X-ray Powder Diffraction Peaks Research Articles

The Use of Fourier Self-Deconvolution to Resolve Overlapping X-Ray Powder Diffraction Peaks

AbstractFourier self-deconvolution has been successfully applied as a means of obtaining semi-quantitative information by resolving the overlapping peaks in X-ray powder diffractograms collected from mixtures of kaolinite and ripidolite. A series of diffractograms were collected from known mixtures of the two minerals. The diffractograms were then processed using Fourier self-deconvolution over a selected range between 23 and 27° 2θ (encompassing the overlapping peaks of kaolinite (002) and ripidolite (004) at 24.85 and 25.13° 2θ, respectively). Once deconvoluted, areas under individual peaks of kaolinite and ripidolite were calculated using curve fitting. The calculated percentage of kaolinite in the mixtures was then plotted versus the true weight percent of kaolinite. The same procedure was conducted on the original diffractograms using only curve fitting without first deconvoluting. A comparison of results shows that, provided the number of peaks are known, both methods give nearly equal results. However, Fourier self-deconvolution, by increasing the resolution, greatly improves the ability to detect overlapping peaks.

Expandable Sepiolite from Ninetyeast Ridge, Indian Ocean

AbstractThe structure of sepiolite from a piston core obtained on Ninetyeast Ridge in the Indian Ocean was modified by exposure to ethylene glycol vapor. With ethylene glycol, the sepiolite Oil X-ray powder diffraction peak expanded from 12.4 to 12.8 Å, and the 130 peak contracted from 4.53 to about 4.45 Å. The cell modification is consistent with concomitant expansion along the c-axis and contraction along the b-axis. This structural distortion is not permanent, however, inasmuch as the sepiolite returned to its original state 6 to 12 hr after it was removed from the ethylene glycol-saturated atmosphere.

New barium tantalum sulphides Part 3. BaTa 2S 5

A new barium tantalum sulphide has been synthesized by the reaction of CS 2 with a mixture of BaCO 3 and Ta 2O 5. The chemical analysis of the compound was performed for 3 components (Ba, Ta and S), and the the chemical composition was found to be BaTa 2S 5. The powder X-ray diffraction peaks were indexable on the basis of a hexagonal cell with lattice constants of a = 3.32A, c = 25.13A. However, the electron diffraction measurements showed that the structure is more complex than that observed by powder X-ray diffraction. The compound indicated metallic behavior and Pauli paramagnetism.

Preparation and Characterization of “PbVS3” a New Composite Layered Compound

Abstract “PbVS3”, a new ternary layered compound, has been obtained. The structure is composed of two kinds of layers of pseudo-tetragonal PbS and pseudo-orthohexagonal VS2. They are alternately stacked together forming composite crystal of LaCrS3 type. All of the powder X-ray diffraction peaks are well indexed on the basis of only a monoclinic PbS subcell.

Influence of Structural and Adsorbed Si on the Transformation of Synthetic Ferrihydrite

