CN105018888B - A kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm - Google Patents
A kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm Download PDFInfo
- Publication number
- CN105018888B CN105018888B CN201510446285.6A CN201510446285A CN105018888B CN 105018888 B CN105018888 B CN 105018888B CN 201510446285 A CN201510446285 A CN 201510446285A CN 105018888 B CN105018888 B CN 105018888B
- Authority
- CN
- China
- Prior art keywords
- substrate
- target
- flatness
- film
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Physical Vapour Deposition (AREA)
- Thin Magnetic Films (AREA)
Abstract
The present invention relates to a kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm.Comprise the following steps：According to molfraction than 50:34:12:4 take Ni, Mn, In, Co metal simple-substance to be positioned over melting in vacuum non-consumable electrode electric arc furnace respectively；5 × 10 will be evacuated in electric arc furnaces‑3Pa, protection gas is filled with, obtains circular target；Substrate after processing and target are placed in vacuum system, are evacuated to 1.0 × 10‑4Pa, substrate are 3~5cm with target distance；Launch laser with laser again, it is 3~4Hz to control frequency, is sputtered 1~3 hour, and the film for requiring thickness is made；Finally pass through 800~900 DEG C of 0.5~3h of annealing, prepare the Ni of high-flatness50Mn34In12Co4Ferromagnetic shape memory alloy film.Ni prepared by the present invention50Mn34In12Co4Alloy firm composition is more accurate, and roughness is lower, and anisotropy is strong；The alloy firm good toughness, intensity are big, and preparation technology is simple, is easy to industrialized production, for micro- intelligent and highly integrated have important practical value.
Description
Technical field
The invention belongs to field of metal alloy technology, is related to a kind of Ni of high-flatness50Mn34In12Co4Alloy firm
Preparation method.
Background technology
Martensite reverse transformation can occur under magnetic fields for Ni-Co-Mn-In monocrystalline, and 3% precompressed shrinkage strain can be made complete
Recovering, the theoretical output stress during being somebody's turn to do is up to 108MPa, high two orders of magnitude of output stress than Ni-Mn-Ga, this
Research makes magnetically driven shape memory alloy stride forward a huge step to practical.But monocrystal material preparation technology it is complicated, into
This height limits their extensive use to a certain extent.And Ni-Mn-Co-In polycrystallines crystal grain orientation is different, neighboring die
Between strain coordination be present, so the maximum reversible strain property in SME is relatively low, so as to limit its extensive use,
It is difficult to meet the requirement of engineer applied and the development of MEMS micro elements.Have many technologies at present alloy firm is made, main bag
Include magnetron sputtering (Magnetron sputtering) technology, pulsed laser deposition (Pulsed Laser Deposition) skill
Art and molecular beam epitaxy (Molecular Beam Epitaxy) technology.Research shows, film is prepared using magnetron sputtering technique
When due to being influenceed by sputter deposition rate, the chemical composition of film is deviateed its stoichiometric proportion, more easily wave
The element of hair deviate it is even more serious, therefore magnetron sputtering technique be not suitable for preparing volatile ferromagnetic shape memory alloy it is thin
Film, and molecular beam epitaxy technique causes development to be restricted because its equipment is expensive, maintenance cost is high.Pulsed laser deposition
(PLD) method belongs to non-equilibrium film-forming method, and the depositing temperature required by the technology growth film is low, and by non-thermal thin
Film deposition technique realizes the same component deposition of film.Laser can not possibly be separated with target during deposition, thus
The chemistry and crystallographic characteristics of target can be copied on film, realize the same component deposition of film.In addition, it is film-made in doping
During, more target alternating sputtering deposition process can be used, by controlling the umber of pulse of each target, it is uniform to prepare arbitrary proportion
The function film of doping.
The content of the invention
The present invention is too big in order to solve existing ferromagnetic shape memory Film roughness, and composition deviates target, and provides one
The Ni of kind high-flatness50Mn34In12Co4The preparation method of alloy firm.
