bluuebunny/crossref_metadata_2025 huggingface dataset:
The Nature of Garnierites—III Thermal Transformations
Authors: Hang Pham Thi , Brindley G. W.
Published: September 2006

Serpentine- and talc-like garnierites described in Parts I and II were heated at various temperatures up to about 1000°C and after each treatment were cooled and examined by X-ray powder diffraction. The serpentine-like garnierites at about 550°C, the temperature at which rapid dehydroxy-lation begins, formed a highly disordered phase. When the NiO content was low (approximately < 20 wt%), the disordered phase transformed directly to an olivine phase around 800°C, but when the NiO content was higher, various transitional phases were formed before an olivine phase appeared around 1000°C. A sepiolite-like phase was obtained with one sample around 800°C, and several samples showed face-centered cubic modifications between 900 and 1000°C.

The talc-like garnierites with low NiO content formed an enstatite phase around 800°C directly following the dehydroxylation reaction, but with high NiO contents an olivine phase became increasingly prominent between 850 and 1000°C. Identification of the mixed crystallizations possibly existing in the initial minerals is scarcely feasible on the basis of the products formed up to 1000°C.
Effect of Particle Thickness on Potassium Exchange from Phlogopite
Authors: Ross G. J. , Rich C. I.
Published: September 2006

Rates of exchange of K with Ca for fine (0·2–2 μm) and coarse (54–75 μm) and for thin and thick (37–45 μm) phlogopite particles were determined using a repeated batch technique, which gave a measure of K selectivity.

Potassium selectivity of the fine fraction was higher than that of the coarse one throughout the exchange process in which 93 per cent of the total K was exchanged from the fine fraction and 100 per cent from the coarse one. Potassium selectivity of the thin 37–45 μm particles was higher initially than that of the thick 37–45 μm particles but the difference disappeared subsequently and practically 100 per cent of the total K was exchanged from both the thin and thick particles.

The results are interpreted as tentatively confirming the hypothesis that bending and deformation of elementary layers during K exchange increase with particle thickness, which in turn increase K exchange and decrease K selectivity.

The K exchange curves for the fine and coarse phlogopite fractions suggest that in natural conditions, as in soils, where K is not continuously removed from solution, vermiculization of coarse mica particles may be not only more complete but also more rapid than vermiculization of fine mica particles.
A Natural 17Å Montmorillonite-Organic Complex from Alleppey, Kerala State-India
Authors: Moum Johan , Rao Chatty N. , Ayyar T. S. R.
Published: September 2006

A black organic-rich alluvial clay from Alleppey, Kerala State, India, gave a well defined 17Å reflection in the natural untreated state. Ethylene glycol and heat treatments showed it to be essentially a smectite. Treatments with H2O2 and 0·1 N NaOH contracted the spacing to about 14Å, indicating that sorbed organic matter was responsible for the original enhanced spacing.

In the natural state, the clay was chiefly divalent with respect to the ions on its exchange sites and was at a pH of 6·2. Subsequent attempts to resorb the organic matter (which had been extracted from the clay by repeated NaOH treatments, converted to the H-form, concentrated and freeze-dried) into the interlamellar space of H2O2-treated clay proved successful only after the pH was brought down to 3•2 and the clay converted to an essentially monovalent state through repeated 1 N NaCl treatments.
The Transference Numbers of the Counter-Ions in Montmorillonite Paste as a Function of Water Film Thickness and Electrolyte Concentration
Authors: Tschapek M. , Grazán A. M.
Published: September 2006

The transference numbers of the counter ions in montmorillonite paste are determined as a function of the thickness of the water film (h) and of the diffuse double layer (1/κ).

From measured E.M.F. values of a cell with two liquid junction potentials (C′KCl solution-paste-C″KCl solution) and by applying the Henderson equation, the transference numbers t+ were calculated. It is shown that the transference numbers of the counter-ions, t+ → 1 if hκ → 0.
The Crystal Structure of Talc
Authors: Rayner J. H. , Brown G.
Published: September 2006

The crystal structure of a sample of talc from Harford County, Maryland, has been determined by least squares refinement from X-ray diffraction photographs. A triclinic cell with a = 5·293, b = 9·179, c = 9·496Å, α = 90·57°, β = 98·91°, γ = 90·03, space group C1̄ is adopted. The layers of the structure have almost monoclinic symmetry but the nearly hexagonal rings of oxygen atoms on the surfaces of the layers, formed by the bases of the silica tetrahedra, are not held in register by interlayer ions as they are in micas but are partly displaced so that the stack of layers forms a triclinic crystal. The hexagons of surface oxygens are distorted by a 3·4° twist of the tetrahedra so that the b axis is 0·2 per cent shorter than in a structure with regular hexagons, and the twist brings the oxygen ions a little closer to the octahedral magnesium ions.
Infrared Study of Attapulgite and HCl Treated Attapulgite
Authors: Mendelovici Efraim
Published: September 2006

Infrared absorption spectra show important changes in the positions and form of the absorption bands of a film of attapulgite after it has been pumped out. An attempt to differentiate among some of the multiple frequencies due to OH groups is based on the information obtained from dehydration and deuteration experiments. The 1198 cm−1 shoulder, characteristic of attapulgite, is assigned to a Si-O vibration. When attapulgite is refluxed with 5N HCl for 5 hr the octahedral layer is dissolved. The acid attack causes the disappearance of the Si-O-Si absorption bands from attapulgite giving rise to a characteristic vibration at 1090 cm−1, as well as another absorption at 960 cm−1. The latter indicates the presence of silanol groups.
Evaluation of Crystallinity in Hydrated Ferric Oxides
Authors: Landa Edward R. , Gast Robert G.
Published: September 2006

