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Gadolinium alloy heats up inside the magnetic field and loses thermal energy to the environment, so it exits the field cooler than when it entered. Magnetic refrigeration is a cooling technology based on the magnetocaloric effect. This technique can be used to attain extremely low temperatures, as well as the ranges used in common refrigerators, depending on the design of the system. The effect was first observed by the German physicist Emil Warburg (1880) and the fundamental principle was suggested by Debye (1926) and Giauque (1927).[1] The first working magnetic refrigerators were constructed by several groups beginning in 1933. Magnetic refrigeration was the first method developed for cooling below about 0.3 K (a temperature attainable by 3He refrigeration, that is pumping on the 3He vapors).
Contents
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1 The magnetocaloric effect o 1.1 Thermodynamic cycle o 1.2 Applied technique 2 Working materials o 2.1 Paramagnetic salts o 2.2 Nuclear demagnetization 3 Commercial development o 3.1 Current and future uses
4 History o 4.1 Room temperature devices 5 See also 6 References 7 Further reading 8 External links
Analogy between magnetic refrigeration and vapor cycle or conventional refrigeration. H = externally applied magnetic field; Q = heat quantity; P = pressure; Tad = adiabatic temperature variation The cycle is performed as a refrigeration cycle, analogous to the Carnot cycle, and can be described at a starting point whereby the chosen working substance is introduced into a magnetic field, i.e., the magnetic flux density is increased. The working material is the refrigerant, and starts in thermal equilibrium with the refrigerated environment.
Adiabatic magnetization: A magnetocaloric substance is placed in an insulated environment. The increasing external magnetic field (+H) causes the magnetic dipoles of the atoms to align, thereby decreasing the material's magnetic entropy and heat capacity. Since overall energy is not lost (yet) and therefore total entropy is not reduced (according to thermodynamic laws), the net result is that the item heats up (T + Tad). Isomagnetic enthalpic transfer: This added heat can then be removed (-Q) by a fluid or gas gaseous or liquid helium, for example. The magnetic field is held constant to prevent the dipoles from reabsorbing the heat. Once sufficiently cooled, the magnetocaloric substance and the coolant are separated (H=0). Adiabatic demagnetization: The substance is returned to another adiabatic (insulated) condition so the total entropy remains constant. However, this time the magnetic field is decreased, the thermal energy causes the magnetic moments to overcome the field, and
thus the sample cools, i.e., an adiabatic temperature change. Energy (and entropy) transfers from thermal entropy to magnetic entropy (disorder of the magnetic dipoles).
Isomagnetic entropic transfer: The magnetic field is held constant to prevent the material from heating back up. The material is placed in thermal contact with the environment being refrigerated. Because the working material is cooler than the refrigerated environment (by design), heat energy migrates into the working material (+Q).
Once the refrigerant and refrigerated environment are in thermal equilibrium, the cycle begins again.
The magnitudes of the magnetic entropy and the adiabatic temperature changes are strongly dependent upon the magnetic order process: the magnitude is generally small in antiferromagnets, ferrimagnets and spin glass systems; it can be substantial for normal ferromagnets which undergo a second order magnetic transition; and it is generally the largest for a ferromagnet which undergoes a first order magnetic transition. Also, crystalline electric fields and pressure can have a substantial influence on magnetic entropy and adiabatic temperature changes. Currently, alloys of gadolinium producing 3 - 4 K per tesla [K/T] of change in a magnetic field can be used for magnetic refrigeration. Recent research on materials that exhibit a giant entropy change showed that Gd5(SixGe1x)4, La(FexSi1x)13Hx and MnFeP1xAsx alloys, for example, are some of the most promising substitutes for gadolinium and its alloys GdDy, GdTb, etc. These materials are called giant magnetocaloric effect (GMCE) materials. Gadolinium and its alloys are the best material available today for magnetic refrigeration near room temperature since they undergo second-order phase transitions which have no magnetic or thermal hysteresis involved.
Unfortunately, the small magnitudes of nuclear magnetic dipoles also makes them less inclined to align to external fields. Magnetic fields of 3 teslas or greater are often needed for the initial magnetization step of NDR. In NDR systems, the initial heat sink must sit at very low temperatures (10100 mK). This precooling is often provided by the mixing chamber of a dilution refrigerator or a paramagnetic salt.
reported a temperature span of 8.7 C.[5] They hope to introduce the first commercial applications of the technology by 2010.
