A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra

Silva, Marcus; O'Bannon, Earl F.; Williams, Quentin

doi:10.2138/am-2018-6253

Title: A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra

Abstract

The Raman and infrared spectra of kernite [Na₂B₄O₆(OH)₂·3H₂O] have been characterized up to ~25 and 23 GPa, respectively, to explore pressure-induced changes in a structurally novel mineral that contains mixed coordination borate groups (threefold and fourfold), as well as both hydroxyl groups and water molecules. BO₃ and BO₄ vibrational modes are characterized in both the Raman and infrared spectra of kernite, and reassignments of some modes are made based on observed pressure shifts. Under compression to ~25 GPa, kernite undergoes three phase transitions: one initiates near ~2.5 GPa, the second occurs at ~7.0 GPa, and the third near 11.0 GPa. The first transition is characterized by a loss of both a subset of the Na-associated modes and a sharp OH peak, and it is fully reversible. The second transition is characterized by the loss of most of the BO₃ modes, some of the BO₄ modes at ~7 GPa, and further broadening of the H₂O and OH peaks. This transition is partially reversible on decompression, but the Raman spectra indicate that the high-pressure structure and its reversion products are likely disordered. The third transition is characterized by the loss of most of the Raman and infrared modes, and it is notmore »« less

Authors:

Silva, Marcus ^[1]; O'Bannon, Earl F. ^[2]; Williams, Quentin ^[3]

Univ. of California, Santa Cruz, CA (United States); New Mexico Institute of Mining and Technology, Socorro, NM (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of California, Santa Cruz, CA (United States)

Publication Date:: Wed Aug 01 00:00:00 EDT 2018

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1479082

Report Number(s):: LLNL-JRNL-747418
Journal ID: ISSN 0003-004X; 900333

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: American Mineralogist

Additional Journal Information:: Journal Volume: 103; Journal Issue: 8; Journal ID: ISSN 0003-004X

Publisher:: Mineralogical Society of America

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 58 GEOSCIENCES; kernite; boron; high-pressure; vibrational spectroscopy

Citation Formats


                    Silva, Marcus, O'Bannon, Earl F., and Williams, Quentin. A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra.  United States: N. p., 2018. 
Web.  doi:10.2138/am-2018-6253.

Copy to clipboard


                    Silva, Marcus, O'Bannon, Earl F., & Williams, Quentin. A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra.  United States.  https://doi.org/10.2138/am-2018-6253

Copy to clipboard


                    Silva, Marcus, O'Bannon, Earl F., and Williams, Quentin. Wed .  
"A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra".  United States.  https://doi.org/10.2138/am-2018-6253.  https://www.osti.gov/servlets/purl/1479082.

Copy to clipboard


                    
@article{osti_1479082,

  title        = {A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra},

  author       = {Silva, Marcus and O'Bannon, Earl F. and Williams, Quentin},

  abstractNote = {The Raman and infrared spectra of kernite [Na2B4O6(OH)2·3H2O] have been characterized up to ~25 and 23 GPa, respectively, to explore pressure-induced changes in a structurally novel mineral that contains mixed coordination borate groups (threefold and fourfold), as well as both hydroxyl groups and water molecules. BO3 and BO4 vibrational modes are characterized in both the Raman and infrared spectra of kernite, and reassignments of some modes are made based on observed pressure shifts. Under compression to ~25 GPa, kernite undergoes three phase transitions: one initiates near ~2.5 GPa, the second occurs at ~7.0 GPa, and the third near 11.0 GPa. The first transition is characterized by a loss of both a subset of the Na-associated modes and a sharp OH peak, and it is fully reversible. The second transition is characterized by the loss of most of the BO3 modes, some of the BO4 modes at ~7 GPa, and further broadening of the H2O and OH peaks. This transition is partially reversible on decompression, but the Raman spectra indicate that the high-pressure structure and its reversion products are likely disordered. The third transition is characterized by the loss of most of the Raman and infrared modes, and it is not reversible on decompression. The decompression products from ~25 GPa have markedly different infrared and Raman spectra from the starting material, and appear to involve different bonding environments of boron than are present in the starting materials: thus, pressure treatment of boron-rich materials may generate novel quenchable structures. Notably, the BO3 groups in kernite are destabilized under compression, with the BO4 groups appearing to be more stable under compression. This shift in coordination may be endemic among borate glasses and crystalline borates under compression. The coordination conversion (and its products on decompression) is likely to highly depend on the detailed topology of the starting materials. Commonalities and differences between the threefold to fourfold transitions in borate systems relative to those in carbonate systems are presented. Lastly our results, combined with prior shock data, indicate that kernite, which may be representative of low-temperature borate minerals, can persist during impact events with peak shock pressures less than ~33 GPa, and the primary polyborate structural units involved in early ribose stabilization would thus survive most impact conditions.},

  doi          = {10.2138/am-2018-6253},

  journal      = {American Mineralogist},

  number       = 8,

  volume       = 103,

  place        = {United States},

  year         = {Wed Aug 01 00:00:00 EDT 2018},

  month        = {Wed Aug 01 00:00:00 EDT 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.2138/am-2018-6253

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 3 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

High‐pressure behavior and phase stability of Na ₂ B ₄ O ₆ (OH) ₂ ·3H ₂ O (kernite)
journal, May 2020

Comboni, Davide; Pagliaro, Francesco; Gatta, G. Diego
Journal of the American Ceramic Society, Vol. 103, Issue 9
DOI: 10.1111/jace.17185

Similar Records in DOE PAGES and OSTI.GOV collections:

