CN103046018B - Method for endowing film with large elastic strain by shape memory alloy - Google Patents
Method for endowing film with large elastic strain by shape memory alloy Download PDFInfo
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- CN103046018B CN103046018B CN201310001136.XA CN201310001136A CN103046018B CN 103046018 B CN103046018 B CN 103046018B CN 201310001136 A CN201310001136 A CN 201310001136A CN 103046018 B CN103046018 B CN 103046018B
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Abstract
The invention relates to a method for endowing a film with large elastic strain by a shape memory alloy. The method comprises the following steps that sedimentation is conducted on the surface of a substrate of the shape memory alloy; the film is obtained; stretching is conducted; stretching strain of the film is achieved; or the sedimentation is conducted on the surface of the substrate of the shape memory alloy subjected to prestretching treatment at a room temperature; the film is obtained; then the film is heated and kept for some time, so that the substrate of the shape memory alloy subjected to the prestretching treatment has phase change shrinkage; and compression strain of the film is achieved. Compared with the prior art, the method has the following technical effects that the method first uses the shape memory alloy to achieve the large elastic strain of the film, and then catalytic activity of the film is improved by regulating and controlling an optical energy gap of the film; the method is simple and obvious in effect; and no rupture occurs while the TiNi substrate drives the ceramic film to achieve large deformation.
Description
Technical field
The present invention relates to a kind of applying shape memory alloy and give the method for the large recoverable strain of film, belong to shape memory alloy material applied technical field.
Background technology
Recoverable strain engineering refers to material applied to additional tensile stress or stress, regulates the physics and chemistry characteristic such as electricity, optics, magnetics, catalysis of material, and then optimize material property by changing interatomic distance.As carrier mobility in semiconductor applications can make silicon by lattice misfit improves 50%, Pt-Cu binary alloy nanoparticle because the strain that lattice misfit produces can improve its catalytic activity, TiO
2material provides the raising catalytic activitys such as internal stress by other element doping, recoverable strain engineering has very important practical value in actual productive life.
Conventionally people adopt the method such as lattice misfit or doping to apply recoverable strain, but these methods are prepared difficulty mostly, and with high costs, deflection is smaller and restive.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of method that realizes the large recoverable strain of film, it is to utilize shape memory alloy to realize the method for the large recoverable strain of film, provides a kind of novel method for the functional performance of thin-film material improves.
For achieving the above object, the invention provides a kind of applying shape memory alloy and give the method for the large recoverable strain of film, it comprises the following steps:
Use pulsed laser deposition (PLD) to deposit on the surface of shape memory alloy substrate and obtain film, then shape memory alloy substrate is stretched, drive the realization of film stretching strain by the tensile deformation of substrate; Or, deposit and obtain film on the surface of the shape memory alloy substrate through preliminary draft processing, then heat and be incubated certain hour, making the described shape memory alloy substrate through preliminary draft processing undergo phase transition contraction, driving the realization of thin film strain by the shrinkage strain of substrate.
In aforesaid method, preferably, the shape memory alloy adopting is TiNi shape memory alloy.
In aforesaid method, preferably, the shape memory alloy adopting is prepared by following steps:
Choose simple substance titanium, the elemental nickel of purity more than 99.9wt.% according to the atomic ratio of 50.2: 49.8;
Simple substance titanium and elemental nickel are put into vacuum tightness higher than 10
-1in the smelting furnace of Pa or protection of inert gas, be smelted into TiNi shape memory alloy, obtain ingot casting;
In vacuum tightness higher than 10
-1in the vacuum of Pa or in protection of inert gas, at 800-1050 DEG C, ingot casting is carried out to homogenizing annealing 5-60h;
Ingot casting after annealing is carried out to cold rolling and 950 DEG C of recrystallization annealings, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to described shape memory alloy substrate;
Deposit and obtain film on the surface of shape memory alloy substrate, then carry out the stretch processing that deflection is 6-12%, realize the stretching strain of film;
The preliminary draft processing of shape memory alloy substrate refers to the anneal of at 300-500 DEG C, described shape memory alloy substrate being carried out 10-30 minute, then carry out at ambient temperature preliminary draft, pre-tension deformation amount is 6-15%, obtains the shape memory alloy through preliminary draft processing;
The shape memory alloy substrate through preliminary draft processing that has deposited film is heated to 80-150 DEG C and be incubated 10-30 minute, return to again room temperature, make the described shape memory alloy substrate through preliminary draft processing undergo phase transition contraction (shrinkage strain amount is pre-tension deformation amount), realize the compressive strain of film.
