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CREATING A MATERIAL ADVANTAGE

CREATING A MATERIAL ADVANTAGE. POLYMER MATRIX COMPOSITES. OPPORTUNITIES and CHALLENGES. Terry MCGRAIL CYTEC ENGINEERED MATERIALS STRATEGIC R&T DIRECTOR WILTON CENTRE UK terry.mcgrail@cytec.com. A market and technology leader in:. Fibre preforms and Resin Infusion PRIFORM ™.

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CREATING A MATERIAL ADVANTAGE

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  1. CREATING A MATERIAL ADVANTAGE POLYMER MATRIX COMPOSITES OPPORTUNITIES and CHALLENGES Terry MCGRAIL CYTEC ENGINEERED MATERIALS STRATEGIC R&T DIRECTOR WILTON CENTRE UK terry.mcgrail@cytec.com

  2. A market and technology leader in: Fibre preforms and Resin Infusion PRIFORM™ Aerospace Composite Prepreg Engineering Adhesives and Primers Carbon fibre Manufacture and Weaving Global Business Sales $620M pa • Products qualified on virtually every military & civil aircraft in the western world • Unequaled aircraft qualification database • Primary supplier of prepreg into Formula 1

  3. Cytec Industries, Inc. (NYSE: CYT) CARBON FIBRE PRODUCTION E M D FIBERITE NARMCO Fothergill ROOTS OF CYTEC ENGINEERED MATERIALS

  4. Composites Use on Large Commercial Transports Tail planes and elevators Ailerons Leading edge slats Fin boxes and rudders % by Weight Interiors: sidewall, ceiling and floor panels; storage and cargo bins; lavatories and galleys Pylon fairings Exteriors: Wing to body fairings Cockpit components Flaps, spoilers and deflectors Doors Radome Engine components and cowlings Air conditioning ductwork TYPICAL CIVIL AIRCRAFT COMPOSITE SECONDARY STRUCTURES • Slower adopter than military • Conservative – safety paramount • Not as “performance” driven—cost is a key issue • Mostly secondary structures and interiors

  5. 787 50% 1995 777 C/E Empanage 1993: A330/340 13% of wing is composite 1989: A320 C/E tail plane % Composite 1986 747 Winglet A380 1985: A310 C/E tail fin box 777 1982 737 C/E Spoiler A330/340 A310 5% 747-400 A300-600 757/767 747 1970 1975 1980 1985 1990 1995 2000 2005 2010 CURRENT & FUTURE COMPOSITE OPPORTUNITIES ON CIVIL AIRCRAFT A350

  6. AIRBUS COMPOSITES USE CURRENT AIRBUS 380 25% weight of composite FUTURE AIRBUS 350 with composite wings >25% composite

  7. BOEING COMPOSITES USE BOEING 787 COMPOSITE FUSELAGE & WINGS TARGET >50% COMPOSITEPROTOTYPE FLYING IN 2008 SOME OF THE CHALLENGES BONDING LARGE COMPOSITE AND METAL STRUCTURES MONITORING THE HEALTH OF BONDS AND STRUCTURES DETECTION OF DAMAGE & REPAIR OF BONDS AND STRUCTURES OPPORTUNITIES FOR SELF-HEALING SUPPLY CHAIN – FIBRES, FABRICS, PREFORMS LIGHTENING STRIKE PROTECTION FIRE, SMOKE TOXICITY

  8. UCAV F-22 Euro Fighter B2 F35 F-35 AV 8B Rafale F/A 22 JSF F18 E/F F18CD C17 F15 Mirage Global Hawk 1970 1980 1990 2000 2010 F-18 UCAV CURRENT and FUTURE OPPORTUNITIES - MILITARY AIRCRAFT

  9. CYCOM 977 THERMOPLASTIC TOUGHENED EPOXY USED ON F22 F-22 Raptor 25% composite by weight • Weight reduction - specific strength • Temperature performance • Stealth characteristics • Radar transparency • Lower cost

