Pressure apparatus of split-octahedron type for x-ray diffraction studies

An apparatus of split-octahedron type has been developed for the study of x-ray diffraction at high pressure. The apparatus consists of a cylinder, a sphere, and an octahedron, all split up and assembled in a multistaged arrangement. Three ways of splitting the innermost octahedron are utilized in matching the cell geometry to the standard camera method. High pressures in excess of 220 kilobars can be generated in the center of the split octahedron by using a composite mixture of diamond powder and epoxy resin as a pressure-transmitting medium. The pressures required for the semiconductor-to-metal transitions of ZnTe, ZnS, GaAs, and GaP are determined by simultaneously monitoring the electrical resistance of the semiconductors and the lattice parameter of sodium chloride.     

High sensitivity image intensifier-TV detector for x-ray diffraction studies

A sensitive, efficient image intensifier-TV x-ray detector is described that has been optimized for a large class of diffraction studies of biological structures. All of the major components are commercially available. The system is well suited to measuring the intensity of diffraction patterns that are weak, or changing with time. Because there is no count rate limitation, it is particularly well suited for studies utilizing the high fluxes of synchrotron sources.     

Adaption of a diamond anvil cell to an automatic four-circle diffractometer for x-ray diffraction

A diamond anvil high-pressure device for x-ray diffraction on single crystals under hydrostatic pressures up to about 100 kilobars has been adapted to the automatic four-circle x-ray diffractometer Philips PW 1100. The mechanical adaption, the centering procedure, and quick pressure calibration on the diffractometer are described. Hints to improve the peak-to-background ratio of the intensity measurements are given.     

A high-pressure cell for kinetic studies on gas hydrates by powder x-ray diffraction

A new high-pressure-low-temperature cell was developed for in situ observations of gas hydrates by powder x-ray diffraction. The experimental setup allows investigating hydrate formation and dissociation as well as transformation processes between different hydrate crystal structures as a function of pressure, temperature, and feed gas composition. Due to a continuous gas flow, the composition of the gas phase is kept constant during the whole experiment. This is crucial for the formation of mixed hydrates formed from feed gas mixtures that contain one or more components in low concentrations. The pressure cell can be used in a pressure range between 0.1 and 4.0 MPa and a temperature range between 248 and 298 K. First results of time-resolved measurements of a mixed structure II CH(4) + iso-C(4)H(10) hydrate and a structure I CO(2) hydrate are presented.     

A new large radius imaging plate camera for high-resolution and high-throughput synchrotron x-ray powder diffraction by multiexposure method

A new large radius imaging plate diffraction camera for high-resolution and high-throughput synchrotron x-ray powder diffraction by means of multiple exposures has been developed for an insertion device beamline of SPring-8, Japan. The new imaging plate camera consists of a large radius cylindrical shape imaging plate cassette that is 400 mm in length and 954.9 mm in cylinder radius. The cassette is designed to be mounted on the 2 theta arm of the diffractometer of BL15XU in SPring-8. One imaging plate covers 24 degrees and several times of exposure changing the 2 theta-setting angle is necessary to obtain whole powder diffraction data up to a high angle region. One pixel of the imaging plate corresponds to 0.003 degrees in 2 theta when the readout pixel size is 50 microm squares. Separately collected data are translated to 2 theta-intensity format and are connected by comparing the peak and background intensity included in the overlapped area. The exposure time is less than 120 s for most samples and the readout time is about 3 min; thus, the total measurement time for one powder diffraction pattern is less than 20 min. The measurement time is the same order as the continuous 2 theta-scanning method of the third generation synchrotron powder diffractometer. The angular resolution of the new imaging plate camera was evaluated by comparing the full width at half maximum of the 111 reflection of NBS-Si. The observed angular resolution is not so high as a powder diffractometer with a Si or a Ge analyzer monochromator in the third generation synchrotron facility but higher than a powder diffractometer with a Ge analyzer monochromator at a bending magnet beamline of the second generation synchrotron. The Rietveld analysis of NBS-CeO2 was successfully carried out with the data taken by the new imaging plate camera.     

Online in situ x-ray diffraction setup for structural modification studies during swift heavy ion irradiation

The high energy density of electronic excitations due to the impact of swift heavy ions can induce structural modifications in materials. We present an x-ray diffractometer called ALIX ("Analyse en Ligne sur IRRSUD par diffraction de rayons X"), which has been set up at the low-energy beamline (IRRadiation SUD - IRRSUD) of the Grand Acce?le?rateur National d'Ions Lourds facility, to allow the study of structural modification kinetics as a function of the ion fluence. The x-ray setup has been modified and optimized to enable irradiation by swift heavy ions simultaneously to x-ray pattern recording. We present the capability of ALIX to perform simultaneous irradiation-diffraction by using energy discrimination between x-rays from diffraction and from ion-target interaction. To illustrate its potential, results of sequential or simultaneous irradiation-diffraction are presented in this article to show radiation effects on the structural properties of ceramics. Phase transition kinetics have been studied during xenon ion irradiation of polycrystalline MgO and SrTiO(3). We have observed that MgO oxide is radiation-resistant to high electronic excitations, contrary to the high sensitivity of SrTiO(3), which exhibits transition from the crystalline to the amorphous state during irradiation. By interpreting the amorphization kinetics of SrTiO(3), defect overlapping models are discussed as well as latent track characteristics. Together with a transmission electron microscopy study, we conclude that a single impact model describes the phase transition mechanism.     

中子衍射应力谱仪垂直聚焦单色器的优化设计

为提高应力谱仪样品处的中子注量率,对垂直聚焦单色器进行了优化设计.应用蒙特卡罗模拟程序MCSTAS对中子衍射应力谱仪的垂直聚焦Ge(511)单色器进行优化计算,得到了垂直聚焦单色器的高度与单晶片之间的倾角等参数的最佳值.然后,对比分析了在垂直聚焦单色器与平板单色器两种情况下样品处的中子注量率.最后,讨论了单色器起飞角对谱仪分辨率的影响.计算结果表明:单色器尺寸为50 mm×150 mm;垂直单色器在样品台中心位置的中子注入量是平板单色器的4.99倍,表明利用垂直单色器可以显著提高应力谱仪样品处的中子注量率.     

A design of backing seat and gasket assembly in diamond anvil cell for accurate single crystal x-ray diffraction to 5 GPa

We designed a new cell assembly of diamond anvil cells for single crystal x-ray diffraction under pressure and demonstrate the application of the cell to the crystallographic studies for ice VI and ethanol high-pressure (HP) phase at 0.95(5) GPa and 1.95(2) GPa, respectively. The features of the assembly are: (1) the platy anvil and unique-shaped backing seat (called as "Wing seat") allowing the extremely wide opening angle up to ±65°, (2) the PFA-bulk metallic glass composite gasket allowing the easy attenuation correction and less background. Thanks to the designed assembly, the R(int) values after attenuation corrections are fairly good (0.0125 and 0.0460 for ice VI and ethanol HP phase, respectively), and the errors of the refined parameters are satisfactory small even for hydrogen positions, those are comparable to the results which obtained at ambient conditions. The result for ice VI is in excellent agreement with the previous study, and that for ethanol HP phase has remarkable contributions to the revision to its structure; the H12 site, which makes gauche molecules with O1, C2, and C3 sites, may not exist so that only trans conformers are present at least at 1.95(2) GPa. The accurate intensities using the cell assembly allow us to extract the electron density for ethanol HP phase by the maximum entropy method.     

Quick-scanning x-ray absorption spectroscopy system with a servo-motor-driven channel-cut monochromator with a temporal resolution of 10 ms

We have developed a quick-scanning x-ray absorption fine structure (QXAFS) system and installed it at the recently constructed synchrotron radiation beamline BL33XU at the SPring-8. Rapid acquisition of high-quality QXAFS data was realized by combining a servo-motor-driven Si channel-cut monochromator with a tapered undulator. Two tandemly aligned monochromators with channel-cut Si(111) and Si(220) crystals covered energy ranges of 4.0-28.2 keV and 6.6-46.0 keV, respectively. The system allows the users to adjust instantly the energy ranges of scans, the starting angles of oscillations, and the frequencies. The channel-cut crystals are cooled with liquid nitrogen to enable them to withstand the high heat load from the undulator radiation. Deformation of the reflecting planes is reduced by clamping each crystal with two cooling blocks. Performance tests at the Cu K-edge demonstrated sufficiently high data quality for x-ray absorption near-edge structure and extended x-ray absorption fine-structure analyses with temporal resolutions of up to 10 and 25 ms, respectively.     

A clamp-type pressure cell for high energy x-ray diffraction

We present a clamp-type pressure cell for high energy x-ray diffraction. The pressure cell was specifically designed for studies of weak superstructure reflections at low temperatures in transition metal oxides, resulting from, e.g., charge density modulations. Using a photon energy of E=100 keV, the bulk properties of single crystals with a volume of typically 2-5 mm3 can be studied in transmission geometry. To demonstrate the performance of the pressure cell, we present data on the charge stripe order in the high-temperature superconductor La1.875Ba0.125CuO4.     

A laboratory based system for laue micro x-ray diffraction

A laboratory diffraction system capable of illuminating individual grains in a polycrystalline matrix is described. Using a microfocus x-ray source equipped with a tungsten anode and prefigured monocapillary optic, a micro-x-ray diffraction system with a 10 microm beam was developed. The beam profile generated by the ellipsoidal capillary was determined using the "knife edge" approach. Measurement of the capillary performance, indicated a beam divergence of 14 mrad and a useable energy bandpass from 5.5 to 19 keV. Utilizing the polychromatic nature of the incident x-ray beam and application of the Laue indexing software package X-Ray Micro-Diffraction Analysis Software, the orientation and deviatoric strain of single grains in a polycrystalline material can be studied. To highlight the system potential the grain orientation and strain distribution of individual grains in a polycrystalline magnesium alloy (Mg 0.2 wt % Nd) was mapped before and after tensile loading. A basal (0002) orientation was identified in the as-rolled annealed alloy; after tensile loading some grains were observed to undergo an orientation change of 30 degrees with respect to (0002). The applied uniaxial load was measured as an increase in the deviatoric tensile strain parallel to the load axis.     

基于凹面光栅的可调高分辨率单色仪结构设计及波长重复性分析

凹面光栅兼具成像和色散的能力,采用凹面光栅分光的单色仪能够很好实现小型化设计和应用到低于200 nm的真空紫外波段。光谱分辨率和波长重复性是单色仪的重要指标,针对单色仪的光谱分辨率,本文将光栅固有分辨率和由狭缝引起的增宽相结合推导出单色仪的光谱分辨率计算模型,利用自研微动狭缝进行实验验证,单色仪分辨率符合理论模型,极限分辨率优于0.1 nm;针对单色仪的波长重复性,在单色仪光机结构参数转换的基础上对波长重复性影响因素进行分析,推导出单色仪的波长重复性计算模型,利用汞灯作为光源进行波长重复性验证其波长重复性优于0.02 nm符合理论计算模型,验证了光机结构设计的有效性和理论分析的正确性。     

椭圆石英弯晶的积分衍射效率标定

椭圆弯晶谱仪具有测谱宽度大,能谱分辨力高等特点,并在"神光II"激光惯性约束聚变实验研究中得到了很好的应用。利用X射线衍射仪铜(Cu)靶X射线管作为X射线线光源,选取合适厚度滤片,抑制Cu-Kβ线及韧致辐射,测量了Cu-Kα能点处二氧化硅石英椭圆弯晶的积分衍射效率和摆动曲线半高全宽,并开展了针对上述两个重要参数随晶体弯曲曲率半径改变的测试验证,预估了能谱分辨力。结果表明,椭圆弯晶的积分衍射效率和摆动曲线半高全宽对晶体弯曲半径改变敏感,通过提高晶体弯曲度可增强晶体"镶嵌"效果。该结果可为下一步优化设计多用途性椭圆弯晶谱仪,以及完善X射线光谱定量化测量提供了数据支撑。     

New reactor dedicated to in operando studies of model catalysts by means of surface x-ray diffraction and grazing incidence small angle x-ray scattering

A new experimental setup has been developed to enable in situ studies of catalyst surfaces during chemical reactions by means of surface x-ray diffraction (SXRD) and grazing incidence small angle x-ray scattering. The x-ray reactor chamber was designed for both ultrahigh-vacuum (UHV) and reactive gas environments. A laser beam heating of the sample was implemented; the sample temperature reaches 1100 K in UHV and 600 K in the presence of reactive gases. The reactor equipment allows dynamical observations of the surface with various, perfectly mixed gases at controlled partial pressures. It can run in two modes: as a bath reactor in the pressure range of 1-1000 mbars and as a continuous flow cell for pressure lower than 10(-3) mbar. The reactor is connected to an UHV preparation chamber also equipped with low energy electron diffraction and Auger spectroscopy. This setup is thus perfectly well suited to extend in situ studies to more complex surfaces, such as epitaxial films or supported nanoparticles. It offers the possibility to follow the chemically induced changes of the morphology, the structure, the composition, and growth processes of the model catalyst surface during exposure to reactive gases. As an example the Pd(8)Ni(92)(110) surface structure was followed by SXRD under a few millibars of hydrogen and during butadiene hydrogenation while the reaction was monitored by quadrupole mass spectrometry. This experiment evidenced the great sensitivity of the diffracted intensity to the subtle interaction between the surface atoms and the gas molecules.     

High-precision laser-assisted absolute determination of x-ray diffraction angles

A novel technique for absolute wavelength determination in high-precision crystal x-ray spectroscopy recently introduced has been upgraded reaching unprecedented accuracies. The method combines visible laser beams with the Bond method, where Bragg angles (θ and -θ) are determined without any x-ray reference lines. Using flat crystals this technique makes absolute x-ray wavelength measurements feasible even at low x-ray fluxes. The upgraded spectrometer has been used in combination with first experiments on the 1s2p(1)P(1) → 1s(2)(1)S(0) w-line in He-like argon. By resolving a minute curvature of the x-ray lines the accuracy reaches there the best ever reported value of 1.5 ppm. The result is sensitive to predicted second-order QED contributions at the level of two-electron screening and two-photon radiative diagrams and will allow for the first time to benchmark predicted binding energies for He-like ions at this level of precision.     

Spatially resolved high-resolution x-ray spectroscopy of high-current plasma-focus discharges

Soft x-ray emission from a Mather-type plasma-focus device (PF-1000) operated at ～400?kJ was measured. The high density and temperature plasma were generated by the discharge in the deuterium-argon gas mixture in the modified (high-current) plasma-focus configuration. A spherically bent mica crystal spectrograph viewing the axial output of the pinch region was used to measure the x-ray spectra. Spatially resolved spectra including the characteristic x-ray lines of highly ionized Ar and continua were recorded by means of an x-ray film. The x-ray emission of PF-1000 device was studied at different areas of the pinch.     

High-pressure x-ray diffraction studies on the structure of liquid silicate using a Paris-Edinburgh type large volume press

An experimental setup for high-pressure liquid structure studies with synchrotron x-ray diffraction using the Paris-Edinburgh press has been installed at station 16-BM-B (HPCAT) of the Advanced Photon Source, Argonne National Laboratory. By collecting energy-dispersive data with a synchrotron white beam at various 2θ angles, the present device allows us to obtain the structure factor, S(Q), over a wide range of Q ( = 4πsinθ∕λ) owing to the excellent angular accessibility up to 37° in 2θ and high energy photons well beyond 100 keV. We have successfully collected XRD data on silicate (albite, NaAlSi(3)O(8)) liquids with Q up to ～22 A?(-1) and pressure up to 5.3 GPa and temperature 1873 K, and obtained the radial distribution function, G(r), with a reasonable resolution. The T-O bond length (where T = Al, Si), which is a fundamental measure of local structure for aluminous silicate consisting of SiO(n) and AlO(n) polyhedra (tetrahedra at 1 atm condition), was found to be slightly shortened to 1.626 A? compared to that of glass at 1 atm. The T-O-T bound angle, which is the linkage of the above polyhedra, is the most responsible for densification. The T-O-T peak in G(r) splits into two peaks, suggesting a differentiation of the bond angle at high-pressure. The present technical development demonstrates that the Paris-Edinburgh press is suitable for studies of silicate liquids under high-pressure conditions.     

Humidity-controlled preparation of frozen-hydrated biological samples for cryogenic coherent x-ray diffraction microscopy

Coherent x-ray diffraction microscopy (CXDM) has the potential to visualize the structures of micro- to sub-micrometer-sized biological particles, such as cells and organelles, at high resolution. Toward advancing structural studies on the functional states of such particles, here, we developed a system for the preparation of frozen-hydrated biological samples for cryogenic CXDM experiments. The system, which comprised a moist air generator, microscope, micro-injector mounted on a micromanipulator, custom-made sample preparation chamber, and flash-cooling device, allowed for the manipulation of sample particles in the relative humidity range of 20%-94%rh at 293 K to maintain their hydrated and functional states. Here, we report the details of the system and the operation procedure, including its application to the preparation of a frozen-hydrated chloroplast sample. Sample quality was evaluated through a cryogenic CXDM experiment conducted at BL29XUL of SPring-8. Taking the performance of the system and the quality of the sample, the system was suitable to prepare frozen-hydrated biological samples for cryogenic CXDM experiments.     

Normalization schemes for ultrafast x-ray diffraction using a table-top laser-driven plasma source

We present an experimental setup of a laser-driven x-ray plasma source for femtosecond x-ray diffraction. Different normalization schemes accounting for x-ray source intensity fluctuations are discussed in detail. We apply these schemes to measure the temporal evolution of Bragg peak intensities of perovskite superlattices after ultrafast laser excitation.     

Setup for in situ x-ray diffraction study of swift heavy ion irradiated materials

An in situ x-ray diffraction (XRD) setup is designed and installed in the materials science beam line of the Pelletron accelerator at the Inter-University Accelerator Centre for in situ studies of phase change in swift heavy ion irradiated materials. A high vacuum chamber with suitable windows for incident and diffracted X-rays is integrated with the goniometer and the beamline. Indigenously made liquid nitrogen (LN2) temperature sample cooling unit is installed. The snapshots of growth of particles with fluence of 90 MeV Ni ions were recorded using in situ XRD experiment, illustrating the potential of this in situ facility. A thin film of C60 was used to test the sample cooling unit. It shows that the phase of the C60 film transforms from a cubic lattice (at room temperature) to a fcc lattice at around T=255 K.