Microstructure and mechanical properties of Ni-rich TiNiZr alloy associated with repeated cold-rolling and annealing
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摘要: TiNi形状记忆合金具有优异的功能特性和结构特性，在多种领域有着明确的目标需求。本文聚焦B2结构奥氏体富镍 TiNi合金，拟通过冷轧退火循环调控TiNi合金微观结构，以期提升合金较低的力学强度和塑性形变能力。系统考察了Ti48.9Ni50.9Zr0.2和Ti47.9Ni51.9Zr0.2合金力学性能和微观结构与冷轧形变以及再结晶退火之间的依赖关系。拉伸力学性能测试表明，冷轧退火循环可显著提升合金综合力学性能，其中Ti48.9Ni50.9Zr0.2合金6道次冷轧退火后抗拉强度从未轧制样品的550 MPa提升至1070 MPa，断后伸长率从4.9%增加至10.0%。通过EBSD、SEM和TEM微观结构观察可以发现，合金多道次冷轧退火后，形变组织和再结晶组织交替变化，合金晶粒显著细化，发生了明显的择优取向，合金织构进一步增强。析出相Ti2Ni和Ti3Ni4破碎细化，纳米级Ti3Ni4与基体间有着良好的晶格匹配性。此外，合金中出现了应力诱发的马氏体以及析出相附近大量高密度位错。合金力学性能与材料微观结构密切相关，强度和塑性提升机制可通过细晶强化、位错强化、沉淀强化和织构强化来理解。Abstract: TiNi shape memory alloys have clear target demand in a variety of fields owing to their excellent structural and functional properties. In this paper, focusing on B2 structural austenitic Ni-rich TiNi alloys, it is proposed to modulate the microstructure of the TiNi alloys through repeated cold rolling annealing, with an expectation to enhancing the lower mechanical strength and plastic deformation ability of the alloys. The dependence of the mechanical properties and microstructure of Ti48.9Ni50.9Zr0.2 and Ti47.9Ni51.9Zr0.2 alloys on cold rolling deformation and recrystallization annealing was systematically investigated. The tensile mechanical property tests showed that the repeated cold rolling annealing could significantly enhance the overall mechanical properties of the alloys, in which the tensile strength of Ti48.9Ni50.9Zr0.2 alloy is increased from 550 MPa in the unrolled samples to 1070 MPa after 6 passes of cold rolling annealing, and the elongation after fracture has grown from 4.9% to 10.0%. The EBSD, SEM and TEM microstructural observation reveals that the deformation and recrystallization structures of the alloy change alternately after multi-pass cold rolling and annealing, and the alloy grains are significantly refined and undergo an obvious preferred grain orientation. In addition, the basal texture of the alloy is further enhanced. The Ti2Ni and Ti3Ni4 precipitates were broken and refined during cold deformation, in which the nano-sized Ti3Ni4 precipitate exhibits a favorable matching with matrix. Furthermore, stress-induced martensite as well as a large number of high-density dislocations in the vicinity of the precipitation phases appeared in the alloy. The mechanical properties of alloys are strongly related to the microstructure, and the strengthening mechanisms can be understood by grain refinement strengthening, dislocation strengthening, precipitation strengthening and texture strengthening.
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Key words:
- TiNi alloy /
- cold-rolled deformation /
- microstructure /
- mechanical properties /
- Ti3Ni4 precipitates
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图 4 TiNiZr合金SEM微观结构图像(背散射模式)及EDS面扫结果
Figure 4. SEM microstructure images (backscatter mode) and the corresponding EDS mappings of the TiNiZr alloys
图 5 TiNiZr合金拉伸力学性能： (a) 应力-应变曲线；(b)拉伸断裂强度和断后伸长率
Figure 5. Tensile mechanical properties of TiNiZr alloys: (a) stress-strain curves; (b) tensile strength and elongation
图 6 不同退火时间Ti47.9Ni51.9Zr0.2 (a) 和 Ti48.9Ni50.9Zr0.2 (b)合金金相微观结构：(a1,b1) 0 min; (a2,b2) 60 min; (a3,b3) 150 min; (a4,b4) 600 min.