An infrared and Raman spectroscopic study of PbSO4-anglesite at high pressures

Journal Article Sawchuk, Krista ; O'Bannon, E F ; Vennari, Cara ; ... - Physics and Chemistry of Minerals

Infrared and Raman spectra of the ABX₄ compound anglesite (PbSO₄) were collected to 43 GPa at 300 K in three separate pressure media. A major transition in the spectra initiates at 23 GPa that is characterized by shifting and/or splitting of most of the fundamental vibrations of the sulfate group. On decompression, PbSO₄ reverts to the ambient anglesite (barite) structure. This transition is kinetically impeded within more hydrostatic pressure media and does not proceed to completion within a neon medium even at pressures as high as 43 GPa. The previously observed spectral shift at 13 GPa occurs in less hydrostatic media (such as 4:1 methanol:ethanol), and involves subtle splitting of a few modes, particularly the (SO₄)^2- tetrahedral stretching and bending-derived Raman and infrared modes. Another possible shift occurs near 33 GPa, and primarily involves the appearance of new sulfate antisymmetric bending modes in the infrared spectrum and the onset of new sulfate antisymmetric stretching modes in the Raman spectrum. It is likely that PbSO₄ begins to convert sluggishly to themore »« less
Cited by 4
https://doi.org/10.1007/s00269-019-01027-z

Full Text Available
Pressure-induced phase transitions in acentric BaHf(BO{sub 3}){sub 2}

Journal Article Mączka, Mirosław ; Szymborska-Małek, Katarzyna ; Sousa Pinheiro, Gardenia de ; ... - Journal of Solid State Chemistry

High-pressure Raman scattering studies revealed that BaHf(BO{sub 3}){sub 2} is more compressible than calcite-type orthoborates and calcite, aragonite or dolomite carbonates. It undergoes a first-order reversible pressure-induced phase transition in the 3.9–4.4 GPa pressure range. Second structural change is observed at 9.2 GPa. The intermediate phase is most likely trigonal. However, Raman results suggest increase in the number of distinct BO{sub 3} groups from two in the ambient pressure phase to at least three in the intermediate phase. This intermediate phase is also strongly compressible and strong pressure dependence of the lattice modes proves that the main changes under pressuremore »« less
https://doi.org/10.1016/J.JSSC.2015.05.002
High-pressure synthesis and crystal structure of the lithium borate HP-LiB{sub 3}O{sub 5}

Journal Article Neumair, Stephanie C ; Vanicek, Stefan ; Kaindl, Reinhard ; ... - Journal of Solid State Chemistry

The new lithium borate HP-LiB{sub 3}O{sub 5} was synthesized under high-pressure/high-temperature conditions of 6 GPa and 1050 deg. C in a multianvil press with a Walker-type module. The compound crystallizes in the space group Pnma (no. 62) with the lattice parameters a=829.7(2), b=759.6(2), and c=1726.8(4) pm (Z=16). The high-pressure compound HP-LiB{sub 3}O{sub 5} is built up from a three-dimensional network of BO{sub 4} tetrahedra and BO{sub 3} groups, which incorporates Li{sup +} ions in channels along the b-axis. Band assignments of measured IR- and Raman spectra were done via quantum-mechanical calculations. Additionally, the thermal behavior of HP-LiB{sub 3}O{sub 5} wasmore »« less
https://doi.org/10.1016/j.jssc.2011.07.011
Effect of pressure on heterocyclic compounds: Pyrimidine and s-triazine

Journal Article Li, Shourui ; Li, Qian ; Li, Wenbo ; ... - Journal of Chemical Physics

We have examined the high-pressure behaviors of six-membered heterocyclic compounds of pyrimidine and s-triazine up to 26 and 26.5 GPa, respectively. Pyrimidine crystallizes in Pna2{sub 1} symmetry (phase I) with the freezing pressure of 0.3 GPa, and transforms to another phase (phase II) at 1.1 GPa. Raman spectra of several compression-decompression cycles demonstrate there is a critical pressure of 15.5 GPa for pyrimidine. Pyrimidine returns back to its original liquid state as long as the highest pressure is below 15.1 GPa. Rupture of the aromatic ring is observed once pressure exceeds 15.5 GPa during a compression-decompression cycle, evidenced by themore »« less
https://doi.org/10.1063/1.4895523
Coordination of B in K{sub 2}OSiO{sub 2}-B{sub 2}O{sub 3}-P{sub 2}O{sub 5} glasses using B K-edge XANES

Journal Article Li, Dien ; Bancroft, G M ; Fleet, M E - American Mineralogist

High-resolution B K-edge X-ray absorption near-edge structure (XANES) spectra of K{sub 2}O-SiO{sub 2}-B{sub 2}O{sub 3}-P{sub 2}O{sub 5} glasses are reported using synchrotron radiation. Two prominent features, peak a at about 194.0 eV and peak b at about 198.0 eV, are observed. In the basis of the qualitative MO diagrams of BO{sub 3}{sup 3{minus}} and BO{sub 4}{sup 5{minus}} clusters, peak a is assigned to the transition of B 1s electrons to the unoccupied B 2p{sub z} ({pi}*) states for threefold-coordinated B ({sup [3]}B), and peak b is assigned to the transition of B 1s electrons to the unoccupied B {sigma}* statesmore »« less
https://doi.org/10.2138/am-1995-9-1001

Similar Records

Title: A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra

Abstract

Citation Formats

High‐pressure behavior and phase stability of Na 2 B 4 O 6 (OH) 2 ·3H 2 O (kernite) journal, May 2020

High‐pressure behavior and phase stability of Na ₂ B ₄ O ₆ (OH) ₂ ·3H ₂ O (kernite)
journal, May 2020