents and alkaline pH largely because of hydroxy-aluminum interlayering in the ciay. On the other hand interlayering was negligible in illite soil samples with low pH; the main effect of electrochemical treatment in this case was the addition of aluminum in exchange sites.
The Determination of Quartz in Sedimentary Rocks Using An X-Ray Diffraction Method
Authors: Till Roger , Spears D. A.
Published: August 2006

An X-ray diffraction method for determining quartz in sediments is described which is both rapid and precise, with a coefficient of variation of 1·9 per cent. Samples are ignited at 950°C prior to X-ray analysis. This removes the interference of clay peaks, increases the relative intensity of the quartz peaks and reduces the initial matrix variation of samples. The peak area ratio of quartz (4·26Å) to an added standard boehmite (6·18 Å) is measured. Quartz content is obtained from a working curve constructed using similar rocks of known free silica content, which were analysed by the method of Trostel and Wynne (1940).
Thermal Decomposition of Organo-Ammonium Compounds Exchanged onto Montmorillonite and Hectorite
Authors: Chou Chung Chi , McAtee James L.
Published: August 2006

A series of organic ammonium ions were exchanged onto clay minerals montmorillonite and hectorite. Thermal effects on these surface modified organic-inorganic complexes were investigated by means of differential thermal analysis and heating-oscillating X-ray diffraction methods. It was found that the organo-clay complexes were dehydrogenated at temperatures from 180 to 350°C, depending on the organic cation used. Following the dehydrogenation, hydrolysis took place leaving a layer of “carbon” on the clay surface. The “carbon” was then oxidized at a temperature of about 550°C. Investigation of possible correlations between the activation energy of dehydrogenation and basicity, boiling point, ionization potential, molecular structure, and carbon-carbon bond distances of the organic cations showed that the geometric factors outweighed the acid, chemical and electronic factors in determining the effect of montmorillonite and hectorite toward the dehydrogenation of organic ions exchanged on the surfaces of these clay minerals.
Acid Dissolution of Chlorites: Release of Magnesium, Iron and Aluminum and Mode of Acid Attack
Authors: Ross G. J.
Published: August 2006

The acid dissolution of 8 chlorites in 2N Si-saturated HCl showed that there was no preferential dissolution of Al in octahedral positions and that the octahedral and tetrahedral sheets in the chlorite structure were equally attacked. An analysis of chemical data suggested a simple two-dimensional diffusion model in which the acid attack on the chlorite particles proceeded from the edges inward leaving a reacted layer which formed a diffusion barrier. Microscopic examination showed, however, that the acid attack was not simply an edge attack but started at any point where cracks, structural defects and weaknesses apparently predisposed sites to acid attack. It was also clear from the formation of etch figures and solution channels that the product layer at least partially dissolved or disintegrated during the progress of acid attack. The residue which remained after acid attack appeared to be an opaline amorphous hydrated silica as was indicated by index of refraction measurements. The orderly arrangement of etch figures on flakes of some chlorites reflected certain crystal symmetry elements. The results indicate that the acid dissolution technique to determine the ratio of Al in octahedral and tetrahedral positions can not be used as an aid in the calculation of structural formulae for chlorites.
Polytypism of Trioctahedral 1:1 Layer Silicates
Authors: Bailey S. W.
Published: August 2006

