CN102443749A - Method for improving performance of fast-setting Ni-Mn-based magnetic refrigeration alloy ribbon material - Google Patents
Method for improving performance of fast-setting Ni-Mn-based magnetic refrigeration alloy ribbon material Download PDFInfo
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- CN102443749A CN102443749A CN2012100002811A CN201210000281A CN102443749A CN 102443749 A CN102443749 A CN 102443749A CN 2012100002811 A CN2012100002811 A CN 2012100002811A CN 201210000281 A CN201210000281 A CN 201210000281A CN 102443749 A CN102443749 A CN 102443749A
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Abstract
The invention relates to a method for improving performance of a fast-setting Ni-Mn-based magnetic refrigeration alloy ribbon material, which belongs to the field of magnetic refrigeration materials. According to the method, ordering transformation temperature of the material is determined by using thermal analysis; then the material is subjected to composite pulsed magnetic field heat treatment at a temperature 30 to 50 K higher than the ordering transformation temperature, wherein, the highest temperature of heating is 1173K, pulse width is 26 ms, acting frequency is 0.3 to 1 Hz, and magnetic induction intensity B is 0.5T to 1.5T. Compared to normal heat treatment, the method provided in the invention has the following advantages: operation is simple, heat treatment temperature is low, and magnetocaloric properties of the fast-setting Ni-Mn-based magnetic refrigeration alloy ribbon material can be effectively improved.
Description
Technical field
The present invention relates to a kind of method that improves the fast Ni-Mn of coagulating base magnetic refrigeration alloy thin band material property, belong to technical field of magnetic.
Background technology
In the world today, Refrigeration Technique plays important effect, particularly at food storage, and air-conditioning, industries such as medical treatment.Modern Refrigeration Technique is based on the refrigeration cycle process of gas compression/expansion basically, and this process not only efficient is low, and energy consumption is high, but also can destroy atmospheric ozone layer or cause Greenhouse effect.Therefore, seek a kind of novel, efficient, energy-conservation and Refrigeration Technique environmental protection and become the problem that current society presses for solution.
The magnetic Refrigeration Technique is to be working medium with the magneticsubstance, comes a kind of green technology of refrigerating by the magnetothermal effect of material itself, and refrigerating efficiency can significantly be saved the energy up to 5 ~ 10 times of traditional gas refrigeration; And the entropy density of solid-state magnetic refrigerating material is much larger than gas, and the refrigerator volume is less, does not need significantly gas compression campaign, and it is reliable to operate steadily; What is more important should technology not have refrigeration agents such as freonll-11, ammonia, can not pollute environment.Therefore, this technology has obtained widespread use in the low temperature field at present, but also is in the experimental exploring stage in the room temperature field, and the magnetothermal effect that how to improve room temperature magnetic refrigerating material at present is that this technology obtains to break through, and gets into the key of commercial applications.Obtain great magnetic entropy variation, mainly contain two kinds of approach: (1) external world applies the upfield; (2) magnetic refrigerating material itself has stronger magnetothermal effect.The former can solve through adopting superconducting magnet, but superconducting magnet makes the magnetic refrigerating system structure complicated especially, and cost is expensive, in practical application in industry, is difficult to promote.Therefore, comparatively feasible way is exactly the magnetic refrigerating material that exploitation has strong magnetothermal effect, becomes so that under the magnetic field that conventional permanent magnet provides, obtain higher magnetic entropy, to satisfy the refrigeration needs.
For the fast thin band material that coagulates, compare the as cast condition material of conventional electric arc furnace preparation, composition is more even, therefore need not the long-time homogenizing quench treatment of high temperature.How to formulate rational heat treatment technology, most important to improving its magnetic heating performance.
Summary of the invention
The purpose of this invention is to provide the magnetic heating performance that a kind of method improves the fast Ni-Mn of coagulating base magnetic refrigeration alloy thin band material, make it have big magnetic entropy and become, to improve the refrigeration capacity of material.