AbstractThe transformation of ferrihydrite to goethite and/or hematite, as influenced by the presence of co-precipitated Si, was investigated by infrared spectroscopy (IR), X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). Ferrihydrite samples having Si/Fe molar ratios ranging from 0 to 1 were synthesized by reacting Fe2(SO4)3 with NaOH to an equilibrium pH of 8.2 in the presence of Na2SiO3. The XRD pattern of the Si-free sample contained five distinct but weak peaks, whereas the patterns of ferrihydrite samples containing Si had only two broad bands. With an increase of the Si/Fe molar ratio from 0.10 to 1.0, the 2.54-Å XRD peak shifted to 2.97 Å, and broad IR bands were observed at 990 cm−1 (Si-O stretching region) and 450 cm−1 (silicate bending region). The intensities of both IR bands increased with increasing Si/Fe molar ratio.Ferrihydrite samples were incubated at room temperature in sodium acetate/acetic acid buffer solutions at pH 3, 5, 7, and 10 and in CaCO3 suspension at pH 8.3 for 10 months. Additional samples were incubated at pH 12.5 at 24°, 40°, 60°, and 91°C for 36 hr. Room-temperature incubation of ferrihydrite samples having Si/Fe molar ratios ≥0.1 at pH 3 for one week resulted in the dissolution of Fe and the precipitation of silica gel. Ferrihydrite samples having Si/Fe molar ratios ≤0.05 transformed to poorly crystalline goethite during room-temperature incubation at pH 5. The rate of transformation and the degree of crystallinity of the product were inversely related to Si/Fe molar ratio, and, with heat treatment, were also dependent on incubation temperature. Siliceous ferrihydrite samples having Si/Fe molar ratios ≥0.10 did not transform to phases having greater crystallinity during incubation at either room temperature in buffered solutions at pH ≥7 for as long as 10 months or at pH 12.5 at 91°C for 36 hr. The XRD peak at 2.97 Å did not shift significantly during incubation procedures, providing evidence that the structure of the high-Si ferrihydrite was not significantly altered.

New barium tantalum sulphides: Part 1. Ba 9Ta 4S 20

A new barium tantalum sulphide, Ba 9Ta 4S 20, has been prepared by two methods; reaction of CS 2 gas over a mixture of BaCO 3 and Ta 2O 5, and reaction of the elements in an evacuated silica tube. The powder X-ray diffraction peaks of the compound were indexed on the basis of a hexagonal cell with lattice constants of a=6.959A and c=21.558A. The electron diffraction measurements also supported this result.

Celadonite and its Transformation to Smectite in an Entisol at Red Rock Canyon, Kern County, California

AbstractA green, Lithic Torriorthent soil derived from a celadonite-rich, hydrothermally altered basalt immediately north of the Mojave Desert region in southern California was studied to investigate the fate of the celadonite in a pedogenic weathering environment. Celadonite was found to be disseminated in the highly altered rock matrix with cristobalite, chalcedony, and stilbite. X-ray powder diffraction (XRD) showed the soil material to contain celadonite having a d(060) value of 1.510 Å, indicative of its dioctahedral nature. Very little smectite was detected in the parent material, whereas Fe-rich smectite was found to be abundant in the soil. The Fe-smectite and celadonite were identified as the sole components of the green-colored clay fraction (<2 µm) of all soil horizons. The soil clay showed a single d(060) value of 1.507 Å, indicating that the smectite was also dioctahedral and that its b-dimension was the same as that of the celadonite. Mössbauer spectroscopy showed that the chemical environments of Fe in the rock-matrix celadonite and in the smectite-rich soil clay were also nearly identical. These data strongly suggest a simple transformation of the celadonite to an Fe-rich smectite during soil formation.Supporting evidence for this transformation was obtained by artificial weathering of celadonite, using sodium tetraphenyl boron to extract interlayer K. The intensity of the 001 XRD peak (at 10.1 Å) of celadonite was greatly reduced after the treatment and a peak at 14.4 Å, absent in the pattern of the untreated material, appeared. On glycolation of the sample, this peak expanded to 17.4 Å, similar to the behavior of the soil smectite. The alteration of celadonite to smectite is a simple transformation requiring only the loss of interlayer K. The transformation is apparently possible under present-day conditions, inasmuch as the erosional landscape position, shallow depth, and lack of significant horizonation indicate that the soil is very young.

