CN101555563A - Gd*Si***Ge***Zn** and Gd*Si***Ge*Zn* alloy with giant magnetocaloric effect under low magnetic field - Google Patents
Gd*Si***Ge***Zn** and Gd*Si***Ge*Zn* alloy with giant magnetocaloric effect under low magnetic field Download PDFInfo
- Publication number
- CN101555563A CN101555563A CNA2009100503283A CN200910050328A CN101555563A CN 101555563 A CN101555563 A CN 101555563A CN A2009100503283 A CNA2009100503283 A CN A2009100503283A CN 200910050328 A CN200910050328 A CN 200910050328A CN 101555563 A CN101555563 A CN 101555563A
- Authority
- CN
- China
- Prior art keywords
- alloy
- magnetic field
- magnetic
- refrigeration
- gd5si
- 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.)
- Granted
Links
Landscapes
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to a Gd5Si(2-x)Ge(2-x)Zn2x alloy and a Gd5Si(2-y)Ge2Zny alloy with giant magnetocaloric effect under a low magnetic field, wherein 2x is more than or equal to 0.001 and less than or equal to 0.8 in the Gd5Si(2-x)Ge(2-x)Zn2x alloy; and y is more than or equal to 0.001 and less than or equal to 0.8 in the Gd5Si(2-y)Ge2Zny alloy. The invention, through alloying of high-conductive electron Zn element on a matrix Gd5Si2Ge2, leads the hybridigation degree of 4f electrons and conduction electrons to change, and induces quantivalency of elements in the alloy and spinwave energy of the alloy to change, so that first order phase transformation of the alloy can easily occur, the alloy is sensitive to response of an additional magnetic field change, a critical magnetic field causing the first order phase transformation of the alloy and magnetic lag generated in a phase change process are reduced, and the magnetocaloric effect of the alloy under the low magnetic field and the efficiency for magnetic refrigeration cycle process are improved.
Description
Technical field
The present invention relates to have under a kind of downfield the Gd of huge magnetothermal effect
5Si
2-xGe
2-xZn
2xAlloy improves room temperature magnetic refrigerating working material Gd under the downfield
5Si
2Ge
2Alloy magnetothermal effect and Curie temperature belong to the technical field of intermetallic compound magneticsubstance.
Background technology
In daily life, traditional refrigeration modes is seen everywhere, and is penetrated into all respects in our the live and work environment, and these refrigeration modes mainly contain three kinds, 1) refrigeration of utilizing the semiconductor heat electrical effect to produce; 2) refrigeration of utilizing the high pressure gas adiabatic expansion to produce; 3) refrigeration of utilizing the material phase transformation to produce.At present; there are a lot of drawbacks in the refrigerating working material of these refrigeration modes and application thereof; low as efficient, price is expensive (semiconductor refrigerating), the noise height; and refrigerating working material is bigger or the like to the pollution of environment; the refrigeration modes that particularly utilizes the gas adiabatic expansion to produce, the extensive application of freon refrigeration working material has produced serious destruction to the ozonosphere of preserving our planet; earth room temperature effect is increasingly sharpened, become international public hazards.In order to protect existent environment of people, United Nations put into effect Montreal Agreement in 2000
[1], the production that to the effect that limits freonll-11 and the use of this agreement.In this case, traditional refrigeration industry is faced with new challenges, and the development of efficient, low energy, pollution-free green environmental-protection refrigeration technology becomes more urgent.
The magnetic Refrigeration Technique is compared with traditional Refrigeration Technique, and having does not have destruction to ozonosphere, no Greenhouse effect, noise is low, advantages such as volume is little, reliability and efficient height enjoy the concern of countries in the world scientific and technological circle, are regarded as following new generation of green environmental protection type refrigeration technology.
It is two kinds of different refrigeration mechanisms that the magnetic refrigeration is compared with the tradition refrigeration.Magnetic refrigeration is by realizing refrigeration in the excitation of magnetic refrigerating working material under adding the action of a magnetic field, the demagnetization process, and traditional gas refrigeration is by realizing refrigeration in the compression of gas working medium material under the compressor effect, the expansion process.Magnetic refrigerating externally-applied magnetic field is equivalent to the compressor in the tradition refrigeration, and because of magnetic field itself possesses magnetic energy, the consumption rate compressor of energy is little in process of refrigeration.Therefore, from the eye of development, compare with traditional Refrigeration Technique, the magnetic Refrigeration Technique has vast potential for future development.