In aforesaid method, preferably, described film is ZnO, TiO
2, CuO, Cu
2o or Co
3o
4film etc.
In aforesaid method, preferably, above-mentioned deposition comprises the following steps:
The ceramic target of film is put into the growth room of pulsed laser deposition device, keeping the distance of ceramic target and substrate is 4.5cm; Growth room's vacuum tightness is evacuated to 10
-3below Pa, keep substrate to heat to 100-500 DEG C in room temperature or by substrate, in growth room, pass into O
2gas, the pressure controlling in growth room is 0.001-100Pa; Open laser apparatus, make laser beam focus on the target surface ablation target of ceramic target, obtain film at shape memory alloy substrate or through the surface deposition of the shape memory alloy substrate of preliminary draft processing, laser energy is 340mJ, and frequency is 5Hz.
In aforesaid method, preferably, the stretching strain of film realizes by following steps: sink to the bottom to having deposited the shape memory alloy of film that to carry out deflection be 10% stretch processing, realize the stretching strain of film; The compressive strain of film realizes by following steps: deposit and obtain film on the surface of the shape memory alloy substrate through preliminary draft processing, then be heated to 100 DEG C and be incubated 20 minutes, return to again room temperature, make the described shape memory alloy substrate through preliminary draft processing undergo phase transition contraction, realize the compressive strain of film.
In aforesaid method, the preparation of target can be carried out according to following steps: weigh pure ZnO, TiO
2, CuO, Cu
2o or Co
3o
4powder, by powder ball milling mix, compression moulding, then sintering at 1000-1300 DEG C, makes ZnO, TiO
2, CuO, Cu
2o or Co
3o
4ceramic target.
Compared with prior art, technical scheme provided by the present invention has following technique effect:
(1) change with common employing compared with the method that the methods such as growth conditions, doping improve material catalytic activity, first Application shape memory alloy of the present invention is realized the large recoverable strain of film, and then the optical energy gap etc. of regulation and control film improves the catalytic activity of material, have that method is simple, the feature of successful;
(2) method that the large recoverable strain of film is given in applying shape memory alloy phase transformation provided by the invention can not rupture in utilizing TiNi substrate to drive ceramic membrane to realize gross distortion.
Brief description of the drawings
Fig. 1 a is the Cu depositing on TiNi substrate in embodiment 1
2o film is at the SEM photo of stretching front surface pattern;
Fig. 1 b is the Cu depositing on TiNi substrate in embodiment 1
2the SEM photo of O film after stretching;
Fig. 2 is the Cu depositing on TiNi substrate in embodiment 1
2the stress-strain curve of O film;
Fig. 3 has deposited Cu in embodiment 1
2the schematic diagram of the TiNi substrate of O film.
Embodiment
Understand for technical characterictic of the present invention, object and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
The present embodiment provides a kind of employing TiNi substrate to realize Cu
2the method of the tension strain of O film, it comprises the following steps:
1, the preparation of TiNi substrate comprises the following steps:
According to Ti: Ni=50.2: 49.8 atomic ratio, choose simple substance titanium, the elemental nickel of purity at 99.9wt.%;
Simple substance titanium and elemental nickel are put into vacuum tightness higher than 10
-1in the smelting furnace of a, be smelted into TiNi shape memory alloy ingot casting;
In vacuum tightness higher than 10
-1in the true air environment of Pa, ingot casting is carried out the homogenizing annealing of 10h at 950 DEG C;
Ingot casting after annealing is carried out cold rolling, middle through 950 DEG C of repeatedly annealing, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to needed TiNi substrate.