Polytypism in trioctahedral 1 : 1 phyllosilicates results from two variable features in the structure. (1) The octabedral cations may occupy the same set of three positions throughout or may alternate regularly between two different sets of positions in successive layers. (2) Hydrogen bonding between adjacent oxygen and hydroxyl surfaces of successive layers can be obtained by three different relative positions of layers: (a) direct superposition of layers, (b) shift of the second layer by a/3 along any of the three hexagonal X-axes of the initial layer, with a positive or negative sense of shift determined uniquely by the octahedral cation set occupied in the lower layer, and (c) shift of the second layer by ± b/3 along Y1 (normal to X1) of the initial layer regardless of octahedral cation sets occupied. Assuming ideal hexagonal geometry, no cation ordering, and no intermixing in the same crystal of the three possible types of layer superpositions, then twelve standard polytypes (plus four enantiomorphs) with periodicities between one and six layers may be derived. Relative shifts along the three X-axes lead to the same layer sequences derived for the micas, namely 1M, 2M1, 3T, 2M2, 2Or, and 6H. Polytypes 1T and 2H1 result from direct superposition of layers. Layer shifts of b/3 lead to polytypes designated 2T, 3R, 2H2, and 6R. The twelve standard 1 : 1 structures can be divided into four groups (A = 1M, 2M1, 3T; B = 2M2, 2Or, 6H; C = 1T, 2T, 3R; D = 2H1, 2H2, 6R) for identification purposes. The strong X-ray reflections serve to identify each group and the weaker reflections differentiate the three structures within each group. Examples of all four groups and of 9 of the 12 individual structures have been identified in natural specimens. Consideration of the relative amounts of attraction and repulsion between the ions in the structures leads to the predicted stability sequence group C > group D > group A > group B, in moderately good agreement with observed abundances of these structural groups.
Pore Size Distributions in Clays
Authors: Diamond Sidney
Published: August 2006

A knowledge of the distribution of pore sizes in clay and soil bodies is a useful element in the microstructural characterization of such materials. Pore-size distributions and total porosity of a number of reference clays, naturally-occurring subsoils, and commercial clay samples prepared in various ways were determined by mercury porosimetry. The range of equivalent pore diameter explored covered almost five orders of magnitude, from several hundred microns down to approximately 150 A. The method and its assumptions are critically evaluated, and measurements of the contact angle of mercury on clays yield values of 139° for montmorillonite and 147° for kaolinite and illite clays. The extent of shrinkage on oven-drying prior to mercury intrusion is assessed in each case and found to vary from insignificant to as much as 30 per cent of the pore space, depending on microstructural state and degree of initial saturation. The development of techniques for water removal which do not involve change in pore structure is explored. Some preliminary results for structurally weak saturated clays suggest that critical-region drying and perhaps freeze-drying procedures may be practical.
The Nature of Interlayering in Mixed-Layer Illite-Montmorillonites
Authors: Reynolds Robert C. , Hower John
Published: August 2006

The nature of interstratification in mixed-layer illite-montmorillonites has been investigated by comparison of diffraction patterns of ethylene glycol and ethylene glycol monoethyl ether treated samples with calculated one-dimensional diffraction profiles. The calculated profiles take into account the effects of particle size distribution, chemical composition, and convolution factors as well as proportions of layers and interstratification type. On the basis of detailed matching of diffraction patterns of monomineralic illite-montmorillonites of known chemical composition it is concluded that there are three types of interstratification: (1) random, (2) allevardite-like ordering, and (3) superlattice units consisting of three illite and one montmorillonite layers (IMII). By comparison of suites of calculated profiles with the diffraction patterns of many samples of illite-montmorillonites it is concluded that virtually all illite-montmorillonites with expandabilities from about 40 to 100 per cent are randomly interstratified (allevardite being exceptional); at >40 per cent montmorillonite layers they almost always have ordered interstratification. Allevardite-like ordering predominates in illitemontmorillonites which have ordered interstratification, with the IMII superlattice varieties confined to samples with about 10 per cent montmorillonite layers.
Adsorption Studies on Kaolinites
Authors: Lloyd Mary K. , Conley Robert F.
Published: August 2006

Adsorption studies have been performed on Georgia kaolins having a broad range of crystallinity and particle size distributions (from 0·1μ to 44μ) using N2 (78°K.), H2O (273°K.), and BuNH2 (298°K.). Using both vapor and liquid phase adsorption techniques, surface affinities of the adsorbates were determined.

Modified Frenkel-Halsey-Hill plots were used to compute the preferential adsorptivity of H2O vapor over N2 (hydrophilicity index, H.I.) as a function of crystallinity index, C.I., and particle size. For amine adsorptivity, non-aqueous adsorption isotherms were obtained.