The nature of freshly-precipitated and aged hydrated ferric oxides prepared by the addition of ferric chloride to KOH was investigated by the use of scanning and transmission electron microscopy, X-ray diffraction, i.r. absorption, and pH 3·0 ammonium oxalate extraction. The results show the fresh material to be essentially non-crystalline hydrated ferric oxide, which when aged at 60°C C and high pH rapidly crystallizes as goethite, without any indication of coexisting hematite. The various methods were evaluated as indices of crystallinity for aging materials. The acid ammonium oxalate method was shown to extract selectively only the non-crystalline portion of such mixtures. The use of X-ray diffraction analysis for estimating aging stage requires elimination of the preferred orientation of the goethite crystals. While both the oxalate and X-ray methods can detect as little as 2 per cent crystallinity, the oxalate method is probably superior for quantitative determinations as it depends directly on an inherent difference in the solubility of the crystalline and non-crystalline materials, rather than on a technique dependent intensity measurement. The use of the intensity of the O-H bending vibrations of the infrared absorption spectra can also potentially detect as little as 2 per cent crystallinity, but the procedure is probably less useful for quantitative determinations than the oxalate or X-ray methods because of the problem of evaluating the area under the peaks.
Interlayer Bonding in Kaolinite, Dickite and Nacrite
Authors: Giese R. F.
Published: September 2006

A simple electrostatic model has been used to demonstrate that the inner surface hydroxyls in kaolinite, dickite and nacrite are responsible for the interlayer bonding in these minerals. The contribution to the interlayer bonding of an individual hydroxyl hydrogen depends on the orientation of the hydroxyl group relative to the 1:1 layer since this orientation determines the H—O interlayer distance. If this distance is much greater than the sum of the van der Waals radii, 2·60 Å, there is essentially no bond. As the distance becomes less than 2·60 Å, the strength of the interlayer bond increases.
Distribution of Major Cations in Estuarine Sediments
Authors: Parashiva Murthy A. S. , Ferrell R. E.
Published: September 2006

This paper reports the measured distribution of major cations in interstitial, exchangeable and non-exchangeable phases of estuarine sediments. The observed changes in ionic ratios result from the valence and dilution effects in the Donnan equilibrium concept according to which the ion exchanger favors the sorption of divalent ions at the expense of monovalent cations and cations migrate to the outer solution. The above findings have direct application to an interpretation of diagenetic changes in clay minerals.
The Experimental Transformation of Mica Toward Smectite; Relative Importance of Total Charge and Tetrahedral Substitution
Authors: Robert M.
Published: September 2006

This article emphasizes the influence of crystal-chemical composition on the ease of transformation of micas to vermiculite or more smectite-like minerals. The swelling test, with glycerol, of Mg-saturated mineral is used to characterize the degree of transformation.

The main structural factors of this evolution are tetrahedral substitution of Si by Al, and total charge. There is a relation between these two factors, i.e. the lower the tetrahedral substitution, the greater can be the charge without affecting the smectite swelling behavior.

In this respect there is a contrast between tri and dioctahedral micas. In the first, tetrahedral Al is so high (> 1·20 for Si4O10) that transformation into smectite must imply modification of the tetrahedral layer. For dioctahedral micaceous phyllites (illites, glauconites) where tetrahedral charge is lower, transformation can be easier. Only a lowering of total charge is needed and reduction-oxidation seems to play a very important role in this process.
The Location of Iron-55, Strontium-85 and Iodide-125 Sorbed by Kaolinite and Dickite Particles
Authors: Fordham A. W.
Published: September 2006

The autoradiographic method at the electron microscope level has been applied successfully to locate the position of sorbed ions and compounds associated with kaolinite and dickite particles. For suitable isotopes, the limit of resolution was about 0·2 μm and would be conceivably less in the most favorable conditions.

Judged by the location of iodide-125 and strontium-85, the majority of positive sites and also the most reactive negative sites were situated at the edges of the clay particles. These conclusions were supported by normal electron microscope examination of mixtures of clay with charged gold and silver iodide sols.

Iron (III) ions, which have been shown to react with kaolinite by chemisorption mechanisms in 0·15 M systems and by both ion exchange and chemisorption in 0·01 M systems, were, in either case, located at edge-sites on the clay. When intentionally precipitated onto dickite, iron (III) hydroxides were distributed evenly over the clay surfaces. However, precipitation was probably initiated at the particle edges.

