bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interaction between Alkali-Halides and Halloysite: I.R. Study of the Interaction between Alkali-Halides and Hydrated Halloysite
Authors: Yariv S. , Shoval S. 
Published: August 2006

AbstractHalloysite was mechanically ground in the presence of NaCl, KCl, RbCl, RbCl and CsCl, and i.r. spectra were recorded after various periods of grinding, up to 10 min. Changes in the wave-numbers and sharpness of absorption bands were interpreted using assignments accepted for kaolinite. Diminution of absorption bands of OH groups and the appearance of new bands indicate formation of complexes of halloysite with KCl, KBr, RbCl, and CsCl. Water was essential in the complex formation, which may be formulated:The amount of the complex formed depended on the salt and the time of grinding. Complex formation requires that the cation be large enough to serve as a “structure breaker” of the interlayer water sheet. Complex formation also requires that the cation be a weak electron acceptor. Grinding also led to changes in the fine structure of the tactoid.The possibility of using the i.r. spectrum of halloysite as a finger print for identification of the mineral is discussed. It was concluded that NaCl is the most reliable dispersing agent to determine whether or not a mineral sample belongs to the kaolinite group. Disks in RbCl may be used to differentiate between kaolinite and hydrated halloysite.
Analysis of Iron-Bearing Clay Minerals by Electron Spectroscopy for Chemical Analysis (ESCA)
Authors: Stucki J. W. , Roth C. B. , Baitinger W. E. 
Published: August 2006

AbstractNontronite and biotite were analyzed by Electron Spectroscopy for Chemical Analysis (ESCA). Both minerals yielded ESCA spectra with well-defined peaks and the elements identified by the ESCA spectra were in good agreement with the molecular formulas. High resolution scans were made of the iron (2p3/2) and oxygen (1s) electron binding energies for oxidized and reduced forms of nontronite and biotite. Binding energies for Fe3+ were observed at 711.8 eV in dithionite-reduced nontronite and in oxidized biotite. Peaks for Fe2+ occurred at 710.0 eV for unaltered biotite, at 709 eV for oxidized biotite and at 708.6 eV for hydrazine-reduced and dithionite-reduced nontronite. The oxygen (1s) peak for unaltered nontronite was skewed to the high energy side of the 530.6 eV maximum, but became more symmetrical as the Fe2+ content increased.
Solubility Diagrams for Explaining Zone Sequences in Bauxite, Kaolin and Pyrophyllite-Diaspore Deposits
Authors: Tsuzuki Yoshiro 
Published: August 2006

AbstractSolubility diagrams defined by log [Al3+] and log [H4SiO4] are given for hydrous alumina or aluminum silicate minerals which appear in bauxite, kaolin and pyrophyllite-diapore deposits. They are constructed based on thermodynamic data of relevant reactions both at the room temperature and at elevated temperatures.An aqueous solution reacts to a mineral, in this case K-feldspar, and, by dissolving it, becomes saturated with respect to a certain mineral. This mineral begins to be precipitated and the solution changes its composition as a result of the precipitation as well as further dissolution of the original mineral. Then, it attains saturation with respect to another mineral, which is precipitated thereafter. Thus, different minerals are precipitated in turn.The sequences of precipitation of minerals can be shown on the diagrams under different conditions. A sequence, aluminum hydroxide → kaolinite or pyrophyllite → silica mineral plus kaolinite or pyrophyllite is expected in a weakly acid solution. In contrast, a sequence, silica mineral → silica mineral plus kaolinite or pyrophyllite is expected in a strongly acid solution. The possibility of application of the sequence of precipitation thus expected to alteration zoning is also discussed.
Surface Charge Variation in Aging Ferric Hydroxide
Authors: Lahann R. W. 
Published: August 2006

AbstractThe variation with time of exchangeable surface charge of amorphous ferric hydroxide in aqueous suspension was monitored by a titration technique. After 120 days, the surface charge of suspensions with initial pH from 8.5 to 10.5 was about one-fourth of the initial value, and goethite had formed from the ferric hydroxide. After the same time interval, the exchangeable surface charge of suspensions with initial pH from 5.5 to 8.0 was about two thirds the original value and the ferric hydroxide was still largely amorphous. The initial rate of crystallization and surface charge reduction increased with initial pH for suspensions with pH from 8.5 to 10.5, whereas the rate of surface charge reduction appeared to be independent of pH for suspensions with initial pH between 5.5 and 8.0. Based on these results it is suggested that at pH from 8.5 to 10.5 ferric hydroxide ages to goethite via a solution stage involving the Fe(OH)4- ion, whereas at pH values below 8.5 ferric hydroxide aging proceeds via mechanisms which do not involve the particle surface or bulk solution.
Free Energy of Formation of Beidellite from Apparent Solubility Measurements
Authors: Misra U. K. , Upchurch W. J. 
Published: August 2006

