CN102978422B - 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-silicon materials with large magnetothermal effect and preparation method thereof and the purposes in magnetic Refrigeration Technique.
Background technology
In recent years, along with modern age the energy worsening shortages and the continuous enhancing of environmental protection consciousness, magnetic Refrigeration Technique receives people and more and more pays close attention to.Magnetic refrigeration refers to magneticsubstance the Refrigeration Technique of a kind of new green environment protection being refrigeration working medium, its ultimate principle is the magnetothermal effect by means of magnetic refrigerating material, namely under referring to the effect of paramagnetic material or soft ferromagnetic outside magnetic field, magnetic moment of atom arranges ordering, during isothermal magnetization, magneticsubstance can release heat, and magnetic entropy reduces simultaneously; And magnetic moment of atom gets back to previous random state when removing magnetic field, magneticsubstance can absorb heat magnetic entropy increase simultaneously.Compared with traditional gas Compressing Refrigeration, magnetic Refrigeration Technique can be realized ideal circulation in principle, obtains the efficiency of maximum possible.Meanwhile, magnetic refrigeration adopts magneticsubstance as refrigeration working medium, to environment without destruction, and has the remarkable advantages such as noise is little, life-span length, good reliability.From the angle of environmental protection, energy-conservation, 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, find novel magnetic materials, study the focus that its magnetothermal effect becomes investigation of materials field, current countries in the world.
The material being applied to magnetic Refrigeration Technique is at first the paramagnetic substance of some weak magnetic, is mainly used in obtaining the very low temperature (mK-μ K) close to OK.1933, Giauque and MacDougall was with Gd
2(SO
4)
38H
2o is that working medium has carried out the experiment of adiabatic demagnetization, and obtains the very low temperature of 0.25K.At present, magnetic Refrigeration Technique has become the indispensable technique means of modern low-temperature physics.Meanwhile, low temperature magnetic Refrigeration Technique can liquified helium and nitrogen, and for industry and civilian, can also liquefy hydrogen, 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 characterizing magnetic refrigerating material magnetothermal effect comprises magnetic entropy and becomes (Δ S) and magnetic refrigerant capacity (RC), and the magnetic entropy change of material generally occurs maximum value near transformation temperature, and Δ S and the RC value of material are larger, and its refrigerating efficiency is higher.At present, the magnetic refrigerating material found in cold zone research mainly comprises rare earth element monocrystalline, polycrystalline material (as Nd, Er and Tm) and rare earth intermetallic compound (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 are not still very high, and the magnetic refrigerating material wherein with one-level magnetic phase transition is (as ErCo
2) usually along with obvious heat stagnation and hysteresis, thus cause magnetic refrigerating material duty in working cycle to decline.
In view of the needs of above research background and the practical application of magnetic Refrigeration Technique, in recent years, the new focus that the magnetic refrigerating material with reversible large magnetothermal effect and high magnetic refrigerant capacity has become magnetic refrigerating material research field is found.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of rare earth-nickel-silicon materials for magnetic refrigeration with reversible large magnetothermal effect, high refrigeration capacity, another object of the present invention is the purposes providing described rare earth-nickel-silicon materials for magnetic refrigeration.
The object of the invention is to be achieved through the following technical solutions:
Prepare a method for the rare earth-nickel-silicon magnetic refrigerating material with large magnetothermal effect, described magnetic refrigerating material is the compound of following general formula: RNiSi, and wherein R is rare earth element, it is characterized in that: described method comprises the steps:
1) take raw material R and Ni, Si and mix;
2) raw material that step 1) configures is put into smelting furnace, smelting furnace vacuumizes rear argon purge, carries out melting afterwards under argon shield to the described raw material configured;
3) by step 2) melted material carries out vacuum annealing process, takes out cooling fast afterwards.
Preferably, in step 1), the ratio of the amount of substance of described raw material R and Ni, Si is the atomic ratio in 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, described in vacuumize the pressure reached be 3 × 10
-3pa or be less than 3 × 10
-3pa; The temperature of described melting is 1300 ° of more than C; The time of described melting is 0.5 ~ 10 minute.
More preferably, in step 2) in, described in vacuumize the pressure reached be 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 for quenching in liquid nitrogen or frozen water.
On the other hand, the present invention also provides a kind of purposes rare earth-nickel-silicon materials being used as refrigerating material, and described rare earth-nickel-silicon materials are the compound of following general formula: RNiSi, and wherein R is rare earth element.
