bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stability of n-Butylammonium Vermiculite in Powder and Flake Forms
Authors: Jiménez de Haro María C. , Ruiz-Conde Antonio , Pérez-Rodríguez José L. 
Published: August 2006

AbstractInteraction between n-butylammonium (BA) chloride and vermiculite from Santa Olalla (Spain) has been studied in large flake (5 × 5 × 0.1 mm) or ground powder (≤80 µm) samples. The differences in adsorption and decomposition of BA ions in both particle sizes have been established. In the interlamellar space, the BA ion remains unaltered in powder samples, but is degraded in flakes. The experimental results suggest decomposition of the BA in the interlamellar space of vermiculite flakes by breaking of the C-N bond. The degradation of BA takes place over a short period. The variety with BA in the interlamellar space is transformed into a new one, due to the degradation of alkylammonium. The transformation occurs through an interstratified phase formed between BA-vermiculite and NH4-vermiculite, and finally a phase appears in which only ammonium is present in the interlamellar space. Due to the many industrial applications of alkylammonium-clays, determination of the stability of alkylammonium in the interlamellar space of clay minerals is of great importance.
Randomly Interstratified Kaolinite-Smectite from Galicia (NW Spain): A New Procedure for Determination
Authors: Corti Giuseppe , Fernández Sanjurjo Maria Jose , Ugolini Fiorenzo Cesare 
Published: August 2006

AbstractA new protocol was developed to examine an assemblage of kaolinite-smectite in a buried horizon of a paleosol developed on gabbro parent material. The new extraction procedure appears suitable for removing kaolinite and for ascertaining the nature of the smectite interstratified with kaolinite. Smectite was identified by X-ray diffraction (XRD) and infrared (IR) patterns, cation exchange capacity (CEC) and chemical analyses.The results obtained provide for increased understanding of the process of transformation of smectite into kaolinite.
Properties of Water in Calcium- and Hexadecyltrimethylammonium-Exchanged Bentonite
Authors: Anderson Michael A. , Trouw Frans R. , Tam Cheok N. 
Published: August 2006

AbstractDynamical and thermodynamic properties of water at room temperature in Ca- and hexade-cyltrimethylammonium- (HDTMA) exchanged bentonite were determined for 4 different water contents (~0.03–0.55 g water g-1 clay). Incoherent quasi-elastic neutron scattering (QENS) was used to measure the translational and rotational mobility of water in the clays, while chilled mirror dewpoint psychrometry measured water activity of the samples, differential scanning calorimetry (DSC) provided information about the temperature of dehydration and X-ray diffraction (XRD) quantified layer spacings for the clays. The neutron scattering data were fit to a jump diffusion model that yielded mean jump lengths, jump diffusion residence times and rotational relaxation times for water in the clays. Mean jump lengths were quite similar for the 2 different cation saturations at equivalent water contents, and decreased with increasing water content. The fitted jump lengths ranged from 0.27–0.5 nm and were 2–4 times larger than that found for bulk water (0.13 nm). Jump diffusion residence times were 3–30 times longer than that for bulk water (1.2 ps) and also decreased with increasing water content. The residence times were somewhat shorter for HDTMA-clay as compared with Ca-clay at equivalent water contents. Rotational motion was less strongly influenced than translational motion by the presence of the clay surface. The energy state of water in the 2 cation saturations were quite different; dehydration temperatures for the HDTMA-clay were approximately 30 °C lower than the Ca-clay at equal water contents, while water activities, as P/P0, were up to 0.6 units higher. A linear relationship was found between water activity and the translational diffusion coefficient, although at the highest water content, the diffusion coefficient of water for the HDTMA-clay was approximately 30% higher than that measured for bulk water.
Five-Coordinate Aluminum in Allophane
Authors: Childs Cyril W. , Hayashi Shigenobu , Newman Roger H. 
Published: August 2006

