bluuebunny/crossref_metadata_2025 huggingface dataset:
Nuclear Magnetic Resonance and X-Ray Photoelectron Spectroscopic Investigation of Lithium Migration in Montmorillonite
Authors: Theng B. K. G. , Hayashi S. , Soma M. , Seyama H.
Published: August 2006

When Li-saturated montmorillonite is heated to 200–300 °C, the Li ions migrate from interlayer positions to sites in the layer structure. However, the identity of these sites has not been clearly established. Here we have investigated the migration of Li ions in montmorillonite, after heat treatment at 250 °C, using chemical and instrumental analyses. The latter include X-ray diffractometry (XRD), 7Linuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Heating causes a large reduction in cation exchange capacity (CEC) and an almost complete loss of interlayer expansion with glycerol as shown by XRD. Static and magic angle spinning (MAS) 7Li-NMR spectroscopy shows that the quadrupole coupling constant of Li increases markedly over the corresponding value for unheated Li-montmorillonite (where Li occupies exchange sites in the interlayer space) and for hectorite (where Li is located in the octahedral sheet). This would indicate that, in heated montmorillonite, Li occupies structural sites of low symmetry which, however, cannot be identified with octahedral vacancies in the layer structure as is commonly assumed. XPS shows that the binding energy (BE) for Li in unheated montmorillonite is comparable to that for other exchangeable cations. Heating broadens the Li 1s band and decreases the BE. The BE for Li in heated montmorillonite is significantly higher than that in either spodumene or lepidolite, where Li is known to occupy octahedral sites. The combined data suggest that heating induces Li to migrate from interlayer sites to ditrigonal cavities in the tetrahedral sheet, rather than into vacancies in the octahedral sheet, of montmorillonite.
NMR Study of Dynamics and Evolution of Guest Molecules in Kaolinite/Dimethyl Sulfoxide Intercalation Compound
Authors: Hayashi Shigenobu
Published: August 2006

Motion of the guest molecules in kaolinite/dimethyl sulfoxide (DMSO) intercalation compounds Al2Si2O5(OH)4∙(CH3)2SO has been studied by means of solid-state nuclear magnetic resonance (NMR) in the temperature range between 300 and 380 K, which is just below the evolution temperature. The 13C magic angle spinning (MAS) NMR spectra show 2 inequivalent methyl carbons: 1 methyl carbon is keyed in the ditrigonal hole of the silicate sheet, while the other is located parallel to the sheet. Above 320 K, the 2 peaks have different intensities, suggesting that the keyed methyl groups from some of the DMSO molecules are released from the hole. The 2H NMR spectra have been measured for kaolinite/DMSO-d6 intercalate. The methyl group of the interlayer DMSO molecule undergoes free rotation around its C3 axis over the temperature range studied. The axis of rotation is fixed at the low temperature (about 160 K), and the methyl group initiates a wobbling motion whose amplitude increases with temperature. The wobbling angles have an anisotropy, estimated from theoretical analysis of the 2H spectral line shapes. The DMSO molecules released from the silicate layer undergo anisotropic rotation of the whole molecule.
Effect of Interaction Between Clay Particles And Fe3+ Ions on Colloidal Properties of Kaolinite Suspensions
Authors: Ma Kunsong , Pierre Alain C.
Published: August 2006

Fine kaolinite suspensions were mixed with unaged or aged FeCl3 in this experiment. The interaction between clay particles and Fe3+ hydrolysis products was studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The proportion of Fe adsorbed was measured and the electrical charge on the clay particles was determined by electrophoresis. The effect of this interaction on flocculation of clay suspensions was investigated in a series of sedimentation tests. The Fe3+ ions acted as counterions when their concentration was low and when unaged FeCl3 solution was used. Otherwise, their hydrolysis complexes acted as a bonding agent between kaolinite particles. The dispersion-flocculation behavior of kaolinite suspensions was found to be in agreement with the theory of Derjaguin, Landau, Verwey and Overbeek (DLVO), as the sedimentation behavior could be predicted from the data of zeta potentials (ζ).
The Effect of Added Polymers on n-Butylammonium Vermiculite Swelling
Authors: Smalley M. V. , Jinnai H. , Hashimoto T. , Koizumi S.
Published: August 2006

A 4-component clay-polymer-salt-water system was studied by neutron scattering. The clay-salt-water system consisted of n-butylammonium vermiculite, n-butylammonium chloride and heavy water, and the volume fraction of clay in the system was held constant, at r = 0.01. Three polymers in the molecular weight range 10,000 to 30,000 were studied, poly(vinyl methyl ether) (PVME), poly (ethylene oxide) (PEO) and poly(acrylic acid) (PAA), at a polymer volume fraction of v = 0.01. The addition of PAA suppressed the clay swelling, irrespective of the salt concentration, c. The addition of the neutral polymers had no effect on the phase transition temperature, Tc, between the gel and tactoid phases of the system, its value remaining at 14 °C for c = 0.1 M and 30 °C for c = 0.01 M. At c = 0.01 M, the neutral polymers also had a negligible effect on the lattice constant d along the swelling axis of the clay colloid, but at c = 0.1 M, the d-value was significantly lower than in the system without added polymer. For a PVME sample of molecular weight 18,000, both d and Tc were measured as a function of ν, for volume fractions between 0 and 0.04. The addition of polymer, up to v = 0.04, had no effect on Tc. However, even for v values as low as 0.001, the vermiculite layers in the gel phase were more parallel and more regularly spaced than in the system without added polymer. In the gel phase, d decreased exponentially as a function of v, from 12 nm at v = 0 to 8 nm at v = 0.04. In the tactoid phase, at T < 14 °C, the d-value in the crystalline regions was equal to 1.94 nm at v = 0 and v = 0.04, showing that the spacing between the vermiculite layers is not affected by the added polymer when they are collapsed by an increase in temperature. The addition of a PVME sample of molecular weight 110,000, at v = 0.001, had no noticeable effect on either d or Tc.
Ca-Rectorite from Sano Mine, Nagano Prefecture, Japan
Authors: Matsuda Toshihiko , Kodama Hideomi , Yang Ann Fook
Published: August 2006

