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Despite lacking accurate knowledge of the sample compositions, these results show with some certainty that the B₂O₃in the glass system forms predominantly planar trig- onal [BO₃] units of bond length 1.371 Å—borne out by the O−B−O angle of 120.4◦

Chapter 5. Antimony Borate Glasses

second B−O peak at 1.477 Å (Fig.5-10) and the total n_BO obtained for the samples (Fig.5-14) confirm that a small proportion of [BO₄] tetrahedral units also exist in the glass structure, the quantity increasing with composition up tox≈ 0.5 and falling there-

after, confirming the findings of previous authors [1, 4, 6]. The Sb₂O₃ present in the glass forms mainly [SbO₃] trigonal pyramids, as in the two crystalline polymorphs of Sb₂O₃, whilst the presence of a second Sb−O distance (first distinguishable at x = 0.4

at a distance of 2.08 Å, and moving to higherrwith increasingx) together with the total Sb−O coordination number indicate the presence of additional antimony oxide units that are coordinated with more than three oxygen atoms.

The most plausible candidate for these units would appear to be [Sb3+O₄] pseudo- trigonal bipyramids of bond length 2.08 Å (as calculated from bond-valence parame- ters), which could be regarded as relaxed versions of the 2+2 units found in Sb₂O₄. The Sb5+ content determined by M¨ossbauer spectroscopy [1] may be present as [Sb5+O₆] octahedra similar to those found in Sb₂O₄ and Sb₂O₅, but relaxed to be closer to the bond-valence prediction of 2.01 Å for six-coordinated Sb5+_{, which would also con-}

ceal the resulting correlation peak beneath the one corresponding to the [SbO₃] trigonal pyramids. However, the total Sb−O coordination numbers obtained for the samples are not consistent with a large quantity of [SbO₄] units: merely assigning all of the Sb5+ detected by M¨ossbauer spectroscopy to [Sb5+O₆] octahedra accounts for much of the measured values (q.v.Table5-6).

There is also evidence that the antimony oxide units introduced into the borate network with increasing x initially distribute themselves homogeneously by breaking boroxol rings, but later retain some Sb−O−Sb connections, allowing B₃O₆structures to persist long after a totally homogeneous mixing of the two glass networks becomes pos- sible. This effect may be due to the presence of the more highly-coordinated [Sb5+O₆] octahedra which are more easily accommodated by the non-planar [SbO₃] units than by displacing the planar [BO₃] triangles.

5.5

Summary

A number of 11_{B-enriched antimony borate glasses (xSb}

2O3·(1−x) B2O3) previously

Chapter 5. Antimony Borate Glasses

analysis, Raman spectroscopy, density measurements and neutron diffraction. EDX data confirmed that the samples did not contain any substantial contaminants, whilst the Raman spectra supported previous findings [4,6] as to a structure primarily consisting of boroxol rings being cleaved by the introduction of Sb3+ions.

Density measurements largely agreed with the literature data when plotted against nominal compositions, but showed discrepancies for two samples when using the x

values obtained by quantitative NMR [1]. Neutron diffraction data were ultimately analysed using both sets of compositions and x values were determined by a set of criteria based on predictions from other techniques and trends apparent in the data.

The B−O correlation was fitted with two peaks, at the distances expected for three- and four-coordinated boron, showing a maximum value of N4 at x ≈ 0.5 and falling

thereafter, consistent with previous findings in the literature, whilst the O−B−O angle indicates that the three-coordinated boron is present predominantly as planar trigonal units: the distinctive peak at 3.6 Å inT(r) suggests that these units are largely organised into boroxol rings as in v-B₂O₃. The total Sb−O coordination number remains fairly constant at ∼3.25 throughout the compositional range studied, this total arising from

fitting two peaks to the first Sb−O correlation. The peak positions indicate that a ma- jority of the antimony occupies [SbO₃] trigonal pyramids, with a minority of [Sb3+O₄] pseudo-trigonal bipyramids also present. Whether [Sb5+O₆] octahedra also occur is less clear, since the bond length is expected to be very similar to that of the [SbO₃] trigonal pyramids, but this seems to be the only explanation for the structural role of the Sb5+ detected by M¨ossbauer spectroscopy.

