ERT Script

Polymers are a crucial part of life. DNA, proteins, starches, cellulose, asphalt, rubber and silk are all naturally occurring polymers. It only took mankind a few million years to realise the significance of these polymers, and begin to mimic, and even compete, with nature. In 1935, the first truly synthetic polymer, nylon 6/6, was invented by Wallace Carothers at the DuPont Experimental Station. Nylon was first used commercially as a nylon-bristled toothbrush and later for stockings. During World War II nylon was used primarily for parachutes, flak vests and other military applications. The light-weight, high-strength fibre Kevlar was also patented by DuPont, in 1962. Nylon and Kevlar differ only as a result of the benzene rings in Kevlar, but the effects of these benzene rings on the properties of Kevlar are profound. Kevlars most famous application is bullet resistant armour, but it has potential in many other fields, including the possible replacement of nylon in parachutes. Both nylon and Kevlar are condensation polymers. This means that they are formed when monomers react and release a small molecule in the process. Nylon is a thermoplastic elastomer, which means it becomes sufficiently fluid when melted that it can be moulded, and that it is highly elastic. Kevlar is also thermoplastic but it has a high melting point, which hinders moulding in production. Both polymers are polyamides. Polyamides are produced via stepgrowth polymerisation where equal parts of a diamine and dicarboxylic acid react. Nylon polymers consist of polyethylene segments separated by peptide units. The two most common versions are nylon 6-6 (or polyhexamethylene adipamide) and nylon 6 (or polycaprolactam). The main difference between nylon 6 and nylon 6-6 is nylon 6 has a much lower melting point. Nylon 6-6 is most common type of nylon used for parachutes. Kevlar, or poly-paraphenylene terephthalamide, is also produced in different grades. Kevlar 29 has approximately half the modulus and twice the elongation of Kevlar 49 (refer to graph) and this is the reason it is the most common grade for parachutes. This link will be explained later, but basically, if the material is not elongated during deceleration, the force will be applied in an instant, potentially damaging the load and parachute. In order to understand the reasons behind the different properties of Nylon 6-6 and Kevlar, their molecular structure must be analysed. Polymer crystallinity is one of the important properties of all polymers. Nylon and Kevlar are both semi-crystalline polymers. Amorphous regions increase the flexibility and lower the tensile moduli of polymers because these sections can stretch outwards. Conversely, crystallinity increases tensile strength, cut resistance, melting points and chemical resistance. This is primarily due to

increased inter-chain bonding within crystalline sections. The degree of crystallinity of Kevlar is determined during processing. Kevlar 29 has a degree of crystallinity of 68% 85% while Kevlar 49 can be up to 95% crystalline, both of which are more crystalline than all types of nylon 6-6. One of the major factors in the strength of polymers is inter-molecular bonding. Hydrogen bonding occurs when a highly electropositive hydrogen atom is attracted to a highly electronegative atom such as nitrogen or oxygen. These hydrogen bonds form between the carbonyl oxygen atoms in one chain and the amide hydrogen atoms in adjacent chains in all polyamides. The most significant effect of the benzene rings is on the orientation of the functional groups in Kevlar. When the functional groups are on the same side of a chain, this is known as a cis-amide linkage, whereas if they are on the same side this is called a trans-amide linkage. In nylon, the incidence of cis-conformations is more regular, and long straight fibres are less common. However, Kevlar molecules rarely form these bends in structure, due to the electrostatic repulsion between the benzene rings. Para linkages are formed between the rings and the atoms on either side, further straightening the chains. The benzene rings increase the linearity of Kevlar molecules, increasing the incidence of hydrogen bonding and thus the crystallinity. This enhances tensile, compressive and shear strengths; cut and tear resistance; and thermal properties of the substance. Aromatic stacking interactions refer to intermolecular attractions between benzene molecules, and are another factor that contributes to Kevlars strength. Benzene molecules have an uneven distribution of charge, with greater electron-density on the face of the ring and reduced electron-density on the edge due to the delocalised pi electrons (refer to and explain diagram). Overall, the covalent bonds holding the molecules together, the hydrogenbonding between chains and the stacking interactions perpendicular to this hydrogen bonding all contribute to Kevlars high isotropic strength. Another key property of both nylon and Kevlar is that they are light-weight. Using organic polymers based on light elements, such as carbon, nitrogen, hydrogen and oxygen, instead of elements with higher atomic masses like transition metals, gives the advantage of low-weight molecular structures. There are three key steps to the production of both polyamides: the production of the polymer itself, spinning and then drawing. Nylon 6-6 is most-commonly produced by the acid-base reaction between hexamethylene diamine and adipic acid where each monomer donates 6 carbons to the chain during polymerisation. When these two chemicals react they produce hexamethylene-diammonium-adipate, more commonly known as nylon salt. This is then heated to 250 C and a pressure of 1.5 MPa. Under these

