CN1298876C - Method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil - Google Patents
Method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil Download PDFInfo
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- CN1298876C CN1298876C CNB2005100201590A CN200510020159A CN1298876C CN 1298876 C CN1298876 C CN 1298876C CN B2005100201590 A CNB2005100201590 A CN B2005100201590A CN 200510020159 A CN200510020159 A CN 200510020159A CN 1298876 C CN1298876 C CN 1298876C
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Abstract
The present invention discloses a method for preparing a Ni-Ti-Hf shaping memory alloy film by cold-rolling ultrathin lamination alloying. Ni foil, Ti foil, Hf foil or Ti-Hf alloy foil with good plasticity and easy deformation are used as raw materials, and the thickness of the foil is determined according to an atomic composition formula Ni<x>(Ni<l-y>Hf<y>)<1-x>. The metal foil is placed in an overlapping mode, and an ultrathin laminated sandwich structure is obtained after large-deformation cold rolling. The cold-rolled ultrathin lamination can carry out cold rolling again after being folded. In this way, an alloy film with uniform components finally can be obtained by diffusion annealing and alloying. The component ratios meet the requirements that 0.40<=x<=0.55 and 0<=y<=0.8. The Ni-Ti-Hf shaping memory alloy film prepared by the method has the advantages of easy component control, fine crystal grain, high fatigue life, large area and low cost.
Description
Technical field
The present invention relates to the shape memory alloy field, be specifically related to a kind of method of method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil.It is simple to have production technique with the film of this method preparation, easy control of components, the advantage that mechanical property is high.
Background technology
Shape memory effect is meant when certain material after the distortion is heated above certain temperature can all or part ofly return to original undeformed shape.Alloy with this effect is called shape memory alloy, and it is a kind of new function material that integrates perception and drive.Up to now, find that the alloy with shape memory effect has tens of kinds, but have the shape memory alloy of better application value at present, can be divided into three major types: 1. Ni-Ti alloy: Ni-Ti by composition; 2. copper base alloy: Cu-Zn-Al, Cu-Al-Ni; 3. ferrous alloy: Fe-Mn-Si, Fe-Ni-Co-Ti.
The Ms point of NiTi base marmem and Cu base marmem generally is not higher than 100 ℃, thereby can only use being lower than under 100 ℃ the condition.Iron-base marmem is unparalleled to memory effect.And many occasions in actual applications; as all need under higher temperature, using shape memory alloy in the devices such as the early warning of fire or overheated situation and automatic protective system, satellite launching tower, rocket engine, overcurrent protection device; particularly in the nuclear reactor engineering, the operating temperature that requires memorial alloy temperature-sensitive driving mechanism is up to 600 ℃.Therefore, in order to satisfy the needs of practical application, people have carried out a series of R and D to high-temperature shape memory alloy.
At present, mainly develop three type high temp shape memory alloys both at home and abroad: CuAlNi based quinary alloy CuAlNiMnX (X=Ti, B, V), NiAl base intermetallic compound NiAlX (X=Fe, Mn, B), NiTi base ternary alloy NiTiX (X=Pd, Pt, Au, Zr, Hf).Problems such as wherein, it is poor to exist temperature-room type plasticity in the CuAlNi base memorial alloy, and transformation temperature instability and heat resistance are low are difficult for solving; Then there are room temperature fragility and Ni in the NiAl base memorial alloy
5Al
3Timeliness is separated out the two big obstacles of using, and therefore the NiTi based high-temperature shape memory alloy day by day attracts much attention in recent years.In the NiTi alloy, add the element that improves transformation temperature and mainly contain Pd, Pt, Au, Zr and Hf, wherein the adding of Pd, Pt, Au makes the cost of alloy very expensive, it is very not remarkable again that Zr improves the effect of alloy phase height, thereby NiTiHf is the great attention that alloy is low with its price, the transformation temperature advantages of higher has been subjected to the investigator.
The content of discovering the Hf in the NiTiHf alloy system is between 0～3% the time, and a minimum value appears in the Ms temperature of alloy; And when Hf content surpassed 3%, the Ms point of alloy constantly raise along with the increase of Hf content; Hf content was at 10%～30% o'clock, and the Ms point of alloy improves the most remarkable.When Hf content was 30%, the Ms of alloy point can be up to more than 500 ℃.Unfortunately when Hf content was higher than 20%, alloy began to become fragile, the serious variation of workability.
Film is because specific surface area is big, and heat-sinking capability is strong, thereby can effectively improve response frequency, and its response frequency of the film of several micron thickness can reach 100HZ.Yet because the fragility of high Hf content NiTiHf alloy adopts conventional cold rolling method to be difficult to prepare the film of thickness less than 100 μ m, prepare the film of thickness, need through the loaded down with trivial details cold rolling annealed repeated treatments that adds, cost costliness less than 100 μ m.Generally adopt sputtering method to prepare the NiTiHf alloy firm now, but be subjected to the thickness of prepared material and the restriction of size, this method is not suitable for general purpose material.Also have and adopt the method for melt-spun to prepare the NiTiHf alloy firm, but its width is restricted.
