CN101413093A - Block gadolinium-based composite amorphous magnetic cooling material and preparation thereof - Google Patents

Block gadolinium-based composite amorphous magnetic cooling material and preparation thereof Download PDF

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CN101413093A
CN101413093A CNA2008100447880A CN200810044788A CN101413093A CN 101413093 A CN101413093 A CN 101413093A CN A2008100447880 A CNA2008100447880 A CN A2008100447880A CN 200810044788 A CN200810044788 A CN 200810044788A CN 101413093 A CN101413093 A CN 101413093A
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gadolinium
based composite
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amorphous magnetic
magnetic
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祖小涛
付浩
余华军
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

The invention provides a massive gadolinium-based composite amorphous magnetic frigorific material and a preparation method thereof, which belong to the field of metal material technology. The massive gadolinium-based composite amorphous magnetic frigorific material has a chemical general formula: Gd60Co26Al14-xGex, wherein x is more than 0 and less than or equal to 10. The main material is a massive amorphous alloy body formed through fusing Gd, Co, Al and Ge and also comprises a Gd5Ge3 crystal primary phase. In a magnetic field of between 0 and 5T, Curie temperature converted from a high-temperature paramagnetic state to a low-temperature ferromagnetic state is between 100 and 200 K; the largest magnetic entropy change of the Curie temperature is more than 7 J/kgK; and the relative refrigerating output is more than 700 J/kg. The preparation method comprises the following steps: firstly, ingredients are subjected to electric arc melting to obtain a Gd60Co26Al14-xGex master alloy; and secondly, a suction casting mould is obtained by a copper mould suction casting method. The massive gadolinium-based composite amorphous magnetic frigorific material has continuous and adjustable Curie temperature, equivalent magnetic entropy change with rare-earth gadolinium, and higher relative refrigerating output which is at least 35 percent higher than that of gadolinium, and is an ideal magnetic frigorific material. The method has the advantages of simple process, easy control of material structure and the like.

Description

A kind of block gadolinium-based composite amorphous magnetic cooling material and preparation method thereof
Technical field
The invention belongs to the metallic substance technical field, relate to magnetic composite amorphous alloy material, especially gadolinium-based composite amorphous magnetic cooling material and preparation method thereof.
Technical background
Room temperature magnetic refrigerating has advantages such as considerable energy saving and green, and its power consumption has only 1/2-1/5 of traditional gas refrigeration, will become the substitute technology of traditional gas refrigeration that current consumption ranked first to a great extent in all industries.Because huge magnetothermal effect (giant magnetocaloric effect, GMEC) discovery of alloy can replace superconducting magnet generation outfield with permanent magnet, and manufacture difficulty and cost reduce greatly.At present, the U.S. (Ames Lab and aerospace company) and Japan (Kyushu Electric Power and Toshiba) have all developed the room temperature magnetic refrigerating model machine that uses permanent magnet, and this makes room temperature magnetic refrigerating step major step to commercial applications.The magnetic refrigeration has enormous and latent market at civil area, as air-conditioning, refrigerator, liquefaction of gases etc.; The magnetic refrigeration also has wide practical use in military field: this field requires the in light weight of low-temperature receiver, vibration and noise are little, working temperature and cold scope are wide, magnetic refrigerator satisfies these requirements fully, for example can be applied to the deuterium ball of freezing laser target shooting, the deuterium and the tritium ball of nucleosynthesis, the cooling of infrared components, the cooling of magnetic window system, the cooling of torpedo recovery vessel superconducting magnet etc.China is refrigeration industry big country, also is to use consumption big country, and the research and development of magnetic Refrigeration Technique have significant important meaning.
