CN105112025B - A kind of solid magnetic refrigerating material, preparation method and magnetic refrigerator - Google Patents

A kind of solid magnetic refrigerating material, preparation method and magnetic refrigerator Download PDF

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CN105112025B
CN105112025B CN201510575569.5A CN201510575569A CN105112025B CN 105112025 B CN105112025 B CN 105112025B CN 201510575569 A CN201510575569 A CN 201510575569A CN 105112025 B CN105112025 B CN 105112025B
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sintering
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CN105112025A (en
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尹海宏
王志亮
宋长青
史敏
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Jiaxing Chuansheng mechanical equipment Co.,Ltd.
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Nantong University
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Abstract

The invention discloses a kind of solid magnetic refrigerating material, preparation method and magnetic refrigerator, and suitable for several K to the extremely low temperature of more than ten K, the chemical formula of the material is Yb1‑xHoxMnO3, wherein 0.05<x<0.95, this material is hexagonal crystal system, space group P63Cm, sinter to obtain using solid reaction process.With the increase of Ho dopings, the lattice constant a of the material is increased monotonically.By to Yb1‑xHoxMnO3Application external magnetic field and induce and produce AFM FM phase transformations, caused magnetic entropy becomes, and magnetic refrigeration can be achieved, and this phase transformation of the material is second-order phase transistion.Using the Yb of the present invention1‑xHoxMnO3Solid magnetic refrigerator, is operable with extremely low temperature made of solid magnetic refrigerating material, can be applied to the leading-edge fields such as helium liquefaction, space probe, satellite, Laser Focusing nuclear fusion.

Description

A kind of solid magnetic refrigerating material, preparation method and magnetic refrigerator
Technical field
The present invention relates to a kind of solid magnetic refrigerating material and its refrigerator, more particularly to (tens below K temperature at low temperature Degree) work magnetic refrigerating material and its refrigerator.
Background technology
Solid refrigerator is a kind of new refrigerator, and for the refrigerator of routine, solid refrigerator is without pressure The complex devices such as contracting machine, circulating refrigerant, with noiseless in the course of the work, without friction, energy consumption is low, high cooling efficiency, knot The advantages that structure is simple, small volume, it is suitable for many special occasions and uses.
In solid refrigerator, one of which solid refrigerator is the magnetic refrigerator using magnetothermal effect (MCE).Material by Atomic building, atom are made up of electronics and atomic nucleus, and electronics has spin magnetic moment to also have orbital magnetic moment, and this causes the original of some materials Son or ion carry magnetic moment.The ion or atomic magnetic moment of magnetic material are rambling, solid magnetic thing when without external magnetic field For matter (system of magnetic ion or atomic building) when being magnetized by magnetic fields, the magnetic order degree of system strengthens (magnetic entropy reduction), Externally release heat；Again by its degaussing, then magnetic order degree decline (magnetic entropy increase), heat is absorbed from the external world again.This magnetic Ion system applies in magnetic field is referred to as magnetothermal effect with the thermal phenomenon appeared in removing process.If two such thermal insulation is gone Exothermic process caused by endothermic process caused by magnetic and adiabatic magnetization is connected with a circulation, passes through certain technology hand Section, can reach the purpose of refrigeration.
P.Langevin is noticed within 1907：During paramagnet adiabatic demagnetization, its temperature can reduce.Nineteen twenty-seven Debye This effect refrigeration can be utilized by having been foretold with Giauque.Giauque in 1933 realizes adiabatic demagnetization refrigeration.From this, extremely low Warm field (mK levels to 16K scopes) magnetic refrigeration has played great role.Present low temperature magnetic Refrigeration Technique comparative maturity.The U.S., day Originally, France develops a variety of low temperature magnetic refrigerators, and pole cryogenic conditions are created for various scientific researches.Such as satellite, In the parameter detecting sum processing system of the spacecrafts such as spaceship, magnetic refrigeration is also used on helium liquefaction refrigeration machine.Last century 70 Later stage in age people circulate the effect freezed by the use of metal gadolinium and its alloy as working medium in 0~7Tesla magnetic field Fruit.1997, the material of USDOE's love Ames Laboratory (Department ofEnergy ' sAmes Laboratory) Material scientist has found that a kind of alloy being made up of Gd, Si and Ge can show huge magnetocaloric effect at room temperature.In recent years More preferable result is achieved using Gd5Si2Ge alloys in the world, in the La-Ca-Sr-Mn-O of perovskite structure manganese systems oxidation Thing is also a kind of up-and-coming magnetic refrigeration working substance.
