Probing of bonding changes in B2O3 glasses at high pressure with inelastic X-ray scattering

Full understanding of atomic arrangement in amorphous oxides both at ambient and high pressure is an ongoing fundamental puzzle. Whereas the structures of archetypal oxide glasses such as v-B2O3 at high pressure are essential to elucidate origins of anomalous macroscopic properties of more complex melts, knowledge of the high-pressure structure and pressure-induced coordination changes of these glasses has remained elusive due to lack of suitable in situ experimental probes. Here, we report synchrotron inelastic X-ray scattering results for v-B2O3 at pressures up to 22.5 GPa, revealing the nature of pressure-induced bonding changes and the structure. Direct in situ measurements show a continuous transformation from tri-coordinated to tetra-coordinated boron beginning at 4–7 GPa with most of the boron tetra-coordinated above 20 GPa, forming dense tetrahedral v-B2O3. After decompression from high pressure the bonding reverts back to tri-coordinated boron but with the data suggesting a permanent densification.

[1]  H. Mao,et al.  Formation and structure of a dense octahedral glass. , 2004, Physical review letters.

[2]  J. Finney,et al.  X-ray-Raman scattering from the oxygen K edge in liquid and solid H 2 O , 2000 .

[3]  G. Cody,et al.  Order and disorder in sodium silicate glasses and melts at 10 GPa , 2003 .

[4]  H. Mao,et al.  The formation of sp3 bonding in compressed BN , 2004, Nature materials.

[5]  M. Fleet,et al.  Coordination of boron in alkali borosilicate glasses using XANES , 1999 .

[6]  P. Wernet,et al.  The Structure of the First Coordination Shell in Liquid Water , 2004, Science.

[7]  R. Youngman,et al.  Short-and Intermediate-Range Structural Ordering in Glassy Boron Oxide , 1995, Science.

[8]  Oshima,et al.  Resonant x-ray Raman scattering in B K alpha emission spectra of boron oxide (B2O3) excited by undulator radiation. , 1993, Physical review letters.

[9]  L. Du,et al.  Pressure-induced structural changes in a borosilicate glass-forming liquid: boron coordination, non-bridging oxygens, and network ordering , 2004 .

[10]  R. Brydson,et al.  Parallel electron energy-losss pectroscopy( PEELS) study of B in minerals: The electron energy-loss near-edge structure (ELNES) of the B K edge , 1995 .

[11]  J. Swenson,et al.  Fraction of boroxol rings in vitreous boron trioxide , 1997 .

[12]  P. J. Bray,et al.  Nuclear magnetic resonance studies of the glasses in the system Na2OB2O3SiO2 , 1978 .

[13]  R. Brydson,et al.  Determination of coordinations and coordination-specific site occupancies by electron energy-loss spectroscopy: An investigation of boron—oxygen compounds , 1993 .

[14]  P. J. Bray,et al.  Nuclear magnetic resonance studies of the glasses in the system PbO–B2O3–SiO2 , 1976 .

[15]  C. Musgrave,et al.  Topological Disorder and Reactivity of Borosilicate Glasses: Quantum Chemical Calculations and 17O and 11B NMR Study , 2001 .

[16]  Wright,et al.  Irreversible structural changes in vitreous B2O3 under pressure. , 1996, Physical review. B, Condensed matter.

[17]  P. J. Bray.  Nuclear magnetic resonance studies of glass structure , 1985 .

[18]  Peter J. Eng,et al.  Bonding Changes in Compressed Superhard Graphite , 2003, Science.

[19]  C. C. Chen,et al.  Ordering of hydrogen bonds in high-pressure low-temperature H2O. , 2005, Physical review letters.

[20]  G. Cody,et al.  Nature of polymerization and properties of silicate melts and glasses at high pressure , 2004 .

[21]  C. Angell,et al.  Pressure Enhancement of Ion Mobilities in Liquid Silicates from Computer Simulation Studies to 800 Kilobars , 1982, Science.

[22]  L. Anovitz,et al.  Boron: mineralogy, petrology and geochemistry , 1996 .

[23]  M. Fleet,et al.  Boron K-edge XANES of borate and borosilicate minerals , 2000 .

[24]  John Kieffer,et al.  Spectroscopic evidence of polymorphism in vitreous B2O3. , 2004, Physical review letters.

[25]  J. Stebbins,et al.  NMR evidence for excess non-bridging oxygen in an aluminosilicate glass , 1997, Nature.

[26]  Bell,et al.  Raman spectroscopy of SiO2 glass at high pressure. , 1986, Physical review letters.

[27]  Paul F. McMillan,et al.  Structure, Dynamics and Properties of Silicate Melts , 1995 .

[28]  W. Schwarz,et al.  K-shell excitations of BF3, CF4 and MBF4 compounds , 1983 .

[29]  S. Lee.  Structure of Silicate Glasses and Melts at High Pressure: Quantum Chemical Calculations and Solid-State NMR , 2004 .

[30]  P. McMillan,et al.  Chapter 11. PRESSURE EFFECTS ON SILICATE MELT STRUCTURE AND PROPERTIES , 1995 .

[31]  J. Yarger,et al.  Al Coordination Changes in High-Pressure Aluminosilicate Liquids , 1995, Science.

[32]  H. Takenaka,et al.  Valence band structure and decay process in the inner-shell excitation of boron oxide , 1999 .

[33]  D. Dingwell,et al.  Peraluminous viscosity maxima in Na2OAl2O3SiO2 liquids: The role of triclusters in tectosilicate melts , 1997 .

[34]  J L Beeby,et al.  Physics of amorphous materials , 1984 .

[35]  G. Cody,et al.  Structure of B2O3 Glass at High Pressure: A 11B Solid-State NMR Study. , 2005, Physical review letters.