Rectorites containing various amounts of Ca were found at the Sano Mine, Nagano Prefecture, Japan. The Ca content in nonexchangeable form varied from 1.0 to 3.9% CaO. With more than 3.4%, they may be called Ca-rectorite. Chemical data of the most Ca-rich sample showed that Ca was the dominant interlayer cation, and gave a structural formula of (Mg0.16)EX(Ca0.59Na0.27K0.17)FIX[Al3.94Mg0.08 Fe0.07Ti0.01](Si5.85Al2.15)O20(OH)4. This sample is apparently the most Ca-rich rectorite reported to date. The Greene-Kelly test and an intercalation examination by octadecylammonium indicated that the expandable component layers were beidellitic. Assuming the tetrahedral composition of the expandable component layers are similar to the average tetrahedral composition of beidellite of (Si3.6Al0.4), the tetrahedral composition of the mica-like component layers was calculated to be (Si2.25Al1.75). This was closer to a brittle mica (margarite) than to a true mica. Examination of chemical data for several Ca-rectorite samples from different localities, including those from the Sano Mine, showed a trend of increasing Ca content as Al increased and Si decreased. Ca-rectorite exhibited characteristic infrared absorption bands at 480, 670–700 and 900–930 cm−1, which became more intense as Ca content increased. These bands also corresponded to major absorption bands of margarite.
Structure Refinement of Synthetic Deuterated Kaolinite by Rietveld Analysis Using Time-of-flight Neutron Powder Diffraction Data
Authors: Akiba Etsuo , Hayakawa Hiroshi , Hayashi Shigenobu , Miyawaki Ritsuro , Tomura Shinji , Shibasaki Yasuo , Izumi Fujio , Asano Hajime , Kamiyama Takashi
Published: August 2006

The crystal structure of synthetic deuterated kaolinite was refined by Rietveld analysis using time-of-flight (TOF) neutron powder diffraction data. For non-hydrogen atoms, Cl symmetry was assumed. Starting models were tested in which only the direction of O-D vectors was varied. The constraints were introduced to all Al-O, Si-O and O-D bonds. The refinement adopting the former gives Pl(C1), a = 5.169(1) Å, b = 8.960(2) Å, c = 7.410(2) Å, α = 91.26(2)°, ß = 104.99(2)°, γ = 89.93(1)°, Rwp = 3.17%, R1 = 5.78% and S = 1.34 with constraints of l(Al-O)= 1.93 ± 0.05 Å, l(Si-O)= 1.62 ± 0.03 Å and l(D-O) = 0.95 ± 0.15 Å. The inner O-D vector points toward the tetrahedral sheet. All inner-surface O-D groups form H bonding with basal O atoms in the next kaolinite layers. The results agreed with those obtained from natural kaolinite.
Migration of Cations in Copper(II)-Exchanged Montmorillonite and Laponite Upon Heating
Authors: Mosser C. , Michot L. J. , Vlllieras F. , Romeo M.
Published: August 2006

Two clay minerals, a dioctahedral, Na-montmorillonite from Wyoming and a trioctahedral, synthetic Na-laponite, were exchanged by cupric (Cu(II)) ions and subsequently heated at 100 °C intervals up to 500 °C. The resulting materials were analyzed by chemical analysis, X-ray diffraction (XRD), cation exchange capacity (CEC) measurements, combined thermogravimetric and differential thermal analysis (TGA-DTA), infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). Montmorillonite exhibits a well-known Hoffmann-Klemen effect in that, when heated, cupric (Cu) ions migrate into the lacunae of the octahedral sheet, where they compensate the negative charge deficit of the clay layer. In the case of laponite, CEC measurements and spectroscopic measurements reveal that Cu ions migrate into the octahedral sheet where they replace Li and Mg ions. After heating at 200 °C, approximately half the interlayer Cu ions are exchanged. The exchange appears to be 1 Cu for 1 Li, resulting in a slight decrease of the negative charge of the layer. After heating at 300 °C, the remaining Cu ions are exchanged by either 1 Mg or 2 Li, which does not result in any further charge reduction. At 400 °C, some of the extracted Mg remigrates into the structure and exchanges some Li (1 Mg for 2 Li). The final product at 400 or 500 °C is then a Li-laponite with Cu(II) in the octahedral sheet.
Cation Ordering in Synthetic Layered Double Hydroxides
Authors: Vucelic M. , Jones W. , Moggridge G. D.
Published: August 2006

