钛与钛铝化合物基合金相变及力学性能的价电子理论研究
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摘要
近年来，钛及钛铝化合物基合金在理论和实验研究与发展上都取得了很大的进展，这些进展是通过合金化、加工技术及热处理来实现的。其进一步的发展要求在相变基本理论方面、相及相界面电子结构、显微组织与其相应性能之间的关系等方面有更深入的研究。本文以EET和改进的TFD理论及合金成分设计价电子理论思想为基础，计算钛及钛铝化合物基合金相及相界面的价电子结构，研究价电子结构参数与相变过程、力学性能的关系，分析常用合金元素的合金化行为。本研究试图从电子结构层次上阐释合金强韧性微观本质，计算钛合金相体积分数与相变温度，基于合金成分与组织结构，定量计算合金力学性能。研究结果归纳如下：
1．阐释了与合金相变及力学性能有关的价电子结构参数，即相结构因子和界面结合因子的概念，给出了钛与钛铝化合物基合金相空间及相界面价电子结构计算模型与方法，计算了钛与钛铝化合物基合金相空间及相界面价电子结构参数。
2．分析了钛合金α和β相相空间及α／β相界面的价电子结构，探讨了相及相界面价电子结构参数与力学性能的关系。当n_A~(β-Ti-M)＞n_A~(β-Ti)时，β稳定元素M有利于β相区的扩展，能够稳定β相，降低β→α转变温度。β稳定元素M均使β-Ti-M固溶体的σ_N值增大，使组成相的原子价态能在更大的范围内变动以适应外界条件的变化，从而使合金相的稳定性增强。含Al、Sn的β相的F值小于β-Ti的F值，含Cr的β相的F仅稍大于β-Ti的F值，因而Al、Sn、Cr不利于β相的稳定性。合金元素的加入均使β-Ti晶格电子密度ρ_V~L下降，使键络强弱分布的差距进一步加大，使合金塑性下降。Ti-4.5Al-5Mo-1.5Cr合金韧性高于Ti-6Al-4V合金的本质原因在于其相及相界面价电子结构优于Ti-6Al-4V合金的价电子结构。
3．基于钛合金基本组成相的晶体结构特点及原子配位关系，定义了能够判断退火与淬火态钛合金中β稳定元素稳定能力的退火临界晶胞系数C_(kt)~M和淬火临界晶胞系数C_(kz)~M。在不同热处理条件下，β稳定元素稳定能力不同，与其原子外层电子结构状态及原子百分比含量x_(at)~M有关，即C_(kt)~M与C_(kz)~M愈大，β稳定元素M的稳定能力愈强，∑x_(at)~M、∑C_(kt)~M、∑C_(kz)~M愈大，钛合金室温组织中β相的体积分数愈多。
4．在退火临界晶胞系数C_(kt)~M和淬火临界晶胞系数C_(kz)~M及β稳定元素原子百分比含量
Great progress are obtained on theoretical and experimental studies and developments in titanium and Ti_Al- and TiAl-base alloys by means of alloying, process technology and heat treatment during recent years, which need profound research on the relationships between basic theories of phase transitions, valence electron structure (VES) of phases and phase-interfaces, microstructures and corresponding mechanical properties for further study. In this paper, Yu's empirical electron theory of solids and molccules (EET) and Cheng's improved Thmoas-Fermi-Dirac (TFD) theory and the valence electron theory of composition design of alloy are applied to calculate the VES and study the relationships between parameters of VES, phase transitions process and mechanical properties and analyze alloying behaviors of alloying elements, attempting to interpret the microscopic principle of strength and ductility of alloy from electron structure level and calculate volume fractions of phases and β transus in titanium alloys and quantitatively calculate mechanical properties of alloy based on alloy composition and structure. The investigation results are listed as following:
1. The parameters of VES related to phase transitions and mechanical properties, i.e., phase structure factors (PSF) and interface conjunction factors (ICF) are interpreted. The calculation model and method of VES of titanium alloys are presented, so the parameters of VES are calculated.
