bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Hydrothermal Transformation Of Sodium And Potassium Smectite Into Mixed-Layer Clay
Authors: Eberl Dennis , Hower John 
Published: August 2006

AbstractThe transformation of sodium and potassium smectite into mixed-layer clay was followed in hydrothermal kinetic experiments. Glasses of beidellite composition and the Wyoming bentonite were used as starting materials. Temperatures ranged between 260 and 490°C at 2 kbar pressure, and run times ranged between 6 hr and 266 days.The course of the reactions was found to be strongly affected by interlayer chemistry. When potassium was the interlayer cation, increasing reaction produced the series: randomly interstratified illite/smectite-ordered interstratified illite/smectite-illite. This sequence is equivalent to that formed in shales during burial diagenesis. With interlayer sodium and temperatures above 300°C, an aluminous beidellite (Black Jack analog)-rectorite-paragonite series was realized. The difference between these two diagenetic families is discussed. Below 300°C, sodium beidellite formed randomly interstratified mixed-layer clay much like potassium beidellite, except that a higher layer charge was required to produce sodium mica-like layers. The higher charge resulted from sodium's higher hydration energy. The difference in hydration energy between potassium and sodium may account for the fixation of potassium rather than sodium in illite during burial diagenesis.The appearance of ordered interlayering in mixed-layer phases is also related to interlayer chemistry. Ordering formed in sodium clays at high expandabilities, whereas it never appeared in the potassium clays above approximately 35% expandable. The appearance of ordering may be partly related to the polarizing power of the mica-like layers.Phase diagrams, constructed from the kinetic experiments and from the composition and occurrence of natural clays, are presented for the systems paragonite and muscovite-2 quartz-kaolinite-excess water. This study also reports the first synthesis of a Kalkberg-type mixed-layer clay.
A Natural Clay Organic Complex from Andalusian Black Earth
Authors: Perez Rodriguez J. L. , Weiss Armin , Lagaly Gerhard 
Published: August 2006

AbstractProtein complexes of smectites in soils are difficult to detect if the usual smectite tests show no peculiarities. Andalusian black earths are typical examples. Investigation of the alkylam-monium derivatives, however, allows detection of adhered macromolecules which might be protein-like although this cannot be proved exactly.Investigation of artificial clay-protein complexes reveals different types of clay protein interactions. Calcium smectites adsorb proteins mainly on the external surfaces, the macromolecules being anchored in the interlayer spaces. Sodium smectites give partial crystalline products in which the silicate layers are distributed in the protein matrix.Exchange of alkylammonium ions can be used as a tool for detection of the protein. If this is adsorbed on external surfaces (calcium smectites) the increased layer separation during the cation exchange enables the macromolecules to slip between the layers and the basal spacing of the alkylammonium derivatives are changed in characteristic ways. The partial crystalline sodium clay-protein complexes are reorganized by alkylammonium ions to regular structures. The proteins are not displaced completely from the silicate surfaces so that the basal spacing of the alkylammonium derivatives are enhanced in comparison with pure montmorillonite.
The Determination of Adsorbed Na, K, Mg and Ca on Sediments Containing CaCO3 and MgCO3
Authors: Neal Colin 
Published: August 2006

AbstractA method for the determination of the cations of Na, K, Mg and Ca adsorbed on clay minerals mixed with CaCO3 and MgCO3 is described. An ethanolic solution of LiCl-CsCl is used to displace the exchangeable cations. Blank determinations performed using either a second ethanolic leach or a second LiCl-CsCl leach, are used to correct for carbonate dissolution. Details of the methods development are given.The method has been tested using mixtures of homoionic forms (Na, K, Mg, Ca) of smectite and kaolinite with either CaCO3 or MgCO3. The smectite and kaolinite were found to have total CECs (with standard deviations) of 765 (4.4) and 39.8 (0.52) mequiv kg−1, respectively. The amount of cation exchanged was found to vary directly with the proportion of clay mineral in the mixture; regression coefficients consistently greater than 0.997 were obtained.Other tests with smectite-CaCO3 mixtures in sea-waters of various salinity vindicated the use of the method with heteroionic forms of smectite. These tests also suggest that the phenomenon of fixation observed in most other studies of clay minerals in estuarine conditions might be redundant. It is contended that there is an urgent need for this suggestion to be tested.
A Proposed Phase Diagram for Illite, Expanding Chlorite, Corrensite and Illite-Montmorillonite Mixed Layered Minerals
Authors: Velde Bruce 
Published: August 2006

