Thermoplastic service temperature

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. 

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. 

A typical phase diagram for such polymers is given in Fig. 18.9. With such crystdline polymers the melting point replaces the as the factor usually determining the maximum service temperature of thermoplastics and minimum service temperature of rubbers. However, being more complicated than amorphous polymers it is more difficult to make generalisations about properties. The following remarks may, however, be pertinent for crystalline polymers ... 

Polydithiazoles Polyoxadiazoles Polyamidines Pyrolyzed polyacrylonitrile Polyvinyl isocyanate ladder polymer Polyamide-imide Polysulfone Decompose at 525°C (977°F) soluble in concentrated sulfuric acid. Decompose at 450-500°C (842-932°F) can be made into fiber or film. Stable to oxidation up to 500°C (932°F) can make flexible elastomer. Stable above 900°C (1625°F) fiber resists abrasion with low tenacity. Soluble polymer that decomposes at 385°C (725°F) prepolymer melts above 405° C (76l.°F). Service temperatures up to 288° C (550°F) amenable to fabrication. Thermoplastic use temperature —102°C (—152°F) to greater than 150° C (302°F) acid and base resistant. 

Yu J.M., Dubios P., and Jerome R., Synthesis and properties of polypsobomylmethacrylate (IBMA)-b-butadiene (BD)-b-IBMA] copolymers New thermoplastic elastomers of a large service temperature range. Macromolecules, 29, 7316, 1996. 

TPEs from thermoplastics-mbber blends are materials having the characteristics of thermoplastics at processing temperature and that of elastomers at service temperature. This unique combination of properties of vulcanized mbber and the easy processability of thermoplastics bridges the gap between conventional elastomers and thermoplastics. Cross-linking of the mbber phase by dynamic vulcanization improves the properties of the TPE. The key factor that controls the properties of TPE is the blend morphology. It is essential that in a continuous plastic phase, the mbber phase should be dispersed uniformly, and the finer the dispersed phase the better are the properties. A number of TPEs from dynamically vulcanized mbber-plastic blends have been developed by Bhowmick and coworkers [98-102]. 

Before briefly discussing each type it is necessary to consider the performance of thermoplastic elastomers, and the problem of defining service temperature limits for them. The structural features that convey the ability to be processed as a thermoplastic are also a limiting factor in their use. Since it is the pseudocrosslinks that allow these materials to develop elastomeric behaviour, any factor which interferes with the integrity of the pseudocrosslinks will weaken the material, and allow excessive creep or stress relaxation to occur under the sustained application of stress and strain. Temperature is obviously one such factor. 

As with most nonpolar hydrocarbon-intense polymers, bitumens exhibit good resistance to attack by inorganic salts and weak acids. They are dark, generally brown to black, and their color is difficult to mask with pigments. They are thermoplastic materials with a narrow service temperature range unless modified with fibrous fillers and/or synthetic resins. They are abundant materials that are relatively inexpensive, thus their use in many bulk applications. 

Some of the conditions used in rubber test methods may need modifying for application to thermoplastic elastomers because of their intrinsic thermoplastic nature. If the temperatures generally used in ageing and compression set tests on thermosetting rubbers were applied to thermoplastic materials they could appear to perform extremely badly. Whether this was significant would depend on the service temperature. Data sheets need to be checked as those for thermoplastic elastomers may have used much lower temperatures that would be found for conventional rubbers, and it is only too easy to get a misleading impression of performance. 

Polysulfide resins combine with epoxy resins to provide adhesives and sealants with excellent flexibility and chemical resistance. These adhesives bond well to many different substrates. Tensile shear strength and elevated-temperature properties are low. However, resistance to peel forces and low temperatures is very good. Epoxy polysulfides have good adhesive properties down to -100°C, and they stay flexible to -65°C. The maximum service temperature is about 50 to 85°C depending on the epoxy concentration in the formulation. Temperature resistance increases with the epoxy content of the system. Resistance to solvents, oil and grease, and exterior weathering and aging is superior to that of most thermoplastic elastomers. 

Parts molded from polyetherimide can be assembled with all common thermoplastic assembly methods. Adhesives that are recommended include epoxy, urethane, and cyanoacrylate. However, service temperature must be taken into consideration in choosing an adhesive because PEI parts are generally used for high-temperature applications. Good adhesion can be effected by simple solvent wipe, but surface treatment by corona discharge, flame treatment, or chromic acid etch will provide the highest bond strengths. 

Organic matrices are divided into thermosets and thermoplastics. The main thermoset matrices are polyesters, epoxies, phenolics, and polyimides, polyesters being the most widely used in commercial applications (3,4). Epoxy and polyimide resins are applied in advanced composites for structural aerospace applications (1,5). Thermoplastics Uke polyolefins, nylons, and polyesters are reinforced with short fibers (3). They are known as traditional polymeric matrices. Advanced thermoplastic polymeric matrices like poly(ether ketones) and polysulfones have a higher service temperature than the traditional ones (1,6). They have service properties similar to those of thermoset matrices and are reinforced with continuous fibers. Of course, composites reinforced with discontinuous fibers have weaker mechanical properties than those with continuous fibers. Elastomers are generally reinforced by the addition of carbon black or silica. Although they are reinforced polymers, traditionally they are studied separately due to their singular properties (see Chap. 3). 

In thermoplastic matrices, the intrinsic characteristics derived from the linear chain structure have to be considered, mainly the capability of flow under stress at high temperatures. Thus, in amorphous and semicrystalline matrices, the service temperatures will be determined by Tg or Tg and T, respectively. Without reinforcement, creep is a major problem at temperatures lying in the interval Tg < T < r , but when the matrices are... 

In recent years new thermoplastic matrices have been developed to improve the stiffness/toughness balance and the service temperature, in comparison to the epoxy thermoset matrices used in high performance composites. These materials, usually referred to as advanced thermoplastic matrices (8), include polymers that have great structural similarities, with aromatic moieties in the main chain spaced by groups of the type diagrammed below. 

In Table 15.3 are shown the chemical structures and Tg and of some representative thermoplastic polymers for use at high temperature (3,9). These matrices have high continuous service temperatures (120-200° C) even under wet environmental conditions. Advantages of thermoplastic over thermoset matrices are their shorter fabrication cycle (generally controlled environment storage is not required) and the possibility to be reprocessed and reconsolidated after manufacture. Poly(ether ether ketone) is a strong contender with epoxy resins for use as a matrix in composite prepregs with carbon fibers to be utilized in structural aircraft components. 

Thermoplastic Type Designation Max. Continuous Service Temperature Comments... 

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