Acta Physica Sinica, Volume. 69, Issue 13, 136101-1(2020)

Molecule-like structural units in silicate-glass-forming oxides

Fa-Qi Wan1, Yan-Ping Ma1、*, Dan-Dan Dong2, Wan-Yu Ding3, Hong Jiang1,5、*, Chuang Dong3,4, and Jian-Xiong He5
Author Affiliations
  • 1Key Laboratory of Special Glass of Hainan Province and State Key Laboratory of South China Sea Resources Utilization, Hainan University, Haikou 570228, China
  • 2College of Physical Science and Technology, Dalian University, Dalian 116622, China
  • 3School of Materials Science and Engineering, Dalian Jiaotong University, Dalian 116028, China
  • 4Key Laboratory for Materials Modification by Laser, Ion and Electron Beam, Dalian University of Technology, Dalian 116024, China
  • 5Hainan Zhonghang Special Glass Technology Co., Ltd. & State Key Laboratory of Special Glass, Haikou 579124, China
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    Figures & Tables(15)
    Electron structure of water molecule[2].
    Crystal structure of β-SiO2 using tetrahedral cluster [Si-O4][3].
    The amorphous structure of glassy silica (SiO2) in two dimensions[4]
    (a) Cluster-plus-glue-atom model[11]; (b) the inter-cluster distance is r3.
    (a)Principal cluster [Si-O4] and [O-Si2] in β-SiO2 structure (space group 194). Large and small spheres are O and Si atoms, respectively; (b) molecule-like structural unit[Si-O4]Si.
    The cell structure of oxides, and large atoms are O: (a) B2O3(P31); (b) B2O3(Cmc21); (c) GeO2(P41212); (d) P2O5(Pnma).
    Clusters in anti-fluorite Li2O, [Li-O4] and [O-Li8] (principal cluster). Large spheres represent O and small spheres represent Li.
    Clusters in NaCl structure of Li2O, [Ca-O6] (principal cluster)and [O-Ca6]. Large spheres represent O and small spheres represent Li.
    Clusters in α-Al2O3 unit cell, including [O-Al4] and [Al-O6] (principal cluster). Small spheres represent Al.
    Clusters in γ-Al2O3 (Al2MgO4 structure), including [O-Al4], [Al-O4] (principal cluster), and [Al-O6]. Small spheres represent Al.
    The cell structure of ZnO, and small spheres represent Ti: (a) ZnO (); (b) ZnO (P63mc).
    Octahedral clusters [Zn-O6] (principal cluster) and [O-Zn6] in ZnO (NaCl structure). Small spheres represent Zn.
    The cell structure of TiO2, and small spheres represent are Ti: (a) TiO2(P42/mnm); (b) TiO2(I41/amd); (c) TiO2( Pbca); (d) TiO2 (P21/m)
    • Table 1. Crystal structure data of Tridymite β-SiO2[19].

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      Table 1. Crystal structure data of Tridymite β-SiO2[19].

      O2Si Structure type O2Si Pearson symbol hP12 Space group P63/mmcNo.194
      a = 0.5052(9) nm c = 0.827(2) nm γ = 120°
      O12c$ {\bar 6}m2$x = 1/3 y = 2/3 z = 1/4 occ. = 1
      Si4f3m. x = 1/3 y = 2/3 z = 0.0620 occ. = 1
      O26g.2/mx = 1/2 y = 0 z = 0 occ. = 1
    • Table 2. Molecule-like structural units of glass-relevant oxides. Molecule-like structural unit, based on principal clusters, are bolded.

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      Table 2. Molecule-like structural units of glass-relevant oxides. Molecule-like structural unit, based on principal clusters, are bolded.

