bluuebunny/crossref_metadata_2025_split huggingface dataset:
Properties of Reduced Charge Montmorillonite: Tetra-Alkylammonium Ion Exchange Forms
Authors: Clementz David M. , Mortland M. M. 
Published: September 2006

AbstractSurface 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.
Mineralogy of Palagonitic Material from the Golan Heights, Israel
Authors: Singer A. 
Published: September 2006

AbstractSideromelane in Pleistocene lapilli-tuff rocks from the Golan Heights had partly altered into palagonite. X-ray and electron diffraction showed that the major part of the clay alteration product is composed of a dioctahedral micaceous mineral with well organized crystallinity along the a- and b-axes. Very poor basal reflections as well as incomplete expansion upon glycerolation and incomplete collapse upon heating were interpreted as being due to random interstratification with chlorite. Electron microscopy showed the particles to be very similar to montmorillonite tactoids. The thermal behavior as well as surface properties were similar to those of montmorillonite. Differential dissolution analysis and infrared spectroscopy failed to indicate amorphous constituents to any significant extent. Chemically the material was enriched in iron, aluminum and titanium and depleted in alkali and alkaline earth cations.A minor component of the clay was found to consist of ‘onion-like’ halloysite. It is suggested that palagonite is a natural precursor for montmorillonite in the volcanic glass-montmorillonite alteration series.
Mineralogy and Cation Exchange Properties of Libby Vermiculite Separates as Affected by Particle-Size Reduction
Authors: Baweja A. S. , Wilding L. P. , McLean E. O. 
Published: September 2006

AbstractA vermiculite (Libby, Montana) sample obtained from the Zonolite company contained mostly coarse-grained separates with only 8–7 per cent clay. The 2–50 μm fraction was used for particle-size reduction studies by wet and dry grinding, and size-fractionated into < 2, 2–5, 5–20 and 20–50 μ sizes. About 18 per cent of the sample was attrited to clay after 64 hr of wet grinding, but as much as 59 per cent of the sample was attrited to clay after only 10 min of dry grinding. There was no evidence of damage to the crystal structure of derived clays or silts except for the 20–50 μm fraction from dry grinding.The observed CEC values of all the fractions decreased as grinding progressed, except for the 2–5 μm fraction from wet grinding where the CEC increased. The decrease in CEC was attributed to an accumulation of biotite, either as a discrete mineral and/or a mixed-layer assemblage of biotite and vermiculite attrited to the clay fraction. In contrast, the fraction showing an increase in CEC was due to an increased concentration of higher charge-density (CEC) vermiculite. Biotite-free CEC data for vermiculite suggested that, in general, the coarser vermiculite separates had a higher CEC than the finer ones.The susceptibility of minerals in the Libby vermiculite to cleavage by grinding was: vermiculite > hydrobiotite > biotite.
‘Vermiculite’ Determination on Whole Soils by Cation Exchange Capacity Methods
Authors: Coffman C. B. , Fanning D. S. 
Published: September 2006

AbstractThe proposed method is a modification of one by Alexiades and Jackson (1965). Calcium exchange capacity (CaEC) and potassium exchange capacity (KEC) are determined, after removal of organic matter and free iron oxides, by saturating the exchange complex with centrifuge washings of pH 7 acetate solutions of Ca or K, respectively. Excess salt in solutions remaining in contact with the soil after saturation is determined by measuring the weight and concentration of the excess solution. The exchangeable cations and excess salt are then replaced by centrifuge washings with 1 N acetate solutions of Mg (for CaEC) or NH4 (for KEC), after overnight 110°C oven-drying to enhance K fixation for KEC. The replaced cations are determined and CaEC and KEC values are calculated. Per cent ‘vermiculite’ is based on the difference between CaEC and KEC (expressed in m-equiv/100 g) and an assumed ‘vermiculite’ in-terlayer exchange capacity of 154 m-equiv/100 g; percentage Vr = (CaEC-KEC/154) × 100. The ‘vermiculite’ interlayer fraction (VIF) of the CaEC may also be calculated; VIF= CaEC-KEC/CaEC. The measured ‘vermiculite’ is shown in quotation marks since the method is open to criticism regarding exactly what is being measured, the assumptions made, etc. and to emphasize that the determination procedure is an operational one for the characterization of cation exchange complexes.Removal of free iron oxides increased both CaEC and KEC values of several soils but percentage Vr was little affected. The amount of K fixation was affected by the drying treatment employed after K saturation (none vs air-drying vs oven-drying). Thoroughly crushing Montana and African vermiculites dramatically increased their CEC and measured ‘vermiculite’ values, but had little effect with two samples of saprolite from chloritic metabasalt.
On Dehydration of Bound Water of Sepiolite
Authors: Nagata Hiroshi , Shimoda Susumu , Sudo Toshio 
Published: September 2006

