Chapter 1 Structure of the Carbon Atom ........................................ 1 1.1. Introduction to the Element Carbon, its Isotopes and Allotropes .......... 1 1.2. Structure of Carbon ...................................................... 2 1.2.1. Structure of the Atom ............................................. 2 1.2.2. Atomic Spectra and Quantum Theory ................................. 2 1.2.3. Directional Characteristics of Atomic Orbitals .................... 6 1.2.4. Hybridization of Atomic Orbitals .................................. 7 1.2.5. Covalence and Molecular Orbitals .................................. 9 References ................................................................... 13 Chapter 2 The Forms of Carbon ................................................ 15 2.1. The Allotropes of Carbon ............................................... 15 2.2. The Carbon Phase Diagram ............................................... 16 2.3. Diamond ................................................................ 17 2.3.1. Occurrence, Production and Uses of Diamond ...................... 17 2.3.1.1. Natural diamonds ....................................... 17 2.3.1.2. High pressure synthetic diamonds ....................... 17 2.3.1.3. Polycrystalline diamond (PCD) .......................... 18 2.3.1.4. Chemical Vapor Deposition (CVD) diamond ................ 18 2.3.1.5. Diamond-like carbon (DLC) .............................. 18 2.3.2. Classification of Diamonds ...................................... 19 2.3.3. Identification of Diamond ....................................... 19 2.3.4. The Crystal Structure of Diamond ................................ 19 2.3.5. The Properties of Diamond ....................................... 20 2.3.5.1. Density ................................................ 20 2.3.5.2. Mechanical properties .................................. 22 2.3.5.2.1. Hardness .................................... 22 2.3.5.2.2. Friction .................................... 22 2.3.5.2.3. Elastic properties .......................... 22 2.3.5.2.4. Strength .................................... 23 2.3.5.3. Thermal properties ..................................... 23 2.3.5.4. Optical properties ..................................... 23 2.3.5.5. Electrical properties .................................. 23 2.3.5.6. Graphitization ......................................... 23 2.3.5.7. Chemical resistance .................................... 23 2.4. Graphite ............................................................... 24 2.4.1. Introduction .................................................... 24 2.4.2. Occurrence, Production and Uses of Graphite ..................... 24 2.4.2.1. Natural graphite ....................................... 24 2.4.2.2. Kish graphite .......................................... 24 2.4.2.3. Synthetic graphite ..................................... 25 2.4.3. Structure of Graphite ........................................... 27 2.4.4. The Properties of Graphite ...................................... 31 2.4.4.1. Density ............................................... 31 2.4.4.2. Mechanical properties ................................. 32 2.4.4.2.1. Elastic properties ......................... 33 2.4.4.3. Thermal properties .................................... 35 2.4.4.4. Electrical properties ................................. 35 2.4.4.5. Chemical resistance ................................... 36 2.5. Pyrolytic Carbon and Pyrolytic Graphite ................................ 38 2.6. Glass-like Carbon ...................................................... 41 2.7. Carbon Fibers .......................................................... 42 2.8. Graphite Whiskers ...................................................... 42 2.9. Vapor-Grown Carbon Fibers (VGCF) and Catalytic Chemical Vapor-Deposited (CCVD) Filaments .............................. 43 2.10. Other Forms of Carbon .................................................. 44 2.10.1. Carbon Black ................................................... 44 2.10.2. Charcoal ....................................................... 45 2.10.3. Coal ........................................................... 45 2.10.4. Coke ........................................................... 46 2.10.5. Soot ........................................................... 46 2.11. New Forms of Carbon .................................................... 46 2.11.1. Fullerenes ..................................................... 46 2.11.1.1. Discovery and production of fullerenes ............... 46 2.11.1.2. Properties and uses of fullerenes .................... 53 2.11.2. Carbon. Nanotubes .............................................. 56 2.11.2.1. Discovery and production of carbon nanotubes ......... 56 2.11.3. Hyperfullerenes ................................................ 59 2.12. Summary of Allotropic Forms of Carbon .................................. 60 References ................................................................... 60 Chapter 3 History and Early Development of Carbon Fibers ..................... 65 3.1. The Early Inventors ..................................................... 65 3.2. Work in the USA ......................................................... 66 3.2.1. Black "Orion" .................................................... 66 3.2.2. Some Early US Carbon Fibers ...................................... 67 3.2.3. More Reent US Carbon Fibers ...................................... 71 3.3. Work in Japan ........................................................... 71 3.3.1. Early Work in Japan with PAN Precursor ........................... 71 3.3.2. Work in Japan with Pitch Precursors .............................. 72 3.4. Work in the UK with PAN Precursors ...................................... 72 3.4.1. Work at RAE, Farnborough ......................................... 72 3.4.1.1. The RAE work with carbon fiber and cross-licencing of their patent ......................................... 72 3.4.1.2. Surface treatment ....................................... 78 3.4.1.3. Testing and properties of single filaments and composites .......................................... 78 3.4.1.4. Composite fabrication ................................... 79 3.4.1.5. Friction and wear ....................................... 79 3.4.2. Work at the Atomic Energy Research Establishment, Harwell ........ 79 3.4.2.1. Fiber production ........................................ 79 3.4.2.2. Surface treatment ....................................... 84 3.4.2.3. Testing and properties of single filaments and composites .......................................... 84 3.4.2.4. Carbon fiber reinforced ceramics, glass and cement ...... 86 3.4.2.5. Carbon fiber reinforced metal composites ................ 87 3.4.2.6. Composite fabrication and design ........................ 89 3.4.3. Work at Rolls Royce, Derby ....................................... 89 3.4.3.1. Fiber production ........................................ 89 3.4.3.2. Factors affecting tensile strength of carbon fibers ..... 91 3.4.3.3. Resin formulation and composite fabrication ............. 92 3.4.3.4. Carbon fiber reinforced metal composites ................ 97 3.4.4. Work at Morganite Modmor, London ................................. 97 3.4.5. Work at Courtaulds, Coventry ..................................... 98 3.4.5.1. Carbon fiber production ................................. 98 3.4.5.2. Early work with X-ray diffraction to establish structure .............................................. 100 3.4.5.3. Precursor technology ................................... 101 3.4.5.4. Oxidation stage ........................................ 103 3.4.5.5. Surface treatment ...................................... 111 3.4.5.6. Testing and properties of virgin carbon fiber and composites ......................................... 112 3.4.5.7. Production procedures using carbon fiber ............... 112 3.4.5.8. Use and design of carbon fiber in composite materials .............................................. 113 3.5. Early UK Prepreggers ................................................... 114 3.5.1. Ciba (ARL) Ltd., Duxford ........................................ 114 3.5.2. Gourtaulds Ltd., Coventry ....................................... 114 3.5.3. Fothergill and Harvey Ltd. (F&H), Littleborough ................. 115 3.5.4. Rotorway Components Ltd., Clevedon .............................. 115 References .................................................................. 115 Chapter 4 Precursors for Carbon Fiber Manufacture ........................... 121 4.1. Introduction ........................................................... 121 4.2. PAN Precursors ......................................................... 121 4.2.1. History ......................................................... 122 4.2.1.1. Commercially available PAN fiber ....................... 122 4.2.2. Requirements for a PAN Precursor ................................ 123 4.2.3. Homopolymer PAN ................................................. 125 4.2.4. Comonomers ...................................................... 125 4.2.5. Methods of Polymerization ....................................... 130 4.2.5.1. Solution polymerization ................................ 130 4.2.5.2. Aqueous dispersion polymerization ...................... 134 4.2.6. Methods of Spinning ............................................. 136 4.2.6.1. Wet spinning ........................................... 136 4.2.6.2. Dry spinning ........................................... 136 4.2.6.3. Air gap spinning ....................................... 