Gd和Gd系合金的磁热效应及组织分析
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摘要
室温磁制冷技术因具有节能、环保等突出优点，越来越受到人们的关注。磁致冷材料作为其中的关键技术，它的发展具有举足轻重的作用。本文首先就磁致冷的基本原理、磁制冷关键技术、磁致冷材料的发展等问题做了简要的概述。本文研究下列问题并取得进展。第一、采用直接和间接测量法测试了不同纯度Gd在低场下(≦1.5T)的磁热效应；采用比热法计算了磁热效应并同实际测量的磁热效应进行了比较，结果表明Gd的磁热效应随着杂质的增加而减小、居里点降低；第二、对Gd_5Si_2Ge_2和Gd_5Si_(1.9)Ge_2Sn_(0.1)合金进行了热处理，实验结果表明高温热处理后，合金铸态的磁热效应得到了改善，其中1200℃/3h液氮冷却热处理后，磁热效应比合金铸态提高3倍多，比钆提高了84％；第三、在Gd_5Si_2Ge_2的研究基础上，采用SEM和XRD等方法，观察Gd_5Si_(1.9)Ge_2Sn_(0.1)合金热处理前后微观组织结构的变化，结果表明在热处理缓慢的冷却条件，合金易于出现第二相；高温保温并快速冷却，有利于形成单相，从而改善了磁热效应。
Magnetic refrigeration technology at the room temperature has attracted more and more people's attention due to its advantages involving in energy saving, environmental protection. To be key issue, magnetic refrigeration material has played an important role in the technology.
Firstly the article briefly introduces the basic principle, the key technology of magnetic refrigeration and the development of magnetic refrigerants. We have researched some questions and made some progress in this research. The article includes three parts: i) directly and indirectly measure the magnetocaloric effect of the different purity Gd under low magnetic field (<1.5T) , and verify the measured accuracy of the magnetocaloric effect adopting heat capacity. The result indicates that the magnetocaloric effect is reduced with increase of the impurity, Curie temperature decreased, ii) Gd5Si2Ge2 and Gd5Si1.9Ge2Sn0.1 alloy are heat-treated. The result indicates magnetocaloric effect of the alloy ingot have been greatly improved by heat treatment at high temperature, especially they has more three times than the former through heat treated by liquid nitrogen holding 1200℃ for 3h. iii) The microstructure of as-cast and heat-treated Gd5Si1 9Ge2Sn0.1 alloy are watched by SEM and XRD in order to find the cohesive relation between the microstructure and properties. The result indicates the alloy easily forms the second phase by the slower cooling during heat treatment, and makes more easily forming the single phase by holding temperature at high temperature and quicker cooling to improve the magnetocaloric effect.
Magnetic refrigeration technology at the room temperature has attracted more and more people's attention due to its advantages involving in energy saving, environmental protection. To be key issue, magnetic refrigeration material has played an important role in the technology.
Firstly the article briefly introduces the basic principle, the key technology of magnetic refrigeration and the development of magnetic refrigerants. We have researched some questions and made some progress in this research. The article includes three parts: i) directly and indirectly measure the magnetocaloric effect of the different purity Gd under low magnetic field (<1.5T) , and verify the measured accuracy of the magnetocaloric effect adopting heat capacity. The result indicates that the magnetocaloric effect is reduced with increase of the impurity, Curie temperature decreased, ii) Gd5Si2Ge2 and Gd5Si1.9Ge2Sn0.1 alloy are heat-treated. The result indicates magnetocaloric effect of the alloy ingot have been greatly improved by heat treatment at high temperature, especially they has more three times than the former through heat treated by liquid nitrogen holding 1200℃ for 3h. iii) The microstructure of as-cast and heat-treated Gd5Si1 9Ge2Sn0.1 alloy are watched by SEM and XRD in order to find the cohesive relation between the microstructure and properties. The result indicates the alloy easily forms the second phase by the slower cooling during heat treatment, and makes more easily forming the single phase by holding temperature at high temperature and quicker cooling to improve the magnetocaloric effect.