Divided according to operating temperature range, magnetic refrigerator can be divided into " high temperature " magnetic refrigerator and " low temperature " magnetic refrigerator, preceding Person is often referred to work in the magnetic refrigerator of 250K temperatures above scopes, and the latter is often referred to work in the magnetic of 80K temperature below scopes Refrigerator.The refrigeration work temperature of usual La systems Mn oxide (i.e. La-Ca-Sr-Mn-O manganese series oxides) close to room temperature, Belong to " high temperature " magnetic refrigerating material.
The content of the invention
It is an object of the invention to provide a kind of new magnetic refrigerating material and its refrigerator, available under extremely low temperature, (several K are extremely More than ten K) refrigeration work.
Above-mentioned purpose is achieved by the following technical solution：
A kind of solid magnetic refrigerating material, the material are ferrimagnet, are made up of tetra- kinds of elements of Yb, Ho, Mn, O, chemical formula For Yb1-xHoxMnO3, x span is 0.01 ＜ x ＜ 0.99；The material crystalline phase is hexagonal crystal system, space group P63Cm, and With the increase of Ho contents, its lattice constant a is increased monotonically；The material induces generation antiferromagnetic-ferromagnetic under external magnetic field (AFM-FM) second-order phase transistion, magnetic entropy is produced in phase transition process and is become, realizes magnetic refrigeration, and the refrigeration work that the material is suitable Temperature is several K to more than ten K.Tested (XRD) by X-ray diffraction, it is known that resulting materials Yb1-xHoxMnO3Crystalline phase to be single Hexagonal crystal phase, space group P63Cm, also, as the increase of Ho dopings, the lattice constant a of the material are increased monotonically, this is Due to Ho3+Ionic radius is more than Yb3+Ionic radius.
The solid magnetic refrigerating material sinters to obtain using solid reaction process, and preparation process specifically comprises the following steps：
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 1-x：x：1, wherein 0.05<x<0.95, purity is actually needed and determined not less than 99.9%, x values foundation；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 200-300 DEG C, in advance The hot time is 2-8h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 2-5h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) being placed in platinum crucible and calcined, calcining heat is 1100-1300 DEG C, Time is 20-40h, is well mixed its each component；
6) after the product cooling obtained step 5), sheet or bulk or spherolite are cold-pressed under 30-80Mpa pressure Shape；
7) product for obtaining step 6) is sintered, sintering time 18-36h, and sintering temperature is 1300-1500 DEG C, Sintering atmosphere is air atmosphere.
8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized.
In above process, sintering can use Muffle furnace to carry out.
A kind of solid magnetic refrigerating material, aforesaid solid magnetic system is replaced with the one or more in tetra- kinds of elements of Er, Tm, Sc, Y Ho elements in cold material composition.
The solid magnetic refrigerating material sinters to obtain using solid reaction process, and preparation process specifically comprises the following steps：
1) one or more, the Yb of Er or Tm or Sc or Y oxide have been weighed according to a certain percentage2O3And MnCO3Powder End, the one or more of the oxide of the Er or Tm or Sc or Y, Yb2O3It is x with MnCO molar ratios：1-x：1, wherein 0.05 <x<0.95, purity is actually needed and determined not less than 99.9%, x values foundation；
2) by the one or more of ready Er or Tm or Sc or Y oxide, Yb2O3Powder is respectively placed in heating furnace Middle preheating, preheating temperature is 200-300 DEG C, preheating time 2-8h, to remove moisture therein；
3) by the powder obtained in step 2) and MnCO3Powder mixes；
4) ball milling 2-5h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) being placed in platinum crucible and calcined, calcining heat is 1100-1300 DEG C, Time is 20-40h, is well mixed its each component；
6) after the product cooling obtained step 5), sheet or bulk or spherolite are cold-pressed under 30-80Mpa pressure Shape；
7) product for obtaining step 6) is sintered, sintering time 18-36h, and sintering temperature is 1300-1500 DEG C, Sintering atmosphere is air atmosphere.
8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized.