136 4.2.6.4. Melt spinning .......................................... 139 4.2.7. Processing Stages ............................................... 141 4.2.8. Modification of Spun Fiber ...................................... 145 4.2.8.1. Stretching ............................................. 145 4.2.8.2. Chemical treatment ..................................... 145 4.2.9. Structure of PAN Fibers ......................................... 146 4.3. Cellulosic Precursors .................................................. 148 4.3.1. Historical Introduction ......................................... 148 4.3.2. Viscose Rayon Process ........................................... 150 4.3.2.1. Introduction ........................................... 150 4.3.2.2. Steeping stage ......................................... 150 4.3.2.3. Shredding and ageing stages ............................ 151 4.3.2.4. Xanthation stage ....................................... 152 4.3.2.5. Mixing and ripening stages ............................. 152 4.3.2.6. Spinning stage ......................................... 152 4.3.2.7. Final treatment stage .................................. 153 4.3.3. Structure of Rayon Fibers ....................................... 154 4.4. Pitch Precursors ....................................................... 156 4.4.1. Introduction .................................................... 156 4.4.1.1. Petroleum pitch ........................................ 157 4.4.1.2. Coal tar pitch ......................................... 158 4.4.2. Characterization of the Pitch ................................... 158 4.4.3. Isotropic Pitches ............................................... 160 4.4.4. Preparation of Mesophase Pitches ................................ 161 4.4.4.1. Introduction ........................................... 161 4.4.4.2. Production of mesophase by pyrolysis ................... 162 4.4.4.3. Production of mesophase by solvent extraction .......... 164 4.4.4.4. Production of mesophase by hydrogenation ............... 164 4.4.4.5. Production of mesophase by catalytic modification ...... 165 4.4.5. Melt Spinning Mesophase Precursor Fibers ........................ 166 4.4.6. Structure of Pitch Precursor .................................... 171 4.5. Other Precursors ....................................................... 171 References .................................................................. 175 Chapter 5 Carbon Fiber Production using a PAN Precursor ..................... 185 5.1. Introduction .......................................................... 185 5.2. Carbon Fiber Manufacturers ............................................ 185 5.3. World Supply of PAN based Carbon Fiber ................................ 186 5.4. Manufacturing Costs of PAN based Carbon Fiber ......................... 187 5.5. Choice of Precursor ................................................... 191 5.6. Desirable Attributes of a PAN based Precursor Polymer and its Subsequent Production ............................................. 192 5.7. Types of PAN based Carbon Fiber ....................................... 194 5.8. A Carbon Fiber Production Line ........................................ 194 5.8.1. Precursor Station ............................................. 194 5.8.2. Oxidation ..................................................... 195 5.8.3. Oxidation Plant ............................................... 196 5.8.4. Removal of Effluent Gases Evolved in the Oxidation Process .... 200 5.8.5. Oxidized PAN Fiber ............................................ 200 5.8.6. Low Temperature Carbonization ................................. 200 5.8.7. High Temperature Carbonization ................................ 200 5.8.8. High Modulus Fiber Production ................................. 202 5.8.9. Shrinkage during the Carbon Fiber Process ..................... 203 5.8.10. Surface Treatment ............................................. 203 5.8.11. Sizing ........................................................ 203 5.8.12. Collection .................................................... 203 5.9. Fine Structure and Texture of PAN based Carbon Fibers ................. 203 5.10. Aspects of Stabilization .............................................. 215 5.10.1. Structure of PAN Fibers Thermally Stabilized at 350° C ........ 218 5.11. Aspects of Carbonization .............................................. 221 5.11.1. Methods of Increasing Fiber Modulus and Effect on Strength .... 225 5.11.1.1. Hot stretching ...................................... 225 5.11.1.2. Effects of neutron irradiation ...................... 228 5.11.1.3. Annealing in the presence of boron .................. 229 5.11.2. Carbon Fiber Yield ............................................ 230 5.12. Relation of Carbon Fiber Tensile Properties to Process Conditions ..... 230 5.13. Developments .......................................................... 232 5.13.1. Improvements in Carbon Fiber Properties ....................... 232 5.13.2. Alternative Polymer Formulations .............................. 232 5.13.3. A Family of Controlled Resistance Carbon Fibers ............... 233 5.14. A Review of the Stabilization of PAN Precursors ....................... 234 5.14.1. Stabilization Schemes of PAN and Associated Observations ...... 235 5.15. Mechanisms for the Carbonization Stages of PAN Carbon Fibers .......... 254 References .................................................................. 259 Chapter 6 Carbon Fiber Production using a Cellulosic based Precursor ........ 269 6.1. Introduction ........................................................... 269 6.2. Current Production ..................................................... 272 6.2.1. Choice of a Suitable Precursor .................................. 272 6.2.2. Pyrolysis ....................................................... 274 6.2.3. Carbonization ................................................... 279 6.2.4. Hot Stretching during Processing of Carbon Fiber ................ 279 6.2.5. Sizing .......................................................... 280 6.3. Mechanisms for the Pyrolysis and Carbonization Stages of Cellulosic based Precursors ............................................ 280 References .................................................................. 292 Chapter 7 Carbon Fiber Production using a Pitch based Precursor ............. 295 7.1. Introduction ........................................................... 295 7.2. Choice of Melt Spun Precursor .......................................... 295 7.3. The Manufacturing Process .............................................. 296 7.3.1. Stabilization (thermosetting) of Spun Fiber ..................... 296 7.3.2. Carbonization ................................................... 301 7.3.3. Graphitization .................................................. 303 7.3.4. Surface Treatment of Pitch based Carbon Fibers .................. 304 7.4. The Structural Ordering and Morphology of Mesophase Pitch Fibers ....... 305 7.4.1. Mechanisms Associated with the Preparation of Pitch Precursors ...................................................... 309 7.4.2. Mechanisms Associated with the Stabilization of Pitch Fiber Precursors ....................................... 320 7.4.3. Mechanisms Associated with the Carbonization of Pitch Fibers .... 321 References .................................................................. 322 Chapter 8 Production of Vapor Grown Carbon Fibers (VGCF) .................... 325 8.1. Introduction ........................................................... 325 8.2. Preparation of VGCF .................................................... 325 8.3. Growth Process ......................................................... 334 8.4. Mode of Tensile Failure ................................................ 339 8.5. Mechanical Properties .................................................. 339 References .................................................................. 343 Chapter 9 Surface Treatment and Sizing of Carbon Fibers ..................... 347 9.1. Introduction ........................................................... 347 9.2. Oxidative Processes .................................................... 347 9.2.1. Gas Phase Oxidation ............................................. 348 9.2.2. Liquid Phase Oxidation .......................................... 350 9.2.3. Anodic Oxidation ................................................ 352 9.3. Plasma ................................................................. 355 9.4. Non-oxidative Surface Treatment—Whiskerization ......................... 356 9.5. Effect of Surface Treatment on Fiber Properties ........................ 357 9.5.1. Introduction .................................................... 357 9.5.2. The Effects of Surface Treatment ................................ 358 9.5.3. Summary ......................................................... 362 9.6. Coupling Agents ........................................................ 363 9.7. Sizing Carbon Fiber .................................................... 363 9.7.1. Deposition from Solution of a Polymer onto the Fiber Surface .... 363 9.7.2. Deposition of a Polymer onto the Fiber Surface by Electrodeposition ............................................... 367 9.7.3. Deposition of a Polymer onto the Fiber Surface by Electropolymerization ................................ 369 References .................................................................. 370 Chapter 10 Guidelines for the Design of Equipment for Carbon Fiber Plant .... 377 10.1. Introduction ......................................................... 