Estimation of Heavy Atom Content and Distribution in Chlorite Using Corrected X-Ray Powder Diffraction Intensities

AbstractThe heavy atom content and distribution in chlorite were estimated using the relative intensities of basal X-ray powder diffraction (XRD) peaks. For these peaks to be meaningful, however, corrections had to be made for the effects of sample thickness, sample length, and preferred orientation of the mineral grains, all of which are 2θ dependent. The effects of sample thickness were corrected for by a simple formula. The effects of sample length were accounted for by using rectangular samples and by ensuring that the sample intersected the X-ray beam through the range of diffraction angles of interest. Preferred orientation of mineral grains were either measured directly or estimated. Estimated values were quicker and easier to obtain and were within 5% of measured values. A comparison of the compositional parameters of chlorite estimated before correcting for these sample effects with those estimated after the corrections had been applied indicate that the uncorrected values differed from the corrected values by as much as 55% of the latter values. Mounts of a single sample prepared by different filter-membrane peel and porous-plate techniques yielded widely different compositions until the measurements were corrected for sample effects. Analyses in triplicate indicated that the XRD intensity ratio 003/001 is preferred for calculating heavy atom distributions and abundances in chlorite because of the relative strength of the 001 peak.

Comparison of Intercalation Methods for Differentiating Halloysite from Kaolinite

AbstractThe intercalation of formamide, potassium acetate, and hydrazine by halloysite and/or ka-olinite-rich samples, with and without subsequent displacement of the interlayer species by water or glycerol/water, has been investigated. Halloysite, as such, or in mixtures with kaolinite is completely expanded by all the treatments used, thereby enabling halloysite concentrations to be determined from the basal X-ray powder diffraction (XRD) peak ratios of the appropriate complexes. The values so obtained are usually proportional to the abundance of tubes, laths, and spherules in the transmission electron micrographs of the samples. The analysis of kaolin samples (halloysite plus kaolinite) by intercalation methods is less straight forward because a proportion of the kaolinite component in the system may not expand, even after lengthy (≥ 18 days) contact of the sample with the intercalating agent. Only prolonged immersion in hydrazine produces complete or nearly complete expansion of this component. When allowance is made for the presence of non-clay mineral components, kaolin-mineral percentages estimated from XRD peak intensity ratios of the hydrazine complexes generally agree with values derived from differential thermal analysis to within ±10%. Kaolinite in mixtures with halloysite cannot be directly determined by intercalation procedures inasmuch as treatments which result in complex formation with kaolinite also expand halloysite. In such systems, kaolinite can be estimated by difference between the concentration of kaolin minerals and halloysite.

Kinetics of β-phase formation in 1- O-alkylglycerols

The rate of β-phase formation in the ether lipids 1- O-alkylglycerols have been investigated at various temperatures. The concentrations of the phases vs. time in 1- O-hexadecylglycerol (C 16G) were measured using automatic X-ray powder diffraction peak area measurements. In 1- O-decylglycerol (C 16G) the rate was estimated using the heat evolved during the transition. At least two factors are important for the low transition rate. At higher temperatures the rate appears to be limited by a low probability of β crystallite formation (nucleation). As the temperature is decreased, crystallite formation probably increases. A second factor involves an activation of the metastable lattice. The activation process results in a lower rate at decreased temperatures. The two factors together give the highest transition rate at the α ↔ sub-α-phase transition temperature.

Saponite from Near Ballarat, California

AbstractWhite saponite occurs in joints and open fracture zones in metamorphosed dolomitic limestone near Ballarat, California. The saponite appears to have formed by hydrothermal alteration, possibly during Pliocene times. The material shows a 06l X-ray powder diffraction peak at 1.529 Å, A12O3 and MgO contents of about 4.4 and 23.5%, respectively, and a half-cell octahedral atoms summation value of about 2.82. The saponite appears to consist of a single, uniform clay species; the main impurities are fine shards of diopside and tremolite. The infrared and thermal properties of the Ballarat saponite are similar to those of the Allt Ribhein saponite. It has a lower water-holding capacity than montmorillonite and is characterized by lower Atterberg limits and expansion pressures and higher compaction densities. The apparent density of the saponite, 2.865 g/cm3, is greater than that of montmorillonite. This saponite is available from the Source Clays Repository of The Clay Minerals Society.