AbstractBound water of sepiolite dehydrates in two steps in the temperature range of 250-650°C, as shown in the TG-curve. These steps are described here as steps II and III. At step II, half of the bound water is removed; other half at step III. From step II to III, discontinuous changes are confirmed in such properties as activation energy of dehydration, a-dimension, axial ratio, and intensities and spacings of X-ray powder reflections. A structural state at step II may be recognized as a distinct phase in the dehydration process.
Iron Oxidation and Reduction Effects on Structural Hydroxyl and Layer Charge in Aqueous Suspensions of Micaceous Vermiculites
Authors: Veith J. A. , Jackson M. L. 
Published: September 2006

AbstractFour Na2S2O4-reduced Na-vermiculites, each with some trioctahedral mica interstratified, were oxidized with H2O2 at pH 6·5 and again reduced with Na2S2O4 in suspensions at pH 7·5–8·0. The layer charge (CEC + K+), measured at pH 6·50, did not change significantly when octahedral Fe was oxidized (7–92 mmole 100g−1) or reduced (6–71 mmole 100 g−1). Electroneutrality was maintained within the octahedral sheet when Fe was oxidized or reduced. When Fe(II) was oxidized, electroneutrality was maintained by deprotonation of octahedral OH− groups,(a){[Fe(II)]2Mg4O4(OH)4}±0⇆{[Fe(III)]2Mg4O4(OH)2O2∗}±0+2e−+2H+${\left\{ {{{\left[ {Fe\left( {II} \right)} \right]}_2}M{g_4}{O_4}{{\left( {OH} \right)}_4}} \right\}^{ \pm 0}}\leftrightarrows{\left\{ {{{\left[ {Fe\left( {III} \right)} \right]}_2}M{g_4}{O_4}{{\left( {OH} \right)}_2}O_2^*} \right\}^ {\pm 0}} + 2{e^ - } + 2{H^ + }$and by ejection of (dissolution of structural) octahedral metallic cations,(b){[Fe(II)]5MgO4(OH)4}±0→{[Fe(III)]4O4(OH)4}±0+5e−+Fe3++Mg2+.${\left\{ {{{\left[ {Fe\left( {II} \right)} \right]}_5}Mg{O_4}{{\left( {OH} \right)}_4}} \right\}^{ \pm 0}} \rightarrow {\left\{ {{{\left[ {Fe\left( {III} \right)} \right]}_4}{O_4}{{\left( {OH} \right)}_4}} \right\}^{ \pm 0}} + 5{e^ - } + F{e^{3 + }} + M{g^{2 + }}.$When Fe(III) was reduced, electroneutrality was maintained by reprotonation of the deprotonated sites (O*, equation a). Reaction (b) was not reversible. Thus, reversibility of the reaction, Fe(II) ⇄ Fe(III) within the octahedral sheet decreased with increasing amount of ejected metallic cations. The amount of Fe(III) and Mg2+ ejected per Fe(II) oxidized was related to the degree of vermiculitization, being greatest with Na-degraded biotite [0·03 Fe3+ and 0·11 Mg2+ per Fe(II) oxidized] and lowest (nearly zero) with South African vermiculite. The number of deprotonated (O*) and reversible sites increased from 0·69 per Fe(II) oxidized with the K-depleted biotite to approximately 1·0 with South African vermiculite. The weathering increment was small since, of the total amount of Fe + Mg, less than 1·3 per cent was ejected from any of the four vermiculitic materials. When biotite was K-depleted, about 20 m-equiv of layer charge per 100g (300°C basis) was lost, while 51 mmole of Fe(II) per 100g was oxidized in the presence of Na2S2O4 and 82 mmoles in its absence in the aqueous suspensions. Since sequential reduction-oxidation-reduction treatments of K-depleted biotite and mica-containing vermiculites did not cause significant changes in layer charge (r2 = 0·04), the layer charge changes were concluded to be entirely independent of the oxidation or reduction of Fe in these minerals.
Swelling of Montmorillonite in Polar Organic Liquids
Authors: Olejnik S. , Posner A. M. , Quirk J. P. 
Published: September 2006

