稀土氟化物纳米复合光学材料的制备及金红石型二氧化钛的HRTEM研究
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摘要
本论文选择当前的热点研究领域一纳米材料为研究对象。在对纳米材料的合成、表征、性质及理论分析中，选择出最佳的制备方法和制备条件。依据此思路，我们认为反相微乳液法和溶剂热法是制备纳米材料的最佳选择。而稀土元素特殊的电子构型，使其具有独特的性质及广泛的应用。通过对这两者的结合，我们制备出了亲油性好、粒径分散均匀的纳米稀土氟化物粒子。再通过本体聚合制备出纳米复合玻璃，测得了Pr~(3+)的吸收，使其应用于光学材料成为可能。
另外，我们也分析了金红石型纳米晶二氧化钛的HRTEM图，认为纳米粒子的非晶程度不同和晶体缺陷的差异，造成系统内能的差异、活化能量阈值的不同。
In this paper, we mainly studied nanomaterials. In the course of synthesis and characterization, we also discussed its properties and theory. According to foregoing work, we selected optimal method and condition about fabrication. Rare earth elements have unique properties and extensive applications owing to their special electronic configuration. Thus, we combined them and attained hydrophobic rare earth nanoparticle. Meantime, we synthesized nanocomposite glass and studied optical properties of the glass. It is possible to apply to nanocomposite optical material.
In addition, we also applied to HRTEM to analyze rutile titania nanocrystals. Every kinds of nanocrystal had different energy threshold of phase transition.
另外，我们也分析了金红石型纳米晶二氧化钛的HRTEM图，认为纳米粒子的非晶程度不同和晶体缺陷的差异，造成系统内能的差异、活化能量阈值的不同。
In this paper, we mainly studied nanomaterials. In the course of synthesis and characterization, we also discussed its properties and theory. According to foregoing work, we selected optimal method and condition about fabrication. Rare earth elements have unique properties and extensive applications owing to their special electronic configuration. Thus, we combined them and attained hydrophobic rare earth nanoparticle. Meantime, we synthesized nanocomposite glass and studied optical properties of the glass. It is possible to apply to nanocomposite optical material.
In addition, we also applied to HRTEM to analyze rutile titania nanocrystals. Every kinds of nanocrystal had different energy threshold of phase transition.
引文
1．高善民，孙树声，前景广阔的纳米材料，化工新型材料，2000，27(6)：39-40
2．张立德，牟季美，纳米材料和纳米结构，科学出版社。2002，59—64
3. Suetsuge Y, The Six Annal. Meeting, PPS., Nice, France,1990:17-18
4．牟季美，张立德，纳米复合材料发展趋势，物理，1996，25(1)：31-36
5．金联明，陈运法，张国昌等，溶胶-凝胶法制备无机．有机杂化材料，功能材料，1999，30(5)：452-455
6. Narita T.,Kikuchi N.,Kawa saki K.,et al., Metalizing of Silicon-Carbide Ceramics with Titanium Vapor, J Ceram soc Jpn.,1997,105(1):68-72
7. Haraguchi K.,Usami T., The Novel Organic-Inorganic Hybrid Materials Composed of Phenolic Resin and Silica, Chem. Lett., 1997:51-52
8. K. Tadanaga, K. Azuta and T. Minami, Preparation of Organic-Inorganic Hybrid Coating Films from Vinyltdethoxysilane-Tetraethoxysilane by the Sol-Gel Method, J.Ceram.Soc.Jpn., 1997,105(7):555-558
9. Schimdt H., NMR Investigation of Chemical Homogeneity in Hybrid Systems, J. sol-gel Sci.&Tech., 1997(8):553-556
10. Avnir D., Levy D., Reisfeld R., The nature of the silica cage as reflected by spectral changes and enhanced photostability of trapped Rhodamine 6G, J. Phy. Chem., 1984, 88:5956-5959
11．钱国栋，王民权，原位合成配合物Eu(DBM)·3H_2O在凝胶玻璃基质中的发光性能，硅酸盐学报，2003，31(1)：47-51
12. Tatsuya Okubo, Keitoshi Haruta, Katsuki Kusakabe,et al., J. Preparation of Sol-Gel Derived Thin Membrane on Porous Ceramic Hollow Fiber by Filtration Technique, Journal of Membrane Science., 1991(59): 73-80
13. Uhimann D.R., Teowee G., Boulton J., The Future of Sol-Gel Science and Technology, J. sol-gel Sci.&Tech., 1997,8:1083-1091
14. Popau M., Kappel J., Schulz J., et al., J. sol-gel Sci. &Tech., 1994:56
15．曹立新，袁迅道等，溶胶-凝胶法制备有机-无机纳米复合材料，应用化学，1998，15(3)：1-5
16．顾豪爽，王世敏等，溶胶-凝胶法制备高取向Bi_4Ti_3O_(12)／SrTiO_3(100)薄膜，物理化学学报，1996，12(1)：63-66
17. Suzuki E Onozato K, A formation of compatible poly(vinyl alcohol)/alumina gel composite and its properties, J. Appl. Polym. Sci., 1990, 39:371-381
18. Schmidt H, Organic modification of glass structure new glasses or new polymers, J. Non-Cryst. Solids., 1989,112:419-423
19. Ellsworth M W, Novak B M, Mutually interpenetrating inorganic-organic networks. New routes into nonshrinking sol-gel composite materials, J Am Chem Soc, 1991, 113:2756-2758
20. Bruce M. Novak, Robert H. Grubbs, The ring opening metathesis polymerization of 7-oxabicyclo[2.2.1]hept-5-ene derivatives: a new acyclic polymeric ionophore, J. Am. Chem. Soc., 1988; 110(3); 960-961
21．邓辉，施冬梅等，有机／无机纳米复合材料的制备方法，现代化工，2000，20(11)：62-64
22．张剑锋，郑强，曹苏华，益小苏，电子束辐照交联CB／HDPE凝胶复合物的阻温特性，高等学校化学学报，1999，20(12)：1974-1977
23．郝凌云，周勇等，紫外辐照同步合成无机-有机聚合物纳米复合材料，稀有金属材料与工程。2001，30(2)：138-140
24．王丽萍，洪广言，无机—有机纳米复合材料，功能材料，1998，15(3)：343-347
25．王铀，沈静姝，制备聚合物纳米复合材料展望，化工新型材料，1998，(1)：8-12
26. Gao M Y, Yang Y, yan g B, et al., Synthesis of PbS nanoparticles in polymer matrices, ChemCommun.,1994, 7: 2779-2781
27. A. Ripamonti and E. MulazziV. Benza, Dynamics of photoexcited states in polyacetylene, Synthetic Metals, 1991, 41-43:59-62
28. Wang Y, Suna A, Mahler W, et al., PbS in polymers. From molecules to bulk solids, J Chem. Phys., 1987, 87: 7315-7322
29. Mahler W, Polymer-trapped semiconductor particles, Inorg. Chem., 1988, 27:
435
30. Watkins J J, Mccarthy T J, Chemistry in Supercritical Fluid-swollen Polymers: Direct Synthesis of Metal/Polymer Nanocomposites, Polym. Mater. Sci. Eng., 1995, 73: 158-162
31．陈笃慧，杨乐夫，BaAl_(12)O_(19)高温热稳定材料制备方法，厦门大学学报(自然科学版)，1997，36(2)：240-245
32. Zhao X K, Xu S, Fendler J H, Ultrasmall magnetic particles in Langmuir-Blodgett films, J. Phys. Chem., 1990, 94: 2573-2581
33. Steehler, J.K.; Lu, W.; Kemery, P.J.; Bohn, P.W. , Electric field induced permeability modulation in pure and mixed Langmuir-Blodgett multilayers of hemicyanine dyes and octadecanoic acid on nanoporous solid supports, Journal of Membrane Science,1998, 139(2): 243-257
34．石春山，稀土功能材料，化学通报，1989，11：24—27
35．张若桦，稀土元素化学，天津：天津科技出版社，1987
36. Dicke G H, Crosswhite H M., The spectra of the doubly and triply ionized rare earths, Appl. Optics., 1963, 2:675-686
37. Blasse G. Handbook in the Physics and Chemistry of Rare Earths, North-HollandPublishing Company, 1979, 4:237
38. Mufit Akinc Akinc, Ahmet Lelikkaya, Advances in Ceramics, 1987, 21:43-45
39. Gary L Messing, Edwin R Fuller Jr Hans, et al, Ceramic Transactions, 1988, V17: Ceramic Powder Science Ⅳ
40．李强，高濂等，纳米Y_2O_3：Eu～(3+)的荧光特性，无机材料学报，1997，12(2)：237-401
41．李强，高濂等，纳米Y_20_3：Eu～(3+)粉体荧光强度的增强，无机材料学报，1998，13(6)：899-903
42. Shea L E, Mckittrick J, Lopez O A, Synthesis of Red-Emitting, Small Particle Size Luminescent Oxides Using an Optimized Combustion Process, J. Am. Ceram. Soc., 1996, 19(12): 3257-3265
43. Hong K S, Meltzer R S, et al, Spectral hole burning in crystalline Eu_2O_3 and Y_2O_3: Eu~(3+) nanoparticles, J. Lumin., 1998, 76-77: 234
44. Sharma P K, Jilavi M H, et al. Tailoring the particle size from μm→nm scale
by using a surface modifier and their size effect on the fluorescence properties of europium doped yttria, J. Lumin., 1999, 82: 187-193
45. Williams D K, Bihari B, Tissue B M., Preparation and Fluorescence Spectroscopy of Bulk Monoclinic Eu~(3+):Y_2O_3 and Comparison to Eu~(3+): Y_2O_3 Nanocrystals, J Phys Chem. B., 1998,102:916-920
46. Bihari B, Eilers H, et al., Spectra and dynamics of monoclinic Eu_2O_3 and Eu~(3+): Y_2O_3 nanocrystals, J. Lumin., 1997, 75: 1-10
47．李强，高濂等，YAG：Ce～(3+)微粉的制备及光谱性能，无机材料学报，1997，12(4)：575-578
48. Riwotzki K, Haase M, Wet-Chemical Synthesis of Doped Colloidal Nanoparticles: YVO_4:Ln (Ln=Eu, Sm, Dy), J. Phys. Chem.B, 1998, 102: 10129-10135
49. Tao Y, Zhao G, EXAFS studies of luminescence centres in Eu~(3+) doped nanoscale phosphors, et. Al., Mater. Letter., 1996, 28: 137-140
50. Meyssamy H, Riwoezki K, Wet-Chemical Synthesis of Doped Colloidal Nanomaterials: Particles and Fibers of LaPO_4: Eu, LaPO_4:Ce, and LaPO_4:Ce,Tb, Adv. Mater., 1999, 11(10): 840-844
51. Tick P A, Borrelli N F, et al, Transparent glass ceramics for 1300 nm amplifier applications, J. Appl. Phys., 1995, 78: 6367-6374
52. Duter D, Bauhofer W, Highly luminescent Eu3+ or Tb3+ doped and ZnO sensitized optical fibers from silicon compartible sealing glasses, Appl. Phys. Lett., 1996, 69: 892
53. Glass W, Toulouse J, Tick P A, Visible emission from rare earth ions in nanocrystal-containing glasses, J. Non-Cryst. Solids., 1997, 222: 258-265
54．汪联辉，章文贡，王文，稀土高分子聚合物及其应用，稀土，1999，20(3)：58—62
2．张立德，牟季美，纳米材料和纳米结构，科学出版社。2002，59—64
3. Suetsuge Y, The Six Annal. Meeting, PPS., Nice, France,1990:17-18
4．牟季美，张立德，纳米复合材料发展趋势，物理，1996，25(1)：31-36
5．金联明，陈运法，张国昌等，溶胶-凝胶法制备无机．有机杂化材料，功能材料，1999，30(5)：452-455
6. Narita T.,Kikuchi N.,Kawa saki K.,et al., Metalizing of Silicon-Carbide Ceramics with Titanium Vapor, J Ceram soc Jpn.,1997,105(1):68-72
7. Haraguchi K.,Usami T., The Novel Organic-Inorganic Hybrid Materials Composed of Phenolic Resin and Silica, Chem. Lett., 1997:51-52
8. K. Tadanaga, K. Azuta and T. Minami, Preparation of Organic-Inorganic Hybrid Coating Films from Vinyltdethoxysilane-Tetraethoxysilane by the Sol-Gel Method, J.Ceram.Soc.Jpn., 1997,105(7):555-558
9. Schimdt H., NMR Investigation of Chemical Homogeneity in Hybrid Systems, J. sol-gel Sci.&Tech., 1997(8):553-556
10. Avnir D., Levy D., Reisfeld R., The nature of the silica cage as reflected by spectral changes and enhanced photostability of trapped Rhodamine 6G, J. Phy. Chem., 1984, 88:5956-5959
11．钱国栋，王民权，原位合成配合物Eu(DBM)·3H_2O在凝胶玻璃基质中的发光性能，硅酸盐学报，2003，31(1)：47-51
12. Tatsuya Okubo, Keitoshi Haruta, Katsuki Kusakabe,et al., J. Preparation of Sol-Gel Derived Thin Membrane on Porous Ceramic Hollow Fiber by Filtration Technique, Journal of Membrane Science., 1991(59): 73-80
13. Uhimann D.R., Teowee G., Boulton J., The Future of Sol-Gel Science and Technology, J. sol-gel Sci.&Tech., 1997,8:1083-1091
14. Popau M., Kappel J., Schulz J., et al., J. sol-gel Sci. &Tech., 1994:56
15．曹立新，袁迅道等，溶胶-凝胶法制备有机-无机纳米复合材料，应用化学，1998，15(3)：1-5
16．顾豪爽，王世敏等，溶胶-凝胶法制备高取向Bi_4Ti_3O_(12)／SrTiO_3(100)薄膜，物理化学学报，1996，12(1)：63-66
17. Suzuki E Onozato K, A formation of compatible poly(vinyl alcohol)/alumina gel composite and its properties, J. Appl. Polym. Sci., 1990, 39:371-381
18. Schmidt H, Organic modification of glass structure new glasses or new polymers, J. Non-Cryst. Solids., 1989,112:419-423
19. Ellsworth M W, Novak B M, Mutually interpenetrating inorganic-organic networks. New routes into nonshrinking sol-gel composite materials, J Am Chem Soc, 1991, 113:2756-2758
20. Bruce M. Novak, Robert H. Grubbs, The ring opening metathesis polymerization of 7-oxabicyclo[2.2.1]hept-5-ene derivatives: a new acyclic polymeric ionophore, J. Am. Chem. Soc., 1988; 110(3); 960-961
21．邓辉，施冬梅等，有机／无机纳米复合材料的制备方法，现代化工，2000，20(11)：62-64
22．张剑锋，郑强，曹苏华，益小苏，电子束辐照交联CB／HDPE凝胶复合物的阻温特性，高等学校化学学报，1999，20(12)：1974-1977
23．郝凌云，周勇等，紫外辐照同步合成无机-有机聚合物纳米复合材料，稀有金属材料与工程。2001，30(2)：138-140
24．王丽萍，洪广言，无机—有机纳米复合材料，功能材料，1998，15(3)：343-347
25．王铀，沈静姝，制备聚合物纳米复合材料展望，化工新型材料，1998，(1)：8-12
26. Gao M Y, Yang Y, yan g B, et al., Synthesis of PbS nanoparticles in polymer matrices, ChemCommun.,1994, 7: 2779-2781
27. A. Ripamonti and E. MulazziV. Benza, Dynamics of photoexcited states in polyacetylene, Synthetic Metals, 1991, 41-43:59-62
28. Wang Y, Suna A, Mahler W, et al., PbS in polymers. From molecules to bulk solids, J Chem. Phys., 1987, 87: 7315-7322
29. Mahler W, Polymer-trapped semiconductor particles, Inorg. Chem., 1988, 27:
435
30. Watkins J J, Mccarthy T J, Chemistry in Supercritical Fluid-swollen Polymers: Direct Synthesis of Metal/Polymer Nanocomposites, Polym. Mater. Sci. Eng., 1995, 73: 158-162
31．陈笃慧，杨乐夫，BaAl_(12)O_(19)高温热稳定材料制备方法，厦门大学学报(自然科学版)，1997，36(2)：240-245
32. Zhao X K, Xu S, Fendler J H, Ultrasmall magnetic particles in Langmuir-Blodgett films, J. Phys. Chem., 1990, 94: 2573-2581
33. Steehler, J.K.; Lu, W.; Kemery, P.J.; Bohn, P.W. , Electric field induced permeability modulation in pure and mixed Langmuir-Blodgett multilayers of hemicyanine dyes and octadecanoic acid on nanoporous solid supports, Journal of Membrane Science,1998, 139(2): 243-257
34．石春山，稀土功能材料，化学通报，1989，11：24—27
35．张若桦，稀土元素化学，天津：天津科技出版社，1987
36. Dicke G H, Crosswhite H M., The spectra of the doubly and triply ionized rare earths, Appl. Optics., 1963, 2:675-686
37. Blasse G. Handbook in the Physics and Chemistry of Rare Earths, North-HollandPublishing Company, 1979, 4:237
38. Mufit Akinc Akinc, Ahmet Lelikkaya, Advances in Ceramics, 1987, 21:43-45
39. Gary L Messing, Edwin R Fuller Jr Hans, et al, Ceramic Transactions, 1988, V17: Ceramic Powder Science Ⅳ
40．李强，高濂等，纳米Y_2O_3：Eu～(3+)的荧光特性，无机材料学报，1997，12(2)：237-401
41．李强，高濂等，纳米Y_20_3：Eu～(3+)粉体荧光强度的增强，无机材料学报，1998，13(6)：899-903
42. Shea L E, Mckittrick J, Lopez O A, Synthesis of Red-Emitting, Small Particle Size Luminescent Oxides Using an Optimized Combustion Process, J. Am. Ceram. Soc., 1996, 19(12): 3257-3265
43. Hong K S, Meltzer R S, et al, Spectral hole burning in crystalline Eu_2O_3 and Y_2O_3: Eu~(3+) nanoparticles, J. Lumin., 1998, 76-77: 234
44. Sharma P K, Jilavi M H, et al. Tailoring the particle size from μm→nm scale
by using a surface modifier and their size effect on the fluorescence properties of europium doped yttria, J. Lumin., 1999, 82: 187-193
45. Williams D K, Bihari B, Tissue B M., Preparation and Fluorescence Spectroscopy of Bulk Monoclinic Eu~(3+):Y_2O_3 and Comparison to Eu~(3+): Y_2O_3 Nanocrystals, J Phys Chem. B., 1998,102:916-920
46. Bihari B, Eilers H, et al., Spectra and dynamics of monoclinic Eu_2O_3 and Eu~(3+): Y_2O_3 nanocrystals, J. Lumin., 1997, 75: 1-10
47．李强，高濂等，YAG：Ce～(3+)微粉的制备及光谱性能，无机材料学报，1997，12(4)：575-578
48. Riwotzki K, Haase M, Wet-Chemical Synthesis of Doped Colloidal Nanoparticles: YVO_4:Ln (Ln=Eu, Sm, Dy), J. Phys. Chem.B, 1998, 102: 10129-10135
49. Tao Y, Zhao G, EXAFS studies of luminescence centres in Eu~(3+) doped nanoscale phosphors, et. Al., Mater. Letter., 1996, 28: 137-140
50. Meyssamy H, Riwoezki K, Wet-Chemical Synthesis of Doped Colloidal Nanomaterials: Particles and Fibers of LaPO_4: Eu, LaPO_4:Ce, and LaPO_4:Ce,Tb, Adv. Mater., 1999, 11(10): 840-844
51. Tick P A, Borrelli N F, et al, Transparent glass ceramics for 1300 nm amplifier applications, J. Appl. Phys., 1995, 78: 6367-6374
52. Duter D, Bauhofer W, Highly luminescent Eu3+ or Tb3+ doped and ZnO sensitized optical fibers from silicon compartible sealing glasses, Appl. Phys. Lett., 1996, 69: 892
53. Glass W, Toulouse J, Tick P A, Visible emission from rare earth ions in nanocrystal-containing glasses, J. Non-Cryst. Solids., 1997, 222: 258-265
54．汪联辉，章文贡，王文，稀土高分子聚合物及其应用，稀土，1999，20(3)：58—62