Report No. 51
REINFORCED PLASTICS
by WING SIEN FONG
August 1969
A private report by the
PROCESS ECONOMICS PROGRAM
STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
CONTENTS
1 INTRODUCTION . . . . . . . . . . , . . . . . . . . . . . . 1
2 SUMMARY a..............,......... 3
3 INDUSTRY STATUS .....................
Introduction .......................
United States ......................
Aircraft ........................ Boats ......................... Construction ...................... Electrical and Electronics ...............
Housewares and Consumer Products ............
Pipes ......................... Recreation .......................
Rockets, Missiles, and Weaponry ............
Transportation .....................
Vessels ........................
Process Equipment (Excluding Vessels and Piping) ....
Underwater Vehicles ..................
Australia ........................ Belgium ......................... Canada ..........................
Denmark ......................... France .......................... Finland ......................... Germany (East) ...................... Germany (West) ...................... Israel .......................... Italy .......................... Japan .......................... Latin America ......................
The Netherlands .....................
Norway .......................... South Africa .......................
Sweden .......................... United Kingdom ......................
USSR ........................... Licensing ........................ Product Failure .....................
15
15 16 25 37 38 40 41 41 42 42 47 47 49 49 50 51 51 52 52 52 52 53 53 53 54 55 55 56 56 56 57 57 57 58
iii
CONTENTS
4 PRINCIPLES OF FIBROUS REINFORCEMENT OF PLASTICS ......
Introduction ........................
Strengthening Mechanism ................... Tensile Load .......................
Compressive Load . . . .................
Laminated Sheets . . . .................
State of Stress . . . . .................
Stress Distribution . .................
Fiber Spacing and Geometry ................
Cure-Shrinkage of Resin ................. Voids ..........................
Interface ......................... Theories ......................... Wettability and Adhesion .................
Coupling Agents .....................
Fracture Behavior .....................
Fracture Initiation and Propagation ...........
Mode of Failure .....................
Corrosion ........................
Resin .................... 99
Reinforcement ................ . . . . . . 154
Temperature ................. . 155
Thermal Properties .............. . . . . . . 155
Weatherability, Water Absorption, and Chemical Resistance 156
Creep .................... ...... 157
Fatigue ................... ...... 157
Impact ................... ...... 157
Electric Properties ............. 158
Radiation .................. ...... 158
Density and Appearance ............ ...... 158
Safety Factor ................ ...... 159
5 GENERAL PROPERTIES AND FACTORS AFFECTING THEM .......
6 RESINS ...........................
ABS (Acrylonitrile-Butadiene-Styrene) ...........
Acetal Resins .......................
Acrylic Resins .......................
Alkyd Resins ........................
Ally1 Resins ........................
Amino Resins ........................ Chlorinated Polyether ...................
61
61
61 61
69 70 70 70 72 72 73 75 75 76 79 84 84 88 89
91
161
161 167 167 168 169 169 170
iv
CONTENTS
6 (Continued)
Epoxy Resins . . . . . . , . EVA (Ethylene-Vinyl Acetate) Fluoroplastics . . . . . . . Furane Resins . . . . . . . High-Temperature Resins . .
Polyimides . . . , . . . . Polybenzimidazole . . . . Polybenzothiazole . . . . Polyquinoxalines , . , . . Borane-Based Resins . . .
Ionomer Resins . . . . . . . Parylene Polymers . . . . . Phenolics . . . . , . . . . Phenoxy Resins . . , . . . . Polyallomer Copolymers . . . Polyamides (Nylons) . . . . Polycarbonate Resins . . . . Polyethylenes . . . . . . . Polyphenylene Oxide Resins . Polypropylenes . . . . . . . Polystyrenes . . . . . . . . Polysulfones . . . . . . . . Polyurethane Resins . . . . Polyvinyl Chloride Resins . Silicones . . . . . . . . . Unsaturated Polyester Resins
............... 171
............... 173
............... 173
............... 175
............... 175
............... 176
............... 177
............... 177
............... 177
............... 177
............... 178
............... 178
............... 179
............... 180
............... 181
............... 181
............... 182
............... 183
............... 184
............... 185
............... 186
............... 187
............... 188 ............... 188
............... 189
............... 190
7 REINFORCEMENTS ......................
Glass .......................... Asbestos ......................... Boron Fibers ....................... Carbon and Graphite Fibers ................ Whiskers ......................... Quartz and Silica Fibers ................. Ceramic Fibers ...................... Metal Fibers ....................... Natural Organic Fibers .................. Synthetic Organic Fibers .................
