CN1246416C - Gadolinium series alloy magnetorefrigerant at atomosphere - Google Patents
Gadolinium series alloy magnetorefrigerant at atomosphere Download PDFInfo
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- CN1246416C CN1246416C CN200310112692.0A CN200310112692A CN1246416C CN 1246416 C CN1246416 C CN 1246416C CN 200310112692 A CN200310112692 A CN 200310112692A CN 1246416 C CN1246416 C CN 1246416C
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- Prior art keywords
- alloy
- series alloy
- magnetic
- series
- room temperature
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- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 150000000921 Gadolinium Chemical class 0.000 title claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000008207 working material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 abstract description 11
- 238000005057 refrigeration Methods 0.000 description 11
- 229910052732 germanium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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Abstract
The present invention relates to a series of better Gd series alloy magnetic refrigerating mediums at room temperature. A Gd1-xMx alloy material is adopted, wherein M is alloy formed from B, C, Al, Si, Fe, Co, Ni, Cr, Mn and Cu, and x is from 0.01 to 0.1; M is preferably Gd<1-x>Fe<x>, Gd<1-x>Co<x> or Gd<1-x>Ni<x> alloy, and X is preferably from 0.02 to 0.10. The curie temperature of the Gd series alloy magnetic refrigerating mediums of the present invention is obviously higher than that of Gd, the Gd series alloy magnetic refrigerating mediums can maintain a similar magnetic entropy change value to Cd, and thus, cost is reduced. Simultaneously, the Gd series alloy magnetic refrigerating mediums have good chemical stability.
Description
One, technical field
The present invention relates to a kind of room temperature magnetic refrigerating alloy, in particular for the Gd of room temperature magnetic refrigerating working material
1-xM
xThe room temperature magnetic refrigerating alloy of series.Gd
1-xM
xRefer to M=B, C, Al, Si, Fe, Co, Ni, Cr, Mn, Cu, Ga, Ge, series alloy.
Two, background technology
Magnetic refrigeration is because of its effect height, and volume is little, low noise, characteristics such as pollution-free and more and more be subjected to various countries scientist's attention.It might substitute traditional gas compression refrigeration modes.Wherein room temperature magnetic refrigerating becomes the focus of recent research because of its conspicuous society and economic benefit.Scientist's joint study of U.S. Ames National Laboratory and NASA has gone out first room temperature low field magnetic refrigeration model machine in the world at the bottom of calendar year 2001, and the research of room temperature magnetic refrigerating has been pushed to a new climax.We know that very important in a magnetic refrigerating system part is exactly a magnetic refrigeration working substance.The most frequently used high temperature magnetic refrigeration working substance is exactly rare earth metal gadolinium (Gd) (it is after the match outer 1T's, and the maximum magnetic entropy variable value is about 2.8J/kg.K) at present.The up-to-date room temperature permanent-magnet type refrigeration model machine of developing selects for use Gd as magnetic refrigeration working substance just.But Gd also has following some shortcoming as magnetic refrigeration working substance: we know that the optimal working temp scope of a magnetic refrigeration working substance is near its Curie temperature (1), the Curie temperature of Gd is near 293-295K (20 ℃), and this temperature is on the low side for the family expenses magnetic refrigerator; (2) Gd is as a kind of rare earth material, its easy oxidation, and chemical stability is bad; (3) Gd is a kind of comparatively expensive rare metal, selects for use to be magnetic refrigeration working substance, and cost is higher.Existing we have developed the novel better magnetic refrigeration working substance of performance of a class, are expected to replace Gd.
Three, summary of the invention
The objective of the invention is: provide a class better room temperature magnetic refrigerating working: Gd
1-xM
x(M=B, C, Al, Si, Fe, Co, Ni, Cr, Mn, Cu, Ga, Ge) series alloy and preparation method.Be expected to replace Gd, performance cost and technology all have obvious benefit.
The object of the present invention is achieved like this: room temperature magnetic refrigerating working: Gd
1-xM
x(M=B, C, Al, Si, Fe, Co, Ni, Cr, Mn, Cu, Ga, Ge) series alloy, the present invention forms Gd with a certain amount of other metals or the nonmetal and Gd mode by melting and fast quenching
1-xM
x(M=B, C, Al, Si, Fe, Co, Ni, Cr, Mn, Cu) series alloy.The mode of melting and fast quenching is preparation method commonly used.
After measuring result showed the formation alloy, its Curie temperature all was improved to some extent.And the measuring result that magnetic entropy becomes shows, after the match outer at 1T, and it is mostly suitable with gadolinium that the magnetic entropy of alloy becomes.We are exposed to this series alloy and Gd in the air together, and after three months, the oxidized and alloy in the surface of Gd keeps good metalluster (to remove Gd
1-xC
xFacile hydrolysis is outer).Result after the test shows the Gd degradation behind the surface oxidation and the performance of this series alloy remains unchanged.
Gd
1-xM
xThe Curie temperature of series alloy is apparently higher than Gd, and can (x=0.01-0.10) keep suitable with Gd in certain compositing range, even slightly high magnetic entropy variate, thereby reduced cost.They also have good chemical stability (Gd simultaneously
1-xC
xOutward).These characteristics make this series alloy be expected to become the better room temperature magnetic refrigerating working of a class performance.
With Gd
1-xFe
xSeries alloy is an example, and its Curie temperature is apparently higher than Gd, and can (in 10%) keep and the similar magnetic entropy variate (see figure 1) of Gd in certain compositing range, thereby has reduced cost.They also have good chemical stability (see figure 2) simultaneously.In other series alloys of our research, remove Gd
1-xC
xOutside the facile hydrolysis, also all have and Gd
1-xFe
xThe advantageous property that series alloy is similar.These characteristics make this series alloy be expected to become the better room temperature magnetic refrigerating working of a class performance.
Four, description of drawings
Fig. 1 is Gd of the present invention
1-xFe
xThe measuring result performance curve that becomes of magnetic entropy
Fig. 2 is Gd of the present invention and Gd
1-xFe
xThe outward appearance photo of alloy
Five, embodiment
Embodiment:
Gd
1-xM
x(M=Al, Si, Fe, Co, Ni, Ga, Ge) embodiment of series alloy is with Gd
1-xFe
xAs its typical case representative: Gd wherein
1-xAl
x, Gd
1-xSi
x, Gd
1-xGa
x, Gd
1-xGe
x, Gd
1-xFe
x, Gd
1-xCo
x, Gd
1-xNi
xThe measuring result that magnetic entropy becomes shows:
Gd
1-xCo
x, Gd
1-xNi
xWith Gd
1-xFe
xSimilar, and Gd
1-xAl
x, Gd
1-xSi
x, Gd
1-xGa
x, Gd
1-xGe
x, Gd
1-xMn
x, Gd
1-xCu
x, performance slightly be inferior to Gd
1-xFe
x(meter that magnetic entropy becomes is understood about reduction 10-20%).Above-mentioned alloy all can form sosoloid.The all desirable 0.01-0.10 of X.Do not have remarkable difference when X gets two values of 0.09-0.098,0.04-0.05 in experiment, the meter that magnetic entropy becomes understands that performance reduces about 10%.And Gd especially
1-xFe
x, Gd
1-xCo
x, Gd
1-xNi
xNo marked difference, it is better that X gets 0.02-0.10.
Gd in the non-metallic element
1-xB
x, Gd
1-xC
xPreparation technology is identical with metal, and its magnetic entropy variate and Gd are similar even be better than Gd.It is better that X gets 0.07-0.10.
The measuring result of part embodiment is as follows: (T
C: Curie temperature; | Δ S
M| maximum magnetic entropy variable.)
| Gd | Gd 0.98Co 0.02 | Gd 0.98Ni 0.02 | Gd 0.98Fe 0.02 | Gd 0.94Fe 0.06 | Gd 0.90Fe 0.10 | Gd 0.93B 0.07 | |
| T C(K) | 294 | 301 | 300 | 298 | 300 | 301 | 298 |
| |ΔS M| (J/kg.K) | 2.8 | 2.6 | 2.7 | 2.8 | 2.8 | 2.7 | 2.9 |
| Gd 0.93C 0.07 | Gd 0.97Si 0.03 | Gd 0.98Ga 0.02 | Gd 0.98Ge 0.02 | Gd 0.99Cu 0.01 | Gd 0.98Mn 0.02 | |
| T C(K) | 300 | 298 | 302 | 302 | 298 | 300 |
| |ΔS M| (J/kg.K) | 2.8 | 2.7 | 2.5 | 2.6 | 2.4 | 2.5 |
Claims (3)
1, a class gadolinium series alloy room temperature magnetic refrigerating working material is characterized in that adopting Gd
1-xM
xAlloy material, M=B, C, Al, Si, Fe, Co, Ni, Cr, Mn or Cu form alloy by itself and Gd, and X gets 0.01-0.10.
2,, it is characterized in that alloy material is Gd by the described gadolinium series alloy of claim 1 room temperature magnetic refrigerating working material
1-xFe
x, Gd
1-xCo
xOr Gd
1-xNi
xAlloy, X gets 0.02-0.10.
3,, it is characterized in that alloy material is Gd by the described gadolinium series alloy of claim 1 room temperature magnetic refrigerating working material
1-xB
xOr Gd
1-xC
x, X gets 0.07-0.10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200310112692.0A CN1246416C (en) | 2003-12-19 | 2003-12-19 | Gadolinium series alloy magnetorefrigerant at atomosphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200310112692.0A CN1246416C (en) | 2003-12-19 | 2003-12-19 | Gadolinium series alloy magnetorefrigerant at atomosphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1552791A CN1552791A (en) | 2004-12-08 |
| CN1246416C true CN1246416C (en) | 2006-03-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200310112692.0A Expired - Fee Related CN1246416C (en) | 2003-12-19 | 2003-12-19 | Gadolinium series alloy magnetorefrigerant at atomosphere |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559944B (en) * | 2014-12-24 | 2018-04-17 | 西安交通大学 | A kind of magnetic refrigerating material and preparation method containing rare-earth hydroxide |
| CN106544602B (en) * | 2016-11-08 | 2018-07-27 | 重庆师范大学 | Become the gadolinium cobalt-based magnetic refrigeration composite material and preparation method thereof of platform with magnetic entropy |
| CN106935348A (en) * | 2017-02-22 | 2017-07-07 | 广东省稀有金属研究所 | A kind of Gd basal cells temperature magnetic refrigerating material and preparation method thereof |
| CN109182873B (en) * | 2018-09-20 | 2020-04-21 | 中国科学院宁波材料技术与工程研究所 | Room-temperature magnetic refrigeration silk screen material and preparation method and application thereof |
-
2003
- 2003-12-19 CN CN200310112692.0A patent/CN1246416C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1552791A (en) | 2004-12-08 |
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