To reach above-mentioned purpose, what the present invention was realized in：A kind of Ni of high-flatness50Mn34In12Co4Alloy firm
Preparation method, comprise the following steps：According to molfraction than 50:34:12:4 take Ni, Mn, In, Co metal simple-substance to put respectively
It is placed in melting in vacuum non-consumable electrode electric arc furnace；5 × 10 will be evacuated in electric arc furnaces-3Pa, protection gas is filled with, obtains circle
Target；Substrate after processing and target are placed in vacuum system, are evacuated to 1.0 × 10-4Pa, substrate temperature are 500~750
DEG C, substrate is 3~5cm with target distance.Launch laser with laser again, it is 3~4Hz to control frequency, is sputtered 1~3 hour, excellent
Select 2 hours, the film for requiring thickness is made；Finally by 800~900 DEG C of annealing 3h, high-flatness is prepared
Ni50Mn34In12Co4Ferromagnetic shape memory alloy film.The annealing time is crystallization time, preferably 850 DEG C of annealing temperature.
Further, described substrate temperature is 550~700 DEG C.
Further, the purity of described Ni metal simple-substances is 99.99at.%.
Further, the purity of described Mn metal simple-substances is 99.95at.%.
Further, the purity of described In metal simple-substances is 99.99at.%.
Further, the purity of described Co metal simple-substances is 99.95at.%.
Further, described noble gas is argon gas.
To ensure the uniformity of alloy composition in fusion process, sample is overturn at least four times and added before each melting
Stirred with magnetic.It can realize that sample is overturn using manipulator, diameter 50mm ingot is obtained after melting.Will after being polished on emery wheel
Ingot is put into the circular target for being cut into that size is diameter 3mm × 2mm on WEDM.
Further, described substrate is quartz glass substrate, and the specification of the substrate is 30mm × 30mm × 3mm；It is described
The processing method of substrate be：Glass substrate first passes through deionization washing, then ultrasound 10~15 minutes in acetone, then with nothing
Water-ethanol cleans, drying.
The Ni of the high-flatness prepared in aforementioned manners is also claimed in the present invention50Mn34In12Co4Alloy firm.
The Ni different, of the invention from existing magnetic shape memory alloy Ni-Mn-In-Co films50Mn34In12Co4It is ferromagnetic
Property shape memory alloy film has advantages below：
1st, Ni prepared by the present invention50Mn34In12Co4The composition of alloy firm is more accurate, realizes consistent with target material composition
Multicomponent compound film；
2nd, Ni prepared by the present invention50Mn34In12Co4The roughness of alloy firm is relatively low, and its average roughness is in 45nm
Left and right；
3rd, Ni prepared by the present invention50Mn34In12Co4The magnetic domain of alloy firm tends to a direction arrangement, and anisotropy is strong；
4th, low in raw material price, rich reserves needed for the present invention, the alloy firm good toughness of preparation, intensity are big, prepare work
Skill is simple, is easy to industrialized production, for solve Ni-Mn-In-Co bulk defects provide new thinking, for micro- intellectuality
There is important practical value with highly integrated.
Brief description of the drawings
Fig. 1 is Ni prepared by the present invention50Mn34In12Co4The AFM shape appearance figures of alloy firm, wherein (a) is substrate temperature
The AFM shape appearance figures of 700 DEG C of obtained alloy firms；(b) be 650 DEG C of obtained alloy firms of substrate temperature AFM shape appearance figures；(c) it is
The AFM shape appearance figures of 600 DEG C of obtained alloy firms of substrate temperature；(d) be 550 DEG C of obtained alloy firms of substrate temperature AFM patterns
Figure；
Fig. 2 is Ni prepared by the present invention50Mn34In12Co4The magnetic domain shape appearance figure of alloy firm, wherein (a) is substrate temperature
The magnetic domain shape appearance figure of 700 DEG C of obtained alloy firms；(b) be 650 DEG C of obtained alloy firms of substrate temperature magnetic domain shape appearance figure；(c)
It is the magnetic domain shape appearance figure of 600 DEG C of obtained alloy firms of substrate temperature；(d) be 550 DEG C of obtained alloy firms of substrate temperature magnetic domain
Shape appearance figure.