  10. CRITERIA FOR MATRIX SELECTION What thermal properties does the application demand? Upper use-temperature USE TEMPERATURE AREA OF APPLICATION POLYMER MATRIX LOW AMBIENT AIRCRAFT INTERIORS PHENOLICS <120oC CIVIL SUBSONIC EPOXY RESINS FORMULA 1 EPOXY TP BLENDS POLYAROMATIC TPs 120-170oC CIVIL & MILITARY EPOXY RESINS SUBSONIC & SUPERSONIC EPOXY TP BLENDS CYANATE ESTERS POLYAROMATIC TPs 170-230oC MILITARY BISMALEIMIDES SUPERSONIC 315-375oC JET ENGINE PROXIMITY POLYIMIDES TS or TP >500oC ENGINE METAL ALLOYS HIGH >>500oC ENGINE & BRAKES CERAMICS CARBON - CARBON

  11. CRITERIA FOR MATRIX SELECTION SELECTION OF MATRIX BY PRICE – RAW MATERIALS + PROCESSING COSTS Cheap TS Phenolics TS Epoxies TP Polyphenylene sulfide (PPS) TS Epoxy/thermoplastic blends T/P TS Bismaleimides (BMIs) TP Polyetherketoneketone (PEKK) TP Polyetherimide (Ultem) TS Cyanate esters TS Polyimide (PMR15) TP Polyetheretherketone (PEEK) Expensive

  12. POLYMER MATRIX EVOLUTION PRE-1980s BRITTLE EPOXY RESINS LOW DAMAGE TOLERANT COMPOSITE STRUCTURES EARLY 1980s THERMOPLASTIC COMPOSITES – APC2 (ICI) HIGH DAMAGE TOLERANCE – AT A PRICE

  13. POLYMER MATRIX EVOLUTION PRE-1980s BRITTLE EPOXY RESINS LOW DAMAGE TOLERANT COMPOSITE STRUCTURES EARLY 1980s THERMOPLASTIC COMPOSITES – APC2 (ICI) HIGH DAMAGE TOLERANCE – AT A PRICE MID-1980s EPOXY:ENGINEERING THERMOPLASTIC BLENDS CIBA; Bucknell & Partridge, Cranfield University;Cecere, Hedricks & McGrath,VPI ICI, Hercules, BASF, Toray IMPROVED EPOXY RESIN TOUGHNESS AFFORDABLE COMPOSITES WITH IMPROVED DAMAGE TOLERANCE NO REDUCTION IN OTHER PROPERTIES AND PROCESSABILTY COMPOSITE USE IN PRIMARY CIVIL AIRCRAFT STRUCTURES TOUGHENED BMIs

  14. TYPICAL EPOXY FORMULATION FOR BLENDING WITH PES

  15. EPOXY:PES COPOLYMER BLENDS VARIATION OF PES-TYPE POLYMER BACKBONE

  16. PES COPOLYMER END-GROUP VARIATIONS The amine end-groups on the polymer can be varied from 0% to 100%

  17. EFFECT ON MORPHOLOGY OF PES END-GROUPS Phase inverted Smaller phase size Phase inverted morphology No chemical reaction between epoxy and PES Co-continuous morphology Covalent bonding between Epoxy and PES Phase inverted morphology Co-inclusions in PES phase

  18. EPOXY:NH2-PES COPOLYMER BLENDS HISTORICAL DATA Thermoplastic Variables versus Morphology & Fracture Toughness G1c MORPHOLOGY Particulate Ribbon Co-continuous Phase inverted MORPHOLOGY Phase inverted Co-continuous NH2-PES copolymer backbone structure Number of reactive ends on NH2-PES copolymer Amount of PES in blend MW of PES copolymer

  19. STRUCTURE-PROPERTY RELATIONSHIPS EPOXY:THERMOPLASTIC BLEND CYCOM 977 range Thermo-mechanical properties Environmental resistance Reaction induced phase separation by spinodal decomposition process Morphology of cured blend CO-CONTINUOUS Thermoplastic copolymer backbone No of reactive ends Mn of thermoplastic copolymer Amount of thermoplastic copolymer Epoxy resin mixture Curing agent Cure temperature Viscosity and processability

  20. EPOXY ENGINEERING POLYMER BLENDS AS COMPOSITE MATRICES ICI in MID-1980s EPOXY:THERMOPLASTIC BLENDS IMPROVED RESIN TOUGHNESS IMPROVED COMPOSITE DAMAGE TOLERANCE NO REDUCTION IN OTHER PROPERTIES AND PROCESSABILTY CYCOM 977 RANGE OF COMPOSITE PREPREGS NOW INDUSTRIAL STANDARD FOR PRIMARY STRUCTURES ON CIVIL AND MILITARY AIRCRAFT

  21. PREPREG - THE MOST EXPENSIVE ROUTE TO COMPOSITE STRUCTURES CHALLENGES THERMOPLASTICS – CHEAPER AND EASIER PROCESSING SUPER-TOUGH THERMOSETTING RESINS CHEAPER & STIFFER REINFORCING FIBRES SIMPLER PREPREGGING PROCESS & LESS SCRAP ROOM TEMP STORAGE & TRANSPORT OF PREPREG LOWER COST PREPREG FABRICATION PROCESSES: - OUT-OF-AUTOCLAVE PROCESSING - AUTOMATIC TAPE-LAYING LESS EXPENSIVE PROCESSING NEEDED ABILITY TO MAKE MORE COMPLEX STRUCTURES INCREASED AUTOMATION

  22. THE CHALLENGE OF PROCESSING COSTS Breakdown of construction costs of aircraft composite part Material cost 25% Total processing cost 75% How do we reduce material costs? How do we reduce processing costs?

  23. Pressure Resin Dry carbon preform Vacuum Heat REDUCE PROCESSING COSTS USING RESIN INFUSION Resin Transfer Moulding (RTM & VARTM) Liquid Resin Infusion (LRI, SCRIMP, RIFT) Resin Film Infusion (RFI) 3D fibre preform for injection with epoxy resin WHY USE RESIN INFUSION? Eliminates prepregging – labour reduction in processing Enables complex & integrated net shape parts to be made in one piece Allows for innovative engineering No autoclave required & lower cost tooling Eliminates the need for fasteners and adhesives so reduces fault lines Tailored fibre placement local property improvement

  24. High viscosity resin - Processable as prepreg Processability Property Property MATRICES FOR COMPOSITES Fluidity of matrix Epoxy resins - low viscosity precursors Crosslinked cured resin Brittle epoxy Poor damage resistance High modulus High temperature + Engineering Thermoplastic Tough Matrix Good damage resistance Cycom 977-2 Not suitable for RI processes

  25. MAJOR DISADVANTAGE OF LRI COMPARED TO PREPREG? High toughness EPOXY:TP blends are too viscous to process because: RI process requires permeation of the resin throughout the fibre preform to get: No voids or porosity in composite structure Complete wetting of fibres for mechanical properties Practicable injection times (resin pot-life) Safe injection temperature & pressure Highly viscous EPOXY:TP blends do not satisfy these criteria

  26. THE PROBLEM - EPOXY:THERMOPLASTIC BLEND VISCOSITY Epoxy resin + hardener + 25% thermoplastic – Cycom 977-2 Epoxy resin + hardener – 977-20 For RI viscosity needs to be < 1000 cps CYTEC SOLUTION – “SOLUBLE FIBRE TECHNOLOGY” - PRIFORM

  27. SOLUBLE FIBRE TECHNOLOGY – THE CONCEPT PRIFORM™ 3D FIBRE PREFORM TP fibre Dissolves 977-2 Composite part INJECT LOW VISCOSITY RESIN 977-20 EPOXY RESIN + CURING AGENT  = <1000 cps EPOXY + CURING AGENT + THERMOPLASTIC MATRIX  = 100K cps WOVEN FABRIC 977-2 RESIN FORMULATION Epoxy resin + hardener 75% w/w Thermoplastic 25% w/w THERMOPLASTIC CO-WEAVE WITH CARBON FIBRE THERMOPLASTIC FIBRES

  28. SOLUBILITY OF THERMOPLASTIC FIBRE IN EPOXY RESIN Fibre dissolution test in 977-20 epoxy at 120oC using hot-stage microscope Single fibre between two microscope slides and 977-20 resin

