CN1276506A - Refrigerating method by phase change induced by electric field - Google Patents

Refrigerating method by phase change induced by electric field Download PDF

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Publication number
CN1276506A
CN1276506A CN99116225A CN99116225A CN1276506A CN 1276506 A CN1276506 A CN 1276506A CN 99116225 A CN99116225 A CN 99116225A CN 99116225 A CN99116225 A CN 99116225A CN 1276506 A CN1276506 A CN 1276506A
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China
Prior art keywords
electric field
refrigeration
ferroelectric
phase
ceramic material
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CN99116225A
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CN1099009C (en
Inventor
张进修
何琴玉
林国淙
黄元士
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Sun Yat Sen University
National Sun Yat Sen University
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National Sun Yat Sen University
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
    • F25B2321/001—Details of machines, plants or systems, using electric or magnetic effects by using electro-caloric effects
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Abstract

A refrigerating method using external electric field to induce phase change of ceramic is disclosed. An electric field is rapidly applied to a ferroelectric ceramic as refrigerating medium and quickly removed from it to induce its internal phase change, which can absorb and release the latent heat for refrigerating. Its advantages are low cost of refrigerating medium, repeatable use and no environmental pollution.

Description

The method of electric field-induced phase transition refrigeration
The present invention relates to a kind of method of refrigeration, particularly a kind of method of utilizing extra electric field to induce the ferroelectric ceramics freezing by change of state.
Except that conductor refrigeration (peltier effect), the existing cooling technic that has obtained to use all is operation material (working medium) to be undergone phase transition and from the absorption of latent heat of phase change with discharge the effect that reaches refrigeration by non-thermal type (pressurization, added electric field or magnetic field).For example, existing refrigerator and air-conditioner all are to utilize the variation of pressure to induce the gas in fluorine Lyons---liquid phase becomes refrigeration.But because the refrigeration working medium fluorine Lyons that once was widely used is progressively forbidden the serious day by day destruction of atmospheric ozone layer, though employing can utilize existing equipment for the new working medium in fluorine Lyons, whether the new working medium with similar structures can be destroyed environment and still remain long-term assessment.In seeking new refrigeration method, near the be applied in the eighties of adiabatic magnetic cooling room temperature once became hot topic.People are making great efforts to seek suitable magnetic cooling medium material, to improve cryomagnetic refrigeration output and efficient.But the difficult labour of highfield is given birth to and the expensive development and the application that has also limited room-temperature magnetic refrigeration of rareearth magnetic material.Depolarization refrigeration and cryomagnetic principle are similar, but because the size of electrode square is bigger than magnetic moment, so the fuel factor that Entropy Changes causes is littler than magnetic cooling, depolarization refrigeration also is difficult to practical application.
The method that the purpose of this invention is to provide a kind of refrigeration, its refrigeration working medium cost is low, can repeat repeatedly to use, and can not cause pollution and destruction to environment.
Feature of the present invention is to adopt ferroelectric ceramic material as refrigeration working medium, add at a slow speed that at ferroelectric ceramic material electric field produces phase transformation to induce it, be transformed into ferroelectric phase by paraelectric phase, the electric field of decorporating fast then makes ferroelectric phase become paraelectric phase, and the speed of ferroelectric ceramic material added electric field is less than the speed of moving back electric field.In whole process of refrigerastion, when ferroelectric ceramics heat release when paraelectric phase becomes ferroelectric phase, when becoming paraelectric phase, ferroelectric phase absorbs heat, using electric field is induced para-electric---and the release and the absorption of the latent heat of phase change that ferroelectric phase produced are freezed, and utilize to change the variation raising refrigerating efficiency that adds, moves back electric field speed.The present invention has modification BaTiO as the ferroelectric ceramic material of refrigeration working medium 3, (Ba 1-xBr) TiO 3(0＜X＜1), (Ba 1-xCa x) (Sn xTi 1-x) O 3(0＜X＜0.2), (Ba 1-xCa x) (Zr xTi 1-x) O 3(0＜X＜0.2), Ba (Sn xTi 1-x) O 3(0＜X＜1), Pb (Ta 0.5Sc O.5) O 3, (Ka 0.8Li 0.4) (Ta 0.7Ni 0.3) O 3, Sr 4Yb 2Fe 3Nb 3O 30, (1-X) Pb (Mg 1/3Nb 3/3) O 3+ XPbTiO 3(0.01＜X＜0.1) (is called for short (PMN-PT), Br xBa 1-xNb 2O 3(0.5＜X＜0.9) etc.The method of added electric field is on ferroelectric ceramic material: adopt added electric field at a slow speed, the time can be from 0.1 second to 10 seconds, when withdrawing from the arena, adopt the method for withdrawing from the arena fast, the time of withdrawing from the arena be 0.1 second to 10 -6Second.
In the present invention, we propose according to the speed scale rate of energy dissipation in phase transformation (heat) circulation: utilize low speed extra show in the pottery and energy net value that the phase transformation circulation of withdrawing from the arena is at a high speed absorbed is also obeyed the characteristics of speed scale, with the low speed extra show latent heat of emitting is minimized, make the latent heat of absorption increase to maximum with withdrawing from the arena fast then, make induced transformation can produce certain refrigerating capacity an electricity circulation.We have realized that the clean cooling amount of once above-mentioned electricity circulation reaches 1.5K～5K.In this course, the merit that outer place is done is except that a part is used for refrigeration, and another part is absorbed by phase transformation acoustic emission and generation of defects and process of self-organization thereof.The then available following method of the self-organizing of defective is eliminated, and adds and withdraws from the arena and make alternating voltage progressively be reduced to zero as regularly carrying out sinusoid, so just can eliminate residual residual polarization (for example, boosting to the civil power in 50 weeks of required voltage).Also can heat 15～20 ℃, be cooled to operating temperature again after making working medium all change paraelectric phase into.In this process of refrigerastion, working medium can be used repeatedly, and cost is reduced greatly, also can not cause the pollution to environment.
Below we are described in further detail the present invention in conjunction with the accompanying drawings.
Fig. 1 is for measuring the installation drawing of electric field-induced phase transition refrigeration.
Fig. 2 is refrigeration ferroelectric ceramics sample structure figure.
Fig. 3 is BaTiO 3Ceramics sample when withdrawing from the arena for 127 ℃, withdraw from the arena the time with the cooling relation curve.
The temperature slippage that Fig. 4 withdraws from the arena and causes when the different operating temperature for the PMN-PT sample.
Among Fig. 1,1 is high voltage source, its high-voltage output end connects ferroelectric ceramics sample 3 through uA ammeter 2, differential thermocouple 4 connects X-t recorder 5, cold and hot end a, the b of thermocouple 4, ferroelectric ceramics sample 3 and thermometer 6 place in the conduction oil 8 that vacuum flask 7 contained, and 9 is fixed support, stationary heat galvanic couple 4 and thermometer 6.
Fig. 2 is the structure chart of Fig. 1 ferroelectric ceramics sample 3, and wherein 3 is the ferroelectric ceramics sample, and 14 is the silver coating of sample surfaces, and 15 for being attached to the mica sheet on silver coating surface, and b is a thermocouple.
Among Fig. 3, sample is doping BaTiO 3Type nano ceramics disk, diameter 10mm, thickness 2mm, 127 ℃ of operating temperatures, applied field intensity are 2500KV/m, abscissa for the time of withdrawing from the arena (minute), ordinate is the temperature difference (K) of sample and medium.Because differential thermocouple cold junction and sample room have pressed from both sides an insulating trip, so measured Δ T and real time postpone to some extent.
Among Fig. 4, sample is PMN-PT ceramic material 95%Pb (Mg 1/3Nb 3/3) O 3+ 5%PbTiO 3, abscissa is represented operating temperature (K), and ordinate is represented sample cooling amount (K), and the cooling amount was with the variation relation of operating temperature when curve 1 was sample added electric field 2500KV/m; The cooling amount was with the variation relation of operating temperature when curve 2 was sample added electric field 1600KV/m; The cooling amount was with the variation relation of operating temperature when curve 3 was sample added electric field 1600KV/m; The cooling amount was with the variation relation of operating temperature when curve 4 was sample added electric field 800KV/m.
Be described further below in conjunction with embodiment.
With Sr 0.7Ba 0.3Nb 3O 8As refrigeration working medium, operating temperature is 60 ℃, sample shape is the disk of diameter 15mm, thickness is 0.5mm, plate silver as electrode on both sides, extra electric field intensity is 1500KV/m, the latent heat of emitting during with 10 seconds extra shows is 0.25J/g, with extra show in 5 seconds, the latent heat of emitting is the 0.3J/g level, and when withdrawing from the arena with 0.1 second, the latent heat of its absorption is the 0.8J/g level, when withdrawing from the arena with 0.01 second, the latent heat of its heat absorption is about 0.9J/g, as with 0.001 second or withdraw from the arena more at a high speed and then can reach the 1J/g level.Therefore, refrigerating capacity hourly can reach the level of 0.36KJ/g, can enter practical stage.We are applied to the following aspects with the research and development of this refrigerating method at present:
1, carries the chilled air fan or the small-sized air-cooler of a heat radiation airduct of only when extra show, working;
2, be used for chip overheating protector (sheet), make chip in use be no more than set point of temperature (such as, 60 or 70 ℃);
3, increase the working medium deal, also can be used for not being with the air-cooler of the little clean cooling power of packaged type of warm-air pipe;
4, be used for not being with warm-air pipe, the packaged type chilled air fan;
5, small-sized medical household freezer;
6, in use adopted " electricity activates and recovers and the hot the recovery " technology that overcomes the electric fatigue that causes owing to self organization phenomenon in the nonequilibrium phase transition.

Claims (5)

1, a kind of method of electric field-induced phase transition refrigeration, it is characterized in that adopting ferroelectric ceramic material as refrigeration working medium, add at a slow speed that at ferroelectric ceramic material electric field produces phase transformation to induce it, be transformed into ferroelectric phase by paraelectric phase, the electric field of decorporating fast then makes ferroelectric phase change paraelectric phase into, and the speed of ferroelectric ceramic material added electric field is less than the speed of moving back electric field.
2, a kind of method of electric field-induced phase transition as claimed in claim 1 refrigeration, it is characterized in that ferroelectric ceramic material at a slow speed the time of added electric field be 0.1 to 10 second, the time of moving back electric field fast is 0.1 to 10 -8Second.
3, a kind of method as claim 1,2 described electric field-induced phase transition refrigeration is characterized in that used ferroelectric ceramic material is (1-X) Pb (Mg 1/3Nb 3/3) O 3+ XPbTiO 3(0.01＜X＜0.1) or Sr 0.7Ba 0.3Nb 2O 6
4, a kind of method as the described electric field-induced phase transition refrigeration of claim 1.2, the intensity that it is characterized in that applied field is 800～2500KV/m.
5, a kind of method of electric field-induced phase transition refrigeration as claimed in claim 3, the intensity that it is characterized in that applied field is 800～2500KV/m.
CN99116225A 1999-06-04 1999-06-04 Refrigerating method by phase change induced by electric field Expired - Fee Related CN1099009C (en)

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CN1099009C CN1099009C (en) 2003-01-15

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295580C (en) * 2001-09-28 2007-01-17 日本电气株式会社 Information processing unit and cooling method thereof
CN100357675C (en) * 2003-06-19 2007-12-26 中国科学院电工研究所 Method for making ferroelectric thin / thick film micro electromechanical refrigerator, its arrangement and refrigerator system
CN100557340C (en) * 2004-10-14 2009-11-04 中国科学院电工研究所 A kind of little refrigerator and refrigerating method thereof
CN106091471A (en) * 2016-06-21 2016-11-09 上海工程技术大学 A kind of electricity card refrigerator
CN106123391A (en) * 2016-06-21 2016-11-16 上海工程技术大学 A kind of all solid state electricity card refrigerator
CN106784291A (en) * 2016-11-18 2017-05-31 南方科技大学 Refrigeration device and preparation method thereof
CN110906583A (en) * 2019-11-21 2020-03-24 华南理工大学 Novel refrigerating plant under electrostatic field effect

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2868519B1 (en) * 2004-03-30 2006-06-16 Christian Muller THERMAL GENERATOR WITH MAGNETO-CALORIC MATERIAL AND METHOD OF GENERATING THERMIES
CN102192614B (en) * 2010-03-12 2012-11-07 香港理工大学 Sheet-type micro refrigerator applying lead-free ferroelectric material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295580C (en) * 2001-09-28 2007-01-17 日本电气株式会社 Information processing unit and cooling method thereof
CN100357675C (en) * 2003-06-19 2007-12-26 中国科学院电工研究所 Method for making ferroelectric thin / thick film micro electromechanical refrigerator, its arrangement and refrigerator system
CN100557340C (en) * 2004-10-14 2009-11-04 中国科学院电工研究所 A kind of little refrigerator and refrigerating method thereof
CN106091471A (en) * 2016-06-21 2016-11-09 上海工程技术大学 A kind of electricity card refrigerator
CN106123391A (en) * 2016-06-21 2016-11-16 上海工程技术大学 A kind of all solid state electricity card refrigerator
CN106784291A (en) * 2016-11-18 2017-05-31 南方科技大学 Refrigeration device and preparation method thereof
CN106784291B (en) * 2016-11-18 2023-08-18 南方科技大学 Refrigerating device and preparation method thereof
CN110906583A (en) * 2019-11-21 2020-03-24 华南理工大学 Novel refrigerating plant under electrostatic field effect

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