Institute of Metals Division - Influence of a Departure from Stoichiometry on the Microhardness of Rutile at Room Temperature (TN)

It has been proposed1'2 that, at low temperatures, point defects are a strengthening factor in inter-metallic compounds whereas, at high temperatures, the deformation is diffusion-controlled and, therefore, an increase in the concentration of point defects tends to soften or increase the plasticity of a compound. More recent investigations, including those of Bloem and Kroger' on PbS, Kramers and smith4 on TiO, and Nadeau5 on LiF, have extended this concept to ionic crystals. Rutile (TiO2) is a tetragonal transition metal oxide which has a defect structure over at least the compositional range. The defect in near-stoichiometric rutile is either an oxygen ion vacancys or a titanium ion interstitial.' This investigation does not contribute to resolving the defect question but either defect would satisfy the results obtained. Six specimens having the same orientation, see Fig., 1, utilized in an independent investigation1' were cut with a diamond saw from a single-crystal boule purchased from the Linde Co. Three specimens were annealed in air at 1200°C for 4 hr and slowly cooled to room temperature in a period of 12 hr. The remaining specimens were reduced in a vacuum of l0 mm Hg at 1200°C for 4 hr and cooled at the same rate in vacuum. The reduced specimens were weighed before and after reduction and, assuming the weight loss to be oxygen, the corresponding oxygen-to-metal ratio is 1.998. All specimens were chemically polished and etched utilizing the techniques described by Hirthe, Adsit, and Brittain." The specimens were embedded in acrylic resin and mounted on a leveling vise in a Kentron micro-hardness tester. A 200-g load was applied to a Knoop indenter with a descent time of 18 sec and a dwell time of 20 sec. Eight indentations were made on a near (171) surface, approximately 3 deg from the (lii) plane, for each orientation of the major axis of the indenter relative to the crystal structure. The dependence of microhardness on orienta-