Preferably, described R is any one in Gd, Tb, Dy, Ho and Er element, or R is any one combination in Ho element and Gd, Tb, Dy and Er element.
Preferably, described material has TiNiSi type orthorhombic crystal structure.
Compared with prior art, the beneficial effect of the rare earth-nickel-silicon materials for magnetic refrigeration provided by the invention is: 1, low field 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, there is good magnetic, heat reversible performance.
Accompanying drawing explanation
Below, describe embodiments of the invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is the room temperature X-ray diffraction spectral line of the HoNiSi of the embodiment of the present invention 1;
Fig. 2 is the null field cooling of HoNiSi under downfield and the thermomagnetization curve of band field cooling of the embodiment of the present invention 1;
Fig. 3 is the isothermal magnetization curve of the HoNiSi of the embodiment of the present invention 1;
Fig. 4 is the Arrott curve of the HoNiSi of the embodiment of the present invention 1;
Fig. 5 is that the magnetic entropy of the HoNiSi of the embodiment of the present invention 1 becomes and temperature curve;
Fig. 6 is the magnetic refrigerant capacity scaling system of the HoNiSi of the embodiment of the present invention 1;
Fig. 7 is the room temperature X-ray diffraction spectral line of the DyNiSi of the embodiment of the present invention 2;
Fig. 8 is the null field cooling of DyNiSi under downfield and the thermomagnetization curve of band field cooling of the embodiment of the present invention 2;
Fig. 9 is the isothermal magnetization curve of the DyNiSi of the embodiment of the present invention 2;
Figure 10 is the Arrott curve of the DyNiSi of the embodiment of the present invention 2;
Figure 11 is that the magnetic entropy of the DyNiSi of the embodiment of the present invention 2 becomes and temperature curve;
Figure 12 is the room temperature X-ray diffraction spectral line of the ErNiSi of the embodiment of the present invention 3;
Figure 13 is the null field cooling of ErNiSi under downfield and the thermomagnetization curve of band field cooling of the embodiment of the present invention 3;
Figure 14 is the isothermal magnetization curve of the ErNiSi of the embodiment of the present invention 3;
Figure 15 is the Arrott curve of the ErNiSi of the embodiment of the present invention 3;
Figure 16 is that the magnetic entropy of the ErNiSi of the embodiment of the present invention 3 becomes and temperature curve.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment provided only in order to illustrate the present invention, instead of in order to limit the scope of the invention.
In the embodiment of the present invention, rare earth metal used and Ni, Si raw material are purchased from Beijing Non-Ferrous Metal Research General Academy, and its purity is all higher than 99.9%.Sample preparation electric arc furnace used is the WK-II type non-consumable arc furnace that Beijing WuKe opto-electrical Technology Co., Ltd produces.Room temperature X-ray diffraction measures the Rigaku D/max-2400 type X-ray diffractometer using Cu K α target.Magnetic Measurement instrument is the MPMS SQUID VSM magnetic measurement systems of U.S. QuantumDesign company designs.
Embodiment 1:
The present embodiment is for illustration of magnetic refrigerating material provided by the invention and preparation method thereof.
1, preparation method:
1) by the atomic ratio weighing in HoNiSi chemical formula, by purity higher than 99.9% commercially available rare earth metal Ho and Ni, the mixing of Si raw material, wherein Ho is by its 2% excessive interpolation at chemical formula HoNiSi atomic percentage, in order to compensate the volatilization of Ho in preparation process;
2) raw material that step 1) prepares is put into electric arc furnace to vacuumize, when vacuum tightness reaches 3 × 10
-3during Pa, after cleaning 2 times with straight argon, melting under 1 atmospheric pure argon protection, the time of melting is 3 minutes, and smelting temperature is 1500 ~ 1550 ° of C;
3) in copper crucible, cooling obtains cast alloy, and wrapped by cast alloy molybdenum foil, being sealed in vacuum tightness is 5 × 10
-3in the silica tube of Pa, 800 ° of C anneal 7 days, take out and quench fast in liquid nitrogen, obtain product.
2, product characterizes and performance measurement:
The room temperature X-ray diffraction spectral line that the present embodiment obtains product is measured, as shown in Figure 1 with X-ray diffractometer.Result shows that product is into the HoNiSi compound of single-phase TiNiSi type orthorhombic crystal structure, and its spacer is Pnma, and lattice parameter is
α=β=γ=90 °.