AbstractThe crystalline and osmotic swelling of Na-, Cs-, Mg- and Ca-montmorillonite has been measured in dimethyl sulphoxide and in formamide, N-methyl formamide, dimethyl formamide, N-methyl acetamide and dimethyl acetamide. These liquids have similar dipole moments but their relative permittivities vary appreciably from values less than water to values greater than water.Na-montmorillonite exhibits osmotic swelling (diffuse double layer development −d(001) ≫ 19 Å) in formamide and N-methyl formamide and Cs gives osmotic swelling behavior in formamide. Cs-montmorillonite in the crystalline swelling region give spacings greater than those found for water with all liquids. Mg- and Ca-montmorillonite did not give spacings greater than 19 Å in any of the liquids studied.The swelling behavior of montmorillonite is affected by relative permittivity but for liquids with a similar relative permittivity methyl substitution in the molecule may prevent the development of diffuse double layers on the particle surfaces.
Erratum to: Factors affecting selected area electron diffraction patterns of micas
Authors: Güven Necip 
Published: September 2006

Necip Guyen: Factors affecting selected area electron diffraction patterns of micas. Clays and Clay Minerals22, 97–106 (1974).On p. 97, lines 3 and 6 of the second paragraph under Lattice Properties of Micas (the equations for ΔPhkl)
Order and Disorder Relations in the Distribution of the Substitutions in Smectites, Illites and Vermiculites
Authors: Besson G. , Mifsud A. , Tchoubar C. , Mering J. 
Published: September 2006

AbstractIt is shown that order-disorder relations in the distribution of the isomorphous substitutions are important in the characterization of different 2/1 phyllosilicates and in the determination of their behavior. These order-disorder relations are shown by selected area diffraction patterns obtained from single crystals. The range of layer charges corresponding to smectites (charge per half-cell <0.6) is that for which phyllosilicates are stable with disordered substitutions. Phyllites with charge >0.6 show anomalous diffusions which indicate that the distributions of exchangeable Ba ions are partially ordered; this result is taken as evidence that the isomorphous substitutions also are partially ordered.
Lath-Shaped Units in Fine-Grained Micas and Smectites
Authors: Güven Necip 
Published: September 2006

AbstractTransmission electron images of fine-grained micas in bentonites exhibit lath-shaped units. These units seem to be associated along the (110) planes—referred to 2M1 mica cell—with perfect registry of their individual lattices. In doing so, they seem to provide lateral growth in the (001) plane. These lath-shaped units are arranged in the [001] direction in modes similar to the stacking of layers in mica polymorphs. Aggregations of lath-shaped units with polycrystalline montmorillonite particles are also observed in several bentonites. From the SAD pattern these laths are inferred to be dioctahedral layer silicates. However, they cannot be exactly identified any further. It is an open question whether these laths have grown from the montmorillonite or are simply entangled with it.
The Synthesis of Zinc Silicates at 20°C and Atmospheric Pressure
Authors: Tiller K. G. , Pickering J. G. 
Published: September 2006

AbstractZinc silicates were synthesized under conditions analogous to surficial weathering environments. The main product, regardless of conditions of precipitation or ageing, was shown by X-ray, i.r., electron microscopic and chemical evidence to be a 2:1 layered zinc silicate equivalent of stevensite. In the presence of aluminium, a 1:1 layered zinc silicate was formed as well, in confirmation of published work. The stability of the zinc silicate, in relation to carbonate, was favoured by the presence of aluminium in the lattice and silicic acid in the equilibrium solution. Zinc layer silicates were formed under conditions that generated orthorhombic zinc hydroxides and/or basic salts in the absence of silicon; the involvement of the brucitic zinc hydroxide (α-form), as proposed by earlier workers, could not be supported. Crystalline zinc layer silicates were formed by the slow evolution of the initial gels. Such layer silicates, but not willemite or hemimorphite, could have an important role in the control of chemical reactions of zinc in soils.
Amorphous Coatings on Particles of Sensitive Clay Soils
Authors: McKyes E. , Sethi A. , Yong R. N. 
Published: September 2006

AbstractPost-glacial Champlain Sea sediments in Quebec and Ontario are often extremely sensitive. Suggestions of considerable amorphous material in these soils come from X-ray diffraction results, as well as electron micrographs. A method for selective dissolution and analysis of amorphous material is used to study two Champlain Sea deposits. The amorphous material removed amounts to 11–12 per cent of the soils and consists mainly of silica and iron oxide. The treated samples have enhanced X-ray diffraction peaks and much cleaner particles as seen by electron microscopy.
Surface Acidity of Montmorillonites
Authors: Frenkel M. 
Published: September 2006

