CN102453466B - Rare earth-copper-aluminum material for magnetic refrigeration and preparation method thereof - Google Patents

Rare earth-copper-aluminum material for magnetic refrigeration and preparation method thereof Download PDF

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CN102453466B
CN102453466B CN2010105153541A CN201010515354A CN102453466B CN 102453466 B CN102453466 B CN 102453466B CN 2010105153541 A CN2010105153541 A CN 2010105153541A CN 201010515354 A CN201010515354 A CN 201010515354A CN 102453466 B CN102453466 B CN 102453466B
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董巧燕
沈保根
陈静
胡凤霞
孙继荣
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Institute of Physics of CAS
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract

The invention provides a rare earth-copper-aluminum material for magnetic refrigeration and a preparation method thereof. The rare earth-copper-aluminum material for magnetic refrigeration is a compound having a general formula of RCuAl, wherein R represents Ho, Er, Dy, Tb or Gd. The rare earth-copper-aluminum material for magnetic refrigeration has a large magnetic entropy change around respective phase change temperatures of rare earth, copper and aluminum, a large magnetic refrigeration capacity, good thermal and magnetic reversible properties, and a low price, and thus the rare earth-copper-aluminum material for magnetic refrigeration is a very ideal middle/low-temperature zone magnetic refrigeration material.

Description

Rare earth-copper-aluminum material freezed for magnetic and preparation method thereof
Technical field
The present invention relates to magneticsubstance, particularly a kind of rare earth-copper-aluminum material for the magnetic refrigeration and preparation method thereof.
Background technology
The world today, Refrigeration & Cryogenic Technique plays a very important role, and is related to numerous key areas of national economy.Tradition gas compression Refrigeration Technique has been widely used in all trades and professions, but it exists that refrigerating efficiency is low, energy consumption large, destroy the shortcomings such as atmospheric environment.The magnetic Refrigeration Technique refers to take a kind of New Refrigerating technology that magneticsubstance is refrigeration working medium.With traditional gas compression Refrigeration Technique, compare, it has energy-efficient, environmental protection, the significant advantage such as reliable and stable, be described as high-new green refrigeration technology, its refrigeration principle is the magnetothermal effect by means of magnetic refrigerating material, under isothermal condition, when magneticstrength increases (magnetization), the magnetic moment of magnetic refrigerating material is tending towards ordered arrangement, and magnetic entropy reduces, to extraneous heat extraction; When the specific magnetising moment weakens (demagnetization), magnetic moment is tending towards lack of alignment, and magnetic entropy increases, and magnetic refrigeration working substance absorbs heat from the external world, thereby reaches the purpose of refrigeration.
Usually, the parameter of measurement magnetic refrigerating material magnetic heating performance is mainly that magnetic entropy becomes and magnetic refrigerant capacity (be RC, refer to transferable heat in a refrigeration cycle).Press operation temperature area and divide, magnetic refrigerating material can be divided into low temperature (15K is following), middle temperature (15K-77K) and high temperature (more than 77K) magnetic refrigerating material.Wherein, in, the cold zone magnetic refrigerating material can be applicable to the extensive concern that the aspects such as nitrogen, liquefaction of hydrogen are subject to domestic and international research institution and branch of industry because of it.At present, the magnetic refrigerating material of finding in this warm area research mainly comprises rare earth element monocrystalline, polycrystalline material, and as Nd, Er or Tm, and rare earth intermetallic compound, as RCoAl (R=Gd, Tb, Dy, Ho, Gd 0.5dy 0.25er 0.25), RNiAl (R=Gd, Tb, Dy, Ho, Gd 1-xer x) etc.But, because the magnetic heating performance of above-mentioned magnetic refrigerating material is also lower, its commercial applications is restricted.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of rare earth-copper-aluminum material for the magnetic refrigeration.
Another object of the present invention is that the preparation method of above-mentioned rare earth-copper-aluminum material is provided.
The objective of the invention is to be achieved through the following technical solutions.On the one hand, the invention provides a kind of rare earth-copper-aluminum material for the magnetic refrigeration, the compound that this rare earth-copper-aluminum material is following general formula: RCuAl, wherein R is Ho, Er, Dy, Tb or Gd.