377 10.2. Precursor Handling ................................................... 377 10.3. Drive Systems ........................................................ 379 10.4. Ovens for Oxidation .................................................. 380 10.5. Removal of Effluent Gases Evolved in the Oxidation Process ........... 383 10.6. Application of an Antistatic Finish .................................. 384 10.7. Plaiter Table ........................................................ 384 10.8. LT Carbonization Furnace ............................................. 384 10.8.1. LT Furnace Gas Seals ......................................... 386 10.8.2. LT Furnace Insulation ........................................ 387 10.8.3. Element Materials for LT Furnaces ............................ 388 10.9. LT Furnace Exhaust Removal ........................................... 392 10.10. HT Carbonization Furnace ............................................. 395 10.10.1. HT Furnace Gas Seals ........................................ 396 10.10.2. HT Furnace Insulation ....................................... 396 10.10.3. Element Materials for HT Furnaces ........................... 397 10.11. Typical Calculations for the Design of an HT Furnace ................. 398 10.12. Sodium Removal ....................................................... 400 10.13. HM Heat Treatment Furnace ............................................ 401 10.13.1. HM Furnace Gas Seals ........................................ 401 10.13.2. HM Furnace Insulation ....................................... 402 10.13.3. HM Furnace Element Design ................................... 402 10.14. Surface Treatment .................................................... 403 10.15. Sizing ............................................................... 404 10.16. Drying ............................................................... 405 10.17. Online Collection .................................................... 409 10.18. Offline Winding ...................................................... 411 10.19. Packaging ............................................................ 415 10.20. Exhaust Systems ...................................................... 415 10.21. Dust Extraction ...................................................... 418 10.22. Application of Closed Circuit Television (CCTV) ...................... 420 References .................................................................. 420 Chapter 11 Operation of Carbon Fiber Plant and Safety Aspects ............... 421 11.1. Introduction ......................................................... 421 11.2. Serendipity .......................................................... 421 11.3. Maintenance .......................................................... 423 11.4. Protecting Electrical Equipment ...................................... 423 11.5. Air Flow Measurement ................................................. 424 11.5.1. Measurement of Pressure ...................................... 424 11.5.2. Determination of Velocity .................................... 424 11.5.3. Determination of Volume Flow ................................. 429 11.6. Collimation and Spreading of Oxidized and Carbonized Fiber ........... 433 11.6.1. Lateral Movement ............................................. 433 11.6.2. Lateral Expansion or Contraction ............................. 434 11.7. Splicing Small Tows .................................................. 435 11.8. Drive Systems and Rotating Rollers ................................... 436 11.9. Precursor Creel ...................................................... 438 11.10. Oxidation Plant ...................................................... 439 11.11. Pyrolysis Plant ...................................................... 440 11.12. Low Temperature Carbonization Furnace ................................ 440 11.13. High Temperature Carbonization Furnace ............................... 441 11.13.1. Calibration of Pyrometer .................................... 441 11.14. High Modulus Furnace ................................................. 442 11.15. Surface Treatment .................................................... 442 11.16. Sizing ............................................................... 443 11.17. Winding .............................................................. 443 11.18. Dealing with Emissions ............................................... 444 11.19. Treatment of Cyanide Effluent ........................................ 444 11.20. Protecting the Environment ........................................... 446 11.21. Safety Committee ..................................................... 448 11.22. COSH-H Requirements .................................................. 448 11.23. Toxicology of Carbon Fibers .......................................... 449 11.23.1. Definitions of Exposure Limits .............................. 449 11.23.2. Data for UK Exposure Limits for Gaseous Emissions ........... 449 11.23.3. Possible Hazards with Carbon and Graphite Fibers ............ 449 11.24. The Risks of Carbon Fiber Composites in a Fire ....................... 450 References .................................................................. 451 Chapter 12 Techniques for Determining the Structure of Carbon Fibers ........ 453 12.1. Introduction ......................................................... 453 12.2. Optical Microscope ................................................... 453 12.3. Scanning Electron Microscope (SEM) ................................... 456 12.4. Transmission Electron Microscope (TEM) ............................... 460 12.5. X-ray Diffraction .................................................... 464 12.5.1. Convention for Axes in Graphite and Carbon Fibers and Dimensional Notation .............................. 464 12.5.2. Wide Angle X-ray Diffraction ................................. 466 12.5.3. Single Crystal X-ray Diffraction ............................. 470 12.5.4. X-ray Powder Diffraction ..................................... 470 12.5.5. Low Angle X-ray Diffraction .................................. 473 12.6. Auger Electron Spectroscopy (AES) .................................... 473 12.7. X-ray Photoelectron Spectroscopy (XPS or ESCA) ....................... 475 12.8. Ultraviolet Photoemission Spectroscopy (UPS) ......................... 477 12.9. Infrared Spectroscopy ................................................ 479 12.9.1. Introduction ................................................. 479 12.9.2. Fourier Transform Infrared Spectroscopy (FTIR) ............... 481 12.9.3. Fourier Transform Infrared/Attenuated Total Reflectance Spectroscopy (FTIR/ATR) .......................... 483 12.10. Electron Energy Loss Spectroscopy (EELS) ............................. 483 12.11. Raman Spectroscopy ................................................... 485 12.11.1. Surface Enhanced Raman Scattering (SERS) .................... 485 12.12. Secondary Ion Mass Spectrometry (SIMS) ............................... 485 12.12.1. Static SIMS ................................................. 486 12.12.2. Dynamic SIMS ................................................ 489 12.12.3. Imaging or Microscope SIMS .................................. 489 12.13. Scanning Tunnelling Microscopy (STM) ................................. 490 12.14. Atomic Force Microscopy (AFM) or Scanning Force Microscopy (SFM) ..... 493 References .................................................................. 494 Chapter 13 Polymer Matrices for Carbon Fiber Composites ..................... 501 13.1. Selected Thermoset Resins ............................................. 501 13.1.1. Introduction .................................................. 501 13.1.2. Phenolic Resins ............................................... 502 13.1.3. Polyester Resins .............................................. 503 13.1.4. Epoxy Vinyl Ester Resins ...................................... 507 13.1.5. Epoxide Resins ................................................ 508 13.1.5.1. Bisphenol resins ................................... 508 13.1.5.2. Novalac resins ..................................... 509 13.1.5.3. Trifunctional resins ............................... 511 13.1.5.4. Tetrafunctional resins ............................. 511 13.1.5.5. Cycloaliphatic resins .............................. 512 13.1.5.6. New developments ................................... 512 13.1.5.7. Epoxy diluents ..................................... 513 13.1.5.8. Characterization of epoxy resins ................... 513 13.1.5.9. Curing epoxide resins .............................. 513 13.1.5.10. Calculating stoichiometric ratios for epoxy resins and curing agents ........................... 519 13.1.6. Cyanate Resins ................................................ 520 13.1.7. Polyimide Resins .............................................. 521 13.1.7.1. Condensation type polyimides ........................ 523 13.1.7.2. Addition type polyimides ............................ 525 13.1.7.2.1. The earliest bismaleimides .............. 525 13.1.7.2.2. Bismaleimides ........................... 527 13.1.7.2.3. Acetylene (ethynyl) terminated polyimides .............................. 529 13.1.8. Special Resin Systems ......................................... 530 13.1.9. Introducing Toughness to Thermoset Resin Systems .............. 530 13.1.9.1. Introduction ........................................ 530 13.1.9.2. Toughening versus flexibilizing ..................... 531 13.1.9.3. Types of elastomeric modifiers ...................... 531 13.1.9.4. Duplex materials .................................... 532 13.1.9.5. Thermoplastic modifiers ............................. 532 13.1.9.6. Effect of carbon fiber reinforcement ................ 533 13.2. Selected Thermoplastic Resins ......................................... 533 13.2.1. Introduction .................................................. 533 13.2.2. Morphology Property Relationships in Semi-crystalline Thermoplastics ................................................ 535 13.2.3. Polyamide (PA) Resins ......................................... 538 13.2.4. Polycarbonate (PC) Resin ...................................... 540 13.2.5. Polyetheretherketone (PEEK) Resin ............................. 540 13.2.6. Polyetherimide (PEI) Resin .................................... 542 13.2.7. Polyethersulfone (PES) Resin .................................. 542 13.2.8. Polyphenylene Sulfide (PPS) Resin ............................. 543 13.3. Improving the Bond with Carbon Fiber/Thermoplastics ................... 543 References .................................................................. 544 Chapter 14 Carbon Fiber Carbon Matrix Composites ............................ 551 14.1. Introduction .......................................................... 551 14.2. Selection of Materials for Carbon-Carbon Processing ................... 552 14.2.1. Types of Reinforcement ........................................ 552 14.2.1.1. Oxidized PAN fiber (opf) ............................ 552 14.2.1.2. PAN based carbon fibers ............................. 552 14.2.1.3. Pitch based carbon fibers (pbcf) .................... 554 14.2.1.4. Cellulose based carbon fibers ....................... 555 14.2.2. Type of Matrix ................................................ 555 14.2.2.1. Thermosetting resin ................................. 556 1. Furan resin ...................................... 556 2. Phenolic resins .................................. 557 3. Polyimide resins ................................. 557 14.2.2.2. Thermoplastic matrix precursors ..................... 558 1. Pitch ............................................ 558 2. Other thermoplastic matrices ..................... 559 14.3. Methods of Processing Carbon-Carbon Matrix Materials .................. 560 14.3.1. Introduction .................................................. 560 14.3.2. Use of Gas Phase Impregnation arid Densification .............. 560 14.3.2.1. Introduction ........................................ 560 14.3.2.2. CVI processes ....................................... 565 1. Isothermal CVI process ........................... 565 2. Thermal gradient CVI process (TG-CVI) ............ 566 3. Pressure gradient process ........................ 566 4. Pulse CVD process ................................ 566 5. Possible new routes .............................. 566 14.3.3. Processing with Thermosetting Resin Matrices .................. 567 14.3.3.1. Low pressure impregnation (LPI) ..................... 567 14.3.3.2. Pressure impregnation and carbonization (PIC) ....... 568 14.3.3.3. Hot isostatic pressure impregnation carbonization (HIPIC) ............................... 568 14.4. Some Thoughts on Carbon-Carbon Processing ............................. 569 14.4.1. Chemical Vapor Deposition ..................................... 569 14.4.2. Liquid Infiltration ........................................... 572 14.5. Provision for Providing Oxidation Protection .......................... 573 14.5.1. Introduction .................................................. 573 14.5.2. The Use of Inhibitors to Provide Oxidation Protection ......... 574 1. Boron ...................................................... 574 2. Phosphorus ................................................. 575 14.5.3. The Use of a Barrier Coating .................................. 575 1. Noble metals ............................................... 575 2. Silicon coatings ........................................... 575 14.5.4. Other Coating Systems ......................................... 578 References .................................................................. 578 Chapter 15 Carbon Fiber Reinforced Ceramic Matrices ......................... 583 15.1. Introduction .......................................................... 583 15.2. Cement, Concrete and Gypsum Matrices .................................. 583 15.2.1. Cement ........................................................ 583 15.2.2. Concrete ...................................................... 584 15.2.3. Concrete Additives ............................................ 584 15.2.3.1. Silica fume ......................................... 584 15.2.3.2. Dispersant .......................................... 584 15.2.3.3. Water reducing agent ................................ 585 15.2.3.4. Accelerator ......................................... 585 15.2.4. Work Undertaken with Mortar and Concrete ...................... 585 15.2.5. Theory ........................................................ 591 15.2.6. Fabrication Processes for cfrc ................................ 591 15.3. Glass Matrices ........................................................ 592 15.3.1. The Glass Matrix .............................................. 592 15.3.2. Methods of Preparation of Carbon Fiber Reinforced Glasses ..... 594 15.3.2.1. Mode of reinforcement ............................... 594 15.3.2.2. Slurry with hot pressing ............................ 594 15.3.2.3. Hot filament winding under tension with hot pressing above the annealing temperature ........ 597 15.3.2.4. Melt infiltration ................................... 597 15.3.2.5. Sol gel ............................................. 598 15.3.3. Work Undertaken with Carbon Fiber Filled Glass Matrices ....... 599 15.3.4. Coating Carbon Fiber to Improve the Bond to a Glass ........... 601 15.4. Ceramic Matrices ...................................................... 602 15.4.1. Processing Ceramic Matrix Composites .......................... 602 15.4.2. Types of Ceramic Matrices ..................................... 602 15.4.2.1. Oxide matrix materials .............................. 603 1. Alumina (Al2O3) ................................... 603 2. Mullite (3Al2O3.2SiO2) ............................ 603 3. Zirconia (ZrO2)................................... 603 15.4.2.2. Non-oxide matrix materials .......................... 603 1. Silicon carbide (SiC) ............................ 603 2. Titanium carbide (TiC) ........................... 604 3. Boron carbide (B4C)............................... 604 4. Titanium boride (TiB2)............................ 604 5. Boron nitride (BN) ............................... 604 6. Aluminium nitride (AlN) .......................... 604 7. Silicon nitride (Si3N4) ........................... 604 15.4.3. Fiber Reinforcement ........................................... 605 15.4.4. Processing Techniques ......................................... 605 15.4.4.1. Slurry infiltration ................................. 605 15.4.4.2. Slip casting ........................................ 605 15.4.4.3. Filament winding .................................... 605 15.4.4.4. Chemical synthesis .................................. 606 1. Sol gel .......................................... 606 2. Polymer precursor ................................ 607 15.4.4.5. Melt infiltration ................................... 609 15.4.4.6. In situ chemical reactions .......................... 611 1. CVI (or CVD) ..................................... 611 2. Slurry pulse/CVI ................................. 612 3. Hot Isotactic Pressing (HIPing) .................. 613 4. Reaction bonding ................................. 614 15.4.4.7. Consolidation and densification ..................... 615 1. Sintering ........................................ 615 2. Pressureless sintering ........................... 615 3. Hot pressing ..................................... 615 15.5.5. Protective Coatings ........................................... 615 15.6.6. Fracture Mechanics ............................................ 617 References .................................................................. 617 Chapter 16 Carbon Fibers in Metal Matrices .................................. 629 16.1. Introduction .......................................................... 629 16.2. Metal Matrix Composites ............................................... 629 16.3. Carbon Fiber for Reinforcement of Metal Matrices ...................... 629 16.4. Coating Processes to Improve Wettability .............................. 631 16.4.1. CVD Process ................................................... 631 16.4.2. Liquid Metal Transfer Agent (LMTA) Technique .................. 632 16.4.3. Cementation ................................................... 632 16.4.4. Electroless Plating ........................................... 632 16.4.5. Electroplating ................................................ 633 16.4.6. Solution Coating .............................................. 633 16.4.7. Flux .......................................................... 634 16.4.8. INCO Ni Coated Carbon Fiber ................................... 634 16.4.9. Other Coating Processes ....................................... 635 16.5. Metal Matrices ........................................................ 635 16.5.1. Aluminium ..................................................... 635 16.5.2. Magnesium ..................................................... 639 16.5.3. Copper ........................................................ 639 16.5.4. Nickel ........................................................ 