At present, in the research of magnetic refrigerating material, with other a few class magnetic refrigeration alloy phase ratios, Gd
5Si
2Ge
2The alloy nontoxicity, transformation temperature has high magnetothermal effect under Δ H=5T magnetic field near room temperature, be considered to a kind of good magnetic refrigerating working material, so this paper selects it as matrix alloy, but also there are some problems in this alloy in the practical application of following magnetic Refrigeration Technique:
1) obtaining huge magnetothermal effect, required outer to add magnetic field too high.Therefore, its research is also only limited to the research (Δ H=5T) of magnetothermal effect under the upfield, someone studies this alloy under Δ H=2T magnetic field, but the magnetothermal effect (14J/kgK) and the Curie temperature (273K) that obtain are lower, and both improve very difficult simultaneously.So the general result that obtains is: this alloy must adopt the superconducting magnet of upfield to realize in the magnetic Refrigeration Technique in future is used, in the present Ames Lab with Gd
5Si
2Ge
2Alloy is the externally-applied magnetic field of the magnetic refrigeration model machine of working material, also is superconducting magnet.The use of superconducting magnet causes the application cost of magnetic Refrigeration Technique to increase, and has limited Gd
5Si
2Ge
2The commercial applications process of alloy in the room temperature magnetic refrigerating technology.
2) Gd
5Si
2Ge
2The Curie temperature of alloy is also lower.For example under Δ H=5T magnetic field, the maximum isothermal magnetic entropy change of alloy of ingot once obtained 18.5J/kgK and 20.0J/kgK, and its Curie temperature is 276K, and the temperature requirement that uses from room temperature has gap.
3) Gd
5Si
2Ge
2Have bigger magnetic lag during alloy generation first-order phase transition, it can influence the maximum performance of cooling cycle system and refrigeration capacity.
Summary of the invention
The objective of the invention is method, improve Gd under the 1.5T downfield with micro-alloying
5Si
2Ge
2Alloy magnetothermal effect and Curie temperature have changed the application theory that the magnetic Refrigeration Technique relies on the upfield, make the alloy become possibility in cheap NdFeB magnetic field application.
Another order of the present invention passes through high conduction electronics Zn element to matrix Gd
5Si
2Ge
2Alloying Treatment, 4f electronics and conduction electron hydridization degree are changed, bring out the spin wave energy variation of the valency and the alloy of element in the alloy, the first-order phase transition of alloy is taken place easily, alloy is responsive to adding the changes of magnetic field response, reduce the critical magnetic lag that produces in magnetic field and the phase transition process of bringing out of alloy generation first-order phase transition, improve the magnetothermal effect of alloy and the efficient of magnetic refrigeration cycle process.
The objective of the invention is to realize by following technical proposals:
The Gd that has huge magnetothermal effect under a kind of downfield
5Si
2-xGe
2-xZn
2xAlloy is characterized in that this alloy has following chemical constitution formula: Gd
5Si
2-xGe
2-xZn
2x, 0.001≤2x≤0.8 wherein.
The Gd that has huge magnetothermal effect under a kind of downfield
5Si
2-yGe
2Zn
yAlloy is characterized in that this alloy has following chemical constitution formula: Gd
5Si
2-yGe
2Zn
y, 0.001≤y≤0.8 wherein.
The Gd that under the 1.5T downfield, has huge magnetothermal effect of the present invention
5Si
2-xGe
2-xZn
2xAnd Gd
5Si
2-yGe
2Zn
yThe preparation technology of alloy is as follows:
The purity of Gd, Si, Ge is respectively 99.99%, and the purity of Zn is 99.5%.Because the Zn fusing point is lower, vapour pressure is than higher, and easy scaling loss in fusion process is so when alloyage, scaling loss is calculated according to 10～80%.Adopt WK-II type non-consumable arc furnace to prepare alloy pig: when vacuum tightness reaches 2～4 * 10
-3During Pa, in stove, charge into the high-purity argon gas clean vacuum chambers once, continue to be evacuated to 2～4 * 10
-3During Pa, in stove, charge into high-purity argon gas once more and carry out melting, the electric current during melting between 150～020A, in order to guarantee the homogeneity of alloying constituent, the alloy pig melting 5 times of overturning repeatedly, the ingot casting of each melting is 10～25g.
