표제지
제출문
원자력신소재개발 과제 구성표
요약문
SUMMARY
목차
Contents 24
제1장 서론 46
제2장 국내외 기술개발 현황 48
제3장 연구개발수행 내용 및 결과 54
제1절 고순도 초미립 분말 제조 54
1. 개요 54
2. 자발착화 연소반응법(Combustion Assisted Process) 56
3. Li계 산화물 분말 제조 공정 58
4. Ni-ZrO₂ 서메트 분말제조 공정 77
5. La-Mn계 세라믹스 89
6. 기타 분말 95
제2절 세라믹스 이온 전도성 박판제조 100
1. 개요 100
2. 3Y+8Y 복합 지르코니아의 제조 및 전기적 성질 변화 102
3. 3Y+8Y 복합지르코니아의 고온 열화 실험 117
4. 전기화학증착법에 의한 전도성 세라믹박막의 제조기술과 그 응용 127
5. 전기적 성능 측정장비 설계 및 제작 148
6. 자발착화합성법으로 제조한 10 mol% Gd₂O₃ 도우프된 CeO₂의 특성평가 154
7. 결론 169
제3절 기반제조공정 연구 172
1. 서론 172
2. 테이프 캐스팅 공정 개발 173
3. sol-gel 공정 개발 175
4. 단결정 성장 공정 개발 177
5. 세라믹스성형 및 소결공정과 연삭가공 공정개발 178
6. 결론 179
7. 연구 성과물 182
제4절 위탁과제 요약 184
1. 위탁과제 현황 184
2. 전자요업재료의 제조 및 물성 연구 184
3. Czochralski 법을 이용한 산화물 단결정의 육성 207
4. 자발착화연소합성법에 의한 Lithium Aluminate 분말합성 215
제5절 전체 결론 220
제4장 연구개발목표 달성도 및 대외기여도 228
제5장 연구개발결과의 활용계획 232
제6장 참고문헌 234
서지정보양식(BIBLIOGRAPHIC INFORMATION SHEET) 455
판권기 457
Table 1-1. Typical Properties of Candidate Ceramic Breeder Materials 437
Table 1-2. Phase Composition of LiAlO₂ Powders Synthesized by Several Methods 438
Table 1-3. Experimental Conditions of Combustion Process of Lithium Nitrate... 439
Table 1-4. Synthetic Conditions of Al₂O₃ Powders and Phase of Product... 439
Table 1-5. Synthetic Conditions of LiAlO₂ Powders and Phase of Product after Combustion 440
Table 1-6. Effect of Mixed Fuel on the Synthesis of LiAlO₂ Powder 441
Table 1-7. Effect of Composition of Fuels on me BET Surface Area 442
Table 1-8. Relative Density versus Sintering Temperature for LiAlO₂ 442
Table 1-9. Element Analysis of the YSZ/Ni Powder Prepared from the... 443
Table 1-10. Specific Surface Area Analysis of me YSZAJi Powder 443
Table 1-11. Effect of Forming Pressure on the Green and Sintered... 444
Table 1-12. Relative Density of 8YSZ-Ni Cermets as a Function of Ni Content 444
Table 1-13. Relative Density of 8YSZ-Ni Cermets after Reduction... 445
Table 1-14. Impurity Analysis of the Combustion Synthesized and... 445
Table 2-1. Fracture Toughness of the Specimens made of 3Y-ZrO₂... 446
Table 2-2. The Electrical Conductivities of the Specimens measured... 446
Table 2-3. Total Conductivities of the Specimens made of 3Y-ZrO₂ and 8Y-ZrO₂... 447
Table 2-4. Combinations of Powder and Ratios of Mixing Powder 448
Table 2-5. Characteristics of Sintered Materials 448
Table 2-6. Chemical Etching Condition of ZrO₂ 449
Table 2-7. Monoclinic ZrO₂ Contents after Annealing at 1000℃ in Air and... 449
Table 2-8. Experimental Conditions for the Growth of Electrochemical... 450
Table 2-9. Characteristics of limiting Current Type Oxygen Sensor 450
Table 2-10. Chemical Analysis of ZrCI₄ and YCl₃· 451
Table 2-11. Dimensions of Various Reaction Tubes 451
Table 2-12. Conditions for Platinum Sputtering 452
Table 2-13. Ionic Radii of Various Elements 453
Table 2-14. The Activation Energies for the Electrical Conductivities... 454
Fig. 1-1. Molecular Structure of Glycine (a), Cihic Acid (b), and Urea (c) 246
Fig. 1-2. Flame Temperatures measured by Two-Color Optical Pyrometry... 247
Fig. 1-3. XRD Patterns for La(Sr)CrO₃ Ash combusted under Three... 248
Fig. 1-4. Schematic Diagram of Combustion Temperature Measuring... 249
Fig. 1-5. XRD Pattern of Powders Synthesized by (a) Cinic acid, (b)... 250
Fig. 1-6. SEM Micrographs of Powders Synthesized by (a) Citric Acid... 251
