CN102978422A - Preparation method and application of rare earth-nickel-silicon material with large magnetothermal effect - Google Patents
Preparation method and application of rare earth-nickel-silicon material with large magnetothermal effect Download PDFInfo
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Abstract
The invention provides a rare earth-nickel-silicon magnetic refrigeration material with large magnetothermal effect and a preparation method and application thereof. The material is a compound with a general formula of RNiSi, wherein R is any one or more than one of elements Gd, Tb, Dy, Ho and Er. The preparation method of the material comprises the following steps of: combining and mixing the raw materials according to a certain proportion, and placing the mixed raw materials in a smelting furnace; vacuumizing, cleaning with argon, and smelting under the protection of argon; performing vacuum annealing on the smelted material; and taking out and quickly cooling. Due to the antiferromagnetic-ferromagnetic magnetic transition induced by magnetic field, large magnetic entropy change and wide working temperature area appear near the phase-transition temperature of the rare earth-nickel-silicon material provided by the invention and particularly HoNiSi; and the rare earth-nickel-silicon material has relatively strong magnetic refrigeration capacity and good thermal and magnetic reversibility, and is a very ideal low-temperature magnetic refrigeration material.
Description
Technical field
The present invention relates to magneticsubstance, particularly a kind of rare earth-nickel with large magnetothermal effect-silicon materials and preparation method thereof and the purposes in the magnetic Refrigeration Technique.
Background technology
In recent years, along with modern age the energy worsening shortages and the continuous enhancing of environmental protection consciousness, the magnetic Refrigeration Technique has been subject to people and has more and more paid close attention to.The magnetic refrigeration refers to the Refrigeration Technique of a kind of new green environment protection take magneticsubstance as refrigeration working medium, its ultimate principle is the magnetothermal effect by means of magnetic refrigerating material, refer to that namely magnetic moment of atom is arranged ordering under the effect of paramagnetic material or soft ferromagnetic outside magnetic field, magneticsubstance can be emitted heat during isothermal magnetization, and magnetic entropy reduces simultaneously; And magnetic moment of atom is got back to previous random state when removing magnetic field, and magneticsubstance can simultaneously magnetic entropy increase of absorbing heat.Compare with traditional gas compression Refrigeration Technique, the circulation of can realizing ideal on principle of magnetic Refrigeration Technique obtains the efficient of maximum possible.Simultaneously, magnetic refrigeration adopts magneticsubstance as refrigeration working medium, and environment without destruction, and is had the remarkable advantages such as noise is little, life-span length, good reliability.From environmental protection, energy-conservation angle, the magnetic Refrigeration Technique has huge research and development potentiality.And as the core of magnetic Refrigeration Technique, the successful research and development of high-performance magnetism refrigerating material are the practical so that business-like keys of magnetic Refrigeration Technique.Given this, seek the novel magnetic material, study the focus that its magnetothermal effect becomes investigation of materials field, present countries in the world.
The material that is applied at first the magnetic Refrigeration Technique is the paramagnetic substance of some weak magnetic, is mainly used in obtaining the very low temperature (mK-μ K) near OK.1933, Giauque and MacDougall were with Gd
2(SO
4)
38H
2O is the experiment that working medium has been carried out adiabatic demagnetization, and has obtained the very low temperature of 0.25K.At present, the magnetic Refrigeration Technique has become the indispensable technique means of modern low-temperature physics.Simultaneously, low temperature magnetic Refrigeration Technique can liquefy helium and nitrogen, for industry and civilian, the hydrogen that can also liquefy prepares the environment-friendly fuel of cleanliness without any pollution.Therefore, the research of low-temperature magnetic refrigeration material receives the very big concern of domestic and international research institution and branch of industry.Usually, the significant parameter that characterizes the magnetic refrigerating material magnetothermal effect comprises that magnetic entropy becomes (Δ S) and magnetic refrigerant capacity (RC), and maximum value generally appears in the magnetic entropy change of material near transformation temperature, and Δ S and the RC value of material are larger, and its refrigerating efficiency is just higher.At present, the magnetic refrigerating material of finding in cold zone research comprises that mainly rare earth element monocrystalline, polycrystalline material (such as Nd, Er and Tm) and rare earth intermetallic compound are (such as DyNi
2, Tb
2PdSi
3, GdPd
2Si and (Gd
0.2Er
0.8) NiAl) etc.But the magnetothermal effect of these materials and magnetic refrigerant capacity still are not very high, and the magnetic refrigerating material that wherein has an one-level magnetic phase transition is (such as ErCo
2) usually be accompanied by obvious heat stagnation and hysteresis, thus cause magnetic refrigerating material duty in working cycle to descend.
In view of the needs of above research background and the practical application of magnetic Refrigeration Technique, in recent years, seek the new focus that the magnetic refrigerating material with reversible large magnetothermal effect and high magnetic refrigerant capacity has become the magnetic refrigerating material research field.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of rare earth-nickel that is used for the magnetic refrigeration with reversible large magnetothermal effect, high refrigeration capacity-silicon materials, a further object of the present invention is to provide the purposes of described rare earth-nickel for the magnetic refrigeration-silicon materials.
The objective of the invention is to be achieved through the following technical solutions:
A kind of method for preparing rare earth-nickel with large magnetothermal effect-silicon magnetic refrigerating material, described magnetic refrigerating material is the compound of following general formula: RNiSi, wherein R is rare earth element, it is characterized in that: described method comprises the steps:
1) takes by weighing raw material R and Ni, Si and mixing;
2) raw material that step 1) is configured is put into smelting furnace, and smelting furnace vacuumizes rear with the argon gas cleaning, under argon shield the described raw material that configures is carried out melting afterwards;
3) with step 2) melted material carries out vacuum annealing and processes, and takes out afterwards fast cooling.
Preferably, in step 1), the ratio of the amount of substance of described raw material R and Ni, Si is the atomic ratio in the RNiSi chemical formula.
Preferably, R is by its 2～5% excessive interpolations at described chemical formula Atom ratio, and more preferably, R is by its 2～3% excessive interpolations at described chemical formula Atom ratio.
Preferably, in step 2) in, the described pressure that reaches that vacuumizes is 3 * 10
-3Pa or less than 3 * 10
-3Pa; The temperature of described melting is 1300 ° more than the C; The time of described melting is 0.5～10 minute.
More preferably, in step 2) in, the described pressure that reaches that vacuumizes is 2 * 10
-3～3 * 10
-3Pa; The temperature of described melting is 1300～1700 ° of C; The time of described melting is 2～3 minutes.
Preferably, in step 3), the temperature of described vacuum annealing is 600～1100 ° of C; The time of described vacuum annealing is 3～30 days.
More preferably, in step 3), the temperature of described vacuum annealing is 700～900 ° of C; The time of described vacuum annealing is 5～15 days; Described Cooling Mode is in quench liquid nitrogen or the frozen water.
On the other hand, the present invention also provide a kind of with rare earth-nickel-silicon materials as the purposes of refrigerating material, described rare earth-nickel-silicon materials are the compound of following general formula: RNiSi, wherein R is rare earth element.
Preferably, described R is any one in Gd, Tb, Dy, Ho and the Er element, and perhaps R is any one combination in Ho element and Gd, Tb, Dy and the Er element.
Preferably, described material has TiNiSi type orthorhombic body structure.
Compared with prior art, the beneficial effect of the rare earth-nickel for the magnetic refrigeration provided by the invention-silicon materials is: 1, a low magnetic entropy becomes large, and wherein the magnetic entropy of HoNiSi becomes under 2T magnetic field up to 17.5J/kgK; 2, refrigeration capacity is strong, and wherein the magnetic refrigerant capacity of HoNiSi is 5T up to 471J/kg(magnetic field); 3, has good magnetic, thermal reversibility matter.