195
195 205 206 208 210 212 213 215 216 217
V
CONTENTS
8 COMPRESSION MOLDING ....................
Advantages and Limitations .................
Types of Compression Molding ................
Presses ..........................
Molds ........................... General Molding Procedure and Conditions ..........
Quality Control .....................
Safety .......................... Cleaning of Equipment ..................
Process Economics . . ................... Mat Molding . . . . . ...................
Review of Processes . ...................
Process Description ................... Process Discussion . ................... Cost Estimates . . . ...................
Premix Molding . , . . ................... Review of Processes ................... Process Description ................... Process Discussion ....................
Cost Estimates ......................
Prepreg Molding ......................
Review of Processes ...................
Process Description ...................
Process Discussion ....................
Cost Estimates ......................
Preform Molding ......................
Review of Processes ...................
Process Description ...................
Process Discussion ....................
Cost Estimates ......................
9 THE LAY-UP METHODS .....................
Introduction ........................
Review of Processes ....................
Resins . . . . . ..................... Reinforcement . ..................... Prepregs . . . . ..................... Gel Coat . . . . ..................... Colorants . . . ..................... Releasing Agents ..................... Hand Lay-Up . . ..................... Spray-Up . . . . ..................... Pressure Lay-Up .....................
219
219 220
223
224 227 229 229 229 229 235 235 235 239 241 251 251
252 257 260 270 270 271 275 276 284 284 286 291 293
303
303 304 304 305 305 305 306 306 310 311 314
vi
CONTENTS
9 (Continued)
Process Descriptions .................... Making of the Mold ....................
Removal of the Finished Part ...............
Quality Control .....................
Finishing of Parts ....................
Safety Precautions ....................
Hand Lay-Up . . . . ...................
Spray-Up . . . . . . ...................
Vacuum-Bag Molding . ...................
Pressure-Bag Molding ...................
Autoclave Molding . ...................
Process Discussion . . ...................
Hand Lay-Up . . . . ...................
Spray-Up . . . . . . ...................
Pressure Lay-Up . . ...................
Cost Estimates . . . . ...................
10 ROTATIONAL MOLDING AND CENTRIFUGAL CASTING . . . . . . . . . 351
Introduction . . . . . . . ................. 351
Limitations and Advantages ................. 351
Review of Processes . . . ................. 352
Rotational Molding . . . ................. 352
Centrifugal Casting . . ................. 355
Process Description . . . ................. 355
Rotational Molding . . . ................. 355
Centrifugal Casting . . ................. 356
Process Discussion . . . . ................. 363
Rotational Molding . . . ................. 363
Centrifugal Casting . . ................. 364
Cost Estimates . . . . . . ................. 365
Rotational Molding . . . ................. 365
Centrifugal Casting . . ................. 366
11 FILAMENT WINDING. .....................
Introduction ........................ Review of Processes ....................
Process ......................... Resins .......................... Reinforcement ......................
Equipment ........................ Winding Pattern .....................
315
315
323 323 324 324 324 326 328 330 330 331 331 332 333 336
381
381 381 381 384 385 385 387
vii
CONTENTS
11 (Continued)
Tensioning ........................ 387
Mandrel ......................... 388
Type of Control ..................... 389
Process Description .................... 389
Process Discussion ..................... 393
Cost Estimates ....................... 395
12 INJECTION MOLDING . . . . . . . . . . . . . . . . . . . . . 403
Introduction ........................ 403
Review of Processes .................... 404
Process ......................... 404
Machine ......................... 406
Process Description .................... 408
Process Discussion ..................... 414
Cost Estimates ....................... 417
13 CONTINUOUS LAMINATION AND PULTRUSION . . . . . . . . . . . . 431
. 431
. 432 432
. 433 447
. 448
. 449
Introduction .......................
