Volume 60 - Issue 6 - December 2012
Letter to the Editor
Hydraulic Characteristics of Bentonite Cake Fabricated on Cutoff Walls
- Stephan A. Jefferis, Carlos Lam
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 557-560
-
- Article
- Export citation
Article
Changes in Structure, Morphology, Porosity, and Surface Activity of Mesoporous Halloysite Nanotubes Under Heating
- Peng Yuan, Daoyong Tan, Faïza Annabi-Bergaya, Wenchang Yan, Mingde Fan, Dong Liu, Hongping He
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 561-573
-
- Article
- Export citation
-
The objective of the present study was to investigate changes in the structural, textural, and surface properties of tubular halloysite under heating, which are significant in the applications of halloysite as functional materials but have received scant attention in comparison with kaolinite. Samples of a purified halloysite were heated at various temperatures up to 1400°C, and then characterized by X-ray diffraction, electron microscopy, Fourier-transform infrared spectroscopy, thermal analysis, and nitrogen adsorption. The thermal decomposition of halloysite involved three major steps. During dehydroxylation at 500–900°C, the silica and alumina originally in the tetrahedral and octahedral sheets, respectively, were increasingly separated, resulting in a loss of long-range order. Nanosized (5–40 nm) γ-Al2O3 was formed in the second step at 1000–1100°C. The third step was the formation of a mullite-like phase from 1200 to 1400°C and cristobalite at 1400°C. The rough tubular morphology and the mesoporosity of halloysite remained largely intact as long as the heating temperature was <900°C. Calcination at 1000°C led to distortion of the tubular nanoparticles. Calcination at higher temperatures caused further distortion and then destruction of the tubular structure. The formation of hydroxyl groups on the outer surfaces of the tubes during the disconnection and disordering of the original tetrahedral and octahedral sheets was revealed for the first time. These hydroxyl groups were active for grafting modification by an organosilane (γ-aminopropyltriethoxysilane), pointing to some very promising potential uses of halloysite for ceramic materials or as fillers for novel clay-polymer nanocomposites.
Structures of the 2:1 Layers of Pyrophyllite and Talc
- Victor A. Drits, Stephen Guggenheim, Bella B. Zviagina, Toshihiro Kogure
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 574-587
-
- Article
- Export citation
-
To determine the relationships between the symmetry of the overall pyrophyllite and talc structure and the symmetry of individual layers, the geometry and symmetry of each 2:1 layer of pyrophyllite and talc were analyzed. For each, the previously published, refined unit cell may be rotated clockwise by ~60° for comparison to a layer unit cell. In pyrophyllite, the layer unit cell is ideal and shown to be orthogonal with C2/m symmetry. The agreement between the refined atomic coordinates and those calculated for the layer with C2/m symmetry confirms that the symmetry of the pyrophyllite layer is C2/m. The obliquity of the pyrophyllite refined cell results from the layer stacking and the choice of unit cell, but the interlayer stacking sequence does not disturb the layer symmetry. In contrast, talc has an oblique layer cell, without a mirror plane. For the most part, the distortion of the talc 2:1 layer is probably caused by an elongation of unshared O-O lateral edges around M1 that creates a slight corrugation of the octahedral sheet surface. Perhaps of lesser importance, the distortion of the talc layer cell may result from Coulombic interactions between cations of adjacent layers, and these cation-to-cation distances are sufficiently large (~6–7.5 Å) that the weak van der Waals forces that stabilize the stacking are not overcome. Because pyrophyllite has a vacant octahedral site, similar interactions are not present, and this results in a more idealized layer symmetry.
Phyllosilicates consisting of layers with an orthogonal cell and mirror plane (pyrophyllite, kaolinite, sudoite) were shown to have similar stacking faults. In these structures, the 2:1 or 1:1 layers have uniform orientation, and stacking faults occur owing to interstratifications of two alternative interlayer displacements in the same crystal that are related by a mirror plane in the projection on the (001) plane. In talc, stacking faults are associated with layer rotations by ±120°, whereas the lateral displacement between the adjacent tetrahedral sheets across the interlayer region is relatively ordered.