Description of drawings
Below, describe by reference to the accompanying drawings embodiments of the invention in detail, wherein:
Fig. 1 is the room temperature X-ray diffraction spectral line of the HoNiSi of the embodiment of the invention 1;
Fig. 2 is the null field cooling of HoNiSi under downfield and the thermomagnetization curve of a band cooling of the embodiment of the invention 1;
Fig. 3 is the isothermal magnetization curve of the HoNiSi of the embodiment of the invention 1;
Fig. 4 is the Arrott curve of the HoNiSi of the embodiment of the invention 1;
Fig. 5 is that the magnetic entropy of the HoNiSi of the embodiment of the invention 1 becomes and the temperature relation curve;
Fig. 6 is the magnetic refrigerant capacity scaling system of the HoNiSi of the embodiment of the invention 1;
Fig. 7 is the room temperature X-ray diffraction spectral line of the DyNiSi of the embodiment of the invention 2;
Fig. 8 is the null field cooling of DyNiSi under downfield and the thermomagnetization curve of a band cooling of the embodiment of the invention 2;
Fig. 9 is the isothermal magnetization curve of the DyNiSi of the embodiment of the invention 2;
Figure 10 is the Arrott curve of the DyNiSi of the embodiment of the invention 2;
Figure 11 is that the magnetic entropy of the DyNiSi of the embodiment of the invention 2 becomes and the temperature relation curve;
Figure 12 is the room temperature X-ray diffraction spectral line of the ErNiSi of the embodiment of the invention 3;
Figure 13 is the null field cooling of ErNiSi under downfield and the thermomagnetization curve of a band cooling of the embodiment of the invention 3;
Figure 14 is the isothermal magnetization curve of the ErNiSi of the embodiment of the invention 3;
Figure 15 is the Arrott curve of the ErNiSi of the embodiment of the invention 3;
Figure 16 is that the magnetic entropy of the ErNiSi of the embodiment of the invention 3 becomes and the temperature relation curve.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, the embodiment that provides is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
Used rare earth metal and Ni in the embodiment of the invention, Si raw material are available from the Beijing Non-Ferrous Metal Research General Academy, and its purity all is higher than 99.9%.The used electric arc furnace of sample preparation is the WK-II type non-consumable arc furnace that the Beijing WuKe opto-electrical Technology Co., Ltd produces.The room temperature X-ray diffraction is measured the Rigaku D/max-2400 type X-ray diffractometer that uses Cu K α target.The Magnetic Measurement instrument is the MPMS SQUID VSM magnetic measurement systems of U.S. QuantumDesign company design.
Embodiment 1:
Present embodiment is used for illustrating magnetic refrigerating material provided by the invention and preparation method thereof.
1, preparation method:
1) presses atomic ratio weighing in the HoNiSi chemical formula, purity being higher than 99.9% commercially available rare earth metal Ho mixes with Ni, Si raw material, wherein Ho is by its 2% excessive interpolation at chemical formula HoNiSi Atom per-cent, in order to the volatilization of compensation Ho in preparation process;
2) raw material that step 1) is prepared is put into electric arc furnace and is vacuumized, when vacuum tightness reaches 3 * 10
-3During Pa, after straight argon cleaning 2 times, melting under 1 atmospheric pure argon protection, the time of melting is 3 minutes, smelting temperature is 1500～1550 ° of C;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum foil, and being sealed in vacuum tightness is 5 * 10
-3In the silica tube of Pa, 800 ° of C anneal 7 days, take out in the liquid nitrogen of quenching fast, obtain product.
2, product characterizes and performance measurement:
Measure the room temperature X-ray diffraction spectral line that present embodiment makes product with X-ray diffractometer, as shown in Figure 1.The result shows that product is into the HoNiSi compound of single-phase TiNiSi type orthorhombic body structure, and its spacer is Pnma, and lattice parameter is
α=β=γ=90 °.
Measure the HoNiSi make at magneticstrength μ in magnetic measurement systems (SQUID VSM)
0Null field cooling (ZFC) under the H=0.05T and band cooling (FC) pyromagnetic (M-T) curve, as shown in Figure 2.Antiferromagnetic-paramagnetism changes can to determine that HoNiSi has from the null field cooling M-T curve, its Ne﹠1﹠el temperature T
NBe 3.8K; In addition, as we know from the figure, ZFC and FC curve well overlap, and show that material has good thermal reversibility.
