CN102828107A - Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials - Google Patents
Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials Download PDFInfo
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- CN102828107A CN102828107A CN2012103713251A CN201210371325A CN102828107A CN 102828107 A CN102828107 A CN 102828107A CN 2012103713251 A CN2012103713251 A CN 2012103713251A CN 201210371325 A CN201210371325 A CN 201210371325A CN 102828107 A CN102828107 A CN 102828107A
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- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
The invention relates to a preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials. According to the practical application requirement of a refrigerator, an alloy as a cast condition is processed into a flake sample with specified dimension and shape, the flake sample is placed into an induction heating device, argon is filled for shielding after vacuumizing, and appropriate frequency and power are selected for carrying out induction heating. Heat input is controlled, thus material temperature is maintained to be in a 1:13 phase forming temperature interval. After set time is up, heating is stopped, and the Ar gas is introduced for cooling, thus the 1:13 phase Ln(Fe,M)13 series magnetic refrigeration materials can be obtained. According to the invention, a self-heating manner is adopted for heating, the sample is uniformly heated, temperature and time are accurate and controllable, heating rate is high, energy conversion efficiency is high, and energy is saved; the obtained sample has higher mechanical properties, is unbreakable and has small grain size; and the preparation method and device disclosed by the invention are applicable to treatment on the flake sample, and the problem that the Ln(Fe,M)13 series magnetic refrigeration materials are difficult to be subjected to machining as the material is brittle after being formed into phase can be effectively solved.
Description
Technical field
The present invention relates to magnetic refrigerating material preparing technical field, particularly Ln (Fe, M)
13Be the preparation method and the device of magnetic refrigerating material.
Background technology
The magnetic Refrigeration Technique realizes refrigeration by means of the magneto-caloric effect of magneticsubstance, has energy-efficient, environmental protection and advantage such as reliable and stable, is a kind of green refrigeration technology, has very wide application prospect.
In existing magnetic refrigerating material, has NaZn
13The Ln of type phase structure (Fe, M)
13Be magnetic refrigerating material (being called for short the 1:13 phase), with its excellent magnetic heating performance, the prices of raw and semifnished materials are cheap in addition, and are nontoxic, and are acknowledged as the magnetic refrigerating material (CN101748326A) of at present tool practical value.
Yet, limitting owing to become machine-processed mutually, 1:13 is difficult to directly form from as cast condition mutually under conventional preparation process condition, often need alloy cast ingot at high temperature be carried out long-time vacuum heat treatment (CN1450190A).Even so, also be difficult to guarantee the uniform component property of 1:13 phase, thereby cause the inequality of material monolithic magnetic property.In addition, long heat treatment also can cause crystal grain to grow up unusually, causes material fragility to increase, and is difficult to machine-shaping, can only use with the particulate state form usually, and material use efficiency is low, and material in use is easy to efflorescence, and this is very unfavorable for practical application.
Though adopt melt-spun method+short time high temperature annealing can make the heat treatment time that obtains the 1:13 phase significantly shorten (CN100567543C),, be difficult to satisfy application demand owing to exist prepared material to be shortcomings such as thin ribbon shaped, easy efflorescence.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of quick cooling that realizes, simplify preparation section greatly, and solve preferably Ln (Fe, M)
13Be the magnetic refrigerating material Cheng Xianghou Ln that is difficult to carry out the mechanical workout problem owing to material becomes fragile (Fe, M)
13Be the preparation method and the device of magnetic refrigerating material.
Technical scheme of the present invention is: and a kind of preparation Ln (Fe, M)
13Be the method for magnetic refrigerating material, specifically comprise following technology: with thickness between 0.5 ~ 2mm sheet Ln (Fe, M)
13Be magnetic refrigerating material, adopt the pulse heating mode, vacuumize, when vacuum tightness reaches 2.0 * 10
-3Pa charges into argon shield, is 60Hz-500kHz in frequency, and power is 10kW-100kW, conduction time T
1=2-20s, power-off time T
2=1-8s heated 10-60 minute, logical argon gas cooling, obtain to have the 1:13 phase sheet Ln (Fe, M)
13It is magnetic refrigerating material.
