Neutron diffraction studies of transition metal nitrides

The magnetic structures of Fe₄N and Mn₄N have been redetermined using neutron diffraction. The magnetic form factors, obtained from polarised neutron data have been shown to be different for the face-centred and corner atoms. A qualitative explanation of the structures of Fe₄N and Mn₄N has been provided from the shapes of the magnetic form factors. Since deceased.     

High-pressure synchrotron x-ray diffraction and Raman spectroscopic study of plumbogummite

PbAl_3(PO_4)_2(OH,H_2O)_6,an important environmental mineral,is in-situ studied by synchrotron x-ray diffraction(XRD)and Raman scattering combined with diamond anvil cells(DACs)at pressures up to～11.0 GPa and room temperature.The XRD results indicate that plumbogummite does not undergo a phase transition between 0 GPa and 10.9 GPa.Moreover,the c axis is more compressible than the a axis,revealing its anisotropic behavior.The pressure-volume data are fitted to the third-order Birch-Murnaghan equation of state to yield the plumbogummite bulk modulus K_0 of 68(1)GPa and K'_0 of 6.1.The [PO_4]~(3-)and [HPO_4]~(2-) Raman vibrational modes exhibit scale nearly linearly as a function of pressure.The [PO4]~(3-) stretching modes are generally more sensitive to pressure than the bending modes.The Grüneisen parameters range from -0.07 to 1.19,with an arithmetic mean of approximately 0.39.     

High pressure,high resolution synchrotron x-ray powder diffraction with a position-sensitive detector

Abstract

We report results of high-pressure experiments with a new diamond-anvil cell in a monochromatic, high-resolution x-ray scattering geometry with alinear position-sensitive detector. The experiments make possible the study of factors controlling line widths of diffraction profiles at pressures in the 100 GPa range, and demonstrate the potential for the use of line profile analysis and Rietveld refinement techniques with high-pressure powder diffraction data. Combined data for various materials indicate that relative contributions to linewidths due to particle size, intrinsic material strength, pressure and state of stress in the sample can be resolved. With light rare-gas solids as pressure-transmitting media, measured FWHMs of the order 0.03? 2 θ corresponding to resolution Δd/d of 2.5 × 10^?3 for 2θ～10-15? are reported. Formation of a high pressure phase appears to involve growth of submicron domains, judging from substantially broadened diffraction peaks under quasihydrostatic conditions. Detailed analysis of complex, non-quenchable high-pressure phases will likely require annealing techniques such as thermal cycling at pressure.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

Electron density distribution of LiMn_2O_4 cathode investigated by synchrotron powder x-ray diffraction

Electron density plays an important role in determining the properties of functional materials. Revealing the electron density distribution experimentally in real space can help to tune the properties of materials. Spinel Li Mn2 O4 is one of the most promising cathode candidates because of its high voltage, low cost, and non-toxicity, but suffers severe capacity fading during electrochemical cycling due to the Mn dissolution. Real-space measurement of electron distribution of Li Mn2 O4 experimentally can provide direct evaluation on the strength of Mn–O bond and give an explanation of the structure stability.Here, through high energy synchrotron powder x-ray diffraction(SPXRD), accurate electron density distribution in spinel Li Mn2 O4 has been investigated based on the multipole model. The electron accumulation between Mn and O atoms in deformation density map indicates the shared interaction of Mn–O bond. The quantitative topological analysis at bond critical points shows that the Mn–O bond is relatively weak covalent interaction due to the oxygen loss. These findings suggest that oxygen stoichiometry is the key factor for preventing the Mn dissolution and capacity fading.     

High pressure x-ray diffraction techniques with synchrotron radiation

This article summarizes the developments of experimental techniques for high pressure x-ray diffraction(XRD) in diamond anvil cells(DACs) using synchrotron radiation. Basic principles and experimental methods for various diffraction geometry are described, including powder diffraction, single crystal diffraction, radial diffraction, as well as coupling with laser heating system. Resolution in d-spacing of different diffraction modes is discussed. More recent progress, such as extended application of single crystal diffraction for measurements of multigrain and electron density distribution, timeresolved diffraction with dynamic DAC and development of modulated heating techniques are briefly introduced. The current status of the high pressure beamline at BSRF(Beijing Synchrotron Radiation Facility) and some results are also presented.     

Colloidal monolayer trapped near a charged wall: a synchrotron x-ray diffraction study

Using x-ray diffraction from microfluidic channel arrays, we have determined concentration profiles of charge-stabilized silica colloids (radius 60+/-2 nm) confined between two like-charged dielectric walls at a few hundred nanometer distance. In solutions of very low ionic strength, strongly repulsive Coulomb interactions drive the colloids toward the central region between the walls. The addition of a small quantity of salt ions (0.2 mM) causes a dense colloidal monolayer to be trapped near the walls.     

Neutron powder diffraction study of methane deuterohydrate by the maximum entropy method

To examine the nature of thermal motions of the CH₄ molecules in the methane deuterohydrate (8CH₄·46D₂O), the scattering length density distribution was observed by the maximum entropy method (MEM) using neutron powder diffraction data measured in the temperature range of 7-185 K. We drew the scattering-length density distribution as three dimensional graphic images and used the same isosurface level for all temperatures. The negative scattering length density, corresponding to the H atoms of CH₄, was observed only in the large cage. The positive scattering length density attributed to the C atom of CH₄ was observed at the center of each cage. With an increase in temperature, the negative and positive scattering length densities in the large cage disappear. The positive scattering length density remains at the center of the small cage regardless of temperature. These results strongly indicate that the motions of CH₄ depend on the cage size and geometry.     

High-pressure x-ray diffraction station at the beijing synchrotron radiation facility

Abstract

In the second phase construction of further insertion devices, beamlines and experimental stations at the Beijing Synchrotron Radiation Facility, a dedicated high-pressure x-ray diffraction station will be constructed. We outline the synchrotron radiation source, beamline optics and high-pressure x-ray diffraction apparatus. This facility is planned to operate for users in 1994.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

Physical properties of niobium and tantalum nitrides

The paper gives experimental data on microhardness, electrical and thermal conductivity, Hall coefficient, and thermal emf of tantalum and niobium nitrides. The electronic structures and phase composition of the compounds are discussed on the basis of the results. The changes in properties which occur when the nitrogen content is increased are the same in both systems. At low nitrogen concentrations the electrical conductivity is mainly of the hole type, and at nitrogen concentrations above about 26 at.% it is electronic.     

Neutron powder diffraction of metal-organic frameworks for hydrogen storage

We review recent structural studies that we have undertaken aimed at elucidating the fundamental properties of metal-organic framework materials and their interactions with hydrogen. We have shown that exposing coordinatively unsaturated metal centers can greatly enhance the hydrogen binding energy and that they result in a significant increase of the surface packing density of adsorbed hydrogen molecules on materials’ surface. We will review some of the structural aspects of these materials, especially the adsorbed hydrogen molecule surface packing density in one type of metal-organic framework, MOF-74, which can be packed even denser than that in solid hydrogen.      

Neutron powder diffraction and superconductivity in Ca substituted Bi-0212

In the system Bi-0212 the carrier concentration can be changed by both cation substitution and oxygen content. The crystal structure of Ca substituted material was refined from neutron powder diffraction data for Bi_0.5Sr_1.5Ca_0.5Y_0.5Cu_1.5Fe_0.5O_y. It is shown that extra oxygen is introduced in the cation layers between the double sheets of Cu/O pyramids. In superconducting material the familar dependence ofT _c on the hole carrier concentration is observed. The higherT _c is situated at 75 K.     

Neutron powder diffraction study of the crystal and magnetic structures of Fe2SiS4

The orthorhombic Fe₂SiS₄ (space group no. 62, Pnma) showing olivine-type structure has been studied. Measurements using neutron powder diffraction experiments were performed at 295, 140, 120, 40, 20 and 10 K in order to determine the crystal and magnetic structures of Fe₂SiS₄ at low temperatures. No crystallographic phase transition was observed between 295 and 10 K while two magnetic transitions were found. One transition around 127 K denotes a change from the paramagnetic (P) to an antiferromagnetic (AF) state while at 30 K the appearance of a ferrimagnetic (Fi) state is observed. Different magnetic models are presented. Relations are found between indirect magnetic interactions, on the one hand, and the Fe(4a), Fe(4c) and sulfur positions, on the other hand, and relations between the crystal structure and the magnetic models are given. The neutron powder diffraction results are compared with results, already reported, of Mössbauer and magnetization measurements.     

Neutron powder diffraction and superconductivity in Ca substituted Bi-0212

In the system Bi-0212 the carrier concentration can be changed by both cation substitution and oxygen content. The crystal structure of Ca substituted material was refined from neutron powder diffraction data for Bi_0.5Sr_1.5Ca_0.5Y_0.5Cu_1.5Fe_0.5O_y. It is shown that extra oxygen is introduced in the cation layers between the double sheets of Cu/O pyramids. In superconducting material the familar dependence ofT _c on the hole carrier concentration is observed. The higherT _c is situated at 75 K.     

Strong atomic displacements around nitrogen in tantalum determined by energy-dispersive x-ray diffraction

The nitrogen induced attenuation of Bragg reflections (static Debye-Waller Factor) of tantalum single crystals containing nitrogen has been measured by energy-dispersive x-ray diffraction. N has been dissolved in Ta up to a concentration ofc=3.3% N/Ta. From a detailed study of the concentration andK dependence (K=scattering vector) of the static Debye-Waller Factor exponent 2L we conclude:i) 2L increases linearly with the nitrogen content forc1.8% N/Ta,ii) The displacements of the atomic shells due to N on the octahedral sites areu ₁=0.45 (5) Å,u ₂=(–)0.11 (2) Å.u ₃=0.25 (2) Å,iii) The thermal vibrations of those atoms close to N are changed, due to the strong static displacements that they experience. The unusual strong and extended displacements around N in Ta are in contradiction to calculations where two-force models have been used. We propose arguments that displacements are responsible for the specific site chosen by hydrogen atoms when they are trapped by nitrogen in Ta.     

Neutron diffraction study of liquid iodine

A theory of molecular diffusion in liquids that takes into account the shape of intermolecular potential wells with a cosine potential produces fine spectral detail in the far infrared. The effect of a static external electric field is to shift this panoply of peaks to higher frequency, increase the number of peaks, and shift their individual relative frequencies and intensities.