CN1161443C - Ordinary-temp magnetically refrigerating material and its preparing process - Google Patents
Ordinary-temp magnetically refrigerating material and its preparing process Download PDFInfo
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- CN1161443C CN1161443C CNB021378770A CN02137877A CN1161443C CN 1161443 C CN1161443 C CN 1161443C CN B021378770 A CNB021378770 A CN B021378770A CN 02137877 A CN02137877 A CN 02137877A CN 1161443 C CN1161443 C CN 1161443C
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000005291 magnetic effect Effects 0.000 claims abstract description 76
- 238000005057 refrigeration Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 10
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 10
- 241000255789 Bombyx mori Species 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 230000005307 ferromagnetism Effects 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000007750 plasma spraying Methods 0.000 claims description 3
- 241001124569 Lycaenidae Species 0.000 claims description 2
- 235000014987 copper Nutrition 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 238000011160 research Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 230000007306 turnover Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The present invention discloses an ordinary-temperature magnetic refrigerating material and a preparing process thereof. The material is prepared from material sheet elements through laminating, wherein boss points are arranged among the material sheet elements; each material sheet element comprises an upper metal skin and a lower metal skin and liquid heat-conductive agents are filled between the metal skins and is mixed with super-paramagnetic or ferromagnetic ordinary-temperature magnetic refrigerating working substance powder to divide and tightly press the metal skins. The preparing process of the material comprises the steps that refrigerating working substances are processed to powder; the refrigerating working substance powder is added to the liquid heat-conductive agents and then, the liquid heat-conductive agents are sealed between the two metal skins; the two metal skins in each material sheet element are divided and tightly pressed; the material sheet elements are laminated to a sheet cluster. The present invention solves the problem of how the ordinary-temperature magnetic refrigerating material being used for ordinary-temperature magnetic refrigeration, isolates the ordinary-temperature magnetic refrigerating material from a heat exchange fluid to prevent the oxidation of the working substances, and strengthens heat transmission between the ordinary-temperature magnetic refrigerating material and the heat exchange fluid by means of the ordinary-temperature magnetic refrigerating material and the liquid.
Description
One, technical field
The present invention relates to a class refrigeration working medium and a method for making thereof, especially for the load moulding and the method for making thereof of the superparamagnetism refrigerating material and the ferromagnetic substance of room temperature magnetic refrigerating.
Two, background technology
The development of modern society and the raising of quality of life require to have comfortable environment, Refrigeration Technique progressively development and ripe as the blood of modern science at nearly 200 years, brought comfortable for human life and enjoyment, also provide research and usage platform to Science and Technology.Because the human energy has 1/3rd to consume on refrigeration, so the situation of Refrigeration Technique is very important to human existence.Refrigeration Technique mainly contains various ways such as vaporizing liquid refrigeration, gas expansion refrigeration, absorption refrigeration, thermoelectric refrigeration, vortex tube refrigeration, thermoacoustic refrigeration, pulse tube refrigeration and magnetic refrigeration, but most popular be vaporizing liquid refrigeration.The vaporizing liquid refrigeration needs to use fluorine Lyons, it not only destroys the ozone environment in the atmospheric layer sky, but also have Greenhouse effect, and therefore refrigeration has directly influenced the use of the energy and the quality of environment, and the New Refrigerating mode of research and development energy-conserving and environment-protective is just very urgent and significant.
The magnetic refrigeration is just confirmed on science in nineteen twenty-six that as a kind of refrigeration modes it has the highest cycle efficiency in theory, and does not have compressor, so the refrigeration modes that has just become the physicist to dream of.But research is afterwards only succeedd near utmost point low temperature field (zero absolute temperature), and has produced the magnetic refrigeration liquefying equipment of helium already.Room temperature magnetic refrigerating part then experienced after the too many failure secular stagnation not before, what progress never.Different with the magnetic refrigeration under the low temperature, room temperature magnetic refrigerating all has special requirement on Recycle design, magnetic refrigeration working substance and magnetic field, and it is very difficult therefore to implement.
1976, the Brown of NASA (NASA) used the gadolinium plate to add the alcohol that is mixed with water and makes cold storage agent in the following temperature difference that at first realizes 38 degree of cryogenic magnetic field environment, has shown the possibility of room temperature magnetic refrigerating to the mankind.
Nineteen eighty-two, the Barclay of the U.S. and Clayart have proposed the new ideas of active magnetic regenerator (AMR), for the room temperature magnetic refrigerating of practicability has been done theoretic preparation.