conditions, these two groups (indicate on PowerPoint) have enough energy undergo a dehydration reaction to form amide bonds. Kevlar on the other hand is formed by the condensation reaction between paraphenylene diamine and molten terephthaloyl chloride, yielding hydrochloric acid as a by-product. After polymerisation, both polymers are then spun through spinnerets to stretch the solutions into long fibres. Following this stage, nylon 6-6 fibres are highly amorphous and need to be cold-drawn to increase their crystallinity. Conversely, once spun Kevlar has a liquid crystal arrangement in solution and already has a high degree of orientation due to structural design and steric hindrances as described before. The degree to which Kevlar is then drawn determines its grade. (Click again) This table summarises the properties of both nylon 6-6 and Kevlar 29. Nylon 6-6 is used in a wide range of applications including parachutes, fabrics and rope. It is useful because it is relatively strong and light weight, thermally resistant, elastic and durable under most conditions. Nylon 6-6 is also much cheaper: nylon 6-6 cloth costs about 6 times less than Kevlar 29. Kevlar 29 is an extremely strong material with an ultimate tensile strength of 3.6 GPa. Parachute materials need to be strong, durable and lightweight for prolonged, safe operation. Both nylon 6-6 and Kevlar are sufficiently light for parachute material, and the mass of the load will out-weigh the effect of using a Kevlar parachute with a density 0.29 g/cm3 higher than nylon. Factors which affect the durability of parachute material are moisture absorption and UV radiation. Polyamides absorb moisture when water molecules form polar bonds with amide groups, and interfere with intermolecular forces. While Kevlar 29 has higher moisture absorption than nylon 6-6, its properties are virtually unaffected by moisture, whereas moisture has been found to lower nylon 6-6s tensile strength by up to 31%. Therefore, if a nylon parachute passes through a cloud, it would reduce its performance more than for a Kevlar parachute. Extended exposure to UV radiation has detrimental effects on mechanical properties. While this is more of an issue for other applications, carbon black can be mixed with polymers, providing proven protection against UV degradation.

The problem with using Kevlar for the chords of a parachute is its high tensile modulus of 70.3 GPa and low resulting elongation. Impulse is a measure of the change in momentum of a mass and is equal to the product of force and time. The force that a parachute needs to apply in order to decelerate a load may harm/damage the load or apply excessive strain to the canopy if it is applied over a short time period. If the material stretches, the force applied to the chords and the load lowers because it is applied over a longer time.

The force required is proportional the mass of the load. Therefore, for parachutes designed for sky-diving this elasticity will not be such a problem because the force required will not harm the person. However, if a parachute is being used to lower supplies or to decelerate vehicles, parachute chords need to be incredibly strong and elastic. Kevlar can be used for the canopy, but is not suitable for the chords in these applications. DuPont manufactures a composite material called Kevlar Elastomer, which consists of a mixture of Kevlar and rubber, combining the strength of Kevlar with the elasticity and flexibility of rubber. This would be a stronger solution compared to nylon or rubber chords.

Polyamides present various environmental problems. Neither nylon nor Kevlar are biodegradable as a result of their strong inter-molecular forces. Kevlar is rarely recycled due to the expense of breaking it down and refining it. Kevlar is also rarely reused because it is used in critical applications like bullet resistant armour and parachutes. A key issue with nylon production is the generation of nitrous oxide, a greenhouse gas, as a by-product. Methods for recycling and reusing both polymers need to be investigated and implemented to minimise environmental impacts. Kevlar 29 and Nylon 6-6 differ physically as a result of the aromatic components within the Kevlar molecules. The benzene rings facilitate greater intermolecular forces and structural linearity, increasing Kevlars crystallinity and strength. While Kevlar is less economical than nylon, it is used in scenarios where safety, not money, is the biggest issue. For this reason, the environmental impact of Kevlar is often not taken into account. Clean ways to dispose and reuse polyamides need to be investigated and promoted. Kevlar is recommended for parachute canopy material in all applications where strength and durability are of paramount importance. Nylon on the other hand is appropriate for basic sky-diving parachutes where the weight of the load is minimal. Neither Kevlar nor nylon is suitable for the cords of a parachute used for high load deceleration, where both high strength and high elongation are required. Overall, nylon 6-6 is used primarily because of its versatility and availability, while Kevlar provides a high-cost, high-performance alternative.