A combined powder X-ray diffraction (XRD) and X-ray absorption (XAS) study of Fe(III) cation ordering within pyroaurite is described. It is concluded that there is no correlation between Fe(III) cation positions over distances of a few tens of angstroms, but that there is a very high level of local ordering, involving the absence of Fe(III)-Fe(III) neighbors. These observations are rationalized in terms of a significant frequency of lattice defects in the form of cation vacancies or Mg for Fe(III) substitutions. These results are expected to be generalizable to other M(II)/M(III) layered double hydroxides (LDHs), but are in contrast to the long-range cation ordering observed in Li/Al LDHs. This raises the interesting possibility of differing properties and stabilities based on the degree of cation ordering.
In SituInfrared Speciation of Adsorbed Carbonate on Aluminum and Iron Oxides
Authors: Su Chunming , Suarez Donald L.
Published: August 2006

Surface adsorption mechanisms of dissolved inorganic carbon species on soil minerals are not well understood. Traditional infrared (IR) study of adsorbed species of inorganic carbon using air-dried samples may not reveal true species in the solid/water interface in suspension. The purpose of this study was to obtain information on interfacial carbonate speciation between solid and aqueous phases. The interaction of bicarbonate and carbonate ions with X-ray amorphous (am) Al and Fe oxides, gibbsite (γ−Al(OH)3) and goethite (α-FeOOH) was examined by electrophoresis andin situattenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The presence of carbonate lowered the electrophoretic mobility and decreased the point of zero charge (PZC) of all minerals, implying specific adsorption. Inner-sphere complexation of bicarbonate and carbonate was supported by a lowering in the anion symmetry due to the interaction with Al and Fe oxide surfaces. Only complexed monodentate carbonate was identified in am-Al(OH)3/aqueous solution at pH 4.1-7.8 when the solid was reacted with either NaHC03or Na2CO3solutions. Am-Al(OH)3was transformed to a crystalline sodium aluminum hydroxy carbonate, dawsonite [NaAl(CO3)(OH)2], and bayerite (α-Al(OH)3) after reacting with 1.0MNa2CO3for 24 h. Gibbsite adsorbed much less carbonate than am-Al(OH)3such that adsorbed carbonate on gibbsite gave weak IR absorption. It is probable that monodentate carbonate is also the complexed species on gibbsite. Evidence suggesting the presence of both surface complexed bicarbonate and carbonate species in the interfacial region of am-Fe(OH)3in suspension and the dependence of their relative distribution on solution pH is shown. Only monodentate carbonate was found in the interfacial region of goethite in 1.0MNaHCO3. A ligand exchange reaction was proposed to describe the interaction of bicarbonate and carbonate with the surface functional groups of Al and Fe oxides.
Formation of Spinel from a Hydrotalcite-Like Compound at Low Temperature: Reaction between Edges of Crystallites
Authors: Hibino Toshiyuki , Tsunashima Atsumu
Published: August 2006

The thermal decomposition behavior of hydrotalcite-like compounds (HTlcs) prepared by reconstruction of calcined HTlcs is described. From the results of X-ray diffraction (XRD), it seems that dicarboxylate intercalates of HTlc calcined at 500 °C are completely reconstructed to Mg-Al-CO3 HTlc by exposure to aqueous Na2CO3. However, the Mg-Al-CO3 HTlc reconstructed under particular conditions yields spinel (MgAl2O4) at 400 °C. This temperature is very low, because Mg-Al-CO3 HTlc that has been reported yields spinel at 900 °C after forming a Mg-Al double oxide. The reconstructed Mg-Al-CO3 HTlc that yields spinel at 400 °C is obtained when the following conditions are fulfilled: the crystallites of the starting dicarboxylate intercalates are coagulated tightly and the calcined HTlcs and reconstructed materials are not ground. The Mg-Al-CO3 HTlc reconstructed under these conditions contains only 55–70% of carbonate anions required by stoichiometry. Therefore, we conclude that the transformation of reconstructed Mg-Al-CO3 HTlc to spinel at 400 °C is the result of a reaction occurring between edges of crystallites.
Properties and Catalytic Activity of Acid-Modified Montmorillonite and Vermiculite
Authors: Ravichandran J. , Sivasankar B.
Published: August 2006

The acidic properties of acid-modified montmorillonite and vermiculite were determined by pyridine and ammonia adsorption to correlate with the alkylating and dehydrating activity of the activated samples. Treatment of the minerals with different concentrations of hydrochloric acid results in the variation of overall acidity and density of acidic sites. Infrared (IR) spectral and differential scanning calorimetric analyses have revealed the presence of Bronsted and Lewis acid sites on the activated samples. The catalytic activity towards the above reaction has been correlated to the acid strength and density of Lewis acid sites. Treatment of montmorillonite with hydrochloric acid in the range of 0.1 and 0.3 M and vermiculite with 0.2 to 0.3 M seemed to be suitable for the conversion of methanol into olefin-rich hydrocarbons. Acid-activated montmorillonite catalyzed the isopropylation of benzene to a maximum extent of 16%, whereas acid-activated vermiculite gave a maximum conversion of only 4%.
Crystal Structure of Tetramethylammonium-Exchanged Vermiculite
Authors: Vahedi-Faridi A. , Guggenheim Stephen
Published: August 2006

Vermiculite crystals from Santa Olalla, Spain, were intercalated with tetramethylammonium (TMA) after Na saturation. The resulting TMA-vermiculite showed near perfect 3-dimensional stacking order with cell parameters of a = 5.353(1) Å, b = 9.273(2) Å, c = 13.616(6) Å, β = 97.68(3)°, and space group C2/m, which indicated a 1M polytype. Single crystal X-ray refinement (R = 0.073, wR = 0.082) located the central atom (N) of the TMA (occupancy at 0.418) and the C atom of 1 methyl group (occupancy at about 0.35). The TMA is offset from the center plane between 2 silicate layers by 1.52 Å, and the methyl group is keyed into the silicate ring of the adjacent silicate layer. This arrangement constrains the positions of the C atoms of the other methyl groups to an opposing plane parallel to the oxygen basal plane. Associated H2O is randomly located between the TMA pillars, and no scattering from these molecules was observed. The calculated height of the TMA molecule is shown to be 4.15 Å.

Steric and electrostatic arguments suggesting that adjacent TMA molecules must alternate apex directions (±c) allow for a description of the local TMA arrangement. This model involves the keying of TMA molecules laterally, thereby explaining why perfect 3-dimensional stacking occurs. The offset of TMA from the center of the interlayer region produces a cavity suitable as an adsorption site for small molecules, such as benzene, which is consistent with the higher than expected adsorption of these molecules in TMA-smectites of high layer charge. This offset also explains the easy expandability of TMA-clays, since only very weak interactions occur between TMA and 1 adjacent silicate layer, thereby allowing molecules to enter the interlayer.
Kaolin Mineralogy of Clays in Paleosol Profiles on the Late-Miocene Sediments in Penghu Islands (Pescadores), Taiwan
Authors: Wang Wei-Min , Yeh Hsueh-Wen , Chen Pei-Yuan , Wang Ming-Kuang
Published: August 2006

Clay mineral compositions from 2 paleosol profiles (Chu-Wan, CW, and Shiao-Men Yu, SMY, profiles) on the late-Miocene sediments in Penghu Islands (Pescadores), Taiwan, are characterized by random X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). By the clay assemblage of the paleosol profile, we want to explore the probable formation mode of the Penghu paleosols.

The paleosol profiles in study are overlain by a layer of basalt flow. However, the clay mineralogy of the 2 paleosols was not altered metasomatically after burial. Results show that 3 distinctive zones of different dominating kaolin-group minerals are apparent in the profiles. In descending order, they are: 1) spheroidal, hollow 7Å-halloysite, 2) platy, irregular-shaped and disordered kaolinite, and 3) platy, irregular-shaped, disordered kaolinite. The relative crystallinity of kaolin minerals of the 3 layers is: layer 2 > layer 3 > layer 1. On the basis of the XRD, TEM analyses and the crystallinity calculations, the distribution of kaolin in Penghu paleosol profiles appears to be unique. Penghu paleosol profiles show systematic change in kaolin crystallinity and polymorphs with depth. Because the clay type is heterogeneous within the profile, this represents that Penghu paleosol profiles were polypedogenic.

The contact between the upper basalt and the paleosol is the erosion surface, so we do not know exactly what the thickness of the original paleosol was. The first layer (about 20 cm) of the profiles appears to be constituents of the original paleosol. It contains high contents of pedogenic (in situ weathering) hematites and 7Å-halloysites, which implies that the local climate of the Penghu Islands at late Miocene was warm and humid. Intense leaching and dry/wet cycle should be the reason for high contents of halloysite (>60%) in the Penghu paleosols. Laterization was the probable pedogenic process for the formation of the paleosols.
Relation of Water and Neutral Organic Compounds in the Interlayers of Mixed Ca/Trimethylphenylammonium-Smectites
Authors: Sheng Guangyao , Boyd Stephen A.
Published: August 2006

Organoclays were prepared by exchanging Ca2+ in a Ca2+-saturated smectite partially or fully with trimethylphenylammonium (TMPA) cations. The mechanistic function of these organoclays as adsorbents for neutral organic compounds in aqueous solution was examined. TMPA cations were found to take a random distribution on the surfaces of mixed Ca/TMPA-smectites. The presence of TMPA, and its random distribution, resulted in water associated with the clay surfaces being held more weakly. Apparently, the interspersing of TMPA and Ca2+ ions prohibits the formation of a stable network of water molecules around Ca2+. Water molecules associated with the siloxane surface in mixed Ca/TMPA-clays are removed during the adsorption of neutral organic compounds from bulk water, leaving only ∼11 strongly held water molecules around each Ca2+, as opposed to ∼58 water molecules in homoionic Ca2+-smectite. These results demonstrate that the amount of water associated with the clay surfaces and interlayers depends on the nature of the exchange cation(s), and not on the amount of available siloxane surface area by itself. We conclude that in TMPA-smectites the TMPA cations function as nonhydrated pillars, and sorption of organic solutes occurs predominantly on the adjacent siloxane surfaces, which are hydrophobic in nature. The water molecules around Ca2+ in mixed Ca/TMPA-smectites obscures some of the siloxane surfaces. This diminishes sorption capacity, in an amount roughly equivalent to the fraction of the CEC occupied by Ca2+, because organic solutes cannot displace the waters of hydration of Ca2+.
An Experimental Study of the Effects of Diagenetic Clay Minerals on Reservoir Sands
Authors: Nadeau Paul H.
Published: August 2006

