Material Properties of Injection Molded Glass and Carbon Fiber Reinforced Thermoplastic Composites A Review SPE Automotive Composites Conference & Exhibition, Sept. 7-9 216 Mark Cieslinski, BASF - Advanced Materials & Systems Research 216 BASF Corporation
Outline 1 2 3 4 About BASF Why Composites? What Influences Composite Properties? Summary 5 216 BASF Corporation 2
Outline 1 2 3 4 About BASF Why Composites? What Influences Composite Properties? Summary 5 216 BASF Corporation 3
BASF We create chemistry Our chemistry is used in almost all industries We combine economic success, social responsibility and environmental protection Sales 215: 7,449 million EBIT 215: 6,739 million Employees (as of December 31, 215): 112,435 6 Verbund sites and 376 other production sites 216 BASF Corporation 4
Research and development at a glance Research for the future: With our innovative products and processes, we provide sustainable solutions for global challenges. Expenditures for research and development 1,953 million, world leader in chemical industry Around 3, research projects Strongest innovation power in the chemical industry (No.1 in the Patent Asset Index TM ) Target 215 achieved: around 1 billion sales with new and improved products or applications that had been on the market since 211 5 6 4 1 1.95 billion 1 Chemicals 11% 2 Performance Products 2% 3 Functional Materials & Solutions 2% 4 Agricultural Solutions 26% 5 Oil & Gas 2% 6 Corporate Research, Other 21% 3 2 216 BASF Corporation 5
Advanced Materials & Systems: Global research Verbund Ludwigshafen Lemfoerde Muenster Wyandotte Shanghai Tarrytown Singapore Duesseldorf Basel Trostberg 216 BASF Corporation 6
Outline 1 2 3 4 About BASF Why Composites? What Influences Composite Properties? Summary 5 216 BASF Corporation 7
Metal replacement: comparison with engineering plastics compounds Material Steel (ferritic, austenitic) Steel (High-strength ) r g/cm³ T m C 7.8 115 (FeC4) Al alloys 2.7 577 (AlSi12) PA66 GF5 (23 C, dry conditions) E GPa s MPa Steel and Al-alloys: Data taken from Hütte (1996) K IC MN/m³ / ² Low density even for highly glass fiber filled PA compound is advantageous Tensile strength of PA compound is high and comparable to soft Al alloys l W/mK 195-21 44-75 5-2 3-6 7.8-195 - 21 13-21 - - 6-8 3-7 23-45 121-237 1.56 26 16.8 24 5-1 (~.5) Stiffness and fracture toughness as well as melting point and thermal conductivity much lower compared to metals 216 BASF Corporation 8
Specific tensile strength & stiffness of PA66 compounds Comparison of glass & carbon fibers High-strength steel Al-alloys Steel Specific tensile strength of highly GF-filled PA compounds similar to Al-alloys and higher than steel Specific stiffness of PA/GF compounds further enhanced by carbon fibers 216 BASF Corporation 9
Outline 1 2 3 4 About BASF Why Composites? What Influences Composite Properties? Summary 5 216 BASF Corporation 1
Question: What injection molding material do we use for our application? Short or Long fiber? Glass or Carbon fiber? Resin? How do these variables transfer to mechanical properties? Modulus Strength Impact Fatigue 216 BASF Corporation 11
Designations of Fiber Lengths Short fibers incorporated into thermoplastic via extrusion compounding, typical average fiber length <.5 mm Long fibers composites retain fiber length in molded part > 1. mm, pultrusion or wet-lay processes are used Extrusion/Injection molding reduces fiber length to a log-normal distribution, described by: Number average fiber length, Ln = Weight average fiber length, Lw = N i L i N i 2 N i L i N i L i Number of Fibers, N i Fiber length distribution Fiber Length, L i Aspect Ratio = Length Diameter 216 BASF Corporation 12