AbstractThe structural formula for K and Mg saturated beidellite was calculated from the total elemental analysis of the < 0.2 μm clay fraction of the B2t horizon of a Mexico soil. The free energies of formation (ΔGfo) of K-beidellite and Mg-beidellite as determined from their apparent solubilities were -2491.3 and -2484.0 ± 3.2 kcal per mole, respectively. The free energies of formation correspond to a clay mineral structure calculated on the basis of a 24 oxygen cell.
The Interaction Between Roundup (Glyphosate) and Montmorillonite. Part II. Ion Exchange and Sorption of iso-Propylammonium by Montmorillonite
Authors: Shoval S. , Yariv S. 
Published: August 2006

AbstractThe adsorption mechanism of iso-propylammonium (PAH+), the cationic component of Roundup, by various homoionic montmorillonites and the structures of the associations obtained in the interlayer space were investigated, using infrared, X-ray, and carbon analysis methods. Adsorption from aqueous and ethanol solutions of Roundup was studied. The infrared spectra were compared with those obtained by the treatment of montmorillonites with ethanol and CCl4 solutions of the free iso-propylamine (PA). The adsorption of PA from ethanol gives rise to protonation of the amine. PA sorbed from CCl4 solution forms an ammonium-amine association. Adsorption of PAH+ from alcohol solution of Roundup occurs by the mechanism of cation exchange. With transition metal exchangeable cations, PAH+ is sorbed in excess, forming hydrogen bonds between NH3+ groups and hydroxyls resulting from dissociation of water molecules. The process of adsorption of PAH+ from aqueous solutions of Roundup depends on the concentration of the solution. If montmorillonite is reacted with 0.5% solution of Roundup, PAH+ is adsorbed by exchanging metal cations and the adsorption capacity of the clay does not exceed the c.e.c. If the montmorillonite is reacted with 5.0% solution of Roundup, the PAH+ exchanges protons originating from the hydrolysis of the interlayer water. Protons which are transferred from the interlayer space to the water solution are accepted by the anion component of Roundup. The amounts of PAH+ adsorbed from concentrated Roundup solutions are much higher than the cation exchange capacity of montmorillonite. Hydrogen bonds are formed between the ammonium and water or hydroxyl groups on the interlayer space. With the trivalent exchange ions Al and Fe, which tend to polymerize in the interlayer space, excess sorption gives rise to hydrogen bonding of NH3+ to oxygen of the polymer.
Neutron Diffraction from Clay-Water Systems
Authors: Cebula D. J. , Thomas R. K. , Middleton S. , Ottewill R. H. , White J. W. 
Published: August 2006

AbstractThe use of neutron diffraction to determine some of the structural properties of montmorillonite-water systems at low water concentrations is described. The samples were prepared by compression or suction to give clay samples with between one and three molecular layers of water between the plates.About 10% of the platelets in the clay are randomly oriented. The remainder are partially oriented in the plane of the sample, with an angular spread of 40° about the mean orientation. It is suggested that these oriented domains are formed from the larger platelets present in the system. The Bragg diffraction pattern is better explained by a disordered lattice model rather than by a mixture model with small particles having a well-defined lattice spacing. We have fitted both the intensities of (00l) reflections and the shape of the (001) reflection quantitatively to a model which allows for a Gaussian spread of platelet spacing about a mean value. The half width of the spread is about 10% of the lattice spacing.No significant structural differences are found between Li, Na, K, and Cs montmorillonites. The method of preparation has no effect on the structural properties of the large platelet particles but does affect the randomly oriented fraction. The lattice spacing of the latter appears to be better defined for samples prepared by compression.Experiments on the variation of lattice spacing with humidity indicate that the structural model we have used is adequate except at humidities where the system is changing over from one to two, or two to three water layers.
Synthesis of the Trimethylsilylation Derivative of Halloysite
Authors: Kuroda Kazuyuki , Kato Chuzo 
Published: August 2006