Despite substantial scientific research efforts, accurate determination of the petrophysical effects of clay minerals on reservoir sands remains problematic. Diagenetic clays such as smectite and illite are of particular interest because of the pronounced effects these clays can have on reservoir quality. Here, results are reported from an experimental study based on the hydrothermal growth of smectite in synthetic sands. The sands contained quartz, dolomite and kaolinite, and were reacted at 175–200°C, for 19–45 d. The hydrothermal reaction can be written as follows:
$$dolomite + kaolinite + quartz \to smectite + calcite + CO2$$ X-ray diffraction (XRD), electron microprobe (EMP) and electron diffraction (ED) analysis show that the synthetic Mg-rich smectite formed is saponite, with a cation exchange capacity (CEC) of about 100 meq/100 g. After reaction, brine permeability reductions of up to 98% were observed from the growth of less than 5% smectite. Scanning electron microscopy (SEM) observations of critical-point-dried reacted samples show that the clay behaves as a pervasive microporous cement with a complex pore-bridging texture affecting most of the available pore space. Morphologically, the clay is similar to naturally occurring diagenetic smectite from Gulf Coast sandstone reservoirs. The delicate clay texture collapses during air-drying and forms pore-lining masses. This phenomenon is similar to that observed for air-dried reservoir samples which contain dispersed diagenetic clays. An air-dried sample, then resaturated with brine, showed a marked increase in permeability. This increase is associated with the irreversible collapse of the clay texture. The experimental results indicate that the growth of diagenetic clay can severely reduce formation permeability, even at very low clay contents. The results also demonstrate the utility of hydrothermal experimental petrophysics for investigating the effects of diagenesis on rock properties.
Low-Temperature Alteration in Tuffs from Yucca Mountain, Nevada
Authors: Banfield Jillian F. , Barker William W.
Published: August 2006

The structure, chemistry and distribution of hydrothermal alteration and weathering products of feldspars and glass in 3 samples of Yucca Mountain tuffs (GSW G4 borehole at a depth of 1531 ft (464 m) and USW GU3 borehole at 1406 ft (426 m) from the Calico Hills Formation and USW G4 at a depth of 272 ft (82.4 m) from the Topobah Springs Member) were examined by high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM). Alteration products are of interest because they may influence the form and distribution of contaminants released from the proposed high-level nuclear waste repository. Samples from the Calico Hills Formation contain alkali-bearing aluminosilicate glass and its alteration products. Zeolites appear to have formed from compositionally similar glass by recrystallization, probably under hydrothermal conditions. Crystals are fibrous and frequently no more than a few tens of nanometers in diameter. Porous aggregates of few-nanometer-diameter, poorly crystalline silica spheres (probably opal C-T) develop adjacent to corroded glass surfaces and zeolite crystals. Finely crystalline Fe-rich smectites coat etched glass surfaces, zeolites and feldspar crystals and occur within opal-like silica aggregates. Microstructures in the clay-dominated coatings and details of smectite-glass interfaces suggest that clays grow in orientations controlled by heterogeneously retreating surfaces and from constituents released at associated glass dissolution sites. The alteration assemblage also includes finely crystalline hematite, goethite, Mn-oxide films and illite formed by alteration of muscovite. The zeolitized sample contains abundant opal-like silica whereas glass in the unzeolitized sample is weathered to smectite-like clays. These differences may be attributed to hydrological and consequent geochemical factors resulting from the higher porosity of zeolitized samples. Exsolved alkali feldspar, which occurs as micron-sized crystals in the Calico Hills Formation and as phenocrysts and in the groundmass of the devitrified Topobah Springs Member, are almost unaltered. Feldspar alteration is confined to cracks and grain boundaries, where minor, poorly crystalline, Fe-bearing aluminosilicate alteration products are developed. In these tuffs, most of the porosity, permeability, high surface area and capacity to affect solution chemistry are associated with products of glass alteration.
XRD Measurement of Mean Thickness, Thickness Distribution and Strain for Illite and Illite-Smectite Crystallites by the Bertaut-Warren-Averbach Technique
Authors: Drits V. A. , Eberl D. D. , Środoń J.
Published: August 2006

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c* direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.
Late-Stage Diagenesis of Illitic Clay Minerals as Seen by Decomposition of X-Ray Diffraction Patterns: Contrasted Behaviors of Sedimentary Basins with Different Burial Histories
Authors: Lanson Bruno , Velde Bruce , Meunier Alain
Published: August 2006

The smectite-to-illite diagenetic transformation has been documented in 5 different sedimentary basins using X-ray diffraction (XRD). Intermediate reaction products coexisting because of the effect of kinetics on this reaction have been characterized using decomposition of XRD patterns and comparison with calculated patterns. The nature and relative abundances of the various subpopulations of particles are shown to vary as a function of the geothermal gradient and of the age of the sediment. In all sedimentary basins that experienced a low steady geothermal gradient the physico-chemical characteristics (coherent scattering domain size [CSDS], junction probabilities) of intermediate mixed-layered illite-smectites (I-S) are similar. However, both the relative abundance and the crystallinity of the end-member illite increase as a function of the age of the sediment.