AbstractNew and published experimental data on hydrothermally treated (2-kbar water pressure, 300–400°C natural clay minerals is used to construct phase diagrams in composition and pressure-temperature space which define the phase relations of mixed layering solid solution in dioctahedral (illite-montmorillonite) and trioctahedral expanding chlorite and corrensite-like minerals. Three major relations are established:(1)The R3+, i.e. Al13+ and/or Fe3+, content of the assemblage will control whether or not an expanding chlorite or corrensite phase will appear. These minerals are R3+-rich in composition as well as R2+ (Mg and Fe2+)-rich.(2)Temperature-pressure variables control the type and composition of the mixed layered illite-montmorillonite mineral which is stable with aluminous phases. A sequence of different types of mixed layered ordering can be established which might be correlated with diagenetic or epimetamorphic grade.(3)The presence of ‘metamorphic’ trioctahedral phyllosilicate phases, i.e. those due to the effects of earliest metamorphism, is correlated with the P-T-X variables. These phases include 7 Å chlorite (iron-rich), 14 Å chlorite and the expanding chlorite and corrensite-like minerals.It is not possible to give absolute temperatures for the different reactions implied by the phase diagram due to the slow rate of crystallization in the experiments. However, the general sequence of assemblages and the phase relations proposed should correspond to those which are encountered in nature when pressure and temperature vary.
Experimental Transformation of 2M Sericite into a Rectorite-Type Mixed-Layer Mineral by Treatment with Various Salts
Authors: Tomita Katsutoshi 
Published: August 2006

AbstractSome dehydroxylated sericites were boiled with solutions of various salts. A rectorite-like regular mixed-layer was formed when 2M sericite was treated with solution containing salts such as NaNO3, Na2SO4, CaSO4, CaCl2, MgCl2 and MgSO4 respectively. A random mica/montmorillonite mixed-layer was formed from 1M sericite. In order to change the 2M sericite into a regularly interstratified mineral, they are heated to the temperature range of dehydroxylation. The formation of a regularly interstratified mineral from 2M sericite can be explained by the change in the (OH) bond direction after the extraction of the potassium ion.
Porphyrin Adsorption by Clay Minerals
Authors: Kosiur David R. 
Published: August 2006

AbstractA study was undertaken to investigate the adsorption of hemin, protoporphyrin and hematoporphyrin by kaolinite and a Ca-montmorillonite in aqueous solutions buffered at pH 4 and 9.Although experimental restrictions at pH 4 prevented the complete characterization of the adsorption isotherms, kaolinite did exhibit a saturation of exchange sites by the cationic porphyrins. Both kaolinite and montmorillonite displayed a similar saturation of sites by the porphyrins in their anionic forms at pH 9. The major differences in the adsorption isotherms are attributed to differences in the exchange capacities of the clays.Adsorption of the porphyrins at pH 9 was inhibited largely by phosphate treatment of the clays; this effect is interpreted as blockage of the anion exchange sites by irreversibly-bound phosphate.
The Co-Ordination of Hydrated Cu(II)- and Ni(II)-Ions on Montmorillonite Surface
Authors: Velghe Firmin , Schoonheydt Robert A. , Uytterhoeven Jan B. 
Published: August 2006

AbstractThe optical spectra of Cu2+ and Ni2+ on Camp Berteau montmorillonite after lyophilization and evacuation at room temperature are characteristic for the presence of Cu(H2O)42+ and Ni(H2O)62+ in the interlamellar space. The most probable ligand field parameters for Cu(H2O)2+4 are Dqxy = 1310 cm−1, Ds = 1807 cm−1 and Dt = 664cm−1. The covalent character of the Cu2+-OH2 bond is not negligible as indicated by the orbital reduction factors k∣∣2 = 0.66 and k⊥2 = 0.76. This is also the case for Ni(H2O)62+ which is characterized by a ligand field strength, Dq = 850 cm−1 and an electronic repulsion parameter B = 920 cm−1. After desorption in vacuum the optical spectra of Cu2+ were poorly resolved, while Ni2+ was present partially as (Ol)3Ni2+, partially as (Ol)3Ni-OH2 where Ol means an oxygen of the hexagonal rings in the tetrahedral layers.
Hydrolysis of Aluminum-Tri-(Sec-Butoxide) in Ionic and Nonionic Media
Authors: Serna Carlos J. , White Joe L. , Hem Stanley L. 
Published: August 2006

AbstractThe hydrolysis of aluminum-tri-(sec-butoxide), ASB, in ionic and nonionic media is shown to be a useful method for the synthesis of aluminum minerals. Infrared and X-ray analysis were used to identify the reaction products. Pseudoboehmite is formed at low water to aluminum ratios. At higher water content, transformation of pseudoboehmite occurs with bayerite as the final phase. Dawsonite-type minerals are produced when ASB is hydrolyzed in the presence of sodium, potassium, or ammonium bicarbonate. Infrared evidence suggests that the carbonate group is more perturbed than indicated by the proposed crystal structure. A compound with a structure like the pyoaurite-sjögrenite group was obtained when ASB reacted with a lithium carbonate solution. The infrared spectrum indicates the possible existence of bicarbonate and carbonate ions between the brucite-like layers.
Trimethylsilylation of Biotite
Authors: Kuroda Kazuyuki , Kato Chuzo 
Published: August 2006

AbstractOrganic solvent soluble organosilicate compounds retaining silicate backbone were obtained by the reaction between biotite and trimethylsilylating reagent. The soluble product which was formed at room temperature or at reflux temperature was a viscous liquid and was soluble in a wide range of organic solvents, but insoluble in water. Molecular weights of the soluble products and their thinlayer chromatograms made it clear that the soluble products consisted of several trimethylsilylated derivatives of silicic acids which were mainly the derivatives of mono- and disilicic acid. The influence of reaction temperature for the trimethylsilylation reaction also was discussed.
Determination of Structural Defects in Phyllosilicates by X-Ray Powder Diffraction—I. Principle of Calculation of the Diffraction Phenomenon
Authors: Plançon A. , Tchoubar C. 
Published: August 2006

AbstractThis paper describes the calculation of the diffracted intensity for models of powdered minerals with lamellar structure, in order to compare experimental and theoretical X-ray diagrams. The calculation takes into account at the same time (i) the possibility of coexistence of different kinds of layers in the stackings, (ii) the possibility of stacking faults between the layers (translative or rotative ones) and (iii) the unavoidable orientation of particles in the powder sample (the method of determination of the orientation is described).
Characterization of the Particle Size and the Crystallinity of Certain Minerals by Infrared Spectrophotometry and other Instrumental Methods—I. Investigations on Clay Minerals
Authors: Hlavay J. , Jonas K. , Elek S. , Inczedy J. 
Published: August 2006

AbstractEffects of particle size, crystallinity and the amount of the structural water in kaolinites on their infrared spectra, were studied. The samples were ground in a vibrating ball-mill, and infrared and X-ray spectra, as well as thermal and specific surface area measurements, were taken on the initial and ground samples. Changes of the 3705-cm−1 infrared band intensity and of the absorbance ratio of the A 3630/A 3705-cm−1 bands were determined as a function of the grinding time. Correlation functions between the absorption ratio, calculated from the infrared spectra, and the average particle size, as well as between the amorphism, calculated from the X-ray spectra, and the average particle size, were obtained.
Hydroxy-Nickel Interlayering in Montmorillonite by Titration Method
Authors: Yamanaka S. , Brindley G. W. 
Published: August 2006

AbstractNickel nitrate solution is potentiometrically titrated (a) with montmorillonite, (b) without montmorillonite, in the nitrate solution. X-ray powder diffraction and chemical analyses are made of the products formed by the clay at various stages of titration. The pH values of the titration curve (a) are lower than those of curve (b) until the brucite-like hydroxynickel interlayer is more or less complete. The resulting product then closely resembles a chlorite. The preferential precipitation of hydroxide in the interlayer region is explained in terms of the acidic character of montmorillonite interlayers.
Observation of the Hydrated form of Tubular Halloysite by An Electron Microscope Equipped with An Environmental Cell
Authors: Kohyama Norihiko , Fukushima Kurio , Fukami Akira 
Published: August 2006

AbstractThe hydrated form of tubular halloysite [halloysite (10 Å)] was observed by a conventional electron microscope equipped with an environmental cell (E.C.), by which the “natural” form was revealed without dehydration of the interlayer water. This study mainly reports the selected area electron diffraction (SAED) analysis of the halloysite (10 Å) and its morphological changes by dehydration. The SAED pattern showed halloysite (10 Å) has two-layer periodicity in a monoclinic structure with the unit cell parameters of a = 5.14 Å, b = 8.90 Å, c = 20.7 Å, β = 99.7°, in space group Cc, and almost the same structure as the dehydrated form of halloysite [halloysite (7 Å)]. This means that the dehydration of the interlayer water did not greatly change or affect the structure of halloysite (10 Å). Accompanying the dehydration of the interlayer water, there appeared along the halloysite tube axis clear stripes that were about 50–100 Å in width. The diameters of the tubular particles also increased about 10%. From the results of various experiments, such as a focussing series, observation of the surface structure by the replica method, observation of end-views of the tubular particles, and others, these two phenomena were explained as follows: Halloysite crystals have “domains” along the c-axis direction, the thicknesses of the “domains” vary ca. 50–100 Å. They are tightly connected with each other when the halloysite is hydrated, but are separated from each other by the dehydration of the interlayer water, whereupon the stripes come into existence along the tube axis. Taking these considerations into account, a model of dehydration is proposed. Moreover, a new method of calculating the β-angle is proposed in the Appendix.
An Experimental Study of Cadmium Ion Exchangeability
Authors: Ferrell R. E. , Price C. A. 
Published: August 2006

AbstractA laboratory study of cadmium exchangeability revealed large differences in extractable cadmium which are dependent on the exchange solution being utilized. The standard exchange solutions employed in this study were: N NaNO3, N NaOAc, N NH4OAc, NCaCl2, and 2N CaCl2, in order of increasing Cd removal. An interpretation of the chemical behavior of Cd and an experiment with mixed sodium nitrate and acetate solutions suggest that cadmium carbonate, octavite, was precipitated when the sediments were saturated with Cd prior to the exchange experiments and that the quantities of Cd recovered in the acetate solutions were erroneously high because of the dissolution of the carbonate material. Dissolution of solid phases, the lack of pH buffering, and the possible formation of a complex hydroxyl chloride salt also made the Cd values obtained with the chloride solutions too high. Sodium nitrate exchange solutions minimize these problems and are thought to best represent the exchangeable cadmium in the sediment.
The Electrostatic Interlayer Forces of Layer Structure Minerals
Authors: Giese Rossman F. 
Published: August 2006

AbstractUsing a simple ionic model, the energy necessary to expand a layer structure by a certain distance can be calculated. This has been done for a series of 15 structures including hydroxides, 2:1 and 1:1 structures of various types. Plots of energy versus separation distance show three major groups which have common bonding properties. For large separations, the group with the strongest interlayer bonds contains the brittle micas, the hydroxides, and the 1:1 structures. Intermediate bonding structures are the normal micas and the weakest bonds occur in the zero layer charge 2:1 structures. The relative energies needed for a given separation are not constant so that for small separations the zero layer charge structures such as talc and pyrophyllite are more strongly bonded than the normal micas. These groupings correlate very well with the expandability of the structures by water and other substances. It is proposed that this approach to the study of the layer structures will provide a simple theory explaining the expansion properties of layer silicates.
Sepiolite Deposits of the Las Vegas, Nevada Area
Authors: Post J. L. 
Published: August 2006

AbstractFour sepiolite deposits of different origin, which occur near Las Vegas, Nevada, are compared and described. They include a playa deposit, a valley terrace deposit, and two types of vein deposits. The physical and chemical characteristics of the four materials are described, the engineering and commercial features are considered, and the varied origins of the sepiolite are discussed. X-ray powder diffraction data, infrared spectra, thermal characteristics, and chemical analyses are given for the Two Crows sepiolite. The vein deposit is proposed for use as a clay mineral reference standard because of its purity and availability. The apparent diverse morphology of the sepiolite deposits is shown with its common, lathlike basic structure.
Kaolinite Intercalation Procedure for all Sizes and Types with X-Ray Diffraction Spacing Distinctive from other Phyllosilicates
Authors: Jackson M. L. , Abdel-Kader F. H. 
Published: August 2006

AbstractKaolinites of all kinds (fine, ‘fireclay,’ ‘type IV,’ etc.), some of which do not expand or expand incompletely with the usual intercalation methods used for comparison, are expanded completely by treatment of dry (110°C) clay with dry CsCl salt, followed by contact with hydrazine for 1 day at 65°C and then with DMSO overnight at 90°C. Comparison treatments were grinding in KOAc, soaking in hydrazine, and Li-DMSO, as well as combination of these. Following the Cs-hydrazine-DMSO treatment, the 7.2 Å spacing of 1:1 dioctahedral layer silicates shifts to 11.2 Å and the 11.2 Å/(7.2 + 11.2 Å) ratio ≃1.0. The trioctahedral 1:1 layer silicates and chlorite are not expanded by the Cs-hydrazine-DMSO procedure.
Reduction and Oxidation of Fe3+ in Dioctahedral Smectites—III. Oxidation of Octahedral Iron in Montmorillonite
Authors: Rozenson I. , Heller-Kallai L. 
Published: August 2006

AbstractStructural Fe2+ in montmorillonite is readily oxidized by contact with water, salt solutions or on mild heating. This is shown clearly by the Mössbauer spectra and is associated with a sharpening of the infrared absorption near 880 cm−1. It was inferred that this band comprises the Fe2+—OH—Al and Fe3+—OH—Al deformations. The rate at which oxidation occurs depends on the exchangeable cations. High acidity of the interlayers is conducive to oxidation, as is contact with Cu2+-containing solutions or concentrated H2O2 solutions.The results show clearly that any chemical treatment of montmorillonite causes changes in the oxidation state of structural iron.
Vanadium-Titanium-Bearing Mixed-Layered Clay from Potash Sulphur Springs, Arkansas
Authors: McCormick George R. 
Published: August 2006

AbstractA unique vanadium-titanium-bearing mixed-layered clay is currently being mined as an ore of vanadium at Potash Sulphur Springs, AR. The clay contains 80% expandable portion and has both a 14.22 and 18.24 Å hydration state in addition to the 9.49 Å dehydrated state; ethylene glycol expands this material to 16.69 Å. The 060 reflection for all hydration states is between 1.50 and 1.51 Å indicating the material is dioctahedral. The “mean chemical formula” calculates as
(Ca0.08 K0.02 Na0.03)0.13 (Al0.11 V0.90 Ti0.19 Fe0.64 Mg0.14)1.98 (Si3.79 Al0.21)4 O10 (OH)2·nH2O.
Copper(II) Interactions with Kaolinite: Factors Controlling Adsorption
Authors: McBride M. B. 
Published: August 2006

AbstractThe adsorption of Cu2+ on kaolinite was studied at different ionic strengths following various treatments of the mineral surface in order to evaluate the conditions influencing adsorption. The data indicate a strong preference of the Na+ exchange form of kaolinite for Cu2+ but a weak affinity of the natural kaolinite for Cu2+. Protons are generated by Cu2+ adsorption, a result of the exchange of surface protons, and possibly the enhancement of Cu2+ hydrolysis at the kaolinite surfaces. The exchange of Na+ by Cu2+ on the kaolinite is not described by the mass-action equation, but can be interpreted in terms of permanent charge sites on the surfaces when the additional factors of Na+-H3O+ exchange and blockage of sites by Al ions are considered.
Differential Scanning Calorimetric study of the Kaolinite: N-Methylformamide Intercalate
Authors: Adams J. M. 
Published: August 2006

AbstractThe thermal decomposition of the kaolinite: N-methylformamide intercalate [Al2Si2O5(OH)4·HCONHCH3] has been studied by differential scanning calorimetry (DSC). The decomposition starts at 355 K, finishes at 450 K and follows Avrami-Erofeev kinetics for α = 0.04–0.96. ΔH for the loss of organic is 19 ± 2 kJ mol−1; the activation energy for the reaction is 30 ± 3 kJ mol−1.
Extrapolation of Aqueous Dissolution Data to Determine Comparative Free Energies of Formation (CΔGf0), and Relative Mineral Stabilities
Authors: Reesman A. L. 
Published: August 2006

AbstractAnalytical data from aqueous dissolution studies of minerals, mineral systems, and naturally equilibrated solutions such as surface waters and groundwaters provide the basic ingredients necessary to calculate comparative solubility (or activity) products (CKs) and comparative free energies of formation (CΔGf0) of possible minerals or hypothetical minerals. Using a thermodynamic approach, quasi-thermodynamic values are obtained which can help in understanding the relative stabilities of different but similar materials and changes in reacting systems. Illite equilibrated solutions demonstrated that: 1) there is a 5 kcal spread in comparative free energies of formation of the five illites used, 2) the comparative stabilities remain about the same when highly simplified but similar hypothetical mineral formulas are considered, and 3) some of these illites are probably not the most stable phase in a closed chemical system at standard temperature and pressure.A “mineral index system” composed of common rock-forming minerals, products of chemical weathering and perhaps hypothetical minerals is proposed, which offers a means of studying naturally equilibrated solutions. Such a system can show changes with respect to CΔGf0 of these minerals at a particular site through time or in relationship to spatial distribution and geologic changes through synchronous sampling at different sites.