bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anion-Exchange Properties of Hydrotalcite-Like Compounds
Authors: Miyata Shigeo 
Published: September 2006

AbstractIon-exchange isotherms between hydrotalcite-like compounds (HT) of the NO3-, Cl-, and SO4- forms and F−, Cl− Br−, I−, OH−, SO42−, CO32−, and Naphthol Yellow S (NYS2−) ions were determined, and the spacing and the width of the 003 reflection were measured as a function of HT composition. The ion-exchange equilibrium constant for HTs of monovalent anions are in the sequence OH− > F− > Cl− > Br− > NO3− > I−, those for divalent anions are in the sequence CO32− > NYS2− > SO42−. The ion-exchange equilibrium constants tend to increase as the diameters of the anions decrease, and the crystallite size in the 001 direction tends to increase with anions having higher selectivity. The OH-form of HT has the smallest basal spacing and the largest crystallite size in the 001 direction.
Hydrogen Atom Positions in Kaolinite by Neutron Profile Refinement
Authors: Adams J. M. 
Published: September 2006

AbstractA structure refinement of kaolinite made using the Rietveld neutron profile refinement technique has given non-hydrogen atom positions which were not significantly different from those given by B. B. Zvyagin in 1960. All of the hydrogen atoms have been located; the three inner-surface hydrogen atoms are involved in interlayer hydrogen bonds with lengths of 2.95(4), 2.95(4), and 3.06(4) Å with O-H ... O angles of 168(4)°, 144(4)°, and 146(4)° respectively. The inner hydrogen atom is located in a position consistent with that found earlier in dickite and muscovite which are the only dioctahedral layer silicates studied by neutron diffraction to date. The O-H vector makes an angle of 34° with the (001) plane, away from the octahedral sheet, and the projection of the vector on to (001) is at ~30° to the b axis.
Extended Version of Gouy-Chapman Electrostatic Theory as Applied to the Exchange Behavior of Clay in Natural Waters
Authors: Neal C. , Cooper D. M. 
Published: September 2006

AbstractA model based on Gouy-Chapman theory, describing the ion exchange behavior of clays in mixed electrolyte solutions is presented. Computed ionic distributions, taking into account variations in relative permittivity, ion activity, and closeness of approach of ions to clay surfaces, are compared with experimental data for smectite and kaolinite in contact with river and saline waters. To obtain reasonable agreement between theoretical prediction and observation the most important extension of Gouy-Chapman theory involves the introduction of a closeness of approach term. Furthermore, the aggregated nature of smectites plays an important part in controlling its exchange properties, whereas a fixed-charge model provides a poor description for the ion exchange properties of kaolinite.
Dehydroxylation, Rehydroxylation, and Stability of Kaolinite
Authors: Hurst Vernon J. , Kunkle Albert C. 
Published: September 2006

AbstractFrom hydrothermal experiments three pressure-temperature-time curves have been refined for the system Al2O3−SiO2−H2O and reversal temperatures established for two of the principal reactions involving kaolinite. The temperatures of three isobaric invariant points enable the Gibbs free energy of formation of diaspore and pyrophyllite to be refined and the stability field of kaolinite to be calculated. The maximal temperature of stable kaolinite decreases from 296°C at 2 kb water pressure to 284°C at water's liquid/vapor pressure, and decreases rapidly at lower pressures. On an isobaric plot of [H4SiO4] vs. °K-1, kaolinite has a wedge-shaped stability field which broadens toward lower temperature to include much of the [H4SiO4] range of near-surface environments. If [H4SiO4] is above kaolinite's stability field and the temperature is < 100°C, halloysite forms rather than pyrophyllite, an uncommon pedogenic mineral. Pyrophyllite forms readily instead of kaolinite above 150°C if [H4SiO4] is controlled by cristobalite or noncrystalline silica.Kaolinite and a common precursor, halloysite, are characteristic products of weathering and hydro-thermal alteration. In sediments, relatively little halloysite has survived due to its low dehydration temperature and instability at low water pressure, but kaolinite commonly has survived since the Devonian Period. In buried sediments, the water pressure and [H4SiO4] requisite for stable kaolinite generally are maintained. In oxidized sediments and in pyritic reduced sediments, kaolinite commonly has survived, but where alkalies, alkaline earths, or aqueous iron has concentrated in the pore fluid, kaolinite has tended to transform to illite, zeolites, berthierine, or other minerals.
Iron Sites in Nontronite and the Effect of Interlayer Cations from Mössbauer Spectra
Authors: Johnston J. H. , Cardile C. M. 
Published: September 2006

