Thermoplastics temperatures

It is understandable that there is more freedom for the creation of intricate shapes in the thermoplastic temperature range than in the thermoelastic range. However, as a result of biaxial orientation, processing in the thermoelastic range yields products with higher strength, and with better barrier characteristics, transparency, and brilliance. 

Polycarbonates are the toughest of all thermoplastics. They are window-clear, amazingly strong and rigid, autoclavable, and nontoxic. They have a brittleness temperature of — 135°C. 

No polymer is ever 100% crystalline at best, patches of crystallinity are present in an otherwise amorphous matrix. In some ways, the presence of these domains of crystallinity is equivalent to cross-links, since different chains loop in and out of the same crystal. Although there are similarities in the mechanical behavior of chemically cross-linked and partially crystalline polymers, a significant difference is that the former are irreversibly bonded while the latter are reversible through changes of temperature. Materials in which chemical cross-linking is responsible for the mechanical properties are called thermosetting those in which this kind of physical cross-linking operates, thermoplastic. 

From the point of view of technology, it is convenient to classify polymers as thermosetting and thermoplastic. The former set by chemical crosslinks introduced during fabrication and hence do not change appreciably in their deformability with changes in temperature. Thermoplastics, on the other hand, soften and/or melt on heating and can therefore be altered in shape by heating... 

We noted above that the presence of monomer with a functionality greater than 2 results in branched polymer chains. This in turn produces a three-dimensional network of polymer under certain circumstances. The solubility and mechanical behavior of such materials depend critically on whether the extent of polymerization is above or below the threshold for the formation of this network. The threshold is described as the gel point, since the reaction mixture sets up or gels at this point. We have previously introduced the term thermