Phenolic Resins: A Century of Progress (eBook)

1: Introduction 13
2: Phenols 19
Phenol 21
Physical Properties of Phenol 22
Chemical Properties of Phenol 23
Phenol Production from Cumene 23
Sources for ``Natural´´ Phenol 29
Global Supply and Use of Phenol 29
Alkylphenols 30
Cresols 30
Xylenols 31
Resorcinol 31
Bisphenol-A 32
References 32
3: Formaldehyde 34
Introduction 35
Chemistry 35
Aldehydes 35
Formaldehyde 35
Chemical Properties of Formaldehyde 36
Manufacturing Processes 37
Silver Catalyst Process 38
Metal Oxide Processes 38
Stabilizer 40
World Market 41
Methanol 41
Market Performers 42
Formaldehyde Uses 43
Health and Safety 45
Other Formaldehyde Materials 46
Paraformaldehyde 46
Trioxane and Cyclic Formals 47
HMTA 47
Other Aldehydes 48
References 49
Chapter 4: Resin Chemistry 50
Introduction 52
Resole 54
Methylol Phenol(s) 54
Addition - Methylolation 55
Novolak 62
Bisphenol F 62
Random 64
High Ortho 66
Heterogeneous/Two-Phase Process 66
Nanotechnology 71
Modified Novolaks 74
Enzyme 74
Reactions 75
Functional Group Appendage to Phenolics: Epoxy 75
Cyanate Ester 77
Benzoxazine 80
Nanomodified Fiber Reinforced Phenolic Type Polymer Matrix Composites 81
Compatibilization and/or Toughening Agents 83
Natural Products 84
Mechanism of Cure 85
Novolak 85
Resole 89
Latent Curing Agents 90
Non-Hexa Cure of Novolaks 91
Solid Resole 91
Bisoxazolines 91
Benzoxazines 92
Oxazolidines 92
Addition Cure Phenolics 93
Trends 95
References 97
Chapter 5: Analyses/Testing 101
Introduction 103
A-Stage, B-Stage, C-Stage, Transitions 103
Raw Materials 104
Wet Chemical Methods (RI, pH, Titration) 105
Formaldehyde 105
Standard Physical and Quality Control Methods - ISO Methods 107
Instrumental Analysis 107
GPC 107
GC and GC-Mass Spectrometry 110
Pyrolysis GC 112
Liquid Chromatography and Liquid Chromatography-MS 112
IR Spectroscopy 114
Raman Spectroscopy 119
NIR Spectroscopy and Other Process Control Instruments 120
NMR Spectroscopy 122
Time of Flight Mass Spectroscopy 126
PES, Atomic Absorption Spectroscopy 126
Thermal Analysis 127
Thermogravimetric Analysis 128
Differential Scanning Calorimetry 129
Dynamic Mechanical Analysis 131
Rheometry 133
Other Thermal Techniques 134
Microscopy 134
Conclusion 138
References 138
Chapter 6: Resole Production 145
Production of Resoles 146
Resoles 146
Raw Materials 147
Molar Ratio 147
Process Parameters 147
Parameters of Resoles 147
Production Process 148
Principle Steps of the Batch Process 148
Continuous Phenolic Resin Manufacturing Processes 149
Modern Batch Manufacturing Processes 150
Raw Material Charging 150
Temperature Control 150
In-line Monitoring 151
Health and Safety Issues 152
References 152
7: Novolak Production 153
Introduction 153
Raw Materials 154
Acid Catalysts 155
Process 156
References 157
Chapter 8: Wood Composite Adhesives 159
Introduction 159
Volume and Region Trends 160
Global Market Factors 163
Environmental Factors 165
Economic Factors 166
Process and Equipment Factors 167
Continuous Press 167
Steam-Air Preheater 167
Radio Frequency Preheater 168
Microwave Preheater 168
Dry Blending on MDF 169
Foam and Liquid Extrusion for Plywood and LVL 169
Application Requirement Factors 170
Plywood 170
Laminated Veneer Lumber 170
Oriented Strand Board 171
Structural Composite Lumber Products 171
Hardboards and Light Fiberboards for Insulation Purposes 172
PB/HDF/MDF 172
Novel Products 173
Bamboo Fused Parquet 173
Scrimber 173
Current Chemistry Solutions 173
