Crystallization of Fe-P amorphous alloys as studied by the EDXD method

The crystallization of amorphous Fe-P alloys, made by electrodeposition, were studied using energy dispersive X-ray diffraction (EDXD), thermomagnetic, and Mössbauer measurements. EDXD proved to be especially useful, because its very short exposure time enabled us to perform isothermal crystallization measurements with practically continuous control by means of diffraction spectra. By measuring the intensity of the appropriate diffraction lines, the crystallization kinetics of each phase could be recorded simultaneously. At 610 K the crystallization of an Fe_81.2P_18.8 amorphous alloy was found to start within 5 min with the primary crystallization ofα-iron. This step is followed by the eutectic crystallization of the stable phasesα-iron and Fe₃P.     

Extended X-ray absorption fine structure investigation of adsorption and separation phenomena of metal ions in organic resin

Analytical technique using organic resins has already been well-developed, and its applications are employed in various fields; nevertheless, the chemical phenomena occurring inside the resin remain unclear for the most part. In the present study, we apply EXAFS spectroscopy to elucidate the adsorption and separation phenomena of metal ions by organic resin. That is, the chemical species of trivalent lanthanides (Ln(III)) adsorbed in a tertiary pyridine resin from hydrochloric acid and nitric acid solutions have been determined by EXAFS. The results in HCl solutions suggest that Ln(III) ions are partly dehydrated in the resin phase, enabling the pyridine groups of the resin and chloride ions to coordinate to the Ln(III) ions in their primary coordination sphere. On the other hand, Ln(III) ions are tightly coordinated by several nitrate ions in HNO3 solutions and they keep forming the nitrate complex even in the resin phase. The lighter Ln of Nd tends to form an anionic nitrate complex, [Nd(NO3)4.nH2O]-, in the resin phase, while the middle Ln of Sm exists as a cationic nitrate complex, [Sm(NO3)2.nH2O]+, for the most part. On the basis of these EXAFS results, the adsorption and separation mechanisms of the pyridine resin in HCl solutions are interpreted as the direct coordination of pyridine groups to metal ions, while the mechanisms in HNO3 solutions are mainly dominated by the anion-exchange reaction between the protonated pyridine groups and the anionic nitrate complexes of Ln(III). The obtained results demonstrate that the hydration of metal ions weakens, and instead, other complexations are enhanced in the resin phase.     

X-ray absorption fine structure combined with X-ray fluorescence spectrometry. Improvement of spectral resolution at the absorption edges of 9-29 keV

X-ray absorption near-edge structure (XANES) suffers from core-hole lifetime broadening at a higher energy absorption edge, such as Sn K (29 keV, Gamma(K) = 8.49 eV). To overcome this problem, emitted Sn Kalpha1 fluorescence from sample was counted using high-energy-resolution fluorescence spectrometer in the XANES measurements. Experimental energy resolution (5.0 eV) was consistent with theoretical values based on the Rowland configuration of the spectrometer. The absorption edge became steeper compared to conventional spectra. The white-line peak due to Sn(II) species became remarkably sharper and more intense in the Sn Kalpha1-detecting Sn K-edge XANES for Pt-Sn/SiO2. To support the semiclassical theory of resonant Raman scattering for the explanation of observed elimination of lifetime width, more resolved XANES data at Cu K, Pb L3, and Sn K in this work were convoluted (filtered) with a Lorentzian of each core-hole lifetime width. The processed data resembled generally well corresponding XANES spectrum measured in transmission mode. The verification based on ab initio XANES calculations was also performed.     

X射线吸收精细结构谱在材料科学中的应用

简单介绍了X射线吸收精细结构谱的物理基础,数据处理方法,讨论了X射线吸收精细结构谱在元素组成,价态和结构环境方面的分析结果。结果显示,在钠钙硅酸盐平板玻璃中,二价铁离子和三价铁离子同时存在。在Ag-Na离子交换后,二价铁离子被银离子氧化成三价铁离子。当Ti2O3和锐钛矿被分别掺入硼硅酸盐玻璃后,钛离子主要以四价存在,Ti^4＋离子占据五重配位点。在玻璃中同时掺入锐钛矿和还原剂C,诱导三价钛离子生成,三价钛离子占据八面体配位点,使得Ti K边预边峰高度降低。包裹在钠钙硅酸盐玻璃中的银纳米颗粒界面存在张应力,使得银晶格膨胀,银原子存在两种结构环境：Ag-O配位和Ag-Ag配位。孤立银原子的存在,使得最近邻Ag-Ag配位数显著降低。     

Reconstruction procedure for 3D micro X-ray absorption fine structure

A new approach for chemical speciation in stratified systems using 3D Micro-XAFS spectroscopy is developed by combining 3D Micro X-ray Fluorescence Spectroscopy (3D Micro-XRF) and conventional X-ray Absorption Fine Structure Spectroscopy (XAFS). A prominent field of application is stratified materials within which depth-resolved chemical speciation is required. Measurements are collected in fluorescence mode which in general lead to distorted spectra due to absorption effects. Developing a reliable reconstruction algorithm for obtaining undistorted spectra for superficial and in-depth layers is proposed and validated. The developed algorithm calculates the attenuation coefficients of the analyte for the successive layers facilitating a new spectroscopic tool for three-dimensionally resolved nondestructive chemical speciation.     

X-ray absorption fine structure investigations on heat-treated Cr-doped titania thin films

Chromium-doped titanium oxide thin films were investigated in the as-deposited state and after thermal treatment (723 K for 3 h in air). X-ray diffraction data revealed an improvement in film crystallinity induced by the thermal treatment. Extended X-ray absorption fine structure data revealed similar atomic neighboring around Cr atoms in both as-deposited and annealed samples. A lattice contraction of ~ 2% is observed in the annealed samples. The 67% enhancement of the amplitude of the Cr 1 s X-ray absorption fine structure pre-edge peak after thermal treatment, which is a sign of “dipole-forbidden” 1 s → 3 d transitions, suggests strong alteration in the number of Cr 3 d vacancies, in spite of similar Cr local environment in the two kinds of investigated samples. We discuss here the Cr⁺ → Cr⁴⁺ and Cr²⁺ → Cr⁶⁺ changes induced by thermal treatment, and/or the evolution in local structures without inversion center.Refractive index dispersion spectra in the visible wavelength domain allowed us to compute the values of the dispersion energy, the single-oscillator energy and the coordination number of Ti atoms in both as-deposited and annealed samples.     

X-ray absorption near edge structure and extended X-ray absorption fine structure analysis of standards and biological samples containing mixed oxidation states of chromium(III) and chromium(VI)

For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately +/-10% of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 A for the Cr(VI) and Cr(III) in the sample, respectively.     

Near-edge X-ray absorption fine structure spectroscopy as a tool for investigating nanomaterials

We have demonstrated near-edge X-ray absorption fine structure (NEXAFS) spectroscopy as a particularly useful and effective technique for simultaneously probing the surface chemistry, surface molecular orientation, degree of order, and electronic structure of carbon nanotubes and related nanomaterials. Specifically, we employ NEXAFS in the study of single-walled carbon nanotube and multi-walled carbon nanotube powders, films, and arrays, as well as of boron nitride nanotubes. We have focused on the advantages of NEXAFS as an exciting, complementary tool to conventional microscopy and spectroscopy for providing chemical and structural information about nanoscale samples.     

Automated chemical analysis of internally mixed aerosol particles using X-ray spectromicroscopy at the carbon K-edge

We have developed an automated data analysis method for atmospheric particles using scanning transmission X-ray microscopy coupled with near edge X-ray fine structure spectroscopy (STXM/NEXAFS). This method is applied to complex internally mixed submicrometer particles containing organic and inorganic material. Several algorithms were developed to exploit NEXAFS spectral features in the energy range from 278 to 320 eV for quantitative mapping of the spatial distribution of elemental carbon, organic carbon, potassium, and noncarbonaceous elements in particles of mixed composition. This energy range encompasses the carbon K-edge and potassium L2 and L3 edges. STXM/NEXAFS maps of different chemical components were complemented with a subsequent analysis using elemental maps obtained by scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM/EDX). We demonstrate the application of the automated mapping algorithms for data analysis and the statistical classification of particles.     

Extended X-ray absorption fine structure (EXAFS) study of secondary phases in Yb2O3-doped Si3N4 ceramics

Liquid-phase sintered Si3N4 doped with Yb2O3 as a sintering aid was characterized by both transmission electron microscopy and extended X-ray absorption fine structure (EXAFS) measurements. Structural information about the secondary phases was obtained with an emphasis being placed on the evaluation of EXAFS data. Two Si3N4 samples were processed which contained either 5 vol% or 10 vol% Yb2O3 as sintering additive. After sintering, only an amorphous secondary phase was observed in the material doped with 5 vol% Yb2O3. The material with the higher Yb2O3 volume fraction underwent a further heat treatment after the densification, in order to crystallize pockets of the secondary phase. This heat treatment resulted in the formation of Yb2Si2O7 at multi-grain junctions, with however, amorphous phases remaining along the grain and phase boundaries. The EXAFS data obtained from the two doped Si3N4 materials were compared with reference spectra obtained on pure Yb2O3 and synthetic Yb2Si2O7. No residual Yb2O3 was determined in the doped Si3N4 materials, independent of the Yb2O3 volume fraction. Compared to synthetic Yb2Si2O7, the secondary phase formed in the 10 vol% Yb2O3 containing material showed only subtle changes in the EXAFS data. A clear distinction between purely amorphous and a combination of crystalline plus amorphous Yb secondary phases was possible, when both doped Si3N4 materials were compared. However, no distinction between the glass phase present at triple junctions and the amorphous residue along grain/phase boundaries was feasible, since a full numerical data evaluation could not be performed.     

The structure of amorphous polystyrene by X-ray scattering and simple conformational analysis

The X-ray diffraction patterns of amorphous (glassy) polystyrene are interpreted by means of intensity functions calculated from model structures of isotactic polystyrene, incorporating only intra-chain interactions. The range of chain conformations or possible complexions is explained by means of the agreement between theoretical and experimental functions and in relation to published data for the conformational energy of polystyrene in solution. The calculations indicate that in the glassy state, isotactic chains adopt conformations characterized by a large phenyl group separation and a degree of rotational disorder defined about skeletal bonds.     

Formation of nanocrystalline phases during thermal decomposition of amorphous Ni-P alloys by isothermal annealing

The microstructure and the average grain size were investigated by x-ray diffraction and transmission electron microscopy for nanocrystalline (n) Ni-P alloys with 18, 19, and 22 at.% P. A detailed study of the nanocrystalline states obtained along different heat treatment routes has been performed: (1) a-->ni by isothermal annealing of the melt-quenched amorphous (a) Ni-P alloys; (2) ni-->nii by isothermal annealing of the nanocrystalline ni state; (3) ni-->nii by linear heating of the ni state. The heats evolved during the structural transformations were determined by differential scanning calorimetry. From these studies, a scheme of the structural transformations and their energetics was constructed, which also includes previous results on phases obtained by linear heating of the as-quenched amorphous state of the same alloys. Grain boundary energies also have been estimated. In some cases it was necessary to assume a variation of the specific grain boundary energy during the phase transformation to understand the enthalpy and microstructure changes during the different heat treatments.     

Production and characterisation of amorphous alloys at varanasi

Amorphous alloys, more commonly referred to as metallic glasses, represent a striking advance in inorganic materials technology of recent times. While the probable atomic arrangements in noncrystalline alloys have aroused scientific curiosity, their unusual mechanical strength, attractive magnetic properties and remarkable corrosion resistance have excited technological interest. This report describes the progress of research at Varanasi on the following aspects: adaptation, innovation and development of techniques for rapid solidification, study and refinement of structural models, calculation of thermodynamic quantities, evaluation of strength and corrosion resistance and studies of glass to crystal transition. A brief report on the progress in research on metallic glasses of the Rapid Solidification group at the Banaras Hindu University, Varanasi.     

块状非晶态镍磷合金的电化学沉积制备与结构研究

采用电化学沉积方法,在不同的工艺条件下,制备块状非晶态Ni-P合金,并研究了工艺条件和磷含量对块状Ni-P合金结构的影响.结果表明,电化学沉积制备块状非晶态Ni-P合金的方法是可行的,较低的pH值、较高的温度和较低的阴极电流密度更有利于非晶态结构的形成.试验中还发现,磷含量是决定块状Ni-P合金结构的主要因素,随着磷含量的增加,块状Ni-P合金由晶态向非晶态结构转变.     

ZrTiCuNiBe块体非晶合金的热电阻特性及电子结构

为了揭示ZrTiCuNiBe块体非晶合金的物理性能,利用电弧炉熔炼及铜模快速铸造的方法,制备Zr41.2Ti13.8Cu12.5Ni10Be22.5块状非晶合金.通过测量热电阻系数和电子能谱,研究了块体非晶合金的热电阻特性和电子结构.研究表明:电阻率随着温度升高而降低,紧临晶化前未出现电阻率极大现象;块体非晶态合金与晶态纯金属相比,锆的电子结合能不发生变化,其余元素电子结构明显改变.