Ti-Al-∑X（X=B，C，Fe，Si，Cr，Nb）系α（α2）/γ相平衡的研究
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摘要
合金化是改善γ-TiAl 基合金性能的有效方法之一,而C、B、Si、Fe 是其中重要的合金化元素,同时加入Cr-Nb、Cr-Si、Nb-Si是重要的合金化方案。本研究采用合金平衡扩散处理法(简称合金法)和扩散偶-电子探针法系统测定了Ti-Al-C、Ti-Al-B、Ti-Al-Si、Ti-Al-Fe 三元系和Ti-Al-Cr-Fe、Ti-Al-Cr-Si、Ti-Al-Nb-Fe 和Ti-Al-Nb-Si 四元系α(α_2)/γ相平衡关系和相平衡成分,成为这些合金系这一相平衡的最系统的研究结果。巨势法是一种富有发展潜力的相平衡计算方法,已在二元系实际相平衡计算中表现出优势。本研究对三元系相平衡的巨势法计算做了较深入的研究,进行了一系列的模型计算,并将其应用于实际合金体系??Ti-Al-Nb 系的相平衡计算。
采用合金法测定了Ti-Al-C、Ti-Al-B、Ti-Al-Si 和Ti-Al-Fe 等三元系的1000~1250℃α(α_2)/γ相平衡关系和成分,根据测定结果分别绘出了0.2 at.%C、0.1at.%B、0.3at.%Si 和1.0at.% Fe 垂直截面相图,并计算了γ相稳定化参数△~*Gi~(α(α_2)→γ)(i=C, B, Si, Fe)。结果表明:
(1) 在Ti-Al二元系中,加入少量的C 和B 使(α(α_2)+γ)/γ相界线向高Al 方向移动,B 还使α(α_2)/(α(α_2)+γ)相界线向高Al 方向移动;加入少量的Si 和Fe使α(α_2)/(α(α_2)+γ)相界线向富Ti方向有较大移动,Fe 还使(α(α_2)+γ)/γ相界线向富Ti方向移动;加入0.1at.%B 使Tα温度降低约18℃,0.3at.%Si、1.0at.%Fe 分别使Tα温度提高约80~110℃和90~110℃,而加入0.2at.%C 对Tα温度影响不大。
(2) C、B和Si在α(α_2)相中的溶解度均大于在γ相中的溶解度,而Fe 在α(α_2)相中的溶解度则小于在γ相中的溶解度,且Fe 在α(α_2)和γ相中的分配比随温度升高而增大。
(3) 当Si含量增加到1.0at%时,组织中出现第三相Ti5Si3。Ti5Si3相的出现使α(α_2)/γ片层组织细化,且粗化困难。
采用本研究设计的简易四元扩散偶-电子探针法,测定了Ti-Al-Cr-Fe 系的
It has been shown that additions of alloying elements such as B, C, Fe, Si, Cr-Nb, Cr-Si and Nb-Si to γ-TiAl-based alloys is an effective method to improve the properties of the alloys. However, the α(α_2)/γphase equilibria in the Ti-Al-X(X=B, C, Fe, Si) ternary systems have not been studied systematically, and the α(α_2)/γphase equilibria in the Ti-Al-Cr-Si, Ti-Al-Cr-Fe, Ti-Al-Nb-Si and Ti-Al-Nb-Fe quarternary systems are never reported. In the present work, the α(α_2)/γphase equilibria in Ti-Al-B, Ti-Al-C, Ti-Al-Fe, Ti-Al-Si, Ti-Al-Cr-Fe, Ti-Al-Cr-Si, Ti-Al-Nb-Fe and Ti-Al-Nb-Si systems have been determined using alloy-equilibrium-diffusion treatment, diffusion couple and electron probe microanalysis (EPMA).
Recent work in our group has indicated that the grand potential method (GPM) is effective to calculate phase equilibrium in binary systems. In the present work, the applicability of GPM in ternary systems has been studied systematically and the α/βand the α/γphase equilibria in the Ti-Al-Nb ternary system has been calculated by GPM.