Figure 6. Metallographic microstructure corresponding to various annealing time of Ti47.9Ni51.9Zr0.2 (a) and Ti48.9Ni50.9Zr0.2 (b): (a1,b1) 0 min; (a2,b2) 60 min; (a3,b3) 150 min; (a4,b4) 600 min
图 7 不同退火时间的Ti47.9Ni51.9Zr0.2 和Ti48.9Ni50.9Zr0.2 合金拉伸力学性能：(a) 应力-应变曲线；(b) 拉伸断裂强度和断后伸长率
Figure 7. Tensile mechanical properties of Ti47.9Ni51.9Zr0.2 and Ti48.9Ni50.9Zr0.2 alloys in different annealing time: (a) stress-strain curves; (b) tensile strength and elongation
图 8 冷轧不同道次Ti48.9Ni50.9Zr0.2合金图谱
Figure 8. XRD analysis of Ti48.9Ni50.9Zr0.2 with different cold rolling passes
图 9 冷轧不同道次Ti48.9Ni50.9Zr0.2合金SEM微观图像(背散射模式)：(a1,a2) 未轧制; (b1,b2) 2道次; (c1,c2) 4道次; (d1,d2) 6道次
Figure 9. SEM images (backscatter mode) of Ti48.9Ni50.9Zr0.2 alloys subjected to different rolling passes: (a1,a2) unrolled; (b1,b2) two pass; (c1,c2) four pass; (d1,d2) six pass
图 10 不同道次冷轧的Ti48.9Ni50.9Zr0.2合金金相微观结构：(a) 未轧制; (b) 2道次; (c) 4道次; (d) 6道次
Figure 10. Metallographic microstructure of Ti48.9Ni50.9Zr0.2 with different rolling passes: (a) unrolled; (b) 2 pass; (c) 4 pass; (d) 6 pass
图 11 不同道次冷轧Ti48.9Ni50.9Zr0.2合金反极图(IPF)，再结晶体积分数分布图(其中蓝色区域为再结晶晶粒区域、黄色区域为晶粒亚结构区域、红色区域为变形区域，各部分体积分数见图中左上角)，{001}面极图和晶粒分布图： (a) 2道次； (b) 4道次；(c) 6道次
Figure 11. Inverse pole figure(IPF) maps, recrystallized fraction component maps (the volume fractions (%) of the recrystallized (blue),substructured (yellow) and deformed (red) regions are given at the top left corners), {001} pole figures and grain size distribution maps of of Ti48.9Ni50.9Zr0.2 alloys subjected to different cold rolling passes: (a) two pass; (b) four pass; (c) six pass
图 12 未冷压 Ti48.9Ni50.9Zr0.2合金TEM微观结构和选区电子衍射(SADP)：(a) 低倍率明场图像； (b) 高倍率明场图像； (c) B2基体和Ti2Ni析出相高分辨界面图像； (d) B2基体和Ti3Ni4析出相高分辨界面图像； (e) 图(b)中A区域电子衍射图；(f) 图(b)中B区域电子衍射图
Figure 12. Microstructure of Ti48.9Ni50.9Zr0.2 alloy after solution treating and aging: the bright-field images and corresponding selected area diffraction pattern(SADP): (a) low magnification image; (b) high magnification image of (a);(c)HRTEM images of (b) showing the interface between B2 matrix and Ti2Ni; (d)HRTEM images of (b) showing the interface between B2 matrix and Ti3Ni4; (e) the SADP image of area A in (b);(f) the SADP image of area B in (b)
图 13 6道次冷轧后Ti48.9Ni50.9Zr0.2合金断口附近TEM微观结构： (a,b) 微观结构明场像； (c) (b)图中红色圆形区域电子衍射图； (d) (b)图中高分辨图像； (e) (d)图中蓝色区域反傅里叶变换图； (f) 亚微米结构明场像
Figure 13. TEM microstructures near fracture surface of six pass cold-rolled Ti48.9Ni50.9Zr0.2 alloy: (a,b) the bright-field images showing the microstructure of six pass sample; (c)the SADP image of area within red circle (b); (d) HRTEM image of (b); (e) IFFT image of blue area in (d); (f) the bright-field images showing the submicron structure
图 14 不同道次冷轧退火后Ti47.9Ni51.9Zr0.2合金SEM微观结构图像：(a) 2道次; (b) 4道次; (c) 6道次，其中(a1-c1)为背散射模式图像，(a2-c2)为二次电子模式图像，(a3-c3)为(a2-c2)的高倍率图像
Figure 14. SEM images of Ti47.9Ni51.9Zr0.2 alloys subjected to different rolling passes and annealing: (a) two pass; (b) four pass; (c) six pass, where (a1-c1) images is in the backscattering pattern; (a2-c2) images is in the secondary electron mode; (a3-c3) is the high magnification images of (a2-c2):
图 15 6道次冷轧后Ti47.9Ni51.9Zr0.2合金断口附近 Ti2Ni和TiNi3析出相TEM微观结构图像
Figure 15. TEM images near fracture surface of six pass cold-rolled Ti47.9Ni51.9Zr0.2 alloy showing the microstructure of the Ti2Ni,TiNi3 in matrix
图 16 不同道次冷轧的Ti48.9Ni50.9Zr0.2 合金拉伸力学性能：(a) 应力-应变曲线；(b)拉伸断裂强度和断后伸长率
Figure 16. Tensile mechanical properties of Ti48.9Ni50.9Zr0.2 alloys in different rolling passes: (a) stress-strain curves; (b) tensile strength and elongation
图 17 不同道次冷轧的Ti47.9Ni51.9Zr0.2合金拉伸力学性能：(a) 应力-应变曲线；(b)拉伸断裂强度和断后伸长率
Figure 17. Tensile mechanical properties of Ti47.9Ni51.9Zr0.2 alloys in different rolling passes: (a) stress-strain curves; (b) tensile strength and elongation
表 1 Ti99.8-xNixZr0.2 (x= 51.9, 50.9, 49.9, 48.9, 47.9)合金EDS 化学组分
Table 1. EDS chemical composition of the Ti99.8-xNixZr0.2 (x= 51.9, 50.9, 49.9, 48.9, 47.9) alloys
Samples Ti(at%) Ni(at%) Zr(at%) Ti47.9Ni51.9Zr0.2 48.10 51.65 0.25 Ti48.9Ni50.9Zr0.2 49.19 50.61 0.20 Ti49.9Ni49.9Zr0.2 49.87 49.94 0.2 Ti50.9Ni48.9Zr0.2 51.09 48.64 0.26 Ti51.9Ni47.9Zr0.2 52.08 47.58 0.35 
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