AbstractSamples of Silica Springs allophane from Tongariro National Park, New Zealand, having Al/Si atomic ratios in the range 1.1-1.9, were studied by 27Al nuclear magnetic resonance (NMR) spectroscopy with high field strength (9.4 and 11.7 T) and fast magic-angle spinning (MAS) (9-13 kHz). Spectra for all samples show peaks for 6- and 4-coordinate Al and also for 5-coordinate Al. For 1 sample, the peak for 5-coordinate Al is dominant. Use of 2 instruments and 2 field strengths allowed the integrity of the spectra and the assignment of 5-coordinate Al to be verified. The “true” chemical shift (after a small correction for quadrupolar shift) observed for 5-coordinate Al in Silica Springs allophane is 36 ± 1 ppm, which is consistent with shifts reported for 5-coordination in well-characterized crystalline structures. We suggest that 5-coordination in Silica Springs allophane is associated with the edges of fragments of incomplete octahedral sheets that are bonded to disordered, though more complete, curved tetrahedral sheets in the primary particles of this allophane. Other allophanes with Al/Si < 2, and which are poor in octahedra relative to tetrahedra, may also have significant Al in 5-coordinate sites.
Characterization of Octahedral Substitutions in Kaolinites Using Near Infrared Spectroscopy
Authors: Petit S. , Madejová J. , Decarreau A. , Martin F. 
Published: August 2006

AbstractFourier transform infrared (FTIR) spectroscopy investigations in the near infrared (N1R) region of synthetic and natural kaolinites with various octahedral substitutions have been carried out in order to elucidate the relationships between the substituted cations and specific features of the NIR spectra. The combination modes of the OH stretching and bending vibrations characterizing Fe(III), Ga(III) and Cr(III) octahedral substitutions are identified in the NIR region at 4466, 4498 and 4474 cm-1, respectively, and the first overtones of the OH stretching vibrations at 7018, 7018 and 6986 cm-1, respectively. As far as we know, the bands of kaolinites containing Ga(III) or Cr(III) have not been reported yet. For both Ga(III) and Cr(III), the NIR observations explain why the bending vibration bands of AlGaOH and AlCrOH groups are not observed in the middle infrared (MIR) region.
Application of an Internal Standard Technique by Transmission X-Ray Diffraction to Assess Layer Charge of a Montmorillonite by Using the Alkylammonium Method
Authors: Janek M. , Smrčok L’. 
Published: August 2006

AbstractTransmission X-ray diffraction (XRD) of C6–16alkylammonium ion-exchanged montmorillonite SAz-1 with Ag-behenate as an internal standard provided accurate estimates ofd(001) values of the alkylammonium ion-exchanged montmorillonite. Inspection ofd(001) values were made to assess the possible formation of gauche conformers (alternate arrangements of the molecules) in the interlayer and to determine the critical carbon chain length,nC. Using conventional constraints fornC(I′) andnC(II) equal to 1.36 and 1.77 nm, respectively, provided ambiguousnC(I′) andnC(II) values. The dependence of full-width at half-maximum values onnCallowed better estimates ofnC(I′) andnC(II) because “integral” and “non-integral” peak characteristics relating to interstratification could be included in the assessment.The effect of inaccurate estimates ofnC(I′) andnC(II) values on calculated interlayer cation exchange capacity (Ci) using two conventional concepts of calculation were compared. It was found that a procedure based on the summation of fractions of the layer charge gave relative errors ofCi<2%, even where the number of carbon atoms corresponding to bothnC(I′) andnC(II) differed by ± 1nCfrom the correct values. This method of calculation ofCiis recommended when reliable values ofCiare needed.
Diffuse Reflectance Spectra of Al Substituted Goethite: A Ligand Field Approach
Authors: Scheinost Andreas C. , Schulze Darrell G. , Schwertmann Udo 
Published: August 2006