Preferably, described rare earth-copper-aluminum material has ZrNiAl type hex crystal structure.
On the other hand, the invention provides a kind of preparation method of the rare earth-copper-aluminum material for the magnetic refrigeration, comprise the following steps: 1) by RCuAl chemical formula atomic percent, take raw material, R, Cu, Al raw material are mixed, wherein R is Ho, Er, Dy, Tb or Gd; 2) by step 1) raw material that is mixed to get puts into electric arc furnace or induction heater, is evacuated to 3 * 10 -3more than Pa, by high-purity argon, clean and melting, smelting temperature is more than 1500 ℃, the cooling cast alloy that obtains; 3) by step 2) cast alloy that obtains carries out the vacuum annealing processing, takes out afterwards cooling fast; Or first by step 2) cast alloy induction melting fast quenching in getting rid of the band machine of obtaining obtains amorphous thin ribbon, then carry out the vacuum annealing processing, take out afterwards cooling fast.
Preferably, the atomic percent of the excessive interpolation 2%～5% of R raw material described preparation method's step 1).
Preferably, described preparation method's step 2), be evacuated to 2 * 10 -3～3 * 10 -3pa.
Preferably, described preparation method's step 2), smelting temperature is 1500 ℃～1700 ℃.
Preferably, described preparation method's step 3) temperature that in, vacuum annealing is processed is 520 ℃～600 ℃, is about to body of casting alloy or amorphous thin ribbon vacuum annealing in the temperature range of 520 ℃～600 ℃.
Preferably, the vacuum tightness that described preparation method's step 3), vacuum annealing is processed is 1 * 10 -4～1 * 10 -5pa.
Preferably, described preparation method's step 3) time that in, vacuum annealing is processed is 2～14 days, is about to body of casting alloy or amorphous thin ribbon vacuum annealing 2 to 14 days.
Being cooled to fast in quench liquid nitrogen or frozen water preferably, described preparation method's step 3).
In preparation method provided by the invention, described step 1) the rare earth element Ho in, Er, Dy, Tb or Gd, in the excessive interpolation of 2%～5% ratio, to compensate its volatilization and scaling loss in experimentation, thereby obtain single-phase.Described step 2), in, due to the easy oxidation of rare earth element, the material preparation should guarantee to carry out under high vacuum environment as far as possible, otherwise can cause compound ratio mismatch, thereby affects into phase, therefore is evacuated to 3 * 10 -3all can realize the object of the invention more than Pa, preferably 2 * 10 -3to 3 * 10 -3between Pa.For will be understood by those skilled in the art that this said " 3 * 10 -3more than Pa " refer in fact on numerical value lower than 3 * 10 -3the vacuum tightness of Pa.In addition, smelting temperature is also extremely important, because if temperature is inadequate, material can not fully melt, and can not prepare the compound needed, and smelting temperature need to be more than 1500 ℃ usually; Yet if excess Temperature may accelerate the volatilization of rare earth element, between 1500 ℃-1700 ℃, be therefore preferred temperature condition.In above-mentioned steps 3) in, after vacuum annealing is processed, stress is discharged, physics and chemistry character will be more stable, and suitable anneal also contributes to material to become phase, and other vacuum tightness, annealing temperature and the time that therefore can achieve the above object also can be used; The present invention is vacuum annealing in the temperature range of 520 ℃-600 ℃ preferably, and more preferably vacuum annealing 2～14 days at this temperature.In addition, described cooling also comprising in the frozen water of for example quenching fast.
In sum, the rare earth-copper-aluminum material (RCuAl, wherein R is Ho, Er, Dy, Tb or Gd) that has that prepared by the present invention has ZrNiAl type hex crystal structure.Existence due to ferromagnetic-paramagnetic phase transformation, rare earth-copper-aluminum material provided by the invention is all presenting than great magnetic entropy variation near transformation temperature separately, there is larger magnetic refrigerant capacity, especially wherein HoCuAl and ErCuAl, their magnetic entropy becomes peak value and reach respectively 14.0J/kgK and 14.7J/kgK under the 0-2T changes of magnetic field.In addition, compound provided by the invention has and also has good magnetic, thermal reversibility matter, and cheap, ideal in, low-temperature magnetic refrigeration material.
