reinforced plastics - · pdf filecanada ..... denmark ... eva (ethylene-vinyl ......

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 ......................




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



Process Discussion . . . . ................. 363



Cost Estimates . . . . . . ................. 365



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 .......................


Continuous Lamination of Flat and Corrugated Sheeting . Prepregs ........................ Sandwich Structures ..................

Pultrusion .......................


Continuous Lamination of Flat and Corrugated Fiber Glass Reinforced Sheeting ..................

Prepregs ........................ Sandwich Structures ..................

Pultrusion .......................


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

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