2. The VES of α phase and β phase and α/β interface are analyzed and the relationships between the parameters of VES and mechanical properties are discussed. When PSF n_A~(β-Ti-M) > n_A~(β-Ti) the β stabilizer M is benefit to the extend of β phase and stabilizes β phase and
decrease β transus. All β stabilizers can increase PSF σ_N of β solid solutions and can make the stability stronger. The PSFs F of β phase with Al, Sn are less than F of β-Ti, F of β phase with Cr is little more than F of β-Ti, so alloying elements Al, Sn and Cr are not benefit to the stability of β phase. The adding of alloying elements decrease lattice electron density ρ_V~L of
1．阐释了与合金相变及力学性能有关的价电子结构参数，即相结构因子和界面结合因子的概念，给出了钛与钛铝化合物基合金相空间及相界面价电子结构计算模型与方法，计算了钛与钛铝化合物基合金相空间及相界面价电子结构参数。
2．分析了钛合金α和β相相空间及α／β相界面的价电子结构，探讨了相及相界面价电子结构参数与力学性能的关系。当n_A~(β-Ti-M)＞n_A~(β-Ti)时，β稳定元素M有利于β相区的扩展，能够稳定β相，降低β→α转变温度。β稳定元素M均使β-Ti-M固溶体的σ_N值增大，使组成相的原子价态能在更大的范围内变动以适应外界条件的变化，从而使合金相的稳定性增强。含Al、Sn的β相的F值小于β-Ti的F值，含Cr的β相的F仅稍大于β-Ti的F值，因而Al、Sn、Cr不利于β相的稳定性。合金元素的加入均使β-Ti晶格电子密度ρ_V~L下降，使键络强弱分布的差距进一步加大，使合金塑性下降。Ti-4.5Al-5Mo-1.5Cr合金韧性高于Ti-6Al-4V合金的本质原因在于其相及相界面价电子结构优于Ti-6Al-4V合金的价电子结构。
3．基于钛合金基本组成相的晶体结构特点及原子配位关系，定义了能够判断退火与淬火态钛合金中β稳定元素稳定能力的退火临界晶胞系数C_(kt)~M和淬火临界晶胞系数C_(kz)~M。在不同热处理条件下，β稳定元素稳定能力不同，与其原子外层电子结构状态及原子百分比含量x_(at)~M有关，即C_(kt)~M与C_(kz)~M愈大，β稳定元素M的稳定能力愈强，∑x_(at)~M、∑C_(kt)~M、∑C_(kz)~M愈大，钛合金室温组织中β相的体积分数愈多。
4．在退火临界晶胞系数C_(kt)~M和淬火临界晶胞系数C_(kz)~M及β稳定元素原子百分比含量
Great progress are obtained on theoretical and experimental studies and developments in titanium and Ti_Al- and TiAl-base alloys by means of alloying, process technology and heat treatment during recent years, which need profound research on the relationships between basic theories of phase transitions, valence electron structure (VES) of phases and phase-interfaces, microstructures and corresponding mechanical properties for further study. In this paper, Yu's empirical electron theory of solids and molccules (EET) and Cheng's improved Thmoas-Fermi-Dirac (TFD) theory and the valence electron theory of composition design of alloy are applied to calculate the VES and study the relationships between parameters of VES, phase transitions process and mechanical properties and analyze alloying behaviors of alloying elements, attempting to interpret the microscopic principle of strength and ductility of alloy from electron structure level and calculate volume fractions of phases and β transus in titanium alloys and quantitatively calculate mechanical properties of alloy based on alloy composition and structure. The investigation results are listed as following:
1. The parameters of VES related to phase transitions and mechanical properties, i.e., phase structure factors (PSF) and interface conjunction factors (ICF) are interpreted. The calculation model and method of VES of titanium alloys are presented, so the parameters of VES are calculated.
2. The VES of α phase and β phase and α/β interface are analyzed and the relationships between the parameters of VES and mechanical properties are discussed. When PSF n_A~(β-Ti-M) > n_A~(β-Ti) the β stabilizer M is benefit to the extend of β phase and stabilizes β phase and
decrease β transus. All β stabilizers can increase PSF σ_N of β solid solutions and can make the stability stronger. The PSFs F of β phase with Al, Sn are less than F of β-Ti, F of β phase with Cr is little more than F of β-Ti, so alloying elements Al, Sn and Cr are not benefit to the stability of β phase. The adding of alloying elements decrease lattice electron density ρ_V~L of
引文
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