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THE EFFECT OF RUTHENIUM ADDITION ON THE PHASE EQUILIBRIA, MECHANICAL PROPERTIES AND OXIDATION RESISTANCE OF TIAL-BASED ALLOYS
Title
THE EFFECT OF RUTHENIUM ADDITION ON THE PHASE EQUILIBRIA, MECHANICAL PROPERTIES AND OXIDATION RESISTANCE OF TIAL-BASED ALLOYS
Creator
Liu, Qizheng
Date
2012-05-11, 2011-12
Description
The high temperature phase equilibria in the Ti-Al-Ru ternary system have been investigated but there remain some ambiguous regions. In this...
Show moreThe high temperature phase equilibria in the Ti-Al-Ru ternary system have been investigated but there remain some ambiguous regions. In this work arc-melted alloys were studied using scanning electron microscopy, X-ray diffraction and optical microscopy to determine the isothermal section of Ti-Al-Ru system at 1200°C. The lattice parameters were calculated from X-ray diffraction pattern for some compounds, including LI, 8-Ruso(TixAlso-x) and (AI6o-xTix)Ru4o. The lattice parameter of these three phases generally increases with Ti content. Enthalpy of formation was also measured for LI and 8-Ruso(TixAlso_x) with direct synthesis calorimeter to compare with the lattice parameter change. The enthalpy of formation of LI matches its lattice parameter change, but 8-Ruso(TixAlso_x) shows a reversed trend. It suggests that addition of Ti introduces a stronger bonding in the 8-B2 phase super-lattice. The phase equilibria are discussed in comparison with published research work. A new three phase region was detected for L t, Y and Til_xAl 1+x by X-ray diffraction. The homogeneity region of (AI6o-xTix)RU4o was found to be much higher than previously reported, with almost constant Ru content. The results from the ternary isothermal section also help to clarify the uncertain parts of the binary Ti-Al phase diagram. Three ternary eutectic reaction temperatures were measured with differential scanning calorimetry and the results were compared with the published liquidus projection. The high temperature compression behavior of TiAl-Ru alloys was studied at different temperatures and strain rates. Ru was found to have a strong strengthening effect on TiAI alloys. However the Ru addition amount was limited by its low solubility in y-TiAI and U2-Ti3AI, and the detrimental effect of excessive ternary phase precipitation. Furthermore, the melting temperature decreases when Ru 2:0.6at% as the alloy composition approaches a ternary eutectic point. The strengthening mechanism is discussed and two separate mechanisms are proposed, viz. solid solution strengthening and refined colony strengthening. Intergranular cracks were found in the alloys with low Ru or no Ru addition, but were barely detected as Ru content increased to above 0.6 at.%. It was suggested that Ru showed a beneficial effect on both strength and ductility of TiAI alloys due to the refined colony size. Three-point bend test results showed that the Ru addition can also improve the room temperature ductility of TiAl alloys. Hot workability was increased according to the compression tests. Thermal-mechanically treated TiAI-Ru had much smaller grain size than the heat-treated samples due to dynamic recrystallization. But it did not show superior strength in the compression test compared to the heat-treated samples. The Zener-Hollomon parameter was calculated from the compression strength of heat-treated TiAI-Ru alloys. Its relationship with dynamic recrystallization and hot work is discussed. The mechanical properties of TiAI-Ru alloys are compared with TiAI-Nb samples and demonstrate a promising combination of strength and ductility. The high-temperature oxidation resistance ofTiAI alloys with constant AI content and different alloying elements was tested with thermogravimetric calorimeter. Both Ru and Nb additions were found to have beneficial effect on the oxidation resistance ofTiAI alloys. While TiAI-Ru showed a slight improvement on the oxidation behavior, TiAI-Nb alloys had much better performance in comparison with TiAI alloys. Complicated oxide scale structure was characterized with the assistance of X-ray diffraction, scanning electron microscopy and Energy-dispersive X-ray spectroscopy analysis. The different oxide scale structure among the TiAl, TiAl-Ru and TiAl-Nb alloys were discussed with respect to their thickness, spatial pattern and composition gradient. The poor oxidation resistance of TiAI alloys at the testing temperature was determined to be attributed to the competition growth between Ah03 as well as Ti02, and the lack of a thick continuous Ah03 layer. The outward diffusion of Ti was found to be the controlling factor and the growth of Ti02 on top level of the oxide scale destroyed the initial Ah03 protection. RU02 was found to be the natural marker of the oxidation process in TiAl-Ru alloys due to its slow diffusion. The repartitioning of Ru in the oxide/substrate boundary was revealed to be the reason of its slight beneficial effect. Nb20 S layer was observed in the oxide scale of TiAl-Nb alloys and it played the role of blocking the outward diffusion of Ti. Thus Nb addition can suppress the growth of Ti02 and promote the formation of a continuous AI 20 3 layer. Treating the TiAI alloys by dipping in hydrofluoric (HF) acid was found to have a dramatic beneficial effect on TiAI alloys. Alloying elements have reversed effect on the HF dipping due to the reduced reaction rate with HF acid. The oxidation rate constant and activation energy were calculated for TiAI alloys with/without alloying addition. They were compared with the published data and the trend with composition change was discussed.
Ph.D. in Materials Science and Engineering, December 2011
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