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CREATING A MATERIAL ADVANTAGE Terry MCGRAIL CYTEC ENGINEERED MATERIALS STRATEGIC R&T DIRECTOR WILTON CENTRE UK terry.mcgrail@cytec.com POLYMER MATRIX COMPOSITES OPPORTUNITIES and CHALLENGES OPPORTUNITIES and CHALLENGES Slide 2 Global Business Sales $620M pa Products qualified on virtually every military & civil aircraft in the western world Aerospace Composite Prepreg Engineering Adhesives and Primers Carbon fibre Manufacture and Weaving Fibre preforms and Resin Infusion PRIFORM A market and technology leader in: Unequaled aircraft qualification database Primary supplier of prepreg into Formula 1 Slide 3 E M D Fothergill NARMCO FIBERITE ROOTS OF CYTEC ENGINEERED MATERIALS Cytec Industries, Inc. (NYSE: CYT) CARBON FIBRE PRODUCTION Slide 4 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 Cockpit components Doors Interiors: sidewall, ceiling and floor panels; storage and cargo bins; lavatories and galleys Radome Air conditioning ductwork Pylon fairings Leading edge slats Ailerons Tail planes and elevators Fin boxes and rudders Engine components and cowlings Exteriors: Wing to body fairings Flaps, spoilers and deflectors % by Weight Composites Use on Large Commercial Transports Slide 5 % Composite 197019751980198519901995200020052010 747 757/767 A300-600 777 A330/340 747-400 A310 5% 50% 1982 737 C/E Spoiler 1995 777 C/E Empanage 1993: A330/340 13% of wing is composite 1989: A320 C/E tail plane 1985: A310 C/E tail fin box 1986 747 Winglet 787 A380 A350 CURRENT & FUTURE COMPOSITE OPPORTUNITIES ON CIVIL AIRCRAFT Slide 6 AIRBUS COMPOSITES USE CURRENT AIRBUS 380 25% weight of composite FUTURE AIRBUS 350 with composite wings >25% composite Slide 7 BOEING 787 COMPOSITE FUSELAGE & WINGS TARGET >50% COMPOSITE PROTOTYPE FLYING IN 2008 BOEING COMPOSITES USE 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 Slide 8 Global Hawk CURRENT and FUTURE OPPORTUNITIES - MILITARY AIRCRAFT F-22 UCAV F-35 JSF F-18 Mirage F15 F18CD C17 AV 8BRafale F18 E/F UCAV Euro Fighter F35 F/A 22 B2 19701980199020002010 Slide 9 F-22 Raptor 25% composite by weight CYCOM 977 THERMOPLASTIC TOUGHENED EPOXY USED ON F22 Weight reduction - specific strength Temperature performance Stealth characteristics Radar transparency Lower cost Slide 10 USE TEMPERATURE AREA OF APPLICATION POLYMER MATRIX LOW AMBIENTAIRCRAFT INTERIORS PHENOLICS 500 o CENGINEMETAL ALLOYS HIGH >>500 o CENGINE & BRAKESCERAMICS CARBON - CARBON What thermal properties does the application demand? Upper use-temperature CRITERIA FOR MATRIX SELECTION Slide 11 Cheap TSPhenolics TSEpoxies TPPolyphenylene sulfide (PPS) TSEpoxy/thermoplastic blendsT/P TSBismaleimides (BMIs) TPPolyetherketoneketone (PEKK) TPPolyetherimide (Ultem) TSCyanate esters TSPolyimide (PMR15) TPPolyetheretherketone (PEEK) Expensive SELECTION OF MATRIX BY PRICE RAW MATERIALS + PROCESSING COSTS CRITERIA FOR MATRIX SELECTION Slide 12 PRE-1980s PRE-1980s BRITTLE EPOXY RESINS BRITTLE EPOXY RESINS LOW DAMAGE TOLERANT COMPOSITE STRUCTURES POLYMER MATRIX EVOLUTION EARLY 1980s EARLY 1980s THERMOPLASTIC COMPOSITES APC2 (ICI) HIGH DAMAGE TOLERANCE AT A PRICE HIGH DAMAGE TOLERANCE AT A PRICE Slide 13 PRE-1980s PRE-1980s BRITTLE EPOXY RESINS BRITTLE EPOXY RESINS LOW DAMAGE TOLERANT COMPOSITE STRUCTURES POLYMER MATRIX EVOLUTION MID-1980s MID-1980s EPOXY:ENGINEERING THERMOPLASTIC BLENDS EPOXY:ENGINEERING THERMOPLASTIC BLENDS CIBA; Bucknell & Partridge, Cranfield University;Cecere, Hedricks & McGrath,VPI CIBA; Bucknell & Partridge, Cranfield University;Cecere, Hedricks & McGrath,VPI ICI, Hercules, BASF, Toray ICI, Hercules, BASF, Toray IMPROVED EPOXY RESIN TOUGHNESS IMPROVED EPOXY RESIN TOUGHNESS AFFORDABLE COMPOSITES WITH IMPROVED DAMAGE TOLERANCE AFFORDABLE COMPOSITES WITH IMPROVED DAMAGE TOLERANCE NO REDUCTION IN OTHER PROPERTIES AND PROCESSABILTY NO REDUCTION IN OTHER PROPERTIES AND PROCESSABILTY COMPOSITE USE IN PRIMARY CIVIL AIRCRAFT STRUCTURES COMPOSITE USE IN PRIMARY