CN1552791A - Gadolinium series alloy magnetorefrigerant at atomosphere - Google Patents

Gadolinium series alloy magnetorefrigerant at atomosphere Download PDF

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CN1552791A
CN1552791A CNA2003101126920A CN200310112692A CN1552791A CN 1552791 A CN1552791 A CN 1552791A CN A2003101126920 A CNA2003101126920 A CN A2003101126920A CN 200310112692 A CN200310112692 A CN 200310112692A CN 1552791 A CN1552791 A CN 1552791A
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alloy
magnetic
series alloy
room temperature
magnetorefrigerant
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CN1246416C (en
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王敦辉
都有为
王嵩岭
韩志达
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Nanjing University
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Nanjing University
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Abstract

An ordinary-temp magnetic refrigerating medium is Gd1-xMx, where M is chosen from B, C, Al, Si, Fe, Co, Ni, Cr, Mn and Cu, and x=0.01-0.1. Its advantages are high Curie point, proper magnetic entropy variation, low cost and good chemical stability.

Description

The better gadolinium series alloy of one class room temperature magnetic refrigerating working
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 a few days ago high temperature magnetic refrigeration working substance is exactly that (it is after the match outer 1T's for rare earth metal gadolinium (Gd), the maximum magnetic entropy variable value is about 2.8J/kg.K). 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. and the while, they also had good chemical stability (Gd 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, its Curie temperature is apparently higher than Gd, and can in certain compositing range, (in 10%) keep and the similar magnetic entropy variate (see figure 1) of Gd, thereby reduce 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 0.98aCo 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
TC(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, the better gadolinium series alloy of class room temperature magnetic refrigerating working is characterized in that adopting Gd 1-xM xAlloy material, M=B, C, Al, Si, Fe, Co, Ni, Cr, the alloy that Mn or Cu form, X gets 0.01-0.10.
2, by the described gadolinium series alloy of claim 1 room temperature magnetic refrigerating working, it is characterized in that Gd 1-xFe x, Gd 1-xCo x, Gd 1-xNi xAlloy, X gets 0.02-0.10.
3,, it is characterized in that the non-metallic element alloy is Gd by the described gadolinium series alloy of claim 1 room temperature magnetic refrigerating working 1-xB x, Gd 1-xC x, X gets 0.07-0.10.
CN200310112692.0A 2003-12-19 2003-12-19 Gadolinium series alloy magnetorefrigerant at atomosphere Expired - Fee Related CN1246416C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104559944A (en) * 2014-12-24 2015-04-29 西安交通大学 Magnetic refrigeration material containing rare earth hydroxide and preparation method thereof
CN106544602A (en) * 2016-11-08 2017-03-29 重庆师范大学 Become gadolinium cobalt-based magnetic refrigeration composite material of platform and preparation method thereof 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
CN109182873A (en) * 2018-09-20 2019-01-11 中国科学院宁波材料技术与工程研究所 A kind of room temperature magnetic refrigerating web material and its preparation method and application

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104559944A (en) * 2014-12-24 2015-04-29 西安交通大学 Magnetic refrigeration material containing rare earth hydroxide and preparation method thereof
CN106544602A (en) * 2016-11-08 2017-03-29 重庆师范大学 Become gadolinium cobalt-based magnetic refrigeration composite material of platform and preparation method thereof 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
CN109182873A (en) * 2018-09-20 2019-01-11 中国科学院宁波材料技术与工程研究所 A kind of room temperature magnetic refrigerating web material and its preparation method and application
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

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