摘要
磁性纳米材料是集磁性材料与纳米材料于一体的功能材料,同时具有磁性材料的磁学性能和纳米材料特殊的物理化学性质,因此磁性纳米材料具有特殊的磁学性能,比如高矫顽力、超顺磁性、低的居里温度以及单磁畴等性质。近些年来,磁性纳米材料已成为研究热点。尖晶石型纳米铁氧体是一类重要的磁性纳米材料,具有很好的电磁性质,己广泛用于生物医学、磁储存材料、催化剂等领域。
本文用溶胶凝胶法制备La3+掺杂Fe304纳米颗粒和CoFe2O4纳米颗粒。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和综合物性测量系统(PPMS)对制备好的样品的结构组成及物相、形貌尺寸和磁学性能进行了研究,分析讨论了制备过程中的参数对样品的影响,为下一步的工作提供实验依据。
通过对研究分析得出：
(1)La3+掺杂Fe304纳米颗粒的制备：自燃烧溶胶凝胶法缩短了样品的制备周期；研究了制备条件对La3+掺杂Fe304纳米颗粒的形貌的影响,得出用自燃烧溶胶凝胶制备的最佳参数为80℃恒温水浴5h、800℃焙烧5h等。
(2) CoFe2O4纳米颗粒的制备：分别用PEG和PVA作为分散剂、凝胶剂制备了颗粒大小均匀的CoFe2O4纳米颗粒；用PEG和PVA制备的纳米颗粒的尺寸分别为20～40nm和～100nm；用PEG制备的CoFe2O4纳米颗粒的剩磁比和饱和磁化强度分别为0.42和143.11emu/g,分析其原因主要是C02+在A位和B位的重新分布；用不同量的PEG时,比较得出：PEG的最佳用量为4g。
Magnetic nanomaterials are function materials which are concentration of magnetic materials and nanomaterials, having both magnetic properties of magnetic materials and special chemical and physical properties of nanomaterials. So, magnetic nanomaterials own special magnetic properties,such as high coercive force,superparamagnetism,low Curie temperature,single magnetic domain and so on. Therefore magnetic nanomaterials have become a hot area of research in recent years. Spinel type ferrite have been used in wide areas such as biomedicine,magnetic storage materials,catalytic agent and so on for their good electromagnetic properties and it is a kind of important magnetic nanomaterials.
In this paper,the Fe3O4nanoparticles doped La3+and CoFe2O4nanoparticles have been prepared by sol-gel method respectively The structure and phase、the size and the shape、the magnetic properties of the nanoparticals prepared were analysised and studied by X-ray diffraction(XRD)、Scanning electron microscope(SEM)、 Physical property measurement system(PPMS),respectively. And parameters which influence chemical and physical properties of samples have been studied in order to find the experimental basis for the next work.
The following results are obtained through the study and analyzing:
(1) The preparation of the FesO4nanoparticles doped La3+:the prepared cycle of the Fe3O4nanoparticles doped La3+is shortened highly when using spontaneous combustion sol-gel method; the morphology of the nanoparticles is the best which are prepared thongh water bathing5h at80℃,calcinating5h at800℃。
(2) The preparation of the CoFe2O4nanoparticles:CoFe2O4nanoparticles whose size is uniform have been synthtized though sol-gel method using polyving akohol(PVA) and polyethylene glycol(PEG) as dispersants and gelatas; And the size of nanoparticles prepared using PEG and PVA as dispersants and gelatas is20～40nm and～100nm respectively; the remanence ratio and the saturation magnetism of the nanoparticals using PEG is0.42and143.11emu/g respectively,it is mostly because that Co2+cations have been redistributed in A site and B site; and when the amount of PEG is different,the morphology and the magnetic properties is different,the morphology and the magnetic properties is the best when the amount of PEG is4g.