AbstractThe 57Fe Mössbauer spectra of untreated, Ca- and K-saturated nontronite from Garfield, Washington, were measured. The spectrum of the untreated sample was computer-fitted to 8 peaks defining two octahedral, a tetrahedral, and an interlayer Fe3+-quadrupole-split doublets. In the Ca- and K-saturated samples interlayer Fe was absent. Spectra of the untreated sample were recorded at increasing increments of background counts from 2.8 × 105 to 9.2 × 106. An evaluation of the initial 4- and 6-peak models and the acceptable 8-peak model, computer-fitted to each spectrum, shows that if the χ2 value is used as a measure of the goodness of the fit, the spectra should be recorded to a background count greater than 3 × 106. The resulting χ2 value then reflects both the validity of the model used and the extent of disorder within the structure. The χ2 value depends linearly on the background counts obtained.A comparison of the spectra of the Ca- and K-saturated samples with that of the untreated sample shows that the interlayer cations exert a considerable influence on the individual component resonances, particularly the outer octahedral doublet. Hence, it is likely that electrostatic interactions of the nearby tetrahedral Fe3+ and the interlayer cations give rise to two distinct electric field gradients within neighboring cis-[FeO4(OH)2] sites, and hence two octahedral Fe3+ doublets in the Mössbauer spectrum. These results are consistent with earlier electron diffraction data in the literature.
Electromobility of Mica Particles Dispersed in Aqueous Solutions
Authors: Pashley R. M. 
Published: September 2006

AbstractMobility measurements were made for dry-ground mica particles dispersed in aqueous KCl, Cr(NO3)3, and cetyltrimethylammonium bromide (CTAB) solutions. In the latter solutions charge reversal occurred at about 2 × 10-6 M and 3 × 10-5 M, respectively. Negative zeta potentials in KCl solutions calculated using the Smoluchowski equation are about one third of the corresponding values obtained from streaming potentials and force measurements using mica sheets. Good agreement, however, was obtained when positively charged groups created during grinding were neutralized, and the zeta potentials were corrected according to the procedure of O'Brien and White with an assumed average particle size of 0.25 μm. When the zeta potentials of positively charged particles were corrected in this way, agreement with values calculated from force measurements was also improved.
Small-Angle X-Ray Powder Diffraction, Morphology, and Structure of Allophane and Imogolite
Authors: van der Gaast S. J. , Wada K. , Wada S.-I. , Kakuto Y. 
Published: September 2006

AbstractSmall-angle X-ray powder diffraction analyses and high-resolution electron microscopy of allophane samples (SiO2/Al2O3 ratio, 1.12 to 1.68) showed that allophanes consist of nearly identical spherical particles with diameters of about 40 Å and retain their characteristic “hollow” spherical morphology at different ambient moisture and even after dehydroxylation by heating at 500° to 600°C. Unheated allophane samples gave another X-ray powder diffraction band whose maximum position varied from 12.3 to 14.5 A depending on their SiO2/Al2O3 ratio. The appearance of this band may denote some long-range ordering in the structure of allophane. Unlike the spherical particles of allophane, the tube unit of imogolite collapsed on dehydroxylation. This observation suggests that imogolite and allophane are different in their framework structures and that a Si- or Si(Al)-tetrahedral sheet rather than an Al-octahedral sheet constitutes the framework structure of allophane, irrespective of its SiO2/Al2O3 ratio.
Structural Studies of Nontronites with Different Iron Contents by 57Fe Mössbauer Spectroscopy
Authors: Cardile C. M. , Johnston J. H. 
Published: September 2006