Embodiment
Present disclosure is described in detail below by embodiment, but is not used in and limits the scope of the invention, such as nothing
Specified otherwise, experimental drug involved in the present invention and raw material are commercially available, vacuum non-consumable electrode used in the present invention
Electric arc furnaces is purchased from Shenyang tech equipment responsibility Co., Ltd.TOL-25B excimer lasers are purchased from peace low-light machine institute, PLD-
450 vacuum systems are purchased from Shenyang tech equipment responsibility Co., Ltd.CSPM5500 types scanning probe microscopy is purchased from basis
Nanometer Instrument Ltd..
Embodiment 1
Tested alloys target from purity be 99.99at.%-Ni, 99.95at.%-Mn, 99.99at.%-In,
Tetra- kinds of metal simple-substances of 99.95at.%-Co, according to molfraction than taking 50 parts of Ni, 34 parts of Mn, In and 4 of 12 parts part of Co to put
Enter in vacuum non-consumable electrode electric arc furnace, first vacuumize furnace chamber before melting, vacuum is up to 5 × 10-3After Pa, Ar protections are filled with
Gas.In order that material composition is uniform, overturn 4 times with manipulator material overturning, at least melting before each melting, and in fusion process
In plus magnetic agitation.Diameter 50mm ingot is obtained after melting.Ingot casting is put into WEDM after being polished on emery wheel
On be cut into size be diameter 3mm × 2mm circular target.Selection specification for 30mm × 30mm × 3mm quartz glass as thin
The substrate of film.Pre-treatment is carried out to quartz glass substrate：Quartz glass substrate is washed by deionization, then surpassed in acetone
Sound 10~15 minutes, last washes of absolute alcohol, drying.Then it is true circular target and quartz glass substrate to be put into PLD-450
In empty set system, 1.0 × 10 are evacuated to-4Pa, quartz glass substrate plate temperature are 700 DEG C, distance between quartz glass substrate and target
For 4cm.Launch laser as lasing light emitter with TOL-25B excimer lasers, it is 4Hz to control frequency, is sputtered 2 hours.Pass through control
Laser processed is beaten in Ni50Mn34In12Co4Time on ferromagnetic shape memory alloy target controls the thickness of film.Most pass through afterwards
850 DEG C of annealing 3h are crossed, prepare Ni50Mn34In12Co4Ferromagnetic shape memory alloy film.
Embodiment 2
Tested alloys target from purity be 99.99at.%-Ni, 99.95at.%-Mn, 99.99at.%-In,
Tetra- kinds of metal simple-substances of 99.95at.%-Co, according to molfraction than taking 50 parts of Ni, 34 parts of Mn, In and 4 of 12 parts part of Co to put
Enter in vacuum non-consumable electrode electric arc furnace, first vacuumize furnace chamber before melting, vacuum is up to 5 × 10-3After Pa, Ar protections are filled with
Gas.In order that material composition is uniform, overturn 4 times with manipulator material overturning, at least melting before each melting, and in fusion process
In plus magnetic agitation.Diameter 50mm ingot is obtained after melting.Ingot casting is put into WEDM after being polished on emery wheel
On be cut into size be diameter 3mm × 2mm circular target.Selection specification for 30mm × 30mm × 3mm quartz glass as thin
The substrate of film.Pre-treatment is carried out to quartz glass substrate：Quartz glass substrate is washed by deionization, then surpassed in acetone
Sound 10~15 minutes, last washes of absolute alcohol, drying.Then it is true circular target and quartz glass substrate to be put into PLD-450
In empty set system, 1.0 × 10 are evacuated to-4Pa, quartz glass substrate plate temperature are 650 DEG C, distance between quartz glass substrate and target
For 4cm.Launch laser as lasing light emitter with TOL-25B excimer lasers, it is 4Hz to control frequency, is sputtered 2 hours.Pass through control
Laser processed is beaten in Ni50Mn34In12Co4Time on ferromagnetic shape memory alloy target controls the thickness of film.Most pass through afterwards