引文
[1]陈艾.走进信息材料的微观世界[M].成都：电子科技大学出版社,2007,73～74
[2]白春礼.纳米科技现在与未来[M].成都：四川教育出版社,2001,14～15
[3]戴兢淘.钴基纳米粒子的制备、表征及磁性质[D].[博士学位论文].苏州：苏州大学,2007
[4]姚嫦娲.热分解法制备纳米材料[D].[硕士学位论文].杭州：浙江大学,2007
[5]赵丽君.掺杂稀土尖晶石型铁氧体纳米晶的结构和磁性能的研究[D].[博士学位论文].长春：吉林大学,2006
[6]R Kubo. Electronic Properties of Metallic Fine Particles [J]. Journal of the Physics Society Japan,1962,17:975-986
[7]R Birringer, H Gleiter and H P Klein, et al. Nanocrystalline materials an approach to a novel solid structure with gas-like disorder? [J]. Physics Letters A,1984,102A(8):365-369
[8]丁浩.纳米抗菌技术[M].北京：化学工业出版社,2008,2-9
[9]高志贤.纳米生物医学[M].北京：化学工业出版社,2007,9-18.
[10]张立德.纳米材料研究的新进展及在21世纪的战略地位[J].中国粉体术,2000,6(1)：1-5
[11]Y B Li, Y Bando and D Golberg, et al. Ga-filled Single-crystalline MgO Nanotube: Wide-temperature Range Nanothermometer [J]. Applied Physical Letters,2003, 83:999-1001
[12]K illiams, P Veenhuizen and R Eritja, et al. Nanotechnology:Carbon nanotubes With DNA recognition [J]. Nature,2002,415:599-600
[13]邓建国.粉体材料[M].成都：电子科技大学出版社,2007：174～176
[14]W P Halperin. Quantum Size Effects in Metal Particles [J]. Reviews of Modern Physics,1986,58:533-606
[15]K J Klabundc, J Stark and O Koper, et al. Nanoerystals as Stoichimetric Reagents with Unique Surface Chemistry [J]. Journal of Physical Chemistry,1996,100:12142-12153
[16]Y Kayanuma. Quantum-size Effects of Interacting Electrons and Holes in Semiconductor Microcrystals with Spherical Shape [J]. Physical Review B,1988,38:9797-9805
[17]A Henglein. Small-Particle Research:Physicochemical Properties of Extremely Small Colloidal Metal and Semiconductor Particles [J]. Chemical Reviews, 1989,89:1861-1873
[18]R Rossetti, J L Ellison and J M Gibson, et al. Size Effects in the Excited Electronic States of Small Colloidal CdS Crystallites [J]. Journal of Chemistry Physical,1984,80:4464-4469
[19]P Ball and L Garwin. Science at the Atomic Scale [J]. Nature,1992,355:761-766
[20]A I Ekimov, A L Efros and A A Onnshchenko. Quantum Size Effect in Semiconductor Microcrystals[J]. Solid State Communications,1985,56:921-924
[21]L E Brus. Electron-electron and Electron-hole Interactions in Small Semiconductor Crystallites:The Size Sependence of the Low Excited Electronic State [J]. Journal of Physical Chemistry,1985,88:4403-4409
[22]L E Brus. Electronic Wave Functions in Semiconductor Clusters:Experiment and Theory [J]. Journal of Physical Chemistry,1986,90:2555-2560
[23]H Tang, G Y Xu and L Q Weng, et al. Luminescence and Photophysical Properties of Colloidal ZnS Nanoparitcles [J]. Acta Meterrialia,2004,52:1489-1494
