Ti-Al-Nb三元系中的合金组织对性能的影响
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摘要
本文参考了大量Ti-Al-Nb系各个温度下的三元相图,以及合金元素对二元Ti-Al相图的影响等文献,在Ti、Al等原子比的基础上,调整Nb的量设计并制备了一系列Ti-Al-Nb三元合金。合金设计的目的是为了获得不同相组成的合金。采用示差热分析方法、X射线衍射分析、电子探针背散射电子成分像及微区成分分析、透射电镜明场像及选区电子衍射以及光学显微组织分析等多种手段确定了在不同温度下实验材料的显微组织形貌及相组成。所有实验样品在实验前都经过1473K,5小时的均匀化处理。
首先,我们选择了不同含Nb量的具有不同相组成的四种Ti-Al-Nb三元合金,它们的名誉化学成分分别为:Ti-47.5Al-5Nb、Ti-42.85Al-14.3Nb、Ti-40Al-20Nb和Ti-35Al-30Nb(at%);它们的相组成分别为:γ-TiAl、γ-TiAl+α_2-Ti_3Al和γ-TiAl+α_2-Ti_3Al+Nb_2Al。对这四种合金进行1273K,100小时的断续氧化实验。研究结果表明,我们所研究的四种Ti-Al-Nb三元合金的高温抗氧化性能都比同样实验条件下的二元Ti-Al合金抗氧化性能好很多,这四种Ti-Al-Nb三元合金在1273K,100小时的断续氧化增重量都小于8mg/cm~2,特别是成分为Ti-42.85Al-14.3Nb的双相合金其氧化增重量仅为2.5mg/cm~2,而二元Ti-Al合金的氧化增重量达到69mg/cm~2。二元Ti-Al合金在1073K,100小时的断续氧化增重量与我们所研究的四种Ti-Al-Nb三元合金在1273K,100小时的断续氧化增重量在一个水平上为1-3mg/cm~2;在这四种Ti-Al-Nb三元合金中,相组成为γ-TiAl+α_2-Ti_3Al的双相合金抗氧化性能最好,分析其原因,一方面是由于两相中固溶了大量的Nb(分别达到13.3at%和19.4at%),另一方面是由于α_2-Ti_3Al的存在使得其主要相γ-TiAl的含Al量相对提高,富Al的γ-TiAl相有利于Al_2O_3的生成及稳定生长。成分为Ti-47.5Al-5Nb的单相γ-TiAl合金由于其含Nb量较少,Nb没有充分起到抑制TiO_2的生长及促进Al_2O_3生成的作用,虽然其比二元Ti-Al合金抗氧化性能要好许多,但仍然没有生成具有保护作用的连续的Al_2O_3保护膜。同样当含Nb量超过20at%时(如Ti-40Al-20Nb和Ti-35Al-30Nb合金)由于氧化生成的Nb_2O_5是一个结构疏松且与基体结合力非常差的氧化膜,在氧化过程中极容易从基体上剥落下来,使其抗氧化性能下降。
在上述抗氧化性能的研究基础上,选择相组成为单相γ-TiAl、双相γ-TiAl+α_2-Ti_3Al和三相γ-TiAl+α_2-Ti_3Al+Nb_2Al,成分分别为Ti-47.5Al-5Nb、Ti-42.85Al-14.3Nb和Ti-40Al-20Nb三种Ti-Al-Nb三元合金,进行从室温至1373K的压缩性能实验及室温和1173K的拉伸性能实验。实验结果表明,Ti-Al-Nb三元单相γ-TiAl合金在低温一侧同二元γ-TiAl合金具有同样的屈服强度450MPa,该强度一致保持到1200K左右,但是在高温一侧的屈服强度要远远高于二元γ-TiAl、Inconel715以及Ti-48Al-2Cr-2Nb等合金,这是因为γ相中固溶了比较多的Nb所造成的。从室温到1373K温度区域内,双相合金和三相合金的屈服强度都比单相合金的高很多,室温屈服强度分别在1150MPa和950MPa,随着温度的上升,屈服强度略呈下降,从1000K开始,屈服强度随着温度的上升下降的幅度加大。在1200K时,双相合金和三相合金的屈服强度仍然保持在600MPa左右,这说明多相组织强化机制对提高Ti-Al合金的高温性能是非常有效的。
拉伸性能的实验结果表明,室温下双相合金的塑性变形能力好于另外两种合金,这主要是因为α_2相的存在降低了合金平均晶粒尺寸,并且由γ和α_2两相构成的层片组织结构以及大量的γ/α_2相界面有利于塑性变形。温度升高可以显著改善双相合金的塑性变形能
Referencing a lot of Ti-Al-Nb ternary phase diagrams and affection of alloy elements on binary Ti-Al phase diagram, a series of Ti-Al-Nb ternary alloy samples were produced by adjusting the contents of Nb and fixing the ratio of Ti and Al to 1. The main purpose of the composition configuration was to prepare the Ti-Al-Nb ternary alloys with different microstructures. Microstructures and phase configurations at different test temperatures were obtained by many different means such as differential thermal analysis, X-ray diffraction analysis, electron probe microanalysis, microscopy, transmission electron microscopy and selected area electron diffraction. All the samples were treated at 1473K for 5hrs before testing.Four Ti-Al-Nb ternary alloys with different composition and microstructures were selected. The nominal composition of the four alloys were Ti-47.5Al-5Nb, Ti-42.8Al-14.2Nb, Ti-40Al-20Nb and Ti-30Al-40Nb (at%), with microstructure γ-TiAl, γ-TiAl+a2-Ti3Al, γ-TiAl+a2-Ti3Al+Nb2Al and γ-TiAl+a2-Ti3Al+Nb2Al respectively. The interrupted isothermal oxidation experiment of the four alloys was carried out at 1273K in air for 100 hours. The results showed that the oxidation behavior of the four Ti-Al-Nb alloys was superior to that of the binary Ti-Al alloys. The mass gains of the alloys after interrupted oxidation test at 1273K for 100 hours were all less than 8mg/cm2. In particular, the y-TiAl+a2-Ti3Al two-phase alloy (Ti-42.85Al-14.3Nb(at%)) showed the best oxidation resistance with a mass gain of only