2, the preparation of surface film comprises the following steps:
(1) by pure Cu
2o powder ball milling mixes, compression moulding, and then sintering at 1000 DEG C, makes Cu
2o ceramic target;
(2) by Cu
2o ceramic target is put into pulsed laser deposition device growth room, and keeping the distance of ceramic target and substrate is 4.5cm; The vacuum tightness of growth room is evacuated to 10
-3below Pa, substrate is heated to 300 DEG C, in growth room, pass into O
2, the pressure controlling in growth room is 10Pa; Open laser apparatus, laser energy is 340mJ, and frequency is 5Hz, allows laser beam focus on the target surface ablation target of ceramic target, and on TiNi substrate, deposition obtains Cu
2o film;
3, the surface deposition of above-mentioned acquisition is had to Cu
2the TiNi substrate 2 (as shown in Figure 3) of O film 1 stretches, and deflection is 10%, stress-strain(ed) curve as shown in Figure 2, film at the SEM photo of strain front and rear surfaces morphology change as shown in Fig. 1 a and Fig. 1 b.
The optical energy gap of finding film by uv-visible absorption spectra is changed to 1.8eV by 2.1eV; By the Cu that applies and do not apply strain preparing under isometric growth condition
2o film is put into respectively methyl orange solution, finds not apply the Cu of strain with the irradiation of high voltage mercury lamp lamp source after 3 hours
2it is that the percent of decolourization of 10mg/L tropeolin-D is 8.6% that O film decomposes concentration, and Cu after strain
2o film decomposition concentration is that the percent of decolourization of 10mg/L tropeolin-D is 15%.
Embodiment 2
The present embodiment provides a kind of employing TiNi substrate to realize TiO
2the method of the tension strain of film, it comprises the following steps:
1, the preparation of TiNi substrate comprises the following steps:
According to Ti: Ni=50.2: 49.8 atomic ratio, choose simple substance titanium, the elemental nickel of purity at 99.9wt.%;
Simple substance titanium and elemental nickel are put into vacuum tightness higher than 10
-1in the smelting furnace of Pa, be smelted into TiNi shape memory alloy ingot casting;
In vacuum tightness higher than 10
-1in the true air environment of Pa, ingot casting is carried out the homogenizing annealing of 10h at 950 DEG C;
Ingot casting after annealing is carried out cold rolling, middle through 950 DEG C of repeatedly annealing, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to needed TiNi substrate.
2, the preparation of surface film comprises the following steps:
(1) by pure TiO
2powder ball milling mixes, compression moulding, and then sintering at 1200 DEG C, makes TiO
2ceramic target;
(2) by TiO
2ceramic target is put into the growth room of pulsed laser deposition device, and keeping the distance of ceramic target and substrate is 4.5cm; The vacuum tightness of growth room is evacuated to 10
-3below Pa, TiNi substrate is heated to 400 DEG C, in growth room, pass into O
2, the pressure controlling in growth room is 0.001Pa; Open laser apparatus, laser energy is 340mJ, and frequency is 5Hz, allows laser beam focus on the target surface ablation target of ceramic target, and on TiNi substrate, deposition obtains TiO
2film;
3, to above-mentioned surface deposition TiO
2the TiNi substrate of film stretches, and deflection is 10%, realizes TiO
2the stretching strain of film.
The optical energy gap of finding film by uv-visible absorption spectra is changed to 2.8eV by 3.3eV; By the TiO that applies and do not apply strain preparing under isometric growth condition
2film is put into respectively methyl orange solution, finds not apply the TiO of strain with the irradiation of high voltage mercury lamp light source after 5 hours
2it is that the percent of decolourization of 10mg/L tropeolin-D is 33.9% that film decomposes concentration, and TiO after strain
2film decomposition concentration is that the percent of decolourization of 10mg/L tropeolin-D is 45.8%.
Embodiment 3
The present embodiment provides a kind of employing TiNi substrate to realize Cu
2the method of the compressive strain of O film, it comprises the following steps:
1, the preparation of TiNi substrate comprises the following steps:
According to Ti: Ni=50.2: 49.8 atomic ratio, choose simple substance titanium, the elemental nickel of purity at 99.9wt.%;
Simple substance titanium and elemental nickel are put into the smelting furnace of the protection of inert gas of 0.5MPa, be smelted into TiNi shape memory alloy ingot casting;
In vacuum tightness higher than 10
-1in the true air environment of Pa, ingot casting is carried out the homogenizing annealing of 10h at 950 DEG C;
Ingot casting after annealing is carried out cold rolling, middle through 950 DEG C of repeatedly annealing, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to needed TiNi substrate;
TiNi substrate is heated 20 minutes under 350 DEG C of conditions, then carry out preliminary draft processing, obtain through pretreated TiNi substrate, pre-tension deformation amount is 6%.