Measured the HoNiSi that makes at T in SQUID VSM system
NNear (temperature range of 2K to 45K) rise the field and the isothermal magnetization curve when falling, as shown in Figure 3.From figure, do not observe the magnetic lag phenomenon, show that the magnetic entropy change of the HoNiSi that present embodiment makes is reversible to magnetic field.
Existing studies show that, 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 then presents positive slope near transformation temperature.Fig. 4 is the Arrott curve of the embodiment 1 compound H oNiSi that records in 2K to 45K temperature range, wherein illustration is T
NArrott curve between the following 2K to 4K.As can be seen from the figure, at T
NThere is obvious negative slope in following Arrott curve, shows at T
NFollowing warm area compound H oNiSi have induced by magnetic field antiferromagnetic-ferromagnetic first-order phase transition.And at T
NAbove Arrott curve all is positive slope, shows that HoNiSi that embodiment 1 makes is at transformation temperature T
NThe paramagnetic-ferromagnetic of above induced by magnetic field becomes typical second-order phase transition mutually.Be well known that to those skilled in the art the material that second-order phase transition occurs has good magnetic, thermal reversibility, it is wider that magnetic entropy becomes the peak, is conducive to its application in magnetic refrigerator.
According to Maxwell relations:
Can become Δ S from isothermal magnetization curve calculation magnetic entropy shown in Figure 3.The HoNiSi of the embodiment 1 that calculates is at transformation temperature T
NNear magnetic entropy becomes and temperature relation curve (Δ S-T), as shown in Figure 5, wherein a1 represents the isothermal magnetic entropy varied curve under the 0-1T changes of magnetic field, b1 represents the isothermal magnetic entropy varied curve under the 0-2T changes of magnetic field, c1 represents the isothermal magnetic entropy varied curve under the 0-3T changes of magnetic field, d1 represents the isothermal magnetic entropy varied curve under the 0-4T changes of magnetic field, and e1 represents the isothermal magnetic entropy varied curve under the 0-5T changes of magnetic field.As we know from the figure, HoNiSi is at T
NOccur the maximum value that magnetic entropy becomes near the temperature, wherein under the 0-5T changes of magnetic field, the maximum magnetic entropy variable of HoNiSi crystalline compound is 26.0J/kgK.Utilize permanent magnet NdFeB can obtain the magnetic field of 2T, so 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 HoNiSi compound reaches 17.5J/kgK.Refrigeration capacity (RC) is to weigh another important parameter of material practical value.Usually, the refrigeration capacity of material in a reversible refrigeration cycle can by
Calculate, wherein T
1And T
2Be respectively the magnetic entropy change cold junction corresponding with the peak width at half height of temperature relation curve and the temperature in hot junction.As shown in Figure 6, can draw according to calculating, the temperature in HoNiSi cold junction and hot junction is respectively 3.2K and 25.9K under the 0-5T changes of magnetic field, and its refrigeration capacity RC maximum value reaches 471J/kg.Table 1 has been listed the maximum magnetic entropy variable of HoNiSi that present embodiment the provides existing rare earth based compound close with its transformation temperature and the contrast of refrigeration capacity.Can find out that by the data in the table 1 HoNiSi of the present invention has more excellent magnetic refrigeration performance.
The contrast of table 1 maximum magnetic entropy variable and refrigeration capacity
When carrying out the preparation of rare earth-nickel-silicon materials, can suitably regulate preparation parameter according to practical situation, as: the addition of rare-earth metal material, smelting temperature, time, vacuum tightness, the time of anneal and temperature etc.