Obtained HoNiSi is above measured at magneticstrength μ in magnetic measurement systems (SQUID VSM)
0null field cooling (ZFC) under H=0.05T and band field cooling (FC) pyromagnetic (M-T) curve, as shown in Figure 2.Antiferromagnetic-paramagnetism changes can to determine that HoNiSi has from null field cooling M-T curve, its Ne&1&el temperature T
nfor 3.8K; In addition, as we know from the figure, ZFC and FC curve well overlaps, and shows that material has good thermal reversibility.
SQUID VSM system measures obtained HoNiSi at T
nnear the rising field and to fall of (temperature range of 2K to 45K) time isothermal magnetization curve, as shown in Figure 3.From figure, do not observe magnetic lag phenomenon, it is reversible for showing that the magnetic entropy of the HoNiSi that the present embodiment obtains becomes magnetic field.
Existing research shows, the phase transition property of compound can be determined by the shape of its Arrott curve, the Arrott slope of a curve of usual first-order phase transition material near transformation temperature is for bearing or there is 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 recorded in 2K to 45K temperature range, and wherein illustration is T
narrott curve between 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 has antiferromagnetic-ferromagnetic first-order phase transition of induced by magnetic field.And at T
nabove Arrott curve, all in positive slope, shows that the obtained HoNiSi of embodiment 1 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 the material of second-order phase transition occurs has good magnetic, thermal reversibility to those skilled in the art, it is wider that magnetic entropy becomes peak, is conducive to its application in magnetic refrigerator.
According to Maxwell relations:
Δ S can be become from the isothermal magnetization curve calculation magnetic entropy shown in Fig. 3.The HoNiSi of the embodiment 1 calculated is at transformation temperature T
nneighbouring magnetic entropy becomes and temperature curve (-Δ S-T), as shown in Figure 5, wherein a1 represents the isothermal magnetic entropy varied curve under 0-1T changes of magnetic field, b1 represents the isothermal magnetic entropy varied curve under 0-2T changes of magnetic field, c1 represents the isothermal magnetic entropy varied curve under 0-3T changes of magnetic field, d1 represents the isothermal magnetic entropy varied curve under 0-4T changes of magnetic field, and e1 represents the isothermal magnetic entropy varied curve under 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 temperature, wherein under 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, therefore the magnetic entropy zoom of material under 0-2T changes of magnetic field is concerned.Under 0-2T changes of magnetic field, the Entropy Changes peak value of HoNiSi compound reaches 17.5J/kgK.Refrigeration capacity (RC) weighs another important parameter of material practical value.Usually, the refrigeration capacity of material in the circulation of reversible refrigeration can be by
calculate, wherein T
1and T
2be respectively the temperature that magnetic entropy becomes the cold junction corresponding with the peak width at half height of temperature curve and hot junction.As shown in Figure 6, can draw according to calculating, under 0-5T changes of magnetic field, the temperature in HoNiSi cold junction and hot junction is respectively 3.2K and 25.9K, and its refrigeration capacity RC maximum value reaches 471J/kg.Table 1 lists HoNiSi that the present embodiment the provides maximum magnetic entropy variable of existing rare earth based compound close with its transformation temperature and contrasting of refrigeration capacity.Can be found out by the data in 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
Variant embodiment 1
When carrying out the preparation of rare earth-nickel-silicon materials, according to practical situation, suitably preparation parameter can be regulated, 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 be:
1) by the atomic ratio weighing in HoNiSi chemical formula, by purity higher than 99.9% commercially available rare earth metal Ho and Ni, the mixing of Si raw material, wherein Ho is by its 5% excessive interpolation at chemical formula atomic percentage;
2) raw material that step 1) prepares is put into electric arc furnace to vacuumize, when vacuum tightness reaches 2 × 10
-3during Pa, after cleaning 2 times with straight argon, melting under 1 atmospheric pure argon protection, the time of melting is 10 minutes, and smelting temperature is 1700 ° of C;
3) in copper crucible, cooling obtains cast alloy, and wrapped by cast alloy molybdenum foil, being sealed in vacuum tightness is 5 × 10
-3in the silica tube of Pa, 900 ° of C anneal 30 days, take out and quench fast in liquid nitrogen, obtain product.