An Electron Paramagnetic Resonance Spectroscopy Investigation of the Retention Mechanisms of Mn and Cu in the Nanopore Channels of Three Zeolite Minerals
- Daniel R. Ferreira, Cristian P. Schulthess, James E. Amonette, Eric D. Walter
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 588-598
-
- Article
- Export citation
-
The adsorption mechanisms of divalent cations in zeolite nanopore channels can vary as a function of their pore dimensions. The nanopore inner-sphere enhancement (NISE) theory predicts that ions may dehydrate inside small nanopore channels in order to adsorb more closely to the mineral surface if the nanopore channel is sufficiently small. The results of an electron paramagnetic resonance (EPR) spectroscopy study of Mn and Cu adsorption on the zeolite minerals zeolite Y (large nanopores), ZSM-5 (intermediate nanopores), and mordenite (small nanopores) are presented. The Cu and Mn cations both adsorbed via an outer-sphere mechanism on zeolite Y based on the similarity between the adsorbed spectra and the aqueous spectra. Conversely, Mn and Cu adsorbed via an inner-sphere mechanism on mordenite based on spectrum asymmetry and peak broadening of the adsorbed spectra. However, Mn adsorbed via an outer-sphere mechanism on ZSM-5, whereas Cu adsorbed on ZSM-5 shows a high degree of surface interaction that indicates that it is adsorbed closer to the mineral surface. Evidence of dehydration and immobility was more readily evident in the spectrum of mordenite than in that of ZSM-5, indicating that Cu was not as close to the surface on ZSM-5 as it was when adsorbed on mordenite. Divalent Mn cations are strongly hydrated and are held strongly only in zeolites with small nanopore channels. Divalent Cu cations are also strongly hydrated, but can dehydrate more easily, presumably due to the Jahn-Teller effect, and are held strongly in zeolites with medium-sized nanopore channels or smaller.
A Molality-Based BET Equation for Modeling the Activity of Water Sorbed on Clay Minerals
- Jacob G. Reynolds, Cliff T. Johnston, Stephen F. Agnew
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 599-609
-
- Article
- Export citation
-
The Brunauer-Emmett-Teller (BET) theory models the effective specific surface area and water content of solids as a function of the relative vapor pressure of water. A modified form of the BET equation has been used successfully to model water activity in concentrated electrolyte solutions as a function of electrolyte concentration. This modified form, referred to here as the Stokes-Robinson BET model, is based on the electrolyte molality rather than on the mass of solute sorbed. The present study evaluates the Stokes-Robinson form of the BET equation to model water-sorption data on two smectites with different layer charges. One smectite was saturated with Na+ and another with Na+, Ca2+, or Mg2+. These results are compared to the Stokes-Robinson BET results of aqueous electrolyte solutions. Given published data on cation exchange capacities and water-vapor sorption isotherms for various clays, the molality of the aqueous phase in contact with the clay surface is calculated and related to water activity. The Stokes-Robinson BET model was found to describe accurately the water activity as a function of cation molality below water activities of 0.5 for the smectites. Good relative agreement was obtained between the number of water binding sites predicted by the model and the experimental data reported in the literature for other smectites. Water molecules were found to have a significantly greater affinity for montmorillonite than electrolyte solutions with the same cation molality as the montmorillonite interlayer. This modified BET approach simplifies water-activity modeling in highly saline environments because the same equation can be used for both the liquid- and mineral-surface phases.
Effects of Hydrothermal Parameters on the Synthesis of Nanocrystalline Zeolite NaY
- Amir Nouri, Mostafa Jafari, Mansour Kazemimoghadam, Toraj Mohammadi
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 610-615
-
- Article
- Export citation
-
Synthesized zeolites are extremely important as industrial minerals and are most commonly prepared using organic templates. Because these organic templates present undesirable environmental hazards, a synthesis method which avoids their use is desirable. The objective of the current study was to develop such a synthesis method. Zeolite NaY was synthesized hydrothermally starting from a mixture of 1.0 Al2O3:10 SiO2:4.6 Na2O:180 H2O molar gel composition, without adding any organic additives. Experiments were carried out to investigate the effects of molar compositions including water content (H2O/SiO2), crystallization conditions including temperature, and time on the crystal size and yield of NaY-type zeolite. The results showed that increasing the crystallization time from 5 to 12 h increased the crystal size, while increasing the crystallization temperature from 80 to 100°C also increased crystallinity. The crystal species of zeolite NaY were characterized by X-ray diffraction, X-ray fluorescence, and scanning electron microscopy analysis. Zeolite NaY crystals in the size range 25–150 nm were synthesized successfully over a period of 8 h at 100°C.
Laboratory-Simulated Diagenesis of Nontronite
- Matthew A. Miller, Andrew S. Madden, Megan Elwood Madden, R. Douglas Elmore
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 616-632
-
- Article
- Export citation
-
Nontronite NAu-1 was exposed to moderate temperature and pressure conditions (250 and 300°C at 100 MPa pressure) in KCl brine to simulate burial diagenetic systems over accelerated time periods appropriate for laboratory experiments. Powder X-ray diffraction and transmission electron microscopy analysis of the coexisting mixed-layer and discrete 10 Å clay reaction products, and inductively coupled plasma-mass spectrometry analysis of the remaining fluids, indicated that the clay retained octahedral Fe and was identified as Fe-celadonite. The release of Fe from smectite during burial diagenesis has been hypothesized as a mechanism for magnetite authigenesis. High Al activity relative to Fe may be critical to the formation of an aluminous illite and any associated authigenic magnetite.
Mineralogy and Geochemistry of the Sedimentary Kaolin Deposits from Sinai, Egypt: Implications for Control by the Source Rocks
- Hassan M. Baioumy, Albert Gilg, Heinrich Taubald
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 633-654
-
- Article
- Export citation
-
Mineralogical and geochemical variations among the Carboniferous and Cretaceous sedimentary kaolin deposits from Sinai provided an opportunity to examine the effect of the source area on compositions of the deposits. The Carboniferous kaolin deposits are mineralogically and geochemically heterogeneous. The Khaboba and Hasbar deposits consist of kaolinite, quartz, anatase, illite, chlorite, zircon, and leucoxene. The shale-normalized rare earth element (REE) patterns of the Khaboba deposit showed a slight LREE over HREE enrichment ((La/Yb)SN = 1.19–1.51) with a MREE depletion (Gd/Gd*SN = 0.51–0.75), while the Hasbar kaolin had a MREE enrichment. The Abu Natash kaolin deposit consisted of kaolinite, anatase, and a little quartz with larger TiO2, Cr, and V and smaller Zr and Nb contents compared to other Carboniferous deposits. The shale-normalized REE patterns of the Abu Natash deposit exhibited a positive Eu anomaly (Eu/Eu*SN = 1.28–1.40) and a MREE enrichment (Gd/Gd*SN = 1.41–2.05). The Cretaceous deposits were relatively homogeneous in terms of mineralogical composition and geochemistry and are composed of kaolinite, quartz, anatase, rutile, zircon, and leucoxene. The Cretaceous kaolin deposits showed mostly flat shale-normalized REE patterns with a variable LREE depletion.
The presence of illite and chlorite, the absence of rutile, large Zr and Nb contents, and the REE patterns suggested a component of weathered low-grade metasediments as a source for the Carboniferous deposits in the Khaboba and Hasbar areas, while the large Ti, Cr, and V, and small quartz contents indicated mafic source rocks for the Abu Natash deposit. The abundance of high-Cr rutile and the absence of illite and chlorite, and large Zr, Ti, Cr, and V contents suggested a mixture of medium- to high-grade metamafic and granitic rocks as source rocks for the Cretaceous kaolin deposits. The occurrence of alkaline rocks in the source of the deposits studied was identified by high-Nb contents and the presence of bastnaesite. The mineralogical and geochemical heterogeneity and lesser maturity of the Carboniferous deposits suggested local sources for each deposit and their deposition in basins close to the sources. The mineralogical and geochemical homogeneity and maturity of the Cretaceous deposits, on the other hand, indicated common sources for all deposits and their deposition in relatively remote basins.
Determination of the Predominant Minerals in Sedimentary Rocks by Chemometric Analysis of Infrared Spectra
- Michal Ritz, Lenka Vaculíková, Eva Plevová, Dalibor Matýsek, Jiří Mališ
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 655-665
-
- Article
- Export citation
-
The objective of the present study was to determine the predominant minerals in sedimentary rocks using Fourier-transform infrared (FTIR) spectroscopy and chemometric analysis. The chemometric analysis was performed on three types of sedimentary rock samples (claystones, clay slates, and sandstones), each with different predominant mineral components. Chemometric models were created to determine the major minerals of the rock samples studied — chlorite, muscovite, albite, and quartz. The FTIR spectra were obtained in transmission mode from pressed pellets of KBr-sample mixtures or by diffuse reflectance from hand-packed mixtures of samples with KBr. Spectral regions measured were 4000-3000 and 1300–400 cm-1, which contained important spectral information for the creation of the chemometric models. Principal component analysis was used in the chemometric method, with calibration models being created by a partial least-squares regression method. The mean relative error, standard error of prediction, and relative standard deviation were calculated for the assessment of accuracy, precision, and reproducibility. The value of the mean relative error was 15–20% for most of the calibration models; the value of the standard error of prediction was up to 6 w/w % for most of the calibration models. The values of the standard relative deviation ranged from ~2 to 8% for calibration models based on diffuse reflectance spectra whereas calibration models based on transmission spectra had values of relative standard deviation of ~15-20%.