AbstractThe 57Fe Mössbauer spectra of a series of untreated and Ca-saturated nontronites showed a predominant Fe3+ resonance which was computer-fitted with two Fe3+ doublets defining iron in non-equivalent cis-FeO4(OH)2 octahedral sites. In most spectra a doublet indicating tetrahedral Fe3+ was fitted and in one untreated sample a doublet indicating interlayer Fe3+ was identified. In a further untreated sample the interlayer iron was present as Fe2+. Upon Ca-saturation the interlayer iron was displaced. It also appears that the interlayer iron was present in at least two different interlayer sites. From the computer-fitted data it was clear that the interlayer cations have a significant effect on the Mössbauer resonances of iron in the two non-equivalent cis-octahedral and the tetrahedral sites of nontronite.
Mechanism of Synthesis of 10-Å Hydrated Kaolinite
Authors: Raythatha Rasik , Lipsicas Max 
Published: September 2006

AbstractThe synthesis of 10-Å hydrated kaolinite was accomplished by: (1) direct reaction of HF with a dimethyl sulfoxide (DMSO)-kaolinite intercalate and water washing; (2) methanol washing of a DMSO-kaolinite intercalate followed by reaction with any alkali fluoride salt and water washing; and (3) room-temperature (RT) water-washing of a methanol-washed DMSO-kaolinite intercalate. In all syntheses the optimum yield required a kaolinite in which DMSO was bound strongly to the interlayer surface. In the first synthesis, water inclusion between clay layers appeared to be facilitated by the reduction of cohesive interlayer forces brought about by replacement of surface and edge OH− by F−. The fluorination reaction was accomplished either by direct reaction of HF or by HF produced through the hydrolysis of NH4F at 60°C. In the second synthesis, intercalated DMSO was replaced by methanol. F− solvated readily in methanol but not in DMSO. Consequently, F− produced through hydrolysis of the alkali fluoride salt entered the interlayer space and contributed to the fluorination reaction. Furthermore, the diffusion of methanol out of the interlayer space during the RT-washing step was slowed by F≈ solvation which aided the exchange of methanol for water. High yields of 10-Å kaolinite hydrate were obtained irrespective of choice of alkali fluoride salt. The third synthesis was dependent on matching the diffusion of methanol out of the interlayer space with diffusion of water into this space. At room temperature the diffusion rates were close enough to maintain the clay in the expanded state throughout the hydration process, and high yields of 10-Å kaolinite hydrate were obtained. At 60°C the diffusion rates were too dissimilar, and very low yields of hydrate were obtained.
Size Distribution of Allophane Unit Particles in Aqueous Suspensions
Authors: Hall P. L. , Churchman G. J. , Theng B. K. G. 
Published: September 2006

AbstractThe size distribution of unit particles of two New Zealand allophanes (An and Rh), in dilute (0.8% w/v) aqueous suspensions, has been determined by small-angle neutron scattering (SANS). In addition, the specific surface area of the samples was measured by ethylene glycol retention, and their morphology examined by high-resolution transmission electron microscopy (HRTEM). The SANS data indicate that although both allophanes are somewhat polydisperse, the average diameter of their unit particles is significantly different, being 56 and 43 Å for allophane-An and allophane-Rh, respectively. Consistent with this observation, the specific surface area of allophane-Rh (897 mVg) is appreciably greater than that of allophane-An (638 m2/g). Under the electron microscope, both samples appear as aggregates of hollow spherules but HRTEM did not clearly distinguish between the two allophanes in that the largest population of spherules had diameters near 50 Å. Because of the assumptions and uncertainties involved in the SANS and surface area measurements, the data must be discussed in terms of their respective ratios. On this basis, the spherule diameter ratio is of the same order of magnitude as the inverse ratio of specific surface area. The latter value is also in reasonably good agreement with the corresponding ratios of phosphate adsorption capacity and BET nitrogen areas, derived from earlier studies.
Hydration States of Interlamellar Chromium Ions in Montmorillonite
Authors: Carr R. Melville 
Published: September 2006

AbstractHydroxychromium montmorillonites were prepared from solutions containing chromium nitrate and varying amounts of NaOH. The reactant Cr ions were hydrolyzed and, in some experiments, were dimerized to a significant extent. The extent of polymerization in the product formed from a solution containing a maximum amount of [Cr2(H2O)8(OH)2]4+ was compared with that in products obtained from solutions containing monomer, [Cr(H2O)5OH]2+, and lesser amounts of the dimer. Despite the uncertainty about the nature and amounts of product interlamellar species, the catalytic effect of the montmorillonite interlayer on the hydrolysis and polymerization of Cr(III) appears to be independent of the nature of the reactant species. The validity of this conclusion depends to a large extent on the reliability of water determination in the clay mineral species, which is estimated to be no better than 5%. The assumption that H2O+ is 'combined’ and H2O— is 'free’ water is shown to be partially true, thereby causing some uncertainty in the interpretations of interlayer compositions.
Properties of Goethites of Varying Crystallinity
Authors: Schwertmann Udo , Cambier Philippe , Murad Enver 
Published: September 2006