The α(α_2)/γphase equilibria at 1000~1250℃in Ti-Al-X(X=B, C, Fe, Si) ternary systems were determined by alloy-equilibrium-diffusion treatment and EPMA. According to the obtained data, the partial vertical sections of Ti-Al-X(X=B, C, Fe, Si) ternary systems have been plotted at 0.1at.%B, 0.2at.%C, 0.3at.%Si and 1.0at.%Fe, respectively. The results are as following:
(1) The addition of B to the Ti-Al binary system results in a shift of both the α(α_2)/(α(α_2)+γ) and the (α(α_2)+γ)/γboundaries to the Al-rich side and 0.1at.%B addition decreases Tαby 18℃. The addition of C leads to a shift of the (α(α_2)+γ)/γboundary to the Al-rich side but the effect of 0.2at.%C addition on Tαis very slight. The addition of 0.3at.%Si increases Tαby 80~110℃and 1.0at.%Fe addition by 90~110℃. However, 1.0at.% Fe addition leads to a limited shift of the (α(α_2)+γ)/γboundary to the Ti-rich side, whereas the effect of 0.3at.%Si addition on the (α(α_2)+γ)/γboundary is quite slight.
(2) The solubilities of B, C and Si in the α(α_2) phase are larger than those in the γphase,
whereas the solubility of Fe in the α(α2) phase is smaller than that in the γphase. With increasing temperature, the partitioning ratio KFeα/γincreases gradually. (3) A third phase Ti5Si3 appears in Ti-46Al-1.0Si alloy and obviously restrain coarsening of primary lamellae of the alloy at elevated temperature. A new method of diffusion couple was designed to determine the α/γphase equilibrium in quarternary systems. By using this method, the α/γphase equilibria at 1150~1250 ℃in the Ti-Al-Cr-Fe, Ti-Al-Cr-Si, Ti-Al-Nb-Fe and Ti-Al-Nb-Si quarternary systems have been determined. Based on the measured α/γphase equilibrium data, the partial isothermal squares for the Ti-Al-Cr-Fe, Ti-Al-Cr-Si, Ti-Al-Nb-Fe and Ti-Al-Nb-Si quarternary systems have been obtained. The results show that the addition of Cr to the Ti-Al-Fe ternary system increases the partitioning ratio KFeα/γat given temperature, whereas the addition of Cr to the Ti-Al-Si ternary system decreases the partitioning ratio KSiα/γ. Both the additions of Si and Fe to the Ti-Al-Cr ternary system increase the partitioning ratio KCrα/γat given temperature. In this work, the principle, equations, approaches and programs for calculating the miscibility gap and the dissimilar phase equilibrium in ternary system by GPM are given systematically. Based on the theoretical analysis, a series of phase diagrams with miscibility gap and dissimilar phase equilibrium in ternary systems at a given temperature have been calculated out with various thermodynamic parameters. The results show that the calculation of phase equilibrium in ternary system by GPM has characteristics of clear geometrical relationship, convenient approach and wide application. Comparing with the usual optimization method for calculating the minimum value of the Gibbs free energe, GPM in ternary system has no convergent problem and has a high calculation efficiency. Based on the GPM in ternary system above, a new method to calculate the phase transition temperature in ternary system was proposed and is also applied to calculate the α→(α+γ) transition temperature Tαin Ti-Al-Nb system. The calculated results agree well with the experimental data. According to experimental data of phase equilibria in ternary system, the methods (the T0 line method and the chemical potential equality method) to determine the binary interaction parameters in metastable phases were proposed. By these methods, the interaction parameters IαA lNb, IγA lNb and IγN bTi are obtained with the subregular solution model based on the experimental data of α/βand α/γphase equilibria in the Ti-Al-Nb ternary system. The interaction parameters, IβT iAl, IγT iAl, IαTi2Al, IαN bTi, IβN bTi and IAβlNb were calculated using the experimental data in the Ti-Al,Al-Nb and Nb-Ti binary systems. Using the obtained thermodynamic parameters above, the phase equilibria α/β, α/γ, α2/γ
in the Ti-Al binary system, L/βin the Al-Nb binary system, α/βin the Nb-Ti binary system, α/β( at 1150℃and 1400℃) and α/γ(at 1150℃, 1200℃, 1250℃, 1300℃and 1400℃) in the Ti-Al-Nb ternary system were calculated. The results are consistent well with the experimental phase diagram.