850 DEG C of annealing 3h are crossed, prepare Ni50Mn34In12Co4Ferromagnetic shape memory alloy film.
Embodiment 3
Tested alloys target from purity be 99.99at.%-Ni, 99.95at.%-Mn, 99.99at.%-In,
Tetra- kinds of metal simple-substances of 99.95at.%-Co, according to molfraction than taking 50 parts of Ni, 34 parts of Mn, In and 4 of 12 parts part of Co to put
Enter in vacuum non-consumable electrode electric arc furnace, first vacuumize furnace chamber before melting, vacuum is up to 5 × 10-3After Pa, Ar protections are filled with
Gas.In order that material composition is uniform, overturn 4 times with manipulator material overturning, at least melting before each melting, and in fusion process
In plus magnetic agitation.Diameter 50mm ingot is obtained after melting.Ingot casting is put into WEDM after being polished on emery wheel
On be cut into size be diameter 3mm × 2mm circular target.Selection specification for 30mm × 30mm × 3mm quartz glass as thin
The substrate of film.Pre-treatment is carried out to quartz glass substrate：Quartz glass substrate is washed by deionization, then in acetone
Ultrasound 10~15 minutes, last washes of absolute alcohol, drying.Then circular target and quartz glass substrate are put into PLD-450
In vacuum system, 1.0 × 10 are evacuated to-4Pa, quartz glass substrate plate temperature are 600 DEG C, quartz glass substrate and target spacing
From for 4cm.Launch laser as lasing light emitter with TOL-25B excimer lasers, it is 4Hz to control frequency, is sputtered 2 hours.Pass through
Control laser is beaten in Ni50Mn34In12Co4Time on ferromagnetic shape memory alloy target controls the thickness of film.Finally
By 850 DEG C of annealing 3h, Ni is prepared50Mn34In12Co4Ferromagnetic shape memory alloy film.
Embodiment 4
Tested alloys target from purity be 99.99at.%-Ni, 99.95at.%-Mn, 99.99at.%-In,
Tetra- kinds of metal simple-substances of 99.95at.%-Co, according to molfraction than taking 50 parts of Ni, 34 parts of Mn, In and 4 of 12 parts part of Co to put
Enter in vacuum non-consumable electrode electric arc furnace, first vacuumize furnace chamber before melting, vacuum is up to 5 × 10-3After Pa, Ar protections are filled with
Gas.In order that material composition is uniform, overturn 4 times with manipulator material overturning, at least melting before each melting, and in fusion process
In plus magnetic agitation.Diameter 50mm ingot is obtained after melting.Ingot casting is put into WEDM after being polished on emery wheel
On be cut into size be diameter 3mm × 2mm circular target.Selection specification for 30mm × 30mm × 3mm quartz glass as thin
The substrate of film.Pre-treatment is carried out to quartz glass substrate：Quartz glass substrate is washed by deionization, then surpassed in acetone
Sound 10~15 minutes, last washes of absolute alcohol, drying.Then it is true circular target and quartz glass substrate to be put into PLD-450
In empty set system, 1.0 × 10 are evacuated to-4Pa, quartz glass substrate plate temperature are 550 DEG C, distance between quartz glass substrate and target
For 4cm.Launch laser as lasing light emitter with TOL-25B excimer lasers, it is 4Hz to control frequency, is sputtered 2 hours.Pass through control
Laser processed is beaten in Ni50Mn34In12Co4Time on ferromagnetic shape memory alloy target controls the thickness of film.Most pass through afterwards
