Polyamide Thermoplastics for Automotive Engine Applications

Polyamide Thermoplastics for Automotive Engine Applications Nathan Bryant ME 4720 Dr. Maher Amer

Polyamide Thermoplastics for Automotive Engine Applications Abstract Polyamide nylons have proven to be a high-performance, engineering polymer. Their high strength, impact toughness, temperature resilience, and oil resistance make them ideal for applications in environments too harsh for other polymers. The mechanical properties are further increased with the addition of reinforcing fibers. One specific application is under-the-hood engine components in automobiles due to its oil resistance and maintained strength under temperature. Current engine components made from polyamide nylons are rocker covers, fuel lines, oil pans, radiators, and belt tensioners to name a few. The benefits of these polymer engine components are decreased weight, ease of manufacturing, and increased corrosion resistance when compared to their aluminum or steel counterparts. These polyamide nylons are processed at lower temperatures than

aluminum or steel. This means parts can be injected molded as opposed to cast like metal, which allows for speedier, more efficient production. The increased use of polyamide nylon engine components results in source reduction of metals; however, these highly recyclable metals are replaced with thermoplastics with limited recyclability, and an increased usage of petrochemicals. To combat this, researchers are seeking to replace the petroleum-based polyamide resin with a renewable, plant oil-based resin. Currently, researchers have had success with castor oil-based polyamide resins. This will result in future, renewable polymers that will both increase manufacturing efficiency and engine performance, while reducing the use of petroleum-based polymer resins.

Polyamide Thermoplastics for Automotive Engine Applications Introduction Polyamide nylons are formed by the condensation polymerization

mechanism. In order to form polymer chains, the monomers must multi-functional. In the case of polyamides, a poly-amine monomer is reacted with a poly-acid monomer, and water is given off as a by-product.

Figure 1: Amidation Reaction A bi-functional monomer is required to form polymer chains, but tri-functional monomers will allow for branching of the polymer chains. Precise control over the polymerization process and the chemistry of the repeat unit allow for fine-tuning of the mechanical, chemical, and thermal properties. Polyamide nylons have high strength and impact toughness due to their crystallinity. Common engineering nylons are thermoplastic, linear polymers with a repeated CONH- amide link. This amide link is polar in nature, and is spaced at a constant increment down the length of the chain. The even spacing of the amide links cause strong intermolecular attraction upon crystallization. Each highly crystallized region is linked by the flexible backbone. This structure causes the polymer to have an increased melting point, and the intermolecular attraction maintains toughness at high temperatures. The spacing between each CONHamide link is a contributing factor to strength and toughness. Polyamide nylons with a higher frequency of amide links will experience increased strength and

Polyamide Thermoplastics for Automotive Engine Applications toughness due to the increased intermolecular attraction (Brydson, 1989, p. 457-

458). Byrdson also states the strength and toughness can be further increased with the addition of chopped glass-strand fibers. Tensile strength is increased, however elongation at break is decreased. Similarly, the fibers increase surface hardness, so impact fracture tends to be brittle instead of ductile (1989, p. 467-468). According to test data from DuPont (2012), their typical polyamide nylon 66 (Zytel) has a modulus of elasticity of 3100 MPa and Charpy impact strength of 5 kJ/m2 at room temperature. The addition of glass fibers increases the modulus of elasticity to 10,000 MPa and Charpy impact strength to 14 kJ/m2. The combination of high crystallinity and glass fiber reinforcement leads to an engineering polymer with excellent mechanical properties. Polyamide nylons have found use in harsh environment applications due to their high resistance to oils and hydrocarbons. This is due to the polar CONHamide link that does not interact with the mostly non-polar hydrocarbons. Although polyamides are not destroyed with oils and hydrocarbon, moisture absorption is a concern. This is due to the hydrogen bonding between the polyamide and the water. This is less of a concern at higher temperatures (>100C) because the water boils off, and the polymer remains sufficiently dry. However, during the molding process, care must be taken to keep the humidity low to prevent deformation and warping of the part. Moisture absorption during molding also reduces glass transition temperature, and reduces mechanical properties at high temperature. Too reduce moisture absorption, aromatic side groups can be added to the polymer to reduce the amount of hydrogen bonding sites along the chain (Kemmish, 2011, p. 51).

Polyamide Thermoplastics for Automotive Engine Applications Furthermore, the level of crystallinity can reduce moisture absorption. The more crystallized the polymer is, the less moisture can be absorbed into the polymer chain. This is due to the high intermolecular bonding within the crystallized regions, which minimizes the amount of available hydrogen bonding sites for the water molecules to bond to (Brydson, 1989, p. 457). The polar nature of the backbone provides chemical resistance to oils and hydrocarbons. This, combined with high crystallinity produces an engineering polymer that retains its strength in harsh chemical environments.

Polyamide nylons have unique thermal properties that make them useful in a wide temperature range. In particular, they have a lower glass transition temperature with a higher melting temperature. Even with high crystallinity, the polymer has a large temperature window of flexibility before melting (Brydson, 1989, p. 463). When glass fibers are added to the polymer, part deformation and stiffness are maintained at temperatures beyond the glass transition temperature. Because of this, the heat distortion temperature is defined as the temperature at which the part begins to deform. Typical, non-reinforced polyamide nylon will begin to deform at temperatures just above the glass transition temperature; however, glass fiber-reinforced nylon will retain its shape almost to its melting temperature (Kemmish, 2011, p. 50, 52). According to test data from DuPont (2012), their typical polyamide nylon 66 (Zytel) has a melting temperature of 263C. When placed under a 1.8 MPa bending stress, the unfilled nylon begins to deflect at 70C; however, the glass fiber-reinforced nylon begins to deflect at 250C. The added glass fibers allow maintained stiffness nearly to the melting point. This

Polyamide Thermoplastics for Automotive Engine Applications

produces an engineering polymer that maintains its mechanical properties in higher temperature environments. Recent State of Knowledge The high strength, impact toughness, temperature resilience, and oil resistance of polyamide nylons make them the ideal candidate for under-the-hood automotive engine components. Their oil resistance allows them to withstand the harsh fuels and lubricants used in the engine. When glass fiber reinforcement is added, the polymer maintains its shape and mechanical properties at the high temperatures within the engine bay. For these reasons, polyamides have become the go-to polymer for fuel lines. Especially with the move towards methanol replacing mineral oil as a fuel additive, highly resistant polymers are a design requirement. DSMs polyamide nylon 46 (Stanyl), has a low interaction with methanol than the existing nylon 66. Stanyl nylon 46 has permeability to methanol added M25 fuel of ~5 g/m2 day, compared to ~23 g/m2 day for nylon 66. When reinforced with glass fibers, nylon 46 has high impact toughness and temperature resistance just shy of its 290C melting temperature (Technology News, 1999, p. 22). These fuel lines have seen great success in the automotive industry due to their oil resistance and simple extrusion manufacturing. Many automotive manufactures are looking to replacing even more metallic components with polymer due to its lighter weight and ease of molding. For example, Daimler-Chrysler has replaced its steel rocker covers with reinforced DuPont nylon 66 on their V6 minivan engines. The rocker covers provide a 65% weight reduction over its steel counterpart. The nylon rocker covers also cut the

Polyamide Thermoplastics for Automotive Engine Applications

time consuming machining and plating that was required for the steel part; instead, the covers are injected molded. The switch from steel to nylon only took 22 weeks from initial design to full production (Mechanical Engineering, 2004, p. 23). Even high wear components are being replaced with polyamide nylons. The Porsche Cayenne timing chain tensioners have been replaced with two grades of DSMs Stanyl nylon 46. The tensioners are molded out of a glass fiber reinforced nylon 46 for high strength at operating temperature, and are coated with a second grade of nylon 46 for wear and oil resistance (Advanced Materials & Processes, May 2005, p. 12-13). The success of polyamide nylons in automotive engines have lead to their use in aircraft jet turbine engines. Rolls Royce has adopted one of DSMs Stanyl glass fiber reinforced nylons for their engine infill panels. One advantage of the nylon is its ability to be molded into the large, complexly shaped panels. A second advantage is its high impact strength in a wide temperature band, which is crucial for resisting bird strikes (Advanced Materials & Processes, Aug. 2005, p. 22-23). The recent transition from metallic parts to polymer ones is promising decreased weight and ease of manufacturing of components. One concern of polyamide nylon engine parts is long-term durability of component, especially when compared to their metallic counterparts. A recent study by Zakaria Mouti et al (2010) investigates the impact resistance of polyamide nylon 66 oil pans when subjected to impact. Metallic oil pans have higher ductility, which aids impact strength, but also have lower corrosion resistance than their nylon counterparts. This is important when considering the oil pan will receive repeated impacts from small road debris. Their test method included both air gun