The cold rolling superthin laminated alloying of latest developments prepares the method for alloy firm, makes us can adopt conventional rolling equipment, and low-cost large-area prepares the NiTiHf shape memory alloy film.This kind method adopts plasticity good, distortion is easy to pure metal or Alloy Foil is starting material, determine the thickness of paper tinsel by the composition proportion of design, the tinsel intermeshing is placed, and the cold rolling back of gross distortion obtains superthin laminated sandwich structure, as required, can be with cold rolling once more after the superthin laminated doubling after cold rolling, so repeatedly, carry out the diffusion annealing alloying at last, obtain the uniform alloy firm of composition.Its technological process of production is seen shown in the accompanying drawing.
Summary of the invention
The purpose of this invention is to provide a kind of conventional rolling equipment that utilizes, by the method for cold rolling superthin laminated alloying, low-cost preparation big area NiTiHf shape memory alloy film.
The atom composition formula of NiTiHf shape memory alloy film is Ni
x(Ti
1-yHf
y)
1-x, its ratio of components satisfies 0.4≤x≤0.55,0≤y≤0.8 respectively.
Cold rolling superthin laminated alloying prepares the method for big area NiTiHf shape memory alloy film: according to the atom composition ratio of design, thin with the Ni paper tinsel, the Ti paper tinsel, Hf paper tinsel or TiHf Alloy Foil are starting material, intermeshing is placed, and the cold rolling back of gross distortion obtains superthin laminated sandwich structure, as required, can be with cold rolling once more after the superthin laminated doubling after cold rolling, so repeatedly.The last insulation in the temperature range of 973K～1373K carried out diffusion annealing, obtains the uniform alloy firm of composition.
Compared with prior art, the present invention has following advantage:
1) adopt cold rolling superthin laminated alloying to prepare the NiTiHf shape memory alloy film first, solved after Hf content surpasses 20at%, alloy is crisp, unmanageable problem.The film of its preparation has shape memory effect and plasticity preferably, can satisfy the requirement as driving material.
2) can prepare large-area NiTiHf shape memory alloy film.Adopt melt-spun and sputtering method can only prepare the film of small area, and adopt the method for cold rolling superthin laminated alloying, can produce width, be fit to large-scale commercial production greater than 100mm, long several meters to tens meters film.
3) Zhi Bei NiTiHf shape memory alloy film height fatigue lifetime.Adopt the TiNiHf alloy firm crystal grain of cold rolling superthin laminated alloying preparation tiny, only several μ m, therefore the low order of magnitude of crystal grain than present alloy has very high fatigue lifetime.
4) prepared film has the characteristics of low-cost and high-performance.Because constituent element has good cold deformation ability, therefore utilize existing cold-rolling equipment just can produce, do not need the specific installation of high event, so cost is lower.Has the very strong market competitiveness.
Description of drawings
The processing route synoptic diagram of method for preparing NiTiHf shape memory alloy film by cold rolling ultra-thin laminated alloy foil of the present invention.
Embodiment
The atom composition formula of the NiTiHf shape memory alloy film of the present invention's preparation is Ni
x(Ti
1-xHf
x)
1-x, ratio of components satisfies respectively: 0.40≤x≤0.55,0≤y≤0.8.
For the alloy of given Hf content, as long as keep Ni content between 40at%～50at%, its Ms point remains unchanged substantially, but after Ni content surpassed 50at%, the Ms of alloy named a person for a particular job and descends significantly.For this reason, Ni content should remain near the 50at%, in preferred embodiment, and 0.45≤x≤0.50.
Because after Hf content is higher than 30at%, the shape memory effect of alloy is variation, so Hf content should be lower than 30at%, in preferred embodiment, and 0≤y≤0.6.
Embodiment 1
Component prescription Ni according to design
0.5(Ti
0.9Hf
0.1)
0.5, adopting thickness is the Ni paper tinsel of 0.100mm, the Ti-10Hf of 0.166mm (atomic percent) Alloy Foil is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/TiHf}.At first be cold rolled to 1.000mm, and then be cold rolled to 0.050mm with 62% deflection, cold rolling film doubling is overlapping, be cold rolled to 0.050mm again, so repeatedly 10 passages.Film with cold rolling 10 passages is incubated 50 hours down in 973K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 341K, and room temperature tensile distortion 6% heating back shape is recovered fully.
Embodiment 2
Component prescription Ni according to design
0.5(Ti
0.8Hf
0.2)
0.5, adopting thickness is the Ni paper tinsel of 0.100mm, the Ti-20Hf of 0.170mm (atomic percent) Alloy Foil is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/TiHf}.At first be cold rolled to 1.000mm, and then be cold rolled to 0.060mm with 63% deflection, cold rolling film doubling is overlapping, be cold rolled to 0.060mm again, so repeatedly 10 passages.Film with cold rolling 10 passages is incubated 40 hours down in 1073K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 376K, and room temperature tensile distortion 4% heating back shape is recovered fully.
