杨金龙教授，1966年5月出生于山西省太原市；1987年，毕业于北京理工大学金属材料及热处理专业，获得学士学位；1990年，毕业于中北大学金属材料及热处理专业，获得硕士学位；1996年，毕业于清华大学材料系无机非金属专业，获得博士学位。1999年5月-2000年8月在瑞士联邦理工大学做博士后研究工作，师从国际著名陶瓷科学家Gauckler教授。1996年8月至今，分别担任清华大学材料系讲师、副教授、教授、博导。2006年7月，被中北大学聘为特聘教授，并担任先进陶瓷实验室主任。2010年5月，被聘为大连交通大学兼职教授。2014年5月，被聘为河北工程大学兼职教授。同时，杨金龙教授担任硅酸盐学报编委，中国硅酸盐学会溶胶凝胶分会理事，材料导报编委，IJMPTInternational Journal of Materials Product and TechnologyGuest Editor。曾获多项荣誉，包括国家技术发明二等奖1项，河北省科技进步二等奖1项，山西省自然科学二等奖1项，其他省部级科技奖项3项，德国纽伦堡国际发明博览会金奖1项，国际发明展览会金奖1项。截至2017年12月31日，通过技术成果鉴定
目錄：
1 Aqueous Colloidal Injection Molding of Ceramics CIMC Based on Gelation 1
11 WhatisColloidalInjectionMolding? 3
111 Colloidal Injection Molding of Ceramics CIMC 3
112 TheFlowchartofCIMC 4
113 The Machine of Colloidal Injection Molding ofCeramics 5
12 Pressure-InducedForming 6
121 Effect of Hydrostatic Pressure on Solidication 6
122 HomogeneityoftheGreenBodies 7
123 Controlling the Inner Stress in the Green Body 7
13 StorageStabilityofCeramicSlurries 10
131 The Importance of Storage Stability of Slurry 10
132 ChemicalStability 10
133 InhibitorforSlurryStorage 12
14 To Prepare High Reliability Ceramic Parts with Complex Shapes： Aqueous Colloidal Injection Molding 13
15 Summary 14
References 16
2 Gel Tape Casting of Ceramic Substrates 17
21 Fundamental Principle and Processing of Aqueous GelTapeCasting 19
211 Tape Casting Types and the Raw Materials Used 19
212 PolymerizationoftheMonomer 23
213 Inuence Factors on Polymerization of the Monomer31
214 ProcessingoftheGelTapeCasting 37
22 Characteristics of Slurries Used for Aqueous GelTapeCasting 40
221 Properties of the Aqueous Ceramic Slurries withBinder 40
222 Inuence of Dispersants on Stability and Rheology of Aqueous Ceramic Slurries with Organic Monomer45
223 Inuence of Plasticizer on Properties of Aqueous CeramicSlurrywithOrganicMonomer 49
224 Inuence of PH Value on Properties of Slurry withOrganicMonomer 50
225 Effects of Surfactant on Wetting and Green Tape ReleasingSeparating 51
226 FoamandPoreElimination 53
227 Sintering of Green Tape Prepared by Slurry54
23 Aqueous Gel Tape Casting with Styrene-Acrylic Latex Binder 55
231 The Importance of Binders in Gel Tape Casting Process 55
232 The Forming Film Mechanism of Latex Binder 58
233 Rheological Properties of the Alumina Slurries withBinder 60
234 The Physical Properties and Microstructure of Green Tapes 61
24 A Gel Tape Casting Process Based on Gelation of Sodium Alginate 63
241 Why Study on Tape Casting of Sodium Alginate 63
242 The Preparation of Aqueous Alumina Suspensions with Sodium Alginate and Calcium Phosphere Tribasic65
243 Control of the Gelation of Sodium Alginate66
244 CharacterizationofGreenTapes 68
25 Spray Trigger Fast-Curing for Gel Tape Casting Process 70
251 TheIdeaofSprayTriggerFast-Curing 70
252 OutlineoftheNewProcess 70
26 Summary 71
References 75
3 Gelation Forming Process for Toxicity-Free or Low-Toxicity System 79
31 Gelation Forming of Ceramic Suspension with Agarose 80
311 CharacteristicsofAgarose 80
312 The Effect of Agarose Contents on the Rheology ofAqueousCeramicSuspensions 82
313 The Forming Courses of the Aqueous Ceramic SuspensionswithAgarose 84
32 Alumina Casting Based on Gelation of Gelatin88
321 CharacteristicsofGelatin 88
322 The Gelation Process of the Ceramic Slurry withGelatinSolution 91
323 Preparation of Green Body Using Slurry withGelatinSolution 93
33 A Casting Forming for Ceramics by Gelatin and Enzyme Catalysis 95
331 ResearchBackground 95
332 Gelation Mechanism of Gelatin Solution with Urea UnderEnzymeCatalysis 97
333 Rheology and Zeta Potential of Alumina Suspension ContainingGelatinandUrea 99
334 Coagulation Forming and Microstructure of Green Body 100
34 Alumina Forming Based on Gelation of Sodium Alginate 102
341 ResearchBackground 102
342 Gelation Principle of Sodium Alginate 104
343 Preparation Process of Alumina Green Bodies andSamplesbySodiumAlginate 107
35 Gelcasting of Silicon Carbide Based on Gelation of Sodium Alginate 110
351 ResearchBackground 110
352 Effect of Dispersant on the Colloidal Behavior oftheSiCSuspension 112
353 Rheological Property of SiC Suspension113
354 Sedimentation Behavior of the SiC Suspension 115
355 Gelation Principle and Process of the Alginate Solution 116
356 Gelation of the SiC Suspension with Alginate 116
36 Alumina Gelcasting with a Low-Toxicity System of HEMA119
361 AcademicIdeaandResearchProgram 119
362 Colloidal Chemistry and Rheological Property 120
363 Binder Burnout and Application of the New System122
37 A Synergistic Low-Toxicity Gelcasting System by Using HEMAandPVP 124
371 AcademicIdeaandResearchProgram 124
372 f Potentials and Rheological Properties 125
373 Activation Energies and Solidication 128
374 Green Strengths and Microstructures 129
375 Exfoliation Elimination Effect and Analysis of the Interaction Between PVP and HEMA Molecules 131
References 134
4 Generation, Development, Inheritance, and Control of the Defects in the Transformation from Suspension to Solid 139
41 Rheological Behaviors of Aqueous Ceramic Suspensions 141
411 Rheological Behaviors of Aqueous Alumina Suspensions 142
412 Effect of Rheological Properties of Suspension onMechanicalStrengthofCeramics 145
413 Effects of Solid Volume Fraction on Colloidal Forming 153
42 GenerationandDevelopmentofDefects 158
421 Generation Mechanisms of Agglomerations inCeramicSuspensions 158
422 Inuences of Idle Time on Microstructures and Mechanical Properties of Green Bodies byDirectCoagulationCasting 165
43 Effect of Ionic Conductance on Preparation of Highly ConcentratedSuspension 174
431 AcademicIdeaandResearchProgram 174
432 The Relationship Between Ion Conductivity ConstantsandSolidsVolumeLoading 176
44 ControlofInnerStressinGreenBody 181
441 Origin, Transformation and Control of Inner Stress inGreenBody 181
442 Release and Control of Inner Stresses in Ceramic GreenBody 187
45 Suppression of Surface Exfoliation with the Addition ofOrganicAgents 195
451 Suppression of Surface Exfoliation by Introducing Polyacrylamide PAM into a Monomer System inSuspension 195
452 Suppression of Surface Exfoliation by Introducing Polyethylene Glycol PEG into Monomer System inSuspension 203
References 221
5 Gelcasting of Non-oxide Ceramics 225
51 Effects of Powder Surface Modication on Concentrated SuspensionPropertiesofSiliconNitride 226
511 Contributing Factor and Elimination of Macropores inSiliconNitrideGreenBodies 226
512 Effect of Foreign Ions on Concentrated Suspension ofSiliconNitride 232
513 Effects of Acid Cleaning and Calcinations on the Suspension Properties of Silicon Nitride 238
514 Effects of Liquid Medium and Surface Group on Dispersibility of Silicon Nitride Powder249
52 GelcastingofSiliconNitrideCeramics 255
521 Preparation of Silicon Nitride Ceramics with Surface-Coated Silicon Nitride Powder255
522 Preparation of Silicon Nitride Ceramics with Surface-Oxidized Silicon Nitride Powder 267
523 Preparation of Silicon Nitride Ceramics Using CombinationProcessing 276
53 Gelcasting of Silicon Carbide Ceramic and Silicon Nitride-BondedSiliconCarbideCeramic 287
531 Gelcasting of Concentrated Aqueous Silicon Carbide Ceramic 287
532 Gelcasting of Aqueous Slurry with Silicon Nitride-BondedSiliconCarbide 294 References 306
6 Applications of New Colloidal-Forming Processes 311
61 CeramicMicrobeads 311
611 The Forming Principle of Ceramic Microbeads BasedonGelcasting 311
612 TheProcessofPreparingMicrobeads 314
613 The Properties of Ceramic Microbeads 314
614 Summary 328
62 Improving the Breakdown Strength of the Rutile Capacitor329
621 The Inuence of Sintering Additives on the Flow Behavior 331
622 CalciningoftheRutileMixture 333
623 The Rheological Behavior of the Calcined Rutile Mixture 334
624 Gelcasting of the Calcined Rutile Mixture335
625 Summary 336
63 Thin-Wall Rutile Tube for Ozone Generator with High DielectricConstant 338
631 ResultsandDiscussions 339
632 Summary 341
64 RefractoryNozzleofZirconia 342
641 Rheological Behaviors of Zirconia Suspensions withDifferentDispersants 343
642 Sediment Stability of Zirconia Suspension withDifferentDispersants 345
643 Preparation of Zirconia Refractory Nozzles346
644 Summary 346
65 Water-Based Gelcasting of Lead Zirconate Titanate348
651 Colloidal Chemistry and Rheological Behavior 350
652 MicrostructureandProperties 354
653 Summary 357
References 357
7 New Methods and Techniques Based on Gelation 359
71 Development Overview and Application of Solid Freeform Fabrication 361
711 Development Overview of Solid Freeform Fabrication361
712 Application of Solid Freeform Fabrication362
72 Development Overview and Application of Freeze-Gelcasting371
721 The Combination of Gelcasting and Freeze-Casting Technique 371
722 Fabrication of Ceramics with Special Porous Structures 372
723 Microstructure and Properties of Porous Alumina Ceramics 378
724 Mechanical Properties and Applications of Alumina CeramicswithUltra-LowDensity 382
73 Solidication of Concentrated Silicon Nitride Suspensions forGelcastingbyUltrasonicEffects 387
731 The Forming Method of Gelcasting Using Ultrasonic Effects 387
732 Preparation of Concentrated Silicon Nitride Suspensions 388
733 Ultrasonic Accelerated Solidication 389
734 Comparison of Thermal-and Ultrasonic-Activated Solidications 392
74 Novel Laser Machining Technology for Alumina Green Ceramic 394
741 LaserMachiningTechnology 394
742 Practical Application of Laser Machining Technology395 References 402
8 Novel In-situ Coagulation Casting of Ceramic Suspensions 405
81 Direct Coagulation Casting of Ceramic Suspension byHighValenceCounter-Ions 407
811 Direct Coagulation Casting by Using Calcium Iodate asCoagulatingAgent 407
812 Direct Coagulation Casting by Using Calcium PhosphateasCoagulatingAgent 423
813 Direct Coagulation Casting by Using Thermo-Sensitive LiposomesasCoagulatingAgent 432
814 Direct Coagulation Casting from Citrate Assisted bypHShift 442
815 Direct Coagulation Casting via High Valence Counter-Ions from Chelation Reaction 474
82 Dispersion Removal Coagulation Casting501
821 DispersantReactionMethod 501
83 DispersantHydrolysisMethod 521
84 DispersantSeparationMethod 532
References 541
Appendix A： The Testing, Analyzing and Sintering Methods Used in Authors Research 549
Appendix B： The Raw Materials Used in Authors Research 551
Index of Scholars 553
Index of Terms 561
Postscript 567
內容試閱：
Introduction
In ancient times, ceramic vessels or crafts were usually manufactured using clay-based natural raw materials. It is well known that the mud mixed clay with water has good plasticity and can be easily processed into products of various shapes. However, the forming techniques used earlier were mainly manual proce-dures. Therefore, to a large extent, the forming of ceramic wares was just a kind of skill or workmanship. By the 1960s, new ceramic materials had already developed into an independent scienti.c system. At the same time, raw materials that were used to manufacture ceramics began to transition from the clay-based system to one with accurate chemistry composition. In particular, for preparing high-performance ceramics, synthetic chemical raw materials, such as Al2O3,ZrO2,Si3N4, and SiC, were mainly used. These ceramics had excellent properties because of their struc-tural characteristics of covalent bond and ionic bond, and were widely considered as candidate materials in many .elds requiring high-temperature resistant, wear-resistant, and corrosion resistant substances. It had been predicted that such materials would be developed rapidly, and various new types of materials with excellent properties would be explored.
By the late 1970s, the emergence of the worldwide oil crisis caused many developed countries led by America and Japan to draft national development plans for high temperature structural ceramic materials used in the .eld of internal combustion engines, especially automobile engines. With excellent properties such as resistance to high temperature, wear, and corrosion, high-performance ceramics were considered the optional material for non-water cooling and adiabatic ceramic engine parts. The forming technique of ceramics was also among the top-ranking research topics.
During the period of the 7th Five-Year Plan and 8th Five-Year Plan in China, around the key components of ceramic insulation engines, an in-depth research on ceramic injection molding, extrusion molding, slip casting, and pressure .ltration was done. Moreover, a few engine parts samples with high performance were prepared. However, because of the high cost, poor performance repeatability, and low yield, the process of industrialization of high-performance ceramics was greatly restricted. After years of research and exploration, there was a growing recognition as the key technology for forming high-performance ceramic materials and parts. The forming technique is not only the precondition for materials design and for-mula, but also the important factor in reducing manufacturing costs and improving the yield and the performance repeatability of products. Simultaneously, several research booms were set off around the new forming technique of ceramics at home and abroad. During the period of the 9th Five-Year Plan in China, in order to achieve high-tech ceramic industrialization at the earliest, the ceramic forming technique with high performance and low cost was granted special funds from the 863 Program.
Along with the research upsurge in the .eld of ceramic engines, there was also considerable interest in the .eld of injection molding of ceramics. On the basis of the theory of plastic injection molding, thermoplastic, thermosetting, and water-soluble organic compounds were used as binders, and then mixed with ceramic powder to prepare a suspension with high volume loading. In addition, ceramic parts with high size precision and complex shape can be prepared by injection molding. It is suitable for automotive and large-scale production. After several decades, owing to in-depth studies on ceramic injection molding, it developed into an integrated science and technology involving rheology, the dynamic molding process of injection suspen-sion and thermal degradation of organic compounds as well as other interdisciplinary technology. However, some problems caused by organic enrichment or particle rearrangement were exposed during the time and energy consuming process of debindering, such as poor uniformity and easy cracking. Therefore, debindering was considered the key issue to be solved, and the solution to lower the organic content gradually became an important research topic. In order to simplify the process of debindering, low-pressure injection molding with some small molecular organics was paid more attention.
After the 1990s, quickset injection molding was invented by B. E. Novich of the
U.S. The pore .uid was used as a carrier in the process, the volume of which did not change with temperature. After the suspension was injected into the container, the carrier was sublimated, and then the green body was solidi.ed by controlling the temperature and pressure. Because of avoiding the polymer organic carrier with large molecule, the problem of organic debindering was solved ingeniously. Due to sig-ni.cant advantages such as high automation and good size precision, injection molding continues to be highly used and is considered a highly competitive forming process.
In the mid-1980s, in order to avoid the dif.culty of debindering in injection molding, which was caused by the large number of organic binders, traditional slip casting was again paid more attention, as it involved less organics and low cost. Moreover, the operation and control were easy in this method. However, because of the green body with low green density and poor strength, it was not suitable for the preparation of high-performance ceramics. On the basis of traditional slip casting, the pressure .ltration and centrifugal casting techniques were developed thereafter. The green bodys density and strength were improved by applied pressure and centrifugal force, and at the same time the complicated debindering process was avoided. However, such processes were also unable to meet the green bodies with high reliability and high performance due to poor uniformity of the green bodies.
After the 1990s, in order to improve the uniformity and reliability of ceramic bodies, forming in situ techniques such as gelcasting, temperature-induced .oc-culation, colloidal vibration casting, and direct coagulation casting were developed. The in situ solidi.cation process is highly regarded because it is the precondition to ensure uniformity and is an important way to improve the reliability of ceramics.
Gelcasting, a novel colloidal forming technology of ceramics, was .rst invented by Oak Ridge National Laboratory ORNL, USA, in 1990. In the gelcasting process, about 24 wt.% acrylamide monomer is added into the ceramic suspen-sion, and then it polymerizes in situ by the interaction of catalysts and initiators. Furthermore, the drying process should take place at room temperature and high humidity for a long time; otherwise, the green bodies would easily crack. In addition, the degree of automation and industrialization of the gelcasting process is poor when compared to injection molding. The ceramic bodies prepared by gel-casting have the obvious advantages of high strength and excellent machinability. Thus, some ceramic parts with complex shape or that are dif.cult to be demolded, just like inside thread, can be passed through green body machining after drying to achieve the required shape and precision. As a kind of brittle and dif.cult-to-machine material, it is very important, even necessary for the bodies to be machined partly, which also provides people a very good idea.
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