bluuebunny/crossref_metadata_2025_split huggingface dataset:
New Data and a Revised Structural Model for Ferrihydrite
Authors: Eggleton Richard A. , Fitzpatrick Robert W. 
Published: August 2006

AbstractSynthetic 2-line and 6-line ferrihydrite samples prepared from ferric nitrate solutions have the bulk compositions Fe4(O,OH,H2O)12 and Fe4,6(O,OH,H2O)12, respectively. The composition depends on crystal size, which averages 20 Å for 2-line and 35 Å for 6-line ferrihydrite. X-ray absorption edge spectra indicate the presence of tetrahedral Fe3+, a conclusion supported by heating experiments which show the development of maghemite after heating to 300°C in the presence of N2, followed by the formation of hematite at higher temperatures. These two reactions are recorded on differential thermal analysis traces by exotherms at 350° and 450°C. Transmission electron microscopy shows that 2-line ferrihydrite has no Z-axis regularity but does show hexagonal 2.54-Å lattice fringes. Six-line ferrihydrite forms faceted crystals having 9.4-Å c-parameter only detectable in dark field. In bright field, 2.54-Å lattice fringes indicate greater atomic regularity than in 2-line ferrihydrite. Analysis of the X-ray powder diffraction pattern of 6-line ferrihydrite suggests a structure based on double-hexagonal close-packed oxygens, containing 36% Fe in tetrahedral sites. Selective chemical dissolution, surface area measurements, and magnetic susceptibility are consistent with the recorded properties of ferrihydrite.
An Occurrence of Authigenic Nacrite
Authors: Bühmann D. 
Published: August 2006

AbstractEuhedral, pseudohexagonal nacrite was discovered as a thin layer coating a carbonaceous shale in the Sherwood Tunnel in Durban, Republic of South Africa. The nacrite apparently formed authigenically within a few weeks at ambient temperature by precipitation from pore solutions, probably as a result of evaporation. This observation suggests that nacrite can no longer be considered to indicate a high-temperature genetic environment. Precipitation from saturated pore solution may have been the mechanism of formation for this kaolin-mineral polymorph.
Analysis and Implications of the Edge Structure of Dioctahedral Phyllosilicates
Authors: White G. Norman , Zelazny L. W. 
Published: August 2006

AbstractCrystal growth theory was applied to describe edge sites of phyllosilicates. Three face configurations were found to exist. One face has one tetrahedral site per tetrahedral sheet and two octahedral one-coordinated sites per crystallographic area ac sin β, where a and c are layer dimensions and β is the angle between them. The other two faces are similar except that they have one less octahedral site which is replaced by one SiIV-O-AlVI site in this same ac sin β area. A transfer of bonding energy from the remaining octahedral site to the SiIV-O-AlVI site is believed to neutralize all edge charge on faces containing these latter sites at normally encountered pHs (pH 3–9). A similar charge rearrangement along the edges results in an apparent decrease in the permanent charge of the mineral with an increase in edge area.On the basis of such an analysis, lath-shaped illite can be described as a very fine grained dioctahedral mica in which the apparent deficient occupancy of the octahedral sheet, presence of excess water, and measurable cation-exchange capacity may in part be the result of a large ratio of edge area to total volume, with no other chemical or structural change in the mica layers. The increasing importance of edge charge relative to layer charge produces erroneous formulae for 2:1 phyllosilicates in very fine grained samples containing fewer than 2 of 3 octahedral sites occupied by cations, on the basis of a 22-charge half cell.
Preparation of Delaminated Clay Having a Narrow Micropore Distribution in the Presence of Hydroxyaluminum Cations and Polyvinyl Alcohol
Authors: Suzuki Kenzi , Mori Toshiaki , Kawase Kaoru , Sakami Hiroshi , Iida Shozo 
Published: August 2006

AbstractThe pillaring of Na-montmorillonite with cationic oligomers of hydroxyaluminum (COHA) in the presence of an aqueous solution of polyvinyl alcohol resulted in the formation of a clay having a large surface area and pore volume. The pore-size distribution determined from a N2 adsorption/desorption hysteresis was narrow and centered at about 25 Å. The peak width at half height in the distribution curve was < 5 Å. As a result of delamination, the layer structure of the prepared clay was found from X-ray powder diffraction measurements to be lost. Short-range ordering, however, still existed in this delaminated clay, because exchangeable cations in the montmorillonite completely exchanged with Al3+, a requisite step for pillaring.The order of adding the starting materials (Na-montmorillonite, polyvinyl alcohol, and COHA) greatly affected the surface area and the pore volume of the delaminated clay. Two orders of addition (Namontmorillonite, then COHA, then polyvinyl alcohol; and COHA, then Na-montmorillonite, then polyvinyl alcohol) gave no measurable surface area and pore volume. Two other orders of addition (polyvinyl alcohol, then COHA, then Na-montmorillonite; and polyvinyl alcohol, then Na-montmorillonite, then COHA) gave surface areas of 107 and 160 m2/g and pore volumes of 0.13 and 0.29 cm3/g, respectively. The amounts of the COHA solution and polyvinyl alcohol added greatly influenced the surface area and pore volume of the delaminated clay. Both properties increased monotonically with increasing amount of added polyvinyl alcohol, and increased to a maximum and then decreased with increasing amount of added COHA solution. The maximum surface area of the prepared delaminated clay was 330 m2/g.
Photostabilization of a Nitromethylene Heterocycle Insecticide on the Surface of Montmorillonite
Authors: Margulies L. , Rozen H. , Cohen E. 
Published: August 2006

AbstractThe photochemical stability of the insecticidal compound tetrahydro-2-(nitromethylene)-2H-1,3-thiazine (NMH) adsorbed on montmorillonite (Mont), in the presence or in the absence of a second organic chromophore was studied. Two different organic dyes were investigated as possible stabilizers of NMH: the divalent cation methyl green (MG) and the monovalent cation thioflavin T (TFT). Samples of free NMH and of the adsorption complexes Mont-NMH, Mont-MG-NMH, and Mont-TFT-NMH were exposed to direct sunlight, and the residual insecticidal activity was estimated. Some photostabilization of the pesticide adsorbed to the clay was observed. The highest degree of photoprotection was achieved in samples containing 0.5 mmole of TFT and 0.2 mmole of NMH/g clay. Increasing the load of TFT to 0.8 mmole/g clay resulted in a complete loss of photostabilization. The interactions of the organic molecules at the clay surface were studied by UV-VIS absorption and Fourier-transform infrared spectroscopy. For the Mont-NMH and Mont-MG-NMH complexes, the observed photostabilization is probably due to clay-NMH interactions. In the Mont-TFT-NMH complex specific interactions between the cationic dye and the pesticide molecules probably occurred as well.
Quantitative Determination of Hematite and Goethite in Lateritic Bauxites By Thermodifferential X-Ray Powder Diffraction
Authors: Boski T. , Herbillon A. J. 
Published: August 2006

AbstractAn X-ray thermodifferential powder diffraction method for the quantitative determination of goethite and hematite in lateritic bauxites has been developed and consists of measuring the integrated intensities of the 012 line of hematite before and after heating the sample at 900°C and of correcting the obtained values by the X-ray mass absorption coefficient of either the untreated or heated matrix. From the corrected line intensities and the chemical analyses, the amounts of iron to be allocated to goethite and hematite in the untreated samples can be estimated. The actual content of goethite and hematite in a sample is calculated by taking into account the degree of Al substitution in each of these minerals. The method was tested on artificial mixtures of goethite and hematite and subsequently used to analyze 98 auger drill samples from lateritic bauxites of Guinea Bissau. The estimated precision of the determination of goethite and hematite content was ±2% (absolute). The method can not be applied to samples containing < 10% Fe2O3 (on a whole weight basis) unless preconcentration is carried out.
X-Ray Diffraction Identification of the Polytypes of Mica, Serpentine, and Chlorite
Authors: Bailey S. W. 
Published: August 2006

