CN106086586A - A kind of high-performance nickel titante series marmem and its preparation method and application - Google Patents
A kind of high-performance nickel titante series marmem and its preparation method and application Download PDFInfo
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- CN106086586A CN106086586A CN201610536412.6A CN201610536412A CN106086586A CN 106086586 A CN106086586 A CN 106086586A CN 201610536412 A CN201610536412 A CN 201610536412A CN 106086586 A CN106086586 A CN 106086586A
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- marmem
- performance
- nickel
- titante series
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
The invention discloses a kind of high-performance nickel titante series marmem, this alloy is made up of titanium, nickel, copper, niobium, zinc element；Following component is included: atomic percent titanium content is 45 50%, the atom percentage content of nickel is 30 34%, the atom percentage content of copper is 10 14%, the atom percentage content of niobium is 1 8%, surplus is zinc by atomic percent.Nanometer Ti is comprised in thin film alloys prepared by the present invention2Cu and Ti2Ni phase, in carrying out deformation process, nanometer noresidue when conversion, shape memory response rate is high, excellent performance.
Description
Technical field
The present invention relates to shape memory alloy material field, be specifically related to a kind of high-performance nickel titante series marmem and system thereof
Preparation Method and application.
Background technology
Marmem has higher restorability deformation because of it, is used widely in productive life.In
State's patent of invention CN102864339A proposes a kind of elastic alloy material, and each composition of described alloy material is contained by atomic percent
Amount is nickel 45-55at%, ferrum 0-10at%, titanium 10-15at%, cobalt 10-15at%, 15-20at%.The alloy of the technical program
Material not only has narrow delayed elastic performance can keep again the alloy material of shape memory effect.Its preparation method includes following
Step: 1), choose the nickel of purity >=99.9%, purity >=99.99% cobalt, the ferrum of purity >=99.9%, purity >=99.9%
Titanium, the gallium of purity >=99.99%；By above-mentioned material according to atomic percentage conc dispensing, it is then placed in smelting furnace and evacuation
To 2.0 × 10-4Pa, is re-filled with argon, inhales casting with mould cooling and obtain alloy blank after melt back；2), by 1) in obtain
Alloy blank seals, and is evacuated to 5.0 × 10-5Pa, is incubated 72 hours at 1000 DEG C, is then cooled to room temperature and obtains super-elasticity
Alloy material.
Chinese invention patent CN102851548A proposes a kind of superelastic alloy, and each composition of its described alloy material is pressed
Atomic percentage conc is nickel 45-55at%, ferrum 0-10at%, titanium 25-35at%, cobalt 10-15at%.2. described in claim 1
Superelastic alloy, respectively forming by atomic percentage conc of its described alloy material is nickel 50at%, ferrum 5at%, titanium 35at%, cobalt
10at%.
Chinese invention patent CN101876016A proposes a kind of rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy, it is provided that
A kind of rare earth Ni-Mg-Co-Ga-based high-temperature shape memory with high martensitic transformation temperature, preferable plasticity and shape-memory properties closes
Gold and preparation method thereof.Chemical formula is (Ni53Mn22Co6Ga19) 100-xAx, the atomic percent of wherein A=Dy, Y, Gd, x
It is 0～1.Nickel, manganese, cobalt, gallium and rare earths material are put into stove, evacuation, is filled with argon, melting, obtain rare earth Ni-Mg-Co-Ga-based
High-temperature shape memory alloy ingot；By rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy ingot heat treatment, furnace cooling；Will be through
The rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy ingot of Overheating Treatment is rolled into sheet alloy material；The lamellar obtained is closed
Gold copper-base alloy is cut into sample, after heat treatment, and ice water quenching, i.e. obtain rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy.
Summary of the invention
Goal of the invention: in order to improve the cycle life of marmem, the technical problem to be solved is to carry
Supply a kind of high-performance nickel titante series marmem.
The present invention also to solve the technical problem that the preparation side that there is provided a kind of high-performance nickel titante series marmem
Method.
The present invention also to solve the technical problem that the application that there is provided a kind of high-performance nickel titante series marmem.
Conventional alloy material deformation will be ruptured for thousand of times, and the method that the present invention uses magnetron sputtering, preparation contains
Unique component and microstructural alloy film material, it is possible to the cycle-index of this alloy is brought up to more than several ten million times.Should
The thickness of alloy firm is 2-50 micron, comprises Ti in its microstructure2Cu and Ti2Ni phase, they are nanocrystalline, are smaller in size than
500 nanometers.
For achieving the above object, the technical solution used in the present invention is: a kind of high-performance nickel titante series marmem, should
Alloy is made up of titanium, nickel, copper, niobium, zinc element.
As preferably, include following component by atomic percent: atomic percent titanium content is 45-50%, the atom hundred of nickel
Proportion by subtraction content is 30-34%, the atom percentage content of copper is 10-14%, the atom percentage content of niobium is 1-8%, surplus is
Zinc.
As preferably, the thickness of above-mentioned high-performance nickel titante series marmem is 2-50 micron.
As preferably, the microstructure of above-mentioned high-performance nickel titante series marmem comprises Ti2Cu and Ti2Ni phase.
As preferably, the Ti in above-mentioned high-performance nickel titante series marmem2Cu and Ti2Being smaller in size than of Ni phase 500 is received
Rice.
The preparation method of above-mentioned high-performance nickel titante series marmem, comprises the following steps:
1) target is prepared according to above-mentioned alloy material；
2) use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 60-70%, proceeds by sputtering sedimentation, controls thickness and is
2-50 micron obtains the marmem of film like；
3) to step 2) marmem of film like that obtains carries out annealing and is thermally treated resulting in high-performance nickel titante series shape note
Recall alloy.
As preferably, above-mentioned annealing heat treatment temperature is 650-720 degree Celsius.
Above-mentioned high-performance nickel titante series marmem is in the application of the aspect such as Industry Control, medical apparatus and instruments.
Beneficial effect: the invention have the advantages that and use the method for the present invention can prepare a kind of high-performance nickel titante series
Marmem, cycle-index is up to more than several ten million times, far above thousand of times of current alloy.This is because it is the most most
When number form shape memory alloys changes under two kinds of crystal lattice states, biphase between conversion incomplete, at metallic high temperature phase (Ovshinsky
Body) in there will be increasing low-temperature phase (martensite) crystal structure, arise that crackle, eventually result in alloy for thousand of times
Fracture.In the present invention, nanometer phase Ti that can be formed2Cu phase and Ti2Ni phase, its size is below 500 nanometers.Work as Ti2Cu phase exists
In two kinds of structures of B2 Yu B19 during conversion, the conversion between them is completely, there is not residual, follows therefore, it is possible to be greatly improved
The ring life-span.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
Embodiment 1: the preparation of high-performance nickel titante series marmem
1, according to titanium: nickel: copper: niobium: the atomic ratio of zinc is that the ratio of 50:34:14::1:1 prepares target；
2, use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 60%, proceeds by sputtering sedimentation, and controlling thickness is 12
Micron；
3, above alloy carrying out heat treatment of annealing, temperature is 650 degrees Celsius and obtains high-performance nickel titante series marmem.
High-performance nickel titante series marmem is circulated life test, after sample carries out 2,000 ten thousand tests, not yet
Fracture.
Nanometer Ti is comprised in this alloy2Cu and Ti2Ni phase, its size 80 ~ 200 nanometer.
Embodiment 2: the preparation of high-performance nickel titante series marmem
1. according to titanium: nickel: copper: niobium: the atomic ratio of zinc is that 48:30:10:8:4 ratio prepares target；
2. use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 60%, proceeds by sputtering sedimentation, and controlling thickness is 32
Micron；
3. more than pair, alloy carries out heat treatment of annealing, and temperature is 680 degrees Celsius and obtains high-performance nickel titante series marmem.
High-performance nickel titante series marmem is circulated life test, after sample carries out 2,000 ten thousand tests, not yet
Fracture.
Nanometer Ti is comprised in this alloy2Cu and Ti2Ni phase, its size 100 ~ 250 nanometer.
Embodiment 3: the preparation of high-performance nickel titante series marmem
1. according to titanium: nickel: copper: niobium: the atomic ratio of zinc be 45:32:13:6:4 ratio prepare target；
2. use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 70%, proceeds by sputtering sedimentation, and controlling thickness is 47
Micron；
3. more than pair, alloy carries out heat treatment of annealing, and temperature is 720 degrees Celsius and obtains high-performance nickel titante series marmem.
High-performance nickel titante series marmem is circulated life test, after sample carries out 2,000 ten thousand tests, not yet
Fracture.
Nanometer Ti is comprised in this alloy2Cu and Ti2Ni phase, its size 80 ~ 160 nanometer.
The preparation of embodiment 4 high-performance nickel titante series marmem
1. according to titanium: nickel: copper: niobium: the atomic ratio of zinc is that the ratio of 46:31:12:8:3 prepares target；
2. use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 65%, proceeds by sputtering sedimentation, and it is 2 micro-for controlling thickness
Rice；
3. more than pair, alloy carries out heat treatment of annealing, and temperature is 685 degrees Celsius and obtains high-performance nickel titante series marmem.
High-performance nickel titante series marmem is circulated life test, after sample carries out 2,000 ten thousand tests, not yet
Fracture.
Nanometer Ti is comprised in this alloy2Cu and Ti2Ni phase, its size 150 ~ 300 nanometer.
The preparation of embodiment 5 high-performance nickel titante series marmem
1. according to titanium: nickel: copper: niobium: the atomic ratio of zinc is that the ratio of 47:33:11:5:4 prepares target；
2. use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 67%, proceeds by sputtering sedimentation, and controlling thickness is 50
Micron；
3. more than pair, alloy carries out heat treatment of annealing, and temperature is 690 degrees Celsius and obtains high-performance nickel titante series marmem.
High-performance nickel titante series marmem is circulated life test, after sample carries out 2,000 ten thousand tests, not yet
Fracture.
Nanometer Ti is comprised in this alloy2Cu and Ti2Ni phase, its size 50 ~ 200 nanometer.