Polyamide Thermoplastics for Automotive Engine Applications and weight dropping techniques to replicate the impact of small stones. Repeated

testing showed that the nylon oil pans are much more susceptible to brittle fracture due to road debris impact. Such brittle fractures are catastrophic, causing loss of engine oil. They add that composites do not possess the ability to deform under impact like metal, and thus tend to fail. They conclude that further research is needed to determine if fracture can be prevented by reinforcing design modifications to the oil pan itself. For the time being, the design limitations of polyamide nylon must be considered when replacing metal in impact prone components. Future Trend Like most polymers, environmental impact is a major concern when it comes to their production and engineering application. Polyamide nylon is typically synthesized from petroleum by-products. These petrochemicals are not only harmful to humans and the environment, but have a limited source and ever increasing cost. Current research in polymer science seeks to replace the petrochemical derived resin with one from castor oil or other plant oils. Castor oil shows good potential due to its both renewable and is biocompatible for medical device usage. Another advantage of castor oil is that is non-edible, and its usage will not cut into food supplies. Research by Sujata Pramanik et al (2012) shows the viability of a castor oil derived, biodegradable resin for use in polyamide nylons. Unlike many polyamides, their experiment sought a thermoset polymer. The polymer demonstrated excellent hardness and chemical resistance, similar to the aforementioned polyamide nylons. Thermosets degrade upon heating, and thus

Polyamide Thermoplastics for Automotive Engine Applications cannot be melted and recycled; however, they noted the castor oil based thermoset fully biodegrades in as little as 6 weeks. They noted its ideal usage as a biodegradable thin film material. Castor oil polyamides are not limited to lab research, but are beginning to see commercial availability. DuPont currently offers grade of their polyamide nylon Zytel with varying levels of castor oil based resin. The Zytel thermoplastic nylon 610 is synthesized from ~60% castor oil, and can be reinforced with glass fibers for increased strength. Nylon 610 has been used by

Japans Denso Corp. to develop a car radiator tank. The component has been tested, and fulfills the necessary design parameters for ruggedness (Plastics Technology, 2011, p. 11). Implementation of castor oil based polyamide nylons in current products show a promising future for environmentally safe polymers. Polyamide nylons have already proven to be a viable replacement material for metals in automotive engine components. This is due to their high strength, impact toughness, temperature resilience, and oil resistance. Their lower processing temperatures make them easier to mold, and require less machining and plating processes. The lighter weight components increase overall vehicle performance and fuel economy. These polymers reduce the sourcing of aluminum and steel, which require large amounts of energy to mine and process. With current research into castor oil based polyamide resins, these polymers can also reduce the sourcing of the typically used petrochemicals. The near future holds a decreased usage of typical metals and plastics, and increased implementation of high-tech, environmentally friendly, biologically derived polymers.

Polyamide Thermoplastics for Automotive Engine Applications References

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Brydson, J. A. (1989). Polyamides and Polyimides. Plastics materials (5th ed., pp. 448496). London: Butterworths. DuPont Zytel: Product Guide and Properties. (2012). Geneva: DuPont. Kemmish, D. (2011). Semi-Aromatic Polyamides. Practical guide to high performance engineering plastics (pp. 47-55). Shrewsbury: iSmithers. Mouti, Z., Westwood, K., Kayvantash, K., & Njuguna, J. (2010). Low Velocity Impact Behavior of Glass Filled Fiber-Reinforced Thermoplastic Engine Components. materials, 3(4), 2463-2473. New Renewably Based Nylon. (2009, September). Plastics Technology, 55, 17. New material for auto fuel systems. (1999, February). Automotive Engineer, 24, 22. Nylon Rocker Covers. (2004, May). Mechanical Engineering, 126, 23. Porsche engine timing chain parts now made of polyamide. (2005, May). Advanced Materials & Processes, 163, 12-13. Pramanik, S., Sagar, K., Konwar, B. K., & Karak, N. (2012). Synthesis, characterization and properties of a castor oil modified biodegradable poly(ester amide) resin. Progress in Organic Coatings, 75(4), 569-578. Thermoplastic panels resist heat in Airbus A380 engine. (2005, August). Advanced Materials & Processes, 163, 22-23.