about 2.5mg/cm2. The mass gain of a binary TiAl alloy used in this study was found to be 69mg/cm2 after treatment at 1273K for lOOhours. The mass gain of Ti-Al binary alloys oxidized at 1073K for 100hours was about l-3mg/cm2 , the same order as that of Ti-Al-Nb ternary alloys. Among the four Ti-Al-Nb ternary alloys investigated, better oxidation resistance showed by the two-phase y-TiAl+a2-Ti3Al alloy may be attributed to the higher amount of Nb presented in both y and a2 phases (13.3at% and 19.4at% respectively). On the other hand, aluminum content of main phase γ in γ+a2 two-phase alloy was relatively higher due to the presence of the a2 phase. The rich aluminum y phase promoted the formation and growth of Al2O3. In the single-phase γ alloy (Ti-47.5Al-5Nb (at%)), less amount of Nb solution in y phase could not inhibit the growth of TiO2 and at the same time accelerate the formation of A12O3, as a result, non-protective oxide of TiO2 dominated the outer oxide scale. The emergence of Nb2O5 in Ti-40Al-20Nb(at%) and Ti-35Al-30Nb(at%) alloys when the Nb content in the Ti-Al-Nb alloy is over 20at% is discussed, and the exfoliation of oxide scale was observed. The relationship between poor oxidation resistance of Ti-40Al-20Nb(at%) and Ti-35Al-30Nb(at%) alloys and the Nb-enriched phase of Nb2Al was investigated.On the basis of the above investigation on the oxidation behavior of Ti-Al-Nb ternary alloys, the three alloys with γ(Ti-47.5Al-5Nb(at%)), y+a2(Ti-42.85Al-14.3Nb(at%)), y-+a2+Nb2Al(Ti-40Al-20Nb(at%)) respectively were selected for compression testing at room temperature, 973K, 1173K and 1373K and tensile testing at room temperature and 1373K. The results showed that the yield strength of the y single phase Ti-Al-Nb ternary alloy was 450Mpa,
which was the same as that of binary y-TiAl alloy at about 1200K, but at higher temperatures, the yield strength was higher than that of y-TiAl binary alloy, Inconel715 and Ti-48Al-2Cr-2Nb etc. alloys. This attributes to that Nb solutes in y phase. The yield strengths of the two-phase and three-phase alloys were higher than that of the single-phase alloy from room temperature to 1173K, which were 1150MPa and 950MPa respectively at room temperature. The yield strength decreased slightly when temperature increased.The results of tensile property experiments showed that plastic property of the two-phase alloy was better than that of single-phase alloy and three-phase alloy. The main reason was that the appearance of a% phase effectively decreased average grain size. Another reason was that the lamellar microstructure consisted of y and a.2 phases and y/a2 interface were clearly favorable for plastic deformation. The ductility of the two-phase alloy improved when temperature increased, tensile elongation was 40.4% at 1173K. However, the ductility of single-phase and three-phase alloys could not increase at 1173K. Characteristics of fracture of the two-phase alloy transformed from cleavage fracture at room temperature to i ductile fracture at 1173K, but that of single-phase and three-phase alloys were all cleavage fracture at room temperature and 1173K. Nt^Al-phase in ternary alloys decreased the continuity of lamellar microstructure consisted of y-phase and a2-phase. The Tab of Nb2Al was 1443K, hence brittle Nb2Al at 1173K made the RT ductility and high