The accompanying drawing explanation
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
The room temperature X-ray diffraction spectral line of the HoCuAl crystalline compound that Fig. 1 is the embodiment of the present invention 1 preparation;
The null field cooling of the HoCuAl crystalline compound that Fig. 2 is the embodiment of the present invention 1 preparation under downfield and the thermomagnetization curve of a band cooling;
The isothermal magnetization curve of the HoCuAl crystalline compound that Fig. 3 is the embodiment of the present invention 1 preparation;
The Arrott curve of the HoCuAl crystalline compound that Fig. 4 is the embodiment of the present invention 1 preparation;
The isothermal magnetic entropy of the HoCuAl crystalline compound that Fig. 5 is the embodiment of the present invention 1 preparation becomes temperature curve;
The room temperature X-ray diffraction spectral line of the ErCuAl crystalline compound that Fig. 6 is the embodiment of the present invention 2 preparations;
The null field cooling of the ErCuAl crystalline compound that Fig. 7 is the embodiment of the present invention 2 preparations under downfield and the thermomagnetization curve of a band cooling;
The isothermal magnetization curve of the ErCuAl crystalline compound that Fig. 8 is the embodiment of the present invention 2 preparations;
The Arrott curve of the ErCuAl crystalline compound that Fig. 9 is the embodiment of the present invention 2 preparations;
The isothermal magnetic entropy of the ErCuAl crystalline compound that Figure 10 is the embodiment of the present invention 2 preparations becomes temperature curve;
The room temperature X-ray diffraction spectral line of the DyCuAl crystalline compound that Figure 11 is the embodiment of the present invention 3 preparations;
The null field cooling of the DyCuAl crystalline compound that Figure 12 is the embodiment of the present invention 3 preparations under downfield and the thermomagnetization curve of a band cooling;
The isothermal magnetic entropy of the ErCuAl crystalline compound that Figure 13 is the embodiment of the present invention 3 preparations becomes temperature curve;
The room temperature X-ray diffraction spectral line of the TbCuAl crystalline compound that Figure 14 is the embodiment of the present invention 4 preparations;
The null field cooling of the TbCuAl crystalline compound that Figure 15 is the embodiment of the present invention 4 preparations under downfield and the thermomagnetization curve of a band cooling;
The isothermal magnetic entropy of the TbCuAl crystalline compound that Figure 16 is the embodiment of the present invention 4 preparations becomes temperature curve;
The room temperature X-ray diffraction spectral line of the GdCuAl crystalline compound that Figure 17 is the embodiment of the present invention 5 preparations;
The null field cooling of the GdCuAl crystalline compound that Figure 18 is the embodiment of the present invention 5 preparations under downfield and the thermomagnetization curve of a band cooling;
The isothermal magnetic entropy of the GdCuAl crystalline compound that Figure 19 is the embodiment of the present invention 5 preparations becomes temperature curve.
Embodiment
Referring to specific embodiment, the present invention is described.It will be appreciated by those skilled in the art that these embodiment are only for the present invention is described, the scope that it does not limit the present invention in any way.
Below in each embodiment, utilize the Rigaku D/MAX-2400 rotating anode X-ray diffractometer of Rigaku to measure the X-ray diffraction spectral line of prepared crystalline compound, concrete parameter arranges as follows: pipe is pressed: 40kV; Pipe stream: 120mA; Scanning speed: 10 °/min; Sweep limit 2 θ: 10 °-90 °.
Utilize MPMS-7 type superconducting quantum magnetometer and the multi-functional physical measurement system of PPMS-14H type of Quantum Design to measure the thermomagnetization curve of prepared crystalline compound under the size of the magnetic field of 0.05T or 0.1T, measure the isothermal magnetization curve of prepared crystalline compound in the changes of magnetic field scope of 0-5T.
embodiment 1the preparation of HoCuAl and performance measurement
The present embodiment is prepared HoCuAl, and measures its performance.
(1) preparation of HoCuAl specifically comprises the following steps:
Step 1): by HoCuAl chemical formula (being atomic ratio) weighing, purity is mixed to the wherein excessive interpolation 5% of Ho (atomic percent) higher than 99.9% commercially available rare earth metal Ho, Cu, Al raw material;
Step 2): by step 1 electric arc furnace put into by the raw material) configured or induction heater vacuumizes, when vacuum tightness reaches 2 * 10 -3～3 * 10 -3during Pa, the high-purity argon that is 99.999% by purity is evacuated to 2 * 10 by vacuum after cleaning 1-2 time again -3～3 * 10 -3during Pa, be filled with the high-purity argon gas protection, the furnace chamber internal gas pressure is 1 normal atmosphere, melting 3-5 time of repeatedly overturning, and smelting temperature is between 1500 ℃-1700 ℃;
Step 3): cooling acquisition cast alloy in copper crucible, cast alloy is wrapped with molybdenum foil, being sealed in vacuum tightness is 5 * 10 -5in the silica tube of Pa, 600 ℃ of anneal 14 days, take out in the liquid nitrogen of quenching fast, obtain product HoCuAl crystalline compound.Perhaps, by the cast alloy coarse breaking, and be with in foraminate silica tube bottom packing into, then silica tube be placed in to the ruhmkorff coil central authorities of getting rid of with in the machine cavity, adopt equally mechanical pump and diffusion pump that cavity is evacuated to high vacuum, pass into high-purity argon gas.Make alloy melting by induction heating under the high-purity argon gas protection, then from the top of silica tube, be blown into the argon gas of certain air pressure, make the nozzle ejection of alloy molten solution process silica tube bottom to the copper roller surface of high speed rotating, obtain amorphous thin ribbon shaped sample.Being sealed in vacuum tightness, be finally 5 * 10 -5in the silica tube of Pa, 600 ℃ of anneal 3 days, take out in the liquid nitrogen of quenching fast, obtain product HoCuAl crystalline compound.
(2) performance measurement of HoCuAl
1) X-ray diffraction spectral line
Utilize X-ray diffractometer to measure the room temperature X-ray diffraction spectral line of gained HoCuAl crystalline compound, as shown in Figure 1.Result shows, the HoCuAl that the product principal phase is ZrNiAl type hex crystal structure, and its spacer is
Figure BSA00000314470600051
lattice parameter
Figure BSA00000314470600052
at 31.7 ° and the 41.4 ° assorted peaks that unknown phase occurs, in Fig. 1, with " * " number, mark.
2) thermomagnetization curve
Null field cooling (ZFC) at the upper HoCuAl crystalline compound of measuring of magnetic measurement systems (SQUID) under magneticstrength H=0.05T and band cooling (FCC) pyromagnetic (M-T) curve, as shown in Figure 2.Can determine the Curie temperature T of HoCuAl crystalline compound from null field cooling M-T curve cfor 12K; In addition, near Curie temperature, ZFC and FCC curve overlap fully, show that material has good thermal reversibility.
3) isothermal magnetization curve and Arrott curve
Fig. 3 is the isothermal magnetization curve of HoCuAl crystalline compound between 5K to 39K, based on this, can obtain the Arrott curve, as shown in Figure 4.The phase transition property of compound can be determined by the shape of its Arrott curve, usually near the Arrott slope of a curve of first-order phase transition material transformation temperature is for bearing or having flex point, and the Arrott curve of second-order phase transition material presents positive slope near transformation temperature.As can be seen from Figure 4, Curie temperature T cnear curve all is positive slope, shows that the HoCuAl crystalline compound is typical second-order phase transition material.The material of known generation second-order phase transition has good magnetic, thermal reversibility, and it is wider that magnetic entropy becomes peak, is conducive to its application in magnetic refrigerator.
4) magnetic entropy becomes temperature curve and magnetic refrigerant capacity
Result based on Fig. 3, according to Maxwell relations:
Figure BSA00000314470600061
can calculate magnetic entropy from this isothermal magnetzation curve becomes.Calculate HoCuAl at T cnear magnetic entropy become to temperature (| Δ S |-T) curve, as shown in Figure 5.As we know from the figure, compound is at T cnear the huge magnetic entropy of appearance becomes, and wherein, under the 0-5T changes of magnetic field, the maximum magnetic entropy variable of HoCuAl crystalline compound is respectively 23.9J/kgK.Owing to utilizing permanent magnet NdFeB can easily obtain the magnetic field of 2T, therefore the magnetic entropy zoom of the material under the 0-2T changes of magnetic field is concerned, under the 0-2T changes of magnetic field, the Entropy Changes peak value of HoCuAl crystalline compound reaches 14.0J/kgK.
