稀土离子掺杂稀土氧化物和稀土氟化物纳米带的制备与表征
|
摘要
稀土发光材料广泛用于照明、显示、检测三大领域,稀土氧化物和稀土氟化物是优良的发光基质材料。稀土纳米发光材料的制备、组成、性质及应用研究是目前稀土发光材料研究领域的热点之一。静电纺丝技术是制备纳米带的良好方法,已经引起了人们的高度重视。因此,利用静电纺丝技术制备稀土离子掺杂的稀土氧化物、氟化物纳米带及其性质研究,将是一个重要而又新颖的研究课题。
本文中以PVP(Mr=90000)为模板、DMF为溶剂和稀土硝酸盐为源料,采用静电纺丝技术,制备了PVP/稀土硝酸盐复合纳米带,讨论了实验参数对复合纳米带形成的影响,获得了制备PVP/稀土硝酸盐复合纳米带的最佳条件。将PVP/稀土硝酸盐复合纳米带进行焙烧,获得了Y_2O_3、Y_2O_3:Eu~(3+)、Y_2O_3:Tb~(3+)、Gd_2O_3、Gd_2O_3:Eu~(3+)、Gd_2O_3:Tb~(3+)纳米带。首次将静电纺丝技术和氟化氢铵氟化法结合,利用气固相反应,将所制备的稀土离子掺杂的稀土氧化物纳米带进行氟化,成功地制备了YF_3:Eu~(3+)、YF_3:Tb~(3+)、GdF_3:Eu~(3+)、GdF_3:Tb~(3+)纳米带。采用XRD、FESEM、TEM、FTIR、荧光光谱等分析技术对样品进行了系统地表征。结果表明,所制备的稀土离子掺杂的稀土氧化物、氟化物纳米带均具有良好的发光性质,获得了一些有意义的结果,为稀土纳米发光材料的进一步深入研究奠定了一定基础。
Rare earth luminescence materials are widely used in the fields of lighting, display and detection. Rare earth oxides and rare earth fluorides are excellent matrixes for luminescent materials. Presently, research on preparation, composition, properties and applications of rare earth luminescent nanomaterials is one of the popular subjects in the field of rare earth luminescent materials. Electrospinning technology is a good way to prepare nanoribbons and has received much attention from scientists. Therefore, it will be an important and novel research subject to prepare rare earth ions-doped rare earth oxides and fluorides nanoribbons via electrospinning and to investigate their characteristics.
In this dissertation, PVP/rare earth nitrates composite nanoribbons were prepared by electrospinning technique using PVP(Mr=90000) as template DMF as solvent and rare earth nitrates as starting materilal. The influences of experimental parameters on the formation of PVP/rare-earth nitrates nanoribbons were systematically discussed, and the optimum preparative conditions were acquired. Y_2O_3, Y_2O_3:Eu~(3+), Y_2O_3:Tb~(3+), Gd_2O_3, Gd_2O_3:Eu~(3+), Gd_2O_3:Tb~(3+) nanoribbons were obtained by calcination of the relevant PVP/rare-earth nitrates nanoribbons. For the first time, rare earth ions-doped rare earth oxides nanoribbons were fluorinated by way of gas-solid phase reaction using the combination of electrospinning and ammonium hydrogen fluoride fluorination method, and YF_3:Eu~(3+), YF_3:Tb~(3+), GdF_3:Eu~(3+), GdF_3:Tb~(3+) nanoribbons were successfully fabricated. The samples were systematically characterized by XRD, FESEM, TEM, FTIR, PL, etc. The results show that both the rare earth ions-doped rare earth oxides and fluorides nanoribbons possess excellent luminescent properties. Some significant results were obtained, and laid solid foundations for the future study of rare earth luminescent nanomaterials.
本文中以PVP(Mr=90000)为模板、DMF为溶剂和稀土硝酸盐为源料,采用静电纺丝技术,制备了PVP/稀土硝酸盐复合纳米带,讨论了实验参数对复合纳米带形成的影响,获得了制备PVP/稀土硝酸盐复合纳米带的最佳条件。将PVP/稀土硝酸盐复合纳米带进行焙烧,获得了Y_2O_3、Y_2O_3:Eu~(3+)、Y_2O_3:Tb~(3+)、Gd_2O_3、Gd_2O_3:Eu~(3+)、Gd_2O_3:Tb~(3+)纳米带。首次将静电纺丝技术和氟化氢铵氟化法结合,利用气固相反应,将所制备的稀土离子掺杂的稀土氧化物纳米带进行氟化,成功地制备了YF_3:Eu~(3+)、YF_3:Tb~(3+)、GdF_3:Eu~(3+)、GdF_3:Tb~(3+)纳米带。采用XRD、FESEM、TEM、FTIR、荧光光谱等分析技术对样品进行了系统地表征。结果表明,所制备的稀土离子掺杂的稀土氧化物、氟化物纳米带均具有良好的发光性质,获得了一些有意义的结果,为稀土纳米发光材料的进一步深入研究奠定了一定基础。
Rare earth luminescence materials are widely used in the fields of lighting, display and detection. Rare earth oxides and rare earth fluorides are excellent matrixes for luminescent materials. Presently, research on preparation, composition, properties and applications of rare earth luminescent nanomaterials is one of the popular subjects in the field of rare earth luminescent materials. Electrospinning technology is a good way to prepare nanoribbons and has received much attention from scientists. Therefore, it will be an important and novel research subject to prepare rare earth ions-doped rare earth oxides and fluorides nanoribbons via electrospinning and to investigate their characteristics.
In this dissertation, PVP/rare earth nitrates composite nanoribbons were prepared by electrospinning technique using PVP(Mr=90000) as template DMF as solvent and rare earth nitrates as starting materilal. The influences of experimental parameters on the formation of PVP/rare-earth nitrates nanoribbons were systematically discussed, and the optimum preparative conditions were acquired. Y_2O_3, Y_2O_3:Eu~(3+), Y_2O_3:Tb~(3+), Gd_2O_3, Gd_2O_3:Eu~(3+), Gd_2O_3:Tb~(3+) nanoribbons were obtained by calcination of the relevant PVP/rare-earth nitrates nanoribbons. For the first time, rare earth ions-doped rare earth oxides nanoribbons were fluorinated by way of gas-solid phase reaction using the combination of electrospinning and ammonium hydrogen fluoride fluorination method, and YF_3:Eu~(3+), YF_3:Tb~(3+), GdF_3:Eu~(3+), GdF_3:Tb~(3+) nanoribbons were successfully fabricated. The samples were systematically characterized by XRD, FESEM, TEM, FTIR, PL, etc. The results show that both the rare earth ions-doped rare earth oxides and fluorides nanoribbons possess excellent luminescent properties. Some significant results were obtained, and laid solid foundations for the future study of rare earth luminescent nanomaterials.
引文
[1]张立德,牟季美.纳米材料和纳米结构.北京:科学出版社,2001:27
[2] K.Sattler, J.M(?)hlbach, E.Recknagel. Generation of Metal Clusters Containing from 2 to 500 Atoms. Phys.Rev.Lett. 1980,45(10):821～824
[3]王仲山,朱庆纲,谈荣生,等.稀土元素在国民经济中的应用及其前景.科技情报开发与经济.1999.5:28～30
[4]薛茂权,熊党生,闫杰.稀土润滑材料的摩擦学研究.稀有金属.2004,28(1):248～251
[5]李建宇.稀土发光材料及其应用.北京:化学工业出版社,2003
[6] Junying Zhang, Zilong Tang, Zhongtai Zhang, et al. Synthesis of nanometer Y_2O_3:Eu phosphor and its luminescence property[J]. Materials Science and Engineering A. 2002,334(1-2):246～249
[7] J.Eid, A.C.Pierre, G.Baret. Preparation and characterization of transparent Eu doped Y_2O_3 aerogel monoliths, for application in luminescence [J]. Journal of Non-Crystalline Solids, 2005,351(3):218～227
[8] S.Yin, M.Shinozaki, T.Sato. Synthesis and characterization of wire-like and near-spherical Eu_2O_3-doped Y_2O_3 phosphors by solvothermal reaction [J]. Journal of Luminescence, 2007,126(2):427～433
[9] Sooyeon Seo, Heesun Yang, Paul H.Holloway. Controlled shape growth of Eu- or Tb-doped luminescent Gd_2O_3 colloidal nanocrystals [J]. Journal of Colloid and Interface Science. 2009,331(1):236～242
[10] Meigui Ou, Brice Mutelet, Matteo Martini, et al. Optimization of the synthesis of nanostructured Tb~(3+)-doped Gd_2O_3 by in-situ luminescence following up [J]. Journal of Colloid and Interface Science. 2009,333(2):684～689
[11] Guixia Liu, Guangyan Hong. Xiangting Dong, et al. Preparation and characterization of Gd_2O_3:Eu~(3+) luminescence nanotubes [J]. Journal of Alloys and Compounds. 2008,466(1-2):512～516
[12] Zhenhe Xu, Jun Yang, Zhiyao Hou, et al. Hydrothermal synthesis and luminescent properties of Y_2O_3:Tb~(3+) and Gd_2O_3: Tb~(3+) microrods [J]. Materials Research Bulletin. 2009, 44(9): 1850～1857
[13] H.Wang, J.Yang, C.M.Zhang, et al. Synthesis and characterization of monodisperse spherical SiO_2@RE_2O_3 (RE=rare-earth elements)and SiO_2@Gd_2O_3:Ln~(3+) (Ln=Eu,Tb,Dy,Sm,Er,Ho) particles with core-shell structure. Journal of Solid State Chemistry. 2009,182(10):2716～2724
[14] A.de J.Morales Ramirez, A.Garcia Murillo, F.de J.Carrillo Romoa, et al. Properties of Gd_2O_3:Eu~(3+),Tb~(3+) nanopowders obtained by sol-gel process [J]. Materials Research Bulletin. 2010, 45(1):40～45
[15] S.Tanabe. Control of 4f-electronic Transition Probability in Optical amplifiers for WDM Telecommunication and Development of Broad-Band Material [J]. Journal of Rare Earths. 2002, 40:148～149
[16]颜豪威.NH_4HF_2氟化法制备稀土氟化物的化学原理及工艺探讨.江西冶金.1995,15(6):31～32
[17]高俊梅,谢萍,石红静,等.氟化氢铵氟化法制备稀土氟化物工艺研究.稀土.2003,24(6):37～39
[18]姜银举.张小琴.石红静.等.氟化氢铵与稀土氧化物氟化反应机理研究.稀土,2005.26(4):39～41
[19]郝占忠.张建良.王斌.RE_2O_3-NH_4HF_2系合成稀土氟化物的反应规律.北京科技大学学报.2007,29(3):272～277
[20]刘文生,云(?)厚,王利刚.静态干法氟化法制备稀土氟化物工艺研究.稀土.2005,26(6):20～22
[21]王亚军,刘前.索全伶,等.稀土氟化物的沉淀方法及组成研究.稀土.2000,21(1):14～18
[22]张茂峰,孟建新,刘应亮.等.LaF_3:Eu~(3+)纳米粒子的水热法制备及发光性质研究.中国稀土学报.2005.23(5):564～567
[23]肖思国,阳效良,丁建文.Er~(3+),Er~(3+)/Yb~(3+)掺杂氟化镧超微材料的光谱特性与上转换发光.物理学报,2009,58(6):3812～3820
[24]陈良冬.郑小睿,丁耘.等.铈铽共惨杂氟化镧纳米晶体的快速合成和荧光特性.无机化学学报.2009.25(2):285～289
[25]德格吉呼.稀土掺杂低维纳米材料的合成及其发光特性研究:[博士学位论文].长春:中国科学院长春光学精密机械研究所.2006
[26]张志峰,李红飞,国富强,等.溶剂萃取法制备的纳米CeF_3紫外吸收性能研究.中国稀土学报.2008,26(4):432～436
[27]涂华民.张秀凤.张迈生.轻稀土氟化物的微波固相快速合成法.稀有金属.2004.28(5):875～879
[28]武安华.徐军.陈红兵,等.氟化物激光晶体及其在固体激光器中的应用.激光与红外.2009,39(1):8～13
[29] H.Y.Wang. Y.Yang. Y Wang, et al. Luminescent Properties of Rare-Earth Oxyfluoride Nanofibers Prepared via Electrospinning [J]. Nanoscience and Nanotechnology. 2009,9(2): 1522～1525
[30] Ya-Ping Du. Ya-Wen Zhang, Ling-Dong Sun, et al. Luminescent Monodisperse Nanocrystals of Lanthanide oxylluoridcs Synthesized from Trilliioroacetate Precursors in High-Boiling Solvents[J]. Phys.Chem.C. 2008. 112(2): 405～415
[31]孙家跃.杨志萍,杜海燕.共沉淀法制备NaYF_4:Tm~(3+),Yb~(3+)的上转换发光.发光学报.2009,30(2):195～200
[32]张国莲.陈廷.纳米纤维的研究现状及其应用.纺织导报.2005(1):12～18
[33]王永芝.杨清彪.李耀先.纳米纤维的性质及应用进展.化工新型材料.2004,32(12):9～12
[34] D Li. Y Xia. Electrospinning of Nanofibers:Reinventing the Wheel. Adv.Mater. 2004, 16(14):1151～1170
[35] Yilgor Demir M.M., Yilgor I., Yilgor E., et al. Electrospinning of polyurethane fibers. Polymer. 2002,43(11):3303-3309
[36] Norris I.D.. Shaker M.M., Ko F.K., MacDiarmid A.G. Electrostatic fabrication of ultrafine conducting fibers: polyaniline/polyethylene oxide blends. Synthetic Metals. 2000,114(2):109～144
[37] Baumgarten P.K. Electrostatic spinning of acrylic microfibers. J.Colloid Interf.Sci. 1971. 36(1):71～79
[38]王新威.胡祖明.潘婉莲.等.电纺丝制备高聚物纳米纤维[D].东华大学学报(自然科学版).2005.31(1):115～119
[39]吴大诚.杜仲良.高绪珊.纳米纤维.北京:化学工业出版社,2003:46
[40] Rayleigh L., On the Equilibrium of Liquid Conducting Masses Charged with Electricity. Phil.Mag. 1882, 14:184～186
[41] Zeleny J. The Electrical Discharge from Liquid Points, and a Hydrostatic Method of Measuring the Electric Intensity at Their Surfaces.Phys.Rev. 1914, 3(2):69～91
[42] Formhals A. Process and apparatus for preparing artificial threads[p]. U.S.Patent No. 1975.504,1934
[43] Taylor G.I. Disintegration of Water Drops in an Electric field, Proc.Roy.Soc.London A, 1964,280:383～397
[44] Simons H.L.,U.S.Patent No.3,280,299,1966
[45] Baumgarten P.K. Electrostatic spinning of acrylic microfibers. J.Colloid Interface Sci. 1971, 36(1):71 ～ 79
[46] Larrando L.and Manley R.ST.J.Electrostatic fiber spinning from polymer melts.Ⅱ. Examination of the flow field in an electrically driven jet[J]. Polym.Sci..Part B:Polym.Phys. 1981, 19(6):921～932
[47] Larrando L.and Manley R.ST.J. Electrostatic fiber spinning from polymer melts.Ⅰ.Experimental observations on fiber formation and properties. J.Polym.Sci..Part B:Polym.Phys. 1981. 19(6):909～920
[48] Larrando L.and Manley R.ST.J. Electrostatic fiber spinning from polymer melts.Ⅲ.Electrostatic deformation of a pendant drop of polymer melt[J]. Polym.Sci.,Part B:Polym.Phys. I981,19(6):933～940
[49] Reneker D,H.and Chun I., Nanometre diameter fibres of polymer,produced by electrospinning.Nanotechnology. 1996.7(3):216～223
[50] Fong H.and Reneker D.H. Elastomeric nanofibers of styrene-butadiene-styrene triblock copolymer. J. Polym.Sci.. PartB:Polym. Phys. 1999,37(24).3488～3493
[51] Chen Z.H..Foster M.D.W S Zhou.et al. Structure of poly(ferrocenyldimethylsilane) in electrospun nanofibers.Macromolecules. 2001,34(18):6156～6158
[52] Fang X.and Reneker D.H. DNA fibers by electrospinning. J.Macromol.Sci.Phys.B.1997,36(2):169～173
[53] Srinivasan G.and Reneker D.H. Structure and morphology of small diameter electrospun aramid fibers. Polym.Intema-tional. 1995,36(2): 195～201
[54] Kim J.S.and Reneker D.H. Polybenzimidazole nanofiber produced by electrospinning, Polym.Eng.Sci. 1999, 39(5):849～854
[55] Huang L., Nagapudi K., Apkarian R.P. et al. Engineered collagen-PEO nanofibers and fabrics. J Biomater Sci. Polym Ed. 2001,12(9):979～993
[56] L.Buttafoco. N.G.Kolkman. P.Engbers-Buijtenhuijs, et al. Electrospinning of collagen and elastin for tissue engineering applications. Biomaterials. 2006. 27(5):724～734
[57] Jia Xu. Jinhui Zhang. Weiquan Gao. et al. Preparation of chitosan/PLA blend micro/nanofibers by electrospinning. Materials Letters. 2009, 63(8):658～660
[58]王永芝.杨清彪.杜建时,等.电纺丝技术-一种高效低耗的纳米纤维制备方法[J].化工新型材料.2005.33(6):12～14
[59] F.Ko, Y.Gogotsi. A.Ali. et al. Electrospinning of Continuous Carbon Nanotube-Filled Nanofiber Yarns[J].Adv.Mater. 2003,15(14): 1161～1165
[60] Xinhua.Zong, Kwangsok.Kim. Dufei.Fang,et al. Structure and process relationship of electrospun bioabsorbable nanofiber membranes. Polymer. 2002. 43(16):4403～4412
[61] S.A.Theron. A.L.Yarin, E.Zussman. et al. Multiple jets in electrospinning:experiment and modeling. Polymer.2005,46(9):2889～2899
[62] D.Li. Y.Wang. Y.Xia. Electrospinning of Polymeric and Ceramic Nanofibers as Uniaxially Aligned Arrays[J].Nano Lett. 2003.3:1167
[63] Choo-Won Kim. Dae-Sik Kim. Scung-Yeon Kang, et al. Structural studies of electrospun cellulose nanofibers[J]. Polymer. 2006. 47(14):5097～5107
[64] Keun-Hyung Lee. Steven Givens. D.Bruce Chase, et al. Electrostatic polymer processing of isotactic poly (4-methyl-1-pentene) fibrous membrane [J]. Polymer. 2006, 47(23):8013～8018
[65] Hohman M M. Shin M, Rutledge G. et al. Electrospinning and electrically forced jets.Ⅰ .Stability theory. Physics of Fluids. 2001,13(8):2201～2220
[66] P.F. Jacobs. Rapid Prototyping and Manufacturing, Fundamentals of Stereolithography. Society of Manufacturing Engineers. Dearborn, MI. 1992:263～277
[67] Shin Y M. Hohman M M, Brenner M P, et al. Experimental characterization of electrospinning:the electrically forced jet and instabilities[J]. Polymer. 2001. 42(25):9955～9967
[68] Chun I. Reneker D H. Fong H.et al. Carbon nanofibers from polyacrylonilrilc and mesophase pitch.J. Adv. Mater. 1999.31(1):36～41
[69] Fong H, Chun I, Reneker D H. Beaded nanofibers formed during electrospinning. Ploymer, 1999, 40(16):4585～4592
[70] J. M. Deitzel, J. Kleinmeyer. D. Harris. et al. The effect of Processing variables on the morphology of electrospun nano-fibers and textiles. Polymer. 2001. 42(1):261～272
[71] Li Lei. Bellan Leon M. Craighead Harold G, et al. Formation and Properties of nylo-6 and nylon-6/montmorillonite composite nanofibers. Polymer. 2006. 47(17):6208～6217
[72] Tao Jing,Shivkumar Satya. Molecular weight dependent structural regimes during the electrospinning of PVA[J]. Mater Lett. 2007, 61(11-12):2325～2328
[73]吕砚山.常见电工电子技术手册[M].北京:化学工业出版社,1995,34～60
[74] Ding Bin. Eiji Kinura, Tomokazu Sato, et al. Fabrication of blend biodegradable nanofibrousnonwoven mats via multi-jet electrospinning. Polymer. 2004,45(6):1895～1902
[75]何创龙,黄争鸣,韩晓建,等.同轴射流技术制备纳米复合材料研究进展.复合材料学报,2005,22(6):1～8
[76] Katta P. Alessandro M, Ramsier R D, et al. Continuous Electrospinning of Aligned Polymer Nanofibers onto a Wire Drum Collector. Nano Lett. 2004. 4(11):2215～2218
[77] Li D. Wang Y. Xia Y. Electrospinning of Polymeric and Ceramic Nanofibers as Uniaxially Aligned Arrays. Nano Lett. 2003,3(8): 1167～1171
[78]邹科,龙云泽,吴佑实.静电纺丝制备纳米纤维的进展及应用.合成纤维工业.2007,30(3):54～57
[79] Goki Eda, James Liu, Satya Shivkumar. Flight path of electrospun polystyrene solutions:Effects of molecular weight and concentration. Materials Letters. 2007, 61(7):1451 ～1455
[80] Yang Q.B.. Li D.M., Hong Y.L.. et al. Preparation and characterization of a PAN nanofibre containing Ag nanoparticles via electrospinning. Synth. Met. 2003, 137(1-3):973～974
[81] Li Dan, Xia Younan. Electrospinning Nanofibers as Uniaxially Aligned Arrays and Layer-by-Layer Stacked Films Advanced Malerials.2004,16(4):361-366
[82] H.Dai. J.Gong. H.kim, D.Lee. A novel method for preparing ultra-fine almina-borate oxide fibres via an electrosping technique. Nanotechnology. 2002. 13(5):674～677
[83] Qiaozhen Yu. Mang Wang, Hongzheng Chen. Fabrication of ordered TiO_2 nanoribbon arrays by electrospinning.Mater Lett. 2010. 64(3):428～430
[84]伊长青.聚乙烯基吡咯烷酮(PVP)生产工艺研究:[工程硕士学位论文].中国石油大学,2007,10
[85]李从举,翟国钧,付中玉,等.聚乙烯吡咯烷酮纳米纤维电纺制备及形貌控制研究.纳米材料与技术应用进展-第四届全国纳米材料会议论文集.2005.12:455～459
[86] K..T.Shalumon. N.S.Binulal, N.Sclvamurugan, et al. Electrospinning of carboxymethyl chitin/poly(vinyl alcohol) nano-fibrous scaffolds for tissue engineering applications. Carbohydrate Polymers. 2009, 77(4):863～869
[87] Kyong Su Rho. Lim Jeong,Gene Lee. et al. Electrospinning of collagen nanofibers:Effects on the behavior of normal human keratinocytes and early-stage wound healing. Biomaterials. 2006, 27(8): 1452～1461
[88] El-Refaie Kenawy.Fouad I. Abdel-Hay. Mohamed H.El-Newehy, et al. Processing of polymer nanofibers through electrospinning as drug delivery systems. Materials Chemistry and Physics. 2009, 113(1):296～302
[89] Shu Zhang. Woo Sub Shim, Jooyoun Kim. Design of ultra-fine nonwovens via electrospinning of Nylon 6:Spinning parameters and filtration efficiency. Materials & Design. 2009.30(9):3659～3666
[90] Schreuder-Gibson HL. Gibson P. Senecal K. et al. Protective Textile Materials Based on Electrospun Nanofibers. Journal of Advanced Materials. 2002. 34(3):44～58
[91] Yang Zhang. Jianping Li, Guimin Ane, et al. Highly porous SnO_2 fibers by electrospinning and oxygen plasma etching and its ethanol-sensing properties. Sensors and Actuators B:Chemical, 2009
[92] Miaoyu Li. Gaoyi Han. Binsheng Yang. Fabrication of the catalytic electrodes for methanol oxidation on electrospinn -ing-derived carbon fibrous mats. Electrochemistry Communications, 2008. 10(6):880～883
[93] D.H.Reneker. I.Chun. Nanometer Diameter Fibers of Polymer Produced by Electrospinning. Nanotechnology. 1996, 7: 216～223.
[94]林红,何明生,李建保,等.高纯超细氧化钇粉体的制备及市场分析.新材料产业.2005.3:52～56
[95]张中太,张俊英.无机光致发光材料及应用.北京:化学工业出版社,2005:92,160
[96]黄世华,由芳田.固体中稀土离子的(?)-5d组态.中国稀土学报.2002,20(6):515～520
[97]孟庆裕,陈宝玖,赵晓霞,等.Tb~(3+)掺杂Y_2O_3纳米晶体中Tb~(3+)离子4f5d跃迁及能量传递的研究.光学学报.2007,27(2):295～302
[98] R. Bazzi. M.A.Flores-Gonzalez. C.Louis, et al. Synthesis and luminescent properties of sub-5-nm lanthanide oxides nanoparticlcs. J.Lumin.. 2003. 102(23):445～450
[99] M.L.pang, J. Lin. J. Fu, et al. Preparation, patterning and luminescent properties of nanocrystalline Gd_2O_3:A (A=Eu~(3+), Dy~(3+), Sm~(3+), Er~(3+)) phosphor films via Pechini sol-gel soft lithography. Opt. Mater. 2003, 23(3-4):547～558
[100] ZHANG Ji-shuang, QIN Wei-ping. ZHANG Ji-sen, et al. Microwave-assisted Solvothermal Synthesis of YF_3:Yb~(3+),Tm~(3+) Nanobundles. Chem.Res.Chinesc U. 2007, 23(6), 733～735
[101] Xiaoliang Yang. Siguo Xiao. J.W.Ding, et al. Luminescence properties of rare earth doped YF_3 and LuF_3 nanoparticles. Journal of Applied Physics. 2008, 103(1): 93～101
[102] Miao Wang. Qing-Li Huang.Jian-Ming Hong, et al. Controlled synthesis of different morphological YF_3 crystalline particles at room temperature. Materials Letters. 2007, 61(10):1960～1963
[103]白鲁刚,颜涌捷,李桂贞,袁远平.用木屑水解残渣制备活性碳的研究.太阳能学报.2002,23(1):55
[104]凌浪生.钙铁矿锰氧化物A位掺杂效应研究:[博士学位论文].合肥:中国科学技术大学.2008.4
[105]皮代波.稀土掺杂氟化物纳米晶体制备及其发光性能:[硕士学位论文].浙江:浙江大学.2005,12
[2] K.Sattler, J.M(?)hlbach, E.Recknagel. Generation of Metal Clusters Containing from 2 to 500 Atoms. Phys.Rev.Lett. 1980,45(10):821～824
[3]王仲山,朱庆纲,谈荣生,等.稀土元素在国民经济中的应用及其前景.科技情报开发与经济.1999.5:28～30
[4]薛茂权,熊党生,闫杰.稀土润滑材料的摩擦学研究.稀有金属.2004,28(1):248～251
[5]李建宇.稀土发光材料及其应用.北京:化学工业出版社,2003
[6] Junying Zhang, Zilong Tang, Zhongtai Zhang, et al. Synthesis of nanometer Y_2O_3:Eu phosphor and its luminescence property[J]. Materials Science and Engineering A. 2002,334(1-2):246～249
[7] J.Eid, A.C.Pierre, G.Baret. Preparation and characterization of transparent Eu doped Y_2O_3 aerogel monoliths, for application in luminescence [J]. Journal of Non-Crystalline Solids, 2005,351(3):218～227
[8] S.Yin, M.Shinozaki, T.Sato. Synthesis and characterization of wire-like and near-spherical Eu_2O_3-doped Y_2O_3 phosphors by solvothermal reaction [J]. Journal of Luminescence, 2007,126(2):427～433
[9] Sooyeon Seo, Heesun Yang, Paul H.Holloway. Controlled shape growth of Eu- or Tb-doped luminescent Gd_2O_3 colloidal nanocrystals [J]. Journal of Colloid and Interface Science. 2009,331(1):236～242
[10] Meigui Ou, Brice Mutelet, Matteo Martini, et al. Optimization of the synthesis of nanostructured Tb~(3+)-doped Gd_2O_3 by in-situ luminescence following up [J]. Journal of Colloid and Interface Science. 2009,333(2):684～689
[11] Guixia Liu, Guangyan Hong. Xiangting Dong, et al. Preparation and characterization of Gd_2O_3:Eu~(3+) luminescence nanotubes [J]. Journal of Alloys and Compounds. 2008,466(1-2):512～516
[12] Zhenhe Xu, Jun Yang, Zhiyao Hou, et al. Hydrothermal synthesis and luminescent properties of Y_2O_3:Tb~(3+) and Gd_2O_3: Tb~(3+) microrods [J]. Materials Research Bulletin. 2009, 44(9): 1850～1857
[13] H.Wang, J.Yang, C.M.Zhang, et al. Synthesis and characterization of monodisperse spherical SiO_2@RE_2O_3 (RE=rare-earth elements)and SiO_2@Gd_2O_3:Ln~(3+) (Ln=Eu,Tb,Dy,Sm,Er,Ho) particles with core-shell structure. Journal of Solid State Chemistry. 2009,182(10):2716～2724
[14] A.de J.Morales Ramirez, A.Garcia Murillo, F.de J.Carrillo Romoa, et al. Properties of Gd_2O_3:Eu~(3+),Tb~(3+) nanopowders obtained by sol-gel process [J]. Materials Research Bulletin. 2010, 45(1):40～45
[15] S.Tanabe. Control of 4f-electronic Transition Probability in Optical amplifiers for WDM Telecommunication and Development of Broad-Band Material [J]. Journal of Rare Earths. 2002, 40:148～149
[16]颜豪威.NH_4HF_2氟化法制备稀土氟化物的化学原理及工艺探讨.江西冶金.1995,15(6):31～32
[17]高俊梅,谢萍,石红静,等.氟化氢铵氟化法制备稀土氟化物工艺研究.稀土.2003,24(6):37～39
[18]姜银举.张小琴.石红静.等.氟化氢铵与稀土氧化物氟化反应机理研究.稀土,2005.26(4):39～41
[19]郝占忠.张建良.王斌.RE_2O_3-NH_4HF_2系合成稀土氟化物的反应规律.北京科技大学学报.2007,29(3):272～277
[20]刘文生,云(?)厚,王利刚.静态干法氟化法制备稀土氟化物工艺研究.稀土.2005,26(6):20～22
[21]王亚军,刘前.索全伶,等.稀土氟化物的沉淀方法及组成研究.稀土.2000,21(1):14～18
[22]张茂峰,孟建新,刘应亮.等.LaF_3:Eu~(3+)纳米粒子的水热法制备及发光性质研究.中国稀土学报.2005.23(5):564～567
[23]肖思国,阳效良,丁建文.Er~(3+),Er~(3+)/Yb~(3+)掺杂氟化镧超微材料的光谱特性与上转换发光.物理学报,2009,58(6):3812～3820
[24]陈良冬.郑小睿,丁耘.等.铈铽共惨杂氟化镧纳米晶体的快速合成和荧光特性.无机化学学报.2009.25(2):285～289
[25]德格吉呼.稀土掺杂低维纳米材料的合成及其发光特性研究:[博士学位论文].长春:中国科学院长春光学精密机械研究所.2006
[26]张志峰,李红飞,国富强,等.溶剂萃取法制备的纳米CeF_3紫外吸收性能研究.中国稀土学报.2008,26(4):432～436
[27]涂华民.张秀凤.张迈生.轻稀土氟化物的微波固相快速合成法.稀有金属.2004.28(5):875～879
[28]武安华.徐军.陈红兵,等.氟化物激光晶体及其在固体激光器中的应用.激光与红外.2009,39(1):8～13
[29] H.Y.Wang. Y.Yang. Y Wang, et al. Luminescent Properties of Rare-Earth Oxyfluoride Nanofibers Prepared via Electrospinning [J]. Nanoscience and Nanotechnology. 2009,9(2): 1522～1525
[30] Ya-Ping Du. Ya-Wen Zhang, Ling-Dong Sun, et al. Luminescent Monodisperse Nanocrystals of Lanthanide oxylluoridcs Synthesized from Trilliioroacetate Precursors in High-Boiling Solvents[J]. Phys.Chem.C. 2008. 112(2): 405～415
[31]孙家跃.杨志萍,杜海燕.共沉淀法制备NaYF_4:Tm~(3+),Yb~(3+)的上转换发光.发光学报.2009,30(2):195～200
[32]张国莲.陈廷.纳米纤维的研究现状及其应用.纺织导报.2005(1):12～18
[33]王永芝.杨清彪.李耀先.纳米纤维的性质及应用进展.化工新型材料.2004,32(12):9～12
[34] D Li. Y Xia. Electrospinning of Nanofibers:Reinventing the Wheel. Adv.Mater. 2004, 16(14):1151～1170
[35] Yilgor Demir M.M., Yilgor I., Yilgor E., et al. Electrospinning of polyurethane fibers. Polymer. 2002,43(11):3303-3309
[36] Norris I.D.. Shaker M.M., Ko F.K., MacDiarmid A.G. Electrostatic fabrication of ultrafine conducting fibers: polyaniline/polyethylene oxide blends. Synthetic Metals. 2000,114(2):109～144
[37] Baumgarten P.K. Electrostatic spinning of acrylic microfibers. J.Colloid Interf.Sci. 1971. 36(1):71～79
[38]王新威.胡祖明.潘婉莲.等.电纺丝制备高聚物纳米纤维[D].东华大学学报(自然科学版).2005.31(1):115～119
[39]吴大诚.杜仲良.高绪珊.纳米纤维.北京:化学工业出版社,2003:46
[40] Rayleigh L., On the Equilibrium of Liquid Conducting Masses Charged with Electricity. Phil.Mag. 1882, 14:184～186
[41] Zeleny J. The Electrical Discharge from Liquid Points, and a Hydrostatic Method of Measuring the Electric Intensity at Their Surfaces.Phys.Rev. 1914, 3(2):69～91
[42] Formhals A. Process and apparatus for preparing artificial threads[p]. U.S.Patent No. 1975.504,1934
[43] Taylor G.I. Disintegration of Water Drops in an Electric field, Proc.Roy.Soc.London A, 1964,280:383～397
[44] Simons H.L.,U.S.Patent No.3,280,299,1966
[45] Baumgarten P.K. Electrostatic spinning of acrylic microfibers. J.Colloid Interface Sci. 1971, 36(1):71 ～ 79
[46] Larrando L.and Manley R.ST.J.Electrostatic fiber spinning from polymer melts.Ⅱ. Examination of the flow field in an electrically driven jet[J]. Polym.Sci..Part B:Polym.Phys. 1981, 19(6):921～932
[47] Larrando L.and Manley R.ST.J. Electrostatic fiber spinning from polymer melts.Ⅰ.Experimental observations on fiber formation and properties. J.Polym.Sci..Part B:Polym.Phys. 1981. 19(6):909～920
[48] Larrando L.and Manley R.ST.J. Electrostatic fiber spinning from polymer melts.Ⅲ.Electrostatic deformation of a pendant drop of polymer melt[J]. Polym.Sci.,Part B:Polym.Phys. I981,19(6):933～940
[49] Reneker D,H.and Chun I., Nanometre diameter fibres of polymer,produced by electrospinning.Nanotechnology. 1996.7(3):216～223
[50] Fong H.and Reneker D.H. Elastomeric nanofibers of styrene-butadiene-styrene triblock copolymer. J. Polym.Sci.. PartB:Polym. Phys. 1999,37(24).3488～3493
[51] Chen Z.H..Foster M.D.W S Zhou.et al. Structure of poly(ferrocenyldimethylsilane) in electrospun nanofibers.Macromolecules. 2001,34(18):6156～6158
[52] Fang X.and Reneker D.H. DNA fibers by electrospinning. J.Macromol.Sci.Phys.B.1997,36(2):169～173
[53] Srinivasan G.and Reneker D.H. Structure and morphology of small diameter electrospun aramid fibers. Polym.Intema-tional. 1995,36(2): 195～201
[54] Kim J.S.and Reneker D.H. Polybenzimidazole nanofiber produced by electrospinning, Polym.Eng.Sci. 1999, 39(5):849～854
[55] Huang L., Nagapudi K., Apkarian R.P. et al. Engineered collagen-PEO nanofibers and fabrics. J Biomater Sci. Polym Ed. 2001,12(9):979～993
[56] L.Buttafoco. N.G.Kolkman. P.Engbers-Buijtenhuijs, et al. Electrospinning of collagen and elastin for tissue engineering applications. Biomaterials. 2006. 27(5):724～734
[57] Jia Xu. Jinhui Zhang. Weiquan Gao. et al. Preparation of chitosan/PLA blend micro/nanofibers by electrospinning. Materials Letters. 2009, 63(8):658～660
[58]王永芝.杨清彪.杜建时,等.电纺丝技术-一种高效低耗的纳米纤维制备方法[J].化工新型材料.2005.33(6):12～14
[59] F.Ko, Y.Gogotsi. A.Ali. et al. Electrospinning of Continuous Carbon Nanotube-Filled Nanofiber Yarns[J].Adv.Mater. 2003,15(14): 1161～1165
[60] Xinhua.Zong, Kwangsok.Kim. Dufei.Fang,et al. Structure and process relationship of electrospun bioabsorbable nanofiber membranes. Polymer. 2002. 43(16):4403～4412
[61] S.A.Theron. A.L.Yarin, E.Zussman. et al. Multiple jets in electrospinning:experiment and modeling. Polymer.2005,46(9):2889～2899
[62] D.Li. Y.Wang. Y.Xia. Electrospinning of Polymeric and Ceramic Nanofibers as Uniaxially Aligned Arrays[J].Nano Lett. 2003.3:1167
[63] Choo-Won Kim. Dae-Sik Kim. Scung-Yeon Kang, et al. Structural studies of electrospun cellulose nanofibers[J]. Polymer. 2006. 47(14):5097～5107
[64] Keun-Hyung Lee. Steven Givens. D.Bruce Chase, et al. Electrostatic polymer processing of isotactic poly (4-methyl-1-pentene) fibrous membrane [J]. Polymer. 2006, 47(23):8013～8018
[65] Hohman M M. Shin M, Rutledge G. et al. Electrospinning and electrically forced jets.Ⅰ .Stability theory. Physics of Fluids. 2001,13(8):2201～2220
[66] P.F. Jacobs. Rapid Prototyping and Manufacturing, Fundamentals of Stereolithography. Society of Manufacturing Engineers. Dearborn, MI. 1992:263～277
[67] Shin Y M. Hohman M M, Brenner M P, et al. Experimental characterization of electrospinning:the electrically forced jet and instabilities[J]. Polymer. 2001. 42(25):9955～9967
[68] Chun I. Reneker D H. Fong H.et al. Carbon nanofibers from polyacrylonilrilc and mesophase pitch.J. Adv. Mater. 1999.31(1):36～41
[69] Fong H, Chun I, Reneker D H. Beaded nanofibers formed during electrospinning. Ploymer, 1999, 40(16):4585～4592
[70] J. M. Deitzel, J. Kleinmeyer. D. Harris. et al. The effect of Processing variables on the morphology of electrospun nano-fibers and textiles. Polymer. 2001. 42(1):261～272
[71] Li Lei. Bellan Leon M. Craighead Harold G, et al. Formation and Properties of nylo-6 and nylon-6/montmorillonite composite nanofibers. Polymer. 2006. 47(17):6208～6217
[72] Tao Jing,Shivkumar Satya. Molecular weight dependent structural regimes during the electrospinning of PVA[J]. Mater Lett. 2007, 61(11-12):2325～2328
[73]吕砚山.常见电工电子技术手册[M].北京:化学工业出版社,1995,34～60
[74] Ding Bin. Eiji Kinura, Tomokazu Sato, et al. Fabrication of blend biodegradable nanofibrousnonwoven mats via multi-jet electrospinning. Polymer. 2004,45(6):1895～1902
[75]何创龙,黄争鸣,韩晓建,等.同轴射流技术制备纳米复合材料研究进展.复合材料学报,2005,22(6):1～8
[76] Katta P. Alessandro M, Ramsier R D, et al. Continuous Electrospinning of Aligned Polymer Nanofibers onto a Wire Drum Collector. Nano Lett. 2004. 4(11):2215～2218
[77] Li D. Wang Y. Xia Y. Electrospinning of Polymeric and Ceramic Nanofibers as Uniaxially Aligned Arrays. Nano Lett. 2003,3(8): 1167～1171
[78]邹科,龙云泽,吴佑实.静电纺丝制备纳米纤维的进展及应用.合成纤维工业.2007,30(3):54～57
[79] Goki Eda, James Liu, Satya Shivkumar. Flight path of electrospun polystyrene solutions:Effects of molecular weight and concentration. Materials Letters. 2007, 61(7):1451 ～1455
[80] Yang Q.B.. Li D.M., Hong Y.L.. et al. Preparation and characterization of a PAN nanofibre containing Ag nanoparticles via electrospinning. Synth. Met. 2003, 137(1-3):973～974
[81] Li Dan, Xia Younan. Electrospinning Nanofibers as Uniaxially Aligned Arrays and Layer-by-Layer Stacked Films Advanced Malerials.2004,16(4):361-366
[82] H.Dai. J.Gong. H.kim, D.Lee. A novel method for preparing ultra-fine almina-borate oxide fibres via an electrosping technique. Nanotechnology. 2002. 13(5):674～677
[83] Qiaozhen Yu. Mang Wang, Hongzheng Chen. Fabrication of ordered TiO_2 nanoribbon arrays by electrospinning.Mater Lett. 2010. 64(3):428～430
[84]伊长青.聚乙烯基吡咯烷酮(PVP)生产工艺研究:[工程硕士学位论文].中国石油大学,2007,10
[85]李从举,翟国钧,付中玉,等.聚乙烯吡咯烷酮纳米纤维电纺制备及形貌控制研究.纳米材料与技术应用进展-第四届全国纳米材料会议论文集.2005.12:455～459
[86] K..T.Shalumon. N.S.Binulal, N.Sclvamurugan, et al. Electrospinning of carboxymethyl chitin/poly(vinyl alcohol) nano-fibrous scaffolds for tissue engineering applications. Carbohydrate Polymers. 2009, 77(4):863～869
[87] Kyong Su Rho. Lim Jeong,Gene Lee. et al. Electrospinning of collagen nanofibers:Effects on the behavior of normal human keratinocytes and early-stage wound healing. Biomaterials. 2006, 27(8): 1452～1461
[88] El-Refaie Kenawy.Fouad I. Abdel-Hay. Mohamed H.El-Newehy, et al. Processing of polymer nanofibers through electrospinning as drug delivery systems. Materials Chemistry and Physics. 2009, 113(1):296～302
[89] Shu Zhang. Woo Sub Shim, Jooyoun Kim. Design of ultra-fine nonwovens via electrospinning of Nylon 6:Spinning parameters and filtration efficiency. Materials & Design. 2009.30(9):3659～3666
[90] Schreuder-Gibson HL. Gibson P. Senecal K. et al. Protective Textile Materials Based on Electrospun Nanofibers. Journal of Advanced Materials. 2002. 34(3):44～58
[91] Yang Zhang. Jianping Li, Guimin Ane, et al. Highly porous SnO_2 fibers by electrospinning and oxygen plasma etching and its ethanol-sensing properties. Sensors and Actuators B:Chemical, 2009
[92] Miaoyu Li. Gaoyi Han. Binsheng Yang. Fabrication of the catalytic electrodes for methanol oxidation on electrospinn -ing-derived carbon fibrous mats. Electrochemistry Communications, 2008. 10(6):880～883
[93] D.H.Reneker. I.Chun. Nanometer Diameter Fibers of Polymer Produced by Electrospinning. Nanotechnology. 1996, 7: 216～223.
[94]林红,何明生,李建保,等.高纯超细氧化钇粉体的制备及市场分析.新材料产业.2005.3:52～56
[95]张中太,张俊英.无机光致发光材料及应用.北京:化学工业出版社,2005:92,160
[96]黄世华,由芳田.固体中稀土离子的(?)-5d组态.中国稀土学报.2002,20(6):515～520
[97]孟庆裕,陈宝玖,赵晓霞,等.Tb~(3+)掺杂Y_2O_3纳米晶体中Tb~(3+)离子4f5d跃迁及能量传递的研究.光学学报.2007,27(2):295～302
[98] R. Bazzi. M.A.Flores-Gonzalez. C.Louis, et al. Synthesis and luminescent properties of sub-5-nm lanthanide oxides nanoparticlcs. J.Lumin.. 2003. 102(23):445～450
[99] M.L.pang, J. Lin. J. Fu, et al. Preparation, patterning and luminescent properties of nanocrystalline Gd_2O_3:A (A=Eu~(3+), Dy~(3+), Sm~(3+), Er~(3+)) phosphor films via Pechini sol-gel soft lithography. Opt. Mater. 2003, 23(3-4):547～558
[100] ZHANG Ji-shuang, QIN Wei-ping. ZHANG Ji-sen, et al. Microwave-assisted Solvothermal Synthesis of YF_3:Yb~(3+),Tm~(3+) Nanobundles. Chem.Res.Chinesc U. 2007, 23(6), 733～735
[101] Xiaoliang Yang. Siguo Xiao. J.W.Ding, et al. Luminescence properties of rare earth doped YF_3 and LuF_3 nanoparticles. Journal of Applied Physics. 2008, 103(1): 93～101
[102] Miao Wang. Qing-Li Huang.Jian-Ming Hong, et al. Controlled synthesis of different morphological YF_3 crystalline particles at room temperature. Materials Letters. 2007, 61(10):1960～1963
[103]白鲁刚,颜涌捷,李桂贞,袁远平.用木屑水解残渣制备活性碳的研究.太阳能学报.2002,23(1):55
[104]凌浪生.钙铁矿锰氧化物A位掺杂效应研究:[博士学位论文].合肥:中国科学技术大学.2008.4
[105]皮代波.稀土掺杂氟化物纳米晶体制备及其发光性能:[硕士学位论文].浙江:浙江大学.2005,12