640 16.5.5. Lead .......................................................... 640 16.5.6. Tin ........................................................... 640 16.6. Techniques for Fabricating Carbon Fiber Reinforced Metal Matrix Composites ............................................... 641 16.6.1. Factors Influencing Processing of Metal Matrix Composites ..... 641 16.6.1.1. Capillary effects ................................... 641 16.6.1.2. Fluid flow into the preform ......................... 641 16.6.1.3. Fiber matrix interactions ........................... 641 16.6.1.4. The solidification process .......................... 642 16.6.2. Processing Methods for Fabricating Metal Matrix Composites .... 642 16.6.2.1. Solid state processing methods ...................... 643 1. Powder metallurgy ................................ 643 2. Diffusion bonding ................................ 643 16.6.2.2. Liquid state processing ............................. 644 1. Melt stirring .................................... 644 2. Compocasting or rheocasting ...................... 644 3. Slurry casting ................................... 644 4. Gravity or vacuum casting ........................ 644 5. Pressure casting ................................. 644 6. Squeeze casting .................................. 644 7. Fiber tow (liquid) infiltration .................. 645 8. Lanxide process .................................. 646 9. Liquid phase hot pressing, liquid phase diffusion bonding or liquid phase sintering ...... 646 16.6.2.3. Deposition processes ................................ 647 1. Ion plating ...................................... 647 2. Plasma spraying .................................. 647 16.6.3. Fundamental Considerations .................................... 647 16.6.3.1. Capillarity ......................................... 647 16.6.3.2. Fluid flow into the preform ......................... 648 16.6.3.3. Fiber matrix interactions ........................... 648 16.6.3.4. The solidification process and matrix microstructure ...................................... 648 References .................................................................. 649 Chapter 17 Testing of PAN Precursor, Virgin Carbon Fibers, Carbon Fiber Composites and Related Products ..................... 657 17.1. Introduction ......................................................... 657 17.2. Testing of PAN Precursor ............................................. 657 17.2.1. Filament Diameter Distribution in PAN Tow .................... 657 17.2.2. Measurement of Precursor d'tex using the Vibroskop (ASTM D1577) ................................................. 660 17.2.3. Determination of Fiber Moisture Content and Fiber Moisture Regain ........................................ 660 17.2.4. Determination of Residual Solvent (NaSCN) in Courtelle Precursor .......................................... 661 17.2.5. Determination of Sodium Content in the Precursor ............. 661 1. Atomic absorption spectrophotometer ....................... 661 2. Ion chromatograph ......................................... 661 17.2.6. Determination of the Soft Finish Content in Courtelle Precursor .......................................... 662 17.2.7. Silver Sulphide Staining Test for Checking Structure of a PAN Precursor ........................................... 662 17.2.8. An Experimental Rig for Determination of Precursor Burn-up Temperature .......................................... 662 17.3. Testing of Oxidized PAN Fiber (OPF) and Virgin Carbon Fiber .......... 662 17.3.1. Mass per Unit Length ......................................... 662 17.3.2. Determination of Density ..................................... 663 17.3.3. Determination of Diameter .................................... 666 1. Mounting a single filament ................................ 666 2. Determining filament diameter using a Watson image shearing eyepiece ............................ 667 3. Determination of filament diameter using a He/Ne laser .... 668 4. Calibration of a Stereoscan with a traceable reference standard ........................................ 669 5. Preparation of a mini composite (impregnated tow) ......... 670 17.3.4. Tensile Testing of Filament .................................. 670 17.3.4.1. Determination of compliance of the tensile test machine system ................................ 670 17.3.4.2. Measurment of filament tensile modulus ............. 671 17.3.4.3. Measurment of filament tensile strength ............ 674 17.3.5. Determination of Oxidized PAN Fiber Finish Content ........... 674 17.3.6. Determination of Carbon Fiber Size Content ................... 676 17.3.7. Conductivity of a Water Extract .............................. 677 17.3.8. Skin Core .................................................... 677 17.3.9. Measurement of Electrical Properties ......................... 678 17.4. Carbon Fiber Tow Testing ............................................. 678 17.4.1. Dry Tow Test ................................................. 678 17.4.2. Testing of the Impregnated Tow ............................... 679 17.5. Testing of Carbon Fiber Yarn and Fabric .............................. 682 17.5.1. Determination of Twist ....................................... 683 17.5.2. Determination of Ends and Picks .............................. 683 17.6. Testing of Matrix .................................................... 684 17.6.1. Fineness of Grind ............................................ 684 17.6.2. Selection of a Suitable Grade of Paper for Resin Coating ..... 684 17.6.3. Determination of Gel Time .................................... 685 1. Using the Kofler hotbench ................................. 685 2. Determination of gel time at ambient temperature .......... 686 17.6.4. Determination of the Viscosity of a Resin Mix ................ 686 17.6.5. Determination of the Epoxy Molar Mass (EMM) of Epoxy Resins ................................................. 687 1. Cetyl trimethylammonium bromide-perchloric acid titration method ..................................... 687 2. Determination of EMM by potentiometric titration .......... 688 17.7. Testing of Carbon Fiber Prepreg ...................................... 688 17.7.1. Mass per unit Area ........................................... 688 17.7.2. Volatiles Content ............................................ 688 17.7.3. Fiber Content ................................................ 688 17.7.4. Resin Gel Time ............................................... 689 17.8. Testing of Carbon Fiber Composite .................................... 689 17.8.1. Introduction ................................................. 689 17.8.2. Preparation of Composite Specimen from Wet Resins ............ 690 17.8.3. Preparation of Composite Specimen from Prepreg Systems ....... 692 17.8.4. Determination of Carbon Fiber Content ........................ 693 17.8.5. Measurement of Tensile Modulus ............................... 693 17.8.6. Measurement Tensile Strength ................................. 695 17.8.7. Measurement of Strain using Resistance Strain Gages .......... 697 17.8.8. Measurment of Shear Strength ................................. 699 17.8.8.1. Interlaminar shear strength ........................ 699 17.8.8.2. In-plane shear tests ............................... 700 1. The torsion test ................................ 700 2. Two-rail or three-rail shear test ............... 701 3. The double V-notch shear (Iosipescu test) ....... 702 4. Tension coupon test ............................. 702 5. The 10° off-axis test ........................... 704 17.8.9. Measurement of Flexural Strength and Modulus ................ 706 17.8.10. Measurement of Uniaxial Compressive Strength and Modulus .... 708 17.8.11. Testing of Fatigue .......................................... 710 17.8.12. Measurement of Creep ........................................ 712 17.8.13. Testing of Impact Behavior .................................. 714 17.8.14. Measurement of Interlaminar Fracture Toughness .............. 714 17.9. Testing of Carbon Fiber Filled Thermoplastics ........................ 714 17.9.1. Measurement of Moisture Content ............................. 714 17.9.2. Molding ..................................................... 715 17.9.3. Determination of Melt Flow Index (MFI) ...................... 717 17.9.4. Impact Testing of Thermoplastics ............................ 718 17.10. Instrumental Analysis ................................................ 718 17.10.1. Optical Microscope .......................................... 718 17.10.2. Laboratory Furnace .......................................... 720 17.10.3. Thermal Analysis ............................................ 721 17.10.3.1. Differential scanning calorimeter (DSC) .......... 721 1. Classical DTA ................................. 721 2. Boersma DTA ................................... 722 3. DSC ........................................... 722 17.10.3.2. Thermogravimetric analysis (TGA) ................. 725 17.10.3.3. Dynamic mechanical analysis (DMA) ................ 726 17.10.3.4. Thermomechanical analysis (TMA) .................. 729 17.10.4. Chromatography .............................................. 729 17.10.5. Infrared Analysis (IR) ...................................... 732 17.10.6. Elemental Analysis .......................................... 735 17.11. Non-destructive Testing (NDT) ........................................ 735 17.11.1. Ultrasonic Testing .......................................... 736 17.11.2. Radiography ................................................. 738 17.11.3. Acoustic Emission ........................................... 