Embodiment 3
Component prescription Ni according to design
0.5(Ti
0.6Hf
0.4)
0.5, adopting thickness is the Ni paper tinsel of 0.100mm, the Ti-40Hf of 0.180mm (atomic percent) Alloy Foil is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/TiHf}.At first be cold rolled to 1.000mm, and then be cold rolled to 0.060mm with 64% deflection, cold rolling film doubling is overlapping, be cold rolled to 0.060mm again, so repeatedly 10 passages.Film with cold rolling 10 passages is incubated 20 hours down in 1173K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 575K, and room temperature tensile distortion 4% heating back shape is recovered fully.
Embodiment 4
Component prescription Ni according to design
0.5(Ti
0.5Hf
0.5)
0.5, adopting thickness is the Ni paper tinsel of 0.110mm, the Ti-50Hf of 0.200mm (atomic percent) Alloy Foil is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/HfTi}.At first be cold rolled to 1.000mm with 68% deflection, and then after being cold rolled to 0.080mm, cold rolling film doubling is overlapping, be cold rolled to 0.080mm again, so repeatedly 10 passages.Film with cold rolling 10 passages is incubated 10 hours down in 1273K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 571K, and room temperature tensile distortion 4% heating back shape is recovered fully.
Embodiment 5
Component prescription Ni according to design
0.5(Ti
0.4Hf
0.6)
0.5, adopting thickness is the Ni paper tinsel of 0.100mm, the Hf-40Ti paper tinsel of 0.200mm is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/HfTi}.At first be cold rolled to 1.200mm with 60% deflection, and then after being cold rolled to 0.080mm, cold rolling film doubling is overlapping, be cold rolled to 0.080mm again, so repeatedly 10 passages.Film with cold rolling 10 passages is incubated 20 hours down in 1173K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 786K, and room temperature tensile distortion 1.5% heating back shape is recovered fully.
Embodiment 6
Component prescription Ni according to design
0.45(Ti
0.6Hf
0.4)
0.55, adopting thickness is the Ni paper tinsel of 0.100mm, the Ti paper tinsel of 0.118mm, and the Hf paper tinsel of 0.100mm is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/Hf/Ti}.At first be cold rolled to 1.100mm with 65% deflection, and then after being cold rolled to 0.080mm, cold rolling film doubling is overlapping, be cold rolled to 0.080mm again, so repeatedly 10 passages.Film with cold rolling 20 passages is incubated 20 hours down in 1173K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 612K, and room temperature tensile distortion 4% heating back shape is recovered fully.
Embodiment 7
Component prescription Ni according to design
0.50(Ti
0.6Hf
0.4)
0.50, adopting thickness is the Ni paper tinsel of 0.120mm, the Ti paper tinsel of 0.116mm, and the Hf paper tinsel of 0.100mm is starting material, by { 10 layers of the overlapping placements of the way of stacking of Ni/Hf/Ti}.At first be cold rolled to 1.200mm with 64% deflection, and then after being cold rolled to 0.090mm, cold rolling film doubling is overlapping, be cold rolled to 0.090mm again, so repeatedly 10 passages.Film with cold rolling 10 passages is incubated 20 hours down in 1173K at last, carries out alloying.The Ms point that electrical resistance method is measured alloy is 573K, and room temperature tensile distortion 4% heating back shape is recovered fully.
Claims (2)
1, a kind of preparation method of NiTiHf shape memory alloy film is characterized in that the paper tinsel with pure metal Ti, metal Ni paper tinsel, and metal Hf paper tinsel or TiHf Alloy Foil are starting material, press atom composition formula Ni
x(Ti
1-yHf
y)
1-xRatio of components satisfies 0.45≤x≤0.55, the thickness of paper tinsel is determined in 0≤y≤0.8, the tinsel intermeshing is placed 10 layers, cold rolling compound with 50%～99% deflection, then with cold rolling once more after the doubling of cold rolling compound lamination, 10 passages so repeatedly, at last with cold rolling compound laminate film, be incubated in 873K～1373K temperature range, the diffusion annealing alloying obtains the uniform alloy firm of composition.
2, the preparation method of shape memory alloy film according to claim 1, the temperature that it is characterized in that diffusion annealing is 973K～1273K, soaking time is 10～50 hours.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59116340A (en) * | 1982-12-24 | 1984-07-05 | Sumitomo Electric Ind Ltd | Production 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 | Production of shape memory alloy with high-temperature phase-transferring function |
| JP2001329351A (en) * | 2000-05-22 | 2001-11-27 | Nippon Metal Ind Co Ltd | Method for manufacturing shape memory alloy by laminated 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 |
-
2005
- 2005-01-13 CN CNB2005100201590A patent/CN1298876C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59116340A (en) * | 1982-12-24 | 1984-07-05 | Sumitomo Electric Ind Ltd | Production 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 | Production of shape memory alloy with high-temperature phase-transferring function |
| JP2001329351A (en) * | 2000-05-22 | 2001-11-27 | Nippon Metal Ind Co Ltd | Method for manufacturing shape memory alloy by laminated 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 |
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