Identifying and characterising the different structural length scales in liquids and glasses: an experimental approach

Abstract

The structure of several network-forming liquids and glasses is considered, where a focus is placed on the detailed information that is made available by using the method of neutron diffraction with isotope substitution (NDIS). In the case of binary network glass-forming materials with the MX 2 stoichiometry (e.g. GeO 2 , GeSe 2 , ZnCl 2 ), two different length scales at distances greater than the nearest-neighbour distance manifest themselves by peaks in the measured diffraction patterns. The network properties are influenced by a competition between the ordering on these ''intermediate'' and ''extended'' length scales, which can be manipulated by changing the chemical identity of the atomic constituents or by varying state parameters such as the temperature and pressure. The extended-range ordering, which describes the decay of the pair-correlation functions at large-r, can be represented by making a pole analysis of the Ornstein-Zernike equations, an approach that can also be used to describe the large-r behaviour of the pair-correlation functions for liquid and amorphous metals where packing constraints are important. The first applications are then described of the NDIS method to measure the detailed structure of aerodynamically-levitated laser-heated droplets of ''fragile'' glass-forming liquid oxides (CaAl 2 O 4 and CaSiO 3 ) at high-temperatures (B2000 K) and the structure of a ''strong'' network-forming glass (GeO 2 ) under pressures ranging from ambient to B8 GPa. The high-temperature experiments show structural changes on multiple length scales when the oxides are vitrified. The high-pressure experiment offers insight into the density-driven mechanisms of network collapse in GeO 2 glass, and parallels are drawn with the high-pressure behaviour of silica glass. Finally, the hydrogen-bonded network of water is considered, where the first application of the method of oxygen NDIS is used to measure the structures of light versus heavy water and a difference of C0.5% is found between the O-D and O-H intra-molecular bond lengths. The experimental data are best matched by using path integral molecular dynamics simulations with a flexible anharmonic water model, and the results support a competing quantum effects model for water in which its structural and dynamical properties are governed by an offset between intra-molecular and inter-molecular quantum contributions.

Topological Ordering and Viscosity in the Glass-Forming Ge–Se System: The Search for a Structural or Dynamical Signature of the Intermediate Phase

“…Another length scale is associated with ordering on an extended range, and manifests itself by the appearance of a principal peak in S NN (q) at q PP , where q PP r nn ≃ 4.5 − 4.8 for glassy Ge x Se 1−x . A competition between the ordering on these two length scales for different classes of binary glass-forming melts influences their relative fragility Salmon, 2007b;Salmon and Zeidler, 2013). The present neutron diffraction work complements previous investigations on the structure of intermediate phase glasses using neutron diffraction (Ramesh Rao et al, 1998), X-ray diffraction (Wang et al, 2004;Sharma et al, 2005), anomalous X-ray diffraction (Hosokawa et al, 2003(Hosokawa et al, , 2011; or a combination of high-energy X-ray diffraction and extended X-ray absorption fine structure (EXAFS) spectroscopy (Shatnawi et al, 2008).…”

Direct observation in 3d of structural crossover in binary hard sphere mixtures

“…We can expect similar behaviour for many dense binary liquid mixtures, such as metals, noble gases and molecules such as CCl 4 and globular proteins which may reasonably be treated as spherical. Neutron scattering experiments, in particular, those which enable the oscillatory decay of g i j (r) to be extracted from the partial structure factors, 35,36 could elucidate further the crossover in a wide range of materials.…”

Materials under pressure

“…Much ground has, however, been covered in recent years in the characterization of glasses at all length scales. 41,42 The local atomic environments such as bonding, coordination, and angular distribution of adjacent units, and their organization on an intermediate scale, have been investigated. These have been linked to the macroscopic mechanical bulk responses to increased load or strain.…”