Nineteen ninety, USDOE subsidy NASA and University of Iowa Ames Lab are carried out the room temperature magnetic refrigerating prototyping based on AMR.In room temperature magnetic refrigerating material research, they find that in 1997 the gadolinium sige alloy has the so-called huge magnetothermal effect above gadolinium, has found the ample scope for abilities for active magnetic regenerator.In the research of room-temperature magnetic refrigerator, through nearly 8 years arduous groping, the reciprocating room temperature magnetic refrigerating machine declaration of human first long-term high-efficient operation of energy in 1997 is come out.The refrigeration working medium of its use is a metal gadolinium ball, and diameter is between 0.1mm ~ 0.3mm, and weight is 3 kilograms, and the cryogenic magnetic field of use is 1.5 ~ 5 teslas, and loop cycle is 6 seconds, turns round 1500 hours.The thermodynamics sophistication reaches 60% when working under 5 tesla magnetic fields, then is approximately 20% when working under 1.5 tesla magnetic fields.This work is indicating the arriving in practical epoch of room temperature magnetic refrigerating technological direction.
Room temperature magnetic refrigerating is the road of refrigerating inevitable development, and it will replace existing refrigeration modes in the near future.The air-conditioning that all and traditional refrigeration modes interrelate, refrigerator and other refrigerators will be finished revolutionary transformation.But room temperature magnetic refrigerating will move towards market at first needs to solve efficiency, integrity problem and economy problems.Along with the progressively maturation of room temperature magnetic refrigerating technology, global refrigeration industry will thoroughly change existing product structure, and its market is inestimable.Freeze since nineteen ninety-seven, room temperature magnetic refrigerating has just begun practical research.Because competition object and reference standard that room temperature magnetic refrigerating requires are traditional steam compression type refrigerations, therefore not only require room temperature magnetic refrigerating to have the advantage of price, and require to have little volume and high working efficiency.For such problem, we think and can solve by improving travelling speed, seek the room temperature magnetic refrigerating material with big magnetothermal effect and increasing mode such as magneticstrength.Because room temperature magnetic refrigerating also uses fluid and room temperature magnetic refrigerating material heat-shift, this has just proposed requirement to the moulding of room temperature magnetic refrigerating material.
Three, summary of the invention
1, goal of the invention: the purpose of this invention is to provide a kind of room temperature magnetic refrigerating material and manufacture method thereof, to reach the refrigerating duty that increases room temperature magnetic refrigerating, improve the heat exchange effect, the oxidation rate of slowing down working medium improves purposes such as its work-ing life.
2, technical scheme: for achieving the above object, a kind of room temperature magnetic refrigerating material of the present invention, it is characterized in that it is to be overrided to form by the material piece unit, be provided with salient point between material piece unit and the material piece unit, make the passage that forms fluid flow between material piece unit and the material piece unit.
Described material piece unit comprises double layer of metal copper up and down, between metallic copper, be filled with the liquid heat conductive agent, be mixed with superparamagnetism or ferromagnetism room-temp magnetic refrigeration working substance powder in this thermal conducting agent, double layer of metal copper piecemeal kills up and down, makes the mutual one by one obstructed minizone of metallic copper intermediate formation.
The grain size 0.005-0.01 millimeter of described superparamagnetism or ferromagnetism room-temp refrigeration working medium powder.
The thickness 0.01-0.05 millimeter of described metallic copper, the unitary thickness 0.05-0.1 of material piece millimeter.
Described salient point be thickness be not more than the material piece element thickness tinsel or between the material piece unit pad on diameter be the spherical metal powder of 0.01-0.1 millimeter.
Described metallic copper is a copper sheet.
Sheet a small bundle of straw, etc. for silkworms to spin cocoons on thickness after described material piece unit laminates mutually is the 0.1-100 millimeter.
The manufacture method of described room temperature magnetic refrigerating material is characterized in that: the powder that superparamagnetism or ferromagnetism room-temp magnetic refrigeration working substance is become particle diameter 0.005-0.01 millimeter by pulverizing, ball milling, plasma spraying or machine tooling; Be ready to the metallic copper of thickness 0.01-0.05 millimeter; The refrigeration working medium powder is joined in the liquid heat conductive agent, and the liquid heat conductive agent that will contain refrigeration working medium again is sealed between two metallic coppers, compresses the material piece unit that makes it to form thickness 0.05-0.1 millimeter; Two metallic copper piecemeals in the material piece unit are killed, make the not connected one by one minizone of formation between metallic copper; The material piece unit is laminated a small bundle of straw, etc. for silkworms to spin cocoons in blocks, between the material piece unit, be provided with salient point, make the passage that is formed with fluid flow between the material piece unit.Described metallic copper adopts copper sheet.The salient point that is provided with between the described material piece unit be thickness be not more than the material piece element thickness tinsel or between the material piece unit pad on particle diameter be the spherical metal powder of 0.01-0.1 millimeter.Sheet a small bundle of straw, etc. for silkworms to spin cocoons on thickness that the material piece unit laminates formation is the 0.1-100 millimeter.