The present invention is a kind of to improve the method for the fast Ni-Mn of coagulating base magnetic refrigeration alloy thin band material property, it is characterized in that having following process and step: (a), confirm the thermal treatment temp of alloy thin band through heat analysis; Measure alloy thin band ordering temperature through thermoanalysis technology, thereby confirm that thermal treatment temp is the above a certain temperature of 30 ~ 50K of its ordering temperature; (b), Ni-Mn base alloy thin band is carried out the thermal treatment in composite pulse magnetic field; Thermal treatment is carried out under protective atmosphere; Its heating top temperature is 1173K; Employed pulsed magnetic field power parameter is: output voltage U=1500 ~ 2200V, and PW 26ms, effect frequency 0.3 ~ 1Hz, the magnetic induction density B of pulsed magnetic field is 0.5T ~ 1.5T.
A kind of thermal treatment unit that is used for the composite pulse magnetic field of aforesaid method of the present invention is characterized in that this device comprises: high-voltage pulse power source, magneticfield coil, heating installation, temperature controlling system, atmosphere protection system, magneticfield coil water cooling plant, silica tube, temperature-control heat couple, shielding gas tracheae, lead and alloy thin band; Alloy thin band is placed on silica tube bottom with the compacting of high temperature cotton, and silica tube is placed on the lap of constant temperature zone of equal magnetic section and the heating installation of magneticfield coil; The atmosphere protection system communicates with silica tube through the shielding gas tracheae, and temperature controlling system is through the temperature in the temperature-control heat couple control silica tube that inserts the silica tube bottom; High-voltage pulse power source is connected with magneticfield coil by lead.
The advantage of the inventive method:
The inventive method is simple to operate, when conventional thermal field is handled, imports pulsed magnetic field, forms Combined Processing.Compare conventional thermal treatment process, the low while of thermal treatment temp can effectively be improved the magnetic heating performance of material, improves the refrigeration capacity of material.
Description of drawings
Fig. 1 is a thermal treatment unit synoptic diagram under the pulsed magnetic field condition of the present invention.
Each digital code is represented as follows among the figure:
The 1-pulse power, 2-magneticfield coil, 3-heating installation, 4-temperature controlling system, 5-atmosphere protection system, 6-magneticfield coil water cooling plant, 7-silica tube, 8-temperature-control heat couple, 9-shielding gas tracheae, 10-lead, 11-alloy thin band.
Embodiment
The inventive method is further specified as follows through specific embodiment at present:
Embodiment 1 adopts single roller to get rid of the Ni of band technology preparation
48Mn
39In
13Alloy thin band, part strip alloy is implemented pulsed magnetic field Combined Processing under the conventional thermal field.Detailed process is following: at first measure its ordering temperature through thermoanalysis technology and be about 920K; During test; Under the Ar atmosphere protection, carry out the thermal treatment in composite pulse magnetic field, alloy thin band 11 is placed on the bottom of silica tube 7, use the high temperature cotton alloy thin band 11 compactings; Silica tube 7 links to each other with atmosphere securing system 5, and before silica tube 7 is put into heating installation 3 thermal treatments, and the induction part through tracheae 9 feeds shielding gas in silica tube 7; Ventilate after several minutes, again silica tube 7 put into the uniform temperature zone part of heating installation 3, and through temperature control thermopair 8 with temperature controlling system 4 with the homo(io)thermism in the thermal treatment silica tube 7 at 950K; Unbalanced pulse power supply then, the setting output voltage is 1800V, act on frequency this moment is 0.5Hz; Pulsewidth 26ms, the pulsed magnetic field size is 1.0T, behind the processing 20min; Shrend immediately obtains the alloy thin band after the thermal treatment.Example will other a part of strip alloy be carried out conventional thermal field processing as a comparison, with sample be sealed in carry out 960K anneal 20min in the silica tube under the Ar atmosphere protection after, shrend immediately.The result is illustrated in the magnetic entropy that records two kinds of different modes material treated under the magneticstrength of 2T and becomes and be respectively 41.4Jkg
-1K
-1And 30.1Jkg
-1K
-1, the magnetic entropy of material becomes the sex change of more conventional thermal treatment magnetic entropy and can improve about 37% under the Combined Processing.
