CN101792123A - La (Fe, al)13-based multi-interstitial hydride and its preparation method and application - Google Patents

La (Fe, al)13-based multi-interstitial hydride and its preparation method and application Download PDF

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CN101792123A
CN101792123A CN201010033971A CN201010033971A CN101792123A CN 101792123 A CN101792123 A CN 101792123A CN 201010033971 A CN201010033971 A CN 201010033971A CN 201010033971 A CN201010033971 A CN 201010033971A CN 101792123 A CN101792123 A CN 101792123A
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hydride
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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 relates to a uniform and stable La (Fe, Al) 13-base multi-gap atom hydride with large magnetic entropy change, having the chemical general formula of La1-a Ra Fe13-b Alb Xc Hd and a cubic NaZn 13 structure, wherein R is one or more rare-earth elements, and X is one or more C, B and the like. The preparation method of the La (Fe, Al) 13-base multi-gap atom hydride comprises the following steps of: firstly preparing La1-a Ra Fe13-b Alb Xc gap master alloy, and then carrying out one-time air suction on La1-a Ra Fe13-b Alb Xc gap master alloy powder to obtain the La1-a Ra Fe13-b Alb Xc Hd multi-gap atom hydride. The rare-earth ferrum-base compound of the invention has adjustable large range of the Curie point, can obtain large magnetic entropy change 40% higher than that of metal Gd especially at room temperature, has no magnetic hysteresis loss and no toxicity, is especially suitable for application and is an ideal room-temperature magnetic refrigerating material.

Description

La (Fe, Al) 13Quito interstitial atom hydride and method for making and application
Technical field
The present invention relates to a kind of magneticsubstance, particularly relate to a kind of stable La with great magnetic entropy variation (Fe, Al) 13Quito interstitial atom hydride.
The invention still further relates to above-mentioned La (Fe, Al) 13The preparation method of Quito interstitial atom hydride.
The invention still further relates to above-mentioned La (Fe, Al) 13The application of Quito interstitial atom hydride aspect magnetic refrigerating material.
Technical background
The magnetic refrigeration is the Refrigeration Technique of an environmental protection.Compare with the expansible Refrigeration Technique with traditional dependence gas compression, the magnetic refrigeration is to adopt magnetic substance 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 refrigeration plant can be done compactlyer.Magnetic refrigeration need not compressor as long as provide required magnetic field with electromagnet or superconductor and permanent magnet, does not have the wear problem of moving parts, so mechanical vibration and noise are less, the reliability height, and the life-span is long.Aspect thermo-efficiency, the magnetic refrigeration can reach 30%～60% of carnot's working cycle, and relies on the 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 magnetothermal 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 magnetothermal effect of magnetic refrigerating material.The magnetothermal 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 temperature becomes the domestic and international research emphasis at the magnetic refrigerating material that the room temperature warm area has great magnetic entropy variation.
1997, the Gschneidner of U.S.'s Ames Lab, Pecharsky found Gd 5(Si xGe 1-x) 4Alloy (US5743095) has huge magnetothermal effect, becomes about 2 times that reach Gd near the magnetic entropy room temperature, and the source of the great magnetic entropy variation of this material is a primary magnetic phase change.Compare with the secondary magnetic phase transition, the magnetic entropy that the material of first-order phase transition takes place becomes and often concentrates near the narrower warm area transformation temperature, according to Maxwell relations, thereby presents higher magnetic entropy variate.Yet, because this material is very high to the requirement of material purities such as rare earth, cost an arm and a leg, and have very big magnetic hysteresis loss, these drawbacks limit its application in practice.Therefore, in the process of exploring novel magnetic refrigerating material, seeking the little first-order phase transition material with great magnetic entropy variation that lags behind has important practical sense.
Has NaZn 13Compound has the highest 3d metal content between the rare-earth transiting group metal of type cubic structure in known rare earth intermetallic compound, and the high symmetry of its structure makes it to have superior soft magnetic performance and high saturation and magnetic intensity in addition.For rare earth-iron base NaZn 13Type cubic structure compound, since positive formation heat between rare earth and the iron, RFe 13Do not exist, need to add elements reduction formation enthalpys such as Al, Si and obtain stable phase.A small amount of be the first-order phase transition material after adding (less than 1.56) Si, have very big magnetic entropy and become, but, can not obtain big refrigeration capacity because the Entropy Changes temperature is striden lessly.Because the second-order phase transition magnetic refrigerating material often has very big Entropy Changes temperature and strides, thereby has very big refrigeration capacity, has caused the very big interest of people.
The basic NaZn of a kind of rare earth iron aluminium (R-Fe-Al) of CN1065294 patent disclosure 13Compound between shaped metal, this based compound have near Curie temperature advantage such as adjustable room temperature, but what take place because of this based compound is typical secondary magnetic phase transition, and it is less that magnetic entropy becomes, and under the changes of magnetic field of 0～1.4 tesla, its magnetic entropy becomes and only is 10～14J/m 3K is for about half of Gd.
In sum, existing second-order phase transition magnetic refrigerating material all be difficult to satisfy simultaneously Curie temperature near room temperature by composition change adjustable on a large scale, have that big magnetic entropy becomes, the requirement of this practicability magnetic refrigerating material of stable performance simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of stable performance and composition have uniformly great magnetic entropy variation La (Fe, Al) 13Quito interstitial atom hydride.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned many interstitial atoms hydride.
For achieving the above object, and La provided by the invention (Fe, Al) 13Quito interstitial atom hydride, its chemical general formula is expressed as: La 1-aR aFe 13-bAl bX cH d, have a cube NaZn 13Structure;
In the chemical general formula:
R satisfies the arbitrary combination 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 is Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, 0＜a≤0.5;
The scope of b is: 0＜b≤3.0;
X satisfies the arbitrary combination of the following element of c scope: C, B, Li, Be for one or more;
The scope of c is: 0＜c≤0.5;
The scope of d is: 0＜d≤5.0;
Described La (Fe, Al) 13In the interstitial atom hydride of Quito, material is under 0～350 ℃ of condition, and the Hydrogen Energy stable existence is among the gap.
Described La (Fe, Al) 13In the interstitial atom hydride of Quito, the magnetic entropy variate under the 0-5T changes of magnetic field is 5-30J/kgK, and transition temperature area is positioned at 200-360K.
The above-mentioned La of preparation provided by the invention (Fe, Al) 13The method of Quito interstitial atom hydride mainly comprises the steps:
A) raw material is placed electric arc furnace in argon shield fusing down;
B) Rong Hua material is handled 850～1050 ℃ of vacuum annealings, and it is the NaZn of 0～0.5 scope that taking-up and rapid quenching are prepared X content c 13Type La 1-aR aFe 13-bAl bX cThe single-phase sample of gap mother alloy;
C) with La 1-aR aFe 13-bAl bX cMother alloy single-phase sample in gap is pulverized, and puts into hydrogen annealing, prepares La 1-aR aFe 13-bAl bX cH dMany interstitial atoms hydride.
Among the described preparation method, the electric arc furnace in the steps A is evacuated to 2 * 10 earlier -5More than the Pa, clean cavity 1～3 time and charge into argon gas to 0.5～1.5 normal atmosphere greater than 99% argon gas with purity again, the electric arc starting the arc, the melting 1～6 time of under argon shield, overturning repeatedly, smelting temperature with fusing till.
Among the described preparation method, the vacuum tightness during the vacuum annealing among the step B is handled is less than 1 * 10 -3Pa; Quenching is to adopt liquid nitrogen or frozen water.
Among the described preparation method, among the step C with La 1-aR aFe 13-bAl bX cMother alloy single-phase sample in gap is pulverized and is the irregular powder of particle diameter less than 2 millimeters, and the used hydrogen purity of annealing is greater than 99%.
Among the described preparation method, Fe, X add with the form of simple substance or Fe-X master alloy.
Among the described preparation method, be used to prepare La among the step B 1-aR aFe 13-bAl bX cH dBetween barrier mother alloy La 1-aR aFe 13-bAl bX cBe fresh mother alloy.
La of the present invention (Fe, Al) 13Quito interstitial atom hydride can be used as magnetic refrigerating material.
Compared with prior art, the invention has the advantages that:
1) the present invention passes through to gap mother alloy La 1-aR aFe 13-bAl bX cIn introduce the gap hydrogen atom once more, prepared a kind of uniform and stable La with great magnetic entropy variation (Fe, Al) 13Quito interstitial atom hydride magnetic refrigerating material, i.e. La 1-aR aFe 13-bAl bX cH dCompound, this compound Curie temperature changes and can regulate continuously on a large scale in 200K～360K interval by composition; Near room temperature, can obtain to be higher than the great magnetic entropy variation of Metal Gd 40%; The interstitial compound performance (structure) of more directly inhaling the hydrogen gained is more stable, still can keep stable performance under normal pressure, room temperature～350 ℃ condition; It is a kind of very ideal room temperature magnetic refrigerating material.
The La with great magnetic entropy variation that 2) preparation provided by the invention is uniform and stable (Fe, Al) 13The method of Quito interstitial atom hydride magnetic refrigerating material, can control and measure the content of gap hydrogen atom in mother alloy more accurately, suction temperature is lower, pressure is littler, and step is simpler, and is resultant that gap hydride is more even, because of 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 1.5C 0.2Room temperature X-ray diffraction (XRD) spectral line, wherein, X-coordinate is a diffraction angle, ordinate zou is a diffracted intensity;
Fig. 2 is the LaFe of the invention process examples preparation 11.5Al 1.5C 0.2H x(x=0,0.5 and 1.0) M-T curve under 100Oe magnetic field, wherein X-coordinate is a temperature, ordinate zou is the specific magnetising moment;
"-●-" represent LaFe 11.5Al 1.5C 0.2H xThe thermomagnetization curve of (x=0,0.5 and 1.0) temperature-rise period;
" zero-" represents LaFe 11.5Al 1.5C 0.2H xThe thermomagnetization curve of (x=0,0.5 and 1.0) temperature-fall period;
Fig. 3 (a) and (b) and the LaFe that (c) is respectively the invention process examples preparation 11.5Al 1.5C 0.2H xThe magnetzation curve of (x=0,0.5 and 1.0), wherein X-coordinate is a magnetic induction density, ordinate zou is the specific magnetising moment;
"-●-" represent LaFe 11.5Al 1.5C 0.2H x(x=0,0.5 and 1.0) rises the isothermal magnetization curve of a process;
" zero-" represents LaFe 11.5Al 1.5C 0.2H xThe isothermal magnetization curve of a process falls in (x=0,0.5 and 1.0);
Fig. 4 is the LaFe of the invention process examples preparation 11.5Al 1.5C 0.2H x(x=0,0.5 and 1.0) magnetic entropy under 2T and 5T magnetic field becomes with the variation of temperature curve, and wherein X-coordinate is a temperature, and ordinate zou is that magnetic entropy becomes;
"-●-" represent LaFe 11.5Al 1.5C 0.2H x(x=0,0.5 and 1.0) isothermal magnetic entropy change-temperature curve under 5T magnetic field;
" zero-" represents LaFe 11.5Al 1.5C 0.2H x(x=0,0.5 and 1.0) isothermal magnetic entropy change-temperature curve under 2T magnetic field;
Fig. 5 is the LaFe of embodiment of the invention preparation 11.5Al 1.5C 0.2H 1.0Thermogravimetric analysis, wherein X-coordinate is a temperature, ordinate zou is that relative mass changes;
"-●-" represent LaFe 11.5Al 1.5C 0.2H 1.0Thermogravimetric analysis;
Embodiment
The present invention by to La (Fe, Al) 13Base gap mother alloy La 1-aR aFe 13-bAl bZ cIn introduce the gap hydrogen atom again, solving the magnetic entropy that Curie temperature is adjustable continuously, maintenance is big on a large scale becomes, this difficult problem of stable performance simultaneously, thereby it is adjustable on a large scale near room temperature to obtain a kind of Curie temperature, no magnetic lag loss, performance (structure) is stable, magnetic entropy become the La that is better than Gd with great magnetic entropy variation (Fe, Al) 13Final gap alloy La can accurately be controlled and measure to Quito interstitial atom hydride magnetic refrigerating material by strict control hydrogen pressure, in the preparation process 1-aR aFe 13-bAl bZ cX dThe content of intermediate gap hydrogen atom
The present invention is achieved through the following technical solutions:
On the one hand, the invention provides a kind of uniform and stable La with great magnetic entropy variation (Fe, Al) 13Quito interstitial atom hydride magnetic refrigerating material, its chemical general formula is: La 1-aR aFe 13-bAl bX cH d, have a cube NaZn 13Structure, wherein:
R satisfies the arbitrary combination 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 is Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, 0＜a≤0.5;
The scope of b is: 0＜b≤3.0;
X satisfies the arbitrary combination of the following element of c scope: C, B, Li, Be for one or more,
The scope of c is: 0＜c≤0.5;
The scope of d is: 0＜d≤3.0.
Preferably, of the present invention uniform and stable have great magnetic entropy variation La (Fe, Al) 13Quito interstitial atom hydride magnetic refrigerating material under 0～350 ℃ of condition, hydrogen still can stable existence among the gap, the magnetic entropy variate under the 0-5T changes of magnetic field is 5-30J/kgK, transition temperature area is positioned at 200-360K.
On the other hand, the invention provides a kind of method that is used to prepare described uniform and stable many interstitial atoms of the rare earth-iron base hydride magnetic refrigerating material with great magnetic entropy variation, described method comprises the steps:
I) press La 1-aR aFe 13-bAl bX cChemical formula batching, wherein R, X, a, b and c are as above-mentioned definition;
Ii) with step I) raw material for preparing puts into electric arc furnace, vacuumizes, and clean furnace chamber and charge into argon gas to 0.5～1.5 normal atmosphere with high-purity argon gas, the electric arc starting the arc, the melting 1～6 time of overturning repeatedly of each alloy pig;
Iii) through step I i) melted alloy pig vacuum annealing under 850～1050 ℃ of conditions, take out afterwards in also quench fast liquid nitrogen or the frozen water and cool off, thereby prepare NaZn 13Type L a 1-aR aFe 13-bAl bX cThe single-phase sample of gap mother alloy; With
The iv) La that step I is ii) prepared 1-aR aFe 13-bAl bX cMother alloy is broken into particle or makes powder, puts into hydrogen annealing, thereby prepares La 1-aR aFe 13-bAl bX cH dMany interstitial atoms hydride; Control hydrogen richness d in the alloy by regulating hydrogen pressure, annealing temperature and time therebetween, the scope of d is as above-mentioned definition.
Preferably, in according to method of the present invention, be used to prepare La 1-aR aFe 13-bAl bX cH dMother alloy La 1-aR aFe 13-bAl bX cBe fresh mother alloy.
Preferably, according to method of the present invention, described step I) purity of employed raw material La, R, Fe, Al and X is preferably greater than 99.9 weight % greater than 99 weight % in, more preferably greater than 99.99 weight %, wherein La, R, Fe, Al and X are as above-mentioned definition.Wherein Fe, X can add with the form of simple substance or Fe-X master alloy.
Preferably, according to method of the present invention, described step I i) smelting temperature in is 1000-2500 ℃, and vacuum tightness is less than 2 * 10 -5Pa, described purity of argon is greater than 99%.
Preferably, according to method of the present invention, the vacuum tightness in the vacuum annealing operation ii) of described step I is less than 1 * 10 -3Pa, annealing time are 1 day to 30 days.
Preferably, according to method of the present invention, the hydrogen pressure of described step I in v) is for greater than 0 normal atmosphere and be less than or equal to 5 normal atmosphere, and the annealing temperature in hydrogen is 0～350 ℃, and annealing time is 1 minute to 1 day.
Preferably, according to method of the present invention, utilize PCT (Pressure-concentration-temperature) experimental analysis instrument to obtain the content of many interstitial atoms hydride intermediate gap hydrogen atom in v) in described step I.
Preferably, according to method of the present invention, described step I v) in disposable suction hydrogen to desired content.
Described step I v) described in the powder made of single-phase sample be particle diameter less than 2 millimeters irregular powder, and in the described hydrogen annealing hydrogen purity greater than 99%.