In magnetic refrigerating magnet technology, magnetic cooling material technology and hot swapping three big gordian techniquies, magnetic cooling material (magnetic working medium) is the technology of core the most.The magnetic heating performance of magnetic cooling material mainly comprises magnetic entropy change, relative refrigerating duty, adiabatic temperature variation, specific heat, thermal conductivity etc.Wherein, magnetic entropy becomes, refrigerating duty, adiabatic temperature variation are the signs of magnetic cooling material magnetothermal effect relatively, be easy to accurate mensuration because of magnetic entropy becomes than the adiabatic temperature variation, thereby people are accustomed to more adopting magnetic entropy change and the covert relative refrigerating duty of closing of magnetic entropy to characterize the magnetothermal effect of magnetic cooling material.Therefore, seek have great magnetic entropy variation and greatly the magnetic cooling material of relative refrigerating duty become the emphasis of research.
The rare earth metal gadolinium is the magnetic cooling material with good magnetic heating performance always, and up to 1997, the Pecharsky of U.S.'s Ames Lab etc. found Gd 5(Si xGe 1-x) 4Alloy (US5743095) has huge magnetothermal effect, becomes about 2 times that reach the metal gadolinium near the magnetic entropy the room temperature.
The crystal alloy with huge magnetothermal effect that has been found that at present has a common ground aspect phase transformation, promptly alloy all has primary magnetic phase change, as Gd 5Si 2Ge 2The first-order phase transition of monoclinic crystal structure to the orthorhombic body structure takes place in alloy when generation high temperature paramagnetic attitude changes to the low temperature ferrimagnetic state; MnAs 1-xSb xAlloy is when cooling, and crystalline structure changes six side NiAs type structures into from quadrature MnP type crystal structure when the paramagnetic-ferromagnetic phase transformation takes place at the Curie temperature place; La (Fe, M) 13Compound also has primary magnetic phase change in the paramagnetic-ferromagnetic transition process, promptly itinerant electron becomes magnetic transition, and this phase transformation shows as the huge lattice negative expansion in Curie temperature place (Δ V/V ≈ 0.02) on macroscopic view.Above characteristics show that this class alloy has one of major reason of huge magnetothermal effect, are exactly alloy when magnetic taking place changing mutually, and first-order phase transition has taken place, and the contribution of first-order phase transition latent heat just makes alloy have huge magnetothermal effect.On the other hand, because first-order phase transition inherent retarding characteristic, these materials are in magnetic history, and the energy that magnetic field provides can not all be converted into magnetothermal effect, promptly produces so-called magnetic hysteresis loss.This is the greatest problem that such crystalline state magnetic cooling material with first-order phase transition faces.In addition, these materials belong to intermetallic compound mostly, have room temperature fragility, and be difficult to machine-shaping, and in use experience remagnetization, contraction-expansion repeatedly, the easy efflorescence of material was lost efficacy.In addition, the existence of toxic elements A s in MnFePAs, the MnAs alloy; The solidity to corrosion of LaFeSi alloy is poor.The magnetic refrigeration model machine that Here it is has developed does not all use the partly cause of above alloy as working medium.Therefore, the crystalline state magnetic cooling material has the advantage of great magnetic entropy variation, but also has some significant disadvantages.Therefore, should research and develop novel method, the novel process that overcomes these shortcomings on the one hand, also need to continue to develop other novel magnetic cooling material on the other hand.
Table 1. can be used as the bulk amorphous alloys of magnetic cooling candidate working medium
Figure A200810044788D00041
*Annotate: all refer to the maximum magnetic entropy variable value of alloy under 0～5T changes of magnetic field.
Table 1 is listed the composite amorphous alloy candidate of the bulk working medium of research and development recently.For the research of crystalline state magnetic cooling material, the magnetothermal effect of bulk amorphous alloys research is in the ascendant.Composite amorphous alloy itself has high resistivity, corrosion-resistant, excellent advantages such as mechanical property, is fit to very much the environment for use of magnetic refrigeration working substance, thereby causes investigator's concern.