AbstractGoethites were synthesized from ferrihydrite in 0.7 M KOH between 4° and 90°C. As temperatures increased, the goethite crystals became larger and of less domainic character, and surface areas decreased from 153 to 9 m2/g. Surface area, oxalate-soluble Fe to total Fe ratios, chemisorbed water, Mössbauer parameters, and dissolution rate in 6 M HCl at 25°C are particle-size controlled, whereas mean crystallite dimensions, a-dimension of the unit cell, differences between the two OH-bending modes, and dehydroxylation temperatures suggest the existence of a low-temperature (high-a-dimension) and a high-temperature (low-a-dimension) goethite, with a narrow transition range at a synthesis temperature of 40°–50°C. Hydrothermal treatment at 125°–180°C of a low-temperature goethite led to a healing of the multidomainic, microporous high-a-dimension goethite into a monodomainic low-a-dimension goethite of similar overall crystal size with the properties of a low-a-dimension goethite.
Effect of Clay Mineralogy and Aluminum and Iron Oxides on the Hydraulic Conductivity of Clay-Sand Mixtures
Authors: Alperovitch N. , Shainberg I. , Keren R. , Singer M. J. 
Published: September 2006

AbstractChanges in hydraulic conductivity and clay dispersivity of clay-sand mixtures (four reference smectites and Fithian illite) as a function of concentration (0.01 M Cl− and distilled water) and sodium adsorption ratio (SAR ≤ 30) of the percolating solution were measured. In addition, the effect of sand percentage, sand particle size, and addition of AlCl3 and FeCl3 on the hydraulic conductivity of the mixtures were measured.Clay dispersion and migration out of the 3% clay columns was substantial. The clay dispersed only in the distilled water system; dispersion increased with an increase in the percentage of exchangeable Na and was about the same for the Wyoming montmorillonite and Fithian illite. Conversely, the clay swelled in the 0.01 M Cl− solution. The swelling of the montmorillonites increased in the order: Upton, Wyoming = Belle Fourche, South Dakota > Polkville, Mississippi > Otay, California, and was higher than that of the Fithian illite. The swelling and dispersion of the clay accounted for the changes in hydraulic conductivity.Mixtures treated with FeCl3 and AlCl3 were leached with NaCl-CaCl2 solutions until the pH of the effluent exceeded 6.5. The composition of the exchangeable phase was then determined by the SAR of the leach solutions. At pH > 6.5, the polycations hydrolyzed and were present as the hydroxy-polymer species. The hydraulic conductivity of the mixtures decreased as exchangeable Na increased, but the decrease was less than in untreated mixtures, AlCl3 was more effective in maintaining hydraulic conductivity than FeCl3. In montmorillonite clay with an ESP of 20, less than 5% of a complete Al-interlayer was enough to prevent a reduction in hydraulic conductivity. Packets in the day systems tested explain the high efficiency of the Fe and Al polycations.
Scanning Electron Microscopic and X-ray Powder Diffraction Study of Manganiferous Bauxite, Kincsesbánya, Hungary
Authors: Bárdossy György , Csordás-Toth Anna , Klug Annamária 
Published: September 2006

AbstractManganiferous karst bauxites are rare on a worldwide scale. One such body, recently mined at Kincsesbánya, Hungary, has been studied by chemical, petrographic, X-ray powder diffraction, scanning electron microscopic, and energy dispersive X-ray analytical techniques. The bauxite deposits of Kinesesbánya are of Paleocene to Lower Eocene age; however, the enrichment of manganese in them was a much later, epigenetic process. Lithiophorite is the main Mn mineral in this bauxite and occurs chiefly in dusters of < 1-μm size crystallites. Well-developed crystallites, however, 5–10 μm in size, line the walls of many microfissures and voids.The oxidation of pyritic bauxite and lignitic clays in the overlying beds apparently mobilized finely disseminated Mn and Fe. Downward-migrating acidic solutions were gradually neutralized, and Mn and Fe minerals precipitated. The manganiferous bauxite was found only along the eastern rim of heavily eroded Middle Eocene sedimentary rocks. Here, epigenetic oxidation and mobilization were optimum. Farther to the east, pyrite-rich overburden and bauxite were apparently eroded away before Fe and Mn could be mobilized.
Polytypism of Micas. III. X-Ray Diffraction Identification
Authors: Weiss Z. , Wiewióra A. 
Published: September 2006

AbstractClassification and identification criteria of maximum-degree-of-order (MDO) polytypes of homo- and meso-octahedral micas based on the distribution of the intensities of 20l (13l) and 02l reflections are proposed. Calculated | F(20l) |2 and | F(02l) |2 values for single crystals of micas with different compositions are given for one-, two-, and three-layer polytypes. Transmission powder diffractometry is proposed as a suitable method for the identification of the different groups of mica polytypes from polycrystalline specimens. Calculated powder patterns and the characteristic properties of the diffraction patterns of random and highly oriented aggregates are employed for identification purposes. The individual MDO polytypes are designated by generalized Ramsdell symbols which also contain information about their position in the classification system.
Nature and Utility of Hexamethylenediamine-Produced Kaolin Floc Structure
Authors: Bundy Wayne M. , Harrison Jack L. 
Published: September 2006

AbstractKaolin floc structures of commercial utility are produced by adsorption of hexamethylenediamine. These flocs are largely face-to-face structures with small diameter platelets of colloidal kaolinite aggregated on larger platelets of kaolinite and muscovite. Because of its higher charge density, muscovite is more effective than kaolinite in scavenging colloidal particles.Although earlier workers have been at odds as to where amines adsorb on kaolinite, the present work indicates that both edge and basal surfaces are involved. Evidence for this contention is two-fold: (1) Face-to-face and edge-to-face flocculation of hexamethylenediamine kaolins has been observed. (2) Polyesters have been observed adsorbed on basal and edge surfaces of ethylenediamine-treated kaolins.The mechanism by which kaolinite particles are bonded together into floc structures is unclear. Bridging by hexamethylenediammonium ions is a probable mechanism up to satisfaction of the cation-exchange capacity; further amine addition continues to promote flocculation. From this observation it is inferred that, in addition to bridging, hydrogen bonding and, perhaps, van der Waals forces are instrumental in floc formation. Although rheologically inferior to the untreated equivalent, these chemically induced flocs of kaolinite provide loosely packed, randomly oriented structures in paper coatings. Improved brightness, opacity, and printability of paper coatings arise from this structure.
Microstructure in Mixed-Layer Illite/Smectite and Its Relationship to the Reaction of Smectite to Illite
Authors: Bell T. E. 
Published: September 2006

AbstractThe reaction of smectite to illite in shale from the COST 1 well in the south Texas Gulf Coast and from altered ash-fall tuffs from the Morrison Formation in New Mexico was investigated using X-ray powder diffraction in conjunction with transmission electron microscopy. In the COST 1 well, the bulk of the detrital clay was originally a K+-deficient mixed-layer illite/smectite (I/S). As the I/S adsorbed K+ released by the dissolution of K-feldspar during burial, the proportion of expandable layers decreased with depth from ~65% near the top of the well to ~25% at 4500 m depth. In contrast, the proportion of low-charged structural planes [<0.8 eq per (Al,Si)4O10 unit] in the I/S decreased gradually from ~40% near the top of the well to ~15% near the bottom. Authigenic smectite with 100% expandable layers from the Morrison Formation tuffs is an alteration product of vitric ash. Where these tuffs have been buried to ~ 1400 m the smectite has reacted to form I/S with ~ 15% expandable layers.Direct lattice images of I/S crystallites from both locations reveal a correspondence between edge dislocations and the interface between illite layers and smectite layers. Al, Si, Fe, Ca, Mg, and Na were apparently mobile along these dislocations as the reaction of smectite to illite proceeded. Al was probably retained within the crystallite when illite layers replaced the smectite layers; however, some of the remaining cations were expelled. Lateral replacement of smectite layers by illite appears to have been the principal growth mechanism.