The basic functional principle of room temperature magnetic refrigerating is the temperature effective that has when utilizing magneticsubstance turnover magnetic field.Because once clean temperature effective is less, need such temperature effective is amplified and accumulation by effective technical means, so need to adopt so-called active magnetic regenerator to achieve the goal.In active magnetic regenerator, magnetic working medium is also served as the role of regenerator simultaneously at refrigerating, need regulate the temperature variation of working medium with the fluid heat transferring in the external world, so heat exchange efficiency and problem such as anti-oxidation also just seem very outstanding when selecting room temperature magnetic refrigerating working for use, need be noted especially.
3, beneficial effect: the present invention compared with prior art, 1), solved the problem, particularly easily oxidation and easily atomizing room temperature magnetic refrigerating material and the size tiny application of superparamagnetic material on room temperature magnetic refrigerating that how room temperature magnetic refrigerating material are used for room temperature magnetic refrigerating its remarkable advantage is:.2), finished the isolated of room temperature magnetic refrigerating material and heat exchanging fluid, prevented the oxidation of working medium.3), strengthened the heat transfer of room temperature magnetic refrigerating material and heat exchanging fluid with room temperature magnetic refrigerating material and liquid
Four, description of drawings
Fig. 1 is the unitary structural representation of material piece of the present invention.
Fig. 2 is of the present invention a small bundle of straw, etc. for silkworms to spin cocoons on structural representation.
Five, embodiment:
Embodiment 1:
The room temperature magnetic refrigerating material that the present invention makes is that 0.1 millimeter material piece unit is overrided to form by thickness, the thickness of formed a small bundle of straw, etc. for silkworms to spin cocoons on is 5 millimeters, between every layer material blade unit and material piece unit, be provided with diameter and be 1 millimeter, highly be 0.05 millimeter little round platform, make the passage that is formed with liquid-flow between the material piece unit every 5 millimeters.The material piece unit is that 0.01 millimeter copper sheet constitutes by two layers of thickness up and down, between two-layer copper sheet, be full of liquid anti-oxidation thermal conducting agent gallium is arranged, be filled with the room temperature magnetic refrigerating material gadolinium as refrigeration working medium in the liquid anti-oxidation thermal conducting agent gallium, the particle diameter of refrigeration working medium is 0.005 millimeter, between the copper sheet impression is arranged up and down every 3 millimeters, make the copper sheet intermediate formation not connected minizone of quadrate one by one.Its concrete manufacture craft is as follows:
1, with the room temperature magnetic refrigerating working gadolinium by machine tooling become small pieces, with pigment broken and ball milling or plasma spraying or lathe directly multiple modes such as processing be processed into the gadolinium ball of suitable size, it is of a size of 0.005 millimeter.
2, be ready to thickness less than 0.01 millimeter copper sheet.
3, tightening seal is gone into room temperature magnetic refrigerating working medium gadolinium ball and anti-oxidation thermal conducting agent gallium between two copper sheets, and the gadolinium ball should be tight as far as possible.It is 0.1 millimeter sheet that these materials are pressed into thickness.On institute compressing tablet surface, be that a diameter is that 1 millimeter height is 0.05 millimeter a little round platform every 5 millimeters.Every 3 millimeters distances, this copper sheet is killed, make the mutual obstructed minizone of quadrate one by one in the middle of copper sheet, to occur.
4, this material piece has been built become sheet and bunch add press fit, to guarantee necessary physical strength.It is excessive not pressurize, in order that guarantee to have between sheet the fluid can the mobile passage.The thickness of sheet bunch is being 5 millimeters.
5, the room temperature magnetic refrigerating material of moulding is suitably cut out like this, just can be used for the room temperature magnetic refrigerating machine.Concrete structure situation is referring to accompanying drawing 1 and accompanying drawing 2.
Embodiment 2: its structure of room temperature refrigerating material and manufacture method are same as embodiment 1 substantially, different is: refrigeration working medium is selected superparamagnetism room temperature refrigeration working medium for use, its particle diameter is 0.001 millimeter, the unitary thickness of material piece is 0.05 millimeter, sprinkle particle diameter and be 0.05 millimeter spherical metal powder between the material piece unit, it is 90 millimeters that the material piece unit laminates sheet a small bundle of straw, etc. for silkworms to spin cocoons on thickness that the back forms.
