Super Structural Plastics Continue to Push the Frontier of Metal Replacement Hyundai Fair June 27-29, 2006
Super Structural Plastics Continue to Push the Frontier of Metal Replacement AGENDA Brief history Current State of Technology Focus on high productivity manufacture Injection Molding Structural, load-bearing applications Future Technology Trends/Challenges 2
Reinforced Engineering Thermoplastics Brief history 35 Carothers 1930 s Polymers: Nylon, Polystyrene, Polyethylene, Acrylics Glass Fibers: Commercial manufacturing process 1940 s Military: Consumer: 1950 s Injection molding process Corvette fiberglass body Glass fiber reinforced resins for Aircraft parts Reinforced plastic boat hulls Fishing rods, Serving trays, Pleasure boats (All Thermosets) 1960 s Introduction and growth of reinforced thermoplastics 47 Thunderbird 53-55 Corvette 1970 s Optimization of manufacturing and molding processes Commercial carbon fibers developed 3
Reinforced Engineering Thermoplastics Reinforced vs. Unreinforced Tensile Strength, MPa 200 180 160 140 120 100 80 60 40 20 0 PA66 PA66 30% GF PA66 40% MR PBT PBT 30% GF 12 10 Modulus, MPa 8 6 4 2 0 PA66 PA66 30% GF PA66 40% MR PBT PBT 30% GF 4
Glass fiber reinforcement Coupling agent Bonding fibers to polymer Uncoupled Coupled 80 6 Tensile Strength, MPa 70 60 50 40 30 20 10 Modulus, MPa 5 4 3 2 1 0 Resin +30% GF +30% GF Coupled 0 Resin +30% GF +30% GF Coupled 5
Current state of technology Primary Reinforcements Fiber Platelet Spherical Glass Glass Glass (solid, hollow) Carbon Mineral Mineral Mineral Aramide Metals Current technical advances Better coupling agents Chemical Resistance Long glass fiber reinforcements Nanocomposites Combinations of reinforcements High performance polymers In-line compounding/molding 6
Metal Replacement - How close are we? Steel Tensile Strength Standard Reinforced Engineering Polymers Future Structural Reinforced Engineering Polymers Al Zn Unreinforced Tensile Modulus 7
Benefits Through Light Weight Strength Superstructural Polymers Magnesium Alloy versus Aluminum = >40% weight savings with comparable strength! 133 up to 163 Aluminum Alloy 95 Mild Steel 52 Zinc 34 0 50 100 150 200 Specific Tensile Strength (MPa/s.g.) 8
Metal / PPS Replacement with Zytel HTN 9
Thermal Management Thermostat Housing Electric Water Pump & Valve Housing End User: Honda / Accord Grade: Zytel HTN51G Requirements: High heat resistance LLC resistance Creep resistance Mechanical Water Pump It runs at the time of an engine drive. It stops at the time of a hybrid motor drive. Radiator Engine Elc. Water pump (HTN51G35HSL) Heater core Thermostat At the time of an engine drive At the time of an idling stop (At the time of a hybrid motor drive) End User: Toyota / Prius Grade: Zytel HTN51G Requirements: LLC resistance Easy assembly with vibration welding 10
Fuel System Fuel Integrated Valve End-user: Honda Grade: Zytel HTN (GR/MR40%) Model : Accord (US model) Requirements: Dimensional Stability Ultrasonic welding Fuel resistance High temp. resistance Fuel Injector End User: Honda Grade: HTN51G Requirements: Cost Reduction Low SG Recycle-ability Process-ability (No flash) Faster cycle time Primary Bobbin HTN51G35HSL 11
Fuel System FUEL CUT OFF VALVE Grade: Zytel HTN 51G Model : Camry 4WD, Estima, etc. Requirements: Dimensional stability Ultrasonic welding Chemical resistance (Gasoline) High temp. resistance 12
Chasis / Powertrain Brake Guide Piston End User: Toyota Grade: HTN 51G Requirement: Chemical resistance (Brake oil) at elevated temp. Weld line strength Good quality for product liability Throttle Valve Gear End User: Model: Grade: Honda Civic HTNWRF51G Requirements: Dimensional stability / Low moisture pick up Low wear / low friction High temp. resistance 13
