CN102925779B - Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion - Google Patents
Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion Download PDFInfo
- Publication number
- CN102925779B CN102925779B CN201210409311.4A CN201210409311A CN102925779B CN 102925779 B CN102925779 B CN 102925779B CN 201210409311 A CN201210409311 A CN 201210409311A CN 102925779 B CN102925779 B CN 102925779B
- Authority
- CN
- China
- Prior art keywords
- electroplating
- alloy
- room temperature
- fine aluminium
- mentioned
- 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
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a method for preparing a cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion. The method comprises the following steps of: performing composite electroplating by taking an aluminum foil as a base material to obtain a Co-Ni alloy layer; and forming a Co-Ni-Al magnetically-controlled shape memory alloy through thermal diffusion. The method is simple in process and high in performance and stability, technical bottleneck problems that the conventional Co-Ni-Al magnetically-controlled memory alloy is large in driving magnetic field and small magnetic field-induced strain and the like are well solved, and practical application of the magnetically-controlled memory alloy to fields such as large-power underwater sonars, micro shifters, vibration and noise control, linear motors, microwave devices and robots is promoted.
Description
Technical field
The present invention relates to magnetic control shape memory Metallic Functional Materials technology of preparing, be specifically related to a kind of method of preparing Co-Ni-Al alloy based on plating thermodiffusion.
Background technology
Magnetic shape memory alloy, (Magnetic Shape Memory Alloy, MSMA) not only has conventional shape-memory alloy and is subject to the thermo-elasticity shape memory effect of Temperature Field Control, and has the magnetic shape memory effect that controlled by magnetic field.Therefore, alloy has large recovery strain, the overall characteristic exporting stress, high response frequency and can accurately control greatly concurrently, make it have important application in fields such as high-power underwater sonar, micro positioner, vibrations and noise control, linear motor, microwave device, robots, a new generation that is expected to become after piezoelectric ceramics and magnetostriction materials drives and sensing material.At present, the magnetic shape memory alloy of having found mainly comprises: Ni is associated golden Ni-Mn-Ga, Ni-Al-Mn, Ni-Co-Al, Ni-Fe-Ga-Co etc.; Co is associated golden Co-Mn, Co-Ni, Co-Ni-Ga etc.; Fe is associated golden Fe-Pd, Fe-Mn-Si, Fe-Ni-Co-Ti, Fe-Pt, etc. wherein, Ni-Mn-Ga alloy is the MSMA finding the earliest, its research is comparatively ripe, the existing report that is applied to the aspect such as linear actuator, linear electric motors, but the stability of alloy property and repeatability are not ideal enough.
Co base ferromagnetic shape memory alloys comprises Co-Ni-Ga and Co-Ni-Al two class alloys, has the advantages such as the large and hot workability excellence of magnetocrystalline anisotropy energy.Co-Ni-Al is unique a kind of MSMA solidifying in eutectic mode, and has the two-phase coexistent district of broad crystallisation scope, and within the scope of functional component, shows abundant multiphase coexistence behavior, and preparation method is relatively simple, cheap, has larger application prospect.
Co-Ni-Al alloy under the preparation conditions such as both at home and abroad researcher adopts routine to solidify, high undercooling solidifies, the method for directional freeze, rapid solidification and powder metallurgy, there is good strain-induced shape memory effect, but still the technical bottleneck that the driving magnetic field of unresolved CoNiAl alloy is large, magneto-strain is little.
Utilization of the present invention is carried out composite plating Co-Ni alloy at aluminium foil, by adjusting heat treatment process parameter, finally prepares the Co-Ni-Al alloy of high comprehensive performance.
Summary of the invention
A kind of method of preparing Co-Ni-Al alloy based on plating thermodiffusion provided by the invention, has the following steps:
1) electroplate Co-Ni alloy layer at fine aluminium substrate surface, in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 10～90%;
2) Co-Ni/Al after electroplating being put into well heater, is 250 DEG C～600 DEG C insulations 60～240 hours in temperature, diffuses to form uniform Co-Ni-Al alloy, takes out after cooling to room temperature with the furnace.
Above-mentioned steps 1) in fine aluminium base material thickness be 0.01mm～0.3mm.