850 DEG C of annealing 3h are crossed, prepare Ni50Mn34In12Co4Ferromagnetic shape memory alloy film.
Ni prepared by embodiment 1~450Mn34In12Co4Alloy firm uses CSPM5500 type scanning probe microscopies pair
Its surface topography, degree of roughness and magnetic domain are analyzed.As a result as Fig. 1,2 and table 1 shown in.As seen from Figure 1, with substrate
The reduction of temperature, the crystal grain distribution of film surface tend to uniformly, size it is gradually smaller, when base reservoir temperature is 600 DEG C, film table
Face crystallite dimension is minimum, and average grain diameter is about 142.1nm.From figure 2 it can be seen that with the reduction of substrate temperature, farmland line side
To huge change gradually occurs.When base reservoir temperature is 700 DEG C, parallel distribution is presented in farmland wall, and farmland line is with a directional spreding
Based on, color change is obvious, and anisotropy is strong.When base reservoir temperature is 650 DEG C, the quantity of farmland line is reduced, and color also becomes single
Adjust, both direction distribution is presented in local farmland line.And when base reservoir temperature is 600 DEG C, magnetic domain becomes tiny, and with both direction
Based on, the labyrinth shape of bending is presented.And when base reservoir temperature is 550 DEG C, magnetic domain becomes larger magnetic line distribution, and farmland wall
It is arranged in parallel.Table 1 is Ni prepared by embodiment 1~450Mn34In12Co4The roughness crystallite dimension data of alloy firm.
As can be seen from Table 1, with the reduction of base reservoir temperature, Ni50Mn34In12Co4The roughness of alloy firm crystal grain is reduced.
The Ni of table 150Mn34In12Co4The roughness and crystallite dimension of ferromagnetic shape memory alloy film
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (4)
- A kind of 1. Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm, it is characterised in that comprise the following steps：Press According to molfraction than 50:34:12:4 to take purity respectively be 99.99at.%Ni, purity 99.95at.%Mn, purity are 99.99at.%In, purity are that 99.95at.%Co metal simple-substances are positioned over melting in vacuum non-consumable electrode electric arc furnace；By electricity 5 × 10 are evacuated in arc stove-3Pa, argon gas is filled with, obtains circular target；Substrate after processing and target are placed in vacuum system In, it is evacuated to 1.0 × 10-4Pa, substrate temperature are 550~700 DEG C, and substrate is 3~5cm with target distance；Laser is used again Launch laser, it is 4Hz to control frequency, is sputtered 2 hours, and the film for requiring thickness is made；Finally by 850 DEG C of annealing 3h, prepare Go out the Ni of high-flatness50Mn34In12Co4Ferromagnetic shape memory alloy film.
- A kind of 2. Ni of high-flatness according to claim 150Mn34In12Co4The preparation method of alloy firm, its feature It is, to ensure the uniformity of alloy composition in fusion process, sample is overturn at least four times and is subject to before each melting Magnetic stirs.
- A kind of 3. Ni of high-flatness according to claim 150Mn34In12Co4The preparation method of alloy firm, its feature It is, described substrate is quartz glass substrate；The processing method of described substrate is：Quartz glass glass substrate first passes through Ion is washed, then ultrasound 10~15 minutes in acetone, then with washes of absolute alcohol, drying.