Minor exceptions to the above conclusions appeared to be caused by basal surface features such as fracture or stress lines, outgrowths or cavities, and if the clays had not been cleaned, by strongly associated impurities such as iron hydroxides.
Adsorption of Pyridine N-Oxide onto Montmorillonite
Authors: Olejnik S. , Posner A. M. , Quirk J. P.
Published: September 2006

Pyridine N-oxide and montmorillonite form interlamellar complexes with basal spacings of 14·7 and 21 Å. The former corresponds to a monolayer with a tilted orientation of the pyridine ring; the latter comprises a double layer of molecules between the clay sheets. Infrared spectra show that pyridine N-oxide bonds through the NO group; in the 21 Å complexes it is coordinated to the exchangeable cations through water molecules acting as bridges which themselves are directly coordinated to the cations. In the 14·7 Å complexes a splitting of the ν(NO) band occurs with the more polarizing cations Mg and Ca; the two bands correspond to pyridine N-oxide molecules directly coordinated to the cation and to other molecules coordinated through bridging by water molecules. Cs montmorillonite forms complexes with a basal spacing of approximately 14·7 Å which also shows a splitting of the ν(NO) band.
Regularly Interstratified Chlorite—Dioctahedral Smectite in Dike-Intruded Shales, Montana
Authors: Blatter C. L. , Roberson H. E. , Thompson G. R.
Published: September 2006

Corrensite or ‘corrensite-like’ minerals occur in dike-intruded shales and siltstones of the Montana Group and Colorado Group (Early Cretaceous) in Western Montana. The < 1 μm size fraction of one specimen of this “corrensite-like” material has been studied in detail. X-ray diffraction data and chemical analysis indicate that this specimen is a regular or nearly regular interstratification of chlorite and dioctahedral smectite. Also described are other samples, which contain corrensite and additional phases. These samples were taken at several localities where basic dikes have intruded these shales and siltstones.
Exchangeable Cation—Structural Parameter Relationships in Montmorillonite
Authors: Lahav N. , Bresler Eshel
Published: September 2006

The interaction between “unhydrated” cations (those not separated from the surface by a solvent sheath) in hole positions and the montmorillonite surface was analyzed theoretically by considering the main contributions to potential energy from the coulombic, hydration, van der Waals, induced dipole, and repulsive energies. The effects on these energy terms of the distance between the cation and the plane of basal oxygens, h, and of the angle of rotation of the silica tetrahedra, θ, were investigated. Increase of θ with h constant increases the absolute values of all but one of the energy terms. The hydration energy is an exception because it is probably independent of θ. For a small cation, the increase in attraction is greater than the increase in repulsion when the value of θ is sufficiently small. As θ increases, the repulsive energy becomes more and more dominant until a minimum potential energy is reached. For large cations, this minimum can occur only above a certain value of h. Thus, the values of the potential energy minimum and of θ at this minimum depend on the cation under study as well as on h. Since the concentration of unhydrated cations in a montmorillonite-water system increases with decreasing water content, it is concluded that θ increases during the drying of homogeneous montmorillonite-water suspensions. This provides a partial explanation for the changes in b-dimension with water content observed by other investigators.
Appearance and Stability of Hydrolyzed Fe(ClO4)3 Solutions
Authors: Hsu Pa Ho
Published: September 2006

Fe(ClO4)3 solutions of different concentration and acidity were studied to search for the factors governing their appearance and stability during aging and to elucidate the mechanisms for the formation of amorphous and crystalline iron(III) hydroxides from slow hydrolysis. It was found that dilute solutions (0·001M or lower) rapidly hydrolyzed to clear sols after a brief induction period. With an increase in iron(III) concentration, one could notice gradual increases in the induction period, turbidity and particle size. Thus, solutions 0·006M to 0·01M in iron(III) developed into dense, cloudy, yellow suspensions impervious to light. The polymeric iron(III) species in the aged 0·02M solution were primarily large particles that settled under gravity, resulting in a suspension of low turbidity. It was also observed that in dilute solutions, the initial polymerization product was amorphous iron(III) hydroxide which yielded X-ray diffraction peaks for FeOOH only after prolonged aging or not at all. In 0·01 and 0·02M solutions, however, crystalline FeOOH was the major product from the very beginning of polymerization. The results suggest that the initial degree of supersaturation with respect to amorphous iron(III) hydroxide is the key factor governing particle size distribution, which in turn governs the appearance, stability and crystallinity of the hydrolyzed product during aging.

The addition of HClO4 to dilute Fe(ClO4)3 solutions decreased, whereas the addition of NaOH to concentrated solutions increased, the degree of supersaturation and, thus, induced changes in induction period, appearance, stability and crystallinity of the hydrolyzed product accordingly.
Occurrence of Collapsed and Expanded Crystals in Montmorillonite-Dextran Complexes
Authors: Olness Alan , Clapp C. E.
Published: September 2006

X-ray diffraction patterns obtained from montmorillonite-dextran complexes prepared with either B-512F or Polytran dextran showed maximum oven-dry crystal expansions of about 5·3 Å. X-ray diffraction patterns of individual complex preparations containing < 20 per cent dextran showed evidence of both expanded and collapsed crystals. The observation of expanded and collapsed crystals in individual preparations has not been previously reported and was apparently related to clay preparation. An estimate of the quantity of dextran which could be interacting with the silicate surface was obtained using polymer adsorption weights and volumes. At maximum adsorption almost all adsorbed B-512F could be in contact with the mineral surface, but only two thirds of the adsorbed Polytran could be in contact with the mineral surface.
The Effect of Aluminum on the Surface Properties of Kaolinite
Authors: Bundy Wayne M. , Murray Haydn H.
Published: September 2006

Aluminum ions as well as hydroxide precipitates promote improved extraction of iron from kaolinites during leaching. Selective aggregation of ultrafine particles in kaolinites, seemingly induced by precipitation of aluminum hydroxide, gives brightness improvement in excess of that which can be ascribed to iron extraction. Aggregation of anatase, a primary discolorant confined mostly to the fine end of the kaolinite particle size distribution, is the suggested mechanism for complementary brightness improvement.

Precipitation of aluminum hydroxide in kaolinite systems substantially changes flocculation characteristics, surface area (methylene blue), and rheology. Edge-edge and edge-face flocculation are promoted where sulfate retention is high, becoming progressively more face-face with sulfate removal. The character of the flocculation can be interpreted by the combined use of surface area and low shear viscosity data.

The extent to which kaolinites can be dispersed after processing increases with increase in sulfate retention. Stability of suspensions deflocculated with polyphosphates shows an inverse relationship, decreasing with increase in sulfate retention.
The Alteration Products of Potassium Depleted Oxybiotite
Authors: Gilkes R. J.
Published: September 2006

Artificial weathering of biotites, which contain various levels of structural ferric iron, by NaCl and NaBPh4 solutions produces minerals and structures similar to those described for naturally weathered biotites. Oxidation of structural iron leads to K removal from alternate layers and development of hydrobiotite. The growth of order with increasing ferric iron content has been assessed by comparison with theoretical calculations for random and most ordered interstratified structures. There is evidence for the existence of two layer types in biotite prior to oxidation. The depression in rates of K release due to oxidation has been confirmed.
The Chemisorption of Anisole on Cu(II) Hectorite
Authors: Fenn D. B. , Mortland M. M. , Pinnavaia Thomas J.
Published: September 2006

The sorption of anisole and some related aromatic ethers on the interlamellar surfaces of Cu(II) hectorite has been investigated by i.r. and e.s.r. spectroscopy. In addition to physical adsorption, anisole forms two distinct types of Cu(II) complexes which are analogous to the type I and II species previously reported for benzene-Cu(II) smectite systems. These complexes can be transformed to type I and II complexes of 4,4’-dimethoxybiphenyl. Possible mechanisms are proposed for the oxidation process. Butyl phenyl ether formed a type II complex with Cu(II)-hectorite, but no dimerization reaction was noted in this system. Phenyl ether and benzyl methyl ether form a type I π complex with Cu(II)-hectorite. No type II analog was noted. E.S.R. spectra of each of the type II ether-Cu(II)-hectorite systems showed a single, narrow band with g near the value expected for a “free spinning” electron. The type I phenyl ether and benzyl methyl ether complexes also exhibited this e.s.r. band. Ag(I) hectorite adsorbs anisole by forming exclusively a type I complex. Na(I) and Co(II) hectorite adsorb anisole by physical means only, indicating association with the silicate surface.
The Alteration of Some Aromatic Amino Acids and Polyhydric Phenols by Clay Minerals
Authors: Thompson Thomas D. , Tsunashina Atsuma
Published: September 2006

These studies concern the catalytic activity of clays on amino acids, particularly tyrosine. Polyhydric phenols were included to help understand the tyrosine reactions.

Below pH 3, tyrosine is adsorbed on clay minerals by cation exchange. Above pH 3, oxidative degradation of tyrosine occurs, the L-isomer altering more rapidly. The rate of alteration depends upon the particular clay mineral, surface modifications such as polyphosphate treatment, heating, and the presence of copper, aluminium, and mercury. A free radical mechanism is proposed for the alteration.
The Influence of the Christiansen Effect on I.R. Spectra of Powders
Authors: Prost R.
Published: September 2006

The Christiansen effect appears in the i.r. spectrum of powders embedded in a solid, liquid or air matrix as an apparently anomalous transmittance (Christiansen peak) of the incident electromagnetic radiations. The peak appears at wavelengths for which the refractive index of the sample and the refractive index of the matrix are equal (Christiansen wavelength: λChr).

On account of the great variation of the sample refractive index in the immediate neighborhood of the absorption bands (anomalous dispersion curve), one often observes the occurrence of a transmittance peak or of a band deformation in this spectral range. A change in the position of this transmission peak with the value of the matrix refractive index is indicative of the Christiansen effect.

The equality of the refractive indices of the sample and of the matrix for μChr has been used to determine some points of the anomalous dispersion curve in the neighborhood of the hydroxyl stretching band (3678 cm−1).

Spectral distortions caused by the Christiansen effect can be reduced by preparing the sample in such a manner that the width at half-maximum (Δν1/2) of the Christiansen peak is several times greater than this of the absorption band itself. Clarke’s theoretical formula, which gives an estimation of Δν1/2, has been qualitatively verified and thus gives an appropriate guide in the choice of the parameters which one can optimize during the sample preparation. One can reduce the Christiansen effect spectral modifications, without running the risk of modifying the sample itself, particularly by overly severe grinding.
Fixing Cation Interaction with Blister-Like Osmotic Swelling on Vermiculite Cleavages
Authors: Sridhar K. , Jackson M. L.
Published: September 2006

The shrinkage of osmotically swollen natural and artificial blisters on vermiculite cleavages by exchange saturation with fixing cations such as Cs+, Rb+, NH4+, and K+ was investigated by replica electron microscopy. Incomplete collapse of either the natural or artificially produced blisters occurred with Cs+, Rb+, and NH4+ saturation, while K+ saturation completely collapsed the artificially produced blisters but not the natural blisters. The reason for incomplete collapse with Cs+, Rb+ and NH4+ was the incomplete replacement (trapping in the flakes) of interlayer hydrated cations such as Na+ shown by electron probe microanalysis. Much less trapping occurred with K+ saturation. Na+ entrapment increased with increasing size and decreasing hydration of cations, i.e. Cs+ >Rb+ >NH4+ >K+.