AbstractSurface acidity of almost homoionic montmorillonites was measured by titrating selected Hammett indicators adsorbed on the clay with n-butylamine.As expected, the acidity is strongly affected by the exchangeable cations and the degree of hydration of the clay. Greater polarizing ability of the interlayer cations increases both the strength and number of acid sites per H0 value. The acidity of ‘activated’ or heated H-montmorillonite does not exceed that of untreated H-montmorillonite. The origin of the negative charge in the montmorillonite appears to affect the acidity of the clay.It is concluded that the very high acidities reported in the literature (H0 < −5·6) are apparent only and are due to physisorption of the indicator.
Swelling and Structural Organization of Saponite
Authors: Suquet H. , de la Calle C. , Pezerat H. 
Published: September 2006

AbstractThe structural formula of Kozfikov saponite (Czechoslovakia) is as follows:
$N{a_{0.005}}C{a_{0.22}}{K_{0.01}}[S{i_{3.30}}A{l_{0.68}}F{e^{3 + }}{}_{0.02}][M{g_{2.50}}F{e^{2 + }}{}_{0.26}F{e^{3 + }}{}_{0.24}]{O_{10}}{(OH)_2}.$
Saturated with 6 different cations (Li, Na, K, Ca, Mg, Ba) its swelling in ethylene glycol, glycerol and water and its homogeneous hydration extents according to the relative humidity have been studied. Our results were compared with those found for montmorillonites, beidellites and vermiculites in order to estimate the respective influence of the surface charge density and the charge localization on the swelling properties. The three-dimensional organization of the saponite is more or less affected by random stacking faults and by multiple b/3 translations according to the exchangeable cation, the swelling state and the nature of the solvation liquid. Our experimental results indicate that the three-dimensional order met in the hydrated saponites can be explained by an anchoring of the layers towards each other by chains made up of cation -dipole interactions and of hydrogen bonds between negatively charged surface oxygens and the interlayer water. This type of interlayer link is relatively weak. It is therefore easy to introduce stacking faults in these edifices in particular by grinding of the samples.
Stability of Mixed Iron and Aluminum Hydrous Oxides on Montmorillonite
Authors: Tullock R. J. , Roth C. B. 
Published: September 2006

AbstractMontmorillonite clay samples were coated with 16 m-equiv/g of clay or iron plus aluminum as hydrous oxides and aged 1 yr, in suspensions of pH 6 or 8. The magnesium exchange capacity (MgEC) decreased linearly with the amount of non-crystalline aluminum hydrous oxide associated with the clay. Eight to 16 m-equiv of iron per g of clay reduced the MgEC by 20 m-equiv/100g at pH 6, but did not affect the MgEC at pH 8. The quantity of non-crystalline aluminum associated with the clay depended on the suspension pH and aging time, and was unaffected by the coprecipitation of 8–16 m-equiv of iron hydrous oxide/g clay. The crystalline form of aluminum hydrous oxide depended on the suspension pH and was shown by X-ray diffraction to be gibbsite at pH 6 and bayerite at pH 8. Gibbsite and bayerite formed rapidly with a rate dependent on the suspension pH when excess non-crystalline aluminum hydrous oxides were present. The quantity of non-crystalline aluminum hydrous oxides remaining after one year in suspensions of iron hydrous oxides and montmorillonite varied from 2·3 m-equiv/g of montmorillonite at pH 8-4·0 m-equiv/g of montmorillonite at pH 6. Differential thermal analysis and MgEC measurements indicated some regular organization of the iron hydrous oxides, however, crystalline iron minerals were not detected by X-ray diffraction.
Kink Block Structures in Clay Organic Complexes
Authors: Lagaly G. , Fitz St. , Weiss Armin 
Published: September 2006

