技术领域technical field
本发明涉及形状记忆合金领域，具体涉及一种冷轧超薄叠层合金化制备NiTiHf形状记忆合金薄膜的方法。用该方法制备的薄膜具有生产工艺简单，成分容易控制，力学性能高的优点。The invention relates to the field of shape-memory alloys, in particular to a method for preparing NiTiHf shape-memory alloy films by cold-rolling ultra-thin lamination alloying. The thin film prepared by the method has the advantages of simple production process, easy control of components and high mechanical properties.
背景技术Background technique
形状记忆效应是指变形后的某种材料受热超过一定温度时能全部或部分恢复到原来未变形的形状。具有这种效应的合金称为形状记忆合金，它是一种集感知和驱动于一体的新型功能材料。迄今为止，发现具有形状记忆效应的合金有数十种，但目前具有较好应用价值的形状记忆合金，按成分可分为三大类：①镍钛合金：Ni-Ti；②铜基合金：Cu-Zn-Al，Cu-Al-Ni；③铁基合金：Fe-Mn-Si，Fe-Ni-Co-Ti。The shape memory effect means that a deformed material can fully or partially return to its original undeformed shape when heated above a certain temperature. Alloys with this effect are called shape memory alloys, which are a new type of functional material that integrates perception and actuation. So far, dozens of alloys with shape memory effect have been found, but the shape memory alloys with good application value can be divided into three categories according to their composition: ① nickel-titanium alloy: Ni-Ti; ② copper-based alloy: Cu-Zn-Al, Cu-Al-Ni; ③ Iron-based alloys: Fe-Mn-Si, Fe-Ni-Co-Ti.
NiTi基形状记忆合金和Cu基形状记忆合金的Ms点一般不高于100℃，因而只能在低于100℃的条件下使用。铁基形状记忆合金无双向记忆效应。而在实际应用中的许多场合，如火灾或过热情形的预警及自动防护系统、卫星发射塔、火箭发动机、电流过载保护器等装置中都需要在更高的温度下使用形状记忆合金，特别是在核反应堆工程中，要求记忆合金热敏驱动器的动作温度高达600℃。因此，为了满足实际应用的需要，人们对高温形状记忆合金进行了一系列的开发和研究。The Ms points of NiTi-based shape memory alloys and Cu-based shape memory alloys are generally not higher than 100°C, so they can only be used at temperatures lower than 100°C. Iron-based shape memory alloys have no two-way memory effect. In many practical applications, such as early warning and automatic protection systems for fire or overheating, satellite launch towers, rocket engines, current overload protectors and other devices, shape memory alloys need to be used at higher temperatures, especially In nuclear reactor engineering, it is required that the operating temperature of the memory alloy thermal driver is as high as 600°C. Therefore, in order to meet the needs of practical applications, people have carried out a series of development and research on high temperature shape memory alloys.
目前，国内外主要开发出三类高温形状记忆合金：CuAlNi基五元合金CuAlNiMnX(X＝Ti，B，V)，NiAl基金属间化合物NiAlX(X＝Fe，Mn，B)，NiTi基三元合金NiTiX(X＝Pd，Pt，Au，Zr，Hf)。其中，CuAlNi基记忆合金中存在着室温塑性差，相变点不稳定及抗热能力低等问题不易解决；NiAl基记忆合金中则存在室温脆性和Ni5Al3时效析出两大应用障碍，因此近年来NiTi基高温形状记忆合金日渐引起人们的注意。向NiTi合金中添加提高相变温度的元素主要有Pd、Pt、Au、Zr和Hf，其中Pd、Pt、Au的加入使合金的造价极为昂贵，Zr提高合金相变点的作用又不十分显著，因而NiTiHf系合金以其价格低、相变温度高等优点受到了研究者的高度重视。At present, three types of high-temperature shape memory alloys have been mainly developed at home and abroad: CuAlNi-based quinary alloy CuAlNiMnX (X=Ti, B, V), NiAl-based intermetallic compound NiAlX (X=Fe, Mn, B), NiTi-based ternary Alloy NiTiX (X=Pd, Pt, Au, Zr, Hf). Among them, in CuAlNi-based memory alloys, there are problems such as poor room temperature plasticity, unstable phase transition point, and low heat resistance that are not easy to solve; in NiAl-based memory alloys, there are two major application obstacles, room temperature brittleness and Ni5 Al3 aging precipitation, so In recent years, NiTi-based high-temperature shape memory alloys have attracted more and more attention. Adding elements to increase the phase transition temperature to NiTi alloys mainly include Pd, Pt, Au, Zr and Hf, among which the addition of Pd, Pt, Au makes the cost of the alloy extremely expensive, and the effect of Zr on increasing the phase transition point of the alloy is not very significant. Therefore, NiTiHf series alloys have been highly valued by researchers due to their low price and high phase transition temperature.
研究发现NiTiHf合金系中的Hf的含量在0～3％之间时，合金的Ms温度出现一最小值；而当Hf含量超过3％时，合金的Ms点随着Hf含量的增加而不断升高；Hf含量在10％～30％时，合金的Ms点提高最为显著。当Hf含量为30％时，合金的Ms点可高达500℃以上。不幸的是当Hf含量高于20％时，合金开始变脆，可加工性严重变差。The study found that when the Hf content in the NiTiHf alloy system is between 0 and 3%, the Ms temperature of the alloy appears a minimum value; and when the Hf content exceeds 3%, the Ms point of the alloy continues to rise with the increase of the Hf content. High; when the Hf content is 10% to 30%, the Ms point of the alloy increases most significantly. When the Hf content is 30%, the Ms point of the alloy can be as high as above 500°C. Unfortunately, when the Hf content is higher than 20%, the alloy starts to become brittle and the machinability is severely deteriorated.
薄膜由于比表面积大，散热能力强，因而能有效提高响应频率，几微米厚的薄膜其响应频率可达到100HZ。然而由于高Hf含量NiTiHf合金的脆性，采用常规冷轧的方法难以制备厚度小于100μm的薄膜，要制备厚度小于100μm的薄膜，需经繁琐的冷轧加退火的反复处理，成本昂贵。现在普遍采用溅射法来制备NiTiHf合金薄膜，但受所制备材料的厚度和大小的限制，这种方法不适合一般用途的材料。也有采用熔体快淬的方法来制备NiTiHf合金薄膜，但其宽度受到限制。Due to the large specific surface area and strong heat dissipation ability of the film, the response frequency can be effectively improved. The response frequency of a film with a thickness of several microns can reach 100HZ. However, due to the brittleness of NiTiHf alloys with high Hf content, it is difficult to prepare films with a thickness of less than 100 μm by conventional cold rolling. To prepare films with a thickness of less than 100 μm, repeated tedious cold rolling and annealing are required, which is expensive. The sputtering method is now widely used to prepare NiTiHf alloy thin films, but limited by the thickness and size of the prepared materials, this method is not suitable for general-purpose materials. There is also a method of rapid quenching of melt to prepare NiTiHf alloy film, but its width is limited.
最近发展的冷轧超薄叠层合金化制备合金薄膜的方法，使得我们能采用常规的轧制设备，低成本大面积制备NiTiHf形状记忆合金薄膜。此种方法采用塑性好，变形容易的纯金属或合金箔为原材料，按设计的成分配比确定箔的厚度，将金属箔交互重叠放置，大变形冷轧后获得超薄叠层的三明治结构，根据需要，可以将冷轧后的超薄叠层对折后再次冷轧，如此反复，最后进行扩散退火合金化，获得成分均匀的合金薄膜。其生产工艺流程见附图所示。The recently developed method of cold-rolling ultra-thin lamination alloying to prepare alloy thin films enables us to use conventional rolling equipment to prepare NiTiHf shape memory alloy thin films in large areas at low cost. This method uses pure metal or alloy foil with good plasticity and easy deformation as the raw material. The thickness of the foil is determined according to the designed composition ratio, and the metal foils are placed alternately. After large deformation cold rolling, an ultra-thin laminated sandwich structure is obtained. If necessary, the cold-rolled ultra-thin laminate can be folded in half and then cold-rolled again, and so on, and finally alloyed by diffusion annealing to obtain an alloy film with uniform composition. Its production process is shown in the attached drawing.
发明内容Contents of the invention
本发明的目的是提供一种利用常规的轧制设备，通过冷轧超薄叠层合金化的方法，低成本制备大面积NiTiHf形状记忆合金薄膜。The purpose of the present invention is to provide a low-cost preparation method of large-area NiTiHf shape memory alloy thin film through cold rolling ultra-thin laminated alloying method using conventional rolling equipment.
NiTiHf形状记忆合金薄膜的原子组成式为Nix(Ti1-yHfy)1-x，其组成比分别满足0.4≤x≤0.55，0≤y≤0.8。The atomic composition formula of the NiTiHf shape memory alloy thin film is Nix (Ti1-y Hfy )1-x , and its composition ratio satisfies 0.4≤x≤0.55 and 0≤y≤0.8 respectively.
冷轧超薄叠层合金化制备大面积NiTiHf形状记忆合金薄膜的方法：根据设计的原子组成比率，以Ni箔薄，Ti箔，Hf箔或TiHf合金箔为原材料，交互重叠放置，大变形冷轧后获得超薄叠层的三明治结构，根据需要，可以将冷轧后的超薄叠层对折后再次冷轧，如此反复。最后在973K～1373K的温度范围内保温进行扩散退火，获得成分均匀的合金薄膜。A method for preparing large-area NiTiHf shape memory alloy films by cold-rolling ultra-thin lamination alloying: according to the designed atomic composition ratio, use thin Ni foil, Ti foil, Hf foil or TiHf alloy foil as raw materials, alternately overlap and place, large deformation cold After rolling, the sandwich structure of the ultra-thin laminate can be obtained. If necessary, the ultra-thin laminate after cold rolling can be folded in half and then cold-rolled again, and so on. Finally, the diffusion annealing is carried out with heat preservation in the temperature range of 973K-1373K to obtain an alloy thin film with uniform composition.
与现有技术相比，本发明具有如下优点：Compared with prior art, the present invention has following advantage:
1)首次采用冷轧超薄叠层合金化法制备了NiTiHf形状记忆合金薄膜，解决了当Hf含量超过20at％后，合金脆，难以加工的问题。其制备的薄膜具有较好的形状记忆效应和塑性，可以满足作为驱动材料的要求。1) For the first time, the NiTiHf shape memory alloy film was prepared by cold rolling ultra-thin laminated alloying method, which solved the problem that the alloy was brittle and difficult to process when the Hf content exceeded 20at%. The film prepared by it has good shape memory effect and plasticity, and can meet the requirements of being a driving material.
2)能制备大面积的NiTiHf形状记忆合金薄膜。采用熔体快淬和溅射法只能制备小面积的薄膜，而采用冷轧超薄叠层合金化的方法，能制取宽度大于100mm、长几米到几十米的薄膜，适合大规模工业生产。2) Large-area NiTiHf shape memory alloy films can be prepared. The melt quenching and sputtering methods can only prepare small-area thin films, but the cold-rolled ultra-thin laminated alloying method can produce thin films with a width greater than 100 mm and a length of several meters to tens of meters, which is suitable for large-scale industries. Production.
3)制备的NiTiHf形状记忆合金薄膜疲劳寿命高。采用冷轧超薄叠层合金化制备的TiNiHf合金薄膜晶粒细小，仅几个μm，比目前合金的晶粒低一个数量级，因此具有很高的疲劳寿命。3) The prepared NiTiHf shape memory alloy film has high fatigue life. The TiNiHf alloy film prepared by cold-rolled ultra-thin lamination alloying has a fine grain size of only a few μm, which is an order of magnitude lower than that of the current alloy, so it has a high fatigue life.
4)所制备的薄膜具有低成本高性能的特点。由于组元具有良好的冷变形能力，因此利用现有的冷轧设备就可生产，不需要昂故的特殊设备，所以成本较低。具有很强的市场竞争力。4) The prepared film has the characteristics of low cost and high performance. Because the component has good cold deformation ability, it can be produced by using existing cold rolling equipment, and does not require expensive special equipment, so the cost is relatively low. Has strong market competitiveness.
附图说明Description of drawings
本发明冷轧超薄叠层合金化制备NiTiHf形状记忆合金薄膜的加工路线示意图。Schematic diagram of the processing route for preparing NiTiHf shape memory alloy film by cold-rolling ultra-thin lamination alloying in the present invention.