      ClassificationOxide (space group)Cationic structural unit (e/u) Anion structural unit (e/u)
      Network formationβ-SiO2 (P63/mmc) [Si-O4]Si = 2{SiO2} (32) [O-Si2]O3= 2{SiO2} (32)
      B2O3 (P31) [B-O3]B = {B2O3} (24) [O-B2]O2 = {B2O3} (24)
      B2O3 (Cmc21) [B-O4]B3O2 = 2{B2O3} (48) [O-B2]O2 = {B2O3} (24)
      [O-B3]O5B1 = 2{B2O3} (48)
      GeO2 (P41212) [Ge-O4]Ge = 2{GeO2} (32) [O-Ge2]O3 = 2{GeO2} (32)
      P2O5 (Pnma) [P-O4]P1O1 = {P2O5} (40) [O-P2]O4 = {P2O5} (40)
      [O-P1]P1O4 = {P2O5} (40)
      Network outside body(Li, Na,K)2O (anti-fluorite $ Fm{\bar 3}m$) [(Li, Na,K)-O4](Li, Na,K)7 = 4{(Li, Na,K)O2} (32) [O-(Li, Na,K)8]O3 = 4{(Li, Na,K)O2} (32)
      (Mg, Ca, Ba)O (Halite, $ Fm{\bar 3}m$) [(Mg, Ca, Ba)-O6](Mg, Ca, Ba)5 = 6{(Mg, Ca, Ba)O} (48) [O-(Mg, Ca, Ba)6]O5 = 4{(Mg, Ca, Ba)O} (48)
      ZrO2 (rutile, P42/mnm) [Zr-O6]Zr2 = 3{ZrO2} (48) [O-Zr3]O5 = 3{ZrO2} (48)
      Network intermediate(Be, Zn)O (sphalerite, P43m) [(Be, Zn)-O4](Be, Zn)3 = 4{(Be, Zn)O} (32) [O-(Be, Zn)4]O3 = 4{(Be, Zn)O} (32)
      (Be, Zn)O (Wurtzite, P63mc) [Zn-O4]Zn3 = 4{ZnO} (32) [O-Zn4]O3 = 4{ZnO} (32)
      (Be, Zn)O (Halite, $ Fm{\bar 3}m$) [Zn-O6]Zn5 = 6{ZnO} (48) [O-Zn6]O5 = 6{ZnO} (48)
      α-Al2O3 ( $ R{\bar 3}c$) [Al-O6]Al3 = 2{Al2O3} (48) [O-Al4]O5 = 2{Al2O3} (48)
      γ-Al2O3 (Spinel, $ Fd{\bar 3}m$) [Al-O4]O2Al3 = 2{Al2O3} (48) [O-Al4]O5 = 2{Al2O3} (48)
      [Al-O6]Al3 = 2{Al2O3} (48)
      Ga2O3 (α-Al2O3, $ R{\bar 3}c$) [Ga-O6]Ga3 = 2{Ga2O3} (48) [O-Ga4]O5 = 2{Ga2O3} (48)
      Ga2O3 (Spinel, $ Fd{\bar 3}m$) [Ga-O4]O2Ga3 = 2{Ga2O3} (48) [O-Ga4]O5 = 2{Ga2O3} (48)
      [Ga-O6]Ga3 = 2{Ga2O3} (48)
      Fe2O3 (α-Al2O3, $ R{\bar 3}c$) [Fe-O6]Fe3 = 2{Fe2O3} (48) [O-Fe4]O5 = 2{Fe2O3} (48)
      Fe3O4 (Spinel, $ Fd{\bar 3}m$) [Fe-O4]Fe2 = {Fe3O4} (32) [O-Fe4]O7Fe2 = 2{Fe3O4} (64)
      [Fe-O6]Fe5O2 = 2{Fe3O4} (64)
      TiO2 (Rutile, P42/mnm) [Ti-O6]Ti2 = 3{TiO2} (48) [O-Ti3]O5 = 3{TiO2} (48)
      TiO2 (Anatase, I41/amd) [Ti-O6]Ti2 = 3{TiO2} (48) [O-Ti3]O5 = 3{TiO2} (48)
      TiO2 (Brookite, Pbca) [Ti-O6]Ti2 = 3{TiO2} (48) [O-Ti3]O5 = 3{TiO2} (48)
      TiO2 (P21/m) [Ti-O4]Ti = 2{TiO2} (32) [O-Ti2]O3 = 2{TiO2} (32)
      [Ti-O3]TiO = 2{TiO2} (32) [O-Ti]O3Ti = 2{TiO2} (32)
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    Fa-Qi Wan, Yan-Ping Ma, Dan-Dan Dong, Wan-Yu Ding, Hong Jiang, Chuang Dong, Jian-Xiong He. Molecule-like structural units in silicate-glass-forming oxides[J]. Acta Physica Sinica, 2020, 69(13): 136101-1

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    Paper Information

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    Received: Dec. 15, 2019

    Accepted: --

    Published Online: Jan. 4, 2021

    The Author Email: Jiang Hong (jhong63908889@sina.com)

    DOI:10.7498/aps.69.20191892

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