Claims (9)
1, a kind of room temperature magnetic refrigerating material, it is characterized in that it is to be overrided to form by the material piece unit, be provided with salient point between material piece unit and the material piece unit, make the passage that forms fluid flow between material piece unit and the material piece unit, described material piece unit comprises double layer of metal copper up and down, between metallic copper, be filled with liquid anti-oxidation thermal conducting agent gallium, be filled with the room temperature magnetic refrigerating material gadolinium as refrigeration working medium in the liquid anti-oxidation thermal conducting agent gallium, double layer of metal copper is killed by piecemeal up and down, makes the mutual one by one obstructed minizone of metallic copper intermediate formation.
2, room temperature magnetic refrigerating material according to claim 1 is characterized in that the grain size 0.005-0.01 millimeter of described superparamagnetism or ferromagnetism room-temp refrigeration working medium powder.
3, room temperature magnetic refrigerating material according to claim 1 is characterized in that the thickness 0.01-0.05 millimeter of described metallic copper, the unitary thickness 0.05-0.1 of material piece millimeter.
4, room temperature magnetic refrigerating material according to claim 1, it is characterized in that described salient point be thickness be not more than the material piece element thickness tinsel or between the material piece unit pad on diameter be the spherical metal powder of 0.01-0.1 millimeter.
5, room temperature magnetic refrigerating material according to claim 1 is characterized in that the sheet a small bundle of straw, etc. for silkworms to spin cocoons on thickness after described material piece unit laminates mutually is the 0.1-100 millimeter.
6, the manufacture method of room temperature magnetic refrigerating material according to claim 1 is characterized in that:
1) superparamagnetism or ferromagnetism room-temp magnetic refrigeration working substance are become the powder of particle diameter .005-0.01 millimeter by pulverizing, ball milling, plasma spraying or machine tooling;
2) be ready to the metallic copper of thickness 0.01-0.05 millimeter;
3) the refrigeration working medium powder is joined in the liquid heat conductive agent, the liquid heat conductive agent that will contain refrigeration working medium again is sealed between two metallic coppers, compresses the material piece unit that makes it to form thickness 0.05-0.1 millimeter;
4) two metallic copper piecemeals in the material piece unit are killed, make the not connected one by one minizone of formation between metallic copper;
5) the material piece unit is laminated a small bundle of straw, etc. for silkworms to spin cocoons in blocks, between the material piece unit, be provided with salient point, make the passage that is formed with fluid flow between the material piece unit.
7, the manufacture method of room temperature magnetic refrigerating material according to claim 7 is characterized in that described metallic copper adopts copper sheet.
8, the manufacture method of room temperature magnetic refrigerating material according to claim 7, it is characterized in that the salient point that is provided with between the described material piece unit be thickness be not more than the material piece element thickness tinsel or between the material piece unit pad on particle diameter be the spherical metal powder of 0.01-0.1 millimeter.
9, the manufacture method of room temperature magnetic refrigerating material according to claim 7 is characterized in that sheet a small bundle of straw, etc. for silkworms to spin cocoons on thickness that the material piece unit laminates formation is the 0.1-100 millimeter.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB021378770A CN1161443C (en) | 2002-07-01 | 2002-07-01 | Ordinary-temp magnetically refrigerating material and its preparing process |
JP2004516429A JP2005536630A (en) | 2002-07-01 | 2003-06-30 | Molding and manufacturing method of room temperature magnetic cooling material combined with high thermal conductive material |
AU2003257765A AU2003257765A1 (en) | 2002-07-01 | 2003-06-30 | A moulding process of composite material including high-thermal--conductor and room-temperature magnetic refrigerant |
US10/519,896 US7621046B2 (en) | 2002-07-01 | 2003-06-30 | Moulding process of composite material including high-thermal conductor and room-temperature magnetic refrigerant |
PCT/CN2003/000507 WO2004003100A1 (en) | 2002-07-01 | 2003-06-30 | A moulding process of composite material including high-thermal-conductor and room-temperature magnetic refrigerant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CNB021378770A CN1161443C (en) | 2002-07-01 | 2002-07-01 | Ordinary-temp magnetically refrigerating material and its preparing process |
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CN1396231A CN1396231A (en) | 2003-02-12 |
CN1161443C true CN1161443C (en) | 2004-08-11 |
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CNB021378770A Expired - Fee Related CN1161443C (en) | 2002-07-01 | 2002-07-01 | Ordinary-temp magnetically refrigerating material and its preparing process |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI403682B (en) * | 2009-09-17 | 2013-08-01 | Delta Electronics Inc | Magnetocaloric structure |
CN102466364B (en) * | 2010-11-05 | 2013-10-16 | 中国科学院理化技术研究所 | Magnetic refrigeration working medium bed and preparation method thereof |
CN103624491A (en) * | 2013-11-22 | 2014-03-12 | 四川大学 | Forming process of magnetic refrigeration material |
CN103759463B (en) * | 2014-01-08 | 2016-02-24 | 中国科学院理化技术研究所 | room temperature magnetic refrigeration system |
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