Another object of the present invention provide above-mentioned preparation Ln (Fe, M)
13Be the device of magnetic refrigerating material, this device comprises induction heating device, sample chamber, vacuum unit and argon bottle;
Wherein, Said sample chamber places induction heating device; One end of said sample chamber with link to each other with said vacuum unit through vacuum valve; The other end links to each other with said argon bottle through the argon gas inflation valve, also is provided with tensimeter that is used to monitor gaseous tension in the sample chamber and the SV that is used for relief pressure on the said sample chamber.
Principle of the present invention is: the heat as cast condition Ln (FeM) that utilizes eddy current to produce
13Be magnetic refrigerating material,, make material temperature remain on 1:13 and coordinate in the phase temperature range through control heat input, reach the specified time after, stop heating, logical Ar air cooling but, thereby obtain the 1:13 phase structure.
The key character of this method is; Before induction heating; Can be according to the refrigerator requirement of actual application, cast alloy is processed into the laminar sample of specified dimension, shape, because thickness of sample is controlled within the penetration depth scope of surface action; Sample can be realized diathermanous formula heating, helps to guarantee into the homogeneity of phase.After heat-processed finished, because sample is laminar, feeding argon gas can cool off fast.In addition,, SV 6 is set for guaranteeing the security of sample chamber, when the sample chamber internal gas pressure surpasses set(ting)value, promptly automatic relief pressure.This setting is particularly conducive to the cooling link after heat-processed finishes, and helps guaranteeing gas flow property in the sample chamber, thereby strengthens cooling.
This patent can satisfy all kinds of Ln (Fe, M)
13Be the preparation demand of magnetic refrigerating material, wherein, Ln can be among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, the Yb etc. one or more, M can for Al, Co, Si, Mn, Ni etc. one or more.In addition, also can satisfy doping C, B all kinds of Ln (Fe, M)
13It is the preparation demand of magnetic refrigerating material.
Beneficial effect of the present invention:
(1) adopt the electromagnetic induction principle direct heating, belong to the autothermal heating, sample is heated evenly, and Heating temperature and heat-up time are accurately controlled, and it is fast to have a heat-up rate, effciency of energy transfer height, the distinguishing feature of save energy;
(2) become phase at the mutually critical warm area of 1:13, speed is fast, and the time is short, and sample purity is high, and in addition, grain-size is little, and the sample that obtains has than high-mechanical property, is difficult for broken;
(3) be particularly suitable for the processing of sheet sample, efficiently solve Ln (Fe, M)
13It is magnetic refrigerating material Cheng Xianghou is difficult to carry out mechanical workout owing to material becomes fragile problem.
Description of drawings
Fig. 1 for the present invention prepare Ln (Fe, M)
13It is the structural representation of the device of magnetic refrigerating material.
Fig. 2 magnetic refrigerating material LaFe
10.8Co
0.7Si
1.5As cast condition sample microtexture photo synoptic diagram.
Fig. 3 magnetic refrigerating material LaFe
10.8Co
0.7Si
1.5The microtexture photo synoptic diagram of sample behind the induction heating.
Fig. 4 magnetic refrigerating material LaFe
10.8Co
0.7Si
1.5C
0.2As cast condition sample microtexture photo synoptic diagram.
Fig. 5 magnetic refrigerating material LaFe
10.8Co
0.7Si
1.5C
0.2The microtexture photo synoptic diagram of sample behind the induction heating.
Fig. 6 magnetic refrigerating material LaFe
10.8Co
0.7Si
1.5C
0.2The microtexture photo synoptic diagram of sample behind the induction heating.
Among the figure:
1. induction heating device, 2. sample chamber, 3. sample, 4 argon gas inflation valves, 5. tensimeter, 6. SV, 7. vacuum valve, 8. vacuum unit, 9 argon bottles.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
As shown in Figure 1, for the present invention prepare Ln (Fe, M)
13It is the device of magnetic refrigerating material.This device comprises induction heating device 1, sample chamber 2, vacuum unit 8 and argon bottle 9;
Wherein, Sample chamber 2 places induction heating device 1; One end of sample chamber 2 with link to each other with vacuum unit 8 through vacuum valve 7; The other end links to each other with said argon bottle 9 through argon gas inflation valve 4, and the tensimeter 5 that is used to monitor gaseous tension in the sample chamber is provided with sample chamber 2 with the SV 6 that is used for relief pressure.
