Graham Bushnell-Wye

A new high-flux chemical and materials crystallography station at the SRS Daresbury. 1. Design, construction and test results

The scattering efficiencies of four test samples given in Table 1 of the original report [Cernik et al. (1997). J. Synchrotron Rad. 4, 279–286] were calculated incorrectly. Corrected values are provided; these are two to three orders of magnitude lower.

An x-ray diffraction and 31P MAS NMR study of rare-earth phosphate glasses, (R2O3)x(P2O5)1-x, x = 0.175-0.263, R = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er

An x-ray diffraction and 31P MAS NMR study of rare-earth phosphate glasses of composition, (R2O3)xP2O5)1-x, where x = 0.175-0.263 and R = La-Er (except for Pm), is presented. The structures of these materials were investigated as a function of (a) rare-earth atomic number and (b) glass composition. The results show an increase in rare-earth coordination number from six to seven as the rare-earth ion increases in size. This effect is most evident for the rare earths, Ce, Pr and Nd, and appears to be independent of composition variation. The implications of sevenfold coordination in these glasses with respect to the possibilities of rare-earth clustering are discussed, as is the role of the incorporation of aluminium impurities in this regard. The increase in levels of cross-linking within the phosphate network, as a consequence of these small amounts of aluminium, is illustrated, as is the changing nature of the phosphate groups as a function of composition. The first reliable and quantitative parametrization of the second and third neighbour R-(O)-P and R-(OP)-O correlations is also given and the stability of the structures to strain when the glasses are drawn as fibres or exposed to different thermal conditions is described.

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.

A novel facility using a Laue focusing monochromator for high-pressure diffraction at the SRS, Daresbury, UK

A novel Laue focusing monochromator has been developed to provide intense X-radiation for high-pressure diffraction experiments. A beamline using this monochromator has been successfully developed on station 9.5 at the SRS, Daresbury Laboratory. Contributions to resolution from monochromator bandpass and divergence due to focusing have been quantified and are used to assess experimental diffraction data from diamond-anvil cells recorded using image plates with X-rays at approximately 30 keV. This optical and beamline design could be readily adapted to use X-rays from a bending magnet on a third-generation synchrotron source.

X-ray diffraction studies of rare-earth metaphosphate glasses

X-ray diffraction measurements have been performed at the Synchrotron Radiation Source, Daresbury, UK, in a structural study of the rare-earth metaphosphate glasses , and , whose compositions were determined by electron microprobe analysis. Such rare-earth metaphosphate glasses containing high concentrations of rare-earth ions are of growing interest in fundamental studies of magnetic glasses and in optical communications and laser technologies. The diffraction results prove to be consistent with a network model which is dominated by a phosphate glass skeleton having three-dimensional connectivity, constructed from tetrahedra linked to adjacent tetrahedra via bridging oxygen atoms. Results relating to rare-earth - oxygen correlations are consistent with a sixfold to eightfold coordination of the rare-earth atoms, with distances showing the trends expected from the lanthanide contraction: a reduction of the rare-earth ionic radii with increasing atomic number.

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.

A neutron and X-ray diffraction study of the influence of deposition conditions on the structure of a-C:H

Abstract The atomic scale structure of amorphous hydrogenated carbon (a-C:H) films prepared from an acetylene precursor by plasma enhanced chemical vapour deposition (PECVD) and a fast-atom source (FAS) have been studied by neutron and X-ray diffraction. The effect of beam energy on the structure of the film is investigated, and comparison is made to samples prepared using at fast atom (neutral particle) source, also using acetylene as the precursor. The results show that, in both deposition methods, increasing the beam energy produces a lower total sp2 hybridised carbon content in the film with evidence for a shift from pure olefinic to some aromatic/graphitic bonding in the FAS samples. The high resolution real-space neutron diffraction data allows a direct determination of the single:double bond ratio, and also shows the presence of sp1 hybridised carbon bonding environments.

The structural characterization of amorphous thin films and coatings in their as-deposited state using x-rays at shallow angles of incidence

We demonstrate the method of x-ray diffraction at shallow angles of incidence, using the intrinsically highly collimated x-ray beam generated by a synchrotron source, to study the atomic-scale structure of amorphous thin films and coatings in their as-deposited (i.e., on-substrate) state. As the incident angle is decreased, scattering from the film/coating can be isolated as contributions from the substrate are reduced. Systems studied include chemical vapor deposition (CVD) diamond films deposited onto both silicon and steel substrates, where evidence of an interfacial region between the film and silicon wafer has been observed, but we focus on a range of amorphous films/coatings (mixed TiO 2 : SiO 2 sol-gel spun films, hydrogenated carbon films and “glassy” carbon coatings, silicon: germanium semiconducting films and alumina coatings). The data are used both to comment upon the systems studied and to elucidate the potential, and the limitations, of the experimental method.

Software for automatic calibration of synchrotron powder diffractometers.

An automatic procedure to calibrate angular-dispersive monochromatic diffraction instruments has been developed at the Daresbury Synchrotron Radiation Source. The procedure uses a macro Language to control the powder diffraction instruments to locate Bragg reflections and perform peak-centre refinement from a standard reference material. The information obtained is used to refine the wavelength of the radiation used and the angular offset of the detector arm. The concept and implementation of the new software are described with applications to demonstrate its viability. The results of a reliability and accuracy study are also presented.

The effect of hydrogen dilution on the structure of a-C:H

Two a-C:H samples were prepared using a fast-atom deposition system from acetylene and an acetylene/hydrogen gas mixture. Their structure was investigated using neutron and x-ray diffraction and infrared spectroscopy measurements. Compositional analysis shows that a 1:1 mixture results in a change from to a-, i.e. has a very small effect on the composition. The diffraction data also show that the addition of hydrogen to the precursor gas has no significant effect on the average bond distances and angles but shows a small change in the H-C-H and C-C-H correlations between the two samples. However, the infrared data show that there are significant changes in the bonding of hydrogen within the sample - changes which do not affect the average network structure. We observe a decrease in the amount of and groups, and an increase in the fraction of and CH groups, with the formation of a second CH bonding environment in the hydrogen-diluted sample. Therefore, in addition to providing useful structural information on these a-C:H samples, this set of experiments illustrates very well the complementary nature of the data from diffraction and spectroscopic techniques.