Yb1-xHoxMnO3Optimal refrigeration work temperature, relative refrigeration work consumption (RCP) with Ho contents it is different and different.Cause This, can change Yb by adjusting Ho contents1-xHoxMnO3Refrigeration work parameter.
In order to extend Yb1-xHoxMnO3Refrigeration work temperature range, it can adopt the following technical scheme that：
Yb is prepared using foregoing solid reaction process flow1-xHoxMnO3, high pressure cold pressing is used as flake；Constantly repeat Such technological process, increase x values every time, Ho content increases in the material for making to obtain every time；The different Ho contents that will be obtained The order that gradually increases according to x values of thin slice be stacked together, the pressure for applying 30-80Mpa again is cold-pressed；Then again It is sintered technique：Sintered in air atmosphere, sintering time 4-32h, sintering temperature is 1300-1500 DEG C.Using so Flow can obtain the Yb of Ho composition gradual changes1-xHoxMnO3Magnetic refrigerating material.
Due to the Yb of different component1-xHoxMnO3It is different in the phase transition temperature of antiferromagnetic-ferromagnetic phase transition (AFM-FM phase transformations), It may be such that magnetic refrigerator operating temperature range is expanded by such content gradually variational technique.It is brilliant because component is gradual change Lattice constant is also gradual change, and stress obtains relaxation to greatest extent, avoids the cracking of material, and its Curie temperature is no longer one Individual temperature spot, but a temperature range, the i.e. material are relaxation sections magnet.
Accordingly, there is provided a kind of solid magnetic refrigerating material, be made up of tetra- kinds of elements of Yb, Ho, Mn, O；And the chemical formula of the material For Yb1-xHoxMnO3, x span is 0 ＜ x ＜ 1 in its chemical formula；And the crystalline phase of the material is hexagonal crystal system, space group is P63cm；And the material is block materials, the content of Yb, Ho element gradually changes in a dimension, with a dimension Its Curie temperature that gradually changes of the content of upper Yb, Ho element forms a temperature range；And the change of the content of Yb, Ho element Trend is opposite, and the content of Mn elements is equally distributed；With any plane of the dimension perpendicular in form the material Each element be equally distributed, and the molar content percentage sum of Yb, Ho element is equal to Mn elements in the plane Molar content percentage；And the material is ferrimagnet, its Curie temperature is not a temperature spot, but a temperature model Enclose, i.e., the material is relaxation sections magnetic material；And the Yb1-xHoxMnO3As the increase of Ho contents, its lattice constant a are mono- Adjust increase；And the Yb1-xHoxMnO3Antiferromagnetic-ferromagnetic (AFM-FM) second-order phase transistion, phase transformation occur for induction under external magnetic field During produce magnetic entropy and become, realize magnetic refrigeration, and the suitable refrigeration work temperature of the material is from several K to more than ten K.
The material is in a dimension, chemical formula Yb1-xHoxMnO3Middle x value progressively increases to 1 by 0.
The solid magnetic refrigerating material sinters to obtain using solid reaction process, and preparation process specifically comprises the following steps：
1) multigroup Yb is weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mole Ratio is 1-x：x：1, x is distributed into arithmetic progression in each group powder, and various powder purities are not less than 99.9%；
2) by ready each group Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, preheating temperature 200-300 DEG C, preheating time 2-8h, to remove moisture therein；
3) by each group powder obtained in step 2) respectively with MnCO3Powder mixes；
4) ball milling 2-5h is carried out to each group mixed-powder obtained in step 3) using planetary ball mill respectively；
5) each group mixed-powder obtained in step 4) is respectively placed in platinum crucible and calcined, calcining heat is 1100-1300 DEG C, time 20-40h, it is well mixed its each component；
6) after each group product cooling obtained step 5), it is cold-pressed into flake under 30-80Mpa pressure respectively；
7) each group product that step 6) obtains is sintered respectively, sintering time 18-36h, sintering temperature 1300- 1500 DEG C, sintering atmosphere is air atmosphere；
8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized；
9) order that the thin slice of obtained different Ho contents gradually increases according to x values is stacked together, applies 30- again 80Mpa pressure is cold-pressed.
10) and then again it is sintered technique：Sintered in air atmosphere, sintering time 4-32h, sintering temperature is 1300-1500℃。
11) natural cooling obtains the Yb of Yb, Ho composition gradual change under air atmosphere1-xHoxMnO3Magnetic refrigerating material.