AbstractThe trimethylsilyl derivative from halloysite was prepared by the reaction of halloysite powder with a trimethylsilylating reagent. The product was organophilic and the results of its infrared spectrum, X-ray powder diffraction pattern, and elemental analysis indicated that the trimethylsilylation occurred on silanol groups in the tetrahedral layer of halloysite after the acid decomposition of the octahedral layer. The thermal stability of the product was evaluated by means of differential thermal analysis. It was not possible to obtain the organic derivative from kaolinite by the same procedure. It is suggested that the differences in the reactivity between halloysite and kaolinite is due to the difference in susceptibility of the clay minerals to acid attack.
Titration of pH-Dependent Sites of Kaolinite in Water and Selected Nonaqueous Solvents
Authors: Loeppert R. H. , Zelazny L. W. , Volk B. G. 
Published: August 2006

AbstractK-saturated kaolinite was titrated in 13 different solvents with tetrabutylammonium hydroxide using a combination electrode for potentiometric determination. The titer of base required to reach the final potentiometric endpoint was dependent on the solvent and increased according to the following solvent order in both the presence and absence of excess neutral salt: methanol ⩽ water < ethanol ⩽ 1-propanol < 1-butanol < 2-propanol < DMF < t-butanol < DMSO < pyridine ⩽ acetonitrile ⩽ methylethyl ketone < acetone. With the protic solvents, titratable acidity increased according to decreasing dielectric constant of the solvent and increasing size and/or branching of the aliphatic constituent. The largest titratable acidities were obtained in the dipolar aprotic solvents with negligible basic character (e.g., acetonitrile, acetone, methylethyl ketone). These results are discussed in terms of solvent properties, solvation characteristics of ions in the solvents, and acid-base behavior of crystalline edge sites.
Infrared and Mössbauer Studies of Reduced Nontronites
Authors: Russell J. D. , Goodman B. A. , Fraser A. R. 
Published: August 2006

AbstractInfrared and Mössbauer spectroscopy show that the extent of the reduction of nontronite is dependent on the chemical composition of the nontronite and on the nature of the reducing agent. Hydrazine reversibly reduces about 10% of the iron in all of the nontronites studied irrespective of composition and it is suggested that the resulting ferrous iron occurs only in distorted octahedral sites. Similar conclusions are reached for the dithionite reduction of the nontronites containing little tetrahedral iron, but for those with more than one in eight silicons replaced by iron, changes brought about by dithionite treatment are irreversible due to dissolution of appreciable quantities of iron. Results from both spectroscopic techniques suggest that iron in tetrahedral sites is preferentially dissolved and that up to 80% of the structural iron can be reduced.Evidence is presented for the formation in these extensively reduced nontronites of a small amount of a mica-like phase resembling celadonite or glauconite, and, as dithionite is used for the pretreatment of soils, the implication of this observation is briefly discussed.The use of deuterated hydrazine as a reducing agent has enabled the nontronite absorption band near 850 cm-1 to be assigned to a Si-O (apical) stretching vibration, which is inactive in the infrared for perfect hexagonal symmetry, but which is activated by distortions in the tetrahedral layer.
Surface Reactions of Parathion on Clays
Authors: Mingelgrin U. , Saltzman Sarina 
Published: August 2006

AbstractThe adsorption-catalyzed degradation of parathion on clay surfaces is a hydrolysis process, proceeding either directly or through a rearrangement step. The rate and mechanism of degradation are dependent on the nature of the clay, its hydration status, and saturating cation. A mechanism for parathion degradation at adsorption sites on clay surfaces, in the absence of a liquid phase, is proposed.
The Crystal Structure of Boehmite
Authors: Christoph Gary G. , Corbató Charles E. , Hofmann Douglas A. , Tettenhorst Rodney T. 
Published: August 2006

AbstractThe crystal structure of a synthetic boehmite sample has been refined to an R of 0.047 in the space group Amam from X-ray powder diffraction data. Inclusion of hydrogen atoms and/or refinement in the space group A21am gave poorer results. Cell dimensions were determined as a = 3.6936 (± 0.0003), b = 12.214 (± 0.001), c = 2.8679 (± 0.0003) Å. All Al-O(OH) distances lie between 1.88 and 1.91 Å. Shared octahedral edges are 2.51–2.52 Å, and unshared octahedral edges are 2.86–2.87 Å, in excellent agreement with those for layered silicates. The O-H … O distance between contiguous octahedral sheets is 2.71 Å. The computed X-ray pattern matches closely with the experimental pattern, indicating the degree to which the crystal structure has been determined.
Cation-Exchange Behavior of Clays and Synthetic Aluminosilica Gels
Authors: Chu C. H. , Johnson L. J. 
Published: August 2006

AbstractCation-exchange capacities determined by methylene blue adsorption (CEC MB) and by the amount of K displaced from a K-saturated clay by NH4 (CEC K//NH4) correlate closely in five soil clays from Pennsylvania, but differ greatly in two soil clays with a large content of amorphous material. CEC MB was found to provide a more precise distinction between montmorillonite and vermiculite than CEC K//NH4. Synthetic aluminosilicate gels showed CEC K//NH4 > CEC Ca/Mg > CEC MB, but no relation to the behavior of the two soil clays with a large content of amorphous material was found.
Mobility and Reactions of VO2+ on Hydrated Smectite Surfaces
Authors: McBride Murray B. 
Published: August 2006

AbstractThe electron spin resonance (ESR) spectra of varying quantities of vanadyl ion (VO2+) adsorbed on hydrated hectorite indicated that hydrolysis of VO2+ was promoted at low levels of adsorption. The hydrolyzed product was adsorbed on the clay surfaces, with a ligand environment that was partially aqueous and partially hydroxide in nature. Greater amounts of VO2+ adsorbed on wetted hectorite obscured the ESR spectrum of the strongly adsorbed hydrolysis product with a solutionlike spectrum. An approximately 50% reduction in rotational mobility of VO2+ relative to solution was indicated by the linewidth of this spectrum. Loss in mobility occurred with reduction of the interlamellar spacing until, under strongly dehydrating conditions, the VO(H2O)52+ ions became aligned with the V=O bond axis normal to the plane of the clay platelets.
Cationic Spin Probes on Hectorite Surfaces: Demixing and Mobility as a Function of Adsorption Level
Authors: McBride M. B. 
Published: August 2006

AbstractThe electron spin resonance (ESR) technique has been used to study the motion and segregation of an organic spin probe cation (4-amino-2,2,6,6-tetramethylpiperidine N-oxide) on K+-hectorite as a function of average surface concentration. The organic cation tends to concentrate in certain interlayers of aqueous hectorite suspensions even when it occupies a small fraction of the cation-exchange sites. This demixing effect is not evident in methanol-solvated hectorite. The average mobility of the probe increases at higher adsorption levels as a result of the shift of the equilibrium in favor of the solution state. Calculated time-averaged orientations of the probe on the clay surfaces are quite different for methanol- and water-solvated systems, emphasizing the importance of the solvent in modifying the surface-cation interaction.
The Influence of Aluminum on Iron Oxides. Part II. Preparation and Properties of Al-Substituted Hematites
Authors: Schwertmann U. , Fitzpatrick R. W. , Taylor R. M. , Lewis D. G. 
Published: August 2006

AbstractAluminum-substituted hematites (Fe2−xAlxO3) were synthesized from Fe-Al coprecipitates at pH 5.5, 7.0, and in 10−1, 10−2, and 10−2 M KOH at 70°C. As little as 1 mole % Al suppressed goethite completely at pH 7 whereas in KOH higher Al concentrations were necessary. Al substitution as determined chemically and by XRD line shift was related to Al addition up to a maximum of 16–17 mole %. The relationship between the crystallographic a0 parameter and Al substitution deviated from the Vegard rule. At low substitution crystallinity of the hematites was improved whereas higher substitution impeded crystal growth in the crystallographic z-direction as indicated by differential XRD line broadening. At still higher Al addition crystal growth was strongly retarded. The initial Al-Fe coprecipitate behaved differently from a mechanical mixture of the respective “hydroxides” and was, therefore, considered an aluminous ferrihydrite.
Preparation of Montmorillonite-Nylon Complexes and Their Thermal Properties
Authors: Kato Chuzo , Kuroda Kazuyuki , Misawa Masahiro 
Published: August 2006

AbstractMontmorillonite-aminocaproic acid complexes (monomer complexes) were prepared by the intercalation of 6-aminocaproic acid to various homoionic (Na+, Ca2+, Mg2+, Co2+, and Cu2+) montmorillonites. Infrared spectra of the monomer complexes indicated that the interaction between the exchangeable cations and the 6-aminocaproic acid increased in the following order: Na-, Ca-, and Mg- < Co- < Cu-montmorillonite-aminocaproic acid complex. Montmorillonite-nylon complexes (polymer complexes) were prepared by thermal treatment of the monomer complexes, which was confirmed by X-ray powder diffraction and infrared spectroscopy the results of which indicated the condensation of 6-aminocaproic acid in the interlayer space.Thermal degradation of montmorillonite-nylon complexes was studied by thermogravimetry. It was found that the thermal stability of the polymer complexes increased in the following order: Cu- < Co- < Na- < Mg- < Ca-montmorillonite-nylon complex.It was suggested that the difference in thermal stability depended upon the length of the polymer chain which might be influenced by the interaction between the exchangeable cations and the 6-aminocaproic acid. The activation energy for the thermal degradation of each montmorillonite-nylon complex was obtained, and the value for Cu-montmorillonite-nylon complex was smaller than that for the other cation-exchanged montmorillonite-nylon complexes.
Determination of the Cation-Exchange Capacity (Layer Charge) of Small Quantities of Clay Minerals by Nephelometry
Authors: Adams J. M. , Evans S. 
Published: August 2006

AbstractNephelometric (light scattering) methods for the determination of Ca and Ba in the 0–30 ppm range, and their application to the estimation of the cation exchange capacity (±10%) of small (≤30 mg) samples of clay minerals, are described and evaluated.
The Diffusion of Interlamellar Water in the 23.3 Å Na-Montmorillonite:Pyridine/H2O Intercalate by Quasielastic Neutron Scattering
Authors: Adams J. M. , Breen C. , Riekel C. 
Published: August 2006

AbstractThe diffusion of water in the title intercalate has been measured by quasielastic neutron scattering. The diffusion coefficient (6.1 × 10−7 cm2 s−1 at 23.5°C) is one order less than that found previously for a sodium-exchanged montmorillonite which, however, contained 4 times as much water in the interlamellar space. The activation energy for the motion has been deduced to be 18 kJ mol−1. Also it has been demonstrated that upon the time scale of the neutron scattering events (faster than 10−9 s) the hydroxyl groups of the clay lattice are not in motion.
Water Vapor Isotherms and Heat of Immersion of Na/Ca-Montmorillonite Systems—II: Mixed Systems
Authors: Keren R. , Shainberg I. 
Published: August 2006

AbstractAdsorption isotherms for water vapor, c-spacing and heat of immersion in water of mixed Na/Ca-montmorillonite were measured at 25°C at various RH. There was good agreement between the calorimetric data, the heat calculated from the isotherms by use of BET equation, and the calculations from the ion-dipole model. It was concluded that the electrostatic forces between the adsorbed cations and the water molecules are the dominant forces in the hydration of the clay. Thus, at low moisture content, only the adsorbed Ca-ions are hydrated. The heat released when Na-platelets condense to form Ca-packets was measured, and it was suggested that this energy term is the driving force for the demixing phenomena.
Thermal Transformation of Chrysotile Studied by High Resolution Electron Microscopy
Authors: de Souza Santos Helena , Yada Keiji 
Published: August 2006

AbstractThermal transformation of chrysotile from Uruaçu District, state of Goiás, Brazil, heated in dry conditions at temperatures from 600°C to 1300°C was studied by high resolution electron microscopy and selected area electron diffraction (SAD). Up to 600°C, no morphological or SAD pattern changes were observed. At 600°C, the fibrils were still crystalline with the characteristics of the clinochrysotile. In addition, a new fringe system of 10–15 Å spacings appeared sporadically parallel to the 7.3 Å fringes of chrysotile. Areas of these extra fringes seem to constitute favorable sites for the nucleation of forsterite. At 650°C, forsterite nuclei appeared inside the nearly amorphous fibrils in the shape of patches consisting of flaky crystallites. At 700°C the chrysotile structure had disappeared; the new spots present in the SAD pattern were indexed as those of forsterite. Between 800–900°C the crystallinity of the patches was clearly demonstrated. From the lattice images in the patches, topotactic relations between chrysotile and forsterite were analyzed. At 1000°C very tiny grains of enstatite were formed mixed with forsterite grains. The SAD pattern is complex due to the coexistence of forsterite, enstatite, and silica-rich amorphous areas. From 1100°C to 1300°C the tridimensional growth of enstatite was promoted. The present results support the topotactic relations between chrysotile and forsterite found by X-ray analysis although differences up to several degrees may exist when these phases are observed microscopically. Evidence suggesting a topotactic growth between forsterite and enstatite was also obtained.