Embodiment 2:
The present embodiment is for illustration of magnetic refrigerating material provided by the invention and preparation method thereof.
1, preparation method:
1) by the atomic ratio weighing in DyNiSi chemical formula, by purity higher than 99.9% commercially available rare earth metal Dy and Ni, the mixing of Si raw material, wherein Dy is by its 2% excessive interpolation at chemical formula D yNiSi atomic percentage;
2) raw material that step 1) prepares is put into electric arc furnace to vacuumize, when vacuum tightness reaches 3 × 10
-3during Pa, after cleaning 2 times with straight argon, melting under 1 atmospheric pure argon protection, the time of melting is 3 minutes, and smelting temperature is 1500 ~ 1550 ° of C;
3) in copper crucible, cooling obtains cast alloy, and wrapped by cast alloy molybdenum foil, being sealed in vacuum tightness is 5 × 10
-3in the silica tube of Pa, 800 ° of C anneal 7 days, take out and quench fast in liquid nitrogen, obtain product.
2, product characterizes and performance measurement:
The room temperature X-ray diffraction spectral line that the present embodiment obtains product is measured, as shown in Figure 7 with X-ray diffractometer.Result shows that product is into the DyNiSi compound of single-phase TiNiSi type orthorhombic crystal structure, and its spacer is Pnma, and lattice parameter is
α=β=γ=90 °.
The DyNiSi that the present embodiment obtains is at magneticstrength μ
0null field cooling (ZFC) under H=0.05T and band field cooling (FC) pyromagnetic (M-T) curve are as shown in Figure 8.Can determine that DyNiSi is at Ne&1&el temperature T from M-T curve
nfor the magnetic transformation of antiferromagnetic-paramagnetic occurs at 8.8K place.At T
nneighbouring ZFC and FC thermomagnetization curve well overlaps, and shows that material has good heat reversible performance.
The obtained DyNiSi compound of the present embodiment near transformation temperature (temperature range of 2K to 50K) isothermal magnetization curve as shown in Figure 9, at T
nthere is a platform in following magnetzation curve, illustrate that DyNiSi compound exists strong magnetocrystalline anisotropy at low temperatures, 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 to induce.In addition, from figure, do not observe magnetic lag phenomenon, it is reversible for showing that the magnetic entropy of DyNiSi becomes magnetic field.
Figure 10 is for calculate this compound at T according to this isothermal magnetzation curve
nthe Arrott curve of temperature neighbouring (i.e. the temperature range of 2K to 50K), wherein illustration is T
narrott curve between 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 has antiferromagnetic-ferromagnetic first-order phase transition of induced by magnetic field.And at T
nabove Arrott curve, all in positive slope, shows that the obtained DyNiSi of embodiment 2 is at transformation temperature T
nthe paramagnetic-ferromagnetic of above induced by magnetic field becomes typical second-order phase transition mutually.
The DyNiSi of the present embodiment is at Ne&1&el temperature T
nneighbouring isothermal magnetic entropy change and temperature curve are as shown in figure 11, wherein a2 represents the isothermal magnetic entropy varied curve under 0-1T changes of magnetic field, b2 represents the isothermal magnetic entropy varied curve under 0-2T changes of magnetic field, c2 represents the isothermal magnetic entropy varied curve under 0-3T changes of magnetic field, d2 represents the isothermal magnetic entropy varied curve under 0-4T changes of magnetic field, and e2 represents the isothermal magnetic entropy varied curve under 0-5T changes of magnetic field.As seen from Figure 11, at T
noccurred positive magnetic entropy variate during to bend down, raised with magnetic field, magnetic entropy variate is gradually by the occasion of changing negative value into, and this is caused by antiferromagnetic-ferromagnetic change magnetic transition owing to there is induced by magnetic field.Under 0-2T changes of magnetic field, the Entropy Changes peak value of DyNiSi compound is at T
nplace reaches 9.3J/kgK, and under 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 lists DyNiSi that the present embodiment the provides maximum magnetic entropy variable of existing rare earth based compound close with its transformation temperature and contrasting of refrigeration capacity.Can be found out by the data in 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
variant embodiment 2
1) by the atomic ratio weighing in DyNiSi chemical formula, by purity higher than 99.9% commercially available rare earth metal Dy and Ni, the mixing of Si raw material, wherein Dy is by its 3% excessive interpolation at chemical formula atomic percentage;
2) raw material that step 1) prepares is put into electric arc furnace to vacuumize, when vacuum tightness reaches 2 × 10
-3during Pa, after cleaning 2 times with straight argon, melting under 1 atmospheric pure argon protection, the time of melting is 2 minutes, and smelting temperature is 1300 ° of C;
3) in copper crucible, cooling obtains cast alloy, and wrapped by cast alloy molybdenum foil, being sealed in vacuum tightness is 5 × 10
-3in the silica tube of Pa, 600 ° of C anneal 3 days, take out and quench fast in liquid nitrogen, obtain product.