AbstractSix standard polytypes of micas exist that have c-periodicities between 1 and 6 layers; these can be subdivided into groups A and B according to whether the octahedral cations are in the same set of positions in every layer or alternate regularly between I and II possible sets of positions (alternate slant directions), respectively. Correspondingly, 12 standard polytypes exist for 1:1 layers of the serpentine-type structures, which are divisible into four groups A-D. Groups A and B differ as in the micas, as do groups C and D. Groups A and B have ±a/3 interlayer shifts, whereas groups C and D have zero or ±b/3 interlayer shifts. Six structural types of semi-randomly or regularly stacked 1-layer chlorites exist that differ in the slant of the interlayer sheet (I or II) and its position (a or b) relative to 6-member rings in adjacent 2:1 layers.Criteria have been established that permit the X-ray diffraction identification of the above-mentioned groups as well as the individual polytypes within each group. These criteria involve inspection of the strong X-ray diffraction reflections of index k = 3n for identification of the groups and of the generally weaker k ≠ 3n reflections for identification of the polytypes (assuming indexing on orthohexagonal axes throughout for convenience). In all hydrous phyllosilicates the octahedral cations and anions repeat at intervals of b/3 and thus contribute strongly to X-ray diffraction reflections of index k = 3n. The intensities of these reflections identify the two mica groups, the four serpentine-type groups, and the six chlorite groups. The periodicities of these reflections along Z* is that between identical octahedral sheets. The basal oxygen atoms do not repeat at intervals of b/3 and are a primary contributor to the intensities of k ≠ 3n reflections. The period along Z* for these reflections is that between identical basal oxygen planes, and the periodicity plus the symmetry identify the individual trioctahedral polytypes. For dioctahedral polytypes of the kaolin-group minerals and chlorites, the position of the vacant octahedral site must be considered also.These general principles can be illustrated especially well by single-crystal precession photographs and extrapolated to powder photographs.
Modification of the Porous Structure and Surface Area of Sepiolite under Vacuum Thermal Treatment
Authors: Grillet Y. , Cases J. M. , Francois M. , Rouquerol J. , Poirier J. E. 
Published: August 2006

AbstractModifications of the external surface area and the two types of microporosity of sepiolite (structural microporosity and inter-fiber porosity) were examined as a function of the temperature of a vacuum thermal treatment to 500°C. The methods used included: reciprocal thermal analysis, N2 and Ar low-temperature adsorption microcalorimetry, gas adsorption volumetry (for N2, Ar, and Kr at 77 K and CO2 at 273 and 293 K), water-vapor adsorption gravimetry, and immersion microcalorimetry into liquid water at 303 K. If the sample was not heated >100°C, only 20% of the structural microporosity was available to N2, whereas 52% was available to CO2 at 293 K. In both experiments, the channels filled at very low relative pressures. At >350°C, the structure transformed to anhydrous sepiolite, which showed no structural microporosity. The inter-fiber microporosity decreased from 0.031 to 0.025 cm3g (as seen with N2), and the external specific surface area decreased from 120 to 48 m2/g. The water adsorption isotherms showed a lower and lower affinity of the external surface of fibers for water as the temperature of thermal treatment increased. The thickness of the bound water on the external surface was estimated to be ≤ 3.5 monolayers, i.e., less than 10 Å.
Quantification Curves for Mica/Smectite Interstratifications by X-Ray Powder Diffraction
Authors: Tomita Katsutoshi , Takahashi Hidewo , Watanabe Takashi 
Published: August 2006

AbstractX-ray powder diffraction (XRD) patterns for many interstratified mica/glycolated smectites were calculated by changing combinations of probabilities and transition probabilities of two-component layers. Three basal XRD reflections, 5. l°–7.6°2θ (p1), 8.9°–10.2°2θ (p2), and 16.1°–17.2°2θ (p3) were selected for the quantification curves. A distinct relationship exists between Δ2θ, (p2–p1) and Δ2θ2 (p3–p2) which shows systematic changes with expandability at constant Reichweite values. The calculated values were plotted with Δ2θ1 and Δ2θ2 as the axes of coordinates, and quantification curves were calculated. The components and stacking parameters of mica/smectites were estimated easily using this diagram. Probabilities of existence of component layers and their transition probabilities for Reichweite (R=0) and (R=l) structures, and special cases of R=2 and R=3 structures were obtained.
Model for Competitive Adsorption of Organic Cations on Clays
Authors: Margulies L. , Rozen H. , Nir S. 
Published: August 2006

AbstractThe adsorption on montmorillonite of two monovalent organic cations, methylene blue (MB) and thioflavin T (TFT), was studied in four different situations: (1) separate adsorption of MB or TFT; (2) competitive adsorption of TFT and Cs; (3) competitive adsorption of the two organic cations from their equimolar solutions; and (4) adsorption of TFT on a clay whose cation-exchange capacity (CEC) had been previously saturated with MB. MB and TFT adsorbed to as much as 120% and 140% of the CEC, respectively. Cs did not appear to compete with TFT for the adsorption sites of the clay. TFT molecules adsorbed more strongly than those of MB and displaced them from the clay surface. A model was developed to evaluate the strength of the clay-organic cation interactions. The specific binding of the cations to the negatively charged surface, determined by solving the electrostatic equations, appears to account for adsorption exceeding the CEC and formation of positively charged complexes, which are due to non-coulombic interactions between the organic ligands.The charge reversal predicted by the model beyond the CEC of the clay was confirmed by microelec-trophoretic experiments. Particles in a sample of montmorillonite loaded with 50 meq TFT/100 g clay moved to the positive electrode, whereas in samples containing the two dyes, MB and TFT, coadsorbed at a total concentration of 100–120 meq/100 g clay, the particles moved to the negative electrode. Binding coefficients describing the formation of neutral and charged complexes of TFT and the clay were larger than those for MB and the clay, thereby explaining the preferential adsorption of TFT observed experimentally. The binding coefficients for the formation of neutral complexes of either MB and TFT and the clay were more than six orders of magnitude larger than those previously reported for inorganic monovalent cations.
Thermal Transformation of Talc as Studied by Electron-Optical Methods
Authors: de Souza Santos Helena , Yada Keiji 
Published: August 2006

AbstractThe thermal decomposition of a fibrous talc was studied by transmission electron microscopy (TEM) and selected-area electron diffraction (SAD). Small changes in the lengths of a and b unit-cell parameters were noticeable at 500°C, but the talc laths did not change morphologically until 800°C. At this temperature striations began to appear in the TEM image, and the talc SAD reflections began to develop faint satellite streaks. At 900°C the striations appeared to be crystallites, and reflections of orthorhombic enstatite were noted. Both TEM and SAD evidence showed that the enstatite crystallites were formed in three orientations corresponding to the three pseudohexagonal a axes of the talc. Thus, triple superposition of the electron diffraction pattern at the three equivalent angles explains the high symmetry star-shaped pattern. At 1000° to 1100°C the enstatite crystallites were shorter and thicker, and the streaks in the SAD pattern were nearly absent. Above 1200°C only one orientation of the enstatite crystallites was found. Noncrystalline regions were also detected at 900°C and became progressively scarce at 1000° and 1100°C. They were not detected at 1200°C. At 1300°C cristobalite was detected in some SAD patterns. The crystallographic axes and unit-cell parameters of the talc and enstatite were also topotactically related as follows: at (5.3 Å)//ce (5.2 Å); bt (9.16 Å)//be (8.8 Å); d(001)t (18.84 Å)//ae (18.2 Å). These results are compatible with an inhomogeneous decomposition mechanism as proposed by earlier workers.
Near-Infrared Reflectance Spectra of Mixtures of Kaolin-Group Minerals: Use in Clay Mineral Studies
Authors: Crowley James K. , Vergo Norma 
Published: August 2006

AbstractNear-infrared (NIR) reflectance spectra for mixtures of ordered kaolinite and ordered dickite have been found to simulate the spectral response of disordered kaolinite. The amount of octahedral vacancy disorder in nine disordered kaolinite samples was estimated by comparing the sample spectra to the spectra of reference mixtures. The resulting estimates are consistent with previously published estimates of vacancy disorder for similar kaolin minerals that were modeled from calculated X-ray diffraction patterns. The ordered kaolinite and dickite samples used in the reference mixtures were carefully selected to avoid undesirable particle size effects that could bias the spectral results.NIR spectra were also recorded for laboratory mixtures of ordered kaolinite and halloysite to assess whether the spectra could be potentially useful for determining mineral proportions in natural physical mixtures of these two clays. Although the kaolinite-halloysite proportions could only be roughly estimated from the mixture spectra, the halloysite component was evident even when halloysite was present in only minor amounts. A similar approach using NIR spectra for laboratory mixtures may have applications in other studies of natural clay mixtures.
Asymmetric Zonation of a Thick Ordovician K-Bentonite Bed at Kinnekulle, Sweden
Authors: Brusewitz Ann Marie 
Published: August 2006

AbstractThe clay fraction of a ∼2-m-thick K-bentonite at Kinnekulle in southwestern Sweden has been studied by X-ray powder diffraction, chemical analyses, and cation-exchange capacity determinations. Previous investigations of the upper half of this bed (B-bed) have shown the clay mineral to be illite/smectite (I/S), containing about 50% illite layers at the center of the bed and 65% illite layers at the upper contact. New data on six samples from the lower part of the bed show no zonation, the I/S containing about 50% illite layers in all samples. The bentonite occurs in limestones and shales overlying a 40-m-thick limestone bed and is overlain by limestones, marls, and shales (∼90 m), which in turn are overlain by a 40-m-thick diabase. The limestones are silicified in contact with the bentonite, particularly beneath the B-bed. The increased K content towards the upper contact may therefore have resulted from diffusion of K-bearing solutions from overlying shales, a process that was impeded in the lower part of the bed, probably by the silicification.
Interaction of Fluazifop with Al-, Fe3+-, and Cu2+-Saturated Montmorillonite
Authors: Micera G. , Pusino A. , Gessa C. , Petretto S. 
Published: August 2006

AbstractThe adsorption of the pesticide Fluazifop, (RS)-2-[4-[[(5-trinuoromethyl)-2-pyridin-yl]oxy]phenoxy] propanoic acid, on homoionic Cu2+-, Fe3+-, and Al-bentonites was investigated by infrared and electron spin resonance spectroscopy. For comparison, the binary complexes of the acid containing the above ions were prepared and characterized. On the whole, the results show that the interaction of the acid with the clay may have involved both the protonation of the pyridine nitrogen atom, due to a proton transfer from the acid metal-bound water, and the formation of direct bonds between the carboxylate groups and the exchange cations. The extent of these interactions was dependent on the nature of the metal ions, the Cu ions being more effective in producing CHCl3-extractable neutral carboxylate complexes, while Al and Fe favored the formation of species bearing protonated nitrogen atoms and un-dissociated carboxyl groups.
Infrared Studies of Surface Acidity and Reversible Folding in Palygorskite
Authors: Blanco C. , Herrero J. , Mendioroz S. , Pajares J. A. 
Published: August 2006

AbstractThe infrared absorption spectra of a palygorskite sample from Cáceres, Spain, showed two previously unreported bands in the OH-stretching region at 3420–3440 and 3220–3230 cm−1 after evacuation at 90°–230°C. These bands, which reached maximum intensity after the sample was heated at 150°C, were assigned to OH in the
$$\begin{array}{*{20}{c}} H \\: \\ {Si - O - Si\,and\,} \\ \end{array}\begin{array}{*{20}{c}} H \\: \\ {Si - O - A1} \\ \end{array}$$ groups, respectively. To characterize the nature of these OH groups, pyridine was adsorbed on the sample. The resultant spectra suggest that at 150°C the palygorskite folded and OH groups protonated, resulting in the formation of a deformed pyridinium ion between 150° and 290°C. A high concentration of thermally stable Lewis-acid sites on the surface of the palygorskite was also noted.
Acid Dissolution of Akaganiéite and Lepidocrocite: The Effect on Crystal Morphology
Authors: Cornell R. M. , Giovanoli R. 
Published: August 2006

AbstractThe rate of dissolution of akaganéite in HCl increased with time over the bulk of the reaction leading to a sigmoid dissolution vs. time curve. The bulk of the dissolution of lepidocrocite could be described by the cube root law. Transmission electron microscopy examination of partly dissolved crystals of akaganéite showed that acid attack proceeded mainly along the [001] direction. Initially, the tapered ends of the crystals became squared, and as dissolution continued the lengths of the crystals decreased steadily. At the same time, the crystals were gradually hollowed out. Acid attack was most pronounced at the edges of the crystals of lepidocrocite and appeared to involve a disruption of the hydrogen bonds that link the sheets of octahedra making up the structure. Defects also acted as sites for preferential acid attack. Dissolution of multi-domainic crystals involved preferential attack along the domain boundaries, as well as at the edges of the crystals. Single-domain crystals were well developed, but appeared to contain internal imperfections, which promoted the formation of holes on the otherwise unreactive (010) faces.