NiTi合金的相变与记忆效应

用X射线衍射、电阻、形状变化、内耗等方法研究等原子NiTi合金在150℃以下发生的相变与记忆效应。X射线衍射结果表明,在45℃左右,合金出现两类相变:马氏体相变与R相变,具有B_2型结构的母相分别转变成单斜畸变B_(10)型马氏体和畸变B_2结构的R相。R相变不是预转变,R相在-185℃仍保持稳定。合金在相变时,电阻和内耗增加。出现电阻峰和内耗峰。在相变温度进行不完全热循环时,开始只出现一个马氏体内耗峰。多次热循环,在马氏体内耗峰的高温侧分裂出一支小内耗峰。这是R相变引起的。升温时,在50～60℃,R相和马氏体开始向B_2相逆转变。在等原子NiTi合金中,相变依下列次序进行,B_2(?)B_2 R B_(19)(?)R B(19)。 NiTi合金的记忆效应是降温时B_2相向R相和马氏体转变及随后升温时,R相和马氏体向B_2相逆转变造成的。     

热处理对激冷Ti-50Ni合金薄带相变和形状记忆行为的影响

用甩带法制备了Ti-50Ni形状记忆合金薄带,用X射线衍射仪、扫描电镜、透射电镜、示差扫描量热仪和弯曲试验研究了Ti-50Ni合金薄带的相组成、显微组织、相变行为和形状记忆效应。结果表明,铸态和400~600℃退火态Ti-50Ni合金薄带的显微组织形态呈树枝状,由马氏体相B19'和母相B2组成,加热/冷却过程中发生A→R→M/M→R→A(A-母相,R-R相,M-马氏体)二阶可逆相变。随退火温度升高,Ti-50Ni合金薄带的相组成和显微组织形态变化不大;马氏体逆相变温度T_A、R正相变温度T_R、R逆相变温度T_(Rr)和马氏体相变热滞ΔT_M升高,马氏体正相变温度T_M下降,R相变热滞ΔT_R缓慢降低;M逆相变峰向高温移动,逐渐与R逆相变峰合并。铸态和退火态Ti-50Ni合金薄带皆具有良好的形状记忆效应。     

退火温度对Ti-51.1Ni形状记忆合金显微组织和相变行为的影响

用X射线衍射仪、示差扫描量热仪和光学显微镜研究了退火温度对Ti-51.1Ni形状记忆合金相组成、显微组织和相变行为的影响。结果表明,350～700℃退火态Ti-51.1Ni合金室温下相由母相B2和马氏体B19'组成。随退火温度(T_a)升高,合金经历回复、再结晶、晶粒长大过程,显微组织逐渐从纤维状向等轴状转变,再结晶温度约为600℃。随T_a升高,合金的冷却/加热相变类型由A→R→M/M→R→A型向A→R→M/M→A型转变(A-母相B2,CsCl型结构;R-R相,菱方结构;M-马氏体B19',单斜结构),T_a高于650℃后R和M相变峰消失。随T_a升高,合金的马氏体相变温度先升高后降低,R相变温度降低,R相变热滞在6.3～8.3℃之间变化。     

时效对富镍Ti-50.7at%Ni形状记忆合金马氏体多步相变行为的影响

采用DSC(差示扫描量热法)热循环研究了Ti-50.7at%Ni形状记忆合金经时效处理后马氏体多步相变演化行为和相变机制。结果表明:合金在250、400、550℃时效1 h水冷后,相变为B2→R,R→M1(沉淀相附近)和R→M2(母相附近)三阶段相变;700℃时效后,相变为B2→M一阶段相变。400℃时效时合金析出的沉淀相Ti3Ni4最多,使Ms(B2→M的起始温度)升至32℃,Af(M→B2的终了温度)升至50℃,马氏体相变温度是由沉淀相Ti3Ni4的析出速率和组织的回复进程共同决定的。     

时效处理对TiNiCr形状记忆合金相变的影响

利用差示扫描量热仪(DSC)、扫描电镜(SEM)和D/max2500PC全自动X射线衍射仪研究了不同时效处理制度下TiNiCr合金相变温度的变化规律.结果表明,该合金随着时效温度增加,逆马氏体相变点As、Af上升,但当时效温度高于700℃时,相变点As、Af降低.该合金在冷却过程中经历了B2→R→B19′两阶段一级相变.通过SEM和XRD衍射研究表明,该合金经时效处理产生了Ti3Ni4析出相诱发了R相变.     

激冷Ti-47Ni合金薄带的组织、相变和形状记忆行为

为了开发微机电系统用快响应微执行器材料,采用熔体快淬法制备了激冷Ti-47Ni(原子分数,%)形状记忆合金薄带,利用CLSM、XRD、DSC和弯曲实验研究了铜辊速率和退火工艺对Ti-47Ni合金薄带显微组织、相组成、相变行为和形状记忆行为的影响。结果表明,不同辊速制备的铸态和300~800℃退火态Ti-47Ni合金薄带的显微组织均呈纵横排列的柱状,辊速越高合金薄带的晶粒越细,退火工艺对合金薄带显微组织影响不大。Ti-47Ni合金薄带的组成相为马氏体(B19'相,单斜结构)+母相(B2相,Cs Cl型结构),冷却/加热时发生B2→B19'/B19'→B2一阶段马氏体相变,正、逆马氏体相变温度分别约为54和81℃,相变热滞约为27℃。随辊速增加,合金薄带马氏体相变温度降低,形状记忆恢复率提高。随退火温度升高,合金薄带相变行为变化不大,形状记忆恢复率在93%~98%之间变化。铸态和退火态Ti-47Ni合金薄带皆具有优异的形状记忆效应。     

固溶态Ti（50＋x）Pd30Ni（20—x）合金中的相变特征

Ti(50 x)Pd30Ni(20-x)合金在固溶处理之后存在2次相变，使用DSC，XRD，DMTA以及TEM等手段研究了这种相变，结果表明，低温马氏体为单斜的B19'相，而高温母相则为体心立方的B2相，在相变过程中点阵的切变以正交的B19马氏体相作为过渡。低温马氏体的弹性模量比高温奥氏体的弹性模量高10GPa。随着频率减小，阻尼增大。在较高的频率下，弹性模量曲线和阻尼曲线对于过渡相的存在反映不明显，室温下马氏体为细狭的板条状，当温度达773K时，合金中有明显的析出物产生。     

热处理工艺对累积叠轧Ti/Ni多层复合材料界面结构的影响

本文研究了热处理对累积叠轧6道次Ti/Ni多层复合箔材界面结构演变的影响。利用扫描电镜(SEM)、能谱分析(EDS)、透射电镜(TEM)、X射线衍射(XRD)及差示扫描量热分析(DSC)对热处理后复合材料的界面结构、相组成、相结构及相变温度等进行测试分析。结果表明：随保温时间的增加,Ti/Ni界面扩散形成的不稳定化合物向稳定态转变,界面Ti、Ni两元素成分曲线由交叉陡变的阶梯状逐渐转为两条近平直的平行线。富Ti的Ti/Ni复合箔材在720℃经热处理后,随时间延长,材料组织从原始的层状结构最终转变为由稳态TiNi和Ti₂Ni两相组成的混合组织。保温时间小于10h时,材料中的TiNi是由具有复杂单斜结构的B19’和CsCl型结构的B2两种物相组成,大于10h时仅存在B19’相。在冷却/加热过程中,材料内部均发生马氏体(A→M/M→A)的可逆相变,并随保温时间的增加,其相变滞后(Ap-Mp)从1h的22.4℃增加到30h的31.9℃。     

辊速对激冷贫镍Ti-Ni形状记忆合金薄带组织和相变的影响

为了开发快响应执行器用Ti-Ni形状记忆合金薄带,采用单辊甩带激冷法制备了Ti-(47,48,49) Ni形状记忆合金薄带,用共聚焦激光显微镜、XRD和示差扫描热分析仪,研究了辊速对贫镍Ti-Ni形状记忆合金薄带显微组织、相组成和相变行为的影响。结果表明,铸态Ti-47Ni、Ti-48Ni、Ti-49Ni形状记忆合金薄带的组织形态呈纵横排列的柱状,辊速越高合金薄带的晶粒越细。3种合金薄带的组成相皆为马氏体M(B19')+母相A(B2),冷却/加热时发生A→M/M→A一阶段马氏体相变。辊速对合金薄带相变类型影响不大,但影响马氏体相变温度和热滞。随辊速增加,Ti-47Ni、Ti-48Ni、Ti-49Ni形状记忆合金薄带马氏体相变温度降低,Ti-49Ni合金薄带马氏体相变热滞减小,Ti-47Ni和Ti-48Ni合金薄带马氏体相变热滞先增大后减小。     

Co对Ti-Ni形状记忆合金相变和形变特性的影响

用热重分析仪、X射线衍射仪、示差扫描量热仪及拉伸试验研究了Co对Ti-49.8Ni(at%,下同)形状记忆合金相变和形变特性的影响。结果表明,中温退火态Ti-49.8Ni合金冷却/加热时的相变类型为A→R→M/M→A(A—母相,R—R相,M—马氏体相);随退火温度升高,该合金的马氏体相变温度升高,R相变温度先升高后降低;该合金室温相组成为马氏体,具有形状记忆效应(SME)。用1%Co置换等量Ti后所得Ti-49.8Ni-1Co合金冷却/加热时的相变类型为A→R→M/M→R→A,相变温度低,室温组成相为母相A,具有超弹性(SE)特性。退火温度低于600℃时,Ti-Ni基合金的SME和SE特性良好,退火温度超过600℃后,合金氧化加剧,SME和SE特性变差,塑性显著提高。     

Twice reverse shape memory effect in CuZnAl shape memory alloy

The variations of the shape memory effects in the Cu-13Zn-15Al(mole fraction, %) alloy upon successive heating (the rate of heating is 5℃/min) have been studied by means of ρ-T curve , shape memory effect measurement, optical metallographical observation and X-ray diffraction. The first abnormal reverse shape memory effect occurs when the tested alloy is heated to the temperature below 320℃ ; when it is heated to the temperature between 320℃ and 450℃, the forward shape memory effect occurs; in the two stages, the shape of the sample remains the same as that in the furnace when it is taken out from the furnace and air-cooled; when the tested alloy is heated to the temperature above 450℃, the shape of the sample remains unchanged during heating, but the second reverse shape memory effect occurs after it is air-quenched.     

Two-way shape memory effect and its stability in Ti-Ni-Hf high temperature shape memory alloy

The two-way shape memory effect(TWSME) in a Ti36 Ni49 Hf15 high temperature shape memory alloy (SMA) was systematically studied by bending tests. In the TiNiHf alloy, the martensite deformation is an effective method to get two-way shape memory effect even with a small deformation strain. The results indicate that the internal stress field formed by the bending deformation is in the direction of the preferentially oriented martensite variants formed during the bending deformation. Upon cooling the preferentially oriented martensite variants form under such an oriented stress field, which should be responsible for the generation of the two-way shape memory effect.Proper training process benefits the formation of the oriented stress field, resulting in the improvement of the twoway shape memory effect. A maximum TWSME of 0.88% is obtained in the present alloy.     

Incomplete transformation of Ti-Ni-X ternary shape memory alloy

If the reverse transformation of a shape memory alloy is arrested, a kinetic stop will appear in the next complete transformation. The kinetic stop temperature has a close relation with the previous arrest temperature. This kinetic stop can be regarded as a ＂memory＂ of the previous arrest temperature. This phenomenon is named temperature memory effect（TME）. The TME induced by incomplete cycling in Ti-Ni-Nb and Ti-Ni-Cu alloys was systematically investigated by performing either a single incomplete cycle, or a sequence of incomplete cycles with different arrested temperatures. The results indicate that TME only exists in the heating process, and TME can occur both in B 19＇→B2 and B 19→B2 reverse transformation during heating process. But, there is no evidence of TME during cooling in the Ti-Ni-X ternary alloys. And the reverse transformation temperature interval （At-As） of the Ti44-Ni47-Nb9 alloy induced by TME can be significantly enlarged compared with that of the Ti-Ni-Cu alloy by performing multi-times incomplete transformation cycling with a decreasing order arrested temperature.     

形状记忆合金微型阀的研制

本文阐述了形状合金的特性,形状记忆合金作为驱动元件,具有结构紧凑、功率重量比大、易控制等优点,大大推动了微型机器人的发展。本课题利用形状记忆合金作为驱动元件,开发了微型气动阀,实现了与微机器人主体的集成。     

Effect of chemical component on shape memory effect of Fe-Mn-Si-Ni-C-RE shape memory alloy

Effect of chemical component on shape memory effect (SME) of Fe-Mn-Si-Ni-C-RE shape memory alloys was studied by bent measurement, thermal cycle training, SEM etc. Results of study indicate that the alloys with high Mn content (25%) appeare better SME, especially in lower strain. SME improves evidently when Si is higher content, especially it's range from 3% up to 4%. But brittleness of Fe-Mn-Si-Ni-C-RE alloy increases by increasing the Si content. SME of the alloy is weakening gradually as carbon content increases under small strain (3%). But in the condition of large strain (above 6%), SME of the alloy whose carbon content ranges from 0.1 % to 0.12% shows small decreasing range, especially of alloy with the addition of compound RE.     