引文
1．龙毅，叶士禄等．低温工程．1991，63(5)：5～11．
2. Gschneidner K A Jr., Pecharsky V K, etal. Materials science forum 315, Tras Tech Publ. 1999: 69～76.
3. Pecharsky V K, Gschneidner K A,Magnetocaloric effect and magntic refrigeration, J.M.M.M, 1999.200(1).44-56.
4．戴闻，沈保根，磁制冷材料研究中的物理问题，中国科学基金，2000，14(4)216-220．
5．戴闻 张亮，在室温磁制冷中铁磁体作为工作物质的可能性，物理．1990，19(12)．-754-758，760．
6. O. Tegus, E. Bruck, K..H..J.Buschow&F.R.de Boer, Transition-metal-based magnetic refrigerants for room-temperature application, Nature: V415, 10 Jan 2002.
7．吴卫 刘晓烈等，磁热效应及磁制冷材料的研究现状，四川工业学院学报．2001，20(1)．-57-60
8．李卓棠等．稀土材料的磁热效应及其应用．化学进展，1995，7(2)：140～150．
9. V.K Pecharsky, Gschneidner K A Jr, Thermodynamics of the magnetocaloric effect,,Physics Review, Physical Review B: V64,144406-13.2001.
10. K.H.J.BvShow, handbook of magnetic materials 1999V(12):429-437.
11. Gchneidner K A Jr., Pecharsky V K. Production of the giant magnetocaloric effect magnetic refrigerant materials Rare Earths: Science, Technology and Applications Ⅲ, 1997: 209.
12. Gschneidner K.A Jr, Pecharsky VK. Magnetocaloric Materials, Annual Review of Material Science, 2000, 30, 387: 429.
13．韩鸿兴，寿卫东，磁制冷循环和磁致冷工质的选择原则，上海机械学院院报，11991，13(1)，317-45．
14．陈国邦等著．最新低温制冷技术．北京：机械工业出版社，1994：53～57．
15. Styert, S.A,Stiding-cycle ratating magnetic refeigerators and heat engines for use near room temperature,Journal of Applied Physics 1978.49(3) 1216-1226.
16．青木良三，串级式旋转室温此制冷机，低温工程，1989(4)：56．
17．戴闻 陈远富，第一台永磁式室温磁制冷机问世，物理．2002，31(8)．-539-539，489．
18. Debye P. Ann phys., 1926,(81): 1154～1160.
19. Giauque WF. J.Amer Chem.Soc., 1927,(49): 1864.
20. Pecharsky V K, Gschneidner K A Jr. Adv. Cryog. Eng., 1996, (42): 423.
21. Langevin P. Magnétisme er théorie des électrons. Ann Chim Phys., 1905,(5): 70～127.
22. Weiss P and Piccard A. Compt Rend, 1918,(166):325～354.
23. Brown G W. J.Appi. Phys., 1976(47): 3673.
24. McMichael R.D, Ritter JJ, etal. J.Appl. Phys., 1993(73): 6946.
25. Levitin R.Z., Snegirev V.V., etal. J M M M 1997(170) :223.
26. Giauque W F and McDougall D P. Phys. Rev., 1933,43:768.
27. Shull R. D, McMichael R.D., etal. Nanostructure Mater. 1993(2):205.
28. Cooke A H, Duffus H J, etal. Philos. Mag. 1953(44):623
29. 龙毅等．仪表材料．1990，21(2)：65～6929.