The characteristics of the inventive method are as described below:
(1) in the inventive method, by to Gd
5Si
2Ge
2The alloy interpolation has high conduction electronics 3d
104s
2The Zn element of (valence electron number is 12) is to Gd
5Si
2Ge
2The Alloying Treatment of compound has improved the magnetothermal effect of alloy under downfield.
(2) covalent radius of Zn element and Si and Ge are almost suitable, and Zn enters Gd
5Si
2Ge
2In the lattice of alloy to (Si, Ge)-(Si, Ge) bond distance of covalent linkage can not produce too big destruction, helps the maintenance of crystalline structure in the alloy.
(3) add an amount of Zn element to Gd
5Si
2Ge
2The Alloying Treatment of compound, reduced the magneticanisotropy energy of alloy, the resistance of alloy neticdomain wall or magnetic moment motion in the first-order phase transition process is reduced, the critical magnetic field of bringing out of first-order phase transition reduces, reduce alloy magnetic lag phenomenon in phase transition process, helped improving the comprehensive magnetic heating performance of alloy.But in order to keep the generation of first-order phase transition in the alloy, the content that adds Zn in the alloy must be moderate.
(4) interpolation of an amount of Zn element makes that the spin wave energy increases by reactive force enhancing between the 4f-4f electronics in the interactional Gd atom of conduction electron ability, and the Gd atomic magnetic moment improves in the alloy; Reduce room temperature Gd
5Si
2Ge
2Monocline phase unit cell volume strengthens the interaction energy between the magnetic Gd atom, and the broadening refrigeration area has improved alloy primary magnetic phase change temperature and refrigeration capacity.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The technological process and the step of the embodiment of the invention are as described below:
At first with treated good high-purity raw Gd, Si, Ge with Gd
5Si
1.8Ge
2Zn
0.2Stoichiometry is prepared burden, and scaling loss is calculated according to 10%.Adopt WK-II type non-consumable arc furnace to prepare alloy pig: when vacuum tightness reaches 2.5 * 10
-3During Pa, in stove, charge into the high-purity argon gas clean vacuum chambers once, continue to be evacuated to 3 * 10
-3During Pa, in stove, charge into high-purity argon gas once more and carry out melting, the electric current during melting between 180A, in order to guarantee the homogeneity of alloying constituent, the alloy pig melting 5 times of overturning repeatedly, the ingot casting of each melting is 25g.Because the scaling loss of Zn, the alloy that melting obtains is Gd
5Si
1.9986Ge
2Zn
0.0014Under the 1.5T externally-applied magnetic field changed, the maximum isothermal magnetic entropy of alloy becomes brought up to 20.70J/kgK (y=0.0014) by 5.03J/kgK (y=0); Curie temperature is brought up to 280K (y=0.0014) by 276K (y=0) respectively; The magnetic refrigeration capacity is brought up to 96.14J/kg (y=0.0014) by 55.30J/kg (y=0) respectively, and magnetic heating performance is higher than the Gd that reports in the present document
5Si
2Ge
2And the performance of GdSiGeGa alloy of ingot under upfield (5T) (| Δ SM|=20.5J/kgK, Tc=276K), the comprehensive magnetic heating performance of alloy is outstanding.
Embodiment 2
At first with treated good high-purity raw Gd, Si, Ge with Gd
5Si
1.5Ge
2Zn
0.5Stoichiometry is prepared burden, and scaling loss is calculated according to 20%.Adopt WK-II type non-consumable arc furnace to prepare alloy pig: when vacuum tightness reaches 3.8 * 10
-3During Pa, in stove, charge into the high-purity argon gas clean vacuum chambers once, continue to be evacuated to 3.3 * 10
-3During Pa, in stove, charge into high-purity argon gas once more and carry out melting, the electric current during melting between 190A, in order to guarantee the homogeneity of alloying constituent, the alloy pig melting 5 times of overturning repeatedly, the ingot casting of each melting is 25g.Because the scaling loss of Zn, the alloy that melting obtains is Gd
5Si
1.987Ge
2Zn
0.013Under 1.5 T externally-applied magnetic fields changed, the maximum isothermal magnetic entropy of alloy becomes brought up to 10.70 J/kgK (y=0.013) by 5.03 J/kgK (y=0); Curie temperature is brought up to 285 K (y=0.013) by 276 K (y=0) respectively; The magnetic refrigeration capacity is brought up to 86.14 J/kg (y=0.013) by 55.30J/kg (y=0) respectively, and the comprehensive magnetic heating performance of alloy is good.
