Volume 59 - Issue 6 - December 2011
Article
The Role of the Nature of Pillars in the Structural and Magnetic Properties of Magnetic Pillared Clays
- Cherifa Bachir, Yanhua Lan, Valeriu Mereacre, Annie K. Powell, Christian Bender Koch, Peter G. Weidler
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 547-559
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Pillared clays (PILCs) with magnetic properties have significant potential for application in industry and the environment, but relatively few studies of these types of materials have been carried out. The aim of the present work was to gain insight into the magnetic and structural properties of pillared clays by examining in detail the influence of the calcination temperature and the nature of different pillared clays on these properties.
Magnetic layered systems from different pillared clays were prepared and characterized. Firstly, Ti-, Al-, and Zr-pillared clays (Ti-PILCs, Al-PILCs, and Zr-PILCs, respectively) were produced at different calcination temperatures and then magnetic pillared clays (Ti-M-PILCs, Al-M-PILCs, and Zr-M-PILCs) were prepared at ambient temperature. The synthesis involves a reduction in aqueous solution of the original Fe-exchanged pillared clay using NaBH4. The structural properties of pillared clays and their magnetic forms were investigated using X-ray diffraction, N2 adsorption, cation exchange capacity determination, and X-ray fluorescence (XRF) measurements. The properties of the magnetic pillared clays were investigated by superconducting quantum interference devices and Mössbauer spectroscopy. An evaluation of the data obtained allowed an estimation of the pillared structure in one PILC-model before and after magnetization. The model was determined on the basis of a simple geometric model and experimental data leading to the calculation of a filling factor (FF) which contained information about the number of intercalated pillared layers and the unaffected layers. In the case of Ti precursors, the best calcination temperature was 400°C, which maintained the highest specific surface area and pore volume with magnetic parameters suitable for magnetic application. Similar experiments with Al- and Zr-pillars have been discussed. A correlation between the XRF data, porosity, FF calculation, and magnetic properties led to the conclusion that the sample Al-M-PILC previously calcined at 500°C was the most stable material after the magnetization process. The same examination in the case of Zr materials suggested that the most stable sample had been calcined at 300°C (sample Zr-M-PILC-300).
Powder X-Ray Diffraction Study of the Hydration and Leaching Behavior of Nontronite
- Nicola V. Y. Scarlett, Mark Raven, Ian Madsen
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 560-567
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Nontronite is a significant component of commercially important nickel laterite ores. Its behavior during high-pressure acid leaching of such ores may have an impact upon the efficiency of the process. The present study was conducted in order to further investigate the response of this material during high-pressure acid leaching. In situ synchrotron powder X-ray diffraction data were collected from a number of nontronite samples during hydration and leaching reactions at ambient and elevated temperatures. The present study followed previous high-pressure acid-leaching studies of nontronite where unexpected contraction and expansion behavior of the clay was observed by means of in situ X-ray diffraction. In the earlier studies the data sets only extended to ~20 Å so that when the nontronite expanded to greater than 19.5 Å (hydrated) the main 001 peak was only partially visible in the observed d-spacing range. The aim of the current work was to collect similar in situ diffraction data over a greater d-spacing range to observe more fully the movement of the main 001 reflection in order to better understand the changes taking place. This work was undertaken at the powder diffraction beamline of the Australian Synchrotron which was configured such that an upper d-spacing limit of ~34.5 Å could be achieved. Suggestions arising out of the previous work were confirmed along with additional information from testing of samples from the Source Clays Repository of The ClayMinerals Society. These results also show contradictory behavior of clays with the layer charge distributed over tetrahedral and octahedral sheets.