Normalized Property Fiber Length Trends 1.2 Modulus 1 Strength Impact Modulus Cox model Strength Kelly-Tyson Model Impact Thomason-Vlug model.8.6.4.2 Notched Charpy Impact.1.1 1 1 1 Fiber Length, mm Modulus Strength 1-4 wt% glass Polypropylene produced via wet-lay process Normalization trend appears independent of concentration for Flexural and Tensile data J. Thomason and M. Vlug, "Influence of fibre length and concentration on the properties of glass fibre-reinforced polypropylene: 4. Impact properties," Composites: Part A, pp. 277-288, 1997. J. Thomason, "The influence of fibre length and concentration on the properties of glass fibre reinforced polypropylene: 5. Injection moulded long and short fiber PP," Composites: Part A, pp. 1641-1652, 22. 216 BASF Corporation 13
Injection Molded Composites Long Glass Fiber - Polypropylene Length Average, Lw Number Average, Ln Fiber length decreases with increasing concentration Modulus linearly increasing with concentration (except >65wt%) J. Thomason, "The influence of fibre length and concentration on the properties of glass fibre reinforced polypropylene. 6. The properties of injection moulded long fibre PP at high fibre content," Composites: Part A, pp. 995-13, 25. 216 BASF Corporation 14
PA66 15% Short Glass 25% Short Glass 3% Short Glass 35% Short Glass 4% Short Glass 5% Short Glass 4% Long Glass 5% Long Glass 6% Long Glass 65% Long Glass PA6 15% Short Glass 25% Short Glass 3% Short Glass 35% Short Glass 4% Short Glass 5% Short Glass 4% Long Glass 5% Long Glass 6% Long Glass PA66 15% Short Glass 25% Short Glass 3% Short Glass 35% Short Glass 4% Short Glass 5% Short Glass 4% Long Glass 5% Long Glass 6% Long Glass 65% Long Glass PA6 15% Short Glass 25% Short Glass 3% Short Glass 35% Short Glass 4% Short Glass 5% Short Glass 4% Long Glass 5% Long Glass 6% Long Glass Modulus, GPa Strength, MPa Ultramid Polyamide Glass Fiber Materials Dry as molded 25 2 Modulus Tensile Modulus Flexural Modulus 5 4 Strength Tensile Strength Flexural Strength 15 3 1 2 5 1 Ultramid PA 66 A Ultramid PA 6 B Ultramid PA 66 A Ultramid PA 6 B Parallel trends in flexural and tensile moduli and strength Modulus independent of fiber lengths in test specimens 216 BASF Corporation 15
PA66 15% Short Glass 25% Short Glass 3% Short Glass 35% Short Glass 4% Short Glass 5% Short Glass 4% Long Glass 5% Long Glass 6% Long Glass 65% Long Glass PA6 15% Short Glass 25% Short Glass 3% Short Glass 35% Short Glass 4% Short Glass 5% Short Glass 4% Long Glass 5% Long Glass 6% Long Glass Charpy Impact Strength, kj/m² Ultramid Impact properties 6 5 4 Notched, Dry, 23C Notched, Dry, -3C 3 2 1 Ultramid PA 66 A Ultramid PA 6 B Long fiber advantage Impact performance 216 BASF Corporation 16
Strain, % Short/Long Creep Performance Ultramid A - 5% glass fiber 1.4 1.2 1.8.6.4.2 Short fiber Long fiber.1 1 1 1 1 1 Time, h PA66 Short Fiber - 4 MPa PA66 Long Fiber - 4 MPa PA66 Short Fiber - 8 MPa PA66 Long Fiber - 8 MPa Creep performance differences more pronounced at higher time scales and higher loadings 216 BASF Corporation 17
Crack growth rate Tensile Stress, MPa Fatigue Behavior Short Glass Fibers Parallel to Flow Direction in Injection Molded Plaque 1 Short & Long Glass Fibers Ultramid A 5% glass fiber PA66 Short Glass PA66 Long Glass 1 1 2 3 wt% fibers in PP Fracture Toughness Increasing fiber content increases toughness while inhibiting crack growth 1 1 1 1 1 1 1 1 1 Number of Cycles Fatigue performance extend due to long fibers creating a fiber network A. Pegoretti and T. Ricco, Fatigue fracture of neat and short glass fiber reinforced polypropylene: effect of frequency and material orientation," Journal of Composite Materials, vol. 34, no. 12, pp. 19-127, 2. 216 BASF Corporation 18
Normalized Composite Properties Fiber Length, mm Fiber Diameter Effects (PA66-3wt% glass) 2.9 1.8 1.6.8.7 52 46 1.4 1.2 1.8.6.4.2 Tensile Strength Tensile Modulus Tensile Strain Flexural Strength Flexural Modulus Notched Izod Impact Strength Unnotched Izod Impact Strength 8 1 12 14 16 18 Fiber Diameter, µm.6.5.4.3.2.1 59 55 33 35 36 34 8 1 12 14 16 18 Fiber Diameter, µm Strength some decrease (14%) Modulus no change (2%) Notched Impact slight increase (7%) Unnotched Impact significant decrease (72%) Average Length Average Aspect Ratio diameter, µm Ln, mm Lw, mm Ln/d Lw/d 1.34.55 34 55 11.4.65 36 59 14.49.73 35 52 17.56.79 33 46 Thomason, "The influence of fibre properties of the performance of glass-fibre-reinforced polyamide 6,6," Composites Science and Technology, vol. 59, pp. 2315-2328, 1999. 216 BASF Corporation 19