Simulating the total correlation functions of the antimony borate system by com- bining weightedv-B₂O₃andv-Sb₂O₃data demonstrated that antimony oxide units ini- tially mix homogeneously with the boroxol rings at low x, but as more Sb₂O₃is added Sb−O−Sb linkages are retained—this may be due to the need to accommodate increas- ing numbers of [Sb5+O₆] octahedra in the network. This effect also means that boroxol rings persist in the glass structure long after the borate and antimony oxide networks could have mixed homogeneously.

References

References

[1] D. Holland, A. C. Hannon, M. E. Smith, C. E. Johnson, M. F. Thomas and A. M. Beesley,

Solid State Nucl. Mag.26, (2004), 172–179. [2] D. Holland, (personal communication) (2008).

[3] E. R. Barney,The Structural Role of Lone Pair Ions in Novel Glasses, PhD Thesis, Uni- versity of Warwick (2008).

[4] K. Terashima, T. Hashimoto, T. Uchino, S.-H. Kim and T. Yoko, J. Ceram. Soc. Jpn.

104(11), (1996), 1008–1014.

[5] J. Goubeau and H. Keller,Z. Anorg. Allg. Chem.272(6), (1953), 303–312.

[6] R. E. Youngman, S. Sen, L. K. Cornelius and A. J. G. Ellison,Phys. Chem. Glasses44(2), (2003), 69–74.

[7] B. N. Meera and J. Ramakrishna,J. Non-Cryst. Solids159, (1993), 1–21.

[8] G. D. Chryssikos, E. I. Kamitsos and W. M. Risen Jr., J. Non-Cryst. Solids 93, (1987), 155–168.

[9] P. A. V. Johnson, A. C. Wright and R. N. Sinclair,J. Non-Cryst. Solids50, (1982), 281– 311.

[10] A. C. Hannon, D. I. Grimley, R. A. Hulme, A. C. Wright and R. N. Sinclair,J. Non-Cryst. Solids177, (1994), 299–316.

[11] E. Kordes,Z. Phys. Chem.B43, (1939), 173–190.

[12] M. Imaoka, H. Hasegawa and S. Shindo,J. Ceram. Soc. Jpn.77(8), (1969), 263–271. [13] N. Mochida and K. Takahashi,J. Ceram. Soc. Jpn.84(9), (1976), 413–420.

[14] T. Honma, Y. Benino, T. Komatsu, R. Sato and V. Dimitrov, J. Chem. Phys. 115 (15), (2001), 7207–7214.

[15] S. Chatlani and J. E. Shelby,Phys. Chem. Glasses-B47(3), (2006), 288–293. [16] A. C. Hannon,Nucl. Instrum. Meth. A551(1), (2005), 88–107.

References

[18] E. R. Barney, (personal communication) (2008).

[19] N. E. Brese and M. O’Keeffe,Acta Crystallogr. B47, (1991), 192–197. [20] A. C. Hannon and J. M. Parker,J. Non-Cryst. Solids274, (2000), 102–109.

[21] A. G. Clare, G. Etherington, A. C. Wright, M. J. Weber, S. A. Brawer, D. D. Kingman and R. N. Sinclair,J. Chem. Phys.91, (1989), 6380–6392.

[22] W. S. Howells, A. K. Soper and A. C. Hannon,Report RAL-90-041, Tech. rep., Rutherford Appleton Laboratory (1990).

[23] C. Svensson,Acta Crystallogr. B31, (1975), 2016–2018. [24] C. Svensson,Acta Crystallogr. B30, (1974), 458–461.

[25] R. L. Mozzi and B. E. Warren,J. Appl. Cryst.3, (1970), 251–257. [26] V. M. Jansen,Acta Crystallogr. B35(3), (1979), 539–542.

[27] P. S. Gopalakrishnan and H. Manohar,Cryst. Struct. Commun.4, (1975), 203–206. [28] J. Amador, E. Guti´errez Puebla, M. A. Monge, I. Rasines and C. Ruiz Valero,Inorg. Chem.

27(8), (1988), 1367–1370.

[29] A. C. Hannon, E. R. Barney, D. Holland and K. S. Knight, J. Solid State Chem. 181, (2008), 1087–1102.