Embodiment 3
At first with treated good high-purity raw Gd, Si, Ge with Gd
5Si
1.8Ge
1.8Zn
0.4Stoichiometry is prepared burden, and scaling loss is calculated according to 5%.Adopt WK-II type non-consumable arc furnace to prepare alloy pig: when vacuum tightness reaches 2.8 * 10
-3During Pa, in stove, charge into the high-purity argon gas clean vacuum chambers once, continue to be evacuated to 3.4 * 10
-3During Pa, in stove, charge into high-purity argon gas once more and carry out melting, the electric current during melting between 150A, in order to guarantee the homogeneity of alloying constituent, the alloy pig melting 5 times of overturning repeatedly, the ingot casting of each melting is 25g.Because the scaling loss of Zn, the alloy that melting obtains is Gd
5Si
1.9995Ge
1.9995Zn
0.001Under 1.5 T externally-applied magnetic fields changed, the maximum isothermal magnetic entropy of alloy becomes brought up to 25.30 J/kgK (2x=0.001) by 5.03 J/kgK (x=0); Curie temperature is brought up to 284K (2x=0.001) by 276K (x=0) respectively; The magnetic refrigeration capacity is brought up to 90.10J/kg (2x=0.001) by 55.30J/kg (x=0) respectively, and magnetic heating performance is higher than the Gd that reports in the present document
5Si
2Ge
2And the performance of GdSiGeGa alloy of ingot under upfield (5T) (| Δ SM|=20.5J/kgK, Tc=276K), the comprehensive magnetic heating performance of alloy is outstanding.
Embodiment 4
At first with treated good high-purity raw Gd, Si, Ge with Gd
5Si
1.75Ge
1.75Zn
0.5Stoichiometry is prepared burden, and scaling loss is calculated according to 10%.Adopt WK-II type non-consumable arc furnace to prepare alloy pig: when vacuum tightness reaches 3.1 * 10
-3During Pa, in stove, charge into the high-purity argon gas clean vacuum chambers once, continue to be evacuated to 3.6 * 10
-3During Pa, in stove, charge into high-purity argon gas once more and carry out melting, the electric current during melting between 116A, in order to guarantee the homogeneity of alloying constituent, the alloy pig melting 5 times of overturning repeatedly, the ingot casting of each melting is 25g.Because the scaling loss of Zn, the alloy that melting obtains is Gd
5Si
1.99Ge
1.99Zn
0.02Under the 1.5T externally-applied magnetic field changed, the maximum isothermal magnetic entropy of alloy becomes brought up to 10.20J/kgK (2x=0.02) by 5.03J/kgK (x=0); Curie temperature is brought up to 284K (2x=0.02) by 276K (x=0) respectively; The magnetic refrigeration capacity is brought up to 101.35J/kg (2x=0.02) by 55.30J/kg (x=0) respectively, and the comprehensive magnetic heating performance of alloy is good.
Claims (2)
1. the Gd that has huge magnetothermal effect under the downfield
5Si
2-xGe
2-xZn
2xAlloy is characterized in that this alloy has following chemical constitution formula: Gd
5Si
2-xGe
2-xZn
2x, 0.001≤2x≤0.8 wherein.