temperature ductility of the three-phase alloy lower.In a word, the results of oxidation resistance and mechanical properties showed that the two-phase alloy of Ti-42.85Al-14.3Nb(at%) had better oxidation resistance and room temperature and elevated temperature general mechanical property. It is potential to assume the application for elevated temperature components below 1173K.On the basis of research results of oxidation and mechanical property test of Ti-42.85Al-41.3Nb(at%), referring to benefit effect of W, Cr on Ti-Al alloy, four alloys were designed and prepared by adding W, Cr to Ti-Al-Nb ternary alloys. Their normal chemistry composition were Ti-41.85AM4.3Nb-2W, Ti-42.85Al-12.3Nb-2W, Ti-42.85Al-12.3Nb-2Cr and Ti-42.85Al-10.3Nb-4Cr(at%). The interrupted oxidation behaviors of the four alloys at 1273K in static air were studied.The microstructure of the four alloys was y+p, due to Nb, W, Cr stabilized (J phase. Addition of W or Cr to Ti-Al-Nb ternary alloys accelerated accumulation of Nb in p phase, this made Nb content of matrix y phase less. This explained why Nb could not improve the oxidation resistance. The addition of Cr made the adhesiveness between oxide and matrix weaker, the formed oxide is liable to breaking off due to thermal stress while cooling. Not only the oxidation resistance of the four alloys with W, Cr to Ti-Al-Nb ternary alloys could not be improved but also get lower than that of Ti-42.85Al-14.3Nb (at%) two-phase alloy.In order to further study the effect of P phase on oxidation resistance, the alloy such as Ti-42.85Al-12.3Nb-2Cr(at%) was heat-treated at 1553K for 2hours and cooled down to 1473K for 6hours and to room temperature in furnace(process2) or in water(process3). The microstructure of the two kinds of the treated alloys were y-TiAl+a2-Ti3Al,
首先,我们选择了不同含Nb量的具有不同相组成的四种Ti-Al-Nb三元合金,它们的名誉化学成分分别为:Ti-47.5Al-5Nb、Ti-42.85Al-14.3Nb、Ti-40Al-20Nb和Ti-35Al-30Nb(at%);它们的相组成分别为:γ-TiAl、γ-TiAl+α_2-Ti_3Al和γ-TiAl+α_2-Ti_3Al+Nb_2Al。对这四种合金进行1273K,100小时的断续氧化实验。研究结果表明,我们所研究的四种Ti-Al-Nb三元合金的高温抗氧化性能都比同样实验条件下的二元Ti-Al合金抗氧化性能好很多,这四种Ti-Al-Nb三元合金在1273K,100小时的断续氧化增重量都小于8mg/cm~2,特别是成分为Ti-42.85Al-14.3Nb的双相合金其氧化增重量仅为2.5mg/cm~2,而二元Ti-Al合金的氧化增重量达到69mg/cm~2。二元Ti-Al合金在1073K,100小时的断续氧化增重量与我们所研究的四种Ti-Al-Nb三元合金在1273K,100小时的断续氧化增重量在一个水平上为1-3mg/cm~2;在这四种Ti-Al-Nb三元合金中,相组成为γ-TiAl+α_2-Ti_3Al的双相合金抗氧化性能最好,分析其原因,一方面是由于两相中固溶了大量的Nb(分别达到13.3at%和19.4at%),另一方面是由于α_2-Ti_3Al的存在使得其主要相γ-TiAl的含Al量相对提高,富Al的γ-TiAl相有利于Al_2O_3的生成及稳定生长。成分为Ti-47.5Al-5Nb的单相γ-TiAl合金由于其含Nb量较少,Nb没有充分起到抑制TiO_2的生长及促进Al_2O_3生成的作用,虽然其比二元Ti-Al合金抗氧化性能要好许多,但仍然没有生成具有保护作用的连续的Al_2O_3保护膜。同样当含Nb量超过20at%时(如Ti-40Al-20Nb和Ti-35Al-30Nb合金)由于氧化生成的Nb_2O_5是一个结构疏松且与基体结合力非常差的氧化膜,在氧化过程中极容易从基体上剥落下来,使其抗氧化性能下降。
在上述抗氧化性能的研究基础上,选择相组成为单相γ-TiAl、双相γ-TiAl+α_2-Ti_3Al和三相γ-TiAl+α_2-Ti_3Al+Nb_2Al,成分分别为Ti-47.5Al-5Nb、Ti-42.85Al-14.3Nb和Ti-40Al-20Nb三种Ti-Al-Nb三元合金,进行从室温至1373K的压缩性能实验及室温和1173K的拉伸性能实验。实验结果表明,Ti-Al-Nb三元单相γ-TiAl合金在低温一侧同二元γ-TiAl合金具有同样的屈服强度450MPa,该强度一致保持到1200K左右,但是在高温一侧的屈服强度要远远高于二元γ-TiAl、Inconel715以及Ti-48Al-2Cr-2Nb等合金,这是因为γ相中固溶了比较多的Nb所造成的。从室温到1373K温度区域内,双相合金和三相合金的屈服强度都比单相合金的高很多,室温屈服强度分别在1150MPa和950MPa,随着温度的上升,屈服强度略呈下降,从1000K开始,屈服强度随着温度的上升下降的幅度加大。在1200K时,双相合金和三相合金的屈服强度仍然保持在600MPa左右,这说明多相组织强化机制对提高Ti-Al合金的高温性能是非常有效的。
拉伸性能的实验结果表明,室温下双相合金的塑性变形能力好于另外两种合金,这主要是因为α_2相的存在降低了合金平均晶粒尺寸,并且由γ和α_2两相构成的层片组织结构以及大量的γ/α_2相界面有利于塑性变形。温度升高可以显著改善双相合金的塑性变形能