The preparation method of HoNiSi can also for:
1) press atomic ratio weighing in the HoNiSi chemical formula, purity is higher than 99.9% commercially available rare earth metal Ho and mixes with Ni, Si raw material, wherein Ho is by its 5% excessive interpolation at chemical formula Atom per-cent;
2) raw material that step 1) is prepared is put into electric arc furnace and is vacuumized, when vacuum tightness reaches 2 * 10
-3During Pa, after straight argon cleaning 2 times, melting under 1 atmospheric pure argon protection, the time of melting is 10 minutes, smelting temperature is 1700 ° of C;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum foil, and being sealed in vacuum tightness is 5 * 10
-3In the silica tube of Pa, 900 ° of C anneal 30 days, take out in the liquid nitrogen of quenching fast, obtain product.
Embodiment 2:
Present embodiment is used for illustrating magnetic refrigerating material provided by the invention and preparation method thereof.
1, preparation method:
1) press atomic ratio weighing in the DyNiSi chemical formula, purity is higher than 99.9% commercially available rare earth metal Dy and mixes with Ni, Si raw material, wherein Dy is by its 2% excessive interpolation at chemical formula D yNiSi Atom per-cent;
2) raw material that step 1) is prepared is put into electric arc furnace and is vacuumized, when vacuum tightness reaches 3 * 10
-3During Pa, after straight argon cleaning 2 times, melting under 1 atmospheric pure argon protection, the time of melting is 3 minutes, smelting temperature is 1500～1550 ° of C;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum foil, and being sealed in vacuum tightness is 5 * 10
-3In the silica tube of Pa, 800 ° of C anneal 7 days, take out in the liquid nitrogen of quenching fast, obtain product.
2, product characterizes and performance measurement:
Measure the room temperature X-ray diffraction spectral line that present embodiment makes product with X-ray diffractometer, as shown in Figure 7.The result shows that product is into the DyNiSi compound of single-phase TiNiSi type orthorhombic body structure, and its spacer is Pnma, and lattice parameter is
α=β=γ=90 °.
The DyNiSi that present embodiment makes is at magneticstrength μ
0Null field cooling (ZFC) under the H=0.05T and band cooling (FC) pyromagnetic (M-T) curve as shown in Figure 8.Can determine that from the M-T curve DyNiSi is at Ne﹠1﹠el temperature T
NThe magnetic transformation of antiferromagnetic-paramagnetic occurs for the 8.8K place.At T
NNeighbouring ZFC and FC thermomagnetization curve well overlap, and show that material has good thermal reversibility matter.
The DyNiSi compound that present embodiment makes near transformation temperature (temperature range of 2K to 50K) the isothermal magnetization curve as shown in Figure 9, at T
NA platform appears in following magnetzation curve, illustrate that there is strong magnetocrystalline anisotropy at low temperatures in the DyNiSi compound, the part magnetic moment just can be magnetized to saturated under lower magnetic field, antiferromagnetic-ferromagnetic change magnetic transition that another part magnetic moment then needs higher magnetic field just can induce.In addition, from figure, do not observe the magnetic lag phenomenon, show that the magnetic entropy change of DyNiSi is reversible to magnetic field.
Figure 10 is for to calculate this compound at T according to this isothermal magnetzation curve
NNear the Arrott curve of (being the temperature range of 2K to the 50K) temperature, wherein illustration is T
NArrott curve between the following 2K to 5K.As can be seen from the figure, at T
NThere is obvious negative slope in following Arrott curve, shows at T
NFollowing warm area Compound D yNiSi have induced by magnetic field antiferromagnetic-ferromagnetic first-order phase transition.And at T
NAbove Arrott curve all is positive slope, shows that DyNiSi that embodiment 2 makes is at transformation temperature T
NThe paramagnetic-ferromagnetic of above induced by magnetic field becomes typical second-order phase transition mutually.