Semiquantitative determination of Na+, by electron probe microanalysis, in vermiculite flakes near the edge revealed that 1 N CsCl entrapped as much as 45·6 per cent while 1 N KCl entrapped only 7·5 per cent. In general, more Na+ was entrapped by 1 N solutions than by dilute solutions. With 0·01 N KCl solution, the Na+ entrapment was only 4·4 per cent. The amount of Na+ at the center of the macroflakes was less than at the edge, apparently as a result of more CEC at frayed edges and (or) because of incomplete diffusion of Na+ to the center. Shrinkage of artificial blisters by K+ could thus be attributed to its more effective removal of the interlayer hydrated cations, whereas the other fixing cations were less effective. Natural blisters on vermiculite from Libby, Montana were not completely collapsed even by K+, apparently because the layer charge density was too low in the blister areas.
Properties of the Zeolite, Faujasite, Substitutional Series: A Review with New Data
Authors: Stamires Dennis N.
Published: September 2006

New information is presented relating to the hydrothermal stability, lattice parameters, and adsorptive, electrical, and catalytic properties of synthetic and natural faujasite. Present concepts concerning the nature and relationship of synthetic and natural faujasite are restated to be consistent with the experimental evidence and the developed physical model. The major structural and physicochemical properties reflect the close similarities and smooth gradations expected of substitutional members of a continuous series. The existing division of the range (2–6) of SiO2/Al2O3 mole ratios (S/A) at 3 into two compositional subranges is shown to be unjustifiable and rather misleading. Individual compositions from these two subranges do not represent distinctly different zeolite species; instead, it is demonstrated that they are members of a continuous series with smoothly changing properties over the studied range of SiO2/Al3O3. Some of the properties of the natural mineral faujasite are found to be very similar to those of the synthetic analogs with the same SiO2/Al2O3 mole ratio.

Finally, a plea is made for a uniform nomenclature which will serve to identify specific (single) compositions (instead of ranges of compositions); reflect the continuity, close similarities and interrelationships in their main structural and physicochemical properties; and also identify the characteristics of the faujasite group.
Particle Size-Shape Relationships in Georgia Sedimentary Kaolins—II
Authors: Olivier J. P. , Sennett Paul
Published: September 2006

Crude sedimentary kaolin clay from central Georgia, U.S.A., which had a wide distribution of particle size, was divided into several size fractions by repeated sedimentation in water. The resulting fractions had approximately a 2:1 ratio in dia. between their upper and lower limits. Each fraction was then studied by transmission and scanning electron microscopy and characterized in terms of surface area (both geometric and by gas adsorption), particle shape and impurity analysis.

Particle diameter determined from measurements made on electron micrographs showed considerable deviation from the diameter obtained by Stokes sedimentation. This deviation was especially large for the coarser particles and could be explained by the microscopically observed porosity of the kaolinite booklets. Imperfect stacking of the crystallites within a kaolinite booklet leads to a moderately regular array of slit-like voids. Effective particle densities as low as about 1·6 have been observed. The pore structure was also investigated by use of mercury intrusion porosimetry.
Elementary Layers in the Interstratified Clay Minerals as Revealed by Electron Microscopy
Authors: Yoshida Tsunoru
Published: September 2006

Interstratified layer structures were studied by electron microscopy and electron diffraction. In order to distinguish between expansible and non-expansible layers, Interstratified mica-smectite was treated with laurylamine hydrochloride solution. Electron micrographs of the layers at the curled edges of the crystals show expanded basal spacings of 24 Å and unexpanded spacings of 10 Å. It was observed that adjacent pairs of expanded and unexpanded layers in the micrographs form non-expansible units. Arrangement of the expanded and unexpanded layers shows that the layers expanded by sorption of laurylammonium ions have expansible and non-expansible surface characteristics on opposite sides of the layer. The relationships between the ratio of component layers and basal spacings in two component systems are discussed.
On the Mechanism of the Adsorption of Trace Copper by Bentonite
Authors: Steger H. F.
Published: September 2006

The adsorption of trace quantities of Cu (3·89 × 10−6 to 3·00 × 10−4 M) by a bentonite clay from calcium acetate solution was studied over the range of pH 4·27–5·87. The data were fitted to an existing adsorption equation and the ‘best’ values of the adsorption parameters were calculated. The proton, cupric ion and mono (hydroxy) cupric complex were found to be the adsorbed species. The adsorption sites are of two types. It has been postulated that the majority of sites are lattice hydroxyl groups located at crystal defects and edges. The remainder arise from organic matter adsorbed by the clay and are the more important in the adsorption of Cu at very low metal concentration and at pH <5·4. The implication of the results on the potential use of bentonite clay to remove trace amounts of Cu from mine waste waters is considered briefly.
Magnetic Behavior of Some Biotite Samples from West Thrace, N.E. Greece
Authors: Anagnostopoulos T. , Calamiotou M. , Sideris C.
Published: September 2006