  29. SOLUBILITY OF PES-COPOLYMER FIBRE IN EPOXY RESIN Fibre dissolution test in 977-20 epoxy at 130oC using hot-stage microscope Single fibre between two microscope slides and 977-20 resin 40 µ diameter thermoplastic fibre Dissolution tests in 977-20 at 130oC Epoxy resin 1 min 2 min 0 min 3 min 6 min 7 min 4 min 5 min Fibre residue

  30. THERMOPLASTIC FIBRE SOLUBILITY Dissolution time of a single fibre in 977-20 versus temperature

  31. Fracture Toughness G1c versus % Thermoplastic Toughened with TP fibre Toughened with TP powder

  32. NEW PROCESSING CYCLE Temperature Curing and phase separation 180 °C Fibre dissolution 120-140 °C Injection 55-85 °C Time

  33. FIBRE DISSOLUTION DURING CURE CYCLE TP fibre is not soluble at resin injection temperature – resin flow front is unaffected TP fibres remain dormant until resin injection has been completed TP fibre slowly dissolves as temperature of mould is raised Dissolved TP then diffuses and enters into reaction with the epoxy The TP phase separates to give co-continuous morphology Epoxy resin is toughened by the TP – identical to 977-2 matrix

  34. PRIFORM 977-20 vs 977-2A: Dry data

  35. PRIFORM 977-20 vs 977-2A: Wet/120°C data

  36. A330/340 SPOILER CENTRE HINGE EXAMPLE • RFI composite Centre Hinge solution • 4 Kg each, • 35% weight reduction • Weight savings = 24 Kg total • Bonded to spoiler/wing • Cost reduction - estimated 25% • Innovative engineering • Centre hinge issues • Machined forged aluminium • 6 Kg each - 12 per aircraft • Labour intensive assembly • Bolted to spoiler/wing

  37. SOLUBLE FIBRE TECHNOLOGY - PRIFORM™ A novel technology for the manufacture of high toughness composite parts for aircraft primary structures via a cost-effective liquid resin infusion process CARBON FIBRE PREFORM FOR INFUSION WITH EPOXY RESIN

  38. COMPOSITE CENTRE FITTING BY RI PROCESS Carbon fibre + TP fibre preform for RI process Finished article! Demonstrator part for the Airbus A340-600 spoiler centre fitting Properties equivalent to Cycom 977-2 Now in production – A340 maiden flight completed Fischer Advanced Composites Components - proprietary design

  39. THE FUTURE FOR COMPOSITES ----------? >50% COMPOSITE UNMANNED MILITARY PLANES >50% COMPOSITE CIVIL AIRCRAFT STRUCTURE FAST SHIPS – RAPID TRANSIT OF MAIL & MILITARY SUPPLIES MILITARY VEHICLES – LIGHTWEIGHT – EASILY TRANSPORTED DOMESTIC CARS – GREEN TECHNOLOGY MASS TRANSPORT – GREEN TECHNOLOGY WIND TURBINES & INDUSTRIAL APPLICATIONS

  40. KEY CHALLENGES LIQUID RESIN INFUSION Match uniaxial prepreg properties Textiles technology – weaving, stitching, NCFs, non-woven fabric, 3D weaving Low viscosity resins – RT injectable Super tough – Boeing Materials Spec 8-276 properties Tough high temperature matrix – BMI? Low temperature curable resins Low cost tooling Engineering design MULTI-FUNCTIONAL COMPOSITES – STRUCTURAL PROPERTIES + ? Lightening strike protection Energy generation and storage Fire, Smoke, Toxicity minimisation Health monitoring In-flight structure adjustment Self-healing

  41. KEY CHALLENGES NANO-TECHNOLOGY COULD THIS GIVE ALL THE ANSWERS?: Mechanical properties – stiffness, strength – weight reduction toughness, damage resistance Electrical properties – conductivity, dielectric, irradiation screening, LSP Energy generation and storage Thermal conductivity Fire resistance Barrier to solvents, water, gases High performance from cheap resins CHALLENGES: Dispersing & exfoliating Characterisation of dispersions Functionalisation versus properties Processing of viscous/thixotropic dispersions Affordability - >>$100/g for SWNTs SHE

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