Refrigeration capacity (RC) is to weigh another important parameter of material practical value.Usually, its large I be take by Entropy Changes-temperature curve the area that peak width at half height surrounded as temperature range and is calculated acquisition.Table 1 has been listed the contrast of the rare earth based compound H oCoAl performance that the HoCuAl crystalline compound is close with its Curie temperature.Visible, under the 0-2T changes of magnetic field, the Entropy Changes peak value of the Entropy Changes peakedness ratio HoCoAl of HoCuAl crystalline compound is large 11%, and the RC of HoCuAl crystalline compound reaches 145J/kg, less by 6% than the RC of HoCoAl.In general, HoCuAl crystalline compound of the present invention has the magnetic heating performance better than HoCoAl, and low price.
Table 1
Figure BSA00000314470600062
embodiment 2the preparation of ErCuAl and performance measurement
The present embodiment is prepared ErCuAl, and measures its performance.
(1) preparation of ErCuAl specifically comprises the following steps:
Step 1): by ErCuAl chemical formula (being atomic ratio) weighing, purity is mixed to the wherein excessive interpolation 2% of Er (atomic percent) higher than 99.9% commercially available rare earth metal Er, Cu, Al raw material;
Step 2): by step 1 electric arc furnace put into by the raw material) configured or induction heater vacuumizes, when vacuum tightness reaches 2 * 10 -3-3 * 10 -3during Pa, the high-purity argon that is 99.999% by purity is evacuated to 2 * 10 by vacuum after cleaning 1-2 time again -3～3 * 10 -3during Pa, be filled with the high-purity argon gas protection, the furnace chamber internal gas pressure is 1 normal atmosphere, melting 3-5 time of repeatedly overturning, and smelting temperature is between 1500 ℃-1700 ℃;
Step 3): cooling acquisition cast alloy in copper crucible, cast alloy is wrapped with molybdenum foil, being sealed in vacuum tightness is 5 * 10 -5in the silica tube of Pa, 600 ℃ of anneal 14 days, take out in the liquid nitrogen of quenching fast, obtain product ErCuAl crystalline compound.Perhaps, by the cast alloy coarse breaking, and be with in foraminate silica tube bottom packing into, then silica tube be placed in to the ruhmkorff coil central authorities of getting rid of with in the machine cavity, adopt equally mechanical pump and diffusion pump that cavity is evacuated to high vacuum, pass into high-purity argon gas.Make alloy melting by induction heating under the high-purity argon gas protection, then from the top of silica tube, be blown into the argon gas of certain air pressure, make the nozzle ejection of alloy molten solution process silica tube bottom to the copper roller surface of high speed rotating, obtain amorphous thin ribbon shaped sample.Being sealed in vacuum tightness, be finally 5 * 10 -5in the silica tube of Pa, 600 ℃ of anneal 3 days, take out in the liquid nitrogen of quenching fast, obtain product ErCuAl crystalline compound.
(2) performance measurement of ErCuAl
1) X-ray diffraction spectral line
Utilize X-ray diffractometer to measure the room temperature X-ray diffraction spectral line of gained ErCuAl crystalline compound, as shown in Figure 6.Result shows, product is into the ErCuAl crystalline compound of single-phase ZrNiAl type hex crystal structure, and spacer is
Figure BSA00000314470600071
its lattice parameter
Figure BSA00000314470600072
2) thermomagnetization curve
Lower the temperature (ZFC) and be with cooling (FC) pyromagnetic (M-T) curve as shown in Figure 7 at the null field of the upper ErCuAl crystalline compound of measuring of magnetic measurement systems (SQUID).Can determine ErCuAl crystalline compound Curie temperature T from the M-T curve cfor 7K.Near transformation temperature, ZFC and FC thermomagnetization curve overlap substantially, show that material has good thermal reversibility matter.