The magnetic behavior of some biotite samples, from volcanic rocks of W. Thrace area, N.E. Greece, was studied in the temperature range from 85 to 270°K and compared with the chemical composition. The magnetization of the samples depends linearly on the applied field, and the magnetic susceptibility obeys the Curie law, showing a typical paramagnetic behavior which is due to Fe2+, Fe3+ and Mn2+ The effective magnetic moment was calculated from the structural formulas of the samples and deviation from the experimental values is discussed.
The Crystal Structure of the Dioctahedral Mica 2M2 Determined by High Voltage Electron Diffraction
Authors: Zhoukhlistov A. P. , Zvyagin B. B. , Soboleva S. V. , Fedotov A. F.
Published: September 2006

The structure of a dioctahedral 2M2 mica was defined by high voltage electron diffraction. The cell parameters are: a = 8·965, b = 5·175, c = 20·31 Å, β = 100° 40′, Z = 4, space group C2/c. Despite the peculiar character of the layer disposition (σ4 σ5 σ4 σ5), the oxygens of the layers are packed according to the cubic law. Consequently, the interlayer cations K have a trigonal prismatic coordination. The angle of tetrahedral twist is 11° 20′. The interatomic distances T-O indicate ordered replacements of Al for Si.
Argillization by Descending Acid at Steamboat Springs, Nevada
Authors: Schoen Robert , White Donald E. , Hemley J. J.
Published: September 2006

Steamboat Springs, Nevada, an area of present-day hot springs, clearly illustrates the genetic dependence of some kaolin deposits on hot-spring activity. Andesite, granodiorite and arkosic sediments are locally altered at the land surface to siliceous residues consisting of primary quartz and anatase, plus opal from primary silicates. These siliceous residues commonly exhibit the textural and structural features of their unaltered equivalents. Beneath the siliceous residues, kaolin and alunite replace primary silicates and fill open spaces, forming a blanketlike deposit. Beneath the kaolin-alunite zone, montmorillonite, commonly accompanied by pyrite, replaces the primary silicates. On the ground surface, the same alteration mineral zones can be traced outward from the siliceous residue; however, hematite rather than pyrite accompanies montmorillonite.

Chemical analysis indicates that sulfuric acid is the active altering agent. The acid forms from hydrogen sulfide that exsolves from deep thermal water, rises above the water table and is oxidized by sulfur-oxidizing bacteria living near the ground surface. This acid dissolves in precipitation or condensed water vapor and percolates downward destroying most of the primary minerals producing a siliceous residue. Coincidence of the water table with the downward transition from siliceous residue to kaolin-alunite signifies decreasing hydrogen metasomatism because of dilution of descending acid by ground water.

In hot-spring areas, beds of siliceous sinter deposited at the surface by hypogene thermal water look, superficially, like areas of surficial acid alteration. Features diagnostic of a surficial alteration are the relict rock structures of a siliceous residue and a kaolin-alunite zone immediately beneath.
Interlamellar Adsorption of Carbon Dioxide by Smectites
Authors: Fripiat J. J. , Cruz M. I. , Bohor B. F. , Thomas Josephus
Published: September 2006

The adsorption of CO2 at low temperature (~ -70°C) on thin films of homoionic smectites was studied by X-ray diffraction and by i.r. absorption. An increase in the d001 spacings of these clay films upon adsorption of CO2 was observed. In addition, a dichroic effect was readily discernible by comparing the i.r. spectra at two different orientations of the smectite films; i.e. with the film normal and tilted 35° with respect to the i.r. beam. The CO2 stretching vibration at 2350 cm-1 was used for the i.r. study. These observations conclusively show that CO2 intercalates the smectite structure rather than being adsorbed only in pores between clay tactoids—the limiting process proposed by other investigators.

Adsorption isotherm data from earlier surface area studies are re-examined here through application of the Dubinin equation. Again, intercalation is demonstrated by convergence of the plotted experimental data for smectites containing large monovalent interlayer cations toward a pore volume that is near the calculated theoretical value for a monolayer of intercalated CO2.

Scanning electron photomicrographs of Li- and Cs- smectites provide additional evidence that aggregation differences are not responsible for the large observed difference in BET surface areas obtained for these smectites with CO2 as the adsorbate. At low magnification, visual differences in macro-aggregates are apparent, but at high magnification no significant differences are observed in the micro-structure of individual aggregates where the major amount of gas adsorption really occurs.
The Interaction of Water with Goethite (α-FeOOH) and Amorphous Hydrated Ferric Oxide Surfaces
Authors: Gast Robert G. , Landa Edward R. , Meyer Gordon W.
Published: September 2006

The interaction of water with synthetically prepared goethite (α-FeOOH) and amorphous hyd-rated ferric oxide surfaces was studied using i.r. absorption and water vapor adsorption measurements. I.R. results show that the last traces of physically adsorbed water are removed from the amorphous material by outgassing at 25°C. In contrast, goethite retains approximately a monolayer of physically adsorbed water with similar outgassing. This monolayer of water on goethite, which is presumably hydrogen-bonded at least in part with structural hydroxyls, is readily exchangeable with D2O.