Fig. 1-7. Enlargement of Fig.1-6(a) 252
Fig. 1-8. XRD Pattern of Al₂O₃ Powders Synthesized by (a),(b) Urea and... 253
Fig. 1-9. SEM Micrographs of Al₂O₃ Powders with Different Momhologies... 254
Fig. 1-10. SEM Micrographs of LiAlO₂ Powders Synthesized by (a) Citric... 255
Fig. 1-11. XRD Pattern of LiAlO₂ Powders Synthesized by Using (a) Urea... 257
Fig. 1-12. TG/DTA Curves of me LiAlO₂ Powder Synthesized by... 258
Fig. 1-13. TG/DTA Curves of the LiAlO₂ Powder Synthesized by... 259
Fig. 1-14. XRD Pattern of LiAlO₂ Powders Synthesized by Urea/Citric Acid... 260
Fig. 1-15. SEM Micrographs of LiAlO₂ Powders Synthesized by Urea/Citric... 261
Fig. 1-16. Effect of Composition of Mixed Fuels on the BET Surface Area 263
Fig. 1-17. Combustion temperature of LiAlO₂ synthesis system with... 264
Fig. 1-18. SEM Micrographs of Powders Ball-milled for 24h 265
Fig. 1-19. Particle Size Distribution of y LiAlO₂ Powders with Milling... 266
Fig. 1-20. SEM Micrographs of Green Body Roduced from (a) Urea- and... 267
Fig. 1-21. Relative Density versus Sintering Temperature for LiAlO₂.... 268
Fig. 1-22. SEM Micrographs of Fracture Surface of LiAlO₂ Sintered at... 269
Fig. 1-23. Phases of As-synthesized Powders reacted with Zirconium... 270
Fig. 1-24. Phases of Assynthesized Powders reacted with Mixture of... 271
Fig. 1-25. X-ray Difhaction Patterns of Ascalcined Li₂ZrO₃ Powders 272
Fig. 1-26. Phase Diagram of Li₂O-ZrO₂ System 273
Fig. 1-27. Spherical Precipitates of Zr-hydroxide prepared by the Thermal... 274
Fig. 1-28. Micrographs of Precipitates mixed with Metal (Li and Zr)... 275
Fig. 1-29. Typical SEM micrographs of as-synthesized Li₂ZrO₃ powders (A) and... 276
Fig. 1-30. Anodic Polarization versus Current Density in Metal-YSZ Cell at... 277
Fig. 1-31. Electrical Conductivity of 8YZ-Ni Cermet as a Function of the... 278
Fig. 1-32. Temperature Dependence of me Electrical Conductivity of... 279
Fig. 1-33. Thermal Expansion Coefficient of 8YZ-Ni Cermet as a Function... 280
Fig. 1-34. Ni-YSZ Cermet Resistance versus Time during Hydrogen... 281
Fig. 1-35. Experimental Procedure for 8YZ-Ni Cermet 282
Fig. 1-36. XRD Patterns of me 8YZ-30Ni (a), 8YZ-40Ni (b), and 8YZ-50Ni... 283
Fig. 1-37. SEM Micrographs of me As-Synthesized ((a), (b)) and the... 284
Fig. 1-39. Effect of Uniaxial Forming Pressure on me Green Density of... 286
Fig. 1-40. Effect of Uniaxial Forming Pressure on me Sintered Density of... 287
Fig. 1-41. SEM Micrographs of the Powder Compacts Made from the... 288
Fig. 1-42. SEM Micrographs of me Fracture Surfaces for me Sintered (a)... 289
Fig. 1-43. SEM Micrographs of me Fracture Surfaces for the Sintered (a)... 290
Fig. 1-44. XRD Patterns of the Assintgred (a) and the Reduced (b)... 291
Fig. 1-45. Sintered Density of the 8YZ-Ni Specimens as a Function of the... 292
Fig. 1-46. Dilatometric Curves of 8YZ and 8YZ-Ni Cermet 293
Fig. 1-47. Effect of Sintering Time on the Sintered Density of 8YZ-Ni... 294
Fig. 1-48. Variation of Relative Density as a Function of me Amount of Ni... 295
Fig. 1-49. Microstructures of the Polished Surfaces of the 8YZ-Ni Cermet 296
Fig. 1-50. Photographs of the Green and Sintered Bodies of the 8YZ-Ni... 297
Fig. 1-51. X-ray Diffraction Pattenl of NiO/3YZ Powder synthesized by the... 298
Fig. 1-52. TEM Micrograph (A) and EDS Result (B) of Combustion... 299
Fig. 1-53. SEM Micrographs of Combustion synthesized NiO/3YZ Powder... 300
Fig. 1-54. X-ray Diffraction Patterns of Ni/3YZ Powder reduced at 900℃... 301
Fig. 1-55. Functionally Graded Ni/3YZ Hot pressed at 1250℃ under 15MPa... 302
Fig. 1-56. X-ray Line Scattering (A) and Mapping (B) Images of Ni/3YZ... 303
Fig. 1-57. Four Point Bending Strength of Ni/3YZ Cermet with Ni Content 304
Fig. 1-58. Fracture Surfaces of Ni/3YZ Cennet : (A) 10 vol% Ni, (B) 30... 305
Fig. 1-59. Fracture Toughness of Ni/3YZ Cermet with Ni Content 306
Fig. 1-60. Perovskite Structure 307
Fig. 1-61. Flow Chart of Tape-casted Process 308
Fig. 1-62. SEM Micrograph of the Microstructure of the Tape-casted... 309
Fig. 1-63. SEM Micrographs of me Microstructure of the Tape-casted... 310
Fig. 1-64. The Variations of Electrical Conductivity (RT) for the... 311
Fig. 1-65. XRD Patterns of ZTA Powders containing ZrO₂ Content of (a) 5... 312
Fig. 1-66. TEM Micrograph of me ZTA Powder containing 20 wt% ZrO₂ 313
Fig. 1-67. SEM Micrographs of (a) As-synthesized and (b) Ball-milled... 314
Fig. 1-68. SEM Micrographs of the ZTA Composites prepared by (a)... 315
Fig. 1-69. X-ray Diffraction Pattern of the Combustion-synthesized Powder 316
Fig. 1-70. Scanning Electron Micrographs of the Combustion- synthesized... 317
Fig. 1-71. Scanning Electron Micrographs of the Combustion-synthesized... 318
Fig. 1-72. Particle Size Distribution of the Combustion- synthesized Powder... 319
Fig. 1-73. Relative Density of the Yttria Specimens sintered for 2 h at... 320
Fig. 1-74. Microstructure of the Yttria Specimen sintered at 1400℃ for 2 h 321
Fig. 2-1. Basic Equivalent Circuits and Frequency Dependences of Complex... 322
Fig. 2-2. The Frequency Dependance of Complex Impedance of the... 323
Fig. 2-3. A Diagram of Electrical Resistance by Grain Boundaries and its... 324
Fig. 2-4. The Relationship of R and X in the Equation of (48) 325
Fig. 2-5. SEM Photograph for Zirconia Powders made by TOSOH Co 326
Fig. 2-6. SEM Photographs of me Microstuctures of me Specimens made... 327
Fig. 2-7. The SEM photograph of the 50% 8Y-ZrO₂+50% 3Y-ZrO₂... 328
Fig. 2-8. X-ray Diffraction Patterns of the Specimens made of 3Y-ZrO₂... 329
Fig. 2-9. Fracture Toughnesses of the Specimens made of 3Y-ZrO₂ and... 330
Fig. 2-10. Impedance Spectra of the Specimens measured at 250℃ in Air 331
Fig. 2-11. (a) A representative Spectrum of 8YZ Specimen measured at... 332
Fig. 2-12. Arrhenius Plots of total Conductivities of the Specimens made of... 333
Fig. 2-13. Crystal Structure of Zirconia(open circle : Zr, closed circle : O) 334
Fig. 2-14. Flow Chart of Experimental Process 335
Fig. 2-15. Schematic Drawing of Gas Tight Holder 336
Fig. 2-16. Schematic Diagrams of High Temperature Degradation Testing... 337
Fig. 2-17. Diffraction Patterns taken from the complex ZrO₂ with 67%... 338
Fig. 2-18. Diffraction Patterns taken from the complex ZrO₂ with... 339
Fig. 2-19. Diffraction Patterns taken from the 100%3Y-ZrO₂ (A) Before... 340
Fig. 2-20. Diffraction Patterns taken hom the 100%8Y-ZrO₂ (A) Before... 341
Fig. 2-21. Diffraction Patterns taken fro the complex ZrO₂ with... 342
Fig. 2-22. Diffraction Patterns taken from the complex ZrO₂ with 33%3Y/... 343
Fig. 2-23. Scanning Electron Micrographs of Before annealed 3Y67%/... 344
Fig. 2-24. Scanning Electron Micrographs of 3Y33%/8Y67% ZrO₂ anealed... 345
Fig. 2-25. Reaction Stages of ElectrochemicaI Vapor Deposition 346
Fig. 2-26. Structural Composition of the Cubic and Tetragonal Phase of... 347
Fig. 2-27. Crtical Grain Size(Dc) as a Function of Yttria Percentage 348
Fig. 2-28. Schematic Representation of Limiting Current Type Oxygen... 349
Fig. 2-29. Voltage-Current Characteristics of limiting Current Type Oxygen... 350
Fig. 2-30. Schematic Diagram of the experimental Apparatus used to grow... 351
Fig. 2-31. Schematic Diagram of the experimental Apparatus used to grow... 352
Fig. 2-32. Schematic Diagram of limiting Current Type Oxygen Sensor by... 353
Fig. 2-33. Schematic Diagram of Perovskite Powder Production Process by... 354
Fig. 2-34. Dependence of Film Composition on Reactor Vapor Phase... 355
Fig. 2-35. X-ray Diffraction Patterns of the YSZ Films deposited at... 356
Fig. 2-36. X-ray Diffraction Patterns of the YSZ Films deposited at... 357
Fig. 2-37. Raman Spectroscopy of me YSZ Films deposited at different... 358
Fig. 2-38. The Relation of Pressure Difference vs. Penetration Depth 359
Fig. 2-39. X-ray Diffraction Patterns of electrochemical Vapor deposited... 360
Fig. 2-40. X-ray Diffraction Patterns of electrochemical Vapor deposited... 361
Fig. 2-41. The Relation of Amount of monoclinic and Y₂O₃ mol% in Films... 362
Fig. 2-42. X-ray Diffraction Patterns of deposited YSZ/Pt Electrode at... 363
Fig. 2-43. X-ray Diffraction Patterns of various heating Scheme (a), (b)... 364
Fig. 2-44. X-ray Diffraction Patterns of the calcined Powders for the... 365
Fig. 2-45. EDS Analysis of Perovskite Powder fabricated by Pechini... 366
Fig. 2-46. X-ray Diffraction Patterns of deposited at (a) YSZ/Pt+... 367
Fig. 2-47. Schematic Diagram of Overall Electrical Performance Measuring... 368
Fig. 2-48. Schematic Diagram of setted Unit Cell in the Gas Tube Part 369
Fig. 2-49. Assembly Drawing of Electrical Performance Measuring... 370
Fig. 2-50. Front View of Electrical Performance Measuring Assembly 371
Fig. 2-51. Top View of Electrical Performance Measuring Assembly 372
Fig. 2-52. Right Side View of Electrical Perfonnance Measuring Assembly 373
Fig. 2-53. Detailed Drawing of Stainless Steel Gas Sealing of Eletrical... 374
Fig. 2-54. Electric Circuit Diagram of Unit Cell Measuring System 375
Fig. 2-55. Flow Chart of I-V Measuring Program 376
Fig. 2-56. Flow Chart of Resistance-Temperature Measuring Program 377
Fig. 2-57. Flow Chart of Resistance-Time Measuring Program 378
Fig. 2-58. Photo of me Electrical Performance Measuring Equipment 379
Fig. 2-59. Photo of Overall the Electrical Performance Measuring System 380
Fig. 2-60. The Variations of pH with the Stirring Time in Various... 381
Fig. 2-61. The Variations of pH with the Stirring Time in the Aqueous... 382
Fig. 2-62. The Variations of pH with the Stirring Time in the Aqueous... 383
Fig. 2-63. DTA and TG Curves of me Recipitates from the Aqueous 0.02... 384
Fig. 2-64. SEM Micrographs of the Recipitates from the Aqueous 0.02mol... 387
Fig. 2-65. XRD Pattern of the Precipitate calcined at 400℃ for 1h in Air 388
Fig. 2-66. TEM Micrograph (a) and Diffraction Pattern (b) of the... 389
Fig. 2-67. TEM Micrograph (a) and Diffraction Pattern (b) of the 10mol%... 390
Fig 2-68. XRD Pattern of the As-synthesized 10 mol% Gd₂O₃ doped CeO₂... 391
Fig. 2-69. Micrograph of the As-synthesized 10 mol% Gd₂O₃ doped CeO₂... 392
Fig. 2-70. Dilatometric Curves for the Green Bodies from the... 393
Fig. 2-71. SEM Micrographs of the Fractured Surfaces of Sintered CeO₂... 394
Fig. 2-72. Dilatorneσic Curves of me Green Bodies made from the 10... 395
Fig. 2-73. SEM Micrograph of the Surface of the Specimen after the... 396
Fig. 2-74. Dilatomenic Curves of me Green Bodies made horn me doped... 397
Fig. 2-75. SEM Micrographs of me Polished MicrosmlCtures of the 10... 398
Fig. 2-76. The Grain Size of me Sintered 10mol% Gd₂O₃ doped CeO₂... 399
Fig. 2-77. The Impedance Spectra of the Pure CeO₂ Pellets sintered at... 400
Fig. 2-78. The Impedance Spectra of the Pure CeO₂ Pellets sintgred at... 401
Fig. 2-79. The Impedance Spectra of the Pure CeO₂ Pellets sintered at... 402
Fig. 2-80. The Impedance Spectra of the 10 mol% Gd₂O₃ doped CeO₂... 403
Fig. 2-81. The Impedance Spectra of the 10 mol% Gd₂O₃ doped CeO₂... 404
Fig. 2-82. The Representadve Impedance Spectra of the sintered Gd-doped... 405
Fig. 2-83. Electrical Conductivity of the 10 mol% Gd₂O₃ doped CeO₂ Pellets... 406
Fig. 2-84. Electrical Conductivity of the 10 mol% Gd₂O₃ doped CeO₂ Pellets... 407
Fig. 2-85. The Activation Energies for the GI(grain interior), GB (grain... 408
Fig. 2-86. The Electrical Conductivities of the 10 mol% Gd₂O₃ doped CeO₂... 409
Fig. 2-87. The Activation Energies for GI(■) and GB(●) Conductivities... 410
Fig 2-88. Compositional Profiles for the Ce and Gd Elements in the 10... 411
Fig 2-89. EDS Data for the Polished Surface of me 10 mol% Gd₂O₃ doped... 412
Fig. 2-90. SEM Micrograph of the 10mol% Gd₂O₃ doped CeO₂ Pellet... 413
Fig. 2-91. Expansion Profiles of the doped CeO₂ with the Measuring... 414
Photo 2-1. SEM Micrographs showing the Effect of gas phase... 415
Photo 2-2. SEM Micrographs of Surface showing the Effect of... 416
Photo 2-3. SEM Micrographs of fractured Surface showing the Effect... 417
Photo 2-4. SEM Micrographs of Penetration Morphology(upper... 418
Photo 2-5. SEM Micrographs showing the deposited YSZ/Pt Electrode... 419
Photo 2-6. Changes in Morphologies of screen printed Pt Electrode... 420
Photo 2-7. Changes in fractured Surface Morpologies of screen... 421
Photo 2-8. Changes in Morphologies of 0.5cm Sputtered Pt Electrode... 422
Photo 2-9. Changes in Morphologies of 1cm Sputtered Pt Electrode... 423
Photo 2-10. Changes in Morphologies of 0.5cm Sputtered Pt Electrode... 424
Photo 2-11. Changes in Morphologies of 1cm Sputtered Pt Electrode... 425
Photo 2-12. Changes in Morphologies of various heating scheme, (a) 426
Photo 2-13. Changes in Morphologies of Pt+La₀.₈₉Sr₀.₁₁MnO₃ Electrode 427
Photo 2-14. SEM Images showing EVD Layer on the... 428
Fig. 3-1. Doctor blade apparams for tape-casting designed by KAERI 429
Fig. 3-2. Tape-casted ZrO₂ plates with holes (A), with size of 5×5cm (B)... 430
Fig. 3-3. Light and hard silica spheres (A) and inner microstructure of sphere... 431
Fig. 3-4 Monodisperse silica powders with a spherical shape prepared by sol-gel... 432
Fig. 3-5. LiNbO₃ single crystal grown by the Czochralski method 433
Fig. 3-6. 3YZ/8YZ composite with a laminated structure (A) and enlarged... 434
Fig. 3-7. Hot pressed ceramics (A) Al₂O₃ and (B) B₄C added SiC 435
Fig. 3-8. Machined Al₂O₃ 436