A kind of magnetic refrigerator, it is described solid containing solid magnetic refrigerating material, and permanent magnet or electromagnet or superconducting electromagnet Body magnetic refrigerating material is foregoing any solid magnetic refrigerating material, or the solid prepared for foregoing any preparation method Magnetic refrigerating material.
Above-mentioned material Yb1-xHoxMnO3AFM-FM phases be changed into the second-order phase transistion of induced by magnetic field, the magnetic entropy of the material becomes measurement It is calculated by equation below：
In above formula, S, H, T, M represent the entropy of material system, magnetic field intensity, thermodynamic temperature, the intensity of magnetization, subscript 0 respectively Initial state and end of a period state are represented respectively with 1.
In actual measurement, carry out with the following method：Measurement at different temperatures is measured first obtains a series of isothermal M-H Hysteresis curve, calculated according still further to such as following formula：
Subscript i represents i-th of data point in test curve in above formula.
By Yb1-xHoxMnO3Solid magnetic refrigerating material is applied to magnetic refrigerator, it is necessary to Yb1-xHoxMnO3Material applies magnetic Field is magnetized；To realize heat exchange action, it is also necessary to by Yb1-xHoxMnO3Solid magnetic refrigerating material passes in and out refrigeration space repeatedly, Ring-type or disc-shaped structure are generally can be made into, is slowly rotated under motor driven, cyclic structure or a discoid part are in In externally-applied magnetic field, another part is in refrigeration space.
In order to lift refrigeration, it is necessary to Yb1-xHoxMnO3Applied field strengths changing value (the △ of solid magnetic refrigerating material H it is) larger.Generally use superconducting magnet applies magnetic field.
Beneficial effects of the present invention：
1st, Yb provided by the invention1-xHoxMnO3Solid magnetic refrigerating material induces in the case where adding external magnetic field produces AFM-FM Second-order phase transistion, produce magnetic entropy and become, magnetic refrigeration can be achieved.Using the Yb of the present invention1-xHoxMnO3Solid magnetic refrigerating material is made Solid magnetic refrigerator, be operable with extremely low temperature, can be applied to helium liquefaction, space probe, satellite, Laser Focusing core and gather The leading-edge fields such as change.
2nd, the Yb of different component is utilized1-xHoxMnO3Antiferromagnetic-ferromagnetic phase transition (AFM-FM phase transformations) phase transition temperature not Together, by the Yb of different component1-xHoxMnO3Magnetic refrigerating material is suppressed, and can obtain the wide magnetic refrigerating material of transition temperature range, so as to So that magnetic refrigerator operating temperature range is expanded.
Embodiment
Technical scheme is specifically introduced with reference to example.
Yb is sintered using solid reaction process1-xHoxMnO3Solid magnetic refrigerating material.
Embodiment 1：
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.9：0.1：1, each dusty material purity is not less than 99.9%；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 250 DEG C, during preheating Between be 5h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 28h, it is well mixed its each component；
6) after the product cooling obtained step 5), bulk is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 28h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized.
Obtain Yb0.9Ho0.1MnO3Solid magnetic refrigerating material, M-H B-H loops under different temperatures are carried out to it and are tested.
Embodiment 2：
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.8：0.2：1, each dusty material purity is not less than 99.9%；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 230 DEG C, during preheating Between be 5h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), bulk is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1450 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized.
Obtain Yb0.8Ho0.2MnO3Solid magnetic refrigerating material.
Embodiment 3：
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.7：0.3：1, each dusty material purity is not less than 99.9%；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 230 DEG C, during preheating Between be 5h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), bulk is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1450 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized.
Obtain Yb0.7Ho0.3MnO3Solid magnetic refrigerating material.