Removal of Hg(II) from an Aqueous Medium by Adsorption onto Natural and Alkyl-Amine Modified Brazilian Bentonite
- Denis L. Guerra, Emiliano M. Silva, Weber Lara, Adriano C. Batista
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 568-580
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Mercury ion removal from waste-waters has been the subject of extensive research. The aim of the present investigation was to report the incorporation of the n-alkylamine molecules onto a bentonite surface and the capacities of these new chelating moieties on this modified bentonite surface for mercury removal from water. Bentonite collected from the Amazon region, Brazil, was used in an intercalation process with polar n-alkylamine molecules of general formula H3C(CH2)n-NH2 (n = 1 to 4) in 1,2-dichloroethane. The natural and modified bentonite samples were characterized by elemental analysis, Xray diffraction, helium picnometry, mercury porosimetry, and 29Si, 27Al, and 13C nuclear magnetic resonance spectroscopy. Because of the increasing size of the molecules attached to the pendant chains, the metal-adsorption capability of the final chelating materials was measured in each case. The adsorption of Hg(II) on natural and modified bentonites was determined under different conditions. The effects of concentration of Hg(II), contact time, and pH were investigated; batch and dynamic adsorption experiments of Hg(II) were conducted on bentonite samples under various conditions. The ability of these materials to remove Hg(II) from aqueous solution was assessed by means of a series of adsorption isotherms at room temperature and pH 4.0. In order to evaluate the bentonite samples as adsorbents in a dynamic system, a glass column was filled with clay samples (1.0 g each) and fed with 1.8 × 10−4 mol dm−3 Hg(II) at pH 4.0. The energetic effects caused by adsorption of metal cations were determined by means of calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such Hg(II)-nitrogen interactions.
Clay-Mineral Formation in Soils Developed in the Weathering Zone of Pyrite-Bearing Schists: A Case Study from The Abandoned Pyrite Mine in Wieściszowice, Lower Silesia, SW Poland
- Łukasz Uzarowicz, Stefan Skiba, Michał Skiba, Branimir Šegvić
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 581-594
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Intense mineral transformations that produce acid soils from weathering zones of pyritebearing rocks, including alterations of layer silicates, are of critical importance to agricultural and environmental interests in various regions of the world. To date, the transformations of layer silicates in these soils have not been studied in detail. The aim of the present investigation was to examine the weathering pathways controlling processes of clay-mineral formation in acidic soils developed near the abandoned pyrite mine in Wieściszowice (Lower Silesia, SW Poland). A sequence of soils, from weakly developed technogenic soils (located on the mine dumps) to well developed natural soils, was selected. Bulk soil material and separated clay fractions were analyzed using X-ray diffractometry, Fouriertransform infrared spectroscopy, and scanning electron microscopy-energy dispersive spectrometry. The profiles analyzed were developed on pyrite-bearing schists containing trioctahedral Mg,Fe-chlorite and dioctahedral micas (muscovite and paragonite). Because of pyrite weathering, all the soils studied were strongly acidic (pH 2.8–4.4). Inherited chlorite and micas (K- and Na-mica) predominated in the clay fractions of soils developed on the mine dumps, whereas clays from natural soils were rich in pedogenic minerals (i.e. smectite, vermiculite, and mixed-layer minerals containing hydrated interlayers). The formation of both vermiculite and smectite at the expense of chlorite was observed in the soils studied. The transformation probably led to smectite formation via intermediate stages of mixed-layer minerals (i.e. chlorite-vermiculite, chlorite-smectite, and/or vermiculite-smectite). The process of chlorite dissolution took place simultaneously with the transformation. Micas were mainly transformed to smectite and mixedlayer mica-smectite. Neoformation of kaolinite occurring in A horizons of the soils investigated was also documented. Metal-hydroxy interlayers in Bw horizons of well developed soils were found. The process of interlayer development appeared to be pH dependent and took place at pH ⩾4.2. The processes of claymineral formation in soils developed in the weathering zone of a pyrite-bearing schist are similar to those occurring in podzols (Spodosols).