Integral entropies of adsorption were evaluated from water vapor adsorption isotherms at 15, 25 and 35°C and compared with values for mobile and immobile layers calculated through application of statistical mechanics (McCafferty and Zettlemoyer, 1970). Entropy values for both the first physically adsorbed monolayer of water on the amorphous material and the second monolayer on goethite were about the same as or greater than those calculated for an immobile layer, indicating strong hydrogen bonding of water by both surfaces. The larger deviation between the entropy values for goethite and those calculated for the immobile layer may be associated with changes in the structure of the first as well as the second physically adsorbed water layers. Surface areas, calculated using the BET method, were 320 and 32 m2 g-1 for the amorphous material and goethite respectively. Since the unit surface activity is probably about the same for the two materials, it follows that as the amorphous material crystallizes to form goethite, there would be a reduction in total surface activity in proportion to the reduction in surface area.
Potassium Selectivity of Clays as Affected by the State of Oxidation of Their Crystal Structure Iron
Authors: Kishk Fawzy M. , El-Sheemy H. M.
Published: September 2006

The Ca-K exchange isotherms were determined at two temperatures for two highly montmorillonitic iron-rich soil clays in their oxidized and reduced states. The thermodynamic parameters K, ΔG0, ΔH0 and ΔS0 were calculated for the exchange reactions.

It was found that the formation of K-clay from Ca-clay in both the oxidized and reduced state was accompanied by negative free energy, enthalpy and entropy changes. The results indicate that K is more strongly bound than Ca by the clay and the Ca-preference shown by the isotherms may be due to entropy changes in solution.

The oxidation of crystal structure iron resulted in an increase in K selectivity of the clay and a decrease in the free energy, enthalpy and entropy changes of the Ca-K exchange reaction. It was concluded that K is more strongly held by the oxidized clay than the reduced one, which is possibly due to a more nearly dioctahedral character in the oxidized than in the reduced state.
Similarities of Rehydration and Rehydroxylation Properties of Rectorite and 2M Clay Micas
Authors: Tomita Katsutoshi
Published: September 2006

Various dehydroxylated micas and rectorites were acid-treated. Rectorite-type mixed-layer mineral was formed from 2M1 and 2M2 mica and random mixed-layer mineral from 1M and 1Md mica. Rectorite was formed again from dehydroxylated rectorite. The rehydration and rehydroxylation properties of dehydroxylated rectorite and 2M sericites were found to be similar.
Infrared Absorption and X-Ray Diffraction Study of Butylammonium Complexes of Phyllosilicates
Authors: Martin-Rubi J. A. , Rausell-Colom J. A. , Serratosa J. M.
Published: September 2006

I.R. absorption and X-ray diffraction data on butylammonium complexes of vermiculites show, when compared with the Wyoming montmorillonite complex, that the tetrahedral location of charge determines the keying of the -NH+3 groups into the ditrigonal cavities and that these groups have their C3 axes perpendicular to the layers. The aliphatic chains adopt different conformations depending on the area available per exchange position; they will either: (a) adopt an ’all-trans’ conformation with their axes inclined 55° to the silicate planes, when the area available is small; (b) rotate 120° around the C1-C2 bond to adopt a flat disposition relative to the layers, when the area available is larger than the area covered by the organic ion.
A Structural Investigation of a Vermiculite-Piperidine Complex
Authors: Iglesias J. E. , Steinfink H.
Published: September 2006

A vermiculite-piperidine complex was investigated by a single crystal three dimensional X-ray diffraction procedure. The complex was prepared by ion exchange of a Na-vermiculite at pH 8. A total of 453 reflections was observed and used in the least squares refinement of the structure. The complex is monoclinic, C2/m, a = 5.346(2) Å, b = 9.256(3) Å, c = 17.57(1) Å, ß = 96.29(9)°. The final R value was 0.17 using anisotropic temperature factors for the silicate atoms and isotropic temperature factors for the carbon atoms. The occupancy factors of the C atoms were considered as variable parameters. The diffraction data were of poor quality because of stacking faults. The results show that the molecules are randomly distributed over the crystallographic sites in the interlayer space and the peaks appearing in the electron density maps can be interpreted as being due to 2 piperidine molecules and two H2O molecules. The orientation of the organic molecules is ambiguous. The electron density peaks fit a model in which the molecules are vertical and their planes form a small dihedral angle, and also fit a model in which the plane of the molecules is parallel to (001). It is quite possible that both types of orientations are present.
Further Investigations on Fulvic Acid-Cu2+-Montmorillonite Interactions
Authors: Kodama H. , Schnitzer M.
Published: September 2006

The major mechanism by which fulvic acid removed Cu2+ from Cu2+-montmorillonite was complexation, most likely chelation. This was confirmed by the use of a specific cupric ion electrode which showed that whereas the total Cu2 + concentration in the supernatant solutions increased with rise in pH, about 7 per cent of the total Cu2+ solubilized by fulvic acid occurred in the ‘free’ or ‘uncomplexed’ form at pH 2.5, only 0.6 per cent was similarly distributed at pH 4.5 and 0.0009 per cent at pH 6.5. External surface area measurements by a dynamic BET method showed the following surface areas: 2.5 m2g-1 for the fulvic acid, 8.0 m2 g-1 for the Cu2+-montmorillonite but 16.1 m2 g-1 for the FA-Cu2+-montmor-illonite complex. Electron micrographs of the FA-clay complex confirmed that fulvic acid was adsorbed in interlamellar spaces and on external surfaces of the Cu2+-montmorillonite.
Internal and External Morphology of Tubular and Spheroidal Halloysite Particles
Authors: Dixon J. B. , Mckee T. R.
Published: September 2006

Tubular halloysite from Wagon Wheel Gap, Colorado and spheroidal halloysite from Redwood County, Minnesota were examined by transmission electron microscopy. Clay samples were prepared by the following techniques: drop-mounted suspension on carbon support films; thin sections of clay in Araldite epoxy resin; and carbon-platinum-palladium single-stage replicas.