[24]Henglein A. Non-metallic silver clusters in aqueous solution:stabilization and chemical reactions [J]. Chemical Physics Letters,1989,154:473-476
[25]Chestnoy N, Harris T D, Bras L E, et al. Luminescence and photophysics of CdS semiconductor clusters:the nature of the emitting electronic state [J]. Journal of Physical Chemistry,1986,90:3393～3402
[26]Wang Y, Herron N. Nanometer-sized semiconductor clusters:materials synthesis,quantum size effects,and photophysical properties [J]. Journal of Physical Chemistry,1991,95: 525～532
[27]张立德,牟季美.纳米材料学[M].沈阳：辽宁科技技术出版社,1994
[28]R Leon, P M Petroff and D Leonard, et al. Spatially Resolved Visible Luminescence of Self-Assembled Semiconductor Quantum Dots [J]. Science,1995,267:1966～1968
[29]王建伟.掺杂的Fe304纳米晶制备及其性能研究[D].[硕士学位论文].济南：济南大学,2010
[30]A J Legget, S Chakxavarty and A T Dorsey, et al. Dynamics of the Dissipative Two-system [J]. Reviews of Modern Physics,1987,59:1～85
[31]严密,彭晓领.磁学基础与磁性材料[M].杭州：浙江大学出版社,2006：113～176
[32]龙毅,张正义,等.新功能磁性材料及其应用[M].北京：北京机械工业出版社,1997：11～14
[33]过璧君.磁记录材料及应用[M].成都：电子科技大学出版社,1991：8-11
[34]张玲.四氧化三铁纳米颗粒及其复合物的制备和研究[D].[博士学位论文].上海交通大学,2007
[35]陈兴,邓兆祥,李宇鹅,等.水热法制备超顺磁性铁氧体纳米微粒[J].无机化学学报,2002,18(5)：460～464
[36]Sorensen C M. In nanoscale materials in chemistry [J]. New York:Jo Wiley and Sons,2001:1694.
[37]单云刚.水热法制备CoFe2O4纳米颗粒及表征[D].[硕士学位论文].武汉：武汉理工大学,2009
[38]邓真娟.不同粒径掺Dy3+铁氧体纳米磁粒子的制备与表征[D].[硕士学位论文].淮南：安徽理工大学,2011
[39]桂维玲.磁共振强磁场中保持稳定悬浮及超顺磁性的微粒粒度研究[J].科学技术与工程,2008,8(8)：2166～2168
[40]姜寿亭,李卫.凝聚态磁性物理[M].北京：科学出版社,2005
[41]del Real R P, Prados C, Pulido E, et al. Dependence of magnetic losses in Fe73.5Cu1Nb3Sii6.5B6 on annraling temperature [J]. Journal of Applied Physics,1993, 73:6618～6619
[42]Wakabayashi T, Serita Y. Magnetic recording in Advanced Photo System cameras [J]. IEEE Transactions on magnetic,1997,33:2659～2664
[43]Ouchi K. Recent advancements in perpendicular magnetic recording [J]. IEEE Transactions on magnetic,2001,37:1217～1222
[44]New R M H, Pease R F W, White R L, et al. Magnetic force microscopy of single-crystal iron particals with uniaxial surface anisotropy [J]. Journal of Applied Physics,1996,79: 5851～5853
[45]White RM. Magnetic recording-Pushing back the superparamagnetic barrier [J]. Journal of magnetism and magnetic materials,2001,226:2042～2045
[46]Cotae C, Baltag O, Olaru R, et al. The study of a magnetic fluid-based sensor [J]. Journal of Magnetism and Magnetic Fluids,1999,201:394～397
[47]Gazeau F, Shilov V, Bacri J C, et al. Magnetic resonance of nanoparticles in a ferrofluid:evidence of thermfluctuational effects [J]. Journal of Magnetism and Magnetic Materials,1999,202:535～546
[48]Tanaka K, Ito T, Kobayashi T, et al. Heat immunotherapy using magnetic nanoparticles and dendritic cell for Tlymphoma [J]. Journal of Bioscience and Bioengineering,2005,100: 112-115
[49]Hayashi T, Hirono S, Tomita M, et al. Magnetic thin film of cobalt nanocrystals encapsulated in graphite-like carbon [J]. Nature,1996,381:112～774
[50]Moser A, Rettner C T, Best M E, et al. Writing and detecting bits at 100 Gbit/in2 in longitudinal magnetic recording media [J]. IEEE Transanctions on Magnetics,2000,36: 2173-2179
[51]Wood R. The feasibility of magnetic recording at 1 Terabit per square inch [J]. IEEE Transactions on Magnetics,2000,36:36～42
[52]Ouyang J, Xu QF, Chu CW, et al. On the mechanism of conductivity enhancement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film through solvent treatment [J]. Polymer.2004,45:8443～8450
[53]田莳.材料物理性能[M].北京：北京航空航天大学出版社,2001,47
[54]白木,周洁.纳米磁性材料及其应用[J].信息记录材料,200,3(2)：38～39
[55]任欢鱼.磁流体的制备与性质研究[J].中国粉体技术,2003,1：21-23
[56]王煦漫,张彩宁,古宏晨.Fe304磁流体制备及其磁性能研究[J].化工新型材料,2009,37(1)：66～68
[57]苑星海,扬丁红,林穗云,等.稀土镝改性铁氧体磁流体的制备与表征[J].纳米科技,2008,5(5)：31～34
[58]马啸华,马淮凌,魏敏.稀土Dy3+改性铁氧体磁流体磁性粒子的制备及性能测试[J].应用化工,2006,35(6)：425～427
[59]Connolly J, St Pierre TG. Proposed biosensors based on time-dependent properties of magnetic fluids [J]. Journal of Magnetism and Magnetic Materials,2001,225:156-160
[60]Hadgia S, Iusan V, Stanci A. A method for magnetic field determination inside magnetic fluids [J]. Journal of Magnetism and Magnetic Materials,1999,201:404～406
[61]Iusan V, Buioca C D, Hadgia S. Magnetic fluids of low viscosity [J]. Journal of Magnetism and Magnetic Materials,1999,201:38～40
[62]Jing Liu, Flores G A, Rongsheng Sheng. In-vitro investigation of blood embolization in cancer treatment using magnetorheological fluids [J]. Journal of Magnetism and Magnetic Materials,2000,225:209～217
[63]黄文艳,杜丕一,翁文剑,等.溶胶直接自蔓延法制备NiZn铁氧体粉末研究[J].材料科学与工程学报,2005,23(5)：528～532
[64]杨洋,刘顺华.镍锌铁氧体的制备及其吸波性能的研究[J].功能材料,2007,38：3001～3004
[65]Meshram MR, Agrawal NK, Sinha B, et al. Characterization of M-type barium hexagonal ferrite-based wide band microwave absorber [J]. Journal of Magnetism and Magnetic Materials,2004,271:207～214
[66]Shin J Y, Oh J H. The microwave absorbing phenomena of ferrite microwave absorbers [J]. IEEE Transactions on Magnetics,1993,29:3437～3439
[67]何华辉,邓联文.纳米磁陛吸波材料研究新进展[J].功能材料信息,2005,2(2)：8-18
[68]田民波.磁性材料[M].北京：清华大学出版社,2001：319～343
[69]Chalastaras A, Malkinski LM, Jung JS. GMR multilayers on a new embossed surface [J]. IEEE Transactions on Magnetics,2004,40:2257～2259
[70]Theresa M, A Pieter R C. Drug delivery systems:entering the mainstream [J]. Science,2004, 303:1818～1823
[71]Lubbe A S, Alexiouc Bergemannc C. Clinical Application of Magnetic Drug Targeting [J]. Journal of surgical research,2001,95(2):200～206
[72]Alexiou C, Jurgons R, Seliger C, et al. Medical applications of magnetic nanoparticles[J]. Journal of nanoscience and nanotechnology,2006,6(10):2762～2768
[73]王胜林,王强斌,古宏晨,等.磁性微球的生物医学应用研究进展[J].化学世界,2001(7)：384～386
[74]陆伟,蒋新国.脑内靶向给药研究进展[J].中国临床药学杂志,2002,11(6)：384～387
[75]李凤生.磁响应纳米四氧化三铁院聚糖复合微球的制备及特性[J].磁性材料及器件,2002,33(6)：1-4
[76]周永国,杨越冬,郭学民,等.磁性壳聚糖微球的制备、表征及其靶向给药研究[J].应用化学,2002,19(12),1178～1182
[77]Ahmad S N, Akin YShaheen S A. Gd5(Si, Ge)4 and Gd2C compounds Candidates for hyperthermia treatment of cancer [J]. Journal of Applied in Physics,2005,97(10):1～3
[78]王世敏,许祖勋,等.纳米材料制备技术[M].北京：化学工业出版社,2002,7-120
[79]李东风,孟哲,贾振斌.化学共沉淀法制备纳米级软磁铁氧体研究进展[J].应用科技,2003,30(4)：54～56
[80]李茹民,刘致阳,张密林.ZnXFe3-xO4的制备及磁性能研究[J].功能材料,2007,38：1000～1002
[81]高小龙.钡铁氧体磁流体的制备和磁粘效应的研究[J].甘肃联合大学学报,2010,24(5):58～61
[82]Zhang Yi, Wang Kai Ren Zhiyan, et al. Structure and magnetic properties of Zn ferritenanoparticles [J]. Journal of Southeast University,2009,25(3):408～412
[83]Yuan H M, Chen J S, Zhu G S, et al. The first organo-templated cobalt phosphate with a zeolite topology [J]. Inorganic chemistry,2000,39:1476～1479
[84]V Pillai, D O Shah. Synthesis of high-coercivity cobalt ferrite particles using water-in-oil micro-emulsions [J]. Journal of Magnetism and Magnetic Materials,1996,163:243～248
[85]冯光峰,黎汉生.双微乳液法制备CoFe2O4纳米颗粒及其磁性能研究[J].材料导报,2007,21(S1)：36～38
[86]张伟,郭翠静,纪荣进,等.溶胶凝胶自燃烧法一步合成钇正铁氧体纳米晶及其性能[J].南京工业大学学报,2010,32(4)：38～43
[87]岳振星,周济,张洪国,等.柠檬酸盐凝胶的自燃烧与铁氧体纳米粉合成[J].硅酸盐学报,1999,27(4)：466～470
[88]苏言杰,张德,徐建梅,等.柠檬酸盐凝胶自燃烧法合成超细粉体[J].材料导报,2006,20：142～144
[89]赵建设,梁永庆,阎鸿君,等.干凝胶自蔓延燃烧法制备纳米级的MnZn铁氧体[J].材料科学与工程学报,2003,21(1)：68～70
[90]段红珍,李巧玲,蔺向阳,等.溶胶-凝胶自燃烧合成BaNd2Ti5O14的凝胶化及热处理研究[J].无机材料学报,2000,15(5)：879～882
[91]王丽,周庆国,孙建荣,等CoFe2O4铁氧体纳米颗粒的结构与磁性[J].磁性材料及器件,2006,37(1)：23～25
[92]刘媛,刘玉存,王建华,等.溶胶-凝胶法制备的纳米NixZn1-xFe2O4铁氧体[J].磁性材料及器件,2011,42(1)：20～22
[93]王敬平,郝险峰,吕敏峰,等.稀土Dy3+掺杂Fe304的合成及电磁性质[J].中国稀土学报,2006,24(4)：461～464
[94]Li Dan, Teoh Wey Yang, Selomulya Cordelia, et al. Flame-sprayed superparamagnetic bara and silica-coated maghemite nanoparticles:Synthesis,characrization,and protein adsorption-desorption[J]. Chemistry of Materials,2006,18:6403-6413
[95]R Sato Turtelli, M Atif, N Mehmood, et al. Interplay between the cation distribution and production methods in cobalt ferrite [J]. Materials Chemistry and Physics,2012,132: 832-838
[96]Zhanyong Wang, Wenjun Fei, Huichun Qian, et al. Structure and magnetic properties of CoFe2O4 ferrites synthesized by sol-gel and microwave calcinations [J]. Journal of Sol-Gel Science Technology,2012,61:289～295
[97]Ennas G, Falqui A, Marra S, et al. Influence of metal content on size, dispersion, and magnetic properties of iron-cobalt alloy nanoparticles embedded in silica matrix [J]. Chemistry of Materials,2004,16:5659～5663
[98]田国徽,张萍,倪明亮,等.高饱和磁化强度Fe304纳米粒子的制备与表征[J].四川有色金属,2009,4：22～27
[99]颜爱国,刘浩梅,刘聘婷,等.Fe304和Zn2+掺杂型Zn1-xFe2+xO4纳米晶的溶剂热合成和电磁性能[J].高等学校化学学报,2010,3(31)：447-451
[100]唐宏志,徐波,王树林,等.MgFe2O4纳米颗粒制备及其电磁性能研究[J].功能材料,2013,6(44)：776～779
[101]Xue Wang, Chen Guo Hu, Yi Yi, et al. Al-doped Fe3O4 Nanoparticles and Their Magnetic Properties [J]. Journal of Superconductivity and Novel Magnetism,2010,23:909～911
[102]V L Pool, M T Klem, C L Chorney, et al. Enhanced magnetism of Fe3O4 nanoparticles with Ga doping [J]. Journal of Applied Physics,2011,109:07B529-1-07B529-3
[103]Radheshyam Rai, Kavita Verma, Seema Sharma, et al. Study of structural and ferromagnetic properties of pure and Cd doped copper ferrite [J]. Journal of Physics and Chemistry of Solids,2011,72:862～868
[104]JIMEI MA.YING WANG, JIANSHE NIU, et al. Synthesis and Characterization of La-Doped Fe3O4-Polyaniline Magnetic Response Nanocomposites [J]. Journal of Macromolecular Science,2006,45:533-540
[105]Zhanyong Wang, Wenjun Fei, Huichun Qian, et al. Structure and magnetic properties of CoFe2O4 ferrites synthesized by sol-gel and microwave calcination [J]. Journal of Sol-Gel Science Technol,2012,61:289～295
[106]C J Briuker and G W Scherer. Sol-Gel Science [J]. The Physics and Chemistry of S-G Processing, A cademic Press, INC,1990
[107]W Geffcken and E Berger. Uber das Zeitgesetz der Auslaugung von Glasern[J]. Naturwissenschafte,1935,23:817～818
[108]H Dislich. Angecoandt Chemie,1971,10(6):363～370
[109]B E Yoldas. Alumina gels that form porous transparent Al2O3 [J]. Journal of Materials Science,1975,10:1856～1860
[110]B E Yoldas. Preparation of glasses and ceramics from metal-organic compounds [J]. Journal of Materials Science,1977,12:1203～1208
[111]袁雪.Co-Zn铁氧体纳米颗粒的制备及磁性研究[D].[硕士学位论文].南京：东南大学,2008
[112]任志艳.纳米铁氧体的磁性研究[D].[硕士学位论文].南京：东南大学,2009
[113]李翠环.尖晶石锌铁氧体纳米颗粒的制备及性能研究[D].[硕士学位论文].兰州：兰州理工大学,2011
[114]李荫远,李国栋.铁氧体物理学[M].北京：科学出版社,26
[115]曹世贺,王军CoFe2O4纳米颗粒的穆斯堡尔谱及磁性能分析[J].人工晶体学报,2011,40(4)：1000～1005
[116]杨贵进,李玲CoFe2O4纳米颗粒的共沉淀法制备及其磁性能[J].电子元件与材料,2008,27(11)：25～27
[117]訾振发,刘强春,戴建明,等.CoFe2O4纳米颗粒磁性能的异常行为[J].中国科学,2012,42(3)：242～248
[118]V Sepelaka, D Baabe, D. Mienert, et al. Evolution of structure and magnetic properties with annealing temperature in nanoscale high-energy-milled nickel ferrite [J]. Journal of Magnetism and Magnetic Materials,2003,257:377～386.