Part VIII - Papers - Activities of Chromium and Titanium in Binary Chromium-Titanium Alloys

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult's law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of 'TiCr, is —0.76' lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,' no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were