The DyNiSi of present embodiment is at Ne﹠1﹠el temperature T
NNear isothermal magnetic entropy change and temperature relation curve are as shown in figure 11, wherein a2 represents the isothermal magnetic entropy varied curve under the 0-1T changes of magnetic field, b2 represents the isothermal magnetic entropy varied curve under the 0-2T changes of magnetic field, c2 represents the isothermal magnetic entropy varied curve under the 0-3T changes of magnetic field, d2 represents the isothermal magnetic entropy varied curve under the 0-4T changes of magnetic field, and e2 represents the isothermal magnetic entropy varied curve under the 0-5T changes of magnetic field.As seen from Figure 11, at T
NPositive magnetic entropy variate occurred when bending down, raise with magnetic field, the magnetic entropy variate is gradually by on the occasion of changing negative value into, this be since occurred induced by magnetic field antiferromagnetic-ferromagnetic change magnetic transition due to.Under the 0-2T changes of magnetic field, the Entropy Changes peak value of DyNiSi compound is at T
NThe place reaches 9.3J/kgK, and under the 0-5T changes of magnetic field, its maximum magnetic entropy variable reaches 22.1J/kgK, calculates its refrigeration capacity RC and reaches 401J/kg.Table 2 has been listed the maximum magnetic entropy variable of DyNiSi that present embodiment the provides existing rare earth based compound close with its transformation temperature and the contrast of refrigeration capacity.Can find out that by the data in the table 2 DyNiSi of the present invention has more excellent magnetic refrigeration performance.
The contrast of table 2 maximum magnetic entropy variable and refrigeration capacity
1) press atomic ratio weighing in the DyNiSi chemical formula, purity is higher than 99.9% commercially available rare earth metal Dy and mixes with Ni, Si raw material, wherein Dy is by its 3% excessive interpolation at chemical formula Atom per-cent;
2) raw material that step 1) is prepared is put into electric arc furnace and is vacuumized, when vacuum tightness reaches 2 * 10
-3During Pa, after straight argon cleaning 2 times, melting under 1 atmospheric pure argon protection, the time of melting is 2 minutes, smelting temperature is 1300 ° of C;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum foil, and being sealed in vacuum tightness is 5 * 10
-3In the silica tube of Pa, 600 ° of C anneal 3 days, take out in the liquid nitrogen of quenching fast, obtain product.
Embodiment 3:
Present embodiment is used for illustrating magnetic refrigerating material provided by the invention and preparation method thereof.
1, preparation method:
1) press atomic ratio weighing in the ErNiSi chemical formula, purity is higher than 99.9% commercially available rare earth metal Er and mixes with Ni, Si raw material, wherein Er is by its 2% excessive interpolation at chemical formula ErNiSi Atom per-cent;
2) raw material that step 1) is prepared is put into electric arc furnace and is vacuumized, when vacuum tightness reaches 3 * 10
-3During Pa, after straight argon cleaning 2 times, melting under 1 atmospheric pure argon protection, the time of melting is 3 minutes, smelting temperature is 1500～1550 ° of C;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum foil, and being sealed in vacuum tightness is 5 * 10
-3In the silica tube of Pa, 800 ° of C anneal 7 days, take out in the liquid nitrogen of quenching fast, obtain product.
2, product characterizes and performance measurement:
The room temperature X-ray diffraction spectral line that present embodiment makes compound as shown in figure 12, the result shows that product is into the ErNiSi compound of single-phase TiNiSi type orthorhombic body structure, its spacer is Pnma, lattice parameter is
α=β=γ=90 °.
The ErNiSi that present embodiment makes is at magneticstrength μ
0Null field cooling (ZFC) under the H=0.05T and band cooling (FC) pyromagnetic (M-T) curve as shown in figure 13.Can determine that from the M-T curve ErNiSi is at Ne﹠1﹠el temperature T
NThe magnetic transformation of antiferromagnetic-paramagnetic occurs for the 4K place.At T
NNeighbouring ZFC and FC thermomagnetization curve well overlap, and show that material has good thermal reversibility matter.