具体实施方式Detailed ways
本发明制备的NiTiHf形状记忆合金薄膜的原子组成式为Nix(Ti1-xHfx)1-x，组成比分别满足：0.40≤x≤0.55，0≤y≤0.8。The atomic composition formula of the NiTiHf shape memory alloy film prepared by the present invention is Nix (Ti1-x Hfx )1-x , and the composition ratios respectively satisfy: 0.40≤x≤0.55, 0≤y≤0.8.
对于给定Hf含量的合金，只要保持Ni含量在40at％～50at％之间，其Ms点基本保持不变，但在Ni含量超过50at％以后，合金的Ms点将大幅度下降。为此，Ni含量应保持在50at％附近，在优选的实施方式中，0.45≤x≤0.50。For an alloy with a given Hf content, as long as the Ni content is kept between 40at% and 50at%, its Ms point remains basically unchanged, but when the Ni content exceeds 50at%, the Ms point of the alloy will drop significantly. For this reason, the Ni content should be kept around 50 at%, in a preferred embodiment, 0.45≦x≦0.50.
因为当Hf含量高于30at％后，合金的形状记忆效应将变差，因此Hf含量应低于30at％，在优选的实施方式中，0≤y≤0.6。Because when the Hf content is higher than 30 at%, the shape memory effect of the alloy will be deteriorated, so the Hf content should be lower than 30 at%, and in a preferred embodiment, 0≤y≤0.6.
实施例1Example 1
根据设计的成分配方Ni0.5(Ti0.9Hf0.1)0.5，采用厚度为0.100mm的Ni箔，0.166mm的Ti-10Hf(原子百分比)合金箔为原材料，按{Ni/TiHf}的堆垛方式重叠放置10层。首先以62％的变形量冷轧到1.000mm，然后再冷轧到0.050mm，将冷轧的薄膜对折重叠，再冷轧到0.050mm，如此反复10道次。最后将冷轧10道次的薄膜于973K下保温50小时，进行合金化。电阻法测定合金的Ms点为341K，室温拉伸变形6％加热后形状完全恢复。According to the designed composition formula Ni0.5 (Ti0.9 Hf0.1 )0.5 , use Ni foil with a thickness of 0.100mm, and Ti-10Hf (atomic percentage) alloy foil with a thickness of 0.166mm as the raw material, stacked according to the stacking method of {Ni/TiHf} Place 10 layers. First cold rolling to 1.000mm with a deformation of 62%, and then cold rolling to 0.050mm, the cold rolled film is folded and overlapped, and then cold rolled to 0.050mm, repeating 10 passes. Finally, the cold-rolled 10-pass film was kept at 973K for 50 hours for alloying. The Ms point of the alloy was determined to be 341K by electrical resistance method, and the shape recovered completely after being heated with 6% tensile deformation at room temperature.
实施例2Example 2
根据设计的成分配方Ni0.5(Ti0.8Hf0.2)0.5，采用厚度为0.100mm的Ni箔，0.170mm的Ti-20Hf(原子百分比)合金箔为原材料，按{Ni/TiHf}的堆垛方式重叠放置10层。首先以63％的变形量冷轧到1.000mm，然后再冷轧到0.060mm，将冷轧的薄膜对折重叠，再冷轧到0.060mm，如此反复10道次。最后将冷轧10道次的薄膜于1073K下保温40小时，进行合金化。电阻法测定合金的Ms点为376K，室温拉伸变形4％加热后形状完全恢复。According to the designed composition formula Ni0.5 (Ti0.8 Hf0.2 )0.5 , use Ni foil with a thickness of 0.100mm, and Ti-20Hf (atomic percentage) alloy foil with a thickness of 0.170mm as the raw material, stacked according to the stacking method of {Ni/TiHf} Place 10 layers. First cold rolling to 1.000mm with a deformation of 63%, and then cold rolling to 0.060mm, the cold rolled film is folded and overlapped, and then cold rolled to 0.060mm, repeating 10 passes. Finally, the cold-rolled 10-pass film was kept at 1073K for 40 hours for alloying. The Ms point of the alloy was determined to be 376K by electrical resistance method, and the shape was completely recovered after being heated with 4% tensile deformation at room temperature.
实施例3Example 3
根据设计的成分配方Ni0.5(Ti0.6Hf0.4)0.5，采用厚度为0.100mm的Ni箔，0.180mm的Ti-40Hf(原子百分比)合金箔为原材料，按{Ni/TiHf}的堆垛方式重叠放置10层。首先以64％的变形量冷轧到1.000mm，然后再冷轧到0.060mm，将冷轧的薄膜对折重叠，再冷轧到0.060mm，如此反复10道次。最后将冷轧10道次的薄膜于1173K下保温20小时，进行合金化。电阻法测定合金的Ms点为575K，室温拉伸变形4％加热后形状完全恢复。According to the designed composition formula Ni0.5 (Ti0.6 Hf0.4 )0.5 , use Ni foil with a thickness of 0.100mm, and Ti-40Hf (atomic percentage) alloy foil with a thickness of 0.180mm as the raw material, stacked according to the stacking method of {Ni/TiHf} Place 10 layers. First cold rolling to 1.000mm with a deformation of 64%, and then cold rolling to 0.060mm, the cold rolled film is folded and overlapped, and then cold rolled to 0.060mm, repeating 10 passes. Finally, the cold-rolled 10-pass film was kept at 1173K for 20 hours for alloying. The Ms point of the alloy was determined to be 575K by the electrical resistance method, and the shape was completely recovered after heating at room temperature with a tensile deformation of 4%.
实施例4Example 4
根据设计的成分配方Ni0.5(Ti0.5Hf0.5)0.5，采用厚度为0.110mm的Ni箔，0.200mm的Ti-50Hf(原子百分比)合金箔为原材料，按{Ni/HfTi}的堆垛方式重叠放置10层。首先以68％的变形量冷轧到1.000mm，然后再冷轧到0.080mm后，将冷轧的薄膜对折重叠，再冷轧到0.080mm，如此反复10道次。最后将冷轧10道次的薄膜于1273K下保温10小时，进行合金化。电阻法测定合金的Ms点为571K，室温拉伸变形4％加热后形状完全恢复。According to the designed composition formula Ni0.5 (Ti0.5 Hf0.5 )0.5 , use Ni foil with a thickness of 0.110mm, and Ti-50Hf (atomic percentage) alloy foil with a thickness of 0.200mm as raw materials, stacked according to the stacking method of {Ni/HfTi} Place 10 layers. First cold rolled to 1.000mm with a deformation of 68%, and then cold rolled to 0.080mm, the cold rolled film was folded and overlapped, and then cold rolled to 0.080mm, repeated 10 times. Finally, the thin film cold-rolled for 10 passes was kept at 1273K for 10 hours for alloying. The Ms point of the alloy was determined to be 571K by electrical resistance method, and the shape was completely recovered after heating at room temperature with a tensile deformation of 4%.
实施例5Example 5
根据设计的成分配方Ni0.5(Ti0.4Hf0.6)0.5，采用厚度为0.100mm的Ni箔，0.200mm的Hf-40Ti箔为原材料，按{Ni/HfTi}的堆垛方式重叠放置10层。首先以60％的变形量冷轧到1.200mm，然后再冷轧到0.080mm后，将冷轧的薄膜对折重叠，再冷轧到0.080mm，如此反复10道次。最后将冷轧10道次的薄膜于1173K下保温20小时，进行合金化。电阻法测定合金的Ms点为786K，室温拉伸变形1.5％加热后形状完全恢复。According to the designed composition formula Ni0.5 (Ti0.4 Hf0.6 )0.5 , Ni foil with a thickness of 0.100mm and Hf-40Ti foil with a thickness of 0.200mm are used as raw materials, and 10 layers are stacked according to the stacking method of {Ni/HfTi}. First cold rolled to 1.200mm with a deformation of 60%, and then cold rolled to 0.080mm, the cold rolled film was folded and overlapped, and then cold rolled to 0.080mm, repeating 10 passes. Finally, the cold-rolled 10-pass film was kept at 1173K for 20 hours for alloying. The Ms point of the alloy was determined to be 786K by the electrical resistance method, and the shape recovered completely after heating at room temperature with a tensile deformation of 1.5%.