Standard Phenol-Formaldehyde Systems 173
Recent Kinetics and Mechanism Research 173
PF Resole Condensation Chemistry 174
Accelerators for PF Resole Condensation 176
Extenders or Partial Phenol Replacement 179
Sugar and Other Carbohydrates 179
Tannins 179
Lignin 180
Urea 181
Resorcinol 181
Wood Pyrolysis Oils 182
New or Alternative Technologies 182
Hybrid Systems 182
PF-MDI Adhesive Systems for Wood Composites 182
PUF Systems 184
Proteinaceous Natural Component Modified Phenol-Formaldehyde Resin 185
Protein-Based Systems 185
MUF/MUpF 186
MDI 186
References 187
Chapter 9: Foam 192
Introduction 193
Foam Structure 193
Foam Applications 195
Floral Foam 195
Insulation Foam 196
Mining Foam 198
New Applications for Phenolic Foams 198
Foam Manufacturing Process 200
Batch Processes 200
Continuous Processes 201
Low Pressure Mixing Heads 201
High Pressure Mixing Heads 201
Foam Formulations 203
Foam Resins 204
Emulsifiers 205
Blowing Agents 205
Acid Catalysts 206
Other Additives 206
Foam Testing 207
Fire Testing 208
Insulation Efficiency/Lambda Value 208
Strength Testing 209
Determination of Saturation Properties 210
Determination of Open/Closed Cell Content 210
References 210
Chapter 10: Mineral Wool Insulation Binders 212
Introduction 213
Global Aspects 213
Glossary of Basic Insulation Terms 214
Types of Mineral Wool 217
Glass Wool 217
Stone Wool 221
Slag Wool 221
Application and Properties of Mineral Wool 221
Binders for Non-Woven Mineral Wool Insulation 223
Phenolic Resins for Insulating Mineral Wool 224
Raw Materials for Phenolic Resins 224
General Chemistry of Phenolic Resins for Insulating Mineral Wool 224
Catalysts 227
Organic Catalyzed Resins 227
Inorganic Catalysed Resins 228
Urea 228
Properties of the Insulation Resins 232
Ammonium Hydroxide 234
De-dusting Oil 237
Emulsifier 237
Silanes 237
Ammonium Sulfate 238
Extenders 242
Water 243
References 243
Chapter 11: Laminates 246
Introduction 246
Surfacing Materials 247
Paper/Resin-Based Surface Materials 247
Decorative Surface Markets 249
Decorative Laminates 251
Impregnation Process 252
Core Layers 252
Decorative Surface 253
Pressing Process 253
HPL Production with Multi Opening Presses 254
HPL Production with Short Cycle Presses 256
CPL Production with Isobaric Continuous Double Band Press 257
Special Features of CPL Process 258
New Developments 258
Laminate Properties 259
Surfaces 259
Core Layers 259
Standard HPL Laminates 259
Post Formable Laminates 260
Compact Boards 260
Fire-Retardant Laminates 261
Trends 261
Miscellaneous Impregnation Applications 262
Industrial Filter Inserts 262
Battery Separators 263
PF-Impregnated Paper for Cooling Pads 263
References 264
12: Composites 265
Introduction 266
Composites Market Segments 267
Resin Developments 268
Fiber Developments 269
Composite Fabrication Processes 271
Introduction 271
Pre-preg 271
Aircraft Interiors 273
Cargo Liners 276
Railway 276
Ballistics 277
Carbon-Phenolic Composites 279
Aircraft Friction 279
Ablatives 281
Process Developments 282
Honeycomb 284
Filament Winding 285
Pultrusion 291
Compression Molding 294
SMC 295
BMC 296
Infusion Molding 298
Resin Transfer Molding 298
Vacuum Assist Resin Transfer Molding 299
SCRIMP 300
Hand Lay-Up 302
Summary/Trends 305
References 306
Chapter 13: Abrasives 309
Introduction 310
Market 313
Raw Materials 315
Grain 315
Filler 319
Glass Cloth 319
Backing Material 320
Structure of Abrasive Products 322
Bonded Abrasive 324
Manufacturing Process 324
Mixing Process 324