Hydro-Mechanical and Chemical-Mineralogical Analyses of the Bentonite Buffer from A Full-Scale Field Experiment Simulating a High-Level Waste Repository
- Ann Dueck, Lars-Erik Johannesson, Ola Kristensson, Siv Olsson, Anders Sjöland
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 595-607
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The effect of exposure to repository-like conditions on compacted Wyoming bentonite was determined by comparing the hydraulic, mechanical, and mineralogical properties of samples from the bentonite buffer of the Canister Retrieval Test (CRT) with those of reference material. The CRT, located at the Swedish Äspö Hard Rock Laboratory (HRL), was a full-scale field experiment simulating conditions relevant for the Swedish, so called KBS-3, concept for disposal of high-level radioactive waste in crystalline host rock. The compacted bentonite, surrounding a copper canister equipped with heaters, had been subjected to heating at temperatures up to 95°C and hydration by natural Na-Ca-Cl type groundwater for almost 5 y at the time of retrieval.
Under the thermal and hydration gradients that prevailed during the test, sulfate in the bentonite was redistributed and accumulated as anhydrite close to the canister. The major change in the exchangeable cation pool was a loss in Mg in the outer parts of the blocks, suggesting replacement of Mg mainly by Ca along with the hydration with groundwater. Close to the Cu canister, small amounts of Cu were incorporated into the bentonite. A reduction of strain at failure was observed in the innermost part of the bentonite buffer, but no influence was noted on the shear strength. No change in swelling pressure was observed, while a modest decrease in hydraulic conductivity was found for the samples with the highest densities. No coupling was found between these changes in the hydro-mechanical properties and the montmorillonite — the X-ray diffraction characteristics, the cation exchange properties, and the average crystal chemistry of the Na-converted <1 μm fractions provided no evidence of any chemical/structural changes in the montmorillonite after the 5 y hydrothermal test.
Illite From Muloorina, South Australia
- Richard A. Eggleton, John Fitz Gerald
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 608-616
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Illite from Muloorina, just south of Lake Eyre in South Australia, is commonly used as a standard ferric iron-bearing illite which has a cation exchange capacity (CEC) of ~22 meq/100 g, too high a value for this clay to conform to the most recent conclusions about illite composition. The objective of the present study was to reassess the Muloorina illite to determine the reason for this high CEC value. The composition determined by X-ray fluorescence analysis calculated to a cation charge of +22 is K0.68(Mg0.39Al1.02Fe0.543+Fe0.042+)[Si3.59Al0.38Fe0.033+]O10(OH)2. X-ray diffraction of glycolated and heated K-saturated Muloorina illite revealed no evidence of expandable layers. The cell dimensions are a = 5.314(1)Å, b = 9.040(1)Å, c = 10.135(3)Å, and b = 100.97(3)° (3σ in parentheses). Transmission electron microscopy revealed that Muloorina illite has a remarkably fine and uniform particle size in the form of irregularly stepped hexagonal crystals, averaging 60 nm in diameter at their widest, and 35 nm thick, each step being ~7 nm high. At most steps and between many steps defects occur where a 2:1 layer terminates, with a wide interlayer spacing beyond, commonly reaching to the crystal edge. Even though uninterrupted stacking of >10 or so 2:1 layers across one crystal is uncommon, the irregular distribution of the dislocations leaves appreciable structural continuity so that the mean diffracting thickness is of the order of 16 nm. Muloorina illite is not an interstratified illite-smectite, but a mica mineral with low-charge regions associated with terminating 2:1 layer defects. Such regions are wedge shaped at the nm scale and stabilized by the bonding of the illitic remainder of that interlayer. Approximately 17% of the total volume of each Muloorina illite crystallite is occupied by such low-charge 2:1 layers.
Adsorption of Neutral Red Dye from an Aqueous Solution onto Natural Sepiolite Using Full Factorial Design
- Semra Çoruh, Feza Geyikçi, Sermin Elevli
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 617-625
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The main objective of factorial design is to construct an empirical model to understand complex phenomena such as a purification process up to a given level of accuracy. The present study aimed to investigate the adsorption of Neutral Red dye (NR) from an aqueous solution onto sepiolite using 24 full factorial design. The combined effect of initial dye concentration, adsorbent dosage, pH, and particle size on adsorption of the dye was studied. The results were analyzed statistically using the student’s t-test, analysis of variance (ANOVA), and an F-test to define important experimental factors and their relative levels of importance. A regression model which may be used to estimate the removal efficiency of NR without performing any experiments was suggested. The coefficient of determination (R2 = 0.9938) indicated that <1% only of the total variations remain unexplained by the regression model. The experimental factors selected were determined to influence the adsorption process, but their relative importance varied according to the following sequence: pH > adsorbent dosage > particle size > initial concentration. The magnitude of the effects measured in this work can be used as a guide for how to adapt the adsorption process for different process conditions. The results also indicated that natural sepiolite is a suitable adsorbent for NR.
