•形状记忆效应:具有一定形状的固体材料(通常是具有热弹性马氏体相变的材料),在某一温度下(处于马氏体状态M f 进行一定限度的塑性变形后,通过加热到某一温度(通常是该材料马氏体完全消失温度A f )上时,材料恢复到变形前的初板条马氏体钢的淬火5•Monoclinic Crystal StructureTwinned Martensite 自协作马氏体Detwinned Martensite非自协作马氏体8发生塑性变形后,经加热到某一温度后能够恢复变形,马氏体在外力下变形成某一特定形状,加热时已发生形变的马氏体会回到原来奥氏形状记忆效应过程的示意图马氏体相变热力学相变产生,M相的化学自由能必须,不过冷到适当低于T0(A相和M相化学自由的温度,相变不能进行,必须过热到适当高于T0的温度,相变才马氏体相和母相化学自11马氏体相变热力学低于Ms温度下,马氏体形成以后,界面上的弹性变形随着马氏体的长大而增加;当表面能、弹性变形能及共格界面能等能量消耗的增加与变化学自由能的减少相等时,马氏体和母相间达到热弹性平衡状态,马氏体停止长大。
CuAlNi合金加热过程中热弹性马氏体相变(马氏体缩小)温度继续下降,马氏体相变驱动力增加,马氏体又继续长大,也可能出现新的马氏体生长。
温度升高,相变驱动力减小,马氏体出现收缩。
CuAlNi合金加热过程中热弹性马氏体相变(马氏体缩小)16伪弹性应力应变示意图17f(a) Shape Memory Effect (b) Superelasticity[100][111]冷却形状记忆效应的三种形式(a)单程(b)双程(c)全程22(a)马氏体状态下未变形(b)马氏体状态下已变形)放入热水中,高温下恢复奥氏体状态,形状完全恢复单程TiNi记忆合金弹簧的动作变化情况24没放入热水前放入热水后冷却至室温后再次放入热水后双程CuZnAl记忆合金花的动作变化情况TiNi合金的全程记忆效应(100℃-室温)TiNi合金的全程记忆效应(低温-100℃)铁磁性形状记忆合金简介温控形状记忆铁磁性铁磁性形状记兼有磁致伸缩材料和传统温控形状记忆材料的优点响应频率快磁致应变大The magnetic easy axis changes from one twin to the other•Weak magnetic anisotropy.Effect of a magnetic fieldWeak anisotropy Strong anisotropyIn systems with strong anisotropy and highly mobile boundaries, field inducedet al. J.Appl.Phys. 92,3867 (2002);Moya et al. Phys. Rev. B 73, 64303 (2006); 74, 24109 (2006).)33(1) Via martensite variant reorientation-Ni2MnGa(2) Via magnetic field induced martensitictransformation-NiMnIn(Sn,Sb)37Ni 2MnGa -crystal structureNi 2MnGa is the most successful magnetic shape memory alloy. It transforms from the Heusler cubic structure to tetragonal on cooling. A 6% magnetic field induced tensile strain hasbeen recorded in a single crystal, by the mechanism of martensite variant reorientation.The absence of a thermal effect makes it suitable for high frequency operations. The mechanical work output, however, is muchlower than those of thermal SMAs .ΔV= -1.30%:The volume change is large. The material is an intermetallic compound and is intrinsically brittle Îtransformation induced cracking . The problem is much less severe with single crystals.Tetragonal MartensiteCubic Austenite-4.45%1.63%aac aaa[100]c expansion by 1.63%[001]c contraction by –4.45%The tetragonal structure is mechanically anisotropic. Themaximum linear strain is when axis [001] is converted to [100]: ~6%Mn Ni38c c(110)c plane of AccNi 2MnGa –structural anisotropy of M(110)c T w i n p l a n e[100]c projection plane of A [100]c projection plane of MMarioni , JMMM, 290-291 (2005) 35Now we have got a working mechanism for shape change39Ni 2MnGa –magnetic anisotropy(110)c[001]c(the c -axis of M)[001]c(the c -axis of M)Structure anisotropy Magnetic anisotropyThe tetragonal structure is a uniaxial structure magnetically. Its c -axis is theeasy direction of magnetization40Li et al, APL, 84, 3594 (2004).Ni 2MnGa –magnetic anisotropyWu et al: APL. 75, 2990 (1999).MartensiteAustenite[001]-3-23015.8x10J/g=4.5x10J/cm 2E H M μΔ=Δ=For a phase transformation at room temperature, the T ΔS energy is typically~80 J/cm 3The driving force is too small to induce austenite -martensite transformationCo 2NiGaNi 2MnGa41Possibility of magnetic fieldinduced deformation viamartensite reorientationMagnetization curves along easy ([001]) and hard([100]) axes of Ni 48Mn 30Ga 22constrained in single variant martensite. The magnetic driving force (energy) is ~0.08 J/cm 3. Likhachev: Phys. Lett. A 275 (2000) 142.Ni 2MnGa deformed along [100] direction at 300 K in martensitic state. Chernenko et al: Phys. Rev.B 69134410 (2004)The mechanical resistive force is ~1.5 MPa and the mechanical frictional energy is 0.09 J/cm 3Ni 2MnGa –magnetic anisotropycaac42Heczko et al. JMMM 226-230 (2001) 996NiMnGa43Heczko et al. JMMM 242–245 (2002) 1446Ni 2MnGa –magnetic field induced martensite reorientation6% strain is induced bymagnetic field via martensite reorientation. The strain is irreversible.NiMnGaFerromagnetic martensite/austeniteparamagnetic austenite/martensite47TiNi 形状记忆合金的应力应变曲线。