In basins that have experienced a higher geothermal gradient, the CSDS of the I-S subpopulation is higher for a given illite content, indicating a slightly different reaction pathway. This difference in the characteristics (peak position and width) of elementary peaks may be used to infer the presence of such a high geothermal gradient when no other data are conclusive. In this case the growth of the illite end-member is favored over the growth of intermediate I-S phases even in young basins. Illitic phases formed from the alteration of kaolin minerals exhibit characteristics similar to the reaction products of the smectite-to-illite diagenetic transformation in the case of a high geothermal gradient. In contrast with what is observed in shale diagenesis, the characteristics of the illitic subpopulations describe a continuum with absolutely no gap in between subpopulations. In sandstone reservoirs, the various subpopulations crystallize simultaneously from a kaolin precursor. As a consequence, no kinship is expected between the various subpopulations.
The Transformation of Illite to Muscovite in Pelitic Rocks: Constraints from X-Ray Diffraction
Authors: Gharrabi M. , Velde B. , Sagon J. -P.
Published: August 2006

The boundary between diagenesis and metamorphism most likely involves the change of illite into mica. Observations of this change can be made using decomposed X-ray diffraction (XRD) spectra of illitic clay mineral assemblages in pelitic sedimentary rocks.

XRD analysis of the (003) diffraction peak of diagenetic illites indicates that there are 2 components, one of small coherent diffraction domains and another of larger domain size. Peak width, shape and position define these fractions. The smaller domain size material in diagenetic rocks is highly illitic (>95%) but contains some smectite layers and can be best described by Gaussian shapes. The grains with larger diffracting domains show no expanding layers.

Metamorphic illites (probably muscovites) show no smectite interlayers in any fraction. In the transition from sedimentary and diagenetic to metamorphic illites, new grains of smectite-free illite are formed at the expense of the older minerals. This suggests that the new metamorphic minerals are recrystallized phases. Metamorphism of illites then produces new mica phases.
Physico-Chemical Characterization and Catalytic Properties of Copper-Doped Alumina-Pillared Montmorillonites
Authors: Bahranowski K. , Gąsior M. , Kielski A. , Podobiński J. , Serwicka E. M. , Vartikian L. A. , Wodnicka K.
Published: August 2006

Cu-doped alumina-pillared montmorillonite samples have been prepared and characterized with X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), electron spin resonance (ESR) and inductive coupled plasma atomic emission spectroscopy (ICP AES) techniques. The results show that the catalysts are porous materials with copper species located in the interlayer, present either as isolated Cu2+ ions anchored at alumina pillars or as patches of amorphous CuO. Catalytic tests with hydroxylation of phenol show that the clay samples possess significant activity for dihydroxybenzene (DHB) formation, comparable with the reference TS-1 catalyst. Experiments with changing the substrate dosing indicate that adsorption and activation of phenol molecules is a necessary condition for the reaction to occur.
State and Location of Water Adsorbed on Clay Minerals: Consequences of the Hydration and Swelling-Shrinkage Phenomena
Authors: Prost R. , Koutit T. , Benchara A. , Huard E.
Published: August 2006

The application of the Frenkel-Halsey-Hill (FHH) formalism to the water desorption isotherms obtained for the whole range of the activity of water with the pressure membrane device (0.98 < aw < 1) and with the desiccator (0 < aw < 0.98) gives information concerning the nature and the relative importance of the 2 mechanisms involved in the dehydration—hydration processes: adsorption and capillary condensation. The state and location of water are described in each domain. An equation that gives the thickness t of the film of water adsorbed on the walls of pores versus the activity of water is developed. This t-curve is used to get, from the desorption isotherm, the pore size distribution curve of the studied hydrated materials. Then concepts of surface and fabric of clay pastes are discussed as a function of hydration and a mechanism is proposed to explain swelling and shrinkage of finely divided materials. Three kinds of surfaces, related to the aggregate fabric, are defined as a function of their capacity to adsorb water. Each kind of surface is determined by a specific technique: the total surface area (St) by ethylene glycol adsorption, the external surface area of particles (Ss) by nitrogen adsorption and the external surface area of aggregates (Se) by hydraulic conductivity measurements. As a consequence it is only with completely dispersed clays that swelling is a function of St. With unwell-dispersed clays, water adsorption, which induces swelling, successively occurs on St, Ss and Se surfaces.
Gallium and Chromium Substitution for Aluminum in Synthesized Beidellite
Authors: Brandt Kerstin B. , Kydd Ronald A.
Published: August 2006

The hydrothermal synthesis of Mg-beidellite in which limited amounts of Ga and Cr are clearly shown to be incorporated into nonexchangeable positions in the clay layer framework is reported for the first time. Elemental analyses indicate that, up to at least 15 mole percent, Ga can replace Al virtually completely; Cr incorporation is more difficult. It appears that the Ga that is incorporated into the beidellite is located primarily in the octahedral sheet. Pillaring of the synthesized beidellite by replacing the Mg2+ with large AlO4Al12(OH)24(H2O)127+ ions showed that approximately 5.5 meq Al3+ was required per g of beidellite to achieve complete pillaring. This amount is very similar to that required for montmorillonite, and suggests that the cation exchange capacity (CEC) of the beidellite is about 98 meq/g.
Influence of Pore Fluid Composition on Volume of Sediments in Kaolinite Suspensions
Authors: Chen J. , Anandarajah A.
Published: August 2006