30. Andres K, Darack S, etal. Physica 86-88 B+C, 1977:1071.
31. Hishimoto T, Kuzuhara T K, etal. Adv. Cryog. Eng. 1986, (32): 279
32. Pecharsky VK, Gschneidner K A Jr.,etal. Adv.Cryog. Eng. 1996,(42):451
33. Korte, B J, Pecharsky V K, Gschneidner K A Jr. J. Appl. Phys., 1998, 84(10): 5677
34. Korte, B J, Pecharsky V K, Gschneidner K A Jr. Adv. Cryog. Eng. 1998, (43): 1737
35. Von Ranke P J, Pecharsky V K, Gschneidner K A Jr. Phys. Rev. B, 1998,58(18): 12110
36. Hishimoto T, Kuzuhara T K, etal. Jpn. J. Appl. Phys. 1987(26): 1673
37. Zimm C B, Ludeman E M, etal. Adv. Cryog. Eng. 1992, (37B): 883
38. Gchneidner K A Jr., Pecharsky V K, Some common misconception magnetic refrigerant materials, Jounal of Applysics,2001,11(90),4614.
39. guo Z B, Du Y W, etal. Phys. Rev. Lett, 1997,78(6): 1142～1144
40. U. S, Dan'kov etal. Rev. Sci. Instrum. 1997(68):2432
41. Nikitin S A, Talalaeva E V, etal. Zh. Eksp. Teor. Fiz. 1978(74):205
42. Ivanova Y I, etal. Fiz. Met. Metalloved. 1981(51):892
43. Benford S M, Brown G V. J.Appl. Phys., 1981(52):2110
44. Skrabek L, Stehno J, etal. Cesk. Cas. Fyz. 1986(36):479.
45. Burkhanov GS, Chistyakov O D, etal. Vysokochisr Veshchestva, 1990(1):204.
46. Korte, BJ, (?)echarsky VK, Gschneidner K A Jr. Adv.Cryog. Eng. 1998,(43): 1737.
47. Pecharsky V K, Gschneidner k A Jr. effect of alloying on the giant magnetocaloric effect of Gd_5Si_2Ge_2 J Magn Magn Mater; 1997,167L:179.
48. Pecharsky V K, Gschneidner k A Jr. Giant magnetocaloric effect in Gd_5Si_2Ge_2. Phy.Rev.Lett 1997, 70(23): 4494.
49. Gschneidner, Karl A. Jr: Pecharsky, Vitalij K. Tunable magnetic regenerator alloys with a giant magnetocaloric effect for magnetic refrigeration from～20 to～290 K.
50. Tomokiyo A, Yayama H, etal. Adv. Cryog. Eng. 1986, (32): 295.
51. Guo Z B, Zhang J R, et al. Appl. Phys. Lett.,1997,70(7): 904～905.
52. Zhang X X, Tajada J, etal. Appl. Phys. Lett.,1996,69: 3596.
53. Zhong W, Chen W, etal. Solid State Commun. 1998(106):55.
54. Chen W, Zhong W, etal. Chinese Phys. Lett., 1998(15):134.
55. X.X..Zhang, GH.When, Magnetic entropy change in Fe-based compound LaFe_(10.6)Si_(2.4).,Applied Physics Letter, V(7), 19,2000(6)3072-3075.
56. H.Wada,Y.Tanade,Giant magmetocaloric effect of MnAsSb,Applied Physics Letters.2001,79(20).3320-3304.
57. Gschneidner, Karl A. Jr; Pecharsky, magnetic refrigeration matrerials(ivited)Journal of Applied Physics 2000,85(8):
58．邵元智，物理学报，纳米Gd二元合金的磁热效应，中山大学学报(自然科学版)，1996，45(10)：49-53．
59．邵元智．纳米磁性体系的Monte Carlo模拟，中山大学学报，2000(7)：56-58．
60．杨玲，张喜燕，磁致冷材料的发展及研究现状，材料导报，2000(14)：35．
61. A.M.Tishin, Magnetic phase and the magnetothermal properties of Gadolinium, Phys. Rev.B 1998(57)6:3478-3489
62. M.Griffel,R.E.Skochdopole,the heat capacity of Gadolinium from 15 to 355K, Phys. Rev. B, 1954,15(93):657-668.
63. G.Glorieus,J Thoen, G. Bednarz, M. A. White, and D.J.W. Geldart. Plays. Rev. B 52,12770(1995)
64. S. Yu. Dan'kov, A.M. Tishin, V.K. Pecharsky, and K.A. Gschneider, Jr., Rev. Sci. Instrum.68,2432(1997).
65. B.R.Gropal,noncontact thermoacoustic method to measure the magnetocaloric effect, Rev.Sci.Instrum,v(66) 1995:231-235.