The magnetic refrigerating material obtained to embodiment one, two, three carries out XRD tests, obtains corresponding lattice constant such as following table It is shown：
Embodiment 4：
A
1) according to molar ratio 1:1 has weighed Yb2O3And MnCO3Powder；
2) by ready Yb2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 240 DEG C, and preheating time is 4h, to remove moisture therein；
3) by the powder obtained in step 2) and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), flake is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) product after step 7) is sintered naturally cools to room temperature；
Obtain YbMnO3Solid magnetic refrigerating material；
B
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.8：0.2：1；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 240 DEG C, during preheating Between be 4h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), flake is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) product after step 7) is sintered naturally cools to room temperature；
Obtain Yb0.8Ho0.2MnO3Solid magnetic refrigerating material；
C
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.6：0.4：1；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 240 DEG C, during preheating Between be 4h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), flake is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) product after step 7) is sintered naturally cools to room temperature；
Obtain Yb0.6Ho0.4MnO3Solid magnetic refrigerating material；
D
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.4：0.6：1；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 240 DEG C, during preheating Between be 4h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), flake is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) product after step 7) is sintered naturally cools to room temperature；
Obtain Yb0.4Ho0.6MnO3Solid magnetic refrigerating material；
E
1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Mol ratio Example is 0.2：0.8：1；
2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 240 DEG C, during preheating Between be 4h, to remove moisture therein；
3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), flake is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) product after step 7) is sintered naturally cools to room temperature；
Obtain Yb0.2Ho0.8MnO3Solid magnetic refrigerating material；
F
1) according to molar ratio 1:1 has weighed Ho2O3And MnCO3Powder；
2) by ready Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 240 DEG C, and preheating time is 4h, to remove moisture therein；
3) by the powder obtained in step 2) and MnCO3Powder mixes；
4) ball milling 4h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1200 DEG C, the time For 24h, it is well mixed its each component；
6) after the product cooling obtained step 5), flake is cold-pressed under 50Mpa pressure；
7) it is sintered what step 6) obtained, sintering time 24h, sintering temperature is 1400 DEG C, and sintering atmosphere is sky Atmosphere is enclosed；
8) product after step 7) is sintered naturally cools to room temperature；
Obtain HoMnO3Solid magnetic refrigerating material；
G
1) material for obtaining above-mentioned steps is according to YbMnO3/Yb0.8Ho0.2MnO3/Yb0.6Ho0.4MnO3/ Yb0.4Ho0.6MnO3/Yb0.2Ho0.8MnO3/HoMnO3Order be superimposed；
2) pressure that the multilayer material obtained to step 1) applies 50Mpa is cold-pressed；
3) technique is sintered to the multilayer material that step 2) obtains：Sintered in air atmosphere, sintering time 30h, Sintering temperature is 1400 DEG C.
The Yb of Yb, Ho composition gradual change is obtained using such flow1-xHoxMnO3Magnetic refrigerating material.
Material obtained by example IV, the material is block materials, and the chemical formula of the material is Yb1-xHoxMnO3, The content of Yb, Ho element gradually changes in one dimension, and the variation tendency of the content of Yb, Ho element is opposite, Mn The content of element is equally distributed, and x value progressively increases to 1 by 0 in its chemical formula in the dimension；With the dimension Spend in vertical any plane that to form each element of the material be equally distributed, and Yb, Ho element rub in the plane Your percentage composition sum is equal to the molar content percentage of Mn elements；And the material is ferrimagnet, its Curie temperature is not It is a temperature spot, but a temperature range, the i.e. material are relaxation sections magnetic materials.The material can suitable refrigeration Operating temperature is from several K to more than ten K.

Claims (7)

  1. A kind of 1. solid magnetic refrigerating material, it is characterised in that：The material is ferrimagnet, by tetra- kinds of element groups of Yb, Ho, Mn, O Into chemical formula Yb1-xHoxMnO3, x span is 0.01 ＜ x ＜ 0.99；The material crystalline phase is hexagonal crystal system, space group For P63Cm, and as the increase of Ho contents, its lattice constant a are increased monotonically；The material induces generation anti-under external magnetic field Ferromagnetic-ferromagnetic (AFM-FM) second-order phase transistion, magnetic entropy is produced in phase transition process and is become, realizes magnetic refrigeration.