Summary of the invention
The object of the present invention is to provide a kind of gadolinium-based composite amorphous magnetic cooling material and preparation method thereof, substitute part aluminium by germanium, at Gd 60Co 26Al 14-xGe xObtaining with large block amorphous in the alloy is matrix, contains the matrix material of small amount of crystal primary phase, improves the Curie temperature of alloy on the one hand, keeps bigger magnetothermal effect of alloy and relative refrigerating duty on the other hand; In addition, amorphous and crystalline composite structure make material have excellent mechanical property.
The objective of the invention is to be achieved through the following technical solutions:
A kind of block gadolinium-based composite amorphous magnetic cooling material, its chemical general formula are Gd 60Co 26Al 14-xGe x, in the formula, 0＜x≤10.The bulk amorphous alloys body of its material of main part for being formed by Gd, Co, Al and Ge fusion, other contains Gd 5Ge 3The crystal primary phase.Under the magnetic field environment of 0～5T, be 100～200K to the Curie temperature that the low temperature ferrimagnetic state changes by high temperature paramagnetic attitude; The maximum magnetic entropy variable of Curie point is greater than 7J/kgK, and refrigerating duty is greater than 700J/kg relatively.
A kind of preparation method of block gadolinium-based composite amorphous magnetic cooling material may further comprise the steps:
Step 1 batching
Press Gd 60Co 26Al 14-xGe xThe chemical formula batching; Wherein the purity of Gd, Co, Al and Ge raw material is more than 99.9% (mass percent);
Step 2 melting
Raw material melting to raw material under the high-purity argon gas protection that step 1 is prepared melts fully, obtains mother alloy;
Step 3 is inhaled and is cast type
The mother alloy of step 2 gained is put into suction cast copper crucible, inhale as required and cast specified shape, obtain final block gadolinium-based composite amorphous magnetic cooling material after the cooling.
The fusion process of step 2 can adopt non-consumable arc furnace, and detailed process is: the raw material that step 1 is prepared is put into non-consumable arc furnace earlier, is evacuated to 3 * 10 -5More than the torr; Clean 1～2 time with the high-purity argon gas purging method then; The melting 4～6 times of under the protection of 1 atmospheric high-purity argon gas, overturning repeatedly at last, smelting temperature with the raw material fusing till.
The shape of inhaling the block gadolinium-based composite amorphous magnetic cooling material cast type described in the step 3 can be shapes such as cylindric, flat column, laminar or strip.
It is that water jacketed copper crucible is forced cooling that step 3 is inhaled the described type of cooling of casting in the type.Need to prove: crucible diameter is more little, and speed of cooling is fast more, the contained Gd of block gadolinium-based composite amorphous magnetic cooling material of final gained 5Ge 3The crystal primary phase is few more; Crucible diameter is big more, and speed of cooling is slow more, the contained Gd of block gadolinium-based composite amorphous magnetic cooling material of final gained 5Ge 3The crystal primary phase is many more.
Block gadolinium-based composite amorphous magnetic cooling material provided by the present invention, i.e. Gd 60Co 26Al 14-xGe x(0＜x≤10) alloy, the Curie temperature of this alloy is adjustable continuously in 100～200K scope, and near the magnetic entropy Curie temperature becomes with the magnetic entropy of metal gadolinium in a disguised form works as, and the relative refrigerating duty of alloy is greater than existing crystalline state and amorphous magnetic cooling material.In addition, because block gadolinium-based composite amorphous magnetic cooling material provided by the present invention is that to contain the main body that crystal goes out looks be the matrix material of amorphous, has more excellent mechanical property than single non-crystalline material.
The preparation method of the compound magnetic cooling material of gadolinium-based bulk amorphous provided by the invention has advantages such as preparation technology is simple, material microstructure easy control of structure system.