Embodiment 3:
The present embodiment is for illustration of magnetic refrigerating material provided by the invention and preparation method thereof.
1, preparation method:
1) by the atomic ratio weighing in ErNiSi chemical formula, by purity higher than 99.9% commercially available rare earth metal Er and Ni, the mixing of Si raw material, wherein Er is by its 2% excessive interpolation at chemical formula ErNiSi atomic percentage;
2) raw material that step 1) prepares is put into electric arc furnace to vacuumize, when vacuum tightness reaches 3 × 10
-3during Pa, after cleaning 2 times with straight argon, melting under 1 atmospheric pure argon protection, the time of melting is 3 minutes, and smelting temperature is 1500 ~ 1550 ° of C;
3) in copper crucible, cooling obtains cast alloy, and wrapped by cast alloy molybdenum foil, being sealed in vacuum tightness is 5 × 10
-3in the silica tube of Pa, 800 ° of C anneal 7 days, take out and quench fast in liquid nitrogen, obtain product.
2, product characterizes and performance measurement:
The present embodiment obtains the room temperature X-ray diffraction spectral line of compound as shown in figure 12, and result shows that product is into the ErNiSi compound of single-phase TiNiSi type orthorhombic crystal structure, and its spacer is Pnma, and lattice parameter is
α=β=γ=90 °.
The ErNiSi that the present embodiment obtains is at magneticstrength μ
0null field cooling (ZFC) under H=0.05T and band field cooling (FC) pyromagnetic (M-T) curve are as shown in figure 13.Can determine that ErNiSi is at Ne&1&el temperature T from M-T curve
nfor the magnetic transformation of antiferromagnetic-paramagnetic occurs at 4K place.At T
nneighbouring ZFC and FC thermomagnetization curve well overlaps, and shows that material has good heat reversible performance.
The ErNiSi of the present embodiment is at T
nwhat (temperature range of 2K to 45K) recorded near temperature rise field and isothermal magnetization curve when to fall as shown in figure 14, from figure, do not observe magnetic lag phenomenon, it is reversible for showing that the magnetic entropy of ErNiSi becomes magnetic field.Figure 15 is for calculate this compound at T according to this isothermal magnetzation curve
nthe Arrott curve of temperature neighbouring (i.e. the temperature range of 2K to 45K), wherein illustration is T
narrott curve between 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 has antiferromagnetic-ferromagnetic first-order phase transition of induced by magnetic field.And at T
nabove Arrott curve, all in positive slope, shows that the obtained ErNiSi of embodiment 3 is at transformation temperature T
nthe paramagnetic-ferromagnetic of above induced by magnetic field becomes typical second-order phase transition mutually.
The ErNiSi of the present embodiment is at Ne&1&el temperature T
nneighbouring isothermal magnetic entropy change and temperature curve are as shown in figure 16, wherein a3 represents the isothermal magnetic entropy varied curve under 0-1T changes of magnetic field, b3 represents the isothermal magnetic entropy varied curve under 0-2T changes of magnetic field, c3 represents the isothermal magnetic entropy varied curve under 0-3T changes of magnetic field, d3 represents the isothermal magnetic entropy varied curve under 0-4T changes of magnetic field, and e3 represents the isothermal magnetic entropy varied curve under 0-5T changes of magnetic field.As can be seen from Figure 16, under 0-2T changes of magnetic field, the Entropy Changes peak value of ErNiSi compound is at T
nplace reaches 8.8J/kgK, and under 0-5T changes of magnetic field, the maximum magnetic entropy variable of ErNiSi is the maximum value of 19.0J/kgK, its refrigeration capacity RC is 309J/kg.