2, the preparation of surface film comprises the following steps:
(1) by Cu
2o powder ball milling mixes, compression moulding, and then sintering at 1100 DEG C of temperature, makes Cu
2o ceramic target;
(2) by Cu
2o ceramic target is put into the growth room of pulsed laser deposition device, and keeping the distance of ceramic target and substrate is 4.5cm; The vacuum tightness of growth room is evacuated to 10
-3below Pa, keep substrate in room temperature, in growth room, pass into O
2, the pressure controlling in growth room is 10Pa; Open laser apparatus, laser energy is 340mJ, and frequency is 5Hz, allows laser beam focus on the target surface ablation target of ceramic target, and on the TiNi substrate through preliminary draft processing, deposition obtains Cu
2o film;
3, the surface deposition preparing is had to Cu
2the TiNi substrate of O film is heated to 100 DEG C of insulations 10 minutes, is then cooled to room temperature, and due to the shape memory effect of TiNi shape memory alloy, the contraction that the TiNi substrate amount of deforming is 6%, drives surperficial Cu
2it is 6% compressive strain that O film is realized deflection.
Embodiment 4
The present embodiment provides a kind of TiNi of employing substrate to realize the method for the compressive strain of ZnO film, and it comprises the following steps:
1, the preparation of TiNi substrate comprises the following steps:
According to Ti: Ni=50.2: 49.8 atomic ratio, choose simple substance titanium, the elemental nickel of purity at 99.9wt.%;
Simple substance titanium and elemental nickel are put into the smelting furnace of the protection of inert gas of 0.5MPa, be smelted into TiNi shape memory alloy ingot casting;
In vacuum tightness higher than 10
-1in the true air environment of Pa, ingot casting is carried out the homogenizing annealing of 10h at 950 DEG C;
Ingot casting after annealing is carried out cold rolling, middle through 950 DEG C of repeatedly annealing, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to needed TiNi substrate;
TiNi substrate is heated and carries out preliminary draft processing in 20 minutes under 350 DEG C of conditions, obtain the TiNi substrate through preliminary draft processing, pre-tension deformation amount is 10%;
2, the preparation of surface film comprises the following steps:
(1) pure ZnO powder ball milling is mixed, compression moulding, then sintering at 1300 DEG C, makes ZnO ceramic target;
(2) ZnO ceramic target is put into the growth room of pulsed laser deposition device, keeping the distance of ceramic target and substrate is 4.5cm; The vacuum tightness of growth room is evacuated to 10
-3below Pa, keep substrate in room temperature, in growth room, pass into O
2, the pressure controlling in growth room is 1Pa; Open laser apparatus, laser energy is 340mJ, and frequency is 5Hz, allows laser beam focus on the target surface ablation target of ceramic target, and on the TiNi substrate through preliminary draft processing, deposition obtains ZnO film;
3, the surface deposition preparing there is is the TiNi substrate of ZnO film be heated to 100 DEG C of insulations 10 minutes, then be cooled to room temperature, due to the shape memory effect of TiNi shape memory alloy, the contraction that the TiNi substrate amount of deforming is 10%, driving surperficial ZnO film to realize deflection is 10% compressive strain.
