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The atomic structure of a germanium doped phosphorous selenide glass of composition Ge2.8P57.7Se39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P4Se3 molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe4 tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P3 ring at the base of the P4Se3 molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understanding of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.

The atomic structure of a germanium doped phosphorous selenide glass of composition Ge2.8P57.7Se39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P4Se3 molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe4 tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P3 ring at the base of the P4Se3 molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understanding of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.

The atomic structure of a germanium doped phosphorous selenide glass of composition Ge2.8P57.7Se39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P4Se3 molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe4 tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P3 ring at the base of the P4Se3 molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understanding of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.

The effect of pressure on the crystal structure of white phosphorus has been studied up to 22.4 GPa. The ?alpha phase was found to transform into the alpha' phase at 0.87 +- 0.04 GPa with a volume change of 0.1 +- 0.3 cc/mol. A fit of a second order Birch- Murnaghan equation to the data gave Vo = 16.94 ? 0.08 cc/mol and Ko = 6.7 +- 0.5 GPa for the alpha phase and Vo = 16.4 +- 0.1 cc/mol and Ko = 9.1 +- 0.3 GPa for the alpha' phase. The alpha' phase was found to transform to the A17 phase of black phosphorus at 2.68 +- 0.34 GPa and then with increasing pressure to the A7 and then simple cubic phase of black phosphorus. A fit of a second order Birch-Murnaghan equation to our data combined with previous measurements gave Vo = 11.43 +- 0.05 cc/mol and Ko = 34.7 +- 0.5 GPa for the A17 phase, Vo = 9.62 +- 0.01 cc/mol and Ko = 65.0 +- 0.6 GPa for the A7 phase and , Vo = 9.23 +- 0.01 cc/mol and Ko = 72.5 +- 0.3 GPa for the simple cubic phase.

The laser heating system for the diamond anvil cell at endstation 2 of beamline 12.2.2 of the Advanced Light Source in Berkeley, CA has been constructed and is available for in-situ high-pressure high-temperature x-ray experiments. The endstation couples a high-brilliance synchrotron x-ray source with an industrial strength laser to heat and probe samples at high pressure in the diamond anvil cell. The system incorporates an 80 watt Nd:YLF (cw) laser operated in TEM01* mode. Double-sided heating is achieved by splitting the laser beam into 2 paths that are directed through the opposing diamond anvils. X-ray transparent mirrors steer the laser beams coaxial with the x-ray beam from the superconducting bending magnet (energy range 6-35 KeV) and direct the emitted light from the heated sample into two separate spectrometers for temperature measurement by spectroradiometry. Objective lenses focus the laser beam to a size of 25 micron diameter (FWHM) in the sample region. An x-ray spot size of 10 micron diameter (FWHM) has been achieved with the installation of a pair of focusing Kirkpatrick-Baez mirrors. A unique aperture configuration has produced an x-ray beam profile that has very low intensity in the tails. The main thrust of the program is aimed at producing in-situ high-pressure high-temperature x-ray diffraction data, but other modes of operation, such as x-ray imaging have been accomplished. Technical details of the experimental setup will be presented along with initial results.

A tensonometer for stretching metal foils has been constructed for the study of strain broadening in x-ray diffraction line profiles. This device, which is designed for use on the powder diffractometer in Station 2.3 at Daresbury Laboratory, allows in-situ measurements to be performed on samples under stress. It can be used for data collection in either transmission or reflection modes using either symmetric or asymmetric diffraction geometries. As a test case, measurements were carried out on a 18mum thick copper foil experiencing strain levels of up to 5 percent using both symmetric reflection and symmetric transmission diffraction. All the diffraction profiles displayed peak broadening and asymmetry which increased with strain. The measured profiles were analysed by the fundamental parameters approach using the TOPAS peak fitting software. All the observed broadened profiles were modelled by convoluting a refineable diffraction profile, representing the dislocation and crystallite size broadening, with a fixed instrumental profile pre-determined using high quality LaB6 reference powder. The de-convolution process yielded "pure" sample integral breadths and asymmetry results which displayed a strong dependence on applied strain and increased almost linearly with applied strain. Assuming crystallite size broadening in combination with dislocation broadening arising from fcc a/2 111 dislocations, we have extracted the variation of mechanic al property with strain. The observation of both peak asymmetry and broadening has been interpreted as a manifestation of a cellular structure with cell walls and cell interiors possessing high and low dislocation densities.

X-ray diffraction and infrared data have been collected from a sample of ettringite from ambient pressure to 6.4 GPa. The sample was found to reversibly transform to an amorphous phase at 3 GPa. The isothermal bulk modulus of ettringite was found to be 27(7) GPa and the incompressibilities of the lattice parameters were found to be 71(30) GPa along a and 108(36) GPa along c.

A new facility for high-pressure diffraction and spectroscopy using diamond anvil high-pressure cells has been built at the Advanced Light Source on Beamline 12.2.2. This beamline benefits from the hard X-radiation generated by a 6 Tesla superconducting bending magnet (superbend). Useful x-ray flux is available between 5 keV and 35 keV. The radiation is transferred from the superbend to the experimental enclosure by the brightness preserving optics of the beamline. These optics are comprised of: a plane parabola collimating mirror (M1), followed by a Kohzu monochromator vessel with a Si(111) crystals (E/DE ~; 7000) and a W/B4C multilayers (E/DE ~; 100), and then a toroidal focusing mirror (M2) with variable focusing distance. The experimental enclosure contains an automated beam positioning system, a set of slits, ion chambers, the sample positioning goniometry and area detectors (CCD or image-plate detector). Future developments aim at the installation of a second end station dedicated for in situ laser-heating on one hand and a dedicated high-pressure single-crystal station, applying both monochromatic as well as polychromatic techniques.