实施例6Example 6
根据设计的成分配方Ni0.45(Ti0.6Hf0.4)0.55，采用厚度为0.100mm的Ni箔，0.118mm的Ti箔，0.100mm的Hf箔为原材料，按{Ni/Hf/Ti}的堆垛方式重叠放置10层。首先以65％的变形量冷轧到1.100mm，然后再冷轧到0.080mm后，将冷轧的薄膜对折重叠，再冷轧到0.080mm，如此反复10道次。最后将冷轧20道次的薄膜于1173K下保温20小时，进行合金化。电阻法测定合金的Ms点为612K，室温拉伸变形4％加热后形状完全恢复。According to the designed composition formula Ni0.45 (Ti0.6 Hf0.4 )0.55 , use Ni foil with a thickness of 0.100mm, Ti foil with a thickness of 0.118mm, and Hf foil with a thickness of 0.100mm as raw materials, according to the stacking method of {Ni/Hf/Ti} Place 10 layers overlapping. First cold rolled to 1.100mm with a deformation of 65%, and then cold rolled to 0.080mm, the cold rolled film was folded and overlapped, and then cold rolled to 0.080mm, repeating 10 passes. Finally, the cold-rolled 20-pass film was kept at 1173K for 20 hours for alloying. The Ms point of the alloy was determined to be 612K by electrical resistance method, and the shape was completely recovered after being heated with 4% tensile deformation at room temperature.
实施例7Example 7
根据设计的成分配方Ni0.50(Ti0.6Hf0.4)0.50，采用厚度为0.120mm的Ni箔，0.116mm的Ti箔，0.100mm的Hf箔为原材料，按{Ni/Hf/Ti}的堆垛方式重叠放置10层。首先以64％的变形量冷轧到1.200mm，然后再冷轧到0.090mm后，将冷轧的薄膜对折重叠，再冷轧到0.090mm，如此反复10道次。最后将冷轧10道次的薄膜于1173K下保温20小时，进行合金化。电阻法测定合金的Ms点为573K，室温拉伸变形4％加热后形状完全恢复。According to the designed composition formula Ni0.50 (Ti0.6 Hf0.4 )0.50 , use Ni foil with a thickness of 0.120mm, Ti foil with a thickness of 0.116mm, and Hf foil with a thickness of 0.100mm as raw materials, according to the stacking method of {Ni/Hf/Ti} Place 10 layers overlapping. First cold rolled to 1.200mm with a deformation of 64%, and then cold rolled to 0.090mm, the cold rolled film was folded and overlapped, and then cold rolled to 0.090mm, repeated 10 times. Finally, the cold-rolled 10-pass film was kept at 1173K for 20 hours for alloying. The Ms point of the alloy was determined to be 573K by electrical resistance method, and the shape was completely recovered after heating at room temperature with a tensile deformation of 4%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100201590ACN1298876C (en) | 2005-01-13 | 2005-01-13 | Method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100201590ACN1298876C (en) | 2005-01-13 | 2005-01-13 | Method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil |
| Publication Number | Publication Date |
|---|---|
| CN1667143A CN1667143A (en) | 2005-09-14 |
| CN1298876Ctrue CN1298876C (en) | 2007-02-07 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100201590AExpired - Fee RelatedCN1298876C (en) | 2005-01-13 | 2005-01-13 | Method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil |
| Country | Link |
|---|---|
| CN (1) | CN1298876C (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108085563A (en)* | 2017-12-18 | 2018-05-29 | 西安赛特思迈钛业有限公司 | A kind of Ni-based quaternary memorial alloy of high temperature titanium |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59116340A (en)* | 1982-12-24 | 1984-07-05 | Sumitomo Electric Ind Ltd | Manufacturing method of shape memory alloy material |
| JPS59116341A (en)* | 1982-12-24 | 1984-07-05 | Sumitomo Electric Ind Ltd | Production of shape memory alloy material |
| CN1085839A (en)* | 1992-10-19 | 1994-04-27 | 中国科学院金属研究所 | Make the process of NiTiNb memorial alloy precision tube |
| EP0709482A1 (en)* | 1994-10-28 | 1996-05-01 | Kazuhiro Otsuka | Method of manufacturing high-temperature shape memory alloys |
| JPH08209314A (en)* | 1994-10-28 | 1996-08-13 | Kazuhiro Otsuka | Method for manufacturing high temperature operating shape memory alloy |
| JP2001329351A (en)* | 2000-05-22 | 2001-11-27 | Nippon Metal Ind Co Ltd | Method of manufacturing shape memory alloy by laminating rolling and shape memory alloy |