Embodiment 5
The present embodiment provides a kind of employing TiNi substrate to realize Co
3o
4the method of the tension strain of film, it comprises the following steps:
1, the preparation of TiNi substrate comprises the following steps:
According to Ti: Ni=50.2: 49.8 atomic ratio, choose simple substance titanium, the elemental nickel of purity at 99.9wt.%;
Simple substance titanium and elemental nickel are put into vacuum tightness higher than 10
-1in the smelting furnace of Pa, be smelted into TiNi shape memory alloy ingot casting;
In vacuum tightness higher than 10
-1in the true air environment of Pa, ingot casting is carried out the homogenizing annealing of 10h at 950 DEG C;
Ingot casting after annealing is carried out cold rolling, middle through 950 DEG C of repeatedly annealing, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to needed TiNi substrate;
2, the preparation of surface film comprises the following steps:
(1) by pure Co
3o
4powder ball milling mixes, compression moulding, and then sintering at 1200 DEG C, makes Cu
2o ceramic target;
(2) by Co
3o
4ceramic target is put into the growth room of pulsed laser deposition device, and keeping the distance of ceramic target and substrate is 4.5cm; The vacuum tightness of growth room is evacuated to 10
-3below Pa, substrate is heated to 500 DEG C, in growth room, pass into O
2, the pressure controlling in growth room is 100Pa; Open laser apparatus, laser energy is 340mJ, and frequency is 5Hz, allows laser beam focus on the target surface ablation target of ceramic target, is obtaining Co through deposition on pretreated TiNi substrate
3o
4film;
3, to above-mentioned surface deposition Co
3o
4the TiNi substrate of film stretches, and deflection is 8%, realizes Co
3o
4deformation of thin membrane amount is 8% stretching strain.
Embodiment 6
The present embodiment provides a kind of TiNi of employing substrate to realize the method for the compressive strain of CuO film, and it comprises the following steps:
1, the preparation of TiNi substrate comprises the following steps:
According to Ti: Ni=50.2: 49.8 atomic ratio, choose simple substance titanium, the elemental nickel of purity at 99.9wt.%;
Simple substance titanium and elemental nickel are put into the smelting furnace of the protection of inert gas of 0.5MPa, be smelted into TiNi shape memory alloy ingot casting;
In vacuum tightness higher than 10
-1in the true air environment of Pa, ingot casting is carried out the homogenizing annealing of 10h at 950 DEG C;
Ingot casting after annealing is carried out cold rolling, middle through 950 DEG C of repeatedly annealing, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to needed TiNi substrate;
TiNi substrate is heated under 350 DEG C of conditions to preliminary draft processing in 30 minutes, obtain through pretreated TiNi substrate, pre-tension deformation amount is 8%;
2, the preparation of surface film comprises the following steps:
(1) pure CuO powder ball milling is mixed, compression moulding, then sintering at 1300 DEG C, makes CuO ceramic target;
(2) CuO ceramic target is put into the growth room of pulsed laser deposition device, keeping the distance of ceramic target and substrate is 4.5cm; The vacuum tightness of growth room is evacuated to 10
-3below Pa, keep substrate in room temperature, in growth room, pass into O
2, the pressure controlling in growth room is 1Pa; Open laser apparatus, laser energy is 340mJ, and frequency is 5Hz, allows laser beam focus on the target surface ablation target of ceramic target, is obtaining CuO film through deposition on pretreated TiNi substrate;
3, the surface deposition preparing there is is the TiNi substrate of CuO film be heated to 100 DEG C of insulations 10 minutes, then be cooled to room temperature, due to the shape memory effect of TiNi shape memory alloy, the contraction that the TiNi substrate amount of deforming is 8%, driving surperficial CuO film to realize deflection is 8% compressive strain.
Claims (8)
1. applying shape memory alloy is given a method for the large recoverable strain of film, and it comprises the following steps:
Use pulsed laser deposition to deposit on the surface of shape memory alloy substrate and obtain film, then shape memory alloy substrate is stretched, drive the realization of film stretching strain by the tensile deformation of substrate; Or, adopt pulsed laser deposition to deposit on the surface of the shape memory alloy substrate through preliminary draft processing and obtain film, then heat and be incubated certain hour, make the described shape memory alloy substrate through preliminary draft processing undergo phase transition contraction, drive the realization of thin film strain by the shrinkage strain of substrate;
Described film is ZnO, TiO
2, CuO, Cu
2o or Co
3o
4film.
2. method according to claim 1, wherein, described shape memory alloy is TiNi shape memory alloy.