Auto E/E / Exterior Motor Brush Holder End User: Grade: HTN 51G Honda Requirements: Heat resistance at an elevated temp. Dimensional stability / low moisture pick up Cost Reduction Recycle-ability Sunroof Guide Bracket End User: Grade: Toyota, GM HTN GR/MR50% Opa,Cardina HUMMER Requirements: Low wear / low abrasion Dimensional stability / low moisture pick up Part strength during roll over Weight reduction Cost down 14
Summary There is still significant opportunity for metalreplacement by using our SuperStructural resins in monolithic parts - and where they work, they will almost always be the most cost-effective solutions v.s. hybrid structures. 15
DuPont Engineering Polymers Rynite Zytel PET Polyester Polymers Nylon Polymers Zytel HTN PPA Polymers Crastin Delrin Hytrel PBT Polyester Polymers Acetal Polymers Structural Product offerings Thermoplastic Polyester Elastomers 16
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Back Up Charts 18
Extending Properties for Reinforced Engineering Polymers Polymer Matrix Materials Primary function: Stabilize fibers Transfer stress between fibers Provide a barrier against adverse environmental effects Important Properties: Modulus Strength Chemical Resistance Resistance to end use environment (Tg, thermal stability) 19
Extending Properties for Reinforced Engineering Polymers Materials: PPA high performance polyamide technology Long glass fiber reinforced PPA and PA66 resins Glass-reinforced polyester Properties: High, consistent stiffness and strength capability Impact performance Creep resistance Structural performance at elevated temperatures 20
Superstructural Key Grades Reinforcement Type Filler Level Zytel HTN51 Zytel HTN52 Zytel HTN53 Zytel HTN54 Zytel PA66 Rynite PET Standard Fiber Length 45 51G45HSL 52G45HSL Rynite 545 50 53G50HSLR 54G50HSLR Rynite 555 (55% glass) 60 70G60HSL Long Length 40 75LG40HSL 50 51LG50HSL 75LG50HSL 60 75LG60HSL 21
Key Features of the Zytel HTN Product Families Superstructural Ultra Stiff High Strength Excellent Creep Resistance HTN51 Series HTN52 Series HTN53 Series HTN54 Series Outstanding retention of properties with moisture Improved dimensional stability Retains high level of stiffness up to 140 C PPA resin Highest melting point and deflection temperature Moldable in water heated tools PPA resin Highest stiffness/strength at ambient temperatures Good toughness Outstanding surface finish Water heated tools Good toughness High burst pressure and knit line strength Retention of properties with moisture Retains high level of stiffness up to 110 C Water heated tools PPA resin 22
High Strength and Stiffness 260 240 Short Glass fiber reinforced engineering polymers Polyamides conditioned to 50% RH 220 Stress at Break (MPa) ISO 527 200 180 160 140 120 PA46 50% GF PA66 43% GF PPS 40% GF PBT 50% GF 100 8 10 12 14 16 18 20 Tensile Modulus DAM (GPa) ISO 527 23
High Strength and Stiffness 260 Short Glass fiber reinforced engineering polymers Polyamides conditioned to 50% RH 240 Higher Performance short glass fiber reinforced PPA1 45% GF 220 PPA3 50% GF Stress at Break (MPa) ISO 527 200 180 160 140 120 PA46 50% GF PA66 43% GF PPA2 45% GF PPA4 50% GF PA66 60% GF PET 45% GF PPS 40% GF PBT 50% GF PET 55% GF 100 8 10 12 14 16 18 20 Tensile Modulus DAM (GPa) ISO 527 24
High Strength and Stiffness 260 Short Glass fiber reinforced engineering polymers Polyamides conditioned to 50% RH 240 Higher Performance short glass fiber reinforced Long glass fiber reinforced PPA1 45% GF PPA1 50% LFRT 220 PA66 50% LFRT PPA3 50% GF Stress at Break (MPa) ISO 527 200 180 160 140 120 PA46 50% GF PA66 40% LFRT PA66 43% GF PP 50% LFRT PPA2 45% GF PPA4 50% GF PA66 60% GF PET 45% GF PPS 40% GF PBT 50% GF PPS 50% LFRT PA66 60% LFRT PET 55% GF 100 8 10 12 14 16 18 20 Tensile Modulus DAM (GPa) ISO 527 25
High Notched Impact Strength and Modulus 70 Short Glass fiber reinforced engineering polymers Polyamides conditioned to 50% RH Notched Charpy Impact Strength (kj/m 2 ) ISO 179 60 50 40 30 20 10 0 PA46 50% GF PA66 43% GF PPS 40%GF 6 8 10 12 14 16 18 20 Tensile Modulus (GPa) ISO 527 26