- A kind of 4. Ni of high-flatness prepared by any method as described in claims 1 to 350Mn34In12Co4Alloy firm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510446285.6A CN105018888B (en) | 2015-07-27 | 2015-07-27 | A kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510446285.6A CN105018888B (en) | 2015-07-27 | 2015-07-27 | A kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105018888A CN105018888A (en) | 2015-11-04 |
| CN105018888B true CN105018888B (en) | 2018-03-20 |
Family
ID=54409181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510446285.6A Active CN105018888B (en) | 2015-07-27 | 2015-07-27 | A kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105018888B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544630B (en) * | 2016-10-25 | 2019-04-09 | 中国计量大学 | A kind of preparation method of high saturation and magnetic intensity manganese bismuth permanent magnets films |
-
2015
- 2015-07-27 CN CN201510446285.6A patent/CN105018888B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Epitaxial growth of single-crystalline Ni46Co4Mn37In13 thin film and investigation of its magnetoresistance;Chao Jing,et al.;《Progress in Natural Science Materials International》;20140214;第24卷;第20页2.experimental * |
| Evidence of Martensitic Phase Transitions in Magnetic Ni-Mn-In Thin Films;A. Sokolov，et al.;《Applied Physics Letters》;20130221;第102卷;第072407-2页左栏 * |
| Microstructure,phase transitions and mechnical properties of Ni50Mn34In16-yCoy alloys;Y.Feng,et al.;《Journal of Alloys and Compounds》;20081117;第476卷;第935页2.experimental，第939页左栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105018888A (en) | 2015-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Texture and microstructure characterization in laser additive manufactured Ti–6Al–2Zr–2Sn–3Mo–1.5 Cr–2Nb titanium alloy | |
| Uchic et al. | A methodology to investigate size scale effects in crystalline plasticity using uniaxial compression testing | |
| Cemin et al. | Benefits of energetic ion bombardment for tailoring stress and microstructural evolution during growth of Cu thin films | |
| KR102359630B1 (en) | W-ni sputter target | |
| CN103572223B (en) | The manufacture method of tantalum target and tantalum target assembly | |
| Cemin et al. | Epitaxial growth of Cu (001) thin films onto Si (001) using a single-step HiPIMS process | |
| Waryoba et al. | Microtexture in additively manufactured Ti-6Al-4V fabricated using directed energy deposition | |
| Gao et al. | Laser-beam powder bed fusion followed by annealing with stress: A promising route for magnetostrictive improvement of polycrystalline Fe81Ga19 alloys | |
| CN104947052A (en) | Method for preparing Ni52Mn24Ga24 alloy film through laser pulse sputtering deposition | |
| Xu et al. | Insight into the structural evolution during TiN film growth via atomic resolution TEM | |
| Brackmann et al. | Glow discharge plasma as a surface preparation tool for microstructure investigations | |
| KR102110462B1 (en) | Method for corrosion resistance alloy thin film with amorphous phase | |
| CN104711471A (en) | Method for preparing NiMnX alloy target | |
| JP2007297679A (en) | Sputtering target of cobalt and manufacturing method therefor | |
| KR101991150B1 (en) | Cobalt sputtering target and production method therefor | |
| CN105018888B (en) | A kind of Ni of high-flatness50Mn34In12Co4The preparation method of alloy firm | |
| Zhang et al. | Mechanical properties improvement of nickel-based alloy 625 fabricated by powder-fed laser additive manufacturing based on linear beam oscillation | |
| Tekumalla et al. | Towards 3-D texture control in a β titanium alloy via laser powder bed fusion and its implications on mechanical properties | |
| JP2007197811A (en) | Sputter target | |
| Bouissil et al. | Properties of a new TiTaZrHfW (N) refractory high entropy film deposited by reactive DC pulsed magnetron sputtering | |
| US6423196B1 (en) | Method of making Ni-Si magnetron sputtering targets and targets made thereby | |
| CN105296925B (en) | The method that laser pulse sputtering sedimentation prepares Ni-Mn-Co-In alloy firms | |
| Utyaganova et al. | Structure and Phase Composition of Ti–6Al–4V Alloy Obtained by Electron-Beam Additive Manufacturing | |
| US6303008B1 (en) | Rotating film carrier and aperture for precision deposition of sputtered alloy films | |
| US20160076137A1 (en) | Crystalline alloy having glass forming ability, method for manufacturing same, alloy target for sputtering, and method for manufacturing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |