CN102087899A - La (Fe, al)13-based hydride magnetic refrigerating material and its preparation method and application - Google Patents

La (Fe, al)13-based hydride magnetic refrigerating material and its preparation method and application Download PDF

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CN102087899A
CN102087899A CN2009102416877A CN200910241687A CN102087899A CN 102087899 A CN102087899 A CN 102087899A CN 2009102416877 A CN2009102416877 A CN 2009102416877A CN 200910241687 A CN200910241687 A CN 200910241687A CN 102087899 A CN102087899 A CN 102087899A
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magnetic
magnetic refrigerating
hydride
refrigerating material
room temperature
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赵金良
沈保根
胡凤霞
沈俊
李养贤
孙继荣
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Institute of Physics of CAS
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Abstract

The invention provides an La (Fe, Al) 13-base hydride magnetic refrigeration material with large magnetic entropy change. The La (Fe, Al) 13-base hydride magnetic refrigeration material has the chemical formula of La1-aRaFe13-bAlbHc and a cubic NaZn13 structure. The preparation method comprises the following steps of: first preparing La1-aRaFe13-bAlb mother alloy through direct smelting and annealing treatment; carrying out one-time air absorption treatment on the La1-aRaFe13-bAlb mother alloy powder, and obtaining an La1-aRaFe13-bAlbHc gap hydride. The Curie point of the rare earth-Fe base intermetallic hydride of the invention can be adjusted in a large range. In particular, magnetic entropy change which is about 25% higher than that of the metal Gd can be obtained near a room temperature. The intermetallic hydride does not have magnetic hysteresis losses or toxicity, is more suitable for application and is an extremely ideal room temperature magnetic refrigeration material. The preparation method has the characteristics of rich raw material reserve, simple technology, adaptability to industrial production and the like.

Description

La (Fe, Al)＜sub〉13＜/sub〉base hydride magnetic refrigerating material and method for making and application
Technical field
The present invention relates to a kind of magnetic material, relate to specifically a kind of La with great magnetic entropy variation (Fe, Al) 13The base hydride magnetic refrigerating material.
The invention still further relates to the preparation method of above-mentioned magnetic refrigerating material.
The invention still further relates to the purposes of above-mentioned magnetic refrigerating material.
Background technology
The magnetic refrigeration is the Refrigeration Technique of an environmental protection.Compare with the Refrigeration Technique of expansion with traditional dependence gas compression, the magnetic refrigeration is to adopt magnetisable material as refrigeration working medium, atmospheric ozone layer is not had destruction, no greenhouse effect, and the magnetic entropy density of magnetic working medium is bigger than gas, so refrigerating plant can be done compactlyer.Aspect the heat efficiency, the magnetic refrigeration can reach the 30%-60% of Carnot cycle, and relies on the kind of refrigeration cycle of the compression-expansion of gas generally can only reach 5%-10%, and therefore, the magnetic Refrigeration Technique has a good application prospect, and is described as high-new green refrigeration technology.Magnetic Refrigeration Technique, especially room temperature magnetic refrigerating technology are because of having the very big concern that huge potential application market is subjected to domestic and international research institution and branch of industry aspect the industries such as family expenses refrigerator, domestic air conditioning, central air-conditioning, supermarket video refrigeration system.
The magnetic heating performance of magnetic refrigeration working substance mainly comprises magnetic entropy change, adiabatic temperature variation, specific heat, thermal conductivity or the like.Wherein, magnetic entropy becomes and adiabatic temperature to change be the sign of magnetic refrigerating material magneto-caloric effect, be easy to accurate mensuration because of magnetic entropy becomes than the adiabatic temperature variation, thereby people more are accustomed to adopting magnetic entropy to become and characterize the magneto-caloric effect of magnetic refrigerating material.The magneto-caloric effect of magnetic refrigerating material (magnetic entropy change, adiabatic temperature change) is one of key factor of restriction magnetic refrigerator refrigerating efficiency, and therefore, seeking Curie point becomes the domestic and international research emphasis at the magnetic refrigerating material that the room temperature warm area has great magnetic entropy variation.
The second-order phase transistion material is not owing to have thermo-lag and magnetic lag, and phase transition temperature wider range, often has bigger refrigerating capacity, has NaZn 13Compound L a between the rare-earth transiting group metal of type cubic structure (Fe, Al) 13Because the cost of raw material is cheap, manufacture craft is simple, and has the second-order phase transistion characteristic so be subjected to people's attention.
The basic NaZn of the disclosed a kind of rare earth iron aluminium of Chinese patent CN1065294 (R-Fe-Al) 13Type intermetallic compound, this based compound have near Curie point advantage such as adjustable room temperature, but because of this based compound magnetic entropy becomes less, and under the changes of magnetic field of 0-1.4 tesla, its magnetic entropy only becomes to being about half of Gd.
Summary of the invention
The object of the present invention is to provide a kind of La (Fe, Al) 13The base hydride magnetic refrigerating material.
Another purpose of the present invention is to provide the preparation method of the above-mentioned hydride magnetic refrigerating material of preparation.
For achieving the above object, the present invention by to La (Fe, Al) 13Foundry alloy La 1-aR aFe 13-bAl bIn introduce gap H atom, solve can make Curie point adjustable continuously on a large scale, can keep big magnetic entropy to become again, thereby obtain a kind of Gd of being better than the La with great magnetic entropy variation (Fe, Al) 13Final interstitial compound La can accurately be controlled and measure to base interstitial compound magnetic refrigerating material by strict control Hydrogen Vapor Pressure, in the preparation process 1-aR aFe 13-bAl bH cIntermediate gap H atom content.
The objective of the invention is to realize by the following technical solutions:
La with great magnetic entropy variation provided by the invention (Fe, Al) 13The base hydride magnetic refrigerating material, its chemical general formula is: La 1-aR aFe 13-bAl bH c, have a cube NaZn 13Structure
Wherein: R satisfies the combination in any of the following rare earth element of a scope: Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc for one or more,
The scope of a is as follows:
When R is the Ce element, 0＜a≤0.9;
When R is Pr, Nd, 0＜a≤0.7;
When R was Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, a was 0～0.5;
The scope of b is: 0＜b≤3.0;
The scope of c is: 0＜c≤3.0;
La with great magnetic entropy variation provided by the invention (Fe, Al) 13The preparation method of base hydride magnetic refrigerating material comprises the steps:
The present invention at first prepares La 1-aR aFe 13-bAl bFoundry alloy, concrete technology is:
1) presses La 1-aR aFe 13-bAl bThe chemical formula weighing mixes rare-earth metal La, R and Fe and Al raw material; Wherein, the excessive interpolation 3～5% of rare-earth metal La and R (atomic percent) compensates volatilization and the scaling loss in the fusion process;