The ErNiSi of present embodiment is at T
N(temperature range of 2K to 45K) records near the temperature rise the field and the isothermal magnetization curve when falling as shown in figure 14, from figure, do not observe the magnetic lag phenomenon, it is reversible that the magnetic entropy that shows ErNiSi becomes magnetic field.Figure 15 is for to calculate this compound at T according to this isothermal magnetzation curve
NNear the Arrott curve of (being the temperature range of 2K to the 45K) temperature, wherein illustration is T
NArrott curve between the following 2K to 4K.As can be seen from the figure, at T
NThere is obvious negative slope in following Arrott curve, shows at T
NFollowing warm area compd E rNiSi have induced by magnetic field antiferromagnetic-ferromagnetic first-order phase transition.And at T
NAbove Arrott curve all is positive slope, shows that ErNiSi that embodiment 3 makes is at transformation temperature T
NThe paramagnetic-ferromagnetic of above induced by magnetic field becomes typical second-order phase transition mutually.
The ErNiSi of present embodiment is at Ne﹠1﹠el temperature T
NNear isothermal magnetic entropy change and temperature relation curve are as shown in figure 16, wherein a3 represents the isothermal magnetic entropy varied curve under the 0-1T changes of magnetic field, b3 represents the isothermal magnetic entropy varied curve under the 0-2T changes of magnetic field, c3 represents the isothermal magnetic entropy varied curve under the 0-3T changes of magnetic field, d3 represents the isothermal magnetic entropy varied curve under the 0-4T changes of magnetic field, and e3 represents the isothermal magnetic entropy varied curve under the 0-5T changes of magnetic field.As can be seen from Figure 16, under the 0-2T changes of magnetic field, the Entropy Changes peak value of ErNiSi compound is at T
NThe place reaches 8.8J/kgK, and under the 0-5T changes of magnetic field, the maximum magnetic entropy variable of ErNiSi is 19.0J/kgK, and the maximum value of its refrigeration capacity RC is 309J/kg.
1) press atomic ratio weighing in the ErNiSi chemical formula, purity is higher than 99.9% commercially available rare earth metal Er and mixes with Ni, Si raw material, wherein Er is by its 2% excessive interpolation at chemical formula Atom per-cent;
2) raw material that step 1) is prepared is put into electric arc furnace and is vacuumized, when vacuum tightness reaches 3 * 10
-3During Pa, after straight argon cleaning 1 time, melting under 1 atmospheric pure argon protection, the time of melting is 0.5 minute, smelting temperature is about 1450 ° of C;
3) cooling obtains cast alloy in copper crucible, and cast alloy is wrapped with molybdenum foil, and being sealed in vacuum tightness is 5 * 10
-3In the silica tube of Pa, 1100 ° of C anneal 5 days, take out in the liquid nitrogen of quenching fast, obtain product.
Preparation the present invention has the raw material of the magnetic refrigerating material of reversible large magnetothermal effect, be not limited in Dy, Ho, Er element, can also be other rare earth elements such as Gd, Tb, or the combination of two or more rare earth element, such as combination of combination, Ho and the Er of Ho and Tb etc., be not repeated at this.
Can find out by above embodiment and performance measurement result, the rare earth-nickel with TiNiSi type orthorhombic body structure of the present invention's preparation-silicon magnetic refrigerating material, it is the RNiSi compound, its Ne﹠1﹠el temperature is between 3K and 20K, antiferromagnetic-ferromagnetic first-order phase transition can occur under induced by magnetic field, showing large magnetothermal effect near the transformation temperature separately, wherein the magnetic entropy of HoNiSi under the 2T changes of magnetic field uprises and reaches 17.5J/kgK, becomes far above the magnetic entropy with other magnetic refrigerating material of warm area.In addition, compound of the present invention also has good magnetic, thermal reversibility matter, is ideal low-temperature magnetic refrigeration material.Preparation provided by the invention has the method for the rare earth-nickel of large magnetothermal effect-silicon magnetic refrigerating material, and it is simple to have preparation technology, is fit to the advantages such as suitability for industrialized production.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " specific examples " etc. means to be contained at least one embodiment of the present invention or the example in conjunction with specific features, structure, material or characteristics that this embodiment describes.In this manual, the schematic statement of above-mentioned term not necessarily referred to identical embodiment.And the specific features of description, structure, material or characteristics can be with suitable mode combinations in any one or more embodiment or example.