3) isothermal magnetization curve and Arrott curve
Near the isothermal magnetization curve of ErCuAl crystalline compound transformation temperature as shown in Figure 8.Calculate the ErCuAl crystalline compound at T according to this isothermal magnetzation curve cnear temperature, the Arrott curve of (being the scope of 2K to 33K), be shown in Fig. 9.As shown in Figure 9, Curie temperature T cnear curve all is positive slope, shows that the HoCuAl crystalline compound is typical second-order phase transition material.
4) magnetic entropy becomes temperature curve and magnetic refrigerant capacity
The ErCuAl crystalline compound magnetic entropy obtained according to the isothermal magnetization curve calculation of Fig. 8 become to temperature (| Δ S m|-T) curve is as shown in figure 10.As can be seen from Figure 10, under the 0-2T changes of magnetic field, the maximum magnetic entropy variable of ErCuAl crystalline compound reaches 14.7J/kgK.Reach 98J/kg by calculating its refrigeration capacity RC.
embodiment 3the preparation of DyCuAl and performance measurement
The present embodiment is prepared DyCuAl, and measures its performance.
(1) preparation of DyCuAl specifically comprises the following steps:
Step 1): by DyCuAl chemical formula (being atomic ratio) weighing, purity is mixed to the wherein excessive interpolation 5% of Dy (atomic percent) higher than 99.9% commercially available rare earth metal Dy, Cu, Al raw material;
Step 2) and step 3) identical with embodiment 1.
(2) performance measurement of DyCuAl
1) X-ray diffraction spectral line
The room temperature X-ray diffraction spectral line of DyCuAl crystalline compound as shown in figure 11.Result shows,
DyCuAl is single-phase ZrNiAl type hex crystal structure, and spacer is
Figure BSA00000314470600081
its lattice parameter
Figure BSA00000314470600082
2) thermomagnetization curve
Pyromagnetic (M-T) curve of DyCuAl crystalline compound as shown in figure 12, can be determined the Curie temperature T of DyGa from the M-T curve cfor 27K.
3) magnetic entropy becomes temperature curve and magnetic refrigerant capacity
Obtain the DyCuAl crystalline compound at this T according to the isothermal magnetization curve calculation cnear magnetic entropy become that curve as shown in figure 13 to temperature (| Δ S |-T).Wherein, under the 0-2T changes of magnetic field, the maximum magnetic entropy variable of DyCuAl is 10.9J/kgK, and its RC is 145J/kg.
embodiment 4the preparation of TbCuAl and performance measurement
The present embodiment is prepared TbCuAl, and measures its performance.
(1) preparation of TbCuA1 specifically comprises the following steps:
Step 1): by TbCuAl chemical formula (being atomic ratio) weighing, purity is mixed to the wherein excessive interpolation 5% of Tb (atomic percent) higher than 99.9% commercially available rare-earth metal Tb, Cu, Al raw material;
Step 2) and step 3) identical with embodiment 1.
(2) performance measurement of TbCuAl
1) X-ray diffraction spectral line
The room temperature X-ray diffraction spectral line of TbCuAl crystalline compound as shown in figure 14.Result shows that TbCuAl is single-phase ZrNiAl type hex crystal structure, and spacer is
Figure BSA00000314470600091
its lattice parameter
Figure BSA00000314470600092
2) thermomagnetization curve
Pyromagnetic (M-T) curve of TbCuAl crystalline compound as shown in figure 15, can be determined the Curie temperature T of DyGa from the M-T curve cfor 52K.
3) magnetic entropy becomes temperature curve and magnetic refrigerant capacity
Obtain the TbCuAl crystalline compound at this T according to the isothermal magnetization curve calculation cnear magnetic entropy become that curve as shown in figure 16 to temperature (| Δ S |-T).Wherein, under the 0-2T changes of magnetic field, the maximum magnetic entropy variable of TbCuAl is 6.3J/kgK, and its RC is 111J/kg.
embodiment 5the preparation of GdCuAl and performance measurement
The present embodiment is prepared GdCuAl, and measures its performance.
