Thermophysical Measurements in Liquid Alloys and Phase Diagram Studies.

Towards the construction of pressure-dependent phase diagrams of binary alloy systems, both thermophysical measurements and thermodynamic modeling are employed. High-accuracy measurements of sound velocity, density, and electrical resistivity were performed for selected metallic elements from columns III to V and their alloys in the liquid phase. Sound velocity measurements were made using ultrasonic techniques, density measurements using the gamma radiation attenuation method, and electrical resistivity measurements were performed using the four probe method. Sound velocity and density data, measured at ambient pressure, were incorporated into a thermodynamic model to calculate the pressure dependence of binary phase diagrams. Electrical resistivity measurements were performed on binary systems to study phase separation and identify phase transitions in the liquid state.

Novel experimental design for high pressure-high temperature electrical resistance measurements in a "Paris-Edinburgh" large volume press.

We present a novel experimental design for high sensitivity measurements of the electrical resistance of samples at high pressures (0-6 GPa) and high temperatures (300-1000 K) in a "Paris-Edinburgh" type large volume press. Uniquely, the electrical measurements are carried out directly on a small sample, thus greatly increasing the sensitivity of the measurement. The sensitivity to even minor changes in electrical resistance can be used to clearly identify phase transitions in material samples. Electrical resistance measurements are relatively simple and rapid to execute and the efficacy of the present experimental design is demonstrated by measuring the electrical resistance of Pb, Sn, and Bi across a wide domain of temperature-pressure phase space and employing it to identify the loci of phase transitions. Based on these results, the phase diagrams of these elements are reconstructed to high accuracy and found to be in excellent agreement with previous studies. In particular, by mapping the locations of several well-studied reference points in the phase diagram of Sn and Bi, it is demonstrated that a standard calibration exists for the temperature and pressure, thus eliminating the need for direct or indirect temperature and pressure measurements. The present technique will allow simple and accurate mapping of phase diagrams under extreme conditions and may be of particular importance in advancing studies of liquid state anomalies.

On the relation between the microscopic structure and the sound velocity anomaly in elemental melts of groups IV, V, and VI.

The sound velocity of some liquid elements of groups IV, V, and VI, as reported in the literature, displays anomalous features that set them apart from other liquid metals. In an effort to determine a possible common origin of these anomalies, extensive neutron diffraction measurements of liquid Bi and Sb were carried out over a wide temperature range. The structure factors of liquid Sb and Bi were determined as a function of temperature. The structure of the two molten metals was carefully analyzed with respect to peak locations, widths, and coordination numbers in their respective radial distribution function. The width of the peaks in the radial distribution functions was not found to increase and even decreased within a certain temperature range. This anomalous temperature dependence of the peak widths correlates with the anomalous temperature dependence of the sound velocity. This correlation may be accounted for by increased rigidity of the liquid structure with temperature. A phenomenological correlation between the peak width and the sound velocity is suggested for metallic melts and is found to agree with available data for normal and anomalous elemental liquids in groups IV-VI.