Embodiment 2 adopts single roller to get rid of the Ni of band technology preparation
55Mn
19.6Ga
25.4Alloy thin band, part thin band material are implemented pulsed magnetic field Combined Processing under the conventional thermal field.Detailed process is following: at first measure its ordering temperature through thermoanalysis technology and be about 915K; During test; Under the Ar atmosphere protection, carry out the thermal treatment in composite pulse magnetic field, alloy thin band 11 is placed on the bottom of silica tube 7, use the high temperature cotton alloy thin band 11 compactings; Silica tube 7 links to each other with atmosphere securing system 5, and before silica tube 7 is put into heating installation 3 thermal treatments, and the induction part through tracheae 9 feeds shielding gas in silica tube 7; Ventilate after several minutes, again silica tube 7 put into the uniform temperature zone part of heating installation 3, and through temperature control thermopair 8 with temperature controlling system 4 with the homo(io)thermism in the thermal treatment silica tube 7 at 960K; Unbalanced pulse power supply then, the setting output voltage is 1800V, act on frequency this moment is 0.5Hz; Pulsewidth 26ms, the pulsed magnetic field size is 1.0T, behind the processing 20min; Shrend immediately obtains the alloy thin band after the thermal treatment.Example will other a part of strip alloy be carried out conventional thermal field processing as a comparison, with sample be sealed in carry out 960K anneal 20min in the silica tube under the Ar atmosphere protection after, shrend immediately.The result is illustrated in the magnetic entropy that records two kinds of different modes material treated under the magneticstrength of 2T and becomes and be respectively 38.2Jkg
-1K
-1And 27.5Jkg
-1K
-1, the magnetic entropy of material becomes the sex change of more conventional thermal treatment magnetic entropy and can improve about 38% under the Combined Processing.
Embodiment 3 adopts single roller to get rid of the Ni of band technology preparation
50Mn
37Sn
13Alloy, part thin band material are implemented pulsed magnetic field Combined Processing under the conventional thermal field.Detailed process is following: at first measure its ordering temperature through thermoanalysis technology and be about 925K, during test, under the Ar atmosphere protection, carry out the thermal treatment in composite pulse magnetic field; Alloy thin band 11 is placed on the bottom of silica tube 7, uses the high temperature cotton with alloy thin band 11 compactings, silica tube 7 links to each other with atmosphere securing system 5; And before silica tube 7 was put into heating installation 3 thermal treatments, the induction part through tracheae 9 fed shielding gas in silica tube 7, ventilate after several minutes; Again silica tube 7 is put into the uniform temperature zone part of heating installation 3, and through temperature control thermopair 8 with temperature controlling system 4 with the homo(io)thermism in the thermal treatment silica tube 7 at 955K, unbalanced pulse power supply then; The setting output voltage is 1800V, and act on frequency this moment is 0.5Hz, pulsewidth 26ms; The pulsed magnetic field size is 1.0T; After handling 20min, shrend immediately obtains the alloy thin band after the thermal treatment.Example will other a part of strip alloy be carried out conventional thermal field processing as a comparison, with sample be sealed in carry out 960K anneal 20min in the silica tube under the Ar atmosphere protection after, shrend immediately.The result is illustrated in the magnetic entropy that records two kinds of different modes material treated under the magneticstrength of 2T and becomes and be respectively 45.4Jkg
-1K
-1And 35.1Jkg
-1K
-1, the magnetic entropy of material becomes the sex change of more conventional thermal treatment magnetic entropy and can improve about 29% under the Combined Processing.
Fig. 1 is the thermal treatment unit in composite pulse of the present invention magnetic field, and this device comprises: high-voltage pulse power source 1, magneticfield coil 2, heating installation 3, temperature controlling system 4, atmosphere protection system 5, magneticfield coil water cooling plant 6, silica tube 7, temperature-control heat couple 8, shielding gas tracheae 9, lead 10 and alloy thin band 11; When appearance dress is placed on the bottom of silica tube 7 with alloy thin band 11, uses the high temperature cotton with alloy thin band 11 compactings, and NiCr-NiSi temperature-control heat couple 8 one ends are inserted to the silica tube bottom, and the other end is connected with temperature controlling system 4; Shielding gas tracheae 9 induction part one end inserts the silica tube bottom, and the other end is connected with atmosphere protection system 5, and shielding gas tracheae 9 outlet gas part one end feeds the silica tube bottom, and the other end feeds atmospheric environment; The silica tube 7 that will install sample in the treating processes is put into the wire spiral heating installation 3 that internal diameter is Ф 25mm, and heating installation 3 is placed in the magneticfield coil 2 that internal diameter is Ф 80mm, and magneticfield coil 2 is connected with high-voltage pulse power source 1 through lead 10, forms the loop line.