Review of Processes ...................
Continuous Lamination of Flat and Corrugated Sheeting . Prepregs ........................ Sandwich Structures ..................
Pultrusion .......................
Process Description ...................
Continuous Lamination of Flat and Corrugated Fiber Glass Reinforced Sheeting ..................
Prepregs ........................ Sandwich Structures ..................
Pultrusion .......................
Process Discussion ....................
Cost Estimates ......................
Continuous Lamination of Flat and Corrugated Fiber Glass Reinforced Sheeting ..................
Pultrusion .......................
Sandwich Structures ..................
Prepregs ........................
. 449
. 450
. 451
. 451
. 455
. 458
. 458
. 460
. 461
. 461
APPENDIX A COST BASIS...................................... 473
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
viii
ILLUSTRATIONS
3.1
3.2
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
8.10
8.11 Matched Metal Die Prepreg Molding . . , . . . . . . . . . 273
8.12 Matched Metal Die Prepreg Molding Effect of Raw Material, Utilities, Fixed Capital-Related and Labor-Related Costs on Production Cost . . . . . . . .
8.13
8.14
8.15 Matched Metal Die Preform Molding . . . . . . . . . . . . 289
Actual and Projected Consumption of Reinforced Plastics in United States . . . . . . . . . . . . . . . . . . . . . .
Production of Reinforced Plastic Pipes in United States .
Matched Metal Die Mat Molding . . . . . . . . . . . . . .
Matched Metal Die Mat Molding Effect of Raw Material on Production Cost . . . . . . . .
Matched Metal Die Mat Molding Effect of Utilities, Fixed Capital-Related and Labor- Related Costs on Production Cost . . . . . . . . . . . . .
Matched Metal Die Mat Molding Effect of Molding Cycle Time on Production Cost . . . . .
Matched Metal Die Mat Molding Effect of Operating Rate on Product Cost . . . . . . . . .
Matched Metal Die Premix Molding . . . . . . . . . . . . .
Matched Metal Die Premix Molding Effect of Raw Material on Production Cost . . . . . . . .
Matched Metal Die Premix Molding Effect of Utilities, Fixed Capital-Related and Labor-Related Costs on Production . . . . . . . . . . . .
Matched Metal Die Premix Molding Effect of Molding Cycle Time on Production Cost . . . . .
Matched Metal Die Premix Molding Effect of Operating Rate and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . .
Matched Metal Die Prepreg Molding Effect of Molding Cycle Time on Production Cost . . . . .
Matched Metal Die Prepreg Molding Effect of Operating Rate and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . .
18
44
237
247
248
249
250
255
266
267
268
269
281
282
283
ix
ILLUSTRATIONS
8.16
8.17
8.18
8.19
9.1
9.2
10.1
10.2
10.3
10.4
10.5
10.6
11.1
11.2
11.3
12.1
12.2
Matched Metal Die Preform Molding
Effect of Raw Material Cost on Production Cost . . . . . .
Matched Metal Die Preform Molding Effect of Utilities, Fixed Capital-Related and Labor-
Related Costs on Production Cost . . . . . . . . . . . . .
Matched Metal Die Preform Molding Effect of Molding Cycle Time on Production Cost . . . . .
Matched Metal Die Preform Molding Effect of Operating Rate and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . .
Reinforced Plastics by Hand Lay-Up, Spray-Up, Vacuum Bag, Pressure Bag, and Autoclave Moldings . . . . . . . .
Lay-Up Effect of Manual Output on Production Cost . . . . . . . .
Rotational Molding of Glass-Reinforced Thermoplastics . .
Centrifugal Casting of Reinforced Plastic Pipes or Other Cylindrical Products . . . . . . . . . . . . . . . .
Rotational Molding of Glass Fiber Reinforced Thermoplastics Effect of Cycle Time on Production Cost . . . . . . . . .