Description of drawings
Fig. 1 is the Gd of the embodiment of the invention 1 preparation 60Co 26Al 10Ge 4The X-ray diffraction spectrum of alloy;
Fig. 2 is the Gd of the embodiment of the invention 1 preparation 60Co 26Al 10Ge 4The differential thermal analysis curve of alloy;
Fig. 3 is the Gd of the embodiment of the invention 1 preparation 60Co 26Al 10Ge 4The thermomagnetization curve of alloy under 200Oe magnetic field;
Fig. 4 is the Gd of the embodiment of the invention 1 preparation 60Co 26Al 10Ge 4Near the isothermal magnetization curve of alloy Curie temperature;
Fig. 5 is the Gd of the embodiment of the invention 1 preparation 60Co 26Al 10Ge 4The magnetic entropy varied curve of alloy;
Fig. 6 is the Gd of the embodiment of the invention 2 preparations 60Co 26Al 6Ge 8The X-ray diffraction spectrum of alloy;
Fig. 7 is the Gd of the embodiment of the invention 2 preparations 60Co 26Al 6Ge 8The differential thermal analysis curve of alloy;
Fig. 8 is the Gd of the embodiment of the invention 2 preparations 60Co 26Al 6Ge 8The thermomagnetization curve of alloy under 200Oe magnetic field;
Fig. 9 is the Gd of the embodiment of the invention 2 preparations 60Co 26Al 6Ge 8Near the isothermal magnetization curve of alloy Curie temperature;
Figure 10 is the Gd of the embodiment of the invention 2 preparations 60Co 26Al 6Ge 8The magnetic entropy varied curve of alloy;
Embodiment
Embodiment 1 Gd 60Co 26Al 10Ge 4(x=4) preparation of alloy and magnetic heating performance
Purity is pressed Gd greater than gadolinium, cobalt, aluminium, the germanium raw material of 99.9% (massfraction) 60Co 26Al 10Ge 4The chemical formula weighing is put into non-consumable arc furnace with the raw material for preparing, and is evacuated to 3 * 10 -5More than the torr; After high-purity argon gas purging method cleaning 1～2 time, the melting of overturning repeatedly under 1 atmospheric high-purity argon gas protection is made mother alloy 4～6 times; To put into by the melted mother alloy of above-mentioned steps and inhale the cast copper crucible, to cast directly be 3 millimeters cylindrical sample with inhaling behind the alloy melting.Metallographicobservation shows that the microstructure characteristic of alloy is is matrix with large block amorphous, contains a small amount of primary crystal phase.X-ray diffraction analysis shows that alloy mainly is made up of amorphous phase, also has a spot of Gd in addition 5Ge 3The crystal phase.Differential scanning calorimetry shows that the second-order transition temperature of alloy is 296 degrees centigrade, and the initial crystallization temperature of alloy is 322 degrees centigrade.Adopt superconducting quantum magnetometer to measure the thermomagnetization curve of alloy, determine that from thermomagnetization curve the Curie temperature of alloy is 140K (133 degrees centigrade).Adopt superconducting quantum magnetometer to measure near the isothermal magnetization curve of alloy Curie temperature, calculate alloy under 0～5T magnetic field according to Maxwell equation, magnetic entropy at the 145K place becomes 8.2J/kgK, and the relative refrigerating duty (=maximum magnetic entropy variable * halfwidth) of calculating alloy according to the magnetic entropy varied curve is 754J/kg, and this relative refrigerating duty (517J/kg) than rare earth metal gadolinium exceeds 46%.
Embodiment 2 Gd 60Co 26Al 6Ge 8(x=8) preparation of alloy and magnetic heating performance
Purity is pressed Gd greater than gadolinium, cobalt, aluminium, the germanium raw material of 99.9% (massfraction) 60Co 26Al 6Ge 8The chemical formula weighing is put into non-consumable arc furnace with the raw material for preparing, and is evacuated to 3 * 10 -5More than the torr; After high-purity argon gas purging method cleaning 1～2 time, the melting of overturning repeatedly under 1 atmospheric high-purity argon gas protection is made mother alloy 4～6 times; To put into by the melted mother alloy of above-mentioned steps and inhale the cast copper crucible, to cast directly be 3 millimeters cylindrical sample with inhaling behind the alloy melting.Metallographicobservation shows that the microstructure characteristic of alloy is is matrix with large block amorphous, contains a small amount of primary crystal phase.X-ray diffraction analysis shows that alloy mainly is made up of amorphous phase, also has a spot of Gd in addition 5Ge 3With other unknown crystal mutually.Differential scanning calorimetry shows that the second-order transition temperature of alloy is 292 degrees centigrade, and the initial crystallization temperature of alloy is 320 degrees centigrade.Adopt superconducting quantum magnetometer to measure the thermomagnetization curve of alloy, determine that from thermomagnetization curve the Curie temperature of alloy is 155K (118 degrees centigrade).Adopt superconducting quantum magnetometer to measure near the isothermal magnetization curve of alloy Curie temperature, calculate alloy under 0～5T magnetic field according to Maxwell equation, magnetic entropy at the 155K place becomes 7.6J/kgK, and the relative refrigerating duty (=maximum magnetic entropy variable * halfwidth) of calculating alloy according to the magnetic entropy varied curve is 768J/kg, and this relative refrigerating duty (517J/kg) than rare earth metal gadolinium exceeds 49%.
The present invention has prepared the compound magnetic cooling material of series of rare earth gadolinium-based bulk amorphous, and its associated magnetic thermal characteristics is listed in table 2.
Table 2 Gd 60Co 26Al 14-xGe xThe magnetic heating performance of (0＜x≤10) alloy
Figure A200810044788D00071

Claims (8)

1, a kind of block gadolinium-based composite amorphous magnetic cooling material, its chemical general formula are Gd 60Co 26Al 14-xGe x, in the formula, 0＜x≤10.
2, block gadolinium-based composite amorphous magnetic cooling material according to claim 1 is characterized in that, the bulk amorphous alloys body of the material of main part of described block gadolinium-based composite amorphous magnetic cooling material for forming by Gd, Co, Al and Ge fusion, and other contains Gd 5Ge 3The crystal primary phase.
3, block gadolinium-based composite amorphous magnetic cooling material according to claim 2, it is characterized in that described block gadolinium-based composite amorphous magnetic cooling material is 100～200K by high temperature paramagnetic attitude to the Curie temperature that the low temperature ferrimagnetic state changes under the magnetic field environment of 0～5T; The maximum magnetic entropy variable of Curie point is greater than 7J/kgK, and refrigerating duty is greater than 700J/kg relatively.
4, the preparation method of block gadolinium-based composite amorphous magnetic cooling material according to claim 1 may further comprise the steps:
Step 1 batching
Press Gd 60Co 26Al 14-xGe xThe chemical formula batching; Wherein the purity of Gd, Co, Al and Ge raw material is more than 99.9% (mass percent);
Step 2 melting
Raw material melting to raw material under the high-purity argon gas protection that step 1 is prepared melts fully, obtains mother alloy;
Step 3 is inhaled and is cast type
The mother alloy of step 2 gained is put into suction cast copper crucible, inhale as required and cast specified shape, obtain final block gadolinium-based composite amorphous magnetic cooling material after the cooling.
5, the preparation method of block gadolinium-based composite amorphous magnetic cooling material according to claim 4, it is characterized in that, the fusion process of step 2 adopts non-consumable arc furnace, and detailed process is: the raw material that step 1 is prepared is put into non-consumable arc furnace earlier, is evacuated to 3 * 10 -5More than the torr; Clean 1～2 time with the high-purity argon gas purging method then; The melting 4～6 times of under the protection of 1 atmospheric high-purity argon gas, overturning repeatedly at last, smelting temperature with the raw material fusing till.
6, the preparation method of block gadolinium-based composite amorphous magnetic cooling material according to claim 4 is characterized in that, the shape of inhaling the block gadolinium-based composite amorphous magnetic cooling material cast type described in the step 3 be cylindric,, flat column, laminar or strip.
7, the preparation method of block gadolinium-based composite amorphous magnetic cooling material according to claim 4 is characterized in that, it is that water jacketed copper crucible is forced cooling that step 3 is inhaled the described type of cooling of casting in the type.
8, the preparation method of block gadolinium-based composite amorphous magnetic cooling material according to claim 6 is characterized in that, the shape of inhaling the block gadolinium-based composite amorphous magnetic cooling material of casting type described in the step 3 is cylindric, and body diameter is 3 millimeters.
CNA2008100447880A 2008-06-25 2008-06-25 Block gadolinium-based composite amorphous magnetic cooling material and preparation thereof Pending CN101413093A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103031478A (en) * 2012-12-12 2013-04-10 电子科技大学 In-situ complex-phase gadolinium-based magnetic refrigeration material having magnetic entropy change platform and preparation method thereof
CN105220082A (en) * 2015-10-20 2016-01-06 宁波工程学院 Gd based amorphous nano matrix material of high-curie temperature and high refrigeration capacity and preparation method thereof
CN105290379A (en) * 2015-11-13 2016-02-03 宋佳 Method for improving forming ability of amorphous alloy
CN105296893A (en) * 2014-07-01 2016-02-03 中国科学院宁波材料技术与工程研究所 High-entropy amorphous alloy and preparation method and application thereof
CN106350690A (en) * 2015-07-17 2017-01-25 中国科学院物理研究所 Rare earth gadolinium-based amorphous alloy stripe used for magnetic refrigerant material in room temperature range, and preparation method of rare earth gadolinium-based amorphous alloy stripe
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
CN106702245A (en) * 2016-12-20 2017-05-24 华南理工大学 Gd-Co-based amorphous and nano-crystalline magnetic refrigeration material and preparation method thereof
CN110504076A (en) * 2019-08-26 2019-11-26 北京科技大学 A kind of highly anticorrosive rare earth magnetic refrigerating material and the application method in refrigeration machine

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103031478A (en) * 2012-12-12 2013-04-10 电子科技大学 In-situ complex-phase gadolinium-based magnetic refrigeration material having magnetic entropy change platform and preparation method thereof
CN105296893B (en) * 2014-07-01 2017-06-06 宁波中科毕普拉斯新材料科技有限公司 A kind of entropy non-crystaline amorphous metal high, its preparation method and application
CN105296893A (en) * 2014-07-01 2016-02-03 中国科学院宁波材料技术与工程研究所 High-entropy amorphous alloy and preparation method and application thereof
CN106350690B (en) * 2015-07-17 2018-06-26 中国科学院物理研究所 Rare earth gadolinium-based AMORPHOUS ALLOY RIBBONS for room temperature magnetic refrigerating material and preparation method thereof
CN106350690A (en) * 2015-07-17 2017-01-25 中国科学院物理研究所 Rare earth gadolinium-based amorphous alloy stripe used for magnetic refrigerant material in room temperature range, and preparation method of rare earth gadolinium-based amorphous alloy stripe
CN105220082A (en) * 2015-10-20 2016-01-06 宁波工程学院 Gd based amorphous nano matrix material of high-curie temperature and high refrigeration capacity and preparation method thereof
CN105220082B (en) * 2015-10-20 2017-03-22 宁波工程学院 Gd-based amorphous nanocrystal composite with high Curie temperature and refrigerating capacity and preparation method of Gd-based amorphous nanocrystal composite
CN105290379B (en) * 2015-11-13 2017-07-11 宋佳 A kind of method for lifting amorphous alloy forming ability
CN105290379A (en) * 2015-11-13 2016-02-03 宋佳 Method for improving forming ability of amorphous alloy
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
CN106702245A (en) * 2016-12-20 2017-05-24 华南理工大学 Gd-Co-based amorphous and nano-crystalline magnetic refrigeration material and preparation method thereof
CN110504076A (en) * 2019-08-26 2019-11-26 北京科技大学 A kind of highly anticorrosive rare earth magnetic refrigerating material and the application method in refrigeration machine
CN110504076B (en) * 2019-08-26 2020-08-21 北京科技大学 High-corrosion-resistance rare earth magnetic refrigeration material and use method thereof in refrigerator

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