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 make amendment 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 (10)
1. method for preparing rare earth-nickel with large magnetothermal effect-silicon magnetic refrigerating material, described magnetic refrigerating material is the compound of following general formula:
RNiSi, wherein
RBe rare earth element, it is characterized in that: described method comprises the steps:
1) takes by weighing raw material
RWith Ni, Si and mixing;
2) raw material that step 1) is configured is put into smelting furnace, and smelting furnace vacuumizes rear with the argon gas cleaning, under argon shield the described raw material that configures is carried out melting afterwards;
3) with step 2) melted material carries out vacuum annealing and processes, and takes out afterwards fast cooling.
2. method according to claim 1 is characterized in that, in step 1), and described raw material
RWith the ratio of the amount of substance of Ni, Si be
RAtomic ratio in the NiSi chemical formula.
3. method according to claim 1 is characterized in that,
RBy its 2 ~ 5% excessive interpolations at described chemical formula Atom ratio, preferably,
RBy its 2 ~ 3% excessive interpolations at described chemical formula Atom ratio.
4. method according to claim 1 is characterized in that, in step 2) in, the described pressure that reaches that vacuumizes is 3 * 10
-3Pa or less than 3 * 10
-3Pa; The temperature of described melting is more than 1300 C; The time of described melting is 0.5 ~ 10 minute.
5. method according to claim 4 is characterized in that, in step 2) in, the described pressure that reaches that vacuumizes is 2 * 10
-3~ 3 * 10
-3Pa; The temperature of described melting is 1300 ~ 1700 C; The time of described melting is 2 ~ 3 minutes.
6. method according to claim 1 is characterized in that, in step 3), the temperature of described vacuum annealing is 600 ~ 1100 C; The time of described vacuum annealing is 3 ~ 30 days.
7. method according to claim 6 is characterized in that, in step 3), the temperature of described vacuum annealing is 700 ~ 900 C; The time of described vacuum annealing is 5 ~ 15 days; Described Cooling Mode is in quench liquid nitrogen or the frozen water.
One kind with rare earth-nickel-silicon materials as the purposes of refrigerating material, it is characterized in that described rare earth-nickel-silicon materials are the compound of following general formula:
RNiSi, wherein
RBe rare earth element.
9. the described rare earth-nickel-silicon materials that utilize is characterized in that as the purposes of refrigerating material according to claim 8, and are described
RBe in Gd, Tb, Dy, Ho and the Er element any one, perhaps
RBe any one combination in Ho element and Gd, Tb, Dy and the Er element.
10. the described rare earth-nickel-silicon materials that utilize is characterized in that as the purposes of refrigerating material described material has TiNiSi type orthorhombic body structure according to claim 8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200253A (en) * | 2015-09-25 | 2015-12-30 | 北京科技大学 | Preparation method of rare earth-nickel-gallium material with colossal magnetic refrigeration capability |
| CN112752824A (en) * | 2018-09-28 | 2021-05-04 | 株式会社东芝 | Cold storage material, refrigerator, superconducting coil built-in device, and method for manufacturing cold storage material |
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| CN101477864A (en) * | 2008-10-15 | 2009-07-08 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Rear earth refrigeration material having large magnetic heating effect and preparation thereof |
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| CN101477864A (en) * | 2008-10-15 | 2009-07-08 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Rear earth refrigeration material having large magnetic heating effect and preparation thereof |
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| 黄鹏等: "室温以上磁制冷材料La(Fe_(1-x)Co_x)_(11.7)Al_(1.3)化合物的研究", 《中国稀土学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200253A (en) * | 2015-09-25 | 2015-12-30 | 北京科技大学 | Preparation method of rare earth-nickel-gallium material with colossal magnetic refrigeration capability |
| CN105200253B (en) * | 2015-09-25 | 2018-02-27 | 北京科技大学 | The preparation method of rare earth nickel gallium material with big magnetic refrigerant capacity |
| CN112752824A (en) * | 2018-09-28 | 2021-05-04 | 株式会社东芝 | Cold storage material, refrigerator, superconducting coil built-in device, and method for manufacturing cold storage material |
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