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 1 preparation LaFe 11.5Al 1.5C 0.2H x(x=0,0.5 and 1.0) many interstitial atoms hydride
Prepare gap mother alloy LaFe by chemical formula 11.5Al 1.5C 0.2, concrete technology is:
I) press chemical formula LaFe 11.5Al 1.5C 0.2Weighing is higher than 99.9% commercially available rare-earth metal La, R and Fe, Fe-C master alloy and Al raw material with purity and mixes; Wherein, the excessive interpolation 5% of rare-earth metal La and R (atomic percent) compensates volatilization and the scaling loss in the fusion process;
Ii) with step I) raw material for preparing puts into electric arc furnace, is evacuated to 2 * 10 -5More than the Pa, clean 1～2 time with common high-purity argon gas purging method after, adopt the usual method melting 1～6 time of under 1 atmospheric high-purity argon gas protection, overturning repeatedly, smelting temperature with fusing till;
Iii) 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 gap mother alloy LaFe 11.5Al 1.5C 0.2Room temperature XRD spectral line, have good single phase property.
Prepare many interstitial atoms hydride LaFe by chemical formula then 11.5Al 1.5C 0.2H 0.5And LaFe 11.5Al 1.5C 0.2H 1.0, to mother alloy LaFe 11.5Al 1.5In introduce gap H atom once more, concrete technology is:
With the fresh LaFe for preparing previously 11.5Al 1.5C 0.2Mother alloy is broken into particle, places high pressure vessel, is evacuated to 2 * 10 -5More than the Pa, under 350 ℃, in high pressure vessel, feed high-purity H 2, gaseous tension is respectively 0.02 and 0.08 normal atmosphere, and keeping inspiratory duration is 1 hour; High pressure vessel is put into room temperature (20 ℃) water, meanwhile, take out remaining hydrogen in the high pressure vessel 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 many interstitial atoms hydride LaFe of 0.5 and 1.0 11.5Al 1.5C 0.2H x
In superconducting quantum magnetometer (SQUID, trade(brand)name: superconductive quantum interference magnetometer, manufacturer's name: Quantum Design, USA, marque: MPMS-7) go up many interstitial atoms of this example hydride LaFe that measures 11.5Al 1.5C 0.2H xThe thermomagnetization curve (M-T) of (x=0,0.5 and 1.0) as shown in Figure 2, can be determined many interstitial atoms hydride LaFe from the M-T curve 11.5Al 1.5C 0.2H xThe Curie temperature T of (x=0,0.5 and 1.0) CBe respectively 218K, 262K and 309K.
On SQUID, measure this many interstitial atoms hydride LaFe 11.5Al 1.5C 0.2H xNear (x=0,0.5 and 1.0) isothermal magnetization curve Curie temperature is as Fig. 3 (a) and (b) with (c).
Concern according to Maxwell ( ∂ S ( T , H ) ∂ H ) T = ( ∂ M ( T , H ) ∂ T ) H , Can become from isothermal magnetization curve calculation magnetic entropy.
Many interstitial atoms hydride LaFe of present embodiment preparation 11.5Al 1.5C 0.2H xCurve as shown in Figure 4 near (x=0,0.5 and 1.0) magnetic entropy change-temperature (Δ S-T) Curie temperature.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, magnetic entropy variation does not reach 11.87J/kg K, 13.32J/kg K, 13.83J/kg K, promptly along with the increase of hydrogen richness, this series alloy magnetic entropy becomes gradually and increases, this did not find in other material before being, this is because the introducing of gap hydrogen atom makes the magnetic moment of this series alloy increase, thereby make the variation of magnetic moment also increase to some extent, concern according to Maxwell, magnetic entropy becomes also and can increase therefore and to some extent, and phase change region narrows down and also helps obtaining bigger magnetic entropy and become in addition.It should be noted that the magnetic entropy near this series alloy room temperature uprises in Metal Gd more than 40%, because these series alloy starting material are many La, Fe, A and the Fe-C alloy etc. of relative Gd cheapness, possesses the condition of heavy industrialization, civil nature production.In addition, with hydride LaFe 11.5Al 1.5H xCompare, sample is more stable, hydrogen still can stable existence under 350 degrees celsius in the gap, as shown in Figure 5, be more suitable for using as magnetic refrigerating material.
Comparative Examples: 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(brand)name: superconductive quantum interference magnetometer, manufacturer's name: QuantumDesign, USA, marque: record MPMS-7) under the 100Oe magnetic field, 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.
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 embodiment.Therefore, without departing from the spirit and scope of the present invention, can make various changes and improvements to embodiment of the present invention.

