Structure of oxychloride glasses by neutron and x-ray  difference  and x-ray photoelectron spectroscopy

Abstract

A previous study of the binary system, [Sb 2 O 3 ] x -[ZnCl 2 ] 1−x (Johnson et al 2003 J. Phys.: Condens. Matter 15 755-64), where nominally x = 0.25, 0.50, 0.75 and 1.00, has been extended to include Sb 2 O 3 -PbCl 2 . Information about the structure has been obtained from a combination of neutron and x-ray diffraction measurements, which were complemented by x-ray photoelectron spectroscopy. The data clearly show preferential bonding of oxygen to antimony and chlorine to zinc or lead in a single-phase glass with minimal change in the polyhedral structure with composition. The structure appears to be controlled by the need to avoid Sb-Cl-Sb links.

Solid-state chemistry of glassy antimony oxides

“…The PRDFs likewise show that there is no long-range order among the various atomic species. The Sb-O RDF peaks around 2.0 Å, which is in line with the experimental characterization of Johnson et al, 25 where simultaneous analysis of neutron and X-ray diffraction (XRD) data gave an Sb-O bond length of 1.99 Å in amorphous Sb 2 O 3 stabilized by ZnCl 2 . The correlation functions from XRD and neutron diffraction also match surprisingly well with the second and the third peaks in the function computed from our a-Sb 2 O 3 model, which indicates that the medium-and longer-range as well as the short-range order in our model also match experiment.…”

“…Note that the density of the amorphous sample is found to be less dense in the experimental study by Johnson et al, e.g. 5.05 g cm À3 for a-Sb 2 O 3 25 The internal coordinates and cell parameters of the final quenched structures were relaxed to minimize the residual stress, with convergence criteria of 10 À4 and 10 À5 eV for the total energy and electronic wavefunctions, respectively.…”

Neutron and x-ray diffraction studies of liquids and glasses

“…Such dual-beam (X+N) studies have been particularly useful for polyatomic oxide glasses (e.g. Benmore et al (2003), Johnson et al (2003), Hoppe et al (2004Hoppe et al ( , 2001Hoppe et al ( , 1998, Karabulut et al (2000)) and for some aqueous solutions (e.g. Bakó et al (1999), Andreani and Petrillo (1987)), molecular liquids (e.g.…”

A Review of High-Energy X-Ray Diffraction from Glasses and Liquids

“…Oxide glasses have particular relevance in geoscience and technology and include soda-lime window glass, borosilicate pyrex glass, lead oxide glassware, aluminosilicate fiberglass, and aluminate glass fiber optics. Much of the research has focused on the short and intermediate range order in silicates [57][58][59][60][61][62][63][64][65], Na-silicates [66,67], germanates [68], borates [69][70][71] aluminates [72][73][74], and aluminosilicates [44,75,76]. XRD PDF data on oxide glasses is highly complimentary to neutron diffraction PDF data since neutrons are more sensitive to the oxygen atoms, often providing a stark contrast in the partial structure factor weighting factors.…”