GRAPHENE NANOPLATELETS REINFORCED BIOBASED POLYAMIDE COMPOSITES * Alper Kiziltas, Jennifer Zhu, Dan Frantz, William Paxton, Hiroko Ohtani, Kevin Ellwood and Debbie Mielewski * Research Scientist, Sustainable Biomaterials and Plastics Group * 9/8/16 SPE ACCE Nanocomposites Session SLIDE 1
Agenda Background Sustainable Materials- Drivers Sustainable Materials - Challenges Graphene and Biobased Polyamides Objective Experimental Section Results Conclusions Acknowledgements SLIDE 2
Ford s Sustainable Materials Strategy Vision Ford Motor Company will ensure that our products are engineered to enable sustainable materials leadership without compromise to Product Quality, Durability, Performance or Economics. Key Positions Recycled and renewable materials must be selected whenever technically and economically feasible. There will be no compromise to Product Quality, Durability & Performance or Economics. We will enhance technologies, tools and enablers to help validate, select and track the use of these materials in our products. The use of recycled and renewable content is increased year by year, model by model where possible. SLIDE 3
Sustainable Materials: Why Now? Increased use of renewable feed stocks and agricultural products, Increased use of recycled or waste by-products, Reduce dependence on foreign petroleum, Improved material life cycle, Improved performance in select functions, Increased consumer awareness. Sugarcane Fermentation Dandelion Corn Bio-based Resins Wheat straw Castor Bottles Jeans Soy Money Coconut Cellulose Palm Recycled Materials Natural Fiber Composites Bio-based Foams SLIDE 4
Sustainability in Automotive Composites This global trend is an opportunity, There are strong industry efforts for cost effective ways of improving the environmental footprint of composites, New functionalities and applications. SLIDE 5
Sustainable Materials - Challenges Renewable/Biobased Materials: Automotive environment, Appearance requirements, Compatibility issues, Sensitive to humidity, Processability -porosity issues, Degradation during processing. Recycled materials: A lack of market for recyclates, A lack of infrastructure, Economics, Mindset and Knowledge gap. Sakai et al. 2014 SLIDE 6
Graphene-Beyond the Sticky Tape Strongest and thinnest material ever measured. Improvement in mechanical and thermal properties. Graphene market will reach nearly $200m in 2026 at the material level.. Intellectual Property Office is an operating name of the Patent Office SLIDE 7
Biobased Engineering Polymers Chin 2013 SLIDE 8
From Zero to Hero: Bio-Based Polyamides Reduce petroleum usage by close to 1 million lbs/yr. Reduce CO2 emissions by 1.1million lbs/yr (compared to PA12). Properties Young's Modulus (MPa) Melting Point (degrees C) Density (g/cm3) Water Uptake (%) kgco2eg/kg Biobased (%) PA6 3000 223 1.14 10.5 9.1 0 PA66 2500 260 1.14 8.2 7.9 0 PA12 1400 178 1.01 1.5 6.9 0 PA11 1100 185 1.03 1.9 4.2 100 PA1010 1800 200 1.06 1.8 4.0 100 PA610 2100 223 1.07 2.9 4.6 62 Kabasci 2013, Arkema SLIDE 9
Objectives To construct various fuel system components from graphene nanoplatelets (GNP) reinforced biobased polyamide (PA 610) nanocomposites. Fabricate GNP-filled PA 610 nanocomposites via melt compounding and injection molding. Characterize the effect of GNP on the mechanical, rheological and thermal properties of PA610 nanocomposites. SLIDE 10
Materials and Formulations Material Product Name Supplier Density PA 610 Vestamid Terra HS18 Evonik 1.07 Graphite Nanoplatelets (GNP) xgnp15 XG Sciences 2.20 PA610 is a renewable, 62% biobased polyamide from castor bean. Samples Name PA610 (%) GNP (%) PA 610 100-2% GNP 98 2 4% GNP 96 4 6% GNP 94 6 8% GNP 92 8 11 SLIDE 11
