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CREATING A MATERIAL ADVANTAGE Terry MCGRAIL CYTEC ENGINEERED MATERIALS STRATEGIC R&T DIRECTOR WILTON CENTRE UK POLYMER MATRIX COMPOSITES.

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Presentation on theme: "CREATING A MATERIAL ADVANTAGE Terry MCGRAIL CYTEC ENGINEERED MATERIALS STRATEGIC R&T DIRECTOR WILTON CENTRE UK POLYMER MATRIX COMPOSITES."— Presentation transcript:

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

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

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

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

5 % Composite /767 A A330/ A310 5% 50% C/E Spoiler C/E Empanage 1993: A330/340 13% of wing is composite 1989: A320 C/E tail plane 1985: A310 C/E tail fin box Winglet 787 A380 A350 CURRENT & FUTURE COMPOSITE OPPORTUNITIES ON CIVIL AIRCRAFT

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

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

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 B

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

10 USE TEMPERATURE AREA OF APPLICATION POLYMER MATRIX LOW AMBIENTAIRCRAFT INTERIORS PHENOLICS <120 o CCIVIL SUBSONIC EPOXY RESINS FORMULA 1EPOXY TP BLENDS POLYAROMATIC TPs o CCIVIL & MILITARYEPOXY RESINS SUBSONIC & SUPERSONICEPOXY TP BLENDS CYANATE ESTERS POLYAROMATIC TPs o CMILITARY BISMALEIMIDES SUPERSONIC o CJET ENGINE PROXIMITYPOLYIMIDES TS or TP >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

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

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

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

14 TYPICAL EPOXY FORMULATION FOR BLENDING WITH PES

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

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 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

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

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

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

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

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

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

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 High viscosity resin - Processable as prepreg Not suitable for RI processes

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

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

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 EPOXY RESIN + CURING AGENT  = <1000 cps THERMOPLASTIC FIBRES CO-WEAVE WITH CARBON FIBRE WOVEN FABRIC 3D FIBRE PREFORM INJECT LOW VISCOSITY RESIN PRIFORM™ TP fibre Dissolves Composite part

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

29 0 min 1 min2 min 3 min 4 min5 min 6 min7 min Fibre dissolution test in epoxy at 130 o C using hot-stage microscope Single fibre between two microscope slides and resin Dissolution tests in at 130 o C SOLUBILITY OF PES-COPOLYMER FIBRE IN EPOXY RESIN 40 µ diameter thermoplastic fibre Epoxy resin Fibre residue

30 Dissolution time of a single fibre in versus temperature THERMOPLASTIC FIBRE SOLUBILITY

31 Fracture Toughness G 1 c versus % Thermoplastic Toughened with TP powder Toughened with TP fibre

32 Curing and phase separation Time Temperature Injection Fibre dissolution °C 180 °C °C NEW PROCESSING CYCLE

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 matrix

34 PRIFORM vs 977-2A : Dry data

35 PRIFORM vs 977-2A : Wet/120°C data

36 A330/340 SPOILER CENTRE HINGE EXAMPLE Centre hinge issues –Machined forged aluminium –6 Kg each - 12 per aircraft –Labour intensive assembly –Bolted to spoiler/wing 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

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

39 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

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 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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