Estimation of Clay Proportions in Mixtures by X-Ray Diffraction and Computerized Chemical Mass Balance

AbstractAs part of a laboratory study of the hydrothermal alteration of kimberlite, a mass balance procedure has been developed for estimating the relative proportions of synthetic phyllosilicate phases— chlorite, vermiculite, smectite, kaolinite and serpentine—present in reaction products. The procedure is based on a combination of X-ray powder diffraction (XRD) measurements (for phase identification), atomic absorption determinations (for total Si, Al, Fe, and Mg) and published analyses of clay minerals (for stoichiometric deductions). It centers on the computer inversion of a 4 × 4 matrix form of four simultaneous equations representing the mass balance of Si, Al, Fe, and Mg in four chosen minerals and incorporates a systematic routine for selecting from all possible permutations of high and low estimates of the mineral chemical analyses acceptable sets of product stoichiometries and phase proportions consistent with the total metal analyses. To minimize uncertainties and computing time, the program takes account of elemental relationships and water mass balances associated with phyllosilicates. It also accommodates data relevant to poorly crystalline phases for which a range of theoretical type-analyses modeled on aluminum oxyhydroxides and 9–11-Å, 2:1 layered aluminosilicates are employed.The procedure produces reliable trends in phase proportions consistent with the intensities of characteristic XRD peaks of clay minerals present in the analyzed mixture; for example, increases in estimated kaolinite proportions correspond with larger 7-Å (and other) peaks in analyzed samples. A precision of 7–25% has been routinely achievable.

Effect of Chemical Pretreatment on X-Ray Powder Diffraction Characteristics of Clay Minerals Derived from Volcanic Ash

AbstractThe effects of NaOAc removal of carbonates, H2O2 removal of organic materials, and sodium citrate-bicarbonate-dithionite (SCBD) removal of iron oxides upon the X-ray powder diffraction (XRD) characteristics of clay minerals present within weathered volcanic ash deposits were examined. All pretreatments of samples derived from the Ae and Bhf horizons containing volcanic ash resulted in dramatic increases in XRD peak intensities, while the treatment of IIC-horizon samples resulted in subdued XRD peak intensities. Also, the chemical treatments produced an apparent increase in the amount of expandable clay minerals within the Ae horizon, due probably to the hydrolysis and removal of interlayer Al3+ when H2O2 and SCBD were used. Hence, poorly ordered and pedogenically modified vermiculite or vermiculite/montmorillonite interstratifications became “weathered” by H+ attack and Al3+ removal in a manner similar to the natural processes which take place in the acid and eluvial A horizon. In addition, possible XRD peak modification due to the dilution of crystalline clay concentrations by amorphous clay-size material appeared to be subordinate to the laboratory-induced chemical alteration of the weathered clay minerals.

The Influence of Aluminum on Iron Oxides. VII. Substitution of Al for Fe in Synthetic Lepidocrocite

AbstractThe presence of Al hydroxy species in solution during the synthesis of lepidocrocite had been previously found to influence the reaction towards goethite formation. However, under certain conditions, which are not unrealistic in terms of the natural soil environment, this influence does not occur, and Al appears to substitute for Fe(III) in the lepidocrocite structure. This substitution causes the unit-cell dimensions to decrease along the “a” direction and to increase along the “b.” From the differential line broadening of X-ray powder diffraction peaks, the incorporation of Al was found to inhibit crystal growth preferentially in the b-axis direction, the hkl peaks being more broadened the higher the value of k relative to h and l. Al-substituted lepidocrocites have been suggested to occur in soils, and although they can be synthesized under conditions approaching those expected in soils, it is considered that their formation in nature is unlikely or restricted to unusual environments.

The Determination of Feldspars in Mudrocks Using an X-Ray Powder Diffraction Method

AbstractLow albite and maximum microcline were the two feldspars identified in Coal Measures mudrocks. Standard feldspars were then used to spike a mudrock base to construct standard working curves based on X-ray powder diffraction peak areas. Boehmite was added as an internal standard and also to correct for orientation effects. The samples were ignited at 950°C before the addition of the internal standard. This is advantageous for several reasons, but a disadvantage is that albite was found to undergo partial conversion to K-feldspar. The conversion was not total and the original albite content could be determined. This method is an extension of an existing method for quartz and therefore feldspars and quartz can be determined simultaneously.

A Relationship Between Crystallographic Properties of Illite and Chemical Properties of Extractable Organic Matter in Pre-Phanerozoic and Phanerozoic Sediments

AbstractCrystallographic properties of illite and chemical properties of organic matter in various mudstones ranging in age from Archean to Miocene were investigated. The breadth of the (001) X-ray powder diffraction peak of illite correlates significantly with the ratio of aliphatic to condensed-aromatic components and the degree of condensation of aromatic rings of the polar (“humic”) fraction of extract-able bituminous organic matter. The broader the diffraction peak, the less highly condensed and aromatic (i.e. less highly humified) is the organic matter associated with the illite. Breadth of illite diffraction peak and degree of humification of polar organic matter vary in a complex and apparently systematic way through geologic time. All of the three different suites of mudstones investigated (“calcareous,” “non-calcareous,” and “glacial” mudstones) gave similar patterns of secular variation. In addition, the ratio of diffraction intensities for the (002) and (001) reflections (I002/I001) of illite in calcareous mudstones and limestones showed a strong negative correlation with geologic age, indicating that the illites in the older rocks are enriched in magnesium with respect to aluminum.The correlation between crystal structure of illite and degree of humification of its associated organic matter could, by itself, be interpreted as an effect of post-depositional maturation processes, whereby “crystallinity” and degree of humification both increased as functions of heat and pressure. However, the patterns of secular variation suggest that the observed variations are primary, or were pre-determined by primary characteristics of the sample materials. The possibility that the original structure and composition of the organic matter influenced post-depositional changes in the crystallographic properties of sedimentary clay minerals, or post-depositional genesis of clay, would seem to merit consideration. The demonstrated relationship between crystallographic properties of illite and the nature of the “humic” matter constitutes evidence that most of the extractable organic matter is truly indigenous to the rock in which it occurs. The results also imply that molecular structure of extractable organic matter can be used in place of the breadth of the (001) diffraction peak of illite as an index of incipient metamorphism within a single formation or stratigraphic sequence, provided the primary characteristics of the organic matter are nearly the same in all samples. This method would have the advantage of being applicable to all sediments, not just those containing illite (specifically, aluminum-rich illite).The secular variation of the I002/I001 ratio of illite in calcareous sediments is provisionally ascribed to diagenetic processes whereby magnesium is abstracted from pore water and groundwater and is gradually assimilated into the crystal structure.

X-Ray Study on Coexistence of the Cubic and the Tetragonal Phases in NiCr2O4

The broadening of X-ray powder diffraction peak just above Tc, the cubic-to-tetragonal transformation temperature, reported by Kino and Miyahara is re-examined and concluded to originate from coexistence of the two phases due to wide distribution of Tc. This distribution of Tc is found to change by the sample treatments; the sample prepared by firing the original materials for longer time has a smaller distribution of Tc. The thermal hysterisis of the transformation is also studied and compared with the free energy expression by Kataoka and Kanamori.

X-Ray Diffraction Measurements on Metallic and Semiconducting Hexagonal NiS

The crystallographic structure of hexagonal NiS has been determined at temperatures above and below the metal-semiconducting transition. The powder x-ray diffraction peak intensities were used to determine the atom positions in both phases. The symmetry of the unit cell is found to change from $\frac{P{6}_{3}}{mmc({D}_{6h}^{{}^{4}})}$ in the metallic phase to $P{6}_{3}mc({C}_{6v}^{4})$ in the semiconducting phase.