Rotational Molding of Glass Fiber Reinforced Thermoplastics Effect of Operating Rate on Production Cost . . . . . . .
Centrifugal Casting of Reinforced Plastic Pipes Effect of Cycle Time on Production Cost . . . . . . . . .
Centrifugal Casting of Reinforced Plastic Pipes Effect of Operating Rate on Production Cost . . . . . . .
Filament Winding . . . . . . . . . . . . . . . . . . . . .
Filament Winding Effect of Cycle Time on Production Cost . . . . . . . . .
Filament Winding Effect of Operating Rate on Production Cost . . . . . . .
Injection Molding of Glass-Fiber Reinforced Thermoplastics
Injection Molding of Glass-Fiber Reinforced Thermoplastics (Polystyrene) Effect of Operating Rate and Production Volume on the Production Cost . . . . . . . . . . . . . . . . . . . . .
299
300
301
302
317
349
359
361
371
372
379
380
391
399
400
411
429
X
ILLUSTRATIONS
13.1 Continuous Lamination and Pultrusion Flowsheet . . . . . . 453
13.2 Continuous Lamination of Sheeting Effect of Raw Material, Labor, and Fixed Capital Related
Costs on Production Cost . . . . . . . . . . . . . . . . . 464
13.3 Continuous Lamination of Sheeting Effect of Production Speed on Production Cost . . . . . . . 465
13.4 Continuous Lamination of Sheeting Effect of Operating Rate on Production Cost . . . . . . . . 466
13.5 Pultrusion Effect of Raw Material, Labor, and Fixed Capital Related Costs on Production Cost . . . . . . . . . . . . . . . . . 469
13.6 Pultrusion Effect of Production Rate on Production Cost . . . . . . . 470
13.7 Pultrusion Effect of Operating Rate on Production Cost . . . . . . . . 471
xi
TABLES
2.1
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
5.1
5.2
5.3
5.4
5.5
Summary of the Process Economics for Various Reinforced Plastics Fabrication Processes Under Certain Assumptions . . . . . . . . , . . . . . . . . . . , . . . 7
Pattern of Consumption of Reinforced Plastics in the
United States . . . . . . . . . . . . . . . . . . . . . . 17
Suppliers of Reinforced Thermosetting Molding Compounds and Premixes . . . . . . . . . . . . . . . . . . . , . . . 21
Suppliers of Preimpregnated Plastics U.S. Companies . . . . . . . . . . . . . . . . . . . . . . 23
Suppliers of Reinforced Thermoplastics U.S. Companies . . . . . . . . . . . . . . . . . . . . . . 27
Glass-Reinforced Thermoplastics Price Ranges , . . . . . . 29
Trade Names of Reinforced Plastics and Related Products . 30
Trade Names of Reinforcements . . . . . . . . . . . . . . 35
Trade Names of Some of the Fabrication Processes and Equipment . . . . . . . . . . . . . . . . . . . . . . . . 36
Some Standard Stock Items of Glass-Fiber Reinforced Plastic Structural Shapes . . . . . . . . . . . . . . . . . . . . 39
Major Producers of Machine-Made Reinforced Plastic Pipes . 43
Typical Properties and Price Range of Some Standard Reinforced Plastic Pipes . . . . . . . . . . . . . . . . . 45
Some Reported Licensing Arrangements for Reinforced Plastics......................... 59
Typical Properties of Various Reinforced Plastics . . . . 93
Effects of Various Factors on the Mechanical Properties of Reinforced Thermosets . . . . . . . . . . . . . . . . . . 101
Effects of Glass Type, Form, Geometry, and Sizing on the Mechanical Properties of Reinforced Plastics . . . . . . . 115
Effects of Environmental Influences, Composition, Glass
Type, Fiber Orientation, and Surfacing Mat on the Mechanical Properties of Reinforced Plastics . . . . . . . 121
Effects of Molding Methods, Molding Conditions and Resin Properties on the Mechanical and Electrical Properties of Reinforced Plastics . . . . . . . . , . . . . . . . . . . 129