Polymer Model of Zeolite Thermochemical Stability
- Randolph Arthur, Hiroshi Sasamoto, Colin Walker, Mikazu Yui
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 626-639
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The polymer model provides a relatively simple and robust basis for estimating the standard Gibbs free energies of formation (ΔGfo) and standard enthalpies of formation (ΔHfo) of clay minerals and other aluminosilicates with an accuracy that is comparable to or better than can be obtained using alternative techniques. The model developed in the present study for zeolites entailed the selection of internally consistent standard thermodynamic properties for model components, calibration of adjustable model parameters using a linear regression technique constrained by ΔGfo and ΔHfo values retrieved from calorimetric, solubility, and phase-equilibrium experiments, and assessments of model accuracy based on comparisons of predicted values with experimental counterparts not included in the calibration dataset. The ΔGfo and ΔHfo predictions were found to average within ±0.2% and ±0.3%, respectively, of experimental values at 298.15 K and 1 bar. The latter result is comparable to the good accuracy that has been obtained by others using a more rigorous electronegativity-based model for ΔHfo that accounts explicitly for differences in zeolite structure based on differences in framework density and unit-cell volume. This observation is consistent with recent calorimetric studies indicating that enthalpies of transition from quartz to various pure-silica zeolite frameworks (zeosils) are small and only weakly dependent on framework type, and suggests that the effects on ΔHfo of differences in framework topology can be ignored for estimation purposes without incurring a significant loss of accuracy. The relative simplicity of the polymer model, together with its applicability to both zeolites and clay minerals, is based on a common set of experimentally determined and internally consistent thermodynamic properties for model components. These attributes are particularly well suited for studies of the effects of water-rock-barrier interactions on the long-term safety of geologic repositories for high-level nuclear waste (HLW).
Hydration Behavior of MX80 Bentonite in a Confined-Volume System: Implications for Backfill Design
- Julia N. Perdrial, Laurence N. Warr
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 640-653
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Bentonites are considered suitable backfill material for planned underground nuclear-waste repositories because of an inherent capacity to self-seal and retain contaminants when hydrated. Barrier effectiveness, however, depends on the physical properties of bentonite after placement in a repository site, where hydration state and bulk density can vary. The objective of the present study was to investigate commercial bentonite MX80 hydration rates and mechanisms during water infiltration into dry, moist, and wet samples using the ‘wet-cell’ X-ray diffraction technique. During experimentation, water enters a small flow-through cell and induces swelling within a confined reaction volume, analogous to clay barriers in excavated underground sites. Results demonstrated the importance of using dry, well compacted (>1.4 g/cm3) bentonite, which became saturated slowly (<2.0 ×10−9 m/s) with minimal water in noninterlayer sites (external-surface sites, or within pores). The significant degree of interlayer expansion dominated by the formation of two and eventually three water layers developed as hydration clusters with greater probabilities for the same thickness to lie in adjacent interlayer sites. The relatively thicker particles and the less accessible surface area of hydrated, initially dry bentonite probably resulted in less pore-controlled diffusion, but also less potential radionuclide adsorption by surface complexation. Moist MX80 had the greatest water uptake, the smallest (1.23 g/cm3) dry bulk density, and the greatest proportion of water in pores and on external surfaces. Water that initially accumulated in pore spaces subsequently acted as a reservoir for interlayer hydration and probable gel formation in trapped voids, which is expected to occur in more loosely filled gaps within an excavated repository.