During use, sheet sample 3 is put into sample chamber 2, make the sample length direction parallel with the inducedmagnetic field direction.Open vacuum valve 7, vacuumize, when vacuum tightness reaches 2.0 * 10
-3During Pa, close vacuum valve 7, open argon gas valve 4, charge into argon gas, change, make the sample chamber internal gas pressure keep negative pressure state, close argon gas valve 4 then through tensimeter 5 detecting pressure.Set induction heating power and heating frequency, open induction heating device 1,, sample temperature is controlled in the one-tenth phase temperature range scope of 1:13 phase through the control energy input.After reaching the specified time, stop heating, charge into the argon gas cooling.To be cooled to room temperature, open the sample chamber, take out sample and get final product.
Embodiment 1:
Adopt LaFe
11.5Si
1.5Magnetic refrigerating material, thickness of sample 2mm adopts 300kHz * 10kW, adopts pulse heating mode (conduction time T
1=12s, power-off time T
2=2s), and heating 60min, then, logical argon gas cooling obtains the material LaFe with 1:13 phase
11.5Si
1.5Magnetic refrigerating material.
Embodiment 2:
Adopt LaFe
11.2Si
1.8Magnetic refrigerating material, thickness of sample 1mm adopts 500kHz * 15kW, adopts pulse heating mode (conduction time T
1=10s, power-off time T
2=2s), and heating 20min, then, logical argon gas cooling obtains the material LaFe with 1:13 phase
11.2Si
1.8Magnetic refrigerating material.
Embodiment 3:
Adopt La
0.8Pr
0.2Fe
11.5Si
1.5Magnetic refrigerating material, thickness of sample 2mm adopts 500Hz * 10kW, adopts pulse heating mode (conduction time T
1=12s, power-off time T
2=2s), and heating 35min, then, logical argon gas cooling obtains the material La with 1:13 phase
0.8Pr
0.2Fe
11.5Si
1.5Magnetic refrigerating material.
Embodiment 4:
Adopt La
0.9Ce
0.1Fe
10.8Co
0.7Si
1.5Magnetic refrigerating material, thickness of sample 0.5mm adopts 60Hz * 50kW, adopts pulse heating mode (conduction time T
1=20s, power-off time T
2=1s), and heating 55min, then, logical argon gas cooling obtains the material La with 1:13 phase
0.9Ce
0.1Fe
10.8Co
0.7Si
1.5Magnetic refrigerating material.
Embodiment 5:
Adopt LaFe
10.8Co
0.7Si
1.5C
0.2Magnetic refrigerating material, thickness of sample 0.5mm adopts 400kHz * 30kW, adopts pulse heating mode (conduction time T
1=8s, power-off time T
2=4s), and heating 45min, then, logical argon gas cooling obtains the material LaFe with 1:13 phase
10.8Co
0.7Si
1.5C
0.2Magnetic refrigerating material.
Embodiment 6
Adopt LaFe
10.8Co
0.7Si
1.5Magnetic refrigerating material, thickness of sample 2mm, its as-cast structure is as shown in Figure 2.Adopt 300kHz * 100kW, adopt pulse heating mode (conduction time T
1=2s, power-off time T
2=1s), and heating 20min, then, logical argon gas cooling obtains the material LaFe with 1:13 phase
10.8Co
0.7Si
1.5Magnetic refrigerating material, its microtexture is as shown in Figure 3.
Embodiment 7
Adopt LaFe
10.8Co
0.7Si
1.5C
0.2Magnetic refrigerating material, thickness of sample 2mm, its as-cast structure is as shown in Figure 4.Adopt 100kHz * 20kW, adopt pulse heating mode (conduction time T
1=10s, power-off time T
2=8s), and heating 30min, then, logical argon gas cooling obtains the material LaFe with 1:13 phase
10.8Co
0.7Si
1.5C
0.2Magnetic refrigerating material, its microtexture photo is as shown in Figure 5.
Adopt LaFe
10.8Co
0.7Si
1.5C
0.2Magnetic refrigerating material, thickness of sample 2mm adopts 1kHz * 60kW, adopts pulse heating mode (conduction time T
1=6s, power-off time T
2=2s), and heating 10min, then, logical argon gas cooling obtains the material LaFe with 1:13 phase
10.8Co
0.7Si
1.5C
0.2Magnetic refrigerating material, its microtexture photo is as shown in Figure 6.
Claims (2)
- The preparation Ln (Fe, M) 13Be the method for magnetic refrigerating material, it is characterized in that, specifically comprise following technology: with thickness between 0.5-2mm sheet Ln (Fe, M) 13Be magnetic refrigerating material, put into the sample chamber, adopt the pulse heating mode, vacuumize earlier, when vacuum tightness reaches 2.0 * 10 -3Pa charges into argon shield, is 60Hz-500kHz in frequency, and power is 10-100kW, conduction time T 1=2-20s, power-off time T 2=1-8s heated 10-60 minute, feed argon gas cooling again after, obtain to have the 1:13 phase sheet Ln (Fe, M) 13It is magnetic refrigerating material.
- One kind prepare the described Ln of claim 1 (Fe, M) 13Be the device of magnetic refrigerating material, it is characterized in that this device comprises induction heating device (1), sample chamber (2), vacuum unit (8) and argon bottle (9);Wherein, Said sample chamber (2) places induction heating device (1); One end of said sample chamber (2) with link to each other with said vacuum unit (8) through vacuum valve (7); The other end links to each other with said argon bottle (9) through argon gas inflation valve (4), also is provided with the SV (6) that is used to monitor the tensimeter (5) of the interior gaseous tension in sample chamber (2) and is used for relief pressure on said sample chamber (2).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210371325.1A CN102828107B (en) | 2012-09-28 | 2012-09-28 | Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials |
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|---|---|---|---|
| CN201210371325.1A CN102828107B (en) | 2012-09-28 | 2012-09-28 | Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials |
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|---|---|
| CN102828107A true CN102828107A (en) | 2012-12-19 |
| CN102828107B CN102828107B (en) | 2014-08-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467928A (en) * | 2018-03-02 | 2018-08-31 | 横店集团东磁股份有限公司 | A method of improving LaFeSi alloy magnetic refrigeration material magnetic entropy varied curve halfwidths |
| CN111072063A (en) * | 2018-10-22 | 2020-04-28 | 天津理工大学 | Perovskite rare earth metal oxide low-temperature magnetic refrigeration material and preparation method thereof |
| CN114058798A (en) * | 2021-11-26 | 2022-02-18 | 上海大学 | Flash annealing process and device for La-Fe-Si series alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748326A (en) * | 2009-10-19 | 2010-06-23 | 北京科技大学 | Preparation method of carbonic rare earth-ferrum, cobalt and silicon compound with NaZn1 structure |
| CN102179502A (en) * | 2011-04-26 | 2011-09-14 | 北京科技大学 | Device and method for preparing metal matrix composite by adopting high-pressure gas to assist infiltration |
-
2012
- 2012-09-28 CN CN201210371325.1A patent/CN102828107B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748326A (en) * | 2009-10-19 | 2010-06-23 | 北京科技大学 | Preparation method of carbonic rare earth-ferrum, cobalt and silicon compound with NaZn1 structure |
| CN102179502A (en) * | 2011-04-26 | 2011-09-14 | 北京科技大学 | Device and method for preparing metal matrix composite by adopting high-pressure gas to assist infiltration |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467928A (en) * | 2018-03-02 | 2018-08-31 | 横店集团东磁股份有限公司 | A method of improving LaFeSi alloy magnetic refrigeration material magnetic entropy varied curve halfwidths |
| CN108467928B (en) * | 2018-03-02 | 2020-01-10 | 横店集团东磁股份有限公司 | Method for improving half-height width of magnetic entropy variation curve of LaFeSi alloy magnetic refrigeration material |
| CN111072063A (en) * | 2018-10-22 | 2020-04-28 | 天津理工大学 | Perovskite rare earth metal oxide low-temperature magnetic refrigeration material and preparation method thereof |
| CN114058798A (en) * | 2021-11-26 | 2022-02-18 | 上海大学 | Flash annealing process and device for La-Fe-Si series alloy |
| CN114058798B (en) * | 2021-11-26 | 2023-07-14 | 上海大学 | Flash annealing process and device for La-Fe-Si alloy |
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| CN102828107B (en) | 2014-08-13 |
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Granted publication date: 20140813 Termination date: 20210928 |