The preparation method of interalloy strip of the present invention:
Related alloy thin band is to adopt single roller to get rid of the preparation of band technology among the present invention.Its preparation technology is following: the used material purity of alloy all is higher than 99.9 wt.%, adopts vacuum arc fumace, under the high-purity argon gas protection, prepares cast alloy.The cast alloy that obtains is put into the silica tube that a lower end is rectangular nozzle (the about 0.5mm of nozzle width), and heat fused and being ejected into on the 10m/s LV copper roller rotating obtains alloy thin band once more.
Claims (2)
1. method that improves the fast Ni-Mn of coagulating base magnetic refrigeration alloy thin band material property is characterized in that having following process and step: (a), confirm the thermal treatment temp of alloy thin band through heat analysis; Measure alloy thin band ordering temperature through thermoanalysis technology, thereby confirm that thermal treatment temp is the above a certain temperature of 30 ~ 50K of its ordering temperature; (b), Ni-Mn base alloy thin band is carried out the thermal treatment in composite pulse magnetic field; Thermal treatment is carried out under protective atmosphere; Its heating top temperature is 1173K; Employed pulsed magnetic field power parameter is: output voltage U=1500 ~ 2200V, and PW 26ms, the effect frequency is 0.3 ~ 1Hz, the magnetic induction density B of pulsed magnetic field is 0.5T ~ 1.5T.
2. a thermal treatment unit that improves the composite pulse magnetic field of the method for coagulating Ni-Mn base magnetic refrigeration alloy thin band material property soon is characterized in that this device comprises: high-voltage pulse power source (1), magneticfield coil (2), heating installation (3), temperature controlling system (4), atmosphere protection system (5), magneticfield coil water cooling plant (6), silica tube (7), temperature-control heat couple (8), shielding gas tracheae (9), lead (10) and alloy thin band (11); Alloy thin band (11) is placed on silica tube (7) bottom with the cotton compacting of high temperature; Silica tube (7) is placed on the lap of constant temperature zone of equal magnetic section and the heating installation (3) of magneticfield coil (2); Atmosphere protection system (5) communicates with silica tube (7) through shielding gas tracheae (9); Temperature controlling system (4) is through the temperature in temperature-control heat couple (8) the control silica tube (7) that inserts silica tube (7) bottom; High-voltage pulse power source (1) is connected with magneticfield coil (2) by lead (10).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122441A (en) * | 2013-02-27 | 2013-05-29 | 上海大学 | Method for expanding magnetic refrigeration temperature area of Ni-Mn-based material |
| CN112375956A (en) * | 2020-11-13 | 2021-02-19 | 东北大学秦皇岛分校 | High-strength NiMnIn alloy and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717901A (en) * | 2009-12-22 | 2010-06-02 | 上海大学 | Process and device for amorphous thin ribbon heat treatment under the action of pulsed magnetic field |
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2012
- 2012-01-04 CN CN2012100002811A patent/CN102443749A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717901A (en) * | 2009-12-22 | 2010-06-02 | 上海大学 | Process and device for amorphous thin ribbon heat treatment under the action of pulsed magnetic field |
Non-Patent Citations (1)
| Title |
|---|
| 吴殿震等: "《磁制冷材料研究进展》", 《材料导报A :综述篇》, vol. 25, no. 8, 31 August 2011 (2011-08-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122441A (en) * | 2013-02-27 | 2013-05-29 | 上海大学 | Method for expanding magnetic refrigeration temperature area of Ni-Mn-based material |
| CN103122441B (en) * | 2013-02-27 | 2014-12-31 | 上海大学 | Method for expanding magnetic refrigeration temperature area of Ni-Mn-based material |
| CN112375956A (en) * | 2020-11-13 | 2021-02-19 | 东北大学秦皇岛分校 | High-strength NiMnIn alloy and preparation method and application thereof |
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Application publication date: 20120509 |