2. the Gd that has huge magnetothermal effect under the downfield
5Si
2-yGe
2Zn
yAlloy is characterized in that this alloy has following chemical constitution formula: Gd
5Si
2-yGe
2Zn
y, 0.001≤y≤0.8 wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100503283A CN101555563B (en) | 2009-04-30 | 2009-04-30 | Gd5Si<2-x>Ge<2-x>Zn<2x> and Gd<5>Si<2-y>Ge2Zn<y> alloy with giant magnetocaloric effect under low magnetic field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100503283A CN101555563B (en) | 2009-04-30 | 2009-04-30 | Gd5Si<2-x>Ge<2-x>Zn<2x> and Gd<5>Si<2-y>Ge2Zn<y> alloy with giant magnetocaloric effect under low magnetic field |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101555563A true CN101555563A (en) | 2009-10-14 |
| CN101555563B CN101555563B (en) | 2011-08-31 |
Family
ID=41173840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100503283A Expired - Fee Related CN101555563B (en) | 2009-04-30 | 2009-04-30 | Gd5Si<2-x>Ge<2-x>Zn<2x> and Gd<5>Si<2-y>Ge2Zn<y> alloy with giant magnetocaloric effect under low magnetic field |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101555563B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576587A (en) * | 2009-08-18 | 2012-07-11 | 荷兰技术基金会 | Polycrystalline magnetocaloric materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465310C (en) * | 2005-12-23 | 2009-03-04 | 上海大学 | Method for preparing room temperature magnetic refrigerating working material Gd5Si2Ge2 |
-
2009
- 2009-04-30 CN CN2009100503283A patent/CN101555563B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576587A (en) * | 2009-08-18 | 2012-07-11 | 荷兰技术基金会 | Polycrystalline magnetocaloric materials |
| CN102576587B (en) * | 2009-08-18 | 2015-11-25 | 荷兰技术基金会 | Polycrystalline magnetocaloric materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101555563B (en) | 2011-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20130200293A1 (en) | La(fe,si)13-based multi-interstitial atom hydride magnetic refrigeration material with high temperature stability and large magnetic entropy change and preparation method thereof | |
| EP2545563A1 (en) | Magnetocaloric materials | |
| Shen et al. | Magnetocaloric effect in La1− xPrxFe10. 7Co0. 8Si1. 5 compounds near room temperature | |
| Zhang et al. | Effects of interstitial H and/or C atoms on the magnetic and magnetocaloric properties of La (Fe, Si) 13-based compounds | |
| CN102453466B (en) | Rare earth-copper-aluminum material for magnetic refrigeration and preparation method thereof | |
| CN103192069B (en) | Rare earth-copper-aluminum nano particle for low-temperature magnetic refrigeration and preparing method of rare earth-copper-aluminum nano particle | |
| CN103194654B (en) | Room-temperature magnetic refrigeration material and preparation process thereof | |
| CN102383018B (en) | Preparation method of rare earth-chrome-silicone-based magnetic refrigerating material | |
| CN101555563B (en) | Gd5Si<2-x>Ge<2-x>Zn<2x> and Gd<5>Si<2-y>Ge2Zn<y> alloy with giant magnetocaloric effect under low magnetic field | |
| CN102881394B (en) | La (Fe, Si) prepared by rare earth purification intermediate product 13base magnetic material, preparation method and purposes | |
| CN103668008B (en) | Thulium base metal glass, preparation method and application | |
| CN102465225B (en) | Magnetic refrigerant material, its preparation method and application | |
| CN106191616A (en) | A kind of magnetic phase transition alloy | |
| CN102703037B (en) | Rare earth-iron-silicon material for magnetic refrigeration, and preparation method and application thereof | |
| CN100567161C (en) | A kind of low-temperature large specific heat magnetic cold-storage material and preparation method thereof | |
| CN102703038B (en) | Gd-based magnetic refrigeration material and preparation method thereof | |
| CN101996720A (en) | Rare earth-gallium material for magnetic refrigeration and preparation method thereof | |
| CN103334043A (en) | Magnetic alloy serving as magnetic refrigeration material | |
| CN102864356B (en) | Rare earth-nickel material and preparation method and application thereof | |
| CN102162056B (en) | Rare earth tin-based low-temperature magnetic refrigeration material and preparation method thereof | |
| CN102978422B (en) | Preparation method and application of rare earth-nickel-silicon material with large magnetothermal effect | |
| CN1312706C (en) | Rare earth iron-base room-temp mangnetic refrigerant material and preparation method thereof | |
| CN108286004A (en) | A kind of rare earth-nickel-aluminum material, preparation method and applications | |
| CN103088246A (en) | Rare earth-Co-Si material used for low temperature magnetic refrigeration, and preparation method and use thereof | |
| CN109801767A (en) | A kind of neodymium cobalt-based magnetic refrigerating material and preparation method thereof with rotation magnetothermal effect |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110831 Termination date: 20170430 |