Crystallinity polyamides

Varlot, K., Reynaud, E., Kloppfer, M. H., Vigier, G., and Varlet, J., Clay-reinforced polyamide preferential orientation of the montmoriUonite sheets and the polyamide crystalline lamellae, J. Polym. ScL B, 39, 1360-1370 (2001). 

Varlot K, Reynaud E, Kloppfer MH, Vigier G, Varlet J (2001) Clay-reinfOTced polyamide preferential orientation of the montmorillonite sheets and the polyamide crystalline lamellae. J Polym Sci B Polym Phys 39 1360-1370... 

Polyamide/ethylene-propylene, with higher crystallinity than other elastomeric polyamides, has improved fatigue resistance and improved oil and weather resistance. and service temperature usually increase with higher polyamide crystallinity. ... 

This amounts to preparing an alternating block copolymer from two prepolymers one (the polyamide) crystalline and the other (the long-chain diol) amorphous. 

When drawdown is high, the film may be uniaxially oriented and the properties of the final film isotropic. In the manufacture of strapping tape this effect is accentuated. If the cast or quenched film is to be used to feed an orientation tine, additional attention must be given to the amorphous—crystalline nature of the film ia the draw processes so that maximum strength can be achieved and uniform gauge and optical quality maintained. Slot casting is used for the orientation of these resins, polyesters, polyamides, and a variety of others. 

Applications. The polyamides have important appHcations. The very high degree of polymer orientation that is achieved when Hquid crystalline solutions are extmded imparts exceptionally high strengths and moduli to polyamide fibers and films. Du Pont markets such polymers, eg, Kevlar, and Monsanto has a similar product, eg, X-500, which consists of polyamide and hydra2ide-type polymers (31) (see High performance fibers Polyamides, fibers). 

Similady, hquid-crystal polymers exhibit considerable order in the hquid state, either in solution (lyotropic) or melt (thermotropic). When crystallized from solution or melt, they have a high degree of extended-chain crystallinity, and thus have superior mechanical properties. Kevlar (Du Pont) is an aromatic polyamide (atamid) with the repeating unit designated as (2). It is spun into... 

The primary driving forces behind investigation of new solvents include environmental concerns and the abiUty to form Hquid crystals in the new solvent systems. By analogy with Kevlar, a synthetic aromatic polyamide fiber, spinning from a Hquid crystalline solution should yield cellulose fibers with improved strength, as has been demonstrated in laboratory experiments. 

In thermoplastic polyurethanes, polyesters, and polyamides, the crystalline end segments, together with the polar center segments, impart good oil resistance and high upper service temperatures. The hard component in most hard polymer/elastomer combinations is crystalline and imparts resistance to solvents and oils, as well as providing the products with relatively high upper service temperatures. 

As is commonly the case with crystalline polymers the glass transition temperature is of only secondary significance with the aliphatic polyamide homopolymers. There is even considerable uncertainty as to the numerical values. Rigorously dried polymers appear to have TgS of about 50°C, these figures dropping towards 0°C as water is absorbed. At room temperature nylon 66 containing the usual amounts of absorbed water appears to be slightly above the T ... 

As with the aliphatic polyamides, the heat deflection temperature (under 1.82 MPa load) of about 96°C is similar to the figure for the Tg. As a result there is little demand for unfilled polymer, and commercial polymers are normally filled. The inclusion of 30-50% glass fibre brings the heat deflection temperature under load into the range 217-231°C, which is very close to the crystalline melting point. This is in accord with the common observation that with many crystalline polymers the deflection temperature (1.82 MPa load) of unfilled material is close to the Tg and that of glass-filled material is close to the T. ... 

The minimum service temperature is determined primarily by the Tg of the soft phase component. Thus the SBS materials ctm be used down towards the Tg of the polybutadiene phase, approaching -100°C. Where polyethers have been used as the soft phase in polyurethane, polyamide or polyester, the soft phase Tg is about -60°C, whilst the polyester polyurethanes will typically be limited to a minimum temperature of about 0°C. The thermoplastic polyolefin rubbers, using ethylene-propylene materials for the soft phase, have similar minimum temperatures to the polyether-based polymers. Such minimum temperatures can also be affected by the presence of plasticisers, including mineral oils, and by resins if these become incorporated into the soft phase. It should, perhaps, be added that if the polymer component of the soft phase was crystallisable, then the higher would also affect the minimum service temperature, this depending on the level of crystallinity. 

The reinforcing filler usually takes the form of fibres but particles (for example glass spheres) are also used. A wide range of amorphous and crystalline materials can be used as reinforcing fibres. These include glass, carbon, boron, and silica. In recent years, fibres have been produced from synthetic polymers-for example, Kevlar fibres (from aromatic polyamides) and PET fibres. The stress-strain behaviour of some typical fibres is shown in Fig. 3.2. 

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