[edit] History
The effect was discovered in pure iron in 1880 by German physicist Emil Warburg. Originally, the cooling effect varied between 0.5 to 2 K/T. Major advances first appeared in the late 1920s when cooling via adiabatic demagnetization was independently proposed by two scientists, Peter Debye in 1926 and William Giauque in 1927. This cooling technology was first demonstrated experimentally by chemist Nobel Laureate William F. Giauque and his colleague D. P. MacDougall in 1933 for cryogenic purposes when they reached 0.25 K.[9] Between 1933 and 1997, a number of advances in utilization of the MCE for cooling occurred.[10][11][12][13] In 1997, the first near room temperature proof of concept magnetic refrigerator was demonstrated by Karl A. Gschneidner, Jr. by the Iowa State University at Ames Laboratory. This event attracted interest from scientists and companies worldwide who started developing new
kinds of room temperature materials and magnetic refrigerator designs.[2] A major breakthrough came 2002 when a group at the University of Amsterdam demonstrated the giant magnetocaloric effect in MnFe(P,As) alloys that are based on earth abundant materials.[14] Refrigerators based on the magnetocaloric effect have been demonstrated in laboratories, using magnetic fields starting at 0.6 T up to 10 T. Magnetic fields above 2 T are difficult to produce with permanent magnets and are produced by a superconducting magnet (1 T is about 20,000 times the Earth's magnetic field).
Institute/Company
Solid refrigerant
Ames, Iowa/Madi Ames February Laboratory/Astrona son, 20, 1997 utics[15] Wisconsin, USA Mater. Science Barcelona, May 2000 Institute Spain [16] Barcelona Yokohama, Summer Chubu Electric/Toshiba[17] Japan 2000 Victoria, British University of July 2001 Victoria[18][19][20] Columbia Canada Madison, September Astronautics[21] Wisconsin, 18, 2001 USA Sichuan Inst. Nanjing, 23 April Tech./Nanjing China 2002 [22] University Yokohama, October 5, Chubu [23] Electric/Toshiba Japan 2002 Yokohama, March 4, Chubu Electric/Toshiba[23] Japan 2003
10 5 (S)
Gd spheres
Rotary
0.95 (P)
21 4 (S)
14 2 (S)
Rotary
95
25 1.5 (P) Gd spheres Gd spheres and 23 1.4 (P) Gd5Si1.985Ge1.985 Ga0.03 powder 27 0.6 (P) Gd1xDyx L.B. 10 0.76 (P) Gd 1xDyx L.B. 1
Lab. Grenoble, dElectrotechnique France [24] Grenoble George Washington USA University [25] Astronautics
[26]
4 5
Victoria, Gd, Gd0.74Tb0.26 British Reciprocat 2006 15 50 2 (S) and Gd0.85Er0.15 0.12 Columbia ing pucks Canada 1 maximum cooling power at zero temperature difference (T=0); 2maximum temperature span at zero cooling capacity (W=0); L.B. = layered bed; P = permanent magnet; S = superconducting magnet University of Victoria[27]
In one example, Prof. Karl A. Gschneidner, Jr. unveiled a proof of concept magnetic refrigerator near room temperature on February 20, 1997. He also announced the discovery of the GMCE in Gd5Si2Ge2 on June 9, 1997 [28] (see below). Since then, hundreds of peer-reviewed articles have been written describing materials exhibiting magnetocaloric effects.
[edit] References
1. ^ Zemansky, Mark W. (1981). Temperatures very low and very high. New York: Dover. p. 50. ISBN 0486-24072-X. 2. ^ a b Karl Gschneidner, Jr. and Kerry Gibson (December 7, 2001). "Magnetic Refrigerator Successfully Tested". Ames Laboratory News Release. Ames Laboratory. http://www.external.ameslab.gov/news/release/01magneticrefrig.htm. Retrieved 2006-12-17. 3. ^ Emsley, John (2001). Nature's Building Blocks. Oxford University Press. p. 342. ISBN 0-19-850341-5. 4. ^ Gibson, Kerry (November 2001). "Magnetic Refrigerator Successfully Tested: Ames Laboratory develoments help push boundaries of new refrigeration technology". INSIDER Newsletter for employees of Ames Laboratory. http://www.ameslab.gov/news/ins01-11Magnetic.htm.(Vol. 112, No.10 ) 5. ^ Milestone in magnetic cooling, Ris News, August 20, 2007. Retrieved August 28, 2007. 6. ^ Gschneidner, Karl A., Jr.; Pecharsky, V. K. and Tsokol1, A.O. Recent developments in magnetocaloric materials Report on Progress in Physics. (2005) Volume 68, pages 14791539. 7. ^ http://www.osti.gov/bridge/purl.cover.jsp?purl=/40784-UgOxYh/webviewable/40784.pdf 8. ^ http://www.ameslab.gov/final/News/1999rel/99crada.html 9. ^ Giauque, W. F.; MacDougall, D. P. (1933). "Attainment of Temperatures Below 1 Absolute by Demagnetization of Gd2(SO4)38H2O". Phys. Rev. 43 (9): 768. Bibcode 1933PhRv...43..768G. doi:10.1103/PhysRev.43.768. 10. ^ Gschneidner, K. A. Jr.; Pecharsky, V. K. (1997). Bautista, R. G.; et al.. eds. Rare Earths: Science, Technology and Applications III. Warrendale, PA: The Minerals, Metals and Materials Society. p. 209.
11. ^ Pecharsky, V. K.; Gschneidner, K. A. Jr. (1999). "Magnetocaloric Effect and Magnetic Refrigeration". J. Magn. Magn. Mater. 200 (13): 4456. Bibcode 1999JMMM..200...44P. doi:10.1016/S03048853(99)00397-2. 12. ^ Gschneidner, K. A. Jr.; Pecharsky, V. K. (2000). "Magnetocaloric Materials". Annu. Rev. Mater. Sci. 30 (1): 387429. Bibcode 2000AnRMS..30..387G. doi:10.1146/annurev.matsci.30.1.387. 13. ^ Gschneidner, K. A. Jr.; Pecharsky, V. K. (2002). Chandra, D.; Bautista, R. G.. eds. Fundamentals of Advanced Materials for Energy Conversion. Warrendale, PA: The Minerals, Metals and Materials Society. p. 9. 14. ^ Tegus, O.; Brck, E.; de Boer, F. R.; Buschow, K. H. J. (2002). "Transition-metal-based magnetic refrigerants for room-temperature applications". Nature 415 (6868): 150152. Bibcode 2002Natur.415..150T. doi:10.1038/415150a. 15. ^ Zimm C, Jastrab A., Sternberg A., Pecharsky V.K., Gschneidner K.A. Jr., Osborne M. and Anderson I., Adv. Cryog. Eng. 43, 1759 (1998). 16. ^ Bohigas X., Molins E., Roig A., Tejada J. and Zhang X.X., IEEE Trans. Magn. 36 538 (2000). 17. ^ Hirano N., Nagaya S., Takahashi M., Kuriyama T., Ito K. and Nomura S. 2002 Adv. Cryog. Eng. 47 1027 18. ^ Rowe A.M. and Barclay J.A., Adv. Cryog. Eng. 47 995 (2002). 19. ^ Rowe A.M. and Barclay J.A., Adv. Cryog. Eng. 47 1003 (2002). 20. ^ Richard M.A., Rowe A.M. and Chahine R., J. Appl. Phys. 95 2146 (2004). 21. ^ Zimm C, Paper No K7.003 Am. Phys. Soc. Meeting, March 4, Austin, Texas (2003) [1] 22. ^ Wu W., Paper No. K7.004 Am. Phys. Soc. Meeting, March 4, Austin, Texas (2003) [2] 23. ^ a b Hirano N., Paper No. K7.002 Am. Phys. Soc. Meeting March 4, Austin, Texas, [3] 24. ^ Clot P., Viallet D., Allab F., Kedous-LeBouc A., Fournier J.M. and Yonnet J.P., IEEE Trans. Magn. 30 3349 (2003). 25. ^ F. Shir, C. Mavriplis, L.H. Bennett, E. Della Torre, "Analysis of room temperature magnetic regenerative refrigeration," International Journal of Refrigeration, 28, 4 (2005) 616. 26. ^ Zimm C, Paper No. K7.003 Am. Phys. Soc. Meeting, March 4, Austin, Texas (2003) [4] 27. ^ Rowe A.M. and Tura A., International Journal of Refrigeration 29 12861293 (2006). 28. ^ http://prola.aps.org/abstract/PRL/v78/i23/p4494_1
Lounasmaa, Experimental Principles and Methods Below 1 K, Academic Press (1974). Richardson and Smith, Experimental Techniques in Condensed Matter Physics at Low Temperatures, Addison Wesley (1988). Lucia, U. General approach to obtain the magnetic refrigeretion ideal Coefficient of Performance COP, Physica A: Statistical Mechanics and its Applications, 387/14 (2008) 34773479, doi:10.1016/j.physa.2008.02.026; see also http://arxiv.org/abs/1011.1684
NASA How does an Adiabatic Demagnetization Refrigerator Work ? What is magnetocaloric effect and what materials exhibit this effect the most? Magnetocaloric materials keep fridges cool by C. Wu Ames Laboratory news release, May 25, 1999, Work begins on prototype magneticrefrigeration unit. Magnetic refrigerator successfully tested Refrigeration Systems Terry Heppenstall's notes, University of Newcastle upon Tyne (November 2000) XRS Adiabatic Demagnetization Refrigerator
Executive Summary: A Continuous Adiabatic Demagnetization Refrigerator (.doc format) (Google cache) Origin and tuning of the magnetocaloric effect in the magnetic refrigerant Mn1.1Fe0.9(P0.8Ge0.2) Magnetic technology revolutionizes refrigeration Evaluation of thermodynamic quantities in magnetic refrigeration [show]
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