Referencing a lot of Ti-Al-Nb ternary phase diagrams and affection of alloy elements on binary Ti-Al phase diagram, a series of Ti-Al-Nb ternary alloy samples were produced by adjusting the contents of Nb and fixing the ratio of Ti and Al to 1. The main purpose of the composition configuration was to prepare the Ti-Al-Nb ternary alloys with different microstructures. Microstructures and phase configurations at different test temperatures were obtained by many different means such as differential thermal analysis, X-ray diffraction analysis, electron probe microanalysis, microscopy, transmission electron microscopy and selected area electron diffraction. All the samples were treated at 1473K for 5hrs before testing.Four Ti-Al-Nb ternary alloys with different composition and microstructures were selected. The nominal composition of the four alloys were Ti-47.5Al-5Nb, Ti-42.8Al-14.2Nb, Ti-40Al-20Nb and Ti-30Al-40Nb (at%), with microstructure γ-TiAl, γ-TiAl+a2-Ti3Al, γ-TiAl+a2-Ti3Al+Nb2Al and γ-TiAl+a2-Ti3Al+Nb2Al respectively. The interrupted isothermal oxidation experiment of the four alloys was carried out at 1273K in air for 100 hours. The results showed that the oxidation behavior of the four Ti-Al-Nb alloys was superior to that of the binary Ti-Al alloys. The mass gains of the alloys after interrupted oxidation test at 1273K for 100 hours were all less than 8mg/cm2. In particular, the y-TiAl+a2-Ti3Al two-phase alloy (Ti-42.85Al-14.3Nb(at%)) showed the best oxidation resistance with a mass gain of only about 2.5mg/cm2. The mass gain of a binary TiAl alloy used in this study was found to be 69mg/cm2 after treatment at 1273K for lOOhours. The mass gain of Ti-Al binary alloys oxidized at 1073K for 100hours was about l-3mg/cm2 , the same order as that of Ti-Al-Nb ternary alloys. Among the four Ti-Al-Nb ternary alloys investigated, better oxidation resistance showed by the two-phase y-TiAl+a2-Ti3Al alloy may be attributed to the higher amount of Nb presented in both y and a2 phases (13.3at% and 19.4at% respectively). On the other hand, aluminum content of main phase γ in γ+a2 two-phase alloy was relatively higher due to the presence of the a2 phase. The rich aluminum y phase promoted the formation and growth of Al2O3. In the single-phase γ alloy (Ti-47.5Al-5Nb (at%)), less amount of Nb solution in y phase could not inhibit the growth of TiO2 and at the same time accelerate the formation of A12O3, as a result, non-protective oxide of TiO2 dominated the outer oxide scale. The emergence of Nb2O5 in Ti-40Al-20Nb(at%) and Ti-35Al-30Nb(at%) alloys when the Nb content in the Ti-Al-Nb alloy is over 20at% is discussed, and the exfoliation of oxide scale was observed. The relationship between poor oxidation resistance of Ti-40Al-20Nb(at%) and Ti-35Al-30Nb(at%) alloys and the Nb-enriched phase of Nb2Al was investigated.On the basis of the above investigation on the oxidation behavior of Ti-Al-Nb ternary alloys, the three alloys with γ(Ti-47.5Al-5Nb(at%)), y+a2(Ti-42.85Al-14.3Nb(at%)), y-+a2+Nb2Al(Ti-40Al-20Nb(at%)) respectively were selected for compression testing at room temperature, 973K, 1173K and 1373K and tensile testing at room temperature and 1373K. The results showed that the yield strength of the y single phase Ti-Al-Nb ternary alloy was 450Mpa,