Comparative example 1
Experimental example:
1. according to 1at% manganese, 0.4at% neodymium, 51at% titanium, 44at% nickel, the proportional arrangement raw material of 3.6at% ferrum；
2. by raw material mix homogeneously, put into non-consumable arc furnace, be evacuated down to 5*10-4Pa, be filled with high-purity argon gas, so
Rear melting 5 times；
3. in vacuum heat treatment furnace, carry out heat treatment: carry out timeliness 2 hours at 500 degree, then 450 degree of timeliness 5 hours；
4. cooling, thus obtains marmem.
Testing result: be circulated life test, sample carries out 8636 test fractures.
The common alloy containing niobium marmem alloy and comparative example 1 that the embodiment of the present invention 1 ~ 5 prepares is carried out
Memory response rate after 1000 deformation:
The above is only the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Saying, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (8)
1. a high-performance nickel titante series marmem, it is characterised in that this alloy is made up of titanium, nickel, copper, niobium, zinc element.
A kind of high-performance nickel titante series marmem the most according to claim 1, it is characterised in that by atomic percent
Including following component: atomic percent titanium content is 45-50%, the atomic percent that atom percentage content is 30-34%, copper of nickel
Be 10-14% than content, the atom percentage content of niobium be 1-8%, surplus be zinc.
A kind of high-performance nickel titante series marmem the most according to claim 1, it is characterised in that described high-performance
The thickness of nickel titante series marmem is 2-50 micron.
A kind of high-performance nickel titante series marmem the most according to claim 1, it is characterised in that described high-performance
The microstructure of nickel titante series marmem comprises Ti2Cu and Ti2Ni phase.
A kind of high-performance nickel titante series marmem the most according to claim 4, it is characterised in that described high-performance
Ti in nickel titante series marmem2Cu and Ti2Ni phase be smaller in size than 500 nanometers.
6. the preparation method of the high-performance nickel titante series marmem described in any one of claim 1 ~ 5, it is characterised in that bag
Include following steps:
1) target is prepared according to above-mentioned alloy material；
2) use magnetron sputtering to prepare the marmem of film like, be evacuated to 10-3More than Pa, is filled with argon, the most again
It is evacuated to 10-3Pa, adjustment running voltage is 500V, sputters dutycycle 60-70%, proceeds by sputtering sedimentation, controls thickness and is
2-50 micron obtains the marmem of film like；
3) to step 2) marmem of film like that obtains carries out annealing and is thermally treated resulting in high-performance nickel titante series shape note
Recall alloy.
The preparation method of high-performance nickel titante series marmem the most according to claim 6, it is characterised in that described in move back
Heat treat temperatures is 650-720 degree Celsius.
8. the high-performance nickel titante series marmem described in any one of claim 1 ~ 5 is in the side such as Industry Control, medical apparatus and instruments
The application in face.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875294A (en) * | 2022-06-07 | 2022-08-09 | 上海工程技术大学 | Titanium-nickel-based alloy material and preparation method and application thereof |
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|---|---|---|---|---|
| US4950340A (en) * | 1987-08-10 | 1990-08-21 | Mitsubishi Kinzoku Kabushiki Kaisha | Intermetallic compound type alloy having improved toughness machinability and wear resistance |
| US20080000556A1 (en) * | 2003-03-25 | 2008-01-03 | Questek Innovations Llc | Coherent Nanodispersion-Strengthened Shape-Memory Alloys |
| CN102690976A (en) * | 2012-05-22 | 2012-09-26 | 北京航空航天大学 | Titanium-zirconium-niobium-iron shape memory alloy and preparation method thereof |
| CN104164648A (en) * | 2014-08-31 | 2014-11-26 | 海安南京大学高新技术研究院 | Narrow-hysteresis submicron-scale shape memory alloy film and preparation method thereof |
| CN104946956A (en) * | 2015-06-09 | 2015-09-30 | 哈尔滨工程大学 | TiNiCuNb shape memory alloy and preparation method thereof |
-
2016
- 2016-07-08 CN CN201610536412.6A patent/CN106086586B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950340A (en) * | 1987-08-10 | 1990-08-21 | Mitsubishi Kinzoku Kabushiki Kaisha | Intermetallic compound type alloy having improved toughness machinability and wear resistance |
| US20080000556A1 (en) * | 2003-03-25 | 2008-01-03 | Questek Innovations Llc | Coherent Nanodispersion-Strengthened Shape-Memory Alloys |
| CN102690976A (en) * | 2012-05-22 | 2012-09-26 | 北京航空航天大学 | Titanium-zirconium-niobium-iron shape memory alloy and preparation method thereof |
| CN104164648A (en) * | 2014-08-31 | 2014-11-26 | 海安南京大学高新技术研究院 | Narrow-hysteresis submicron-scale shape memory alloy film and preparation method thereof |
| CN104946956A (en) * | 2015-06-09 | 2015-09-30 | 哈尔滨工程大学 | TiNiCuNb shape memory alloy and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875294A (en) * | 2022-06-07 | 2022-08-09 | 上海工程技术大学 | Titanium-nickel-based alloy material and preparation method and application thereof |
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