xiii
TABLES
5.6
5.7
5.8
6.1
6.2
7.1
7.2
7.3
7.4
7.5
7.6
7.7
8.1
8.2
8.3
8.4
8.5
8.6
Effects of Reinforcements Other Than Glass Fibers on Mechanical and Thermal Properties of Reinforced Plastics . 135
Effects of Void Content, Temperature, and Pressure for High Temperature Polymide Systems on the Mechanical and
Electrical Properties of Reinforced Plastics . . . . . . . 137
Effects of Various Factors on the Properties of Reinforced Thermoplastics . . . . . . . . . . . . . . . . 139
Properties, Prices, and Availability of Reinforced
Molding Compounds of Some Resins . . . . . . . . . . . . . 163
Commercial Classification of Polyester Resins . . . . . . 193
Typical Chemical Compositions of Various Types of Glass . 197
Typical Properties of Various Types of Glass Fibers . . . 199
Properties of Chrysotile and Crocidolite . . . . . . . . . 207
Typical Physical Properties of Some Whiskers . . . . . . . 211
Typical Physical Properties of Some Inorganic Fibers . . . 214
Typical Physical Properties of Some Natural Organic Fibers 217
Typical Physical Properties of Some Synthetic Organic Fibers.......................... 218
Compression Molding
Approximate Usable Area and Prices of Commercial Compres- sion Presses for Reinforced Plastics Molding . . . . . . . 232
Compression Molding Summary of Advantages, Limitations, Molding Characteristics and Typical Products of Matched Metal Die Mat, Premix, Prepreg, and Preform Molding . . . . . . . . . . . . . . . 233
Matched Metal Die Mat Molding Major Process Equipment and Utilities Summary . . . . . . 237
Matched Metal Die Mat Molding Total Capital Investment . . . . . . . . . . . . . . . . . 243
Matched Metal Die Mat Molding Production Costs . . . . . . . . . . . . . . . . . . . . . 245
Matched Metal Die Premix Molding Major Process Equipment and Utilities Summary . . . . . . 255
xiv
TABLES
8.7
8.8
8.9
8.10
8.11
8.12
8.13
8.14
8.15
8.16
9.1
9.2
9.3
9.4 Lay-Up Methods
9.5
9.6
Total Capital Investment . . . . . . . . . . . . . . . . .
Hand Lay-Up of Reinforced Plastics Production Costs . . . . . . . . . . . . . . . . . . . . .
Spray-Up of Reinforced Plastics Production Costs . . . . . . . . . . . . . . . . . . . . .
Matched Metal Die Premix Molding Total Capital Investment . . . . . . . . . , . . . . . . .
Matched Metal Die Premix Molding Production Costs . . . . . . . . . . . . . . . . . . . . .
Matched Metal Die Premix Molding Approximate Costs for Rectangular Trough Mixers . . . . .
Matched Metal Die Premix Molding Extruders for Premix Molding Compound . . . . . . . . . .
Matched Metal Die Prepreg Molding Major Process Equipment and Utilities Summary . . . . . .
Matched Metal Die Prepreg Molding Total Capital Investment . . . . . . . . . . . . . . . . .
Matched Metal Die Prepreg Molding Production Costs . . . . . . . . . . . . . . . . . . , . .
Matched Metal Die Preform Molding Major Process Equipment and Utilities Summary . . . . . .
Matched Metal Die Preform Molding Total Capital Investment . . . . . . . . . . . . . . . . .
Matched Metal Die Preform Molding Production Costs . . . . . . . . . . . . . . . . . . . . .
The Lay-Up Methods Advantages and Disadvantages in Hand Lay-Up, Spray-Up,
Vacuum Bag, Pressure Bag, and Autoclave Moldings of Reinforced Plastics . . . . . . . . . . . . . . . . . . .
Colorants for Unsaturated Polyester and Epoxy Resins . . .
Reinforced Plastics by Hand Lay-Up, Spray-Up, Vacuum Bag, Pressure Bag, and Autoclave Moldings Major Process Equipment List . . . . . . . . . . . . . . .
262
263
265
265
273
278
279
289
295
297
307
309
317
341
343
344
xv
TABLES
9.7
9.8
10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
11.1
11.2
11.3
11.4
12.1
Vacuum Bag, Pressure Bag, Autoclave Molding of Reinforced
Plastics Via Hand Lay-Up Production Costs . . . . . . . .
Vacuum Bag, Pressure Bag, Autoclave Molding of Reinforced Plastics Via Spray-Up Production Costs . . . . . . . . . . . . . . . . . . . . .
Rotational Molding of Glass-Reinforced Thermoplastics Major Process Equipment and Utilities Summary . . . . . .
Centrifugal Casting of Reinforced Plastic Pipes or Other Cylindrical Products Major Process Equipment and Utilities Summary . . . . . .
Rotational Molding of Glass-Reinforced Thermoplastics Total Capital Investment . . . . . . . . . . . . . . . . .
Rotational Molding of Glass-Fiber Reinforced Thermoplastics Production Cost . . . . . . . . . . . . . . . . . . . . .
Rotational Molding of Glass-Reinforced Thermoplastics Approximate Prices for Various Commercial Standard Rotational Molding Machines . . . . . . . . . . . . . . .
Centrifugal Casting of Reinforced Plastic Pipes or Other Cylindrical Products . . . . . . . . . . . . . . . . . . .
Centrifugal Casting of Reinforced Plastic Pipes or Other Cylindrical Products Total Capital Investment . . . . . . . . . . . . . . . . .
Centrifugal Casting of Reinforced Plastic Pipes or Other Cylindrical Products Production Cost . . . . . . . . . . . . . . . . . . , . .
Filament Winding Major Process Equipment and Utility Summary . . . . . . .
Filament Winding Total Capital Investment . . . . . . . . . . . . . . . . .
Filament Winding Production Cost . . . . . . . . . . . . . . . . . . . . .
Filament Winding Approximate Prices for Various Filament Winding Machines .
Injection Molding of Glass-Fiber Reinforced Thermoplastics Major Process Equipment and Utilities Summary . . . . . .
345
347
359
361
368
369
373
374
375
377
391
397
398
401
411
xvi
TABLES
12.2
12.3
12.4
12.5
12.6
12.7
13.1
13.2
13.3
13.4
13.5
13.6
13.7
13.8
Injection Molding of Glass-Fiber Reinforced Thermoplastics Conditions for Molding . . . . . . . . . . . . . . . . . . 413
Injection Molding of Glass-Fiber Reinforced Thermoplastics
Total Capital Investment . . . . . . . . . . . . . . . . . 421
Injection Molding of Glass-Fiber Reinforced Thermoplastics (Polystyrene) Production Cost for the Commercial Reinforced Pellet Process . . . . . . . . . . . . . . . . . . . . . . . . . . 423
Injection Molding of 3% Glass-Fiber Reinforced Thermo- plastics (Polystyrene) Production Costs for the Super-concentrate Process . . . .
Injection Molding of 3046 Glass-Fiber Reinforced Thermo- plastics (Polystyrene)
425
Production Cost for the Direct-Injection Process . . . . . 427
Injection Molding 430
Continuous Lamination and Pultrusion Preparation Methods for Reinforced Plastic Sheet . . . . . . . . . . . . . . .
Continuous Lamination and Pultrusion Compositions and Preparation Methods for Prepregs . . . . . . . . . . . . .
435
441
Continuous Lamination of Flat and Corrugated Fiberglass Reinforced Sheet Major Process Equipment and Utility Summary . . . . . . .
Pultrusion Major Process Equipment and Utility Summary . . . . . . .
Continuous Lamination of Flat and Corrugated Fiberglass Reinforced Sheet Total Capital Investment . . . . . . . . . . . . . . . . .
Continuous Lamination of Flat and Corrugated Fiberglass Reinforced Sheet Production Costs . . . . . . . . . . . . . . . . . . . . .
Pultrusion Total Capital Investment . . . . . . . . . . . . . . . . .
Pultrusion
452
453
462
463
467
Production Costs . . . . . . . . . . . . , . . . . . . . . 468
xvii