CN106048378B - A kind of high-performance marmem and its preparation method and application - Google Patents

A kind of high-performance marmem and its preparation method and application Download PDF

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CN106048378B
CN106048378B CN201610539769.XA CN201610539769A CN106048378B CN 106048378 B CN106048378 B CN 106048378B CN 201610539769 A CN201610539769 A CN 201610539769A CN 106048378 B CN106048378 B CN 106048378B
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marmem
performance
film
alloy
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CN106048378A (en
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杨卫国
朱文建
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Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a kind of high-performance marmem, the alloy is made up of titanium, nickel, copper, niobium element；Include following component by atomic percent：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%, surplus is niobium.Nanometer Ti is included in thin film alloys prepared by the present invention2Cu and Ti2Ni phases, in deformation process is carried out, the nanometer mutually noresidue in conversion, excellent performance.

Description

A kind of high-performance marmem and its preparation method and application
Technical field
The present invention relates to shape memory alloy material field, and in particular to a kind of high-performance marmem and its preparation Methods and applications.
Background technology
Marmem is used widely in production and living because it has higher restorability deformation.In State patent of invention CN102864339A proposes a kind of elastic alloy material, and each composition of the alloy material is contained by atomic percent Measure as nickel 45-55at%, iron 0-10at%, titanium 10-15at%, cobalt 10-15at%, 15-20at%.The alloy of the technical program Material not only has the alloy material that narrow hysteresis elastic performance and can enough keeps SME.Its preparation method includes following Step：1) nickel of purity >=99.9%, is chosen, the cobalt of purity >=99.99%, the iron 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 vacuumizes To 2.0 × 10-4Pa, argon gas is re-filled with, cooling down suction casting with mould after melt back obtains alloy blank；2), will obtain in 1) Alloy blank seals, and is evacuated to 5.0 × 10-5Pa, 72 hours are incubated at 1000 DEG C, room temperature is subsequently cooled to and obtains super-elasticity Alloy material.
Chinese invention patent CN102851548A proposes a kind of superelastic alloy, and each composition of its alloy material is pressed Atomic percentage conc is nickel 45-55at%, iron 0-10at%, titanium 25-35at%, cobalt 10-15at%.2. described in claim 1 Superelastic alloy, each composition of its alloy material are nickel 50at%, iron 5at%, titanium 35at% by atomic percentage conc, cobalt 10at%.
Chinese invention patent CN101876016A proposes a kind of rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy, there is provided 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, wherein A=Dy, Y, Gd, x atomic percent For 0~1.Nickel, manganese, cobalt, gallium and rare earths material are put into stove, vacuumized, argon gas is filled with, melting, obtains rare earth Ni-Mg-Co-Ga-based High-temperature shape memory alloy ingot；Rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy ingot is heat-treated, 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；Obtained sheet is closed Golden material is cut into sample, after heat treatment, ice water quenching, that is, obtains rare earth Ni-Mg-Co-Ga-based high-temperature shape memory alloy.
The content of the invention
Goal of the invention：In order to improve the cycle life of marmem, the technical problems to be solved by the invention are to carry A kind of high-performance marmem is supplied.
The present invention also technical problems to be solved there is provided a kind of preparation method of high-performance marmem.
The present invention also technical problems to be solved there is provided a kind of application of high-performance marmem.
Conventional alloy material deforms thousands of times and will be broken, and the method that the present invention uses magnetron sputtering, preparation contain Unique component and microstructural alloy film material, can bring up to the cycle-index of the alloy more than several thousands of times.Should The thickness of alloy firm is 2-50 microns, and Ti is included in its microstructure2Cu and Ti2Ni phases, to be nanocrystalline, size is less than for they 500 nanometers.
To achieve the above object, the technical solution adopted by the present invention is：A kind of high-performance marmem, the alloy by Titanium, nickel, copper, niobium element are formed.
Preferably, include following component by atomic percent：Atomic percent titanium content is 45-50%, the atom of nickel Degree is 30-34%, the atom percentage content of copper is 10-14%, surplus is niobium.
Preferably, the thickness of above-mentioned high-performance marmem is 2-50 microns.
Preferably, Ti is included in the microstructure of above-mentioned high-performance marmem2Cu and Ti2Ni phases.
Preferably, the Ti in above-mentioned high-performance marmem2Cu and Ti2The size of Ni phases is less than 500 nanometers.
The preparation method of above-mentioned high-performance marmem, comprises the following steps：
1) target is prepared according to above-mentioned alloy material；
2) marmem of film-form is prepared using magnetron sputtering, is evacuated to 10-3More than Pa, argon gas is filled with, so It is evacuated to 10 again afterwards-3Pa, adjustment operating voltage are 500V, sputter dutycycle 60-70%, proceed by sputtering sedimentation, are controlled Thickness is that 2-50 microns obtain the marmem of film-form；
3) marmem of the film-form obtained to step 2) carries out annealing heat-treats and obtains high-performance shape memory Alloy.
Preferably, above-mentioned annealing heat-treats temperature is 650-720 degrees Celsius.
Application of the above-mentioned high-performance marmem in Industry Control, medicine equipment etc..
Beneficial effect：The present invention has advantages below：A kind of high-performance shape note can be prepared using the method for the present invention Recall alloy, cycle-index is up to more than several thousands of times, far above thousands of times of current alloy.Because current most of shapes When memorial alloy changes under two kinds of crystal lattice states, the conversion between two-phase is incomplete, the meeting in metallic high temperature phase (austenite) There is increasing low-temperature phase (martensite) crystal structure, thousands of times will be cracked, eventually results in alloy fracture. In the present invention, the nanometer phase Ti that can be formed2Cu phases and Ti2Ni phases, its size is below 500 nanometers.Work as Ti2Cu phases are in B2 and B19 When being changed in two kinds of structures, the conversion between them is complete, in the absence of residual, therefore can greatly improve cycle life.
Embodiment
Make further illustrate to the present invention with reference to embodiment.
Embodiment 1：The preparation of high-performance marmem
1st, according to titanium：Nickel：Copper：The atomic ratio of niobium is 50：34：14：2 ratio prepares target；
2nd, the marmem of film-form is prepared using magnetron sputtering, is evacuated to 10-3More than Pa, argon gas is filled with, so It is evacuated to 10 again afterwards-3Pa, adjustment operating voltage are 500V, sputter dutycycle 60%, proceed by sputtering sedimentation, control thickness For 12 microns；
3rd, annealing heat-treats are carried out to above alloy, temperature is 650 degrees Celsius and obtains high-performance marmem.
Cycle life test is carried out to high-performance marmem, it is still unbroken after sample carries out 2 thousands of times tests.
Nanometer Ti is included in the alloy2Cu and Ti2Ni phases, 80~120 nanometers of its size.
Embodiment 2：The preparation of high-performance marmem
1. according to titanium：Nickel：Copper：The atomic ratio of niobium is 48：30：10：12 ratios prepare target；
2. preparing the marmem of film-form using magnetron sputtering, 10 are evacuated to-3More than Pa, argon gas is filled with, so It is evacuated to 10 again afterwards-3Pa, adjustment operating voltage are 500V, sputter dutycycle 60%, proceed by sputtering sedimentation, control thickness For 32 microns；
3. alloy more than pair carries out annealing heat-treats, temperature is 680 degrees Celsius and obtains high-performance marmem.
Cycle life test is carried out to high-performance marmem, it is still unbroken after sample carries out 2 thousands of times tests.
Nanometer Ti is included in the alloy2Cu and Ti2Ni phases, 80~150 nanometers of its size.
Embodiment 3：The preparation of high-performance marmem
1. according to titanium：Nickel：Copper：The atomic ratio of niobium is 45：32：13：10 ratio prepares target；
2. preparing the marmem of film-form using magnetron sputtering, 10 are evacuated to-3More than Pa, argon gas is filled with, so It is evacuated to 10 again afterwards-3Pa, adjustment operating voltage are 500V, sputter dutycycle 70%, proceed by sputtering sedimentation, control thickness For 47 microns；
3. alloy more than pair carries out annealing heat-treats, temperature is 720 degrees Celsius and obtains high-performance marmem.
Cycle life test is carried out to high-performance marmem, it is still unbroken after sample carries out 2 thousands of times tests.
Nanometer Ti is included in the alloy2Cu and Ti2Ni phases, 50~120 nanometers of its size.
The preparation of the high-performance marmem of embodiment 4
1. according to titanium：Nickel：Copper：The atomic ratio of niobium is 46：31：12：11 ratio prepares target；
2. preparing the marmem of film-form using magnetron sputtering, 10 are evacuated to-3More than Pa, argon gas is filled with, so It is evacuated to 10 again afterwards-3Pa, adjustment operating voltage are 500V, sputter dutycycle 65%, proceed by sputtering sedimentation, control thickness For 2 microns；
3. alloy more than pair carries out annealing heat-treats, temperature is 685 degrees Celsius and obtains high-performance marmem.
Cycle life test is carried out to high-performance marmem, it is still unbroken after sample carries out 2 thousands of times tests.
Nanometer Ti is included in the alloy2Cu and Ti2Ni phases, 50~100 nanometers of its size.
The preparation of the high-performance marmem of embodiment 5
1. according to titanium：Nickel：Copper：The atomic ratio of niobium is 47：33：11：9 ratio prepares target；
2. preparing the marmem of film-form using magnetron sputtering, 10 are evacuated to-3More than Pa, argon gas is filled with, so It is evacuated to 10 again afterwards-3Pa, adjustment operating voltage are 500V, sputter dutycycle 67%, proceed by sputtering sedimentation, control thickness For 50 microns；
3. alloy more than pair carries out annealing heat-treats, temperature is 690 degrees Celsius and obtains high-performance marmem.
Cycle life test is carried out to high-performance marmem, it is still unbroken after sample carries out 2 thousands of times tests.
Nanometer Ti is included in the alloy2Cu and Ti2Ni phases, 50~100 nanometers of its size.
Comparative example 1
1. according to 1at% manganese, 0.4at% neodymiums, 51at% titaniums, 44at% nickel, 3.6at% iron proportional arrangement raw material；
2. raw material is well mixed, it is put into non-consumable arc furnace, is evacuated down to 5*10-4Pa, is filled with high-purity argon Gas, then melting 5 times；
3. it is heat-treated in vacuum heat treatment furnace:Timeliness is carried out at 500 degree 2 hours, then 450
Spend timeliness 5 hours.
4. cooling, thus obtains marmem.
Testing result：Cycle life test is carried out, sample carries out 8636 test fractures.
The alloy of marmem containing niobium and the common alloy of comparative example 1 that the embodiment of the present invention 1~5 is prepared are carried out Memory response rate after 1000 deformation
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (4)

1. a kind of high-performance marmem, it is characterised in that the alloy is made up of titanium, nickel, copper, niobium element, described height Performance marmem, include following component by atomic percent：Atomic percent titanium content is 45-50%, the atom hundred of nickel It is 30-34% to divide than content, the atom percentage content of copper is 10-14%, the atom percentage content of niobium is 2 ~ 12%, described High-performance marmem is the alloy of film-form, and the alloy thickness of the film-form is 2-50 microns, described high-performance Ti is included in the microstructure of marmem2Cu and Ti2Ni phases, the Ti in described high-performance marmem2Cu with Ti2The size of Ni phases is less than 500 nanometers；
The preparation method of described high-performance marmem, comprises the following steps：
1）Target is prepared according to above-mentioned alloy material；
2）The marmem of film-form is prepared using magnetron sputtering, is evacuated to 10-3More than Pa, it is filled with argon gas, Ran Houzai It is evacuated to 10-3Pa, adjustment operating voltage are 500V, sputter dutycycle 60-70%, proceed by sputtering sedimentation, control the thickness to be 2-50 microns obtain the marmem of film-form；
3）To step 2）The marmem of obtained film-form carries out annealing heat-treats and obtains high-performance marmem.
2. the preparation method of the high-performance marmem described in claim 1, it is characterised in that comprise the following steps：
1）Target is prepared according to above-mentioned alloy material；
2）The marmem of film-form is prepared using magnetron sputtering, is evacuated to 10-3More than Pa, it is filled with argon gas, Ran Houzai It is evacuated to 10-3Pa, adjustment operating voltage are 500V, sputter dutycycle 60-70%, proceed by sputtering sedimentation, control the thickness to be 2-50 microns obtain the marmem of film-form；
3）To step 2）The marmem of obtained film-form carries out annealing heat-treats and obtains high-performance marmem.
3. the preparation method of high-performance marmem according to claim 2, it is characterised in that at the annealing heat It is 650-720 degrees Celsius to manage temperature.
4. application of the high-performance marmem in terms of Industry Control, medicine equipment described in claim 1.
CN201610539769.XA 2016-07-08 2016-07-08 A kind of high-performance marmem and its preparation method and application Expired - Fee Related CN106048378B (en)

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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

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