3. method according to claim 1 and 2, wherein, described shape memory alloy is prepared by following steps:
Choose simple substance titanium, the elemental nickel of purity more than 99.9wt.% according to the atomic ratio of 50.2:49.8;
Simple substance titanium and elemental nickel are put into vacuum tightness higher than 10
-1in the smelting furnace of Pa or protection of inert gas, be smelted into TiNi shape memory alloy, obtain ingot casting;
In vacuum tightness higher than 10
-1in the vacuum of Pa or in protection of inert gas, at 800-1050 DEG C, ingot casting is carried out to homogenizing annealing 5-60h;
Ingot casting after annealing is carried out to cold rolling and 950 DEG C of recrystallization annealings, obtain the sheet material that thickness is 0.5mm;
Further sheet material line cutting and mechanical polishing are obtained to described shape memory alloy substrate.
4. method according to claim 1, wherein, described preliminary draft processing refers to the anneal of at 300-500 DEG C, described shape memory alloy substrate being carried out 10-30 minute, then at room temperature carries out preliminary draft, pre-tension deformation amount is 6-15%.
5. method according to claim 3, wherein, described preliminary draft processing refers to the anneal of at 300-500 DEG C, described shape memory alloy substrate being carried out 10-30 minute, then at room temperature carries out preliminary draft, pre-tension deformation amount is 6-15%.
6. method according to claim 1, wherein, described deposition comprises the following steps:
The growth room that the ceramic target of preparation respective films is put into pulsed laser deposition device, keeping the distance of ceramic target and substrate is 4.5cm;
Growth room's vacuum tightness is evacuated to 10
-3below Pa, keep substrate to heat to 100-500 DEG C in room temperature or by substrate, in growth room, pass into O
2gas, the pressure controlling in growth room is 0.001-100Pa;
Open laser apparatus, make laser beam focus on the target surface ablation target of ceramic target, obtain film at shape memory alloy substrate or through the surface deposition of the shape memory alloy substrate of preliminary draft processing, laser energy is 340mJ, and frequency is 5Hz.
7. according to the method described in any one in claim 1,2,4,5,6, wherein, the stretching strain of described film realizes by following steps: carry out to having deposited the shape memory alloy substrate of film the stretch processing that deflection is 6-12%, realize the stretching strain of film;
The compressive strain of described film realizes by following steps: deposit and obtain film on the surface of the shape memory alloy substrate of processing through preliminary draft 6-15%, then be heated to 80-150 DEG C and be incubated 10-30 minute, return to again room temperature, make the described shape memory alloy substrate through preliminary draft processing undergo phase transition contraction, realize the compressive strain of film.
8. method according to claim 3, wherein, the stretching strain of described film realizes by following steps: carry out to having deposited the shape memory alloy substrate of film the stretch processing that deflection is 6-12%, realize the stretching strain of film;
The compressive strain of described film realizes by following steps: deposit and obtain film on the surface of the shape memory alloy substrate of processing through preliminary draft 6-15%, then be heated to 80-150 DEG C and be incubated 10-30 minute, return to again room temperature, make the described shape memory alloy substrate through preliminary draft processing undergo phase transition contraction, realize the compressive strain of film.
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CN1752246A (en) * | 2005-10-19 | 2006-03-29 | 哈尔滨工业大学 | TiNi plate spring for low frequency vibration damping and making method thereof |
CN101773686A (en) * | 2009-01-09 | 2010-07-14 | 沈阳天贺新材料开发有限公司 | Shape memory alloy simulated nanometer film coating biological and medicinal implant material |
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US6770176B2 (en) * | 2002-08-02 | 2004-08-03 | Itn Energy Systems. Inc. | Apparatus and method for fracture absorption layer |
US9863031B2 (en) * | 2006-11-27 | 2018-01-09 | Lifetech Scientific (Shenzhen) Co., Ltd. | Method for preparing a coating of the surface of medical devices made of nickel-titanium alloy |
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CN1752246A (en) * | 2005-10-19 | 2006-03-29 | 哈尔滨工业大学 | TiNi plate spring for low frequency vibration damping and making method thereof |
CN101773686A (en) * | 2009-01-09 | 2010-07-14 | 沈阳天贺新材料开发有限公司 | Shape memory alloy simulated nanometer film coating biological and medicinal implant material |
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