| US6454913B1 (en)* | 2001-07-12 | 2002-09-24 | Delphi Technologies, Inc. | Process for deposition of sputtered shape memory alloy films |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59116340A (en)* | 1982-12-24 | 1984-07-05 | Sumitomo Electric Ind Ltd | Manufacturing method of shape memory alloy material |
| JPS59116341A (en)* | 1982-12-24 | 1984-07-05 | Sumitomo Electric Ind Ltd | Production of shape memory alloy material |
| CN1085839A (en)* | 1992-10-19 | 1994-04-27 | 中国科学院金属研究所 | Make the process of NiTiNb memorial alloy precision tube |
| EP0709482A1 (en)* | 1994-10-28 | 1996-05-01 | Kazuhiro Otsuka | Method of manufacturing high-temperature shape memory alloys |
| JPH08209314A (en)* | 1994-10-28 | 1996-08-13 | Kazuhiro Otsuka | Method for manufacturing high temperature operating shape memory alloy |
| JP2001329351A (en)* | 2000-05-22 | 2001-11-27 | Nippon Metal Ind Co Ltd | Method of manufacturing shape memory alloy by laminating rolling and shape memory alloy |
| US6454913B1 (en)* | 2001-07-12 | 2002-09-24 | Delphi Technologies, Inc. | Process for deposition of sputtered shape memory alloy films |
| Publication number | Publication date |
|---|---|
| CN1667143A (en) | 2005-09-14 |
| Publication | Publication Date | Title |
|---|---|---|
| CN105856727B (en) | A kind of multiple layer of copper/titanium composite panel and preparation method thereof | |
| CN102925771B (en) | High-room-temperature ductility magnesium alloy material | |
| CN109604963B (en) | Preparation method of heterogeneous high-entropy alloy with variable modulation period and modulation ratio | |
| CA2773708A1 (en) | Method for production of an iron-chromium alloy | |
| CN105058914A (en) | Layered Ti-Ni shape memory composite material and preparation method thereof | |
| CN106011708A (en) | Heat treatment technology for 8021 high-performance aluminum foil for soft package | |
| JP2011214103A (en) | Method of manufacturing magnesium alloy material and magnesium alloy material | |
| JP5581505B2 (en) | Magnesium alloy sheet | |
| CN1844429A (en) | Ni-based alloy composite substrate and its melting preparation method | |
| CN1298876C (en) | Method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil | |
| CN100342050C (en) | Production of TiNiCu shape memory alloy thin membrane by cold rolling superthin laminated alloy | |
| CN1295367C (en) | Production of TiNiPd shape memory alloy thin membrane by cold rolling superthin laminated alloy | |
| CN1330781C (en) | Production of CuALNiMn shape memory alloy thin membrane by cold rolling superthin laminated alloy | |
| Tada et al. | Effect of Al addition on superelastic properties of aged Ti–Nb–Zr–Al quaternary alloys | |
| CN1667144A (en) | Preparation of NiAl Shape Memory Alloy Thin Films by Alloying Ultrathin Laminates by Cold Rolling | |
| Meng et al. | Structure of martensite in sputter-deposited (Ni, Cu)-rich Ti–Ni–Cu thin films containing Ti (Ni, Cu) 2 precipitates | |
| CN112853230A (en) | Low-layer-dislocation-energy face-centered cubic structure high-entropy shape memory alloy and preparation method thereof | |
| Yao et al. | Characterization of free-standing nanocrystalline Ni55. 2Mn24. 7Ga19. 9Gd0. 2 high temperature shape memory thin film | |
| CN107090557A (en) | A kind of aluminium alloy and preparation method for being used to prepare inexpensive high temperature resistant brazed aluminum/steel composite strip | |
| JP4222444B2 (en) | Ti-Ni-Cu-based shape memory alloy | |
| JP2000119787A (en) | Magnesium alloy, structure of magnesium alloy, and method of manufacturing the same | |
| WO1987003305A1 (en) | Corrosion-resistant copper alloy | |
| ZU et al. | Microstructural development and its effects on mechanical properties of Al/Cu laminated composite | |
| US20030168334A1 (en) | High temperature shape memory alloy thin film | |
| CN1727513A (en) | A kind of preparation method of nickel base amorphous alloy coating |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20070207 Termination date:20100222 |