Claims (10)

  1. A La (Fe, Al) 13Quito interstitial atom hydride, its chemical general formula is expressed as: La 1-aR aFe 13-bAl bX cH d, have a cube NaZn 13Structure;
    In the chemical general formula:
    R satisfies the arbitrary combination 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 is Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, 0＜a≤0.5;
    The scope of b is: 0＜b≤3.0;
    X satisfies the arbitrary combination of the following element of c scope: C, B, Li, Be for one or more;
    The scope of c is: 0＜c≤0.5;
    The scope of d is: 0＜d≤5.0;
  2. La 2. as claimed in claim 1 (Fe, Al) 13Quito interstitial atom hydride, wherein, described material is under 0～350 ℃ of condition, and the Hydrogen Energy stable existence is among the gap.
  3. La 3. as claimed in claim 1 or 2 (Fe, Al) 13Quito interstitial atom hydride, wherein, the magnetic entropy variate under the 0-5T changes of magnetic field is 5-30J/kgK, transition temperature area is positioned at 200-360K.
  4. One kind prepare the described La of claim 1 (Fe, Al) 13The method of Quito interstitial atom hydride mainly comprises the steps:
    A) raw material is placed electric arc furnace in argon shield fusing down;
    B) Rong Hua material is handled 850～1050 ℃ of vacuum annealings, and it is the NaZn of 0～0.5 scope that taking-up and rapid quenching are prepared X content c 13Type La 1-aR aFe 13-bAl bX cThe single-phase sample of gap mother alloy;
    C) with La 1-aR aFe 13-bAl bX cMother alloy single-phase sample in gap is pulverized, and puts into hydrogen annealing, prepares La 1-aR aFe 13-bAl bX cH dMany interstitial atoms hydride.
  5. 5. preparation method as claimed in claim 4, wherein, the electric arc furnace in the steps A is evacuated to 2 * 10 earlier -5More than the Pa, clean cavity 1～3 time and charge into argon gas to 0.5～1.5 normal atmosphere greater than 99% argon gas with purity again, the electric arc starting the arc, the melting 1～6 time of under argon shield, overturning repeatedly, smelting temperature with fusing till.
  6. 6. preparation method as claimed in claim 4, wherein, the vacuum tightness during the vacuum annealing among the step B is handled is less than 1 * 10 -3Pa; Quenching is to adopt liquid nitrogen or frozen water.
  7. 7. preparation method as claimed in claim 4, wherein, among the step C with La 1-aR aFe 13-bAl bX cMother alloy single-phase sample in gap is pulverized and is the irregular powder of particle diameter less than 2 millimeters, and the used hydrogen purity of annealing is greater than 99%.
  8. 8. preparation method as claimed in claim 4, wherein, Fe, X add with the form of simple substance or Fe-X master alloy.
  9. 9. preparation method as claimed in claim 4 wherein, is used to prepare La among the step B 1-aR aFe 13-bAl bX cH dBetween barrier mother alloy La 1-aR aFe 13-bAl bX cBe fresh mother alloy.
  10. The described La of claim 1 (Fe, Al) 13The application of Quito interstitial atom hydride aspect magnetic refrigerating material.
CN201010033971A 2010-01-07 2010-01-07 La (Fe, al)13-based multi-interstitial hydride and its preparation method and application Pending CN101792123A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104593631A (en) * 2013-10-31 2015-05-06 包头稀土研究院 A rare earth-iron-silicon-boron-hydrogen material preparing method
CN113661143A (en) * 2019-07-23 2021-11-16 松下知识产权经营株式会社 Method for producing thin film and laminate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104593631A (en) * 2013-10-31 2015-05-06 包头稀土研究院 A rare earth-iron-silicon-boron-hydrogen material preparing method
CN104593631B (en) * 2013-10-31 2018-05-15 包头稀土研究院 A kind of method for preparing Rare-earth Iron silicon boron hydrogen material
CN113661143A (en) * 2019-07-23 2021-11-16 松下知识产权经营株式会社 Method for producing thin film and laminate
CN113661143B (en) * 2019-07-23 2024-03-08 松下知识产权经营株式会社 Method for producing film and laminate

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Application publication date: 20100804