2) raw material that step 1 is prepared is put into arc furnace, is evacuated to 2 * 10 -5More than the torr, clean 1-2 time with common high-purity argon gas cleaning method after, adopt usual way melting 3-6 time of under 1 atmospheric high-purity argon gas protection, overturning repeatedly, smelting temperature is with till melting;
3) handled 2-15 days 900～1050 ℃ of vacuum annealings through the melted material of step 2, take out afterwards and quench fast liquid nitrogen or water in, prepare La (Fe, Al) 13Base foundry alloy La 1-aR aFe 13-bAl b
The present invention is in order further to prepare La 1-aR aFe 13-bAl bH cGap hydride, further comprising the steps of:
Above-mentioned steps 3 is prepared La 1-aR aFe 13-bAl bFoundry alloy is broken into particle or wears into 100nm～200 μ m powder; Foundry alloy particle or powder are placed high-pressure bottle, be evacuated to 2 * 10 -5More than the torr, under 250-350 ℃, feed high-purity H 2, gas pressure is greater than 0, less than 2 atmospheric pressure, keeping inspiratory duration was greater than 0, less than 5 hours; High-pressure bottle is put into water be cooled to room temperature, venting is to 1 atmospheric pressure, by regulating temperature and H 2Pressure obtains many interstitial atoms compound L a of desired content 1-aR aFe 13-bAl bH c
The invention has the advantages that:
The present invention passes through to foundry alloy La 1-aR aFe 13-bAl bIn introduce gap H atom, prepared a kind of La with great magnetic entropy variation (Fe, Al) 13Base hydride magnetic refrigerating material, i.e. La 1-aR aFe 13-bAl bH cCompound, this compound Curie point changes and can regulate continuously on a large scale in 120K～360K interval by composition; Can obtain near the room temperature than also big about 25% the magnetic entropy change of Metal Gd; And still can keep stable performance under normal pressure, 350 ℃ of conditions, be a kind of very desirable room temperature magnetic refrigerating material.
Preparation provided by the invention have great magnetic entropy variation La (Fe, Al) 13The method of base hydride magnetic refrigerating material, can control and measure the content of gap H atom in foundry alloy accurately, pressure of inspiration(Pi) is little, step is simple, employed raw material contains a large amount of relatively inexpensive Fe, Al etc., have abundant raw material, remarkable advantage such as with low cost, in addition, the present invention also has the advantages such as suitability for industrialized production that preparation technology is simple, be suitable for magnetic refrigerating material.
Description of drawings
Fig. 1 is the LaFe of the invention process examples preparation 11.5Al 1.5Room temperature X-ray diffraction (XRD) spectral line, wherein, abscissa is the angle of diffraction, ordinate is a diffracted intensity;
Fig. 2 is the LaFe of the invention process examples preparation 11.5Al 1.5H x(x=0.12,0.6 and 1.3) M-T curve under 100 Oe magnetic fields, wherein abscissa is a temperature, ordinate is the magnetization; Curve among Fig. 2:
"-●-" represent LaFe 11.5Al 1.5H xThe thermomagnetization curve of (x=0.12,0.6 and 1.3) temperature-rise period
" zero-" represents LaFe 11.5Al 1.5H xThe thermomagnetization curve of (x=0.12,0.6 and 1.3) temperature-fall period
Fig. 3 is the LaFe1 of the invention process examples preparation 1.5Al 1.5H 0.6The isothermal magnetization curve, wherein abscissa is a magnetic flux density, ordinate is the magnetization;
"-●-" represent LaFe1 under the different temperatures 1.5Al 1.5H 0.6Rise the isothermal magnetization curve of a process
" zero-" represents LaFe1 under the different temperatures 1.5Al 1.5H 0.6The isothermal magnetization curve of a process falls
Fig. 4 is the LaFe1 of the invention process examples preparation 1.5Al 1.5H 0.6The Arrott curve, wherein abscissa be magnetic flux density square, ordinate is the ratio of the magnetization and magnetic flux density;
Fig. 5 is the LaFe1 of the invention process examples preparation 1.5Al 1.5H 0.6Magnetic entropy under 1T, 2T, 3T, 4T, 5T magnetic field becomes with the variation of temperature curve, and wherein abscissa is a temperature, and ordinate is that magnetic entropy becomes.
" ■-" represents LaFe1 1.5Al 1.5H 0.6Isothermal magnetic entropy change-temperature curve under 1T magnetic field
"-●-" represent LaFe1 1.5Al 1.5H 0.6Isothermal magnetic entropy change-temperature curve under 2T magnetic field
"-▲-" represent LaFe1 1.5Al 1.5H 0.6Isothermal magnetic entropy change-temperature curve under 3T magnetic field
"-
Figure G2009102416877D00041
-" represent LaFe1 1.5Al 1.5H 0.6Isothermal magnetic entropy change-temperature curve under 4T magnetic field
"-◆-" represent LaFe1 1.5Al 1.5H 0.6Isothermal magnetic entropy change-temperature curve under 5T magnetic field
Fig. 6 is the LaFe1 of the invention process examples preparation 1.5Al 1.5H 1.3The isothermal magnetization curve, wherein abscissa is a magnetic flux density, ordinate is the magnetization;
"-●-" represent LaFe1 under the different temperatures 1.5Al 1.5H 1.3Rise the isothermal magnetization curve of a process
" zero-" represents LaFe1 under the different temperatures 1.5Al 1.5H 1.3The isothermal magnetization curve of a process falls
Fig. 7 is the LaFe1 of the invention process examples preparation 1.5Al 1.5H 1.3The Arrott curve, wherein abscissa be magnetic flux density square, ordinate is the ratio of the magnetization and magnetic flux density;
Fig. 8 is the LaFe1 of the invention process examples preparation 1.5Al 1.5H 1.3Magnetic entropy under 1T, 2T, 3T, 4T, 5T magnetic field becomes with the variation of temperature curve, and wherein abscissa is a temperature, and ordinate is that magnetic entropy becomes.
" ■-" represents LaFe1 1.5Al 1.5H 1.3Isothermal magnetic entropy change-temperature curve under 1T magnetic field