Reported in this paper is a study of the influence of pore fluid composition on sediment volume of kaolinite suspensions. Laboratory tests have been conducted with kaolinite in water with NaCl, CaCl2 and A1C13 of different concentrations and in 10 types of organic liquids of varying values of static dielectric constant. The types of tests performed include regular suspension tests and leaching and cyclic leaching tests on kaolinite sediments. In the leaching tests, sediments formed during the regular suspension tests in water of low salt concentration were subsequently leached with water of high salt concentration. In the cyclic leaching tests, the salt concentration was increased and then decreased. The purpose of the leaching and cyclic leaching tests was to study the change in existing equilibrium fabric caused by subsequent changes in the concentration of salt in pore fluid. Results of the suspension tests indicate that sediment volume of a water suspension decreases with increase in ion concentration and increase in valence of cation. Leaching and cyclic leaching tests indicate that substantial change in salt concentration is required to change the existing fabric. The effect of dielectric constant of pore fluid on sediment volume is somewhat complex. As the dielectric constant increases from 1.9 for heptane to 110 for formamide, sediment volume first decreases, assuming a minimum at 24 for ethanol, increases with a maximum at 80 for water, and decreases again until 110 for formamide. An approximate physico-chemical analysis model is used to interpret some of the data in a quantitative manner. In the analysis model, recently developed theories of double-layer repulsive and van der Waals attractive forces are combined to simulate the behavior of suspensions.
Nanomorphology of Kaolinites: Comparative SEM and AFM Studies
Authors: Zbik Marek , Smart Roger St. C.
Published: August 2006

Nanomorphological structure of well-crystallized Georgia and poorly crystallized North Queensland kaolinite particles have been compared using field emission scanning electron microscopy (SEM) and atomic force microscopy (AFM). In general, there is good agreement in information from the 2 very different imaging techniques. AFM gives more detailed information on step and ledge dimensions, microvalleys and crystallographic orientation of irregularities on basal planes and edges of the crystallites. There are major differences in nanomorphology and surface structure between the 2 kaolin samples with the Georgia kaolin showing 200–500-nm, relatively flat basal planes with some cascade-like step growth 50–100 nm wide. The edges, apparently flat and right-angled in SEM images, appear beveled in AFM images due to artifacts from the aspect ratio of the AFM tip. The North Queensland kaolinite has much more complex surface structure with anhedral crystallites attached to larger particles, high density of steps and nm-scale irregularities (often crystallographically directed). The additional step edge site contribution from the attached crystallites is estimated as a minimum of 6%, giving a total edge contribution above 30% of the kaolinite total surface area. These structures will generate a substantial pH-dependent charge across the surfaces of the North Queensland kaolinite platelets. An idealized, uniform, pH-independent, negatively charged basal plane cannot be assumed from these structures. There is also some evidence, from both SEM and AFM images, of curvature in the thinner, poorly ordered structures of the North Queensland kaolinite particles.
Light Scattering Study on Sol-Gel Transformation of SiO2 Colloid at Extremely High Concentrations
Authors: Xu Yingnian , Koga Yoshikata
Published: August 2006

Ludox SiO2 sols with a reasonably uniform size of 12 nm and in the high concentration of 10 to 40 wt% were transformed to gels by lowering the pH. The process from sol to gel, followed by light scattering, did not show a sign of fractal growth within the length scale of observation (>0 nm). Rather, a density fluctuation due to a dynamic (non-equilibrium) disorder was apparent. Together with the results of viscosity measurements, it was concluded that the process consists of 3 stages: 1) A dynamic (non-equilibrium) density fluctuation grows rapidly. 2) Such density fluctuation acquires some order. 3) The entire bulk loses fluidity and becomes a macroscopic gel.
Pedogenic Formation of High-Charge Beidellite in a Vertisol of Sardinia (Italy)
Authors: Righi Dominique , Terribile Fabio , Petit Sabine
Published: August 2006

The fine clay (<0.1 μm) fraction of a clayey soil (Vertisol) from Sardinia (Italy) was studied by means of X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, cation exchange capacity (CEC) and surface area measurements. Smectites were the dominant clay minerals both in the parent material and the soil horizons. The magnitude and location of the smectites’ layer-charges were analyzed using the Hofmann & Kiemen effect (suppression of the octahedral charge following lithium-saturation and heating). The amount of montmorillonite layers was evaluated by measuring the reduction of total surface area and CEC after suppression of octahedral charges and subsequent collapse of montmorillonite interlayers. Reduction of total surface area and CEC after fixation of K and irreversible collapse of interlayers were used to quantify high-charge layers before and after the suppression of octahedral charges. This allowed us to evaluate the amount of tetrahedral high-charge layers. The smectites in the parent material were montmorillonitic-beidellitic mixed layers and exhibited a small proportion of high-charge layers; in particular, layers with a high tetrahedral charge were a very minor component. In the upper soil horizons, the amount of montmorillonitic layers decreased whereas the amount of smectite layers with a high tetrahedral charge increased. FTIR spectroscopy indicated more Fe for Al substitution in the smectites of the soil horizons than in the smectites of the parent material. The results suggested that octahedral charged smectite layers (montmorillonitic) were altered, whereas high-charge beidellitic layers were formed in this soil environment characterized by rather high pH (>8.0).
Rapid, Accurate Phase Quantification of Clay-Bearing Samples using a Position-Sensitive X-Ray Detector
Authors: Batchelder Meryl , Cressey Gordon
Published: August 2006