Both types of dehydrated halloysite have interlayer separations between packets of layers. Halloysite tubes are composed of packets as thin as five layers which sometimes reveal a rolled interior configuration in cross-sectional view. Thicker tubes are composed of many layers per packet. Some large tubes appear in cross section as folded packets of layers. The interior morphology of spheroidal halloysite particles is more irregular and the layer structure is more discontinuous than in most tubes. The spheroidal halloysite of this study is characterized by external tangential plates with hexagonal shape suggestive of kaolinite.
Gas Sorption in Clay Mineral Systems
Authors: Aylmore L. A. G.
Published: September 2006

Sorption isotherms for four gases (N2, A, Kr and CO2), commonly used in specific surface area and pore structure measurements, have been accurately determined on a number of clay mineral and oxide systems.

Specific surface areas obtained by application of the BET theory to these isotherms illustrate the extent to which the apparent cross-sectional areas for these sorbed gases vary with surface structure, exchangeable cation and microporosity.

V-n plots for nitrogen adsorption on these materials using nitrogen adsorption on crystalline materials of large crystal size as a standard isotherm provide appreciable ranges of linearity in each case. The specific surface areas obtained from these straight line plots agree well with the corresponding BET values. The linearity of these plots for illite clays indicates the absence of capillary condensation and that adsorption in slit-shaped pores takes place largely by the formation of physically adsorbed layers on the surfaces.

Much larger BET specific surface areas were obtained from carbon dioxide sorption at 196 K on goethite, hematite and gibbsite than from nitrogen, argon and krypton sorption at 78°K. It is suggested that enhanced sorption of CO2 into microporous regions of the oxides, inaccessible to the other gases. occurs in a similar fashion to that frequently observed for coal and charcoal materials. V-n plots for CO2 sorption in these materials using that for an illite clay as a standard isotherm, support this conclusion.

Considerably lower BET specific surface areas were obtained for CO2 sorption on kaolinite than were obtained for nitrogen, argon and krypton sorption. The shape of the V-n plots for CO2 sorption on kaolinite compared with illite suggest that an initial specific adsorption of CO2 on the kaolinite is followed by a change in state with the completion of this layer, allowing normal multilayer formation to proceed.
A Preparative Technique for Electron Microscopic Examination of Colloid Particles
Authors: Greene R. S. B. , Murphy P. J. , Posner A. M. , Quirk J. P.
Published: September 2006

Adsorption of clay particles from very dilute aqueous suspensions onto positively charged films (Cytochrome C) on carbon coated support grids has been used to obtain well dispersed samples of the particles suitable for detailed electron microscopic examination. The natural negative charge of the carbon coated grid was used for ferric polycations and precipitates.
Hydrothermal Origin of the Clays from the Upper Slopes of Mauna Kea, Hawaii
Authors: Ugolini F. C.
Published: September 2006

The soils of the summit region of Mauna Kea are similar to the soils of the high mountain deserts and to the soils of cold deserts. Dramatic differences, however, exist between the soils of the summit and other neighboring cones and the soils of the glaciated terrain. The soils of some of the cones of the summit area are clay rich and contain phyllosilicate minerals; the soils of the glaciated terrain are sandy and contain X-ray amorphous clay. Montmorillonite and a Mg-rich trioctahedral mineral identified as saponite are the clay minerals of the summit. Because the summit area of Mauna Kea supported an ice cap at the time of the formation of the cones, the origin of the smectite minerals could have resulted from the alteration of the tephra by steam and water released in the melting of the ice. Hypogene fluids are, however, more likely to be responsible for the genesis of the phyllosilicate minerals.
Properties of Reduced Charge Montmorillonite: Tetra-Alkylammonium Ion Exchange Forms
Authors: Clementz David M. , Mortland M. M.
Published: September 2006

Surface properties of reduced charge montmorillonites (RCM) whose exchange capacities were saturated with tetra-alkylammonium cations, were studied with X-ray diffraction, nitrogen, and water adsorption. Methods were utilized for preparing montmorillonite of varying charge and of swelling reduced-charge clay with ethanol. As charge reduction proceeds, all layers retain some exchangeable cations until about half the original charge is reached at which point collapsed layers begin to appear and increase to about 60 per cent at maximum charge reduction. Charge reduction thus appears to proceed in a non-homogeneous fashion. When saturating exchange sites with tetra-alkylammonium ions in ethanol solvent, intercalation of salt in uncharged layers was noted if the samples were not completely washed. Nitrogen adsorption isotherms at liquid nitrogen temperatures showed considerable interlamellar penetration of tetramethylammonium (TMA+) clays, resulting in high calculated surface areas. Much less adsorption on the tetra-n-propylammonium (TPA+) clays was observed. Surface areas were increased upon reduction of charge up to the point where collapsed layers began to be appreciable, whereupon measured areas decreased. Water adsorption isotherms reflected the hydration properties of the exchangeable cation as well as the surface available for adsorption.