NiTi基形状记忆合金弹热效应及其应用研究进展

doi:10.11868/j.issn.1001-4381.2020.000780

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摘要

NiTi合金作为性能最优异的形状记忆合金之一，已经广泛应用于航空航天、电子、建筑、生物医学等领域。近年来，NiTi基合金极佳的力学性能、巨大的弹热效应和良好的机械加工性使其在弹热制冷领域引起了广泛关注。然而，传统NiTi二元合金超弹性应力滞后大，超弹性和弹热效应循环稳定性差，达不到实际应用所需的长期服役要求。本文介绍了NiTi基合金的弹热效应研究进展，从掺杂合金元素、热机械处理、改变制备方法等角度综述了近几年NiTi基合金弹热效应改进优化的研究进展，同时本文也简要介绍了已经开发的基于NiTi基合金的弹热装置或原型机。但是目前NiTi基合金弹热材料的研究和原型机的开发仍处于实验阶段，实现其商业化应用需要进一步深入研究和优化，未来前者研究重点将集中在材料小型化、合金化或特殊处理及改变循环方式等方面，后者也将从提高热量传输效率、加强热量交换、减小摩擦等损耗、改进机械负载和循环模式等方面不断优化和完善。

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	朱雪洁
	钟诗江
	杨晓霞
	张学习
	钱明芳
	耿林

关键词 ： NiTi基合金, 弹热效应, 固体制冷, R相变, 超弹性, 循环稳定性

Abstract：

NiTi-based shape memory alloys (SMAs) are one of the SMAs with most outstanding properties, and have been widely applied in aviation, space, electronics, construction, biomedicine and other fields. In recent years, the elastocaloric refrigeration based on elastocaloric effect (eCE) of NiTi alloys has attracted increasing attentions since their excellent mechanical properties, huge elastocaloric strength and good machinability. However, conventional binary NiTi alloys cannot meet the requirements of long-life service since their large superelastic stress hysteresis and poor cyclic stability of superelasticity and eCE. In this paper, the research progress of eCE for NiTi-based alloys was reviewed. The effect of doping alloying element, thermomechanical treatment and novel processing techniques on eCE of NiTi-based alloys were surnmarized. In addition, the developed elastocaloric devices or prototypes based on NiTi-based alloys were also briefly introduced. However, the current researches on NiTi-based elastocaloric materials and the development of prototypes are still in the experimental stage. To realize their commercial application requires further in-depth research and optimization. In the future, the research priorities for the former will concentrate on material miniaturization, alloying or applying special treatment as well as changing circulation methods and so on. On the other hand, the research priorities for the latter will focus on improving heat transfer efficiency, strengthening heat exchange, reducing friction and other losses, and improving mechanical loadings as well as circulation modes.

Key words： NiTi-based alloys elastocaloric effect (eCE) solid-state refrigeration R phase transition superelasticity cycling stability

收稿日期: 2020-08-19 出版日期: 2021-03-20

中图分类号:

TG139⁺6

基金资助:国家自然科学基金项目(51701052)

通讯作者: 张学习 E-mail: xxzhang@hit.edu.cn

作者简介: 张学习(1975-), 男, 教授, 博士, 研究方向: 形状记忆合金磁热及弹热性能研究, 联系地址: 黑龙江省哈尔滨市西大直街92号哈尔滨工业大学材料科学与工程学院(150001), E-mail: xxzhang@hit.edu.cn

引用本文:

朱雪洁, 钟诗江, 杨晓霞, 张学习, 钱明芳, 耿林. NiTi基形状记忆合金弹热效应及其应用研究进展[J]. 材料工程, 2021, 49(3): 1-13.
Xue-jie ZHU, Shi-jiang ZHONG, Xiao-xia YANG, Xue-xi ZHANG, Ming-fang QIAN, Lin GENG. Research progress in elastocaloric effect and its application of NiTi-based shape memory alloys. Journal of Materials Engineering, 2021, 49(3): 1-13.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2020.000780 或 http://jme.biam.ac.cn/CN/Y2021/V49/I3/1

Fig.1 形状记忆合金弹热效应示意图^[25]

Fig.2 Ni_50.4Ti_49.6合金薄膜在0.02 s^-1应变速率变形过程中的温度和应变分布图以及超弹性曲线^[33] (a)加载过程温度和应变分布(数字对应于(b)图)；(b)包括加载图像采集点的应力-应变曲线；(c)卸载过程温度和应变分布(数字对应于(d)图)；(d)包括卸载图像采集点的应力-应变曲线

Fig.3 Ni_50.9Ti_49.1合金薄板的弹热性能^[42] (a)不同循环条件下的疲劳寿命；(b)不同机械循环条件下的绝热温变；(c)6%预应变、1%应变振幅下循环应力-应变曲线；(d)10%预应变、1%应变振幅下循环应力-应变曲线

Fig.4 纳米沉淀相诱发的应变玻璃转变Ni_51.3Ti_48.7合金等温熵变随温度变化曲线(插图为应变玻璃转变时产生的等温熵变峰)^[48]

Fig.5 纳米晶Ti₅₀Ni₄₄Cu₅Al₁合金不同循环次数的绝热温变值^[8]