738 17.12. Supplement 1 ......................................................... 738 17.12.1. Sinclair's Loop Test for Filament Testing ................... 738 1. Tension testing .......................................... 739 2. Compression testing ...................................... 739 References .................................................................. 739 Chapter 18 Statistics and Statistical Process Control (SPC) ................. 747 18.1. Frequency Distribution ............................................... 747 18.2. Location of Data ..................................................... 748 18.3. Measures of Dispersion ............................................... 750 18.4. Standard Error ....................................................... 751 18.5. Sample Correlation Coefficient ....................................... 751 18.6. Linear Regression .................................................... 752 18.7. Normal Distribution .................................................. 753 18.8. Weibull Distribution ................................................. 756 18.9. Variation ............................................................ 756 18.10. Control Chart Method ................................................. 758 18.11. Statistical Process Control Charts ................................... 758 18.11.1. Average and Range (x and R) Chart ........................... 760 18.11.2. Mean and Standard Deviation (x and σ) Chart ................. 764 18.11.3. Median Control Chart ........................................ 766 18.11.4. Rules for Detecting Out-of-control Conditions on Control Charts .............................................. 766 18.11.5. Cumulative Sum Chart (Cusum) ................................ 769 18.12. Capability Index ..................................................... 770 18.13. Failure Mode Effect Analysis (FMEA) .................................. 771 References .................................................................. 771 Chapter 19 Quality Control .................................................. 773 19.1. Inhouse Testing ....................................................... 773 19.2. Quality Management and Quality Assurance Standards .................... 773 19.3. The ISO 9000 Family of Standards and Quality Systems .................. 774 Para 4.1 Management Responsibility ................................... 774 Para 4.2 Quality System .............................................. 774 Para 4.3 Contract Review ............................................. 774 Para 4.4 Design Control .............................................. 774 Para 4.5 Document Control and Data ................................... 774 Para 4.6 Purchasing .................................................. 774 Para 4.7 Control of Customer Supplied Product ........................ 774 Para 4.8 Product Identification and Traceability ..................... 774 Para 4.9 Process Control ............................................. 774 Para 4.10 Inspection and Testing ...................................... 774 Para 4.11 Control of Inspection, Measuring and Test Equipment ......... 775 Para 4.12 Inspection and Test Status .................................. 775 Para 4.13 Control of Non-Conforming Product ........................... 775 Para 4.14 Corrective and Preventive Action ............................ 775 Para 4.15 Handling, Storage, Packaging, Preservation and Delivery ..... 775 Para 4.16 Control of Quality Records .................................. 775 Para 4.17 Internal Quality Audits ..................................... 775 Para 4.18 Training .................................................... 775 Para 4.19 Servicing ................................................... 775 Para 4.20 Statistical Techniques ...................................... 775 19.4. Quality Gurus ......................................................... 775 19.4.1. The Early Americans ........................................... 776 19.4.1.1. W Edwards Deeming ................................... 776 19.4.1.2. Joseph M Juran ...................................... 778 19.4.1.3. Armand V Fiegenbaum ................................. 779 19.4.2. The Japanese Gurus ............................................ 779 19.4.2.1. Dr Kaoru Ishikawa ................................... 779 19.4.2.2. Dr Genichi Taguchi .................................. 780 19.4.2.3. Shigeo Shindo ....................................... 781 19.4.3. The New Western Group of Gurus ................................ 782 19.4.3.1. Philip B Crosby ..................................... 782 19.4.3.2. Tom Peters .......................................... 783 19.4.3.3. Claus Moller ........................................ 784 19.5. Quality Circles ....................................................... 785 19.6. Total Quality Management .............................................. 786 19.7. Quality Costing ....................................................... 788 References .................................................................. 789 Chapter 20 Properties of Carbon Fibers ...................................... 791 20.1. The Role of Carbon Fibers ............................................ 791 20.2. Types of Carbon Fibers Available in the World Market ................. 792 20.3. Tensile Properties ................................................... 800 20.4. Factors Effecting Composite Strength ................................. 808 20.5. The Importance of Critical Aspect Ratio .............................. 810 20.6. Elastic Constants .................................................... 811 20.7. Flexural Properties .................................................. 814 20.8. Effect of Surface Treatment and Sizing on Composite Properties ....... 815 20.9. Compression Properties ............................................... 817 20.10. Thermal Properties ................................................... 823 20.11. Thermal Expansion of Carbon Fibers ................................... 829 20.12. Thermal Conductivity of Carbon Fibers ................................ 831 20.13. Creep Properties ..................................................... 831 20.14. Impact Strength and Fracture Toughness ............................... 833 20.15. Fatigue Properties ................................................... 834 20.16. Electrical Properties ................................................ 834 20.17. Chemical Resistance .................................................. 836 20.17.1. Intercalation ............................................... 837 20.18. Friction and Wear .................................................... 837 20.19. Hybrid Composites .................................................... 838 20.20. Some Selected Properties of Composites ............................... 839 20.20.1. Thermoplastic Polymer Matrices .............................. 839 20.20.2. Cement Matrices ............................................. 839 20.20.3. Glass and Ceramic Matrices .................................. 841 20.20.4. Carbon-Carbon ............................................... 844 20.21. Metal Matrices ....................................................... 845 References .................................................................. 849 Chapter 21 Manufacturing Techniques for Carbon Fiber Reinforced Composites in Thermoset and Thermoplastic Matrices ............... 861 21.1. Carbon Fiber Reinforcement and Architecture ........................... 861 21.1.1. Virgin Carbon Fiber ........................................... 861 21.1.2. Non-woven Discontinuous Reinforcement (Staple Fiber) .......... 863 21.1.2.1. Adhesive bonded reinforcements ...................... 863 1. Chopped strand mat (csm) ......................... 863 2. Carbon fiber tissue .............................. 864 3. Carbon fiber paper reinforcement ................. 864 21.1.2.2. Needled mat ......................................... 864 21.1.2.3. Milled fiber ........................................ 864 21.1.2.4. Chopped carbon fiber ................................ 865 21.1.3. Unidirectional Fabrics ........................................ 865 21.1.3.1. Non-woven UD fabrics ................................ 865 21.1.3.2. Woven UD fabrics .................................... 866 1. Warp UD fabric ................................... 866 2. Weft UD fabric ................................... 866 21.1.4. Woven Fabrics (2-D Planar or Biaxial Reinforcement) ........... 866 1. Plain or square weave ...................................... 868 2. Basket (Hopsack) weave ..................................... 868 3. Leno weave ................................................. 869 4. Mock Leno weave ............................................ 870 5. Twill weave ................................................ 871 6. Satin weave ................................................ 871 7. High modulus (non-crimp) weave ............................. 872 21.1.5. Woven Spread Tow .............................................. 872 21.1.6. Knitted Fabrics ............................................... 872 21.1.6.1. Weft knitting ....................................... 874 1. Plain knitting ................................... 874 21.1.6.2. Warp knitting ....................................... 876 1. Plain tricot ..................................... 877 2. Raschel .......................................... 877 21.1.7. Inlaid Fabrics ................................................ 877 21.1.8. Braiding ...................................................... 877 21.1.8.1. Forms of braiding ................................... 879 1. Flat braids ...................................... 879 2. Sleevings ........................................ 879 3. Wide braided fabric .............................. 879 4. Overbraids ....................................... 880 21.1.8.2. Braid architecture .................................. 880 1. Biaxial 2-D braid ................................ 880 2. Triaxial 3-D braid ............................... 881 21.1.9. 3-D Reinforcements ............................................ 882 21.1.9.1. Multiaxial non-crimp reinforcements ................. 882 1. Producing a stitched fabric by the simultaneous stitch process ................................... 883 2. Producing a stitched fabric by the weave and stitch process ................................... 885 3. Double bias fabrics .............................. 885 4. Triaxial weave ................................... 885 5. Quadraxial ....................................... 889 21.1.9.2. Woven 3-D fabrics ................................... 889 21.1.9.3. Proprietary 3-D weaving processes ................... 889 21.1.9.4. Knitted 3-D fabrics ................................. 890 21.1.9.5. Braided 3-D multiaxial .............................. 890 21.1.9.6. n-D orthogonal blocks ............................... 891 21.1.9.7. Aztex Inc Z-FiberTM .................................. 893 21.2. Core Materials ........................................................ 893 21.3. Manufacturing Processes for Carbon Fibers in Thermoset Matrices ....... 894 21.3.1. Contact Molding Wet Lay-up ................................... 894 21.3.1.1. Hand lay-up (contact molding) ...................... 895 21.3.1.2. Spray lay-up ....................................... 895 21.3.2. Hot Press Matched Metal Molding ............................... 896 21.3.2.1. Thermoset dough molding compound (DMC) ............. 896 21.3.2.2. Thermoset bulk molding compound (BMC) .............. 896 21.3.2.3. Thermoset sheet molding compound (SMC) ............. 896 21.3.3. Resin Transfer Molding (RTM) ................................. 897 21.3.3.1. Dow AdvRTMTM ........................................ 898 21.3.3.2. Vacuum assisted resin transfer molding (VARTM) ..... 900 21.3.3.3. Vacuum infusion processing (VIP) ................... 901 21.3.3.4. Seemann Composite Resin Infusion Molding Process (SCRIMPTM) .......................................... 901 21.3.3.5. Resin infusion under flexible tooling (RIFT) ....... 901 21.3.3.6. Vacuum infusion molding process (VIMP) ............. 901 21.3.3.7. SP Resin Infusion Technology (SPRINTTM) ........,.... 901 21.3.3.8. Resin film infusion (RFI) .......................... 902 21.3.4. Sequential Multiport Resin Injection System (SMRIM) .......... 904 21.3.5. Reaction Injection Molding (RIM) ............................. 904 21.3.6. Centrifugal Molding .......................................... 904 21.3.7. Preparation of Fiber Preforms ................................ 904 21.3.8. Flow and Cure Monitoring of Resin Infusion Processes ......... 904 21.3.9. Filament Winding ............................................. 905 1. Hoop winding .............................................. 906 2. Helical winding ........................................... 906 3. Polar winding ............................................. 906 4. Multiaxial winding ........................................ 907 5. Variants of multiaxial winding ............................ 907 21.3.10. Pultrusion ................................................... 909 1. Reinforcement handling .................................... 910 2. Resin impregnation ........................................ 911 3. Pre-die forming ........................................... 911 4. Heated die to shape and cure the resin .................... 911 5. Pulling unit to provide traction .......................... 912 6. Cut off saw ............................................... 912 7. Post cure oven ............................................ 912 21.3.11. Prepreg Molding .............................................. 913 21.3.11.1. Prepreg manufacture ............................... 913 21.3.11.2. Manufacture of composites from prepreg ............ 916 1. Ply cutting and stacking prepreg ............... 916 2. Compression molding of prepreg ................. 916 3. Vacuum bag molding ............................. 916 4. Press-clave molding ............................ 917 5. Autoclave molding .............................. 918 6. QuickstepTM Molding ............................. 920 7. Tube rolling ................................... 921 8. Automatic tape lay-up .......................... 921 21.3.12. Fiber Placement Systems ...................................... 921 21.3.13. Mold Release ................................................. 922 1. Polyvinyl alcohol (PVA) ................................... 923 2. Waxes ..................................................... 923 3. Internal mold release agents .............................. 923 4. Silicones ................................................. 923 5. Fluorocarbons ............................................. 923 6. New products .............................................. 923 21.4. Carbon Fibers in Thermoplastic Matrices ............................... 923 21.4.1. The Importance of Critical Aspect Ratio ...................... 923 21.4.2. Preparation of Thermoplastic Molding Compounds ............... 924 21.4.2.1. Sizing carbon fiber with compatible thermoplastic polymer size ......................... 924 21.4.2.2. Manufacture of thermoplastic molding compound ...... 924 1. Short fiber process ............................. 924 2. Long fiber process .............................. 924 21.4.3. Injection Molding ............................................ 925 21.4.4. Film Stacking Process ........................................ 927 21.4.5. Thermoplastic Prepreg ........................................ 927 1. Molding carbon fiber/PEI laminate ......................... 928 2. Platen pressing of carbon fiber/PEEK laminate ............. 928 21.4.6. Thermoplastic Filament Winding ............................... 928 21.4.7. Thermoplastic Pultrusion ..................................... 929 21.4.8. Continuous Fiber Reinforced Plastic Materials ................ 929 21.5. Hybrid Composites ..................................................... 929 References .................................................................. 930 Chapter 22 Design ........................................................... 935 22.1. Design Considerations ................................................ 935 22.2. Micromechanics ....................................................... 935 22.3. Selection of Materials ............................................... 940 22.4. Elastic Behavior of Multidirectional Laminates ....................... 940 22.5. Choice of Composite Manufacturing Method ............................. 943 22.6. Bonding and Joining .................................................. 943 22.7. Fabrication .......................................................... 944 22.8. Testing and Inspection ............................................... 944 22.9. Smart Devices ........................................................ 944 22.10. Design Cases ......................................................... 945 22.10.1. Expanding Core Technique .................................... 945 22.10.2. A Yacht Mast ................................................ 946 References .................................................................. 946 Supplementary Bibliography .................................................. 947 Chapter 23 The Uses of Carbon Fibers ........................................ 951 23.1. Uses of Oxidized PAN Fiber (OPF) ..................................... 951 23.1.1. Flameproof Applications ...................................... 951 23.1.1.1. Aviation and aerospace ............................. 953 23.1.1.2. Industrial workwear ................................ 954 23.1.1.3. Defence and law enforcement ........................ 954 23.1.1.4. Transportation and furnishings ..................... 955 23.1.1.5. Cable insulation ................................... 955 23.1.2. Friction Materials ........................................... 955 23.1.3. Gland Packings ............................................... 955 23.1.4. Precursor for PAN based Carbon Fiber and Activated Carbon Fibers ...................................... 955 23.2. Uses of Virgin Carbon Fiber .......................................... 955 23.2.1. Activated Carbon Fibers (ACF) ................................ 955 23.2.2. Molecular Sieves ............................................. 958 23.2.3. Catalysts .................................................... 958 23.2.4. Biomedical Applications ...................................... 958 23.3. Electrical Applications .............................................. 960 23.3.1. Electrical Conduction ........................................ 960 23.3.2. Tailored Resistance Carbon Fiber ............................. 960 23.3.3. Cathodic Protection .......................................... 960 23.3.4. Elimination of Static ........................................ 960 23.3.5. Electrodes ................................................... 961 23.3.6. Batteries .................................................... 962 23.3.6.1. Lithium Ion Batteries .............................. 962 23.3.7. Fuel Cells ................................................... 964 23.3.7.1. Alkaline Fuel Cell (AFC) ........................... 965 23.3.7.2. Proton Exchange Membrane Fuel Cell (PEMFC) ......... 966 23.3.7.3. Phosphoric Acid Fuel Cell (PAFC) ................... 967 23.3.7.4. Molten Carbonate Fuel Cell (MCFC) .................. 968 23.3.7.5. Solid Oxide Fuel Cell (SOFC) ....................... 969 23.3.7.6. Carbon fiber in fuel cells ......................... 969 23.4. Thermal Insulation ................................................... 970 23.5. Packing Materials and Gaskets ........................................ 973 23.6. Carbon Fibers in Thermoset Matrices .................................. 973 23.6.1. Aerospace ................................................... 973 23.6.1.1. Defence aircraft .................................. 973 23.6.1.2. Civil aircraft .................................... 973 23.6.1.3. Helicopters ....................................... 977 23.6.1.4. Aero engines ...................................... 977 23.6.1.5. Propeller blades .................................. 977 23.6.1.6. Antenna, lightening conductors .................... 979 23.6.1.7. Gliders and sailplanes ............................ 982 23.6.1.8. Unmanned Aerial Vehicles (UAVs) ................... 982 23.6.1.9. Stealth aerial vehicles ........................... 982 23.6.2. Space ....................................................... 982 23.6.3. Rocket Motor Cases .......................................... 983 23.6.4. Flywheels ................................................... 983 23.6.5. Marine Applications ......................................... 987 23.6.5.1. Yachts ............................................ 987 23.6.5.2. Submarines ........................................ 989 23.6.5.3. Air cushion vehicle ............................... 989 23.6.6. Oil Exploration ............................................. 989 23.6.7. Automobile and Racing Car Applications ...................... 991 23.6.7.1. Chassis, body and interior ........................ 991 23.6.7.2. Brakes and clutches ............................... 992 23.6.7.3. Suspension systems ................................ 992 23.6.7.4. Push rods ......................................... 993 23.6.7.5. Air bags .......................................... 993 23.6.8. Heavy Goods Vehicles and Buses .............................. 993 23.6.8.1. Drive shafts ...................................... 993 23.6.8.2. Buses ............................................. 994 23.6.9. CNG Storage Cylinders ....................................... 994 23.6.10. Motor Bikes ................................................. 994 23.6.11. Railways .................................................... 995 23.6.12. Engineering and Textile Applications ........................ 995 23.6.12.1. Structural work .................................. 995 23.6.12.2. Robot arms ....................................... 995 23.6.12.3. Rollers .......................................... 995 23.6.13. Turbine Blades .............................................. 995 23.6.13.1. Wind turbine blades .............................. 995 23.6.13.2. Tidal turbine blades ............................. 997 23.6.14. Textile Applications ........................................ 998 23.6.15. Chemical and Nuclear Applications ........................... 998 23.6.16. Medical and Prosthetic Applications ......................... 998 23.6.16.1. Hospital equipment .............................. 1000 23.6.17. Dental ..................................................... 1000 23.6.18. Sports and Leisure Goods ................................... 1001 23.6.18.1. Bicycles, tandem ............................... 1001 23.6.18.2. Bows and arrows ................................ 1002 23.6.18.3. Rifles ......................................... 1002 23.6.18.4. Skis and ski sticks ............................ 1002 23.6.18.5. Snowboards ..................................... 1002 23.6.18.6. Baseball bats .................................. 1002 23.6.18.7. Cricket bats ................................... 1003 23.6.18.8. Hockey sticks .................................. 1003 23.6.18.9. Golf shafts and heads .......................... 1003 23.6.18.10. Tennis, racquetball, badminton and squash racquets ................................ 1004 23.6.18.11. Snooker and pool cues .......................... 1004 23.6.18.12. Fishing rods and reels ......................... 1005 23.6.18.13. Hang glider .................................... 1005 23.6.18.14. Canoe paddles .................................. 1005 23.6.18.15. Wind surfing ................................... 1005 23.6.19. Musical Instruments and Hi-Fi .............................. 1005 23.6.19.1. Loudspeaker cones ............................... 1006 23.6.19.2. Carbon fiber cable .............................. 1006 23.6.19.3. Satellite reflectors ............................ 1006 23.6.19.4. Stringed instruments ............................ 1006 23.6.19.5. Bows for cello and violin ....................... 1007 23.6.20. Other End Uses in Thermoset Matrices ....................... 1007 23.6.20.1. Model aeroplanes ................................ 1007 23.6.20.2. Knives, fountain pens, watches .................. 1007 23.6.20.3. Precision instruments ........................... 1008 23.6.20.4. Tripods ......................................... 1008 23.6.20.5. Optical instruments ............................. 1008 23.6.20.5.1. Telescopes ......................... 1008 23.6.20.5.2. Binoculars ......................... 1009 23.6.21. Furniture .................................................. 1009 23.6.22. Carbon Fiber and Wood ...................................... 1009 23.7. Carbon Fibers in Thermoplastic Matrices ............................. 1009 23.7.1. Thermoplastic Molding Compounds ............................. 1010 23.8. Carbon Fibers for Carbon-Carbon Applications ........................ 1010 23.8.1. Carbon-Carbon Braking Systems ............................... 1011 23.8.2. Carbon-Carbon Clutches and Limited Slip Differentials ....... 1018 23.8.3. Carbon-Carbon in Space ...................................... 1020 23.8.4. Carbon-Carbon for Aircraft .................................. 1021 23.8.5. Rocket Motor Nozzles and Expansion Tubes .................... 1021 23.8.6. Carbon-Carbon in Engines .................................... 1022 23.8.7. Carbon-Carbon for Biomedical End Uses ....................... 1022 23.8.8. Carbon-Carbon in Industry ................................... 1022 23.8.9. Carbon-Carbon as a Dielectric Heat Sink ..................... 1023 23.9. Carbon Fibers in Cement and Concrete ................................ 1023 23.9.1. Carbon Fibers in Cement and Concrete ........................ 1024 23.9.2. Carbon Fiber Cement as a Replacement for Asbestos Cement .... 1024 23.9.3. Strengthening of Reinforced Concrete Chimneys, Columns, Beams and Retrofits ......................................... 1024 23.9.4. New Structures with cfrp .................................... 1030 23.10. Carbon Fibers in Glass Matrices ..................................... 1031 23.10. Carbon Fibers in Ceramic Matrices ................................... 1031 23.11. Carbon Fibers in Metal Matrices ..................................... 1031 23.12.1. Electromagnetic Interference (EMI) and Heat Dissipation .... 1031 23.13. Other End Uses for Carbon Fibers .................................... 1032 References ................................................................. 1032 Chapter 24 Looking to the Future ........................................... 1043 24.1. The Future ........................................................... 1043 24.2. The Production Process ............................................... 1043 24.2.1. Precursor Developments ....................................... 1043 24.2.2. Plant Developments ........................................... 1044 24.3. Carbon Fiber ......................................................... 1044 24.4. Composite Manufacturing Techniques ................................... 1045 24.5. Quality Management Standards ......................................... 1045 24.6. Recycling ............................................................ 1046 24.7. Innovative Developments .............................................. 1046 24.8. Conclusion ........................................................... 1047 Appendix Appendix 1 Glossory ..................................................... 1049 Appendix 2 The Elements ................................................. 1061 Appendix 3 The Greek Alphabet ........................................... 1063 Appendix 4 Some Definitions and Handy Conversion Factors ................ 1065 Appendix 5 ISO Standard Prefixes for SI Units ........................... 1067 Appendix 6 Interconversion of Common English and SI Units ............... 1069 Appendix 7 Textile Terminology .......................................... 1073 Appendix 8 Temperature Estimation from Color ............................ 1075 Appendix 9 Humidities over Saturated Salt Solutions ..................... 1077 Appendix 10 Wet and Dry Bulb Humidity Table .............................. 1079 Appendix 11 Detection of Cyanide [1] ..................................... 1081 Appendix 12 British Standards on Quality ................................. 1083 Appendix 13 Abbreviations used in Spectroscopy and Microscopy ............ 1087 Appendix 14 Typical Properties of Unreinforced Plastic Polymers .......... 1089 Appendix 15 Acronyms for Thermoplastic Polymers .......................... 1117 Appendix 16 Companies Involved with Carbon Fibers and their Composites Throughout the World ......................................... 1119 Index ...................................................................... 1133