High Notched Impact Strength and Modulus 70 Short Glass fiber reinforced engineering polymers Polyamides conditioned to 50% RH Notched Charpy Impact Strength (kj/m 2 ) ISO 179 60 50 40 30 20 10 0 Higher Performance short glass fiber reinforced PA46 50% GF PA66 43% GF PPA3 50% GF PA66 60% GF PPA4 50% GF PPS 40%GF PET 45% GF PPA1 45% GF PET 55% GF 6 8 10 12 14 16 18 20 Tensile Modulus (GPa) ISO 527 27
High Notched Impact Strength and Modulus Notched Charpy Impact Strength (kj/m 2 ) ISO 179 70 Glass fiber reinforced engineering polymers Polyamides conditioned to 50% RH DuPont EP Superstructural standard glass fiber reinforced products Zytel 75LG60HSL 60 DuPont EP Superstructural long glass fiber reinforced products Zytel 75LG50HSL 50 Zytel HTN51LG50HSL Zytel 40 75LG40HSL 30 PA46 50% GF PP 50% Long glass 20 PA66 43% GF Zytel HTN53G50HSLR Zytel 70G60HSL Zytel HTN54G50HSLR PPS 40%GF 10 Rynite 545 Rynite 555 Zytel HTN 51G45HSL 0 6 8 10 12 14 16 18 20 Tensile Modulus (GPa) ISO 527 28
LFRT - Long Fiber Reinforced Thermoplastics Pellet Dimensions: Standard vs. LFRT pellets Standard pellet compounding LFRT pellets from pultrusion process Fiber length in granules 8-12 mm Fiber length in molded parts are typically 3 4 mm versus 0.3 mm for standard glass fiber resins Component design plus processing conditions govern average fiber length and therefore part performance 29
LFRT - Increased Multiaxial Impact Performance 25 20 Energy to Max max Load load Total Energy Total energy 15 Joules 10 5 0 DAM ISO 663 3 mm Disc PA66 50% GR BK Zytel 75LG50L NC010 PA66 50% GF PA66 50% LFRT 30
Properties of PPA 50% LFRT vs. PPA 45% GF Stress at Break, MPa 280 260 240 220 200 180 160 140 120 18000 17000 16000 15000 14000 13000 12000 11000 10000 DAM DAM Flexural Modulus, MPa 50%RH 50%RH 80 70 60 50 40 30 20 10 0 50% LFRT 45% GF Notched Charpy Impact, kj/m^2 DAM 50%RH Long Glass vs. Short Glass PPA: 5% Higher Tensile Strength 10-20% Higher Modulus 4-7X Higher Notched Impact Strength 31
Creep Resistance at High Temperatures PPA 50% LFRT vs. PPA 45% GF DMA Accelerated Flexural Creep at 28 MPa, 150C PPA 50% LFRT vs. PPA 45% GF DAM Total Strain, % 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 1 10 100 1000 10000 100000 1000000 hrs Long Glass vs.short Glass PPA: Better Creep resistance at load and temperature extremes 32
Modulus vs Temperature PPA 50% LFRT vs. PPA 45% GF Tensile Modulus, Mpa 24000 20000 16000 12000 8000 4000 Tensile Modulus vs. Temperature PPA 50% LFRT vs. PPA 45% GF DAM Long Glass vs.short Glass PPA: Higher Stiffness throughout temperature range Similar retention of properties at 50%RH conditions 0-40C 23C 80C 100C 130C 150C 175C 200C Temperature, C Tensile Modulus vs. Temperature PPA 50% LFRT vs. PPA 45% GF 24000 50%RH Tensile Modulus, MPa 20000 16000 12000 8000 4000 0 23C 80C 100C 130C 150C Temperature, C 33
Reinforced Engineering Thermoplastics Current and Future Technology Trends High performance matrix polymers Longer glass fiber length Expanded use of carbon fiber Thermoplastic nanocomposites Polymeric fibers and self-reinforced polymers High strength, reinforced polymer fibers Combined multi-material reinforcements Metal plastic hybrid systems Engineered fiber/fabric composites, laminates and hybrids Bio-derived polymer matrices Natural fiber composites 34
Reinforced Engineering Thermoplastics Current and Future Challenges High volume, consistent supply of advanced reinforcements Polymer manufacture/compounding Optimum molding processes High productivity molding/forming processes Recycle-ability Painting and finishing Joining multi-materials systems Material property databases and end-user materials knowledge Fire and low temperature performance Part repair strategies 35