AbstractComplexes of n-tetradecylammonium-beidellite with n-alkanols
${\rm{(n - }}{{\rm{C}}_{{\rm{14}}}}{{\rm{H}}_{{\rm{29}}}}{\rm{N}}{{\rm{H}}_{\rm{3}}}^{\rm{+}}{\rm{)_{{\rm{0,44}}}(n - C_{{\rm{x}}}}}{{\rm{H}}_{{\rm{2x}}}}{\rm{+}}{}_{\rm{1}}{\rm{OH) }}{}_{{\rm{1,56}}}{{\rm{\{ M}}{{\rm{g}}_{{\rm{0,28}}}}{\rm{A}}{{\rm{l}}_{{\rm{1,81}}}}{{\rm{(OH)}}_{\rm{2}}}{\rm{S}}{{\rm{i}}_{{\rm{3,56}}}}{\rm{Al}}{}_{{\rm{0,44}}}{\rm{O_{{10\}} }}}^{{\rm{0,44 - }}}}$ (x = 8–22) have been prepared and characterized by their basal spacings and by measurements of the specific heat cp.The compounds undergo a series of reversible phase transitions ${\beta _1} \rightleftharpoons...\rightleftharpoons{\beta_i}\rightleftharpoons...\rightleftharpoons{\beta_\omega}\rightleftharpoons{\alpha_1}...\rightleftharpoons{\alpha_j}$ with rising temperature. The maximum number ω of β-phases depends upon the chain lengths and increases from 1 with decanol to 6 with docosanol. Due to the evaporation of alkanol the number of χ-phases is not yet established in all details.The β-transitions correspond to conformational changes of the alkyl chains via rotational isomerisation, especially kink formation. The β-phases become unstable if the kink concentration exceeds 0,14 kinks/-CH2-. The β/α-transition is probably caused by a rearrangement into special gauche-block structures.
Soil Minerals in the System Al2O3-SiO2-H2O: Phase Equilibrium Model
Authors: Chesworth Ward 
Published: September 2006

AbstractMineralogical reactions in the system Al2O3-SiO2-H2O are examined and an isothermal, isobaric cross-section of the portion of the system applicable to soil genesis, is determined. The relevance of the cross-section to soil mineralogy is discussed.
Heterogeneity of Charge Density Distribution in Montmorillonite as Inferred from Cobalt Adsorption
Authors: Peigneur P. , Maes A. , Cremers A. 
Published: September 2006

AbstractA comparison is made of the ion exchange behavior, towards the cobalt ion, of five sodium montmorillonite clays. The selectivity for the bivalent ion at low cobalt loading is correlated with the average dimensions of the particles in the various clays, as characterized by several methods. The data are interpreted in terms of a higher selectivity of the bivalent ions for the broken bonds located at the edges of the clay crystals. Using a model comprising two areas of different charge densities, the experimental differences in behavior can be predicted reasonably well.
A Quantitative Method for the Determination of Montmorillonite in Soils
Authors: Levy Rachel , Francis C. W. 
Published: September 2006

AbstractA quantitative method for determination of montmorillonite in the soil clay fraction, using X-ray spectrometry, is proposed. The method is based on the fact that polyvinylpyrrolidone (PVP) is adsorbed on the interlayer surfaces of montmorillonite, giving a first order c-axis spacing of 26 Å, while it is not adsorbed on other swelling clays. The experimental conditions to obtain a maximum height of the X-ray diffraction peak, and the effect of the mass adsorption coefficient of vermiculite on the intensity of montmorillonite, were investigated. Soil montmorillonite was determined by the method of known additions, measuring the intensity of the X-ray diffraction peak before and after the addition of small and known amounts of Wyoming montmorillonite.
Swelling Chlorite in a Soil of the Dominican Republic
Authors: Rich C. I. , Bonnet Juan A. 
Published: September 2006

AbstractA 1–0·2 μm fraction from a soil in the Dominican Republic was studied by X-ray diffraction combined with solvation, cation saturation, and heat treatments. I.R., thermal (DTA, TGA) and chemical analyses were also made. This soil is saline and alkaline and its mineral composition is greatly influenced by the lacustrine parent material and poor drainage.In addition to swelling chlorite, illite, kaolinite, carbonates and quartz are present in the 1–0·2 μm fraction. The swelling chlorite expanded to over 18 Å when Mg saturated and solvated with glycerol or water. Lower spacings with other cations and ethylene glycol were observed. 1 N HCl treatment partially removed the interlayer hydroxides in the chlorite and 6 N HCl destroyed the mineral. The mineral gave a reflection close to 14 Å up through 600°C but collapsed at higher temperatures to 10·2 Å.
Hydrothermal Syntheses of Amino Acid-Montmorillonites and Ammonium-Micas
Authors: Tsunashima A. , Kanamaru F. , Ueda S. , Koizumi M. , Matsushita T. 
Published: September 2006

AbstractAn attempt has been made to synthesize nitrogenous clay minerals hydrothermally from silica-alumina gels in the presence of amino acids, namely glycine and lysine. The products have been characterized by X-ray powder diffraction, by analyses for C and N contents, and by their infrared spectra.Amino acid-montmorillonites have been prepared under hydrothermal conditions of 200–250°C and 1000 atm. Above 250°C the amino acids were degraded to ammonium ions, and ammonium-micas were obtained. Syntheses without the addition of amino acids to gels yielded kaolinite.The role of organic compounds in the formation of clay minerals seems to be of considerable geochemical significance.