Above-mentioned steps 1) in electroplating technique flow process be: at room temperature to the clean oil removing of fine aluminium substrate surface distilled water flushing, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up.
Above-mentioned plating is taking fine aluminium as anode, and the formula of described electroplate liquid is: single nickel salt 100～250 g/L, sodium-chlor 10～20 g/L, boric acid 20～40 g/L, rose vitriol 10～120 g/L, asccharin 1g/L; Continuous current in electroplating process, electric current 0.15A, bath pH value is 4.6.Adjust the Co-Ni alloy layer that electroplate liquid composition and electroplating parameter can obtain heterogeneity on fine aluminium base material.
Above-mentioned steps 2) in well heater be retort furnace or vacuum oven; Retort furnace, for avoiding coating oxidation, is taked to pass into nitrogen, argon gas or hydrogen shield gas, or Co-Ni/Al is put into carbon reducing agent material and heat.
Above-mentioned steps 2) in soaking time determine according to fine aluminium base material and thickness of coating, be heated to diffusion and obtain the even Co-Ni-Al alloy of composition.
Beneficial effect of the present invention:
1. adopt composite electric plating method on aluminium base, to prepare Co-Ni alloy, control the parameters such as thermal treatment process, the composition of coating and the thickness of matrix, prepare high comprehensive performance Co-Ni-Al alloy.
2. equipment cost and the technical requirements of preparation Co-Ni-Al alloy are low, only need simple power supply and well heater can prepare Co-Ni-Al alloy.
3. preparation method's technique of the present invention is simple, and stability is good, solves preferably the Pinch technology difficult points such as the driving magnetic field that current C o-Ni-Al magnetic control memorial alloy remains is large, magneto-strain is little.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail.
Embodiment 1
1) at the fine aluminium substrate surface of 0.05mm thickness, under room temperature to the clean oil removing of distilled water flushing for fine aluminium substrate surface, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up.
The compositing formula of above-mentioned electroplate liquid is: single nickel salt 250g/L, sodium-chlor 10 g/L, boric acid 40 g/L, rose vitriol 55 g/L, asccharin 1g/L; Electroplating parameter is: continuous current in plating process, and electric current 0.15A, bath pH value is 4.6.Stop electroplating sample and dry up, obtain Co-54.2%Ni alloy layer, wherein in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 54.2%;
2) Co-54.2%Ni/Al sample after electroplating is put into retort furnace, obtaining composition be incubated 60 hours under temperature is 550 DEG C, argon gas atmosphere after is Co-45.0%Ni-17%Al alloy.
3) take out after cooling to room temperature with the furnace.
Embodiment 2
1) at the fine aluminium substrate surface of 0.1mm thickness, under room temperature to the clean oil removing of distilled water flushing for fine aluminium substrate surface, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up.
The compositing formula of above-mentioned electroplate liquid is: single nickel salt 100g/L, sodium-chlor 20 g/L, boric acid 40 g/L, rose vitriol 120 g/L, asccharin 1g/L; Electroplating parameter is: continuous current in plating process, and electric current 0.15A, bath pH value is 4.6.Stop electroplating sample and dry up, obtain Co-9.9%Ni alloy layer, wherein in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 9.9%;
2) Co-9.9%Ni/Al sample after electroplating is put into Vacuum Heat and come out of the stove, after temperature is to be incubated 200 hours at 300 DEG C, obtaining composition is Co-6.0%Ni-40.0%Al alloy.
3) take out after cooling to room temperature with the furnace.
Embodiment 3
1) at the fine aluminium substrate surface of 0.2mm thickness, under room temperature to the clean oil removing of distilled water flushing for fine aluminium substrate surface, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up.
The compositing formula of above-mentioned electroplate liquid is: single nickel salt 175g/L, sodium-chlor 20 g/L, boric acid 20 g/L, rose vitriol 10 g/L, asccharin 1g/L; Electroplating parameter is: continuous current in plating process, and electric current 0.15A, bath pH value is 4.6.Stop electroplating sample and dry up, obtain Co-41.5%Ni alloy layer, wherein in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 41.5%;
2) Co-41.5%Ni/Al sample after electroplating being put into retort furnace, is that after 180 hours, to obtain composition be Co-35.0%Ni-14.5%Al alloy for 400 DEG C, nitrogen atmosphere insulation in temperature.