Variant embodiment 3
1) by the atomic ratio weighing in ErNiSi chemical formula, by purity higher than 99.9% commercially available rare earth metal Er and Ni, the mixing of Si raw material, wherein Er is by its 2% excessive interpolation at chemical formula atomic percentage;
2) raw material that step 1) prepares is put into electric arc furnace to vacuumize, when vacuum tightness reaches 3 × 10
-3during Pa, after cleaning 1 time with straight argon, melting under 1 atmospheric pure argon protection, the time of melting is 0.5 minute, and smelting temperature is 1450 ° of about C;
3) in copper crucible, cooling obtains cast alloy, and wrapped by cast alloy molybdenum foil, being sealed in vacuum tightness is 5 × 10
-3in the silica tube of Pa, 1100 ° of C anneal 5 days, take out and quench fast in liquid nitrogen, 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, as the combination of Ho and Tb, the combination of Ho and Er etc., be not repeated at this.
Can be found out by above embodiment and performance measurement result, rare earth-nickel-silicon the magnetic refrigerating material of TiNiSi type orthorhombic crystal structure that prepared by the present invention have, i.e. RNiSi compound, its Ne&1&el temperature is between 3K and 20K, antiferromagnetic-ferromagnetic first-order phase transition can be there is under induced by magnetic field, near respective transformation temperature, show large magnetothermal effect, wherein the magnetic entropy of HoNiSi under 2T changes of magnetic field uprises and reaches 17.5J/kgK, becomes far above the magnetic entropy of same other magnetic refrigerating material of warm area.In addition, compound of the present invention also has good magnetic, heat reversible performance, is ideal low-temperature magnetic refrigeration material.Preparation provided by the invention has the method for the rare earth-nickel-silicon magnetic refrigerating material of large magnetothermal effect, has preparation technology simple, is applicable to the advantages such as suitability for industrialized production.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " specific examples " etc. means to describe in conjunction with this embodiment are contained at least one embodiment of the present invention or example.In this manual, identical embodiment is not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although make 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 based on content disclosed by the invention or improve, and these amendments and improvement be all within the spirit and scope of the present invention.
Claims (6)
1. prepare the method for the rare earth-nickel-silicon magnetic refrigerating material with large magnetothermal effect for one kind, described magnetic refrigerating material is the compound of following general formula: RNiSi, wherein R is rare earth element, and this magnetic refrigerating material has TiNiSi type orthorhombic crystal structure, and described preparation method comprises the steps:
1) take raw material R and Ni, Si and mix, wherein, R is by its 2 ~ 5% excessive interpolations at described chemical formula Atom ratio;
2) by step 1) raw material that configures puts into smelting furnace, and smelting furnace vacuumizes rear argon purge, carries out melting afterwards under argon shield to the described raw material configured; Wherein, vacuumizing the pressure reached described in is 3 × 10
-3pa or be less than 3 × 10
-3pa; The temperature of described melting is more than 1300 DEG C; The time of described melting is 0.5 ~ 10 minute;
3) by step 2) melted material carries out vacuum annealing process, takes out cooling fast afterwards; Wherein, the temperature of described vacuum annealing is 600 ~ 1100 DEG C; The time of described vacuum annealing is 3 ~ 30 days, and Cooling Mode is for quenching in liquid nitrogen or frozen water.
2. method according to claim 1, is characterized in that, in step 1) in, the ratio of the amount of substance of described raw material R and Ni, Si is the atomic ratio in RNiSi chemical formula.
3. method according to claim 1, is characterized in that, in step 2) in, described in vacuumize the pressure reached be 2 × 10
-3~ 3 × 10
-3pa; The temperature of described melting is 1300 ~ 1700 DEG C; The time of described melting is 2 ~ 3 minutes.
4. method according to claim 1, is characterized in that, in step 3) in, the temperature of described vacuum annealing is 700 ~ 900 DEG C; The time of described vacuum annealing is 5 ~ 15 days.
5. rare earth-nickel-silicon materials are used as a purposes for refrigerating material, it is characterized in that, described rare earth-nickel-silicon materials are the compound of following general formula: RNiSi, and wherein R is rare earth element, and this refrigerating material has TiNiSi type orthorhombic crystal structure.
6. according to claim 5 rare earth-nickel-silicon materials are used as the purposes of refrigerating material, it is characterized in that, described R is any one in Gd, Tb, Dy, Ho and Er element, or R is any one combination in Ho element and Gd, Tb, Dy and Er element.
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