Molding 326
Cure 328
Phenolic Resin for Bonded Abrasive 329
Liquid Resin 332
Powder Resin 333
Cut-off Wheels 334
Depressed Center Grinding Wheels (Rough Grinding Wheels) 335
Grinding Wheel with Coolant Water 336
Heavy-Duty Grinding Wheel 336
Diamond Grinding Wheels and CBN Grinding Wheels 338
Others 338
Coated Abrasives 339
Manufacturing Process 339
Make Coat 341
Size Coat 341
Heating 342
Processing 342
Phenolic Resin for Coated Abrasive 343
Abrasive Cloth (Abrasive Belt, Roll, Sheet, Flap Wheel) 343
Abrasive Paper (Sandpaper) 344
Non-woven Fabric 344
References 345
Chapter 14: Friction 346
Introduction 347
Application of Friction 348
Disk Pads are Classified into Five Types 349
Asbestos Type of Disk Pads 349
Semi-Metallic Type of Disk Pads 349
Low Steel Type of Disk Pads 349
Non-Asbestos Organic Type of Disk Pads 349
Carbon Silicon Brakes (SGL Carbon, Germany) 349
Brake Linings 350
Clutch Facings 350
Raw Materials 351
Disk Pads 351
Brake Lining 352
Clutch Facing 353
Manufacturing Process 353
Disk Pad 353
Brake Lining 354
Clutch Facing 354
Friction Requirements 356
Stability of Friction Coefficient in Each Temperature Region 356
Low Wear 356
Reduced Noise and Judder 356
Reduced Damage to the Rotor 357
Reduce the Burden on the Environment 357
Design and Control of Phenolic Resin Properties 357
Evaluation Method of Brake 361
References 361
Chapter 15: Photoresists 363
History of Photoresists 363
DNQ - Novolak Photoresists 364
Phenolic Resins for Photoresist 366
Meta-Para Cresol Novolaks 366
Analysis of Phenolic Resins for Photoresist 368
Relationship of Resin Properties and Photoresist Properties 369
Improvement of Photoresist Properties 369
Improvement by Changing the Type of Phenol Monomers 369
Enhanced Behavior with Different Aldehydes 372
Improvement in the Control of Resin Structure 374
Consistency 376
Photoresist Purity 377
Phenolic Resins for Semiconductor Photoresist 378
Phenolic Resin for LCD Photoresist 379
Summary 380
References 381
Chapter 16: Phenolic Molding Compounds 383
Introduction 384
Characteristics and Formulations 385
Novolak Phenolic Resins (Two-Stage Phenolic) 385
Single-Stage Phenolic Resin 386
Organic Fillers 386
Inorganic Fillers 386
Other Fillers 387
Lubricating Fillers 387
Sliding Wear Test Conditions 388
Fillers to Improve Toughness 388
Colorant Fillers 389
Lubricants 389
Production of Phenolic Molding Compounds 389
Molding Process 392
Basic Molding Methods 392
Compression Molding 392
Advantages 393
Limitations 393
Transfer Molding 393
Advantages 394
Limitations 394
Injection Molding 394
Advantages 396
Limitations 396
High Advantage Molding Process 396
High Temperature Molding 396
Advantages 396
Live Sprue Molding 397
Injection Compression 397
Test Methods for Phenolic Molding Materials 398
Standard Test Methods 398
Flowability Test 401
Orifice Flow Method [2] 401
Spiral Flow (Farrell Flow) Method [3] 402
Disk Flow Method [4] 402
Cup Flow Method [4, 5] 402
Torque Rheometer Method [6] 402
Reliability Test 403
Fatigue Test 403
Applications 404
Electrical Applications 404
Electronics Applications 406
Commutator Applications 406
Automotive Applications 408
Air Supply Systems 408
Intake Manifold 408
Throttle Bodies 409
Exhaust Gas Recycling Thermal Insulation 409
Cooling Systems 410
Fuel Systems 411
Fuel Pump Housing/Impeller 411
Brake Systems 411
Disc Brake Caliper Piston 411
Antilock Braking System Components 412
Pulleys 413
Cog Belt Pulleys - Belt Driven Camshaft 414
Multi-V Pulleys 414
Transmission Systems 414
Torque Converter Stator and Thrust Washers 414
Clutch Actuation Pistons 415
Valve Block for Dual Clutch Transmissions 416
Automotive DC Motor Systems 416
Comparison with Other Materials 417
Comparison with Engineering Thermoplastics 417
Comparison with Die Cast Aluminum 420
New Phenolic Molding Compounds 422
Long Fiber Reinforced Materials 422
Carbon Fiber Reinforced Phenolic Molding Compounds 425
New Technical Developments 428
Finite Element 428
Component Loads and Constraints 429
Models and Methods 429
Calculation Data 430
Result Interpretation 431
Flow Simulation 431
3D Flow Simulation Software 431
Model, Sprue, Runners, and Gates 431
Mold Cavities Orientation 432
Mold and Insert Temperatures 433
Air Vents 433
Injection Cycle Profile 433
Result Interpretations 433
Mold Filling and Mass Temperature 433
Tracer Particles 433
Encapsulated Air 434
Degree of Cure 434
Fatigue Fracture Behavior of Glass-Filled Phenolic Compounds 435
Recycling 437
References 437
Chapter 17: Alkyl Phenol Resins in Adhesive and Rubber Applications 438
Introduction 438
Phenolic Resins in Rubber Based Adhesives 438
Chloroprene Rubber Based Contact Adhesives 439
Nitrile Butadiene Rubber Based Adhesives 440
Other Adhesives that Use Phenolic Resins 440
Rubber Based Pressure Sensitive Adhesives 440
Phenolic Resins in Rubber Compounding 441
Rubber Tackifier Resins 442
Rubber Curing Resins 444
Rubber Reinforcing Resins 447
Adhesion Promoters for Rubber Compounds 448
Summary 449
References 449
Chapter 18: Foundry 450
Introduction (Economic and Technical Survey) 450
Hot Curing Processes 461
The Shell Molding Process 461
Sand Coating (Conditioning) 462
Hot Coating 462
Warm Coating 463
Fabrication of Cores and Shells 463
The Hot-Box Process 465
The Warm-Box Process 467
Cold Curing with Direct Addition of a Curing Agent (No Bake Process) 468
Acid Curing 469
No Bake Curing with Added Esters 473
Effect of Alkali Metals on Mechanical Reclamation 474
Effect of Alkali Metals on Thermal Reclamation 474
No Bake Process with Isocyanate Curing 475
Polyol Urethane No Bake 478
Alkyd Oil No Bake Process with Isocyanate Curing 480
Gas Curing Processes Using Phenolic Resin Binders 480
The Polyurethane Cold-Box Process 481
Biodiesel UCB 486
TEOS UCB 490
The Methyl Formate Process 492
The CO2-Resole Process 494
The Acetal Process 494
Other Gassing Processes 494
Hybrid UCB 495
Emissions from Phenolic Binder Systems 496
Low Emission Binders 497
General Remarks on Core/Mold Fabrication Processes Using Phenolic Resins 497
References 499
Chapter 19: Phenolic Resin for Refractories 502
Introduction 502
Methods of Classification 503
Chemical Composition 503
Refractory Shape 503
Refractory Manufacturing Process 505
Mixing 506
Molding 506
Heating/Firing Refractory Brick 506
Binder Used With Refractory 507
Applications of Refractory 507
Features of Phenolic Resin for Refractory 509
Ratio of Fixed Carbon 509
Environmental Impact 510
Carbonization Mechanism of Phenolic Resin 511
Use of Phenolic Resin for Refractories 513
Future Development 514
References 514
Chapter 20: Recycling 515
Introduction 516
Mechanical Recycling 516
Feedstock Recycling 517
Pyrolysis 517
Solvolysis/Hydrolysis 518
Supercritical or Subcritical Fluid Technology 518
Energy Recovery 521
Summary 521
References 522
Chapter 21: Future Aspects 523
All is Not Negative for Phenolic Resins as they Enter the Twenty-first Century! 524
: Index 527