66. Gschneidner K A, Pecharsky A O, Production of the giant magnetocaloric effect magnetic refrigerant materials, Rare Earths and Actinides Science[R]. Technology and Applications, 2000(Ⅳ):63.
67. Benford S M, Brown G V. J. Appl. Phys., 1981(52): 2110.
68．陈远富，室温磁致冷GdSiGe系合金的磁热效应、磁相变及机制研究，四川大学博士学位论文，2001年5月：26．
69. Wang J L, Zhao R W, etal. J. Appl. Phys., 1994(76): 6740.
70. Yang Yingchang, Pan Qi, etal. J. Appl. Phys., 1992(72): 2989.
71．[苏]B．C．科瓦连科著，李云盛等译．金相显示剂手册，国防工业出版社，1983：120
72. Roman W. A., J. Less-common Metals, 1966,V.10, No.2, P150.
73. Zimm C., Stemberg A., etal. to be presented at Appliance Manufacturer Conference & Expo., Oct 12-14,1998.
74．桑丹．那日，钆在室温附近的磁热效应，内蒙古大学学报，20003(4)：361-365。
75. S. Meyers, L.S. Chumbley, etc, Determination of phases in as prepared Gd_5(Si_xGe_(1-x))_4,Scipta Materialia 47(2002)509-514
76. Pecharsky V K, Gschneidner k A Jr. Journal of Alloys and Compounds 260(1997)98-106.
77．李卓棠，吴佩放等．巨磁热效应材料Gd_5(SixGe_(1x))_4三元合金的制备及晶体结构，上海大学学报(自然科学版)，2000，6：35-39．
2. Gschneidner K A Jr., Pecharsky V K, etal. Materials science forum 315, Tras Tech Publ. 1999: 69～76.
3. Pecharsky V K, Gschneidner K A,Magnetocaloric effect and magntic refrigeration, J.M.M.M, 1999.200(1).44-56.
4．戴闻，沈保根，磁制冷材料研究中的物理问题，中国科学基金，2000，14(4)216-220．
5．戴闻 张亮，在室温磁制冷中铁磁体作为工作物质的可能性，物理．1990，19(12)．-754-758，760．
6. O. Tegus, E. Bruck, K..H..J.Buschow&F.R.de Boer, Transition-metal-based magnetic refrigerants for room-temperature application, Nature: V415, 10 Jan 2002.
7．吴卫 刘晓烈等，磁热效应及磁制冷材料的研究现状，四川工业学院学报．2001，20(1)．-57-60
8．李卓棠等．稀土材料的磁热效应及其应用．化学进展，1995，7(2)：140～150．
9. V.K Pecharsky, Gschneidner K A Jr, Thermodynamics of the magnetocaloric effect,,Physics Review, Physical Review B: V64,144406-13.2001.
10. K.H.J.BvShow, handbook of magnetic materials 1999V(12):429-437.
11. Gchneidner K A Jr., Pecharsky V K. Production of the giant magnetocaloric effect magnetic refrigerant materials Rare Earths: Science, Technology and Applications Ⅲ, 1997: 209.
12. Gschneidner K.A Jr, Pecharsky VK. Magnetocaloric Materials, Annual Review of Material Science, 2000, 30, 387: 429.
13．韩鸿兴，寿卫东，磁制冷循环和磁致冷工质的选择原则，上海机械学院院报，11991，13(1)，317-45．
14．陈国邦等著．最新低温制冷技术．北京：机械工业出版社，1994：53～57．
15. Styert, S.A,Stiding-cycle ratating magnetic refeigerators and heat engines for use near room temperature,Journal of Applied Physics 1978.49(3) 1216-1226.
16．青木良三，串级式旋转室温此制冷机，低温工程，1989(4)：56．
17．戴闻 陈远富，第一台永磁式室温磁制冷机问世，物理．2002，31(8)．-539-539，489．
18. Debye P. Ann phys., 1926,(81): 1154～1160.
19. Giauque WF. J.Amer Chem.Soc., 1927,(49): 1864.
20. Pecharsky V K, Gschneidner K A Jr. Adv. Cryog. Eng., 1996, (42): 423.
21. Langevin P. Magnétisme er théorie des électrons. Ann Chim Phys., 1905,(5): 70～127.
22. Weiss P and Piccard A. Compt Rend, 1918,(166):325～354.
23. Brown G W. J.Appi. Phys., 1976(47): 3673.
24. McMichael R.D, Ritter JJ, etal. J.Appl. Phys., 1993(73): 6946.
25. Levitin R.Z., Snegirev V.V., etal. J M M M 1997(170) :223.
26. Giauque W F and McDougall D P. Phys. Rev., 1933,43:768.
27. Shull R. D, McMichael R.D., etal. Nanostructure Mater. 1993(2):205.
28. Cooke A H, Duffus H J, etal. Philos. Mag. 1953(44):623
29. 龙毅等．仪表材料．1990，21(2)：65～6929.
30. Andres K, Darack S, etal. Physica 86-88 B+C, 1977:1071.
31. Hishimoto T, Kuzuhara T K, etal. Adv. Cryog. Eng. 1986, (32): 279
32. Pecharsky VK, Gschneidner K A Jr.,etal. Adv.Cryog. Eng. 1996,(42):451
33. Korte, B J, Pecharsky V K, Gschneidner K A Jr. J. Appl. Phys., 1998, 84(10): 5677
34. Korte, B J, Pecharsky V K, Gschneidner K A Jr. Adv. Cryog. Eng. 1998, (43): 1737
35. Von Ranke P J, Pecharsky V K, Gschneidner K A Jr. Phys. Rev. B, 1998,58(18): 12110
36. Hishimoto T, Kuzuhara T K, etal. Jpn. J. Appl. Phys. 1987(26): 1673
37. Zimm C B, Ludeman E M, etal. Adv. Cryog. Eng. 1992, (37B): 883
38. Gchneidner K A Jr., Pecharsky V K, Some common misconception magnetic refrigerant materials, Jounal of Applysics,2001,11(90),4614.
39. guo Z B, Du Y W, etal. Phys. Rev. Lett, 1997,78(6): 1142～1144
40. U. S, Dan'kov etal. Rev. Sci. Instrum. 1997(68):2432
41. Nikitin S A, Talalaeva E V, etal. Zh. Eksp. Teor. Fiz. 1978(74):205
42. Ivanova Y I, etal. Fiz. Met. Metalloved. 1981(51):892
43. Benford S M, Brown G V. J.Appl. Phys., 1981(52):2110
44. Skrabek L, Stehno J, etal. Cesk. Cas. Fyz. 1986(36):479.
45. Burkhanov GS, Chistyakov O D, etal. Vysokochisr Veshchestva, 1990(1):204.
46. Korte, BJ, (?)echarsky VK, Gschneidner K A Jr. Adv.Cryog. Eng. 1998,(43): 1737.
47. Pecharsky V K, Gschneidner k A Jr. effect of alloying on the giant magnetocaloric effect of Gd_5Si_2Ge_2 J Magn Magn Mater; 1997,167L:179.
48. Pecharsky V K, Gschneidner k A Jr. Giant magnetocaloric effect in Gd_5Si_2Ge_2. Phy.Rev.Lett 1997, 70(23): 4494.
49. Gschneidner, Karl A. Jr: Pecharsky, Vitalij K. Tunable magnetic regenerator alloys with a giant magnetocaloric effect for magnetic refrigeration from～20 to～290 K.
50. Tomokiyo A, Yayama H, etal. Adv. Cryog. Eng. 1986, (32): 295.
51. Guo Z B, Zhang J R, et al. Appl. Phys. Lett.,1997,70(7): 904～905.
52. Zhang X X, Tajada J, etal. Appl. Phys. Lett.,1996,69: 3596.
53. Zhong W, Chen W, etal. Solid State Commun. 1998(106):55.
54. Chen W, Zhong W, etal. Chinese Phys. Lett., 1998(15):134.
55. X.X..Zhang, GH.When, Magnetic entropy change in Fe-based compound LaFe_(10.6)Si_(2.4).,Applied Physics Letter, V(7), 19,2000(6)3072-3075.
56. H.Wada,Y.Tanade,Giant magmetocaloric effect of MnAsSb,Applied Physics Letters.2001,79(20).3320-3304.
57. Gschneidner, Karl A. Jr; Pecharsky, magnetic refrigeration matrerials(ivited)Journal of Applied Physics 2000,85(8):
58．邵元智，物理学报，纳米Gd二元合金的磁热效应，中山大学学报(自然科学版)，1996，45(10)：49-53．
59．邵元智．纳米磁性体系的Monte Carlo模拟，中山大学学报，2000(7)：56-58．
60．杨玲，张喜燕，磁致冷材料的发展及研究现状，材料导报，2000(14)：35．
61. A.M.Tishin, Magnetic phase and the magnetothermal properties of Gadolinium, Phys. Rev.B 1998(57)6:3478-3489
62. M.Griffel,R.E.Skochdopole,the heat capacity of Gadolinium from 15 to 355K, Phys. Rev. B, 1954,15(93):657-668.
63. G.Glorieus,J Thoen, G. Bednarz, M. A. White, and D.J.W. Geldart. Plays. Rev. B 52,12770(1995)
64. S. Yu. Dan'kov, A.M. Tishin, V.K. Pecharsky, and K.A. Gschneider, Jr., Rev. Sci. Instrum.68,2432(1997).
65. B.R.Gropal,noncontact thermoacoustic method to measure the magnetocaloric effect, Rev.Sci.Instrum,v(66) 1995:231-235.
66. Gschneidner K A, Pecharsky A O, Production of the giant magnetocaloric effect magnetic refrigerant materials, Rare Earths and Actinides Science[R]. Technology and Applications, 2000(Ⅳ):63.
67. Benford S M, Brown G V. J. Appl. Phys., 1981(52): 2110.
68．陈远富，室温磁致冷GdSiGe系合金的磁热效应、磁相变及机制研究，四川大学博士学位论文，2001年5月：26．
69. Wang J L, Zhao R W, etal. J. Appl. Phys., 1994(76): 6740.
70. Yang Yingchang, Pan Qi, etal. J. Appl. Phys., 1992(72): 2989.
71．[苏]B．C．科瓦连科著，李云盛等译．金相显示剂手册，国防工业出版社，1983：120
72. Roman W. A., J. Less-common Metals, 1966,V.10, No.2, P150.
73. Zimm C., Stemberg A., etal. to be presented at Appliance Manufacturer Conference & Expo., Oct 12-14,1998.
74．桑丹．那日，钆在室温附近的磁热效应，内蒙古大学学报，20003(4)：361-365。
75. S. Meyers, L.S. Chumbley, etc, Determination of phases in as prepared Gd_5(Si_xGe_(1-x))_4,Scipta Materialia 47(2002)509-514
76. Pecharsky V K, Gschneidner k A Jr. Journal of Alloys and Compounds 260(1997)98-106.
77．李卓棠，吴佩放等．巨磁热效应材料Gd_5(SixGe_(1x))_4三元合金的制备及晶体结构，上海大学学报(自然科学版)，2000，6：35-39．