3) take out after cooling to room temperature with the furnace.
Embodiment 4
1) at the fine aluminium substrate surface of 0.15mm thickness, under room temperature to the clean oil removing of distilled water flushing for fine aluminium substrate surface, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up.
The compositing formula of above-mentioned electroplate liquid is: single nickel salt 250g/L, sodium-chlor 20 g/L, boric acid 30 g/L, rose vitriol 10 g/L, asccharin 1g/L; Electroplating parameter is: continuous current in plating process, and electric current 0.15A, bath pH value is 4.6.Stop electroplating sample and dry up, obtain Co-88.3%Ni alloy layer, wherein in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 88.3%;
2) Co-88.3%Ni/Al sample after electroplating being put into retort furnace, is that after 80 hours, to obtain composition be Co-80%Ni-9.4%Al alloy to the coated lower insulation of 600 DEG C, carbon dust in temperature.
3) take out after cooling to room temperature with the furnace.
Embodiment 5
1) at the fine aluminium substrate surface of 0.3mm thickness, under room temperature to the clean oil removing of distilled water flushing for fine aluminium substrate surface, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up.
The compositing formula of above-mentioned electroplate liquid is: single nickel salt 220g/L, sodium-chlor 15 g/L, boric acid 40 g/L, rose vitriol 50 g/L, asccharin 1g/L; Electroplating parameter is: continuous current in plating process, and electric current 0.15A, bath pH value is 4.6.Stop electroplating sample and dry up, obtain Co-49.9%Ni alloy layer, wherein in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 49.9%;
2) Co-49.9%Ni/Al sample after electroplating is put into retort furnace, be 450 DEG C in temperature, come out of the stove at Vacuum Heat that after 240 hours, to obtain composition be Co-14.9%Ni-70.2%Al alloy in interior insulation.
3) take out after cooling to room temperature with the furnace.
Claims (4)
1. a method of preparing Co-Ni-Al alloy based on plating thermodiffusion, is characterized in that the method has the following steps:
1) electroplate Co-Ni alloy layer at fine aluminium substrate surface, in above-mentioned Co-Ni alloy layer, the mass ratio of nickel is 10～90%; Above-mentioned electroplating technique flow process is: at room temperature to the clean oil removing of fine aluminium substrate surface distilled water flushing, in the pickling solution that the nitric acid that to be placed on by volume ratio after clean oil removing be 20%, the hydrofluoric acid that volume ratio is 1% and surplus deionized water form, at room temperature etching time is 40 hours; Then use deionized water washing; Under room temperature, sample is put into and mixed by 15 g/L single nickel salts and 112 g/L Trisodium Citrates the solution that the pH value that forms is 13 and activate, be placed in afterwards electroplate liquid and electroplate; Stopping electroplating sample dries up; Above-mentioned plating is taking fine aluminium as anode; The formula of described electroplate liquid is: single nickel salt 100～250 g/L, sodium-chlor 10～20 g/L, boric acid 20～40 g/L, rose vitriol 10～120 g/L, asccharin 1g/L; Continuous current in electroplating process, electric current 0.15A, bath pH value is 4.6;
2) Co-Ni/Al after electroplating being put into well heater, is 250 DEG C～600 DEG C insulations 60～240 hours in temperature, diffuses to form uniform Co-Ni-Al alloy, takes out after cooling to room temperature with the furnace.
2. method according to claim 1, is characterized in that: above-mentioned steps 1) in fine aluminium base material thickness be 0.01mm～0.3mm.
3. method according to claim 1, is characterized in that: above-mentioned steps 2) in well heater be retort furnace or vacuum oven; Retort furnace, for avoiding coating oxidation, is taked to pass into nitrogen, argon gas or hydrogen shield gas, or Co-Ni/Al is put into carbon reducing agent material and heat.
