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G N Greaves

Publications and source records attributed to G N Greaves.

10 recordsLinked to original sources
PubMed2005

Identifying vibrations that destabilize crystals and characterize the glassy state.

High-resolution inelastic neutron scattering was used to identify major sources of low-frequency vibrations in zeolite crystals. Dispersed and nondispersed modes were found, both of which are prominent in the early stages of compressive amorphization but decline dramatically in strength once a glass of conventional density is created. By identifying the dispersed modes with the characteristic vibrations of the various secondary building units of zeolitic structures, the Boson peak, a characteristic of the glassy state, can be attributed to vibrations within connected rings of many different sizes. The nondispersed phonon features in zeolites, retained in the amorphized glass, were also replicated in silica. These modes are librational in origin and are responsible for destabilizing the microporous crystalline structure, for converting the resulting glass from a low- to a high-density phase, and for the associated changes in network topology that affect the Boson peak.

Journal Article↗
PubMed2004

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.

Equipment Design↗
PubMed2003

The rheology of collapsing zeolites amorphized by temperature and pressure.

Low-density zeolites collapse to the rigid amorphous state at temperatures that are well below the melting points of crystals of the same composition but of conventional density. Here we show, by using a range of experimental techniques, how the phenomenon of amorphization is time dependent, and how the dynamics of order-disorder transitions in zeolites under temperature and pressure are equivalent. As a result, thermobaric regions of instability can be charted, which are indicative of polyamorphism. Moreover, the boundaries of these zones depend on the rate at which temperature or pressure is ramped. By directly comparing the rheology of collapse with structural relaxation in equivalent melts, we conclude that zeolites amorphize like very strong liquids and, if compression occurs slowly, this is likely to lead to the synthesis of perfect glasses.

Crystallography↗
PubMed2003

A SAXS/WAXS XAFS study of crystallisation in cordierite glass.

New Cr X-ray absorption fine structure (XAFS) data have been combined with the results of small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) experiments to probe in detail the crystallisation mechanism in cordierite (Mg2Al4Si5O18) glass doped with 0.34 mol% Cr2O3. By direct comparison with chromo-aluminate spinels (MgCr2xAl2(1 - x)O4) Cr XAFS is used to determine the composition of the devitrified Cr species. This is identified as MgCr(0.18)Al(1.82)O4, which can be directly related to the Cr content in the starting glass and as a result the total crystalline volume in the fully developed ceramic is predicted to be 4%. In situ WAXS not only reveals the presence of the spinel phase but also a silica-rich stuffed quartz phase. This grows independently of the spinel and is probably nucleated from the glass surface. From our knowledge of the compositions of both crystalline phases we are able to deduce that the SAXS contrast between the surrounding glass and the spinel crystallites is 30 times greater than that between the quartz crystallites and the glass matrix, and therefore dominates the measured scattered intensity and the SAXS invariant that is derived from it. As a consequence we are able to show that the spinel crystalline volume fraction inherent in the SAXS is in close agreement with the 4% value obtained from the Cr XAFS. Furthermore in situ SAXS reveals the gradual development of the spinel particle size and shape during heat treatment. This is conducted in the super-cooled region just above the glass transition temperature, Tg. By employing a two-step annealing process nucleation can be separated from growth and from time-resolved SAXS measurements the alumino-chromate nanocrystals are found to be closely monodispersed. Over a total time course of 600 min they grow from rough crystallites to smooth spherical particles of radius 21 +/- 2 nm, with a final density of (1.2 +/- 0.4) x 10(21) m(-3). As the process of ceramic formation takes place in the viscous melt, growth is indeed found to be limited by diffusion and is complete when all the Cr is exhausted. We use this comprehensive in situ study of crystallisation in cordierite glass to demonstrate the advantages of combining SAXS, WAXS and XAFS for probing the time-resolved chemistry, the microstructure and its development from nucleation sites, that underpins the processing of nanoparticle ceramics.

Journal Article↗
PubMed2001

Liquid alumina: detailed atomic coordination determined from neutron diffraction data using empirical potential structure refinement.

The neutron scattering structure factor S(N)(Q) for a 40 mg drop of molten alumina (Al2O3) held at 2500 K, using a laser-heated aerodynamic levitation furnace, is measured for the first time. A 1700 atom model of liquid alumina is generated from these data using the technique of empirical potential structural refinement. About 62% of the aluminum sites are 4-fold coordinated, matching the mostly triply coordinated oxygen sites, but some 24% of the aluminum sites are 5-fold coordinated. The octahedral aluminum sites found in crystalline alpha-Al2O3 occur only at the 2% level in liquid alumina.

Journal Article↗
PubMed1997

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.

Journal Article↗
PubMed1995

Examination of the mixed-alkali effect in (Li,Na) disilicate glasses by nuclear magnetic resonance and conductivity measurements.

Results from 29Si, 23Na and 7Li magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy, 7Li NMR relaxation and electrical conductivity in a series of [Li(1-x).Nax]2O.2SiO2 (disilicate) glasses are used to investigate the mixed-alkali effect. From the 29Si NMR spectra there is relatively little change of the network with alkali composition. 23Na and 7Li NMR linewidths and shifts change continuously as a function of composition, indicating that the alkali ions are intimately and uniformly mixed rather than separated into lithium and sodium-rich domains. The activation energy from electrical conductivity shows a distinct maximum at the central composition (x = 0.5), whereas the local activation energy for lithium motion determined from NMR shows only a smaller but monotonic increase as the lithium-content decreases.

Electric Conductivity↗
PubMed1990

Biotransformation of intracellular minerals by zinc ions in vivo and in vitro.

Inorganic granules of the general type CaMgP2O7 are found within cells of a wide range of species. The granules are amorphous to X-rays and occur in membrane-bound compartments. They accumulate a variety of cations from the body fluids of these animals. The interaction of zinc ions with pyrophosphate granules from cells of the snail Helix aspersa have been studied in vivo and in vitro by X-ray absorption spectroscopy and X-ray diffraction. The in vivo deposits incorporate zinc and remain amorphous although the pyrophosphate is hydrolysed to orthophosphate. In this in vitro reaction the mineral becomes crystalline but there is little change in the form of the The results clearly indicate a role for the cellular system in maintaining the amorphous state and in the hydrolysis of pyrophosphate to orthophosphate. As such they provide a model system for some of the changes observed in precursors of bone mineral and in pathological changes in the calcification of cartilage.

Animals↗
PubMed1984

The local environment of metal sites in intracellular granules investigated by using X-ray-absorption spectroscopy.

We report the use of X-ray-absorption spectroscopy (x.a.s.) to study the local atomic environment of cations in intracellular granules from the hepatopancreas of Helix aspersa. Both the calcium K-edge in these concretions and the manganese K-edge in doped specimens were measured. Electron-microprobe measurements confirm that the introduced Mn2+ is concentrated in irregular growths on the surfaces of the granules. The near-edge structure (x.a.n.e.s.) of calcium is similar to that of manganese, indicating that the oxygen-co-ordination spheres of both cations share a similar symmetry. From the extended structure (e.x.a.f.s.) the metal-oxygen bond lengths of 0.230 nm (2.30A) for Ca-O and 0.218 nm (2.18A) for Mn-O [+/- 0.004 nm (0.04A)] were determined, reference being made to a variety of model compounds. The low density of the granules (2.07 g/cm3), together with the local atomic distribution, suggest an open hydrated structure for these phosphate deposits. Detailed analysis of the distribution of nearest-neighbour oxygen atoms demonstrates that this is asymmetric and considerably broader for Ca2+ than for Mn2+. Compared with the model compounds, the Ca2+ environment in the granules is similar to that observed in Ca2P2O7. I.r. spectra indicate the presence of condensed phosphate groups in the granules, with the strong possibility these are pyrophosphate (P2O7(4-) groups.

Animals↗