which was the same as that of binary y-TiAl alloy at about 1200K, but at higher temperatures, the yield strength was higher than that of y-TiAl binary alloy, Inconel715 and Ti-48Al-2Cr-2Nb etc. alloys. This attributes to that Nb solutes in y phase. The yield strengths of the two-phase and three-phase alloys were higher than that of the single-phase alloy from room temperature to 1173K, which were 1150MPa and 950MPa respectively at room temperature. The yield strength decreased slightly when temperature increased.The results of tensile property experiments showed that plastic property of the two-phase alloy was better than that of single-phase alloy and three-phase alloy. The main reason was that the appearance of a% phase effectively decreased average grain size. Another reason was that the lamellar microstructure consisted of y and a.2 phases and y/a2 interface were clearly favorable for plastic deformation. The ductility of the two-phase alloy improved when temperature increased, tensile elongation was 40.4% at 1173K. However, the ductility of single-phase and three-phase alloys could not increase at 1173K. Characteristics of fracture of the two-phase alloy transformed from cleavage fracture at room temperature to i ductile fracture at 1173K, but that of single-phase and three-phase alloys were all cleavage fracture at room temperature and 1173K. Nt^Al-phase in ternary alloys decreased the continuity of lamellar microstructure consisted of y-phase and a2-phase. The Tab of Nb2Al was 1443K, hence brittle Nb2Al at 1173K made the RT ductility and high temperature ductility of the three-phase alloy lower.In a word, the results of oxidation resistance and mechanical properties showed that the two-phase alloy of Ti-42.85Al-14.3Nb(at%) had better oxidation resistance and room temperature and elevated temperature general mechanical property. It is potential to assume the application for elevated temperature components below 1173K.On the basis of research results of oxidation and mechanical property test of Ti-42.85Al-41.3Nb(at%), referring to benefit effect of W, Cr on Ti-Al alloy, four alloys were designed and prepared by adding W, Cr to Ti-Al-Nb ternary alloys. Their normal chemistry composition were Ti-41.85AM4.3Nb-2W, Ti-42.85Al-12.3Nb-2W, Ti-42.85Al-12.3Nb-2Cr and Ti-42.85Al-10.3Nb-4Cr(at%). The interrupted oxidation behaviors of the four alloys at 1273K in static air were studied.The microstructure of the four alloys was y+p, due to Nb, W, Cr stabilized (J phase. Addition of W or Cr to Ti-Al-Nb ternary alloys accelerated accumulation of Nb in p phase, this made Nb content of matrix y phase less. This explained why Nb could not improve the oxidation resistance. The addition of Cr made the adhesiveness between oxide and matrix weaker, the formed oxide is liable to breaking off due to thermal stress while cooling. Not only the oxidation resistance of the four alloys with W, Cr to Ti-Al-Nb ternary alloys could not be improved but also get lower than that of Ti-42.85Al-14.3Nb (at%) two-phase alloy.In order to further study the effect of P phase on oxidation resistance, the alloy such as Ti-42.85Al-12.3Nb-2Cr(at%) was heat-treated at 1553K for 2hours and cooled down to 1473K for 6hours and to room temperature in furnace(process2) or in water(process3). The microstructure of the two kinds of the treated alloys were y-TiAl+a2-Ti3Al,
引文
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