The rapid phase quantification method using X-ray diffraction (XRD) with a position-sensitive detector (PSD), outlined by Cressey and Schofield (1996), has been extended to facilitate mineral phase quantification of clay-bearing samples. In addition, correction factors for differences in matrix absorption effects have been calculated and applied. The method now enables mudrock mineralogy to be quantified rapidly and efficiently. Using this approach overcomes many of the problems hitherto associated with the quantitative analysis of clay minerals, in particular the effects of preferred orientation of crystallites and variable sample-area irradiation, that make the task of quantification extremely difficult by conventional Bragg-Brentano scanning diffractometry.
Preparation, Characterization and Electrochemistry of Synthetic Copper Clays
Authors: Xiao Jun , Villemure Gilles
Published: August 2006

Hydrothermal treatment of aqueous mixtures of sodium hydroxide, copper chloride and excess sodium silicate (Si/Cu ≥ 2) at 150 °C produced blue powders. Scanning electron microscopy/energy dispersive X-ray (SEM/EDX) analysis of the products show they all had similar chemical compositions, with Si/Cu ratios of approximately 1.33, the value expected for 2:1 trioctahedral phyllosilicates. Their X-ray diffraction (XRD) patterns were consistent with that of swelling smectite-type clays. Reaction mixtures that did not contain excess Si (Si/Cu ≤ 1.33) did not produce smectites. They gave gray mixtures of amorphous silicates and copper oxides, with some phyllosilicates. A mixture containing a Si/Cu ratio of 5.2 heated at 250 °C under 500 psi of Ar gave a pale blue solid containing a Si/Cu ratio of approximately 1, the value expected for chrysocolla. Transmission electron microscopy (TEM) showed this product had a well-ordered layered structure. Its XRD powder pattern was consistent with that of chrysocolla. This clay did not swell very much on exposure to glycol vapors. Peaks were observed in the cyclic voltam-mogram of electrodes modified with films of these synthetic Cu-clays. They were attributed to electrochemical activity of Cu(II) centers in the lattice of the clays. The presence of these redox active Cu(II) sites greatly improved charge transport in the films. Much larger voltametric waves were observed for [Os(bpy)3]2+ ions (“bpy” = the ligand 2,2′bipyridyl) adsorbed in films of the synthetic Cu-clays than in films of a natural montmorillonite. The larger peak currents obtained corresponded to 10- to 15-fold increases in the fractions of the adsorbed ions that were electrochemically oxidizable in the modified electrodes.
Geochemistry and Paragenesis of Heulandite Cements in a Miocene Marine Fan-Delta System of the Pohang Basin, Republic of Korea
Authors: Noh Jin Hwan
Published: August 2006

In the Pohang area of Korea, heulandite occurs as cements in conglomerate and sandstone of a Miocene marine fan-delta system resting on Eocene dacitic volcanics. Three types of heulandite cements are distinguishable in the fan-delta sediments on the basis of texture, chemical composition and authigenic mineral association. The earliest type I heulandite (Si/(A1+Fe): 3.5–3.8) occurs as microcrystalline (10–30 μm) in situ crystallites that replace volcanic matrix and are intermixed with early-formed smectite. Type II heulandite (Si/(A1+Fe): 3.2–3.6) occurs as medium-grained (30–60 μm) crystal aggregates rimming intergranular cavities. Type III heulandite (Si/(A1+Fe): 3.6–4.1) is the last to form and is a composite phase of heulandite-clinoptiloite, which occurs as unusually coarse (50–200 μm) single-crystal cement associating with late-formed smectite and hematite.

These characteristic heulandite cements were formed by alteration of volcaniclastic sediment during shallow burial (burial temperature: 40–60 °C) and uplift in marine pore fluid diluted by meteoric water. Sr isotope data for heulandite II (87Sr/86Sr: 0.706565–0.706598) and heulandite III (87Sr/86Sr: 0.707347–0.707432) indicate that the pore fluid was progressively mixed with meteoric water during burial and uplift but the Ca in the pore-filling heulandites has been derived mainly from dissolution of carbonate cements. Heulandite III, heulandite-clinoptilolite, was formed with an unusual coarsening and chemical zoning at somewhat diluted and disequilibrium conditions caused by the migration of oxygen-rich meteoric water during or after uplifting.
Structural and Textural Modifications of Palygorskite and Sepiolite Under Acid Treatment
Authors: Myriam M. , Suárez M. , Martín-Pozas J. M.
Published: August 2006

Sepiolite from Mara (Zaragoza, Spain) and palygorskite from Attapulgus (Georgia, USA) were activated by treatment at different concentrations with solutions of boiling HCl under reflux conditions. The natural and treated solids were characterized by mineralogical, chemical and textural analyses.

Acid attack resulted in a progressive dissolution of the octahedral layer of these silicates. Silica contents increased and octahedral cations (Al, Mg and Fe) decreased with the intensity of the acid attack. In both cases, fibrous free silica was obtained.

The sepiolite was destroyed more rapidly than palygorskite under the conditions used because of its magnesic composition and the larger size of its structural microchannels. The maximum increase in specific surface area was obtained for sepiolite at 3 N and for palygorskite at 9 N. Cleaning and disaggregation of the particles and the increase in the number of micropores were responsible for this increase in specific surface area.