Fig.6 Ti_52.6Ni_47.4合金不同应力下B19′相变和R相变最大可逆熵^[26]

Material	ρ/(kg·m^-3)	c/(J·kg^-1·K^-1)	M_s/K	ε/%	ΔS_t/(J·kg^-1·K^-1)	(dT/dσ)/(K·MPa^-1)	Δσ/MPa	ΔS_iso/(J·kg^-1·K^-1)	ΔT_adi/K	Ref
Cu_68.1Zn_15.8Al_16.1(SC)	7710	432	234	8	23.7	0.50	143	20.7		[3]
Cu₆₈Zn₁₆Al₁₆(bulk)	7710	430	205	7.1	17.9	0.51	250		-6— -7	[4]
Cu_71.5Al_17.5Mn₁₁(bulk)	7400	455	239	9	25	0.54	200		-12.8	[5]
Fe₄₉Rh₅₁(bulk)	9800	470	316	0.3	13	-0.02	529		-5.7	[9]
Fe_68.8Pd_31.2(SC)^a	8900	400	250	2		1	200		-3	[10]
Ni_45.7Mn_36.6In_13.3Co_5.1(bulk)	8100	462	284	1	21		100		+3.5/-2.5	[12]
Ni₅₄Fe₁₉Ga₂₇(bulk)	8450	470	280	2.2	10.5		130		-5	[13]
Ni_43.5Co_6.5Mn₃₉Sn₁₁(bulk)	8065	500	260	4	13.5	0.21	310	11.1		[14]
Ni_50.8Ti_49.2(bulk)^a	6500	424	222	4	63	0.11	700	37	+18/-11	[40]
Ni_51.3Ti_48.7(bulk)^a	6500	550	220	8			300	26		[48]
Ni₅₀Ti_45.3V_4.7(bulk)^a	6500	510	278	4.3	32		300		-12	[52]
Ni₄₅Ti_47.25Cu₅V_2.75(bulk)^a	6500	460	295	5					-18.4	[27]
Ti₅₀Ni₄₄Cu₅Al₁(bulk)^b	6500	550	300	4.9	33.7	0.19	500	37.5	-17.4	[8]
Ti₅₀Ni₄₈Fe₂(bulk)^c	6500	480	283	0.5	21	0.04	200		-2.7	[59]
Ni₅₀Ti₅₀(wire)^a	6500	550		8.5	40		500		+25.5/-17	[6]
Ni_47.4Ti_52.6(wire)^a	6500	550	303	7	60-80	0.2	175	60-70		[26]
Ni_50.5Ti_49.5(wire)^a	6500	550	210	6		0.16	700	65		[7]
Ni_48.9Ti_51.1(wire)^a	6500	450	295	6		0.13	700	35	+25/-21	[38]
Ni_50.4Ti_49.6(wire)^a	6500	550		6.5		0.18	750	43		[39]
Ni_47.4Ti_52.6(wire)^c	6500	550	310	0.5	17.8	0.05	160	13		[26]
Ni_50.5Ti_49.5(wire)^c	6500	550	318	0.6	23.4	0.05	340	21		[46]
Ni_50.8Ti_49.2(wire)^c	6500	470	319	0.7	12.2		300		-2	[45]
Ni_50.4Ti_49.6(film)^a	6500	550		7.5			400		9	[41]
Ni_50.4Ti_49.6(film)^a	6500	450	250	5.3	76	0.11	500		+17/-16	[33]
Ti_54.9Ni_32.5Cu_12.6(film)^b	6500	837	318	1.7	52		380		+4.1/-6.1	[41]
Ti_54.7Ni_30.6Cu_12.3Co_2.4(film)^b	6500	420	263	1.8		0.10	450	40	-12	[34]
Ni_50.5Ti_49.5(foil)^a	6500	550	281	8	35		1300		+58	[31]
Ti_50.5Ni_49.1Fe_0.4(foil)^a	6500	500		4.2	80		520		+22/-17	[35]
Ni_50.8Ti_49.2(sheet)^a	6500	550	314	5	37	0.17	700		-24	[47]
Ni_50.4Ti_49.6(SC)^a	6500	590	218			0.12	500	51	-14.2	[28]
Ni_50.8Ti_49.2(SC)^a	7600	590	218	6.2	51.7	0.14	450		-18.2	[29]
Ni_50.8Ti_49.2(AM)^a	6500	550	280	9.2			1400		-18.6	[60]
Ni_46.6Ti_53.4(AM)^d	6500	550	334	5	45		1200		+9.5/-7.5	[61]

Table 1 形状记忆合金的弹热效应

Fig.7 激光定向能量沉积(L-DED)技术制备的Ni_51.5Ti_48.5/Ni₃Ti纳米复合材料10⁶次机械循环前后超弹性和弹热性能^[64] (a)压缩应力-应变曲线；(b)绝热温变；(c)不同材料的等温和绝热加卸载过程滞后环面积和COP_materials/COP_carnot

Fig.8 基于Ti_50.5Ni_49.1Fe_0.4合金桥的热泵结构原理图(a)单桥结构；(b)双桥结构^[72]；(c)改良后的凸双桥结构；(d)改良后的凹双桥结构^[73]

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