采用合金法测定了Ti-Al-C、Ti-Al-B、Ti-Al-Si 和Ti-Al-Fe 等三元系的1000~1250℃α(α_2)/γ相平衡关系和成分,根据测定结果分别绘出了0.2 at.%C、0.1at.%B、0.3at.%Si 和1.0at.% Fe 垂直截面相图,并计算了γ相稳定化参数△~*Gi~(α(α_2)→γ)(i=C, B, Si, Fe)。结果表明:
(1) 在Ti-Al二元系中,加入少量的C 和B 使(α(α_2)+γ)/γ相界线向高Al 方向移动,B 还使α(α_2)/(α(α_2)+γ)相界线向高Al 方向移动;加入少量的Si 和Fe使α(α_2)/(α(α_2)+γ)相界线向富Ti方向有较大移动,Fe 还使(α(α_2)+γ)/γ相界线向富Ti方向移动;加入0.1at.%B 使Tα温度降低约18℃,0.3at.%Si、1.0at.%Fe 分别使Tα温度提高约80~110℃和90~110℃,而加入0.2at.%C 对Tα温度影响不大。
(2) C、B和Si在α(α_2)相中的溶解度均大于在γ相中的溶解度,而Fe 在α(α_2)相中的溶解度则小于在γ相中的溶解度,且Fe 在α(α_2)和γ相中的分配比随温度升高而增大。
(3) 当Si含量增加到1.0at%时,组织中出现第三相Ti5Si3。Ti5Si3相的出现使α(α_2)/γ片层组织细化,且粗化困难。
采用本研究设计的简易四元扩散偶-电子探针法,测定了Ti-Al-Cr-Fe 系的
It has been shown that additions of alloying elements such as B, C, Fe, Si, Cr-Nb, Cr-Si and Nb-Si to γ-TiAl-based alloys is an effective method to improve the properties of the alloys. However, the α(α_2)/γphase equilibria in the Ti-Al-X(X=B, C, Fe, Si) ternary systems have not been studied systematically, and the α(α_2)/γphase equilibria in the Ti-Al-Cr-Si, Ti-Al-Cr-Fe, Ti-Al-Nb-Si and Ti-Al-Nb-Fe quarternary systems are never reported. In the present work, the α(α_2)/γphase equilibria in Ti-Al-B, Ti-Al-C, Ti-Al-Fe, Ti-Al-Si, Ti-Al-Cr-Fe, Ti-Al-Cr-Si, Ti-Al-Nb-Fe and Ti-Al-Nb-Si systems have been determined using alloy-equilibrium-diffusion treatment, diffusion couple and electron probe microanalysis (EPMA).
Recent work in our group has indicated that the grand potential method (GPM) is effective to calculate phase equilibrium in binary systems. In the present work, the applicability of GPM in ternary systems has been studied systematically and the α/βand the α/γphase equilibria in the Ti-Al-Nb ternary system has been calculated by GPM.
