CN104947053A - Preparation method of high-manganese alloy film Mn53Ni23Ga24 - Google Patents
Preparation method of high-manganese alloy film Mn53Ni23Ga24 Download PDFInfo
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- CN104947053A CN104947053A CN201510447634.6A CN201510447634A CN104947053A CN 104947053 A CN104947053 A CN 104947053A CN 201510447634 A CN201510447634 A CN 201510447634A CN 104947053 A CN104947053 A CN 104947053A
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Abstract
The invention provides a preparation method of a high-manganese alloy film Mn53Ni23Ga24. The preparation method comprises the following steps: taking metal simple substances, namely Mn, Ni and Ga as target raw materials with the mole fraction ratio of Mn to Ni to Ga being 53:23:24, placing the target raw materials in a non-consumable vacuum arc furnace for smelting, vacuumizing to 5*10<-3>Pa, and then introducing shielding gas, so as to obtain a round target material; placing a pre-processed base plate and the target material in a vacuum system, and vacuumizing to 1.0*10<-4>Pa, wherein the temperature of the base plate is 500-700 DEG C, and the interval between the base plate and the target material is 3-5 cm; emitting lasers by a laser device, controlling the frequency to be 3-4 Hz, and sputtering for 1-3 hours, so as to prepare a film with required thickness; finally, annealing the film at the temperature of 800-900 DEG C, so as to obtain the high-manganese alloy film Mn53Ni23Ga24. According to the Mn53Ni23Ga24 alloy film prepared by the preparation method, the components are more precise, the roughness is low, the surface is smoother, the anisotropism is good, the martensite phase transformation temperature of the film is equivalent to that of block materials, required raw materials are low in price and rich in reserves, and the prepared alloy film is excellent in tenacity, high in strength, simple in technology, and easy for industrial production.
Description
Technical field
The invention belongs to field of metal alloy technology, relate to novel method prepared by a kind of high ferromanganese magnetic shape memory alloy film, specifically a kind of high manganese film Mn
53ni
23ga
24preparation method.
Background technology
Magnetic shape memory alloy is as a kind of novel intelligent material, and the most outstanding physical property feature is that this class alloy both magnetic changes and thermoelastic martensitic transformation.The magnetic shape memory alloy candidate material majority reported is Heusler alloy, has the L2 of high-sequential
1structure.Nearest research finds Mn
2niGa alloy uniquely has non-L2
1the Heusler alloy of structure, martensite lattice │ 1-c/a │ can reach 21.3%, ferrimagnetism occurs in Martensitic Transformation to ferromagnetic transformation, is a kind of novel magnetic shape memory alloy with larger application potential.At present, be no more than the research and development of the Mn-Ni-Ga alloy of 50at.% about Mn content in prior art, the preliminary study martensitic transformation of alloy, and reported the calculated results of the basic physical properties such as electronic structure and magnetic ordering structure, this result shows to there is Mn-Mn atom antiferromagnetic coupling in alloy magnetic ordering structure, limits the raising of alloy saturation magnetization.At present, the relation between alloy material weave construction and performance is driven also not have system to be comprehensively familiar with for this New Magnetic Field Controlled, meanwhile, Mn
2the problems such as NiGa alloy transformation temperature is lower, fragility is larger limit the application of alloy.These become the Main Bottleneck of magnetic driven memory alloy application and development, also be difficult to the requirement meeting engineer applied and the development of MEMS micro element simultaneously, along with the development of science and technology, device is gradually to microminiaturized, intelligent development, research and development have uniform composition, good stability, thin-film material that toughness is strong are very important, for micro-intellectuality and highly integratedly have important practical value.
Summary of the invention
The present invention is in order to solve existing ferromagnetic shape memory alloy Mn
2the problems such as NiGa fragility is large, intensity is low, and a kind of high manganese film Mn is provided
53ni
23ga
24preparation method.This film performance is excellent, further increases magnetic-field-induced strain amount, the threshold value of magnetic entropy change and field drives reverse transformation.
The present invention is achieved in that a kind of high manganese film Mn
53ni
23ga
24preparation method, carry out as follows: get Mn, Ni, Ga metal simple-substance respectively as target raw material according to molfraction than 53:23:24, target raw material is positioned over non-consumable arc furnace molten in, be evacuated to 5 × 10
-3after Pa, be filled with protection gas, obtain circular target; Pretreated substrate and target are put into vacuum system, is evacuated to 1.0 × 10
-4pa, substrate temperature is 500 ~ 700 DEG C, preferably 600 DEG C, and substrate and target spacing are 3 ~ 5cm, preferred 4cm; Use laser apparatus Emission Lasers again, controlled frequency is 3 ~ 4Hz, sputters 1 ~ 3 hour, preferably 2 hours, the film of obtained required thickness; Finally anneal film at 800 ~ 900 DEG C 0.5 ~ 3h, prepares high manganese film Mn
53ni
23ga
24.This annealing time is crystallization time, annealing temperature preferably 850 DEG C, time 3h.
Further, the purity of described Ni metal simple-substance is 99.99at.%.
Further, the purity of described Mn metal simple-substance is 99.95at.%.
Further, the purity of described Ga metal simple-substance is 99.99at.%.
Further, described protection gas is argon gas.
For ensureing the homogeneity of alloy composition in fusion process, before each melting, by sample upset at least four times and in addition magnetic stirs.Mechanical manipulator can be adopted to realize sample upset, after melting, obtain the ingot of diameter 50mm.Ingot is put into circular target WEDM being cut into and being of a size of diameter 3mm × 2mm after polishing by emery wheel.
Described substrate is quartz glass substrate, and this substrate specification is 30mm × 30mm × 3mm.
The treatment step of described quartz glass substrate is: glass substrate, first through deionization washing, then in acetone ultrasonic 10 ~ 15 minutes, then use washes of absolute alcohol, is dried.
The present invention also asks the high manganese film Mn protecting aforesaid method to prepare
53ni
23ga
24.
Different from existing magnetic shape memory alloy Ni-Mn-Ga film, Mn prepared by the present invention
53ni
23ga
24ferromagnetic shape memory alloy film has the following advantages:
1, the high manganese film Mn for preparing of the present invention
53ni
23ga
24composition achieve the multi-element compounds film consistent with target material composition, than adopting, the Mn-Ni-Ga alloy firm composition prepared of additive method is more accurate;
2, the high manganese film Mn for preparing of the present invention
53ni
23ga
24ferromagnetic shape memory alloy film is lower than the roughness of existing Mn-Ni-Ga alloy firm, surface more smooth;
3, the high manganese film Mn for preparing of the present invention
53ni
23ga
24anisotropy is strong;
4, the high manganese film Mn for preparing of the present invention
53ni
23ga
24martensitic transformation temperature suitable with block materials;
5, low in raw material price required for the present invention, rich reserves, preparation alloy firm good toughness, intensity is large, preparation technology is simple, being easy to suitability for industrialized production, providing new thinking for solving Mn-Ni-Ga bulk defect, for micro-intellectuality and highly integratedly have important practical value.
Accompanying drawing explanation
Fig. 1 is Mn prepared by the present invention
53ni
23ga
24the AFM shape appearance figure of alloy firm, wherein (a) is the AFM shape appearance figure of crystallization time 0.5h alloy firm, the AFM shape appearance figure of (b) crystallization time 3h alloy firm;
Fig. 2 is Mn prepared by the present invention
53ni
23ga
24the magnetic domain shape appearance figure of alloy firm, wherein (a) is the magnetic domain shape appearance figure of crystallization time 0.5h alloy firm, the magnetic domain shape appearance figure of (b) crystallization time 3h alloy firm;
Fig. 3 is Mn prepared by the present invention
53ni
23ga
24the DSC curve of alloy firm, wherein (a) crystallization time 0.5h, (b) crystallization time 3h; Curve 1,3 is heating curve, and 2,4 is temperature lowering curve.
Embodiment
Content of the present invention is described in detail below by embodiment; but be not used in and limit the scope of the invention; if no special instructions; all commercially, vacuum non-consumable electrode electric arc furnace used in the present invention is purchased from Shenyang tech equipment responsibility company limited for experimental drug involved in the present invention and raw material.TOL-25B excimer laser is purchased from peace low-light machine institute, and PLD-450 vacuum system is purchased from Shenyang tech equipment responsibility company limited.CSPM5500 type Scanning Probe Microscopy is purchased from basis nanometer Instrument Ltd..
Embodiment 1
Getting purity is that 99.95at.%-Mn, 99.99at.%-Ni, 99.99at.%-Ga tri-kinds of metal simple-substances are as target raw material, than 53:23:24, target raw material is put into vacuum non-consumable electrode electric arc furnace according to molfraction, first vacuumized by furnace chamber before melting, vacuum tightness reaches 5 × 10
-3after Pa, be filled with Ar and protect gas.In order to make material composition even, with mechanical manipulator material overturning before each melting, at least melting overturns 4 times, and adds magnetic agitation in fusion process.The ingot that diameter is about about 50mm is obtained after melting.Ingot casting is put into circular target WEDM being cut into and being of a size of diameter 3mm × 2mm after polishing by emery wheel.Selection specification is the substrate of silica glass as film of 30mm × 30mm × 3mm.Pre-treatment is carried out to glass substrate: washed through deionization by glass substrate, then in acetone ultrasonic 10 ~ 15 minutes, last washes of absolute alcohol, dry.Then circular target and glass substrate are put into PLD-450 vacuum system, be evacuated to 1.0 × 10
-4pa, glass substrate temperature is 600 DEG C, and glass substrate and target spacing are 4cm.With TOL-25B excimer laser as laser source Emission Lasers, controlled frequency is 4Hz, sputters 2 hours, the film of obtained required thickness.Eventually pass 850 DEG C of annealing, crystallization 0.5h prepares high manganese film Mn
53ni
23ga
24.
Embodiment 2
Getting purity is that 99.95at.%-Mn, 99.99at.%-Ni, 99.99at.%-Ga tri-kinds of metal simple-substances are as target raw material, than 53:23:24, target raw material is put into vacuum non-consumable electrode electric arc furnace according to molfraction, first vacuumized by furnace chamber before melting, vacuum tightness reaches 5 × 10
-3after Pa, be filled with Ar and protect gas.In order to make material composition even, with mechanical manipulator material overturning before each melting, at least melting overturns 4 times, and adds magnetic agitation in fusion process.The ingot that diameter is about about 50mm is obtained after melting.Ingot casting is put into circular target WEDM being cut into and being of a size of diameter 3mm × 2mm after polishing by emery wheel.Selection specification is the substrate of silica glass as film of 30mm × 30mm × 3mm.Pre-treatment is carried out to glass substrate: washed through deionization by glass substrate, then in acetone ultrasonic 10 ~ 15 minutes, last washes of absolute alcohol, dry.Then circular target and glass substrate are put into PLD-450 vacuum system, be evacuated to 1.0 × 10
-4pa, glass substrate temperature is 600 DEG C, and glass substrate and target spacing are 4cm.With TOL-25B excimer laser as laser source Emission Lasers, controlled frequency is 4Hz, sputters 2 hours, the film of obtained required thickness.Eventually pass 850 DEG C of annealing, crystallization 3h prepares high manganese film Mn
53ni
23ga
24.
By the Mn of above-mentioned preparation
53ni
23ga
24alloy firm adopts CSPM5500 type Scanning Probe Microscopy to analyze its surface topography, degree of roughness and magnetic domain, and result is as shown in Fig. 1,2 and table 1.As seen from Figure 1, along with the increase of film crystallization time, the crystal grain distribution of film surface is tending towards evenly, size has almost no change.As can be seen from Figure 2, along with the increase of film crystallization time, line direction, farmland changes less, and color slightly increases.By the Mn of above-mentioned preparation
53ni
23ga
24alloy firm adopts DSC to carry out the measurement of transformation temperature, and the speed of intensification and cooling is 20 DEG C/min.As seen from Figure 3, along with the increase of film crystallization time, the phase transformation peak of alloy becomes crack, and transformation temperature has almost no change.
Mn prepared by table 1 the present invention
53ni
23ga
24the roughness of alloy firm and grain-size data
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a high manganese film Mn
53ni
23ga
24preparation method, it is characterized in that, carry out as follows: get Mn, Ni, Ga metal simple-substance respectively as target raw material according to molfraction than 53:23:24, target raw material is positioned over non-consumable arc furnace molten in, be evacuated to 5 × 10
-3after Pa, be filled with protection gas, obtain circular target; Pretreated substrate and target are put into vacuum system, is evacuated to 1.0 × 10
-4pa, substrate temperature is 500 ~ 700 DEG C, and substrate and target spacing are 3 ~ 5cm; Use laser apparatus Emission Lasers again, controlled frequency is 3 ~ 4Hz, sputters 1 ~ 3 hour, the film of obtained required thickness; Finally anneal film at 800 ~ 900 DEG C 0.5 ~ 3h, prepares high manganese film Mn
53ni
23ga
24.
2. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, the purity of described Ni metal simple-substance is 99.99at.%.
3. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, the purity of described Mn metal simple-substance is 99.95at.%.
4. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, the purity of described Ga metal simple-substance is 99.99at.%.
5. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, described protection gas is argon gas.
6. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, for ensureing the homogeneity of alloy composition in fusion process, before each melting, by sample upset at least four times and in addition magnetic stirs.
7. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, described substrate is quartz glass substrate.
8. a kind of high manganese film Mn according to claim 1
53ni
23ga
24preparation method, it is characterized in that, the treatment step of described quartz glass substrate is: glass substrate, first through deionization washing, then in acetone ultrasonic 10 ~ 15 minutes, then use washes of absolute alcohol, is dried.
9. the high manganese film Mn prepared as any one method of claim 1 ~ 8
53ni
23ga
24.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108251805A (en) * | 2017-12-22 | 2018-07-06 | 南京理工大学 | It is a kind of to realize hexagonal Mn with Ru buffer layers3The method of Ga film preparations |
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| CN1610020A (en) * | 2004-09-24 | 2005-04-27 | 中国科学院物理研究所 | Magnetic material with bidirectional shape memory effect and single-crystal producing method thereof |
| CN102345105A (en) * | 2011-09-28 | 2012-02-08 | 东北石油大学 | Preparation method of high-residual internal stress Ni-Mn-Ga magnetically-driven memory alloy film |
| WO2015019513A1 (en) * | 2013-08-09 | 2015-02-12 | Jx日鉱日石金属株式会社 | Process for manufacturing neodymium-iron-boron-based rare earth powder or sputtering target, neodymium-iron-boron-based rare earth powder or sputtering target, and neodymium-iron-boron-based thin film for rare earth magnet or manufacturing process therefor |
-
2015
- 2015-07-27 CN CN201510447634.6A patent/CN104947053A/en active Pending
Patent Citations (3)
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|---|---|---|---|---|
| CN1610020A (en) * | 2004-09-24 | 2005-04-27 | 中国科学院物理研究所 | Magnetic material with bidirectional shape memory effect and single-crystal producing method thereof |
| CN102345105A (en) * | 2011-09-28 | 2012-02-08 | 东北石油大学 | Preparation method of high-residual internal stress Ni-Mn-Ga magnetically-driven memory alloy film |
| WO2015019513A1 (en) * | 2013-08-09 | 2015-02-12 | Jx日鉱日石金属株式会社 | Process for manufacturing neodymium-iron-boron-based rare earth powder or sputtering target, neodymium-iron-boron-based rare earth powder or sputtering target, and neodymium-iron-boron-based thin film for rare earth magnet or manufacturing process therefor |
Non-Patent Citations (3)
| Title |
|---|
| F.J.CASTAñO ET AL: "Structure and thermomagnetic properties of polycrystalline Ni-Mn-Ga thin films", 《JOURNAL OF APPLIED PHYSICS》 * |
| 刘超: "磁控溅射Ni-Mn-Ga合金薄膜的相变行为与性能", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 叶志镇等: "《半导体薄膜技术与物理》", 31 December 2014, 浙江大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108251805A (en) * | 2017-12-22 | 2018-07-06 | 南京理工大学 | It is a kind of to realize hexagonal Mn with Ru buffer layers3The method of Ga film preparations |
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Application publication date: 20150930 |
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