Ti-Ni形状记忆合金多阶段可逆相变的类型及其演化过程

用示差扫描量热仪(DSC)和部分热循环分析法研究了350-800℃退火态和300-500℃时效态Ti-(50.2-50.8)Ni(原子分数,%)形状记忆合金多阶段可逆相变的类型及其演化过程.结果表明,这些合金发生R和马氏体两种可逆相变,相变可以一阶段完成,也可以多阶段完成.时效态合金的相变比退火态复杂,时效温度越低相变越复杂.若用DSC曲线上冷却相变峰数/加热相变峰数表示相变类型,则退火态和时效态合金冷却/加热时可以发生1/1,2/1,2/2,3/2和3/3等类型的相变.给出了各类相变发生的热处理工艺.多阶段可逆相变是一个渐变过程,在冷却相变峰的温度区间进行部分热循环时,随冷却停止(加热开始)温度降低,逆相变峰温度降低.     

DSC study on temperature memory effect of NiTi shape memory alloy

A systematic study on the temperature memory effect （TME） in a polycrystalline NiTi shape memory alloy was presented. The investigation was carded out through a series of differential scanning calorimeter （DSC） tests. Two types of tests were conducted, namely single-step test and multi-step test. The influence of the step temperature on the peak/trough temperatures in the subsequent heating process and the associated energy absorption/release in the phase transformations was investigated. Using a simple theoretical model, the exact mechanism behind TME was studied.     

Microstructure evolution in CoNiGa shape memory alloys

Magnetic shape memory CoNiGa alloys hold great promise as new smart materials due to the good ductility and a wide range of martensitic transformation (MT) temperatures as well as magnetic transition points. This paper reports the results of investigations on the equilibrium phase constitution and microstructure evolution in quenched or aged CoNiGa alloys using the optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) methods. The dendritic γ phase decreases as lowering of Ga content in studied two series of samples (Co₅₀Ni_50 − xGa_x, x = 0–50 and Co_100 − 2yNi_yGa_y, y = 15–35). Some γ′ precipitates with different morphologies were found in given alloys conducted with water quenching (WQ) at 800 °C or long-time ageing at 300 °C. After 800 °C quenching, the γ′ phase has a rod-like shape for the Co₅₀Ni₃₀Ga₂₀ alloy but shows a Widmanstätten morphology as Ga increases to 25 at%, and trends to be block structure in further high Ga content alloy. In the case of 300 °C aged alloys, the γ′ particles prefer to nucleate in interior of γ phase or at the interface of β–γ. We also presented an illustrative vertical section phase diagram keeping 50 at% Co, and isothermal section phase diagram at 1150 and 800 °C of the CoNiGa system. Based on the schematic ternary phase diagram, the composition scope which potentially holds over the magnetic pure martensite phase structure at room temperature (RT) was pointed out. It is believed that this optimized range alloys would play an important role in the functional materials design for application.     

形状记忆合金等离子束流的焊接

采用高能密度等离子束流对TiNi形状记忆合金板材进行焊接性研究.部分设计并建立了高能密度等离子束流试验装置系统.确定了参数之间的关系以及合适的参数调节范围.进而总结出可供工程应用的工艺参数范围.分别对焊接接头各部分微观组织特点、组织结构、记忆性能、抗拉强度进行了研究.研究发现,焊缝组织晶粒粗大,有新相Ni3Ti和Ti2Ni的析出;焊接热影响区窄;焊接接头的形状恢复率是母材的93.8%;母材抗拉强度为1 205 MPa,经500℃保温1 h热处理,焊接接头抗拉强度达750MPa,是母材抗拉强度的62.2%,断裂部位在焊缝中心.     

热处理和循环应变对TiNiZr合金形状记忆行为的影响

利用拉伸实验、光学显微镜和透射电镜研究了退火工艺、时效工艺和循环应变对Ti-50.8Ni-0.1Zr合金形状记忆行为的影响。350~400 ℃和600~700 ℃退火态合金呈超弹性(SE),450~550 ℃退火态合金呈形状记忆效应(SME);300 ℃/(1~50 h)和400 ℃/1 h时效态合金呈SE,400 ℃/(5~50 h)和500 ℃/(1~50 h)时效态合金呈SME。随退火温度升高,合金应力应变曲线平台应力σ_M先降低后升高,最小值200MPa在500 ℃退火后取得;残余应变ε_R先升高后降低,最大值2.64%在500 ℃退火后取得。随时效时间延长,300 ℃时效态合金的σ_M降低,ε_R始终较小;400 ℃和500 ℃时效态合金的σ_M降低,ε_R先升高后趋于稳定。随循环次数增加,呈SE的合金由部分非线性SE转变为完全非线性SE,且σ_M和能耗△W先降低后趋于稳定;呈SME的合金的σ_M和△W先降低后趋于稳定。