"-●-" represent LaFe1 1.5Al 1.5H 1.3Isothermal magnetic entropy change-temperature curve under 2T magnetic field
"-▲-" represent LaFe1 1.5Al 1.5H 1.3Isothermal magnetic entropy change-temperature curve under 3T magnetic field
"-
Figure G2009102416877D00051
-" represent LaFe1 1.5Al 1.5H 1.3Isothermal magnetic entropy change-temperature curve under 4T magnetic field
"-◆-" represent LaFe1 1.5Al 1.5H 1.3Isothermal magnetic entropy change-temperature curve under 5T magnetic field
"---" represents Comparative Examples Metal Gd isothermal magnetic entropy change-temperature curve under 5T magnetic field
Embodiment
The concrete example of following reference illustrates the present invention.It will be appreciated by those skilled in the art that these embodiment only are used to illustrate purpose of the present invention, the scope that it does not limit the present invention in any way.
Embodiment:
Preparation LaFe1 1.5Al 1.5H x(x=0.12,0.6 and 1.3)
At first prepare foundry alloy LaFe1 by chemical formula 1.5Al 1.5, concrete technology is:
1) presses chemical formula LaFe 11.5Al 1.5Weighing is higher than 99.9% commercially available rare-earth metal La, Fe and Al raw material with purity and mixes; Wherein, the excessive interpolation 5% of rare-earth metal La (atomic percent) compensates volatilization and the scaling loss in the fusion process;
2) raw material that step 1 is prepared is put into arc furnace, is evacuated to 2 * 10 -5More than the torr, clean 1-2 time with common high-purity argon gas cleaning method after, adopt usual way melting 3-6 time of under 1 atmospheric high-purity argon gas protection, overturning repeatedly, smelting temperature is with till melting;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum sheet, is sealed in the vitreosil pipe, quenches after 1000 ℃ of two weeks of annealing in the liquid nitrogen, obtains this based compound sample.
(Rigaku company produces, model: RINT2400) measured room temperature X ray (XRD) diffract spectral line of sample, the result shows that sample is NaZn to utilize Cu target X-ray diffractometer 13Cubic crystal structure, Fig. 1 illustrate foundry alloy LaFe 11.5Al 1.5Room temperature XRD spectral line, have good single phase property.
Prepare compound L aFe1 by chemical formula then 1.5Al 1.5H 0.12, LaFe 11.5Al 1.5H 0.6, LaFe 11.5Al 1.5H 1.3, to foundry alloy LaFe 11.5Al 1.5The middle gap H atom of introducing, concrete technology is:
Fresh LaFe with step 3 preparation 11.5Al 1.5Foundry alloy is broken into particle, places high-pressure bottle, is evacuated to 2 * 10 -5More than the torr, under 350 ℃, in high-pressure bottle, feed high-purity H 2, gas pressure is respectively 0.035,0.201,0.492 atmospheric pressure, and keeping inspiratory duration is 1 hour; High-pressure bottle is put into room temperature (20 ℃) water, meanwhile, take out remaining hydrogen in the high-pressure bottle with mechanical pump, be cooled to room temperature, (Beijing Non-Ferrous Metal Research General Academy's production) calculating of analyzing and weigh according to PCT (Pressure-concentration-temperature) ability meter obtains H content and is about 0.12,0.6 and 1.3 interstitial compound LaFe 11.5Al 1.5H x
In superconducting quantum magnetometer (SQUID, trade name: superconductive quantum interference magnetometer, manufacturer's name: Quantum Design, USA, marque: MPMS-7) go up this example interstitial compound LaFe that measures 11.5Al 1.5H xThe thermomagnetization curve (M-T) of (x=0.12,0.6 and 1.3) as shown in Figure 2, can be determined N T from the M-T curve NPerhaps Curie point T CBe respectively 225K, 249K and 295K.
On SQUID, measure this interstitial compound LaFe 11.5Al 1.5H 0.6And LaFe 11.5Al 1.5H 1.3Near isothermal magnetization curve Curie temperature (as Fig. 3 and shown in Figure 6) can be made Arrott (M by the isothermal magnetization curve 2=H/M) figure (as Fig. 4 and shown in Figure 7) is by Arrott curve LaFe as can be seen 11.5Al 1.5H 0.6And LaFe 11.5Al 1.5H 1.3All show tangible second-order phase transistion characteristic.
Concern according to Maxwell
( ∂ S ( T , H ) ∂ H ) T = ( ∂ M ( T , H ) ∂ T ) H , Can become from isothermal magnetization curve calculation magnetic entropy.
The interstitial compound LaFe of present embodiment preparation 11.5Al 1.5H 0.6And LaFe 11.5Al 1.5H 1.3Curve as shown in Figure 5 and Figure 8 near magnetic entropy change-temperature Curie temperature (Δ S-T).As can be seen from the figure, at T CThe place very large magnetic entropy occurred and has become, under 0～5T changes of magnetic field, and LaFe 11.5Al 1.5H 0.6And LaFe 11.5Al 1.5H 1.3Magnetic entropy variation does not reach 11.6J/kg K and 12.3J/kg K, LaFe as can be seen 11.5Al 1.5H 1.3Magnetic entropy no-load voltage ratio Metal Gd is at the maximum magnetic entropy variable under the 0-5T changes of magnetic field (9.8J/kg K) taller about 25%.
Below described the present invention in detail, to those skilled in the art, should be understood that above-mentioned embodiment should not be understood that to limit scope of the present invention with reference to concrete execution mode.Therefore, without departing from the spirit and scope of the present invention, can make various changes and improvements to embodiment of the present invention.
Comparative example: rare metal Gd
Select typical room temperature magnetic refrigerating material Gd (purity is 99.9%) for use as a comparative example.At superconducting quantum magnetometer (SQUID, trade name: superconductive quantum interference magnetometer, manufacturer's name: QuantumDesign, USA, marque: record MPMS-7) under the 100 Oe magnetic fields, its Curie temperature is 293K, under the 0-5T changes of magnetic field, records Curie temperature place magnetic entropy and becomes 9.8J/kg K.

Claims (7)

  1. A La (Fe, Al) 13The base hydride magnetic refrigerating material, its chemical general formula is: La 1-aR aFe 13-bAl bH c, have a cube NaZn 13Structure;
    In the chemical general formula:
    R satisfies the combination in any of the following rare earth element of a scope: Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc for one or more,
    The scope of a is as follows:
    When R is the Ce element, 0＜a≤0.9;
    When R is Pr, Nd, 0＜a≤0.7;
    When R was Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, a was 0～0.5;
    The scope of b is: 0＜b≤3.0;
    The scope of c is: 0＜c≤3.0.
  2. One kind prepare the described La of claim 1 (Fe, Al) 13The method of base hydride magnetic refrigerating material, key step is:
    1) presses La 1-aR aFe 13-bAl bThe chemical formula weighing mixes rare-earth metal La, R, Fe and Al raw material; Wherein, excessive interpolation 3～5% atomic percents of rare-earth metal La and R;
    2) put into arc furnace after the raw material mixing with step 1, be evacuated to 2 * 10 -5More than the torr, clean with high-purity argon gas, the melting 3～6 times of under 1 atmospheric argon shield, overturning repeatedly, smelting temperature is with till melting;
    3) material after step 2 melting is 900～1050 ℃ of vacuum annealings, take out and quench liquid nitrogen or frozen water in, prepare La 1-aR aFe 13-bAl bFoundry alloy;
    4) La that step 3 is prepared 1-aR aFe 13-bAl bFoundry alloy is broken into particle or clays into power;
    5) foundry alloy particle or the powder with step 4 places high-pressure bottle, is evacuated to 2 * 10 -5More than the torr, 250-350 ℃ feeds down hydrogen, and Hydrogen Vapor Pressure is less than or equal to 2 atmospheric pressure greater than 0, and inspiratory duration is less than or equal to 5 hours greater than 0, and high-pressure bottle is cooled to room temperature, obtain La (Fe, Al) 13The base hydride magnetic refrigerating material.
  3. 3. by the described method of claim 2, wherein, be used in the step 5 prepare La (Fe, Al) 13The foundry alloy La of base hydride magnetic refrigerating material 1-aR aFe 13-bAl bBe fresh foundry alloy.
  4. 4. by the described method of claim 2, wherein, the temperature of high-pressure bottle is 250-350 ℃ when feeding hydrogen in the step 5.
  5. 5. by the described method of claim 2, wherein, step 5 mesohigh container is to put into liquid nitrogen or frozen water is cooled to room temperature, and venting is to 1 atmospheric pressure.
  6. The described La of claim 1 (Fe, Al) 13The application of base hydride aspect magnetic refrigerating material.
  7. 7. by the described application of claim 6, wherein, be as room temperature magnetic refrigerating material.
CN2009102416877A 2009-12-02 2009-12-02 La (Fe, al)13-based hydride magnetic refrigerating material and its preparation method and application Pending CN102087899A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103639415A (en) * 2013-12-11 2014-03-19 江苏大学 Preparation method for high-performance rare earth-iron-based magnetic cooling materials
CN105314598A (en) * 2015-11-24 2016-02-10 沈阳理工大学 A high-pressure synthesis method for flaky La (Fe, si)13-based hydride bulk material with high-efficiency room-temperature magnetic refrigeration performance

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103639415A (en) * 2013-12-11 2014-03-19 江苏大学 Preparation method for high-performance rare earth-iron-based magnetic cooling materials
CN103639415B (en) * 2013-12-11 2016-04-06 江苏大学 The preparation method of a kind of high-performance rare-earth-iron-based magnetic cooling material
CN105314598A (en) * 2015-11-24 2016-02-10 沈阳理工大学 A high-pressure synthesis method for flaky La (Fe, si)13-based hydride bulk material with high-efficiency room-temperature magnetic refrigeration performance

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Application publication date: 20110608