AbstractPrevious investigations of goethite revealed a substantial variation of color and diffuse reflectance spectra (DRS) in the extended visible range (350–2200 nm). To better understand the causes of this variability and to assess the potential of DRS as a mineralogical tool, we investigated the DRS of pure and Al-substituted goethite, α-Fe1−xAlxOOH with x from 0 to 0.33, and mean crystal lengths (MCL) from 170 to 1800 nm. The strongly overlapping ligand field bands were extracted by fitting the single-electron transitions 6A1 → 4T1, 6A1 → 4T2, 6A1 → (4E; 4A1), and 6A1 → 4E(4D) as functions of the ligand field splitting energy, 10 Dq, and the interelectronic repulsion parameters, Racah-B and -C. With x increasing from 0 to 0.33, 6A1 → 4T1 decreased from 10,590 to 10,150 cm−1 (944 to 958 nm), and 6A1 → 4T2 decreased from 15,310 to 14,880 cm−1 (653 to 672 nm), while 10 Dq increased from 15,770 to 16,220 cm−1. From the change of 10 Dq we calculated a decrease of the Fe-(O,OH) distances from 202.0 to 200.9 pm (−0.5%). This decrease is smaller than the average decrease of all (Al,Fe)-(O,OH) distances (−1.8%) calculated from the change of the unit-cell lengths (UCL). That is, there remains a substantial difference in size between the larger Fe- and the smaller Al-occupied octahedra in the solid solution which may indicate the existence of diaspore clusters within the goethite structure. The increasing strain in the crystal structure due to the size mismatch and limited contractibility of the oxygen cage around Fe may be the primary reason for Al substitution being restricted to x < 0.33. The bands 6A1 → (4E; 4A1) and 6A1 → 4E(4D) did not shift, indicating a constant covalency of the Fe-(O,OH) bonds with B = 628 cm−1 and C = 5.5B. Whereas variation of band energies could be explained in terms of the Fe-(O,OH) ligand field, the variation of color and band intensities was mainly determined by crystal size. Although our study confirmed the potential of DRS for mineralogical investigations, there is still a gap between the fundamental theory and the explanation of some spectral features.
Fe3+-Rich Montmorillonite-Beidellite Series in Ayvacik Bentonite Deposit, Biga Peninsula, Northwest Turkey
Authors: Çoban Fazli , Işik Ece Ö. 
Published: August 2006

AbstractThe Ayvacık bentonites, products of Miocene calc-alkaline volcanic rocks, are composed of smectite of the montmorillonite-beidellite series. Fault-related hydrothermal solutions have altered andesitic rocks to dioctahedral smectites. Differences in the micro-morphology of the two end-members are distinguished by scanning electron microscopy (SEM) studies. The beidellite particles are of delicate ribbons and rosette habits, whereas montmorillonite particles are very thin, curled sheets and flakes. Clay size (<2 µm) fractions contain (in wt. %) 54.90–56.80 SiO2, 19.65–28.54 Al2O3, 0.45–6.28 Fe2O3, 0.10–1.72 CaO, 0.80–4.15 MgO, 0.55–1.88 K2O, and 0.08–1.15 Na2O, which confirm that the beidellites are Fe-rich (5.06–6.28 wt. %), except for one sample (0.45 wt. % Fe2O3). The Greene-Kelly test (Li-saturation and heating) gave very good results for the measurement of the d(001) of the two end-members. Nickel, Ti, and Cr enrichment in smectite is related to the chemical composition of hydrothermal solutions that passed through the ophiolite complex.
Surface Layer Types of Kaolinite: A High-Resolution Transmission Electron Microscope Study
Authors: Ma Chi , Eggleton Richard A. 
Published: August 2006