Properties Normalized to 4% Short Glass Ultramid A3W - 4 wt% Short/Long, Glass/Carbon Fiber 3. 2.5 2. 1.5 4% Short Glass 4% Long Glass 4% Short Carbon 4% Long Carbon Long glass fibers Impact Properties 1. Carbon fibers.5. Tensile Modulus Tensile Strength Strain at Break Flexural Modulus Typical properties of glass and Carbon fiber Glass Carbon Density, g/cm 3 2.5 2.6 1.7 1.8 Tensile Modulus, GPa 7 8 225 275 Tensile Strength, GPa 1.5 3.5 2.5 5 Elongation at Break, %.5 2 1.8 3.2 Flexural Strength Charpy notched impact strength Stiffness Strength 216 BASF Corporation 2
Relative specific properties to 4% Short Glass Fiber Ultramid A Specific Properties Normalized to 4% Short Glass 4 3.5 3 2.5 2 1.5 1.5 Tensile Modulus Tensile Strength Strain at Break Specific Property = Flexural Modulus 4% Short Glass 4% Long Glass 4% Short Carbon 4% Long Carbon Flexural Strength Property Composite Density Charpy notched impact strength Advantages of carbon fiber become more pronounced for light-weighting applications Long glass fiber impact properties not as significant improvement 216 BASF Corporation 21
Number Average Fiber Length, mm Tensile Modulus, GPa Tensile Strength, MPa Notched Charpy Impact Strength, Glass and carbon fiber at equal volume% in polypropylene 16 14 12 1 8 6 4 2 Short Glass Short Carbon 2 4 6 Weight % Property Carbon Glass Diameter, µm 7.5 13.8 Tensile Strength, MPa 395 1956 Tensile Modulus, GPa 238 78.5 Stiffness translated from fiber properties 7 6 5 4 3 2 Short Glass 1 Short Carbon 2 4 6 Weight %.7.6.5.4.3.2 kj/m 2 7 6 5 4 3 2 Short Glass 1 Short Carbon 2 4 6 Weight % 48 46 43 Aspect Ratios 39 37 31 Strength & Impact less driven by fiber properties more likely aspect ratio & sizing.1 2 4 6 Weight % Short Glass Short Carbon S.-Y. Fu, B. Lauke, E. Mäder, C.-Y. Yue and X. Hu, "Tensile properties of short-glass-fiber- and short-carbon-fiber-reinfoced polypropylene composites," Composites: Part A, pp. 1117-1125, 2. S. Fu, B. Lauke, E. Mäder, X. Hu and C. Yue, "Fracture resistance of short-glass-fiber-reinforced and short-carbon-fiber-reinforced polypropylene under Charpy impact load and its dependence on processing," Journal of Materials Processing Technology, pp. 51-57, 1999. 216 BASF Corporation 22
Tensile Modulus, GPa Tensile Strength, MPa Ultramid Properties with Temperature 4 35 4% Carbon Dry 35 3 Dry 3 25 2 15 1 5% Glass 25 2 15 1 PA66 5% Short Glass PA66 5% Long Glass PA66 4% Short Carbon PA66 4% Long Carbon PA66 PA66 5% Short Glass PA66 5% Long Glass PA66 4% Short Carbon PA66 4% Long Carbon PA66 5 PA66 5-4 -2 2 4 6 8 1 12 14 16 Temperature, C -4-2 2 4 6 8 1 12 14 16 Temperature, C Fiber network from long fibers improves modulus at elevated temperatures 216 BASF Corporation 23
Tensile Strength, MPa Tensile Modulus, GPa Resin Formulation - Ultramid A 18 16 14 12 1 8 6 4 2 3 25 Short Glass Fiber 1 2 3 4 5 6 Fiber Content, wt% Heat Aging Resistant Impact Modified Flame Retardant Stabilized Stabilized Short Glass Fiber Notched Charpy Impact Strength, kj/m 2 45 4 35 3 25 2 15 1 5 Short Glass Fiber Short Glass Fiber + Impact Modifier Long Glass Fiber 1 2 3 4 5 6 7 Fiber Content, wt% 2 15 General trends of property improvement with concentration appear to be universal 1 5 Some additives necessary for the end-use application can negatively effect properties 1 2 3 4 5 6216 BASF Corporation 24
General Summary Property Modulus Strength Strain at Break Increase Concentration Increase Fiber Length Carbon Fiber (relative to glass) - Notched Impact - Creep Fatigue Performance at Higher Temperatures *Concentration, length and fiber type are not completely independent variables Properties in the end-use part are largely influenced by processing: Fiber Orientation Fiber Length (aspect ratio) 216 BASF Corporation 25
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