(1) preparation of GdCuAl specifically comprises the following steps:
Step 1): by GdCuAl chemical formula (being atomic ratio) weighing, purity is mixed to the wherein excessive interpolation 5% of Gd (atomic percent) higher than 99.9% commercially available rare metal Gd, Cu, Al raw material;
Step 2) and step 3) identical with embodiment 1.
(2) performance measurement of GdCuAl
1) X-ray diffraction spectral line
The room temperature X-ray diffraction spectral line of GdCuAl crystalline compound as shown in figure 17.Result shows, TbCuAl is single-phase ZrNiAl type hex crystal structure, and spacer is
Figure BSA00000314470600093
its lattice parameter
Figure BSA00000314470600094
2) thermomagnetization curve
Pyromagnetic (M-T) curve of GdCuAl crystalline compound as shown in figure 18.Can determine the Curie temperature T of DyGa from the M-T curve cfor 52K.
3) magnetic entropy becomes temperature curve and magnetic refrigerant capacity
Obtain the TbCuAl crystalline compound at this T according to the isothermal magnetization curve calculation cnear magnetic entropy become that curve as shown in figure 19 to temperature (| Δ S |-T).Wherein, under the 0-2T changes of magnetic field, the maximum magnetic entropy variable of GdCuAl is 5.2J/kgK, and its RC is 169J/kg.
Although made specific descriptions with reference to the above embodiments for the present invention, but for the person of ordinary skill of the art, should be appreciated that and can modify or improve based on content disclosed by the invention, and these modifications and improving all within the spirit and scope of the present invention.

Claims (9)

1. the rare earth-copper-aluminum material for magnetic refrigeration, the compound that this rare earth-copper-aluminum material is following general formula: RCuAl, wherein R is Ho or Er;
The preparation method of described rare earth-copper-aluminum material comprises the following steps:
1) press the weighing of RCuAl chemical formula atomic percent, R, Cu, Al raw material are mixed, wherein R is Ho or Er;
2) raw material step 1) is mixed to get is put into electric arc furnace or induction heater, is evacuated to 3 * 10 -3more than Pa, by high-purity argon, clean and melting, smelting temperature is more than 1500 ℃, the cooling cast alloy that obtains; Wherein saidly be evacuated to 3 * 10 -3more than Pa, be lower than 3 * 10 on index value -3the vacuum tightness of Pa;
3) by step 2) cast alloy that obtains carries out the vacuum annealing processing, takes out afterwards cooling fast; Perhaps first by step 2) cast alloy induction melting fast quenching in getting rid of the band machine of obtaining obtains amorphous thin ribbon, then carry out the vacuum annealing processing, take out afterwards cooling fast.
2. the rare earth-copper-aluminum material for the magnetic refrigeration according to claim 1, is characterized in that, described rare earth-copper-aluminum material has ZrNiAl type hex crystal structure.
3. the rare earth-copper-aluminum material for the magnetic refrigeration according to claim 1 and 2, is characterized in that the atomic percent of the excessive interpolation 2%～5% of R raw material in described step 1).
4. the rare earth-copper-aluminum material for magnetic refrigeration according to claim 1 and 2, is characterized in that described step 2) in be evacuated to 2 * 10 -3pa～3 * 10 -3pa.
5. the rare earth-copper-aluminum material for magnetic refrigeration according to claim 1 and 2, is characterized in that described step 2) in smelting temperature be 1500 ℃～1700 ℃.
6. the rare earth-copper-aluminum material for the magnetic refrigeration according to claim 1 and 2, is characterized in that, the temperature that in described step 3), vacuum annealing is processed is 520 ℃～600 ℃.
7. the rare earth-copper-aluminum material for the magnetic refrigeration according to claim 1 and 2, is characterized in that, the vacuum tightness that in described step 3), vacuum annealing is processed is 1 * 10 -4pa～1 * 10 -5pa.
8. the rare earth-copper-aluminum material for the magnetic refrigeration according to claim 1 and 2, is characterized in that, the time that in described step 3), vacuum annealing is processed is 2～14 days.
9. the rare earth-copper-aluminum material for the magnetic refrigeration according to claim 1 and 2, is characterized in that, being cooled to fast in described step 3) quenched in liquid nitrogen or frozen water.
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