AbstractHigh-resolution transmission electron microscopy (HRTEM) examinations have indicated that three types of surface layers may exist in natural kaolinite crystals. Type 1 has the expected 7-Å surface layer as terminations. Type 2 has one 10-Å pyrophyllite-like (or low-charge beidellite-like) layer as the surface layer on one side of a kaolinite particle (i.e., the layer sequence is TOTOTO … TOTOTOT, where T stands for tetrahedral sheet, O for octahedral sheet). Some industrial-grade highly-ordered kaolinites have such a 10-Å 2:1 surface layer on one side of the crystal. The spacing between the 10-Å layer and the adjacent 7-Å layer is not expandable. Type 3 kaolinite has one or several 10-Å collapsed smectite-like layers at one or both sides of a stack, i.e., (TOT)TOTO … TOTOTOT(TOT), forming a special kind of kaolinite-smectite interstratification. This type has only been recognized in some poorly-ordered kaolinites. The surface smectite layer(s) contribute to higher cation exchange capacity (CEC) values. These 10-Å surface layers were not detectable by X-ray diffraction (XRD). HRTEM and electron diffraction examination also revealed the structural features of individual kaolinite crystals. All kaolinites (from various origins and sources) studied show C-face-centering Of non-hydrogen atoms. Defects within the layer structure are common in both well-ordered kaolinite and poorly-ordered kaolinite.
Structural Study of Tetramethylphosphonium-Exchanged Vermiculite
Authors: Vahedi-Faridi A. , Guggenheim Stephen 
Published: August 2006

AbstractVermiculite from Santa Olalla, Spain, was intercalated with tetramethylphosphonium [P(CH3)4+ = TMP], using a TMP-bromide solution at 70°C for three weeks. The resulting TMP-exchanged vermiculite, which contained a small (<5% of a site) amount of residual interlayer Ca, showed near perfect three-dimensional stacking. Cell parameters are a = 5.3492(8) Å, b = 9.266(2) Å, c = 14.505(6) Å, β = 97.08(2)°, space group is C2/m, and polytype is lM. Single-crystal X-ray refinement (R = 0.052, wR = 0.061) located two crystallographically unique sites for the phosphorus atoms (TMP molecule). The phosphorus atoms are occupied partially [P1 = 0.146(6), P2 = 0.098(5)] and are offset from the central plane of the interlayer by 1.23 Å to form two P-rich planes in the interlayer. Electrostatic interactions between the P cations and basal oxygen atoms essentially balance the negative charge associated with Al for Si substitutions in the tetrahedral sites. In addition, the orientations of the TMP molecules are probably different owing to packing constraints. The H2O site is located in the center of the interlayer, at the center of the silicate ring, and ∼3.09 Å from the Ca, which is also located on the central plane of the interlayer. Other H2O molecules are present in the interlayer, but could not be located by the diffraction experiment because they are randomly positioned in the interlayer. The tetrahedral rotation angle, α, is affected by the intercalation of TMP relative to tetramethylammonium (TMA), thus indicating that 2:1 layers are not simply rigid substrates, and that dynamic interactions occur during reactions involving adsorption and exchange.
Comparison of Adsorption of Phosphate, Tartrate, and Oxalate on Hydroxy Aluminum Montmorillonite Complexes
Authors: He J. Z. , De Cristofaro A. , Violante A. 
Published: August 2006

AbstractCompetitive adsorption between phosphate, tartrate and oxalate was studied on two hydroxy aluminum montmorillonite complexes (AlMt1.6 and AlMt6), which were prepared by adding a base to pH 5.5 to samples containing 1.6 and 6.0 mol Al per kg clay. The quantities of phosphate, tartrate and oxalate adsorbed were more closely related to the amount of OH-Al species coatings on the montmorillonite than to the surface area of the complexes. The adsorption capacity of phosphate was much greater than that of tartrate or oxalate for both samples. Adding molar amounts of oxalate and tartrate resulted in an oxalate/tartrate adsorption ratio (Rf) of ∼1. However, in the presence of phosphate, Rf values were <1.0, and the Rf values decreased with increasing amounts of added phosphate, indicating that tartrate competed with phosphate more effectively than oxalate. The presence of tartrate also reduced phosphate adsorption by the complexes. The efficiency of tartrate in reducing phosphate adsorption increased by increasing the initial tartrate/phosphate molar ratio and by adding tartrate 2 h before phosphate addition. Tartrate and oxalate added as a mixture in equimolar quantities were much more effective in inhibiting phosphate sorption than tartrate alone under the same organic ligand concentrations, probably because more sites with high affinity for both the organic ligands were occupied by tartrate and oxalate than by tartrate alone. The efficiency of tartrate alone, or combined with oxalate, in preventing phosphate adsorption was greater for the complex containing a lesser amount of OH-Al species coating the montmorillonite surfaces. This result may be attributable to a greater proportion of sites specific for organic ligands present on AlMt1.6 compared to AlMt6 complex.
Clay Diagenesis in the Sandstone Reservoir of the Ellon Field (Alwyn, North Sea)
Authors: Hassouta Lhoussain , Buatier Martine D. , Potdevin Jean-Luc , Liewig Nicole 
Published: August 2006