CIVIL AIRCRAFT STRUCTURES EARLY 1980s EARLY 1980s THERMOPLASTIC COMPOSITES APC2 (ICI) HIGH DAMAGE TOLERANCE AT A PRICE HIGH DAMAGE TOLERANCE AT A PRICE TOUGHENED BMIs BMIs Slide 14 TYPICAL EPOXY FORMULATION FOR BLENDING WITH PES Slide 15 VARIATION OF PES-TYPE POLYMER BACKBONE EPOXY:PES COPOLYMER BLENDS Slide 16 PES COPOLYMER END-GROUP VARIATIONS The amine end-groups on the polymer can be varied from 0% to 100% Slide 17 EFFECT ON MORPHOLOGY OF PES END-GROUPS Phase inverted morphology No chemical reaction between epoxy and PES Phase inverted morphology Co-inclusions in PES phase Phase inverted Smaller phase size Co-continuous morphology Covalent bonding between Epoxy and PES Slide 18 MORPHOLOGY Particulate Ribbon Co-continuous Phase inverted EPOXY:NH 2 -PES COPOLYMER BLENDS MORPHOLOGY Phase inverted Co-continuous HISTORICAL DATA Thermoplastic Variables versus Morphology & Fracture Toughness G 1 c NH 2 -PES copolymer backbone structure Amount of PES in blend Number of reactive ends on NH 2 -PES copolymer MW of PES copolymer Slide 19 STRUCTURE-PROPERTY RELATIONSHIPS EPOXY:THERMOPLASTIC BLEND CYCOM 977 range Thermo-mechanical properties Environmental resistance Morphology of cured blend CO-CONTINUOUS Thermoplastic copolymer backbone N o of reactive ends Mn of thermoplastic copolymer Amount of thermoplastic copolymer Epoxy resin mixture Curing agent Cure temperature Viscosity and processability Reaction induced phase separation by spinodal decomposition process Slide 20 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 EPOXY ENGINEERING POLYMER BLENDS AS COMPOSITE MATRICES Slide 21 PREPREG - THE MOST EXPENSIVE ROUTE TO COMPOSITE STRUCTURES THERMOPLASTICS CHEAPER AND EASIER PROCESSING SUPER-TOUGH THERMOSETTING RESINS CHEAPER & STIFFER REINFORCING FIBRES SIMPLER PREPREGGING PROCESS & LESS SCRAP ROOM TEMP STORAGE & TRANSPORT OF PREPREG CHALLENGES LOWER COST PREPREG FABRICATION PROCESSES: - AUTOMATIC TAPE-LAYING - OUT-OF-AUTOCLAVE PROCESSING LESS EXPENSIVE PROCESSING NEEDED ABILITY TO MAKE MORE COMPLEX STRUCTURES INCREASED AUTOMATION Slide 22 THE CHALLENGE OF PROCESSING COSTS How do we reduce material costs? How do we reduce processing costs? Material cost 25% Total processing cost 75% Breakdown of construction costs of aircraft composite part Slide 23 Pressure Resin Heat Vacuum Dry carbon preform REDUCE PROCESSING COSTS USING 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 WHY USE 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 Slide 24 MATRICES FOR COMPOSITES Processability Fluidity of matrix Epoxy resins - low viscosity precursors Crosslinked cured resin High temperature High modulus Property Brittle epoxy Poor damage resistance + Engineering Thermoplastic Tough Matrix Good damage resistance Cycom 977-2 High viscosity resin - Processable as prepreg Not suitable for RI processes Slide 25 MAJOR DISADVANTAGE OF LRI COMPARED TO PREPREG? 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 High toughness EPOXY:TP blends are too viscous to process because: Highly viscous EPOXY:TP blends do not satisfy these criteria Slide 26 THE PROBLEM - EPOXY:THERMOPLASTIC BLEND VISCOSITY For RI viscosity needs to be < 1000 cps Epoxy resin + hardener + 25% thermoplastic Cycom 977-2 Epoxy resin + hardener 977-20 CYTEC SOLUTION SOLUBLE FIBRE TECHNOLOGY - PRIFORM Slide 27 977-2 RESIN FORMULATION Epoxy resin + hardener 75% w/w Thermoplastic 25% w/w SOLUBLE FIBRE TECHNOLOGY THE CONCEPT EPOXY + CURING AGENT + THERMOPLASTIC MATRIX = 100K cps THERMOPLASTIC 977-20 EPOXY RESIN + CURING AGENT = THE FUTURE FOR COMPOSITES ----------? >50% COMPOSITE CIVIL AIRCRAFT STRUCTURE DOMESTIC CARS GREEN TECHNOLOGY MASS TRANSPORT GREEN TECHNOLOGY FAST SHIPS RAPID TRANSIT OF MAIL & MILITARY SUPPLIES MILITARY VEHICLES LIGHTWEIGHT EASILY TRANSPORTED >50% COMPOSITE UNMANNED MILITARY PLANES WIND TURBINES & INDUSTRIAL APPLICATIONS Slide 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 Slide 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