Within any geographic deposit, crystallinity exhibits an inconsistent pattern with respect to particle size. A single generality is the tendency for crystallinity to increase toward the fine particle size range, D → 0·2μ. Adsorptivities of N2, H2O, and BuNH2 show no dependence upon crystallinity within a given particle size range. However, F.H.H. compensated slopes, describing the preferential adsorptivity over N2, show a definite decrease as crystallinity increases. A striking anomaly occurs in the vicinity of 0·2 > C.I. > 0·7 where H.I. increases briefly then returns to the original trend. The rate of decrease of H.I. vs. C.I. is consistently steeper with increasing particle size. Adsorption of water vapor most likely occurs as a 1:1 configuration on each silica-alumina edge group, 1:1 on each basal silica, and 1:2 (hindered configuration) on each basal alumina group.

The data suggest that amines adsorb preferentially and quantitatively on the edges, i.e. the Lewis and Bronsted acid sites, and follow a Langmuir pattern.
Iron Alkoxide Obtained by Reacting Iron Oxides with Glycerol
Authors: Fuls P. F. , Rodrique L. , Fripiat J. J.
Published: August 2006

Goethite, lepidocrocite and hematite were reacted with glycerol and reaction products were studied at various steps of the reaction. After a treatment of 16 hr at 245°C the final form of the reaction product, a deep green soft solid, was obtained whatever the starting material. According to hydrolysis and chemical analysis, the reaction product can be identified as iron alkoxide. Hydrolysis of the solid by boiling water yielded glycerol and a strongly magnetic material characterized by a spinel structure like maghemite and magnetite.

The iron alkoxide is seen by electron microscope as large well-formed hexagonal platelets. The similarity between a and b parameters of this compound and those of brucite suggests that the iron alkoxide structure is based on an iron (II and III) octahedral layer. The glycerol chains should be located between the sheets. Two models were proposed in which iron and oxygen, linked to the chain of glycerol, could be accommodated in octahedral layers giving a basal distance of 8·1 Å.

At least two steps are involved in the formation of the iron alkoxide: (1) a rearrangement of the structure of the starting material with accomodation of carbon in the structure and (2) a reduction of ferric iron.
Surface Area of Homoionic Illite and Montmorillonite Clay Minerals as Measured by the Sorption of Nitrogen and Carbon Dioxide
Authors: Aylmore L. A. G. , Sills I. D. , Quirk J. P.
Published: August 2006

The surface areas obtained by application of the B.E.T. theory to adsorption isotherms of nitrogen and carbon dioxide gases at 77°K and 195°K respectively on homoionic samples of illite and montmorillonite clays have been examined. The isotherms were obtained using a standard volumetric adsorption system and the results are compared with those obtained by Thomas and Bohor (1968) using a dynamic sorption system.

Small amounts of residual water have been shown to have a marked influence on the accessibility of the internal surfaces of the montmorillonite clays to nitrogen and carbon dioxide adsorption, in this respect the standard outgassing procedure under high vacuum seems more efficient than that used in dynamic systems. The present data indicate that provided the sample has been satisfactorily outgassed there is little penetration of nitrogen or carbon dioxide gases into the quasi-crystalline regions of montmorillonite clays. With the exception of the caesium saturated montmorillonites the surfaces of the clays are more accessible to the smaller nitrogen molecules than to carbon dioxide assuming the values used for molecular area are correct.
I.R. Study of Alkyl-Ammonium Vermiculite Complexes
Authors: Serratosa J. M. , Johns W. D. , Shimoyama A.
Published: August 2006

Two octyl-ammonium vermiculite complexes with different 001 periodicities have been studied by i.r. spectroscopy. In each case i.r. spectroscopy affords information on the orientation of the — NH3+ groups and the strength of the hydrogen bond between these groups and the silicate oxygen surfaces. Also a perturbation of the vibration of the OH groups of the silicate has been observed that seems to be related to the distance from the center of the layer at which the — NH3+ groups are situated.

The i.r. results are discussed in relation to the structural models deduced from X-ray analysis.