Production :TSE+IM PA 610 Graphene Melt Compounding TSE Dry Ground Mixture Injection Molding ASTM Test Samples SLIDE 12
Experimental Approaches Tensile and Flexural Strength Tensile and Flexural MOE Elongation at Break Impact Strength Composites Glass Transition Temperature Melting Temperature Crystallization Temperature Thermal Stability DTGA Temperature Residual Mass Viscosity Elastic and Loss Modulus Loss Factor Van-Gurp-Palmen Plot SEM SLIDE 13 13
Elastic and Loss Modulus Elastic Modulus (Pa) 10000 1000 100 10 PA 610 2% GNP 4% GNP 6% GNP 8% GNP Loss Modulus (Pa) 10000 1000 100 10 PA 610 2% GNP 4% GNP 6% GNP 8% GNP 1 0.01 0.1 1 10 Frequency (Hz) 1 0.01 0.1 1 10 Frequency (Hz) The higher the GNP content of the composite, the higher the modulus. 14 SLIDE 14
Complex Viscosity 10000 Complex Viscosity (Pa.s) 10000 PA 610 2% GNP 4% GNP 6% GNP 8% GNP 1000 100 10 Complex Viscosity (Pa) 1000 100 0.1 Hz 1 Hz 10 Hz 40 Hz 1 10 0.01 0.1 1 10 PA 610 2 4 6 8 Frequency (Hz) Filler Loading (%) The complex viscosity of % GNP reinforced composites was higher than the neat PA 610. 15 SLIDE 15
Loss Factor and Van Gurp-Palmen Plot PA 610 2% GNP 4% GNP 6% GNP 8% GNP 100 Loss Factor 1 Phase Angle ( ) 10 PA 610 2% GNP 4% GNP 6% GNP 8% GNP 0.1 1 10 Frequency (Hz) 1e+1 1e+2 1e+3 1e+4 1e+5 Complex Modulus (Pa) The loss factor decreased with incorporation of GNP. 16 SLIDE 16
Steady-shear Viscosity Steady-shear Viscosity (Pa.s) 10000 PA 610 2% GNP 4% GNP 6% GNP 8% GNP 1000 100 Steady-shear Viscosity (Pa) 10000 1000 100 0.05 1/s 0.5 1/s 5 1/s 0.1 1 10 10 PA 610 2 4 6 8 Shear Rate (1/s) Filler Loading (%) The higher the GNP content of the composite, the higher the shear viscosity. 17 SLIDE 17
Tensile Properties Tensile Stress at Max. Load (MPa) 60 55 50 45 40 35 30 PA 610 2 4 6 8 Filler Loading (%) GNP increased the stiffness of the composite (8% GNP improved 93%). Stress at 5% strain decreased with the addition of GNP 5.0 4.5 4.0 3.5 3.0 2.5 2.0 Young's Modulus (GPa) 18 SLIDE 18
Flexural Properties Flexural Stress (MPa) 80 75 70 65 60 55 50 PA 610 2 4 6 8 Filler Loading (%) GNP increased the stiffness of the composite (8% GNP improved 18%). Stress at 5% strain increased with the addition of GNP. 2.3 2.2 2.1 2.0 1.9 1.8 1.7 Flexural Modulus of Elasticity (GPa) 19 SLIDE 19
Impact Properties 70 Impact Strength (J/m) 60 50 40 30 20 PA 610 2 4 6 8 Filler Loading (%) Impact strength decreases with filler loading (8% GNP has 47% lower impact strength than PA 610). 20 SLIDE 20
Thermal Properties (TGA and DSC) Temp at 10% mass loss ( C) Final Ash Content @ 600 C (%) PA 610 435.3 1.5 2% GNP 434.6 3.3 4% GNP 435.7 5.6 6% GNP 437.5 8.2 8% GNP 439.4 9.7 Sample Name T crys ( C) T melt ( C) PA 610 192.8 223.3 2% GNP 203.3 223.2 4% GNP 205.2 223.3 6% GNP 206.2 226.2 8% GNP 206.4 223.8 SLIDE 21
Morphological Properties Neat PA610 8% GNP SLIDE 22
Conclusions Tensile and flexural moduli increased with GNP filler loading. Elastic and loss modulus of the composites increased with increasing GNP percent. PA 610 composites behave as pseudo-plastic fluids. The higher the GNP content of the composite, the higher the shear viscosity and elastic modulus. This research will contribute positively using graphene based materials as a powerful next generation composite material in the automotive industry. SLIDE 23
Acknowledgements Sustainable Biomaterials and Plastics Group. XG Sciences. Evonik. James Boileau. SLIDE 24
Whether you believe you can or believe you can t, either way you re right -Henry Ford THANK YOU! SLIDE 25
SLIDE 26