  2. A kind of 2. preparation method of solid magnetic refrigerating material as claimed in claim 1, it is characterised in that：Burnt using solid reaction process Knot obtains, and preparation process specifically comprises the following steps：
    1) Yb has been weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Molar ratio is 1- x：x：1, wherein 0.05<x<0.95, purity is actually needed and determined not less than 99.9%, x values foundation；
    2) by ready Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 200-300 DEG C, during preheating Between be 2-8h, to remove moisture therein；
    3) by obtained in step 2) two kinds of powder and MnCO3Powder mixes；
    4) ball milling 2-5h is carried out to the mixed-powder obtained in step 3) using planetary ball mill；
    5) mixed-powder obtained in step 4) is placed in platinum crucible and calcined, calcining heat is 1100-1300 DEG C, the time For 20-40h, it is well mixed its each component；
    6) after the product cooling obtained step 5), the cold moudling under 30-80Mpa pressure；
    7) product for obtaining step 6) is sintered, sintering time 18-36h, and sintering temperature is 1300-1500 DEG C, sintering Atmosphere is air atmosphere；
    8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized.
  3. 3. the preparation method of solid magnetic refrigerating material according to claim 2, it is characterised in that：The sintering process is in horse Not carried out in stove.
  4. A kind of 4. solid magnetic refrigerating material, it is characterised in that：
    The material is made up of tetra- kinds of elements of Yb, Ho, Mn, O；And
    The chemical formula of the material is Yb1-xHoxMnO3, x span is 0 ＜ x ＜ 1 in its chemical formula；And
    The crystalline phase of the material is hexagonal crystal system, space group P63cm；And
    The material is block ferrimagnet, and the content of Yb, Ho element gradually changes in a dimension, and Yb, Ho member The variation tendency of the content of element is opposite, and the content of Mn elements is equally distributed；Any flat with the dimension perpendicular In face form the material each element be equally distributed, and in the plane Yb, Ho element molar content percentage it With the molar content percentage equal to Mn elements；And
    The Yb1-xHoxMnO3With the increase of Ho contents, its lattice constant a is increased monotonically；And
    The Yb1-xHoxMnO3Antiferromagnetic-ferromagnetic (AFM-FM) second-order phase transistion, phase transition process occur for induction under external magnetic field Middle generation magnetic entropy becomes, and realizes magnetic refrigeration.
  5. 5. solid-state magnetic refrigerating material according to claim 4, it is characterised in that：The material is in a dimension, chemical formula Yb1-xHoxMnO3Middle x value progressively increases to 1 by 0.
  6. A kind of 6. preparation method of solid magnetic refrigerating material as described in claim 4 or 5, it is characterised in that：The material is adopted Sinter to obtain with solid reaction process, preparation process specifically comprises the following steps：
    1) multigroup Yb is weighed according to a certain percentage2O3、Ho2O3And MnCO3Powder, the Yb2O3、Ho2O3And MnCO3Molar ratio is 1-x：x：1, x is distributed into arithmetic progression in each group powder, and various powder purities are not less than 99.9%；
    2) by ready each group Yb2O3、Ho2O3Powder is respectively placed in heating furnace and preheated, and preheating temperature is 200-300 DEG C, in advance The hot time is 2-8h, to remove moisture therein；
    3) by each group powder obtained in step 2) respectively with MnCO3Powder mixes；
    4) ball milling 2-5h is carried out to each group mixed-powder obtained in step 3) using planetary ball mill respectively；
    5) each group mixed-powder obtained in step 4) is respectively placed in platinum crucible and calcined, calcining heat 1100- 1300 DEG C, time 20-40h, it is well mixed its each component；
    6) after each group product cooling obtained step 5), it is cold-pressed into flake under 30-80Mpa pressure respectively；
    7) each group product that step 6) obtains is sintered respectively, sintering time 18-36h, sintering temperature 1300-1500 DEG C, sintering atmosphere is air atmosphere；
    8) by step 7) sinter after product naturally cool to room temperature, make wherein metallic element obtain it is fully oxidized；
    9) order that the thin slice of obtained different Ho contents gradually increases according to x values is stacked together, applies 30- again 80Mpa pressure is cold-pressed；
    10) and then again it is sintered technique：Sintered in air atmosphere, sintering time 4-32h, sintering temperature 1300- 1500℃；
    11) natural cooling obtains the Yb of Yb, Ho composition gradual change under air atmosphere1-xHoxMnO3Magnetic refrigerating material.
  7. 7. a kind of magnetic refrigerator, containing solid magnetic refrigerating material, and permanent magnet or electromagnet or superconducting electromagnet, its feature exists In：The solid magnetic refrigerating material is the solid magnetic refrigerating material as described in claim 1 or 4 or 5 is any.
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