AbstractThe nature, composition, and relative abundance of clay minerals in the sandstones of the Brent Group reservoir were studied between 3200–3300 m in a well of the Ellon Field (Alwyn area, North Sea). The sandstones have a heterogeneous calcite cement which occurred during early-diagenesis. Clay diagenesis of the cemented and uncemented sandstones was investigated using optical microscopy, scanning electron microscopy (SEM), X-ray diffraction analyses (XRD), and infrared spectroscopy (IR). The influence of cementation on clay neoformation is demonstrated in this study. Detrital illite and authigenic kaolinite are present in both the calcite-cemented and uncemented sandstones suggesting that kaolinite precipitated before calcite cementation. In the uncemented sandstones, blocky dickite replaces vermiform kaolinite with increasing depth. At 3205 m, authigenic illite begins to replace kaolinite and shows progressive morphological changes (fibrous to lath-shape transition). At 3260 m, all sandstones are not cemented by calcite. Illite is the only clay mineral and shows a platelet morphology.In the cemented samples, vermiform kaolinite is preserved at all depths, suggesting that dickite transformation was inhibited by the presence of the calcite cement. This observation suggests that calcite cement would prevent fluid circulation and dissolution-precipitation reactions.
Effect of Phosphate on the Crystallization of Hematite, Goethite, and Lepidocrocite from Ferrihydrite
Authors: Gálvez Natividad , Barrón Vidal , Torrent José 
Published: August 2006

AbstractWe investigated the crystallization of ferrihydrite prepared by hydrolysis of Fe(NO3)3 solutions containing phosphate. Crystallization was studied at different pH (3–9), temperatures (298, 323, and 373 K), and initial P/Fe atomic ratios for periods to 730 d. Generally, crystallization was inhibited or only poorly crystallized lepidocrocite was formed at P/Fe > 2.5%. Phosphate favored the formation of hematite over goethite at all temperatures for most of the pH and P/Fe ranges investigated. This result is consistent with a model in which phosphate acts as a template for hematite formation, in analogy with other anions, such as oxalate. However, goethite was preferentially formed at alkaline pH and P/Fe > 1%, probably because high phosphate concentration resulted in a large increase in the negative charge of the ferrihydrite particles. This resulted in turn in less aggregation, a process that is known to precede dehydration to hematite. Phosphate greatly influenced the morphology of hematite and goethite. Hematite was often ellipsoidal or spindle-shaped. Twinned goethite crystals with a hematite core were formed at alkaline pH at P/Fe > 1%. Both hematite and goethite particles incorporated phosphate in an occluded form not desorbable by repeated alkali treatments.
Structural Study of Monomethylammonium and Dimethylammonium-Exchanged Vermiculites
Authors: Vahedi-Faridi A. , Guggenheim Stephen 
Published: August 2006