The α(α_2)/γphase equilibria at 1000~1250℃in Ti-Al-X(X=B, C, Fe, Si) ternary systems were determined by alloy-equilibrium-diffusion treatment and EPMA. According to the obtained data, the partial vertical sections of Ti-Al-X(X=B, C, Fe, Si) ternary systems have been plotted at 0.1at.%B, 0.2at.%C, 0.3at.%Si and 1.0at.%Fe, respectively. The results are as following:
(1) The addition of B to the Ti-Al binary system results in a shift of both the α(α_2)/(α(α_2)+γ) and the (α(α_2)+γ)/γboundaries to the Al-rich side and 0.1at.%B addition decreases Tαby 18℃. The addition of C leads to a shift of the (α(α_2)+γ)/γboundary to the Al-rich side but the effect of 0.2at.%C addition on Tαis very slight. The addition of 0.3at.%Si increases Tαby 80~110℃and 1.0at.%Fe addition by 90~110℃. However, 1.0at.% Fe addition leads to a limited shift of the (α(α_2)+γ)/γboundary to the Ti-rich side, whereas the effect of 0.3at.%Si addition on the (α(α_2)+γ)/γboundary is quite slight.
(2) The solubilities of B, C and Si in the α(α_2) phase are larger than those in the γphase,
whereas the solubility of Fe in the α(α2) phase is smaller than that in the γphase. With increasing temperature, the partitioning ratio KFeα/γincreases gradually. (3) A third phase Ti5Si3 appears in Ti-46Al-1.0Si alloy and obviously restrain coarsening of primary lamellae of the alloy at elevated temperature. A new method of diffusion couple was designed to determine the α/γphase equilibrium in quarternary systems. By using this method, the α/γphase equilibria at 1150~1250 ℃in the Ti-Al-Cr-Fe, Ti-Al-Cr-Si, Ti-Al-Nb-Fe and Ti-Al-Nb-Si quarternary systems have been determined. Based on the measured α/γphase equilibrium data, the partial isothermal squares for the Ti-Al-Cr-Fe, Ti-Al-Cr-Si, Ti-Al-Nb-Fe and Ti-Al-Nb-Si quarternary systems have been obtained. The results show that the addition of Cr to the Ti-Al-Fe ternary system increases the partitioning ratio KFeα/γat given temperature, whereas the addition of Cr to the Ti-Al-Si ternary system decreases the partitioning ratio KSiα/γ. Both the additions of Si and Fe to the Ti-Al-Cr ternary system increase the partitioning ratio KCrα/γat given temperature. In this work, the principle, equations, approaches and programs for calculating the miscibility gap and the dissimilar phase equilibrium in ternary system by GPM are given systematically. Based on the theoretical analysis, a series of phase diagrams with miscibility gap and dissimilar phase equilibrium in ternary systems at a given temperature have been calculated out with various thermodynamic parameters. The results show that the calculation of phase equilibrium in ternary system by GPM has characteristics of clear geometrical relationship, convenient approach and wide application. Comparing with the usual optimization method for calculating the minimum value of the Gibbs free energe, GPM in ternary system has no convergent problem and has a high calculation efficiency. Based on the GPM in ternary system above, a new method to calculate the phase transition temperature in ternary system was proposed and is also applied to calculate the α→(α+γ) transition temperature Tαin Ti-Al-Nb system. The calculated results agree well with the experimental data. According to experimental data of phase equilibria in ternary system, the methods (the T0 line method and the chemical potential equality method) to determine the binary interaction parameters in metastable phases were proposed. By these methods, the interaction parameters IαA lNb, IγA lNb and IγN bTi are obtained with the subregular solution model based on the experimental data of α/βand α/γphase equilibria in the Ti-Al-Nb ternary system. The interaction parameters, IβT iAl, IγT iAl, IαTi2Al, IαN bTi, IβN bTi and IAβlNb were calculated using the experimental data in the Ti-Al,Al-Nb and Nb-Ti binary systems. Using the obtained thermodynamic parameters above, the phase equilibria α/β, α/γ, α2/γ
in the Ti-Al binary system, L/βin the Al-Nb binary system, α/βin the Nb-Ti binary system, α/β( at 1150℃and 1400℃) and α/γ(at 1150℃, 1200℃, 1250℃, 1300℃and 1400℃) in the Ti-Al-Nb ternary system were calculated. The results are consistent well with the experimental phase diagram.
引文
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