Configurational constraints on glass formation in the liquid calcium aluminate system

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Structure and triclustering in Ba-Al-O glass

Glass-forming ability in the (BaO) x(Al 2O 3) 1-x system (0≤x≤1) was investigated by using the containerless aerodynamic levitation and laser-heating method. The main glass-forming region was found to occur for 0.40(2) ≤x≤ 0.48(2), where there is insufficient oxygen to form an ideal network of corner-sharing AlO 4 tetrahedra in which the oxygen atoms are twofold coordinated, with another narrow glass-forming region at x = 0.62(2) around the eutectic composition. The glass corresponding to x = 0.4 was chosen for further investigation by using both neutron and x-ray diffraction, and a detailed atomistic model was built by applying a combination of molecular dynamics and reverse Monte Carlo methods. The results show a network structure based predominantly on corner-sharing tetrahedral AlO 4 motifs in which triclusters (OAl 3 units formed by three tetrahedral Al atoms sharing a common vertex) play an integral part, with as many as 21% of the oxygen atoms involved in these configurations. The barium ions bind to an average of 7.4 O atoms, most of which are twofold-coordinated bridging oxygen atoms. The larger size of barium compared to calcium narrows the range of glass-forming compositions in alkaline-earth aluminates such that the main glass-forming range corresponds to a regime in which an oxygen-deficient Al-O network is stabilized by the formation of triclusters

Neutron diffraction as a probe of liquid and glass structures under extreme conditions

Scanning electron micrograph taken of palladium/platinum coated structures with an FEI Quanta 600 FEG environmental scanning electron microscope

Structure of levitated Si-Ge melts studied by high-energy x-ray diffraction in combination with reverse Monte Carlo simulations

The short-range order in liquid Si, Ge and binary Six-Ge1-x alloys (x = 0.25, 0.50, 0.75) was studied by x-ray diffraction and reverse Monte Carlo simulations. Experiments were performed in the normal and supercooled liquid states by using the containerless technique of aerodynamic levitation with CO2 laser heating, enabling deeper supercooling of liquid Si and Si-Ge alloys than previously reported. The local atomic structure of liquid Si and Ge resembles the beta-tin structure. The first coordination numbers of about 6 for all compositions are found to be independent of temperature indicating the supercooled liquids studied retain this high-density liquid (HDL) structure. However, there is evidence of developing local tetrahedral ordering, as manifested by a shoulder on the right side of the first peak in S(Q) which becomes more prominent with increasing supercooling. This result is potentially indicative of a continuous transition from the stable HDL beta-tin (high pressure) phase, towards a metastable low-density liquid phase, reminiscent of the diamond (ambient pressure) structure

Neutron diffraction of calcium aluminosilicate glasses and melts

International audienceThe combination of neutron diffraction with aerodynamic levitation and laser heating, pioneered by Neville Greaves and co-workers about 15 years ago, is an important tool for studying the structure of liquid melts. Since the first work on liquid Al2O3 published in 2001, the technique has been largely improved and experiments are now routinely performed at neutron sources, providing interesting structural information on various materials.In this paper, the structure of glass-forming compounds in the system CaO-Al2O3-SiO2 was measured by applying neutron diffraction with aerodynamic levitation. Results obtained in the liquid state above the melting point and from the glass at room temperatures are presented. Various compositions were studied by increasing the silica content and by changing the ratio CaO/Al2O3. As observed using other methods, the main structural changes relate to modification of the Al-O short range order