AbstractVermiculite crystals from Santa Olalla, Spain, were first Na exchanged and then intercalated with monomethylammonium (= NH3(CH3)+, MMA) and dimethylammonium (= NH2(CH3)2+, DMA) molecules, respectively, by immersion in 1 M ammonium-chloride solutions at 65°C for 2–3 wk. MMA-and DMA-exchange with vermiculite resulted in crystals with near perfect three-dimensional stacking, suitable for single crystal X-ray diffraction analysis. Unit cell parameters are: a = 5.353(2) Å, b = 9.273(3) Å, c = 11.950(6) Å, and ß = 98.45(4)° for MMA-exchanged vermiculite and a = 5.351(2) Å, b = 9.268(4) Å, c = 12.423(8) Å, and ß = 98.33(5)° for DMA-exchanged vermiculite. Refinement results are R = 0.059 and wR = 0.073 (MMA-exchanged vermiculite) and R = 0.059 and wR = 0.064 (DMA-exchanged vermiculite). The results are based on structures which show substitutional disorder, and thus the presented models are derived from average structures.There are two distinct sites for the MMA molecule in MMA-exchanged vermiculite. One crystallo-graphically unique MMA is oriented such that the N-C axis of the molecule is perpendicular to the basal oxygen plane, with the N ion offset from the center of the interlayer by 1.04 Å. The other MMA is located such that the N ion is at the center of the interlayer between adjacent 2:1 layers, presumably with the N-C axis of the molecule oriented parallel to the basal oxygen plane. This represents the first known occurrence of an organic molecule located exactly between the two adjacent 2:1 layers. Both sites are located between hexagonal cavities of adjacent layers. DMA molecules in DMA-exchanged vermiculite are located such that the N ion is offset from the central plane in the interlayer by 0.95 A. A static model is proposed with two orientations of DMA to produce a DMA “zigzag” orientation of molecules parallel to the (001) plane. The plane defined by the C-N-C atoms in the molecule is perpendicular to the (001) plane. An alternate model is more dynamic, and it involves the rotation of DMA molecules about one C-N axis.Identical starting material was used in previous studies on tetramethylammonium (TMA)-exchanged vermiculite and tetramethylphosphonium (TMP)-exchanged vermiculite. The effect of onium-ion substitutions on the 2:1 layer shows that the tetrahedral rotation angle, α, is significantly smaller for MMA-and DMA-exchanged vermiculite vs. TMA and TMP-exchanged vermiculite. Tetrahedral and octahedral bond distances of the 2:1 layer of the TMA, TMP, MMA, and DMA-exchanged structures may be explained by the location of the organic cation relative to the basal oxygen atom plane and by the differences in the geometries of the organic molecule. Thus, the 2:1 layer is affected by the interlayer molecule, and the 2:1 layer is not a rigid substrate, but interacts significantly with the onium ions.
Hydrothermal Conversion of Trachytic Glass to Zeolite. 3. Monocationic Model Glasses
Authors: De’ Gennaro Maurizio , Langella Alessio , Cappelletti Piergiulio , Colella Carmine 
Published: August 2006

AbstractExperiments on zeolitization were conducted on four synthetic monocationic glasses (Na, K, Ca, or Mg-rich glass) with Si/Al molar ratios of 2.67, similar in acidity to many volcanic glasses of partially zeolitized Italian tuffs. The products of the hydrothermal treatment at 100, 150, and 200°C of single glasses or glass mixtures with deionized H2O or monosaline solutions (NaCl, KCl, CaCl2) were characterized by X-ray diffraction, thermal, microscopic and chemical analyses. Chemical analyses of mother liquors were also performed. Mineral assemblages, containing chabazite, phillipsite, analcime, and K-feldspar, very similar to those found in altered, volcaniclastic alkali-trachytic or trachytic glass deposits were produced. Potassium was essential to chabazite and phillipsite crystallization, although phillipsite was obtained also in Ca-Na mixed systems. Sodium was necessary for analcime formation. Calcium plays only a secondary role in zeolitization, and magnesium does not favor zeolite crystallization but promotes the formation of smectite. Glass composition determines the mineral assemblages obtained and hence in those commonly found in nature.