4. method according to claim 1, is characterized in that: above-mentioned steps 2) in soaking time determine according to fine aluminium base material and thickness of coating, be heated to diffusion and obtain the even Co-Ni-Al alloy of composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409311.4A CN102925779B (en) | 2012-10-24 | 2012-10-24 | Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409311.4A CN102925779B (en) | 2012-10-24 | 2012-10-24 | Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102925779A CN102925779A (en) | 2013-02-13 |
| CN102925779B true CN102925779B (en) | 2014-08-13 |
Family
ID=47640702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210409311.4A Active CN102925779B (en) | 2012-10-24 | 2012-10-24 | Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102925779B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107584134B (en) * | 2017-09-20 | 2019-06-21 | 安徽大学 | Method for preparing millimeter spherical semi-hard magnetic Co-Ni amorphous alloy by microwave electric spark |
| CN113684389B (en) * | 2021-08-16 | 2022-07-29 | 大连大学 | Method for improving superelasticity of Co-Ni-Al magnetic memory alloy by controlling gamma phase distribution |
| CN113667860A (en) * | 2021-08-17 | 2021-11-19 | 宁波微泰真空技术有限公司 | Ultra-pure copper-aluminum ingot and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219092C (en) * | 2003-04-08 | 2005-09-14 | 中国科学院金属研究所 | High-damping shape memory alloy |
| JP3872323B2 (en) * | 2001-09-21 | 2007-01-24 | 独立行政法人科学技術振興機構 | Co-Ni-Ga based Heusler type magnetic shape memory alloy and method for producing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4737518B2 (en) * | 2005-05-23 | 2011-08-03 | Ｎｅｃトーキン株式会社 | Ti-Ni-Nb alloy element |
-
2012
- 2012-10-24 CN CN201210409311.4A patent/CN102925779B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3872323B2 (en) * | 2001-09-21 | 2007-01-24 | 独立行政法人科学技術振興機構 | Co-Ni-Ga based Heusler type magnetic shape memory alloy and method for producing the same |
| CN1219092C (en) * | 2003-04-08 | 2005-09-14 | 中国科学院金属研究所 | High-damping shape memory alloy |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-328436A 2006.12.07 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102925779A (en) | 2013-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102246248B (en) | Magnetic alloy material through coating and preparation method thereof | |
| CN102925779B (en) | Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion | |
| CN102013488A (en) | Tin/copper foam alloy cathode material for lithium ion cells and preparation method thereof | |
| CN101899640B (en) | Preparation method for copper-chromium alloy surface alloying | |
| CN105603424B (en) | β (Ni, Pt) Al coatings that a kind of Si is modified and preparation method thereof | |
| CN102671942B (en) | Preparation method for copper-steel composite | |
| CN104078230A (en) | Intergranular insulated high-silicon electrical steel core and preparation method thereof | |
| CN101942663B (en) | Compound method for preparing magnesium alloy having superhydrophobic surface | |
| CN105063685A (en) | Nickel plated copper product containing nickel-cobalt alloy clad layer, and preparation method and application thereof | |
| CN109457278B (en) | Step-by-step preparation of TiSi on titanium alloy surface2Method for preparing (Ni, Ti) Si composite coating | |
| CN102560445B (en) | Process for chemically and compositely plating nickel and phosphorus on sintered neodymium iron boron | |
| CN103014414A (en) | TiNi-base shape memory alloy containing components in graded distribution and preparation method thereof | |
| Harimkar et al. | Spark plasma sintering of amorphous-crystalline laminated composites | |
| CN103773991B (en) | High-strength conductive copper rod material and preparation method thereof | |
| CN101250705B (en) | Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture | |
| CN106356187B (en) | Ooze dysprosium technique in a kind of neodymium iron boron surface | |
| CN102673040B (en) | Cu-Ni functionally gradient material and preparation method thereof | |
| CN109402531A (en) | A kind of Fe-based amorphous nanocrystalline alloy porous catalyst and its preparation method and application based on hypergravity solidification | |
| CN103474642B (en) | A kind of tin oxide negative material for lithium ion battery and preparation method thereof | |
| TWI376833B (en) | Method for preparing a surface modification coating of metal bipolar plates | |
| CN103490053B (en) | A kind of preparation method of the carbon nano tube-doped tin oxide negative material for lithium ion battery | |
| CN111926366A (en) | Sintered neodymium-iron-boron magnet surface corrosion-resistant coating and preparation method thereof | |
| CN102994944A (en) | Process method for alloying on low-carbon steel surface by employing ferrosilicon powder | |
| CN107475563B (en) | One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof | |
| CN104294211B (en) | Aluminizing medium adds anhydrous SmCl3the method preparing Ni-Al high-temperature oxidation resistant composite coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |