A synchrotron X-ray diffraction deconvolution method for the measurement of residual stress in thermal barrier coatings as a function of depth.

The average residual stress distribution as a function of depth in an air plasma-sprayed yttria stabilized zirconia top coat used in thermal barrier coating (TBC) systems was measured using synchrotron radiation X-ray diffraction in reflection geometry on station I15 at Diamond Light Source, UK, employing a series of incidence angles. The stress values were calculated from data deconvoluted from diffraction patterns collected at increasing depths. The stress was found to be compressive through the thickness of the TBC and a fluctuation in the trend of the stress profile was indicated in some samples. Typically this fluctuation was observed to increase from the surface to the middle of the coating, decrease a little and then increase again towards the interface. The stress at the interface region was observed to be around 300 MPa, which agrees well with the reported values. The trend of the observed residual stress was found to be related to the crack distribution in the samples, in particular a large crack propagating from the middle of the coating. The method shows promise for the development of a nondestructive test for as-manufactured samples.

3D chemical imaging in the laboratory by hyperspectral X-ray computed tomography.

We report the development of laboratory based hyperspectral X-ray computed tomography which allows the internal elemental chemistry of an object to be reconstructed and visualised in three dimensions. The method employs a spectroscopic X-ray imaging detector with sufficient energy resolution to distinguish individual elemental absorption edges. Elemental distributions can then be made by K-edge subtraction, or alternatively by voxel-wise spectral fitting to give relative atomic concentrations. We demonstrate its application to two material systems: studying the distribution of catalyst material on porous substrates for industrial scale chemical processing; and mapping of minerals and inclusion phases inside a mineralised ore sample. The method makes use of a standard laboratory X-ray source with measurement times similar to that required for conventional computed tomography.

Real time chemical imaging of a working catalytic membrane reactor during oxidative coupling of methane.

We report the results from an operando XRD-CT study of a working catalytic membrane reactor for the oxidative coupling of methane. These results reveal the importance of the evolving solid state chemistry during catalytic reaction, particularly the chemical interaction between the catalyst and the oxygen transport membrane.

Pixellated Cd(Zn)Te high-energy X-ray instrument.

We have developed a pixellated high energy X-ray detector instrument to be used in a variety of imaging applications. The instrument consists of either a Cadmium Zinc Telluride or Cadmium Telluride (Cd(Zn)Te) detector bump-bonded to a large area ASIC and packaged with a high performance data acquisition system. The 80 by 80 pixels each of 250 µm by 250 µm give better than 1 keV FWHM energy resolution at 59.5 keV and 1.5 keV FWHM at 141 keV, at the same time providing a high speed imaging performance. This system uses a relatively simple wire-bonded interconnection scheme but this is being upgraded to allow multiple modules to be used with very small dead space. The readout system and the novel interconnect technology is described and how the system is performing in several target applications.

X-ray colour imaging.

A prototype X-ray colour imaging system has been assembled using the principle of tomographic energy-dispersive diffraction imaging (TEDDI). The new system has been tested using samples of nylon-6, aluminium powder and deer antler bone. Non-destructive three-dimensional images of the test objects have been reconstructed on a 300 microm scale with an associated diffraction pattern at each voxel. In addition, the lattice parameters of the polycrystalline material present in the sampled voxels have been determined using full pattern refinement methods. The use of multiple diffracted parallel colour X-ray beams has allowed simultaneous spatially resolved data collection across a plane of the sample. This has simplified the sample scan motion and has improved data collection times by a factor scaling with the number of detector pixels. The TEDDI method is currently limited to thin samples (approx. 1-2mm) with light atoms owing to the very low detection efficiency of the silicon detector at X-ray energies above 25 keV. We describe how these difficulties can be removed by using semiconductor detectors made from heavier atomic material.

Application notes on the use of softer X-rays for anomalous powder diffraction.

An in-vacuum diffractometer has been modified to collect powder diffraction data from a sample of promazine hydrochloride. Strong anomalous contrast has been observed at, or close to, the sulphur edge. Based on the data collected, a bespoke diffractometer has been designed that, together with minor changes to the geometry of the experiment, will enable the routine collection of powder data at absorption edges below 5.5 keV.

The new materials processing beamline at the SRS Daresbury, MPW6.2.

A new beamline (MPW6.2) has been designed and built for the study of materials during processing where three synchrotron techniques, SAXS, WAXS and XAS, are available simultaneously. It has been demonstrated that Rietveld refinable data can be collected from silicon SRM 640b over a 60 degrees range in a time scale of 1 s. The data have been refined to a chi(2) of 2.4, the peaks fitting best to a Pearson VII function or with fundamental parameters. The peak halfwidths have been found to be approximately constant at 0.06 degrees over a 120 degrees angular range indicating that the instrumental resolution function has matched its design specification. A quantitative comparison of data sets collected on the same isotactic polypropylene system on MPW6.2 and DUBBLE at the ESRF shows a 17% improvement in angular resolution and a 1.8 improvement in peak-to-background ratio with the RAPID2 system; the ESRF data vary more smoothly across detector channels. The time-dependent wide-angle XRD was tested by comparing a hydration reaction of gypsum-bassanite-anhydrite with energy-dispersive data collected on the same system on the same time scale. Three sample data sets from the reaction were selected for analysis and gave an average chi(2) of 3.8. The Rietveld-refined lattice parameters are a good match with published values and the corresponding errors show a mean value of 3.3 x 10(-4). The data have also been analysed by the Pawley decomposition phase-modelling technique demonstrating the ability of the station to quickly and accurately identify new phases. The combined SAXS/WAXS capability of the station was tested with the crystallization and spinodal decomposition of a very dilute polymer system. Our measurements show that the crystallization of a high-density co-polymer (E76B38) as low as 0.5% by weight can be observed in solution in hexane. The WAXS and SAXS data sets were collected on the same time scale. The SAXS detector was calibrated using a collagen sample that gave 30 orders of diffraction in 1 s of data collection. The combined XRD and XAS measurement capability of the station was tested by observing the collapse and re-crystallization of zinc-exchanged zeolite A (zeolite Zn/Na-A). Previous studies of this material on station 9.3 at the SRS were compared with those from the new station. A time improvement of 38 was observed with better quality counting statistics. The improved angular resolution from the WAXS detector enabled new peaks to be identified.

New high- and low-temperature apparatus for synchrotron polycrystalline X-ray diffraction.

A high-temperature furnace with an induction heater coil and a cryogenic system based on closed-cycle refrigeration have been assembled to enhance the non-ambient powder diffraction facilities at the Synchrotron Radiation Source, Daresbury Laboratory. The commissioning of the high- and low-temperature devices on the high-resolution powder diffractometer of Station 2.3 is described. The combined temperature range provided by the furnace/cryostat is 10-1500 K. Results from Fe and NH(4)Br powder samples are presented to demonstrate the operation of the apparatus. The developments presented in this paper are applicable to a wide range of other experiments and diffraction geometries.

Station 16.3: a high-resolution single-crystal diffraction facility at the SRS, Daresbury.

SRS station 16.3 is now a fully scheduled user facility for high-resolution and high-energy single-crystal X-ray diffraction. It is based on a large three-axis diffractometer, designed and constructed at Daresbury for a wide range of physics and materials science applications. Served by wiggler 16 (a 6 T superconducting wavelength-shifter), the station has access to a broad spectrum of photon energies, extending to over 50 keV, and is designed for simple polarization-state tuning by motorized height adjustment of all optical components. This paper outlines the key design features and some of the science projects carried out during the first year of operation.

A New High-Flux Chemical and Materials Crystallography Station at the SRS Daresbury. 1. Design, Construction and Test Results.

A new single-crystal diffraction facility has been constructed on beamline 9 of the SRS at Daresbury Laboratory for the study of structural problems in chemistry and materials science. The station utilizes up to 3.8 mrad horizontally from the 5 T wiggler magnet which can be focused horizontally and vertically. The horizontal focusing is provided by a choice of gallium-cooled triangular bent Si (111) or Si (220) monochromators, giving a wavelength range from 0.3 to 1.5 A. Focusing in the vertical plane is achieved by a cylindrically bent zerodur mirror with a 300 mum-thick palladium coating. The station is equipped with a modified Enraf-Nonius CAD-4 four-circle diffractometer and a Siemens SMART CCD area-detector system. High- and low-temperature facilities are available to cover the temperature range from about 80 to 1000 K. Early results on test compounds without optimization of the beam optics demonstrate that excellent refined structures can be obtained from samples giving diffraction patterns too weak to be measured with conventional laboratory X-ray sources, fulfilling a major objective of the project.

High-Pressure Cell for the Study of In-Situ Hydrates Using Energy-Dispersive X-ray Diffraction.

A high-pressure low-temperature cell has been developed for in-situ diffraction studies of carbon dioxide and propane gas hydrate crystallization. The design and implementation of the cell, which can operate up to 3.5 MPa and down to 253 K, are described. Using synchrotron energy-dispersive X-ray diffraction, the first growth of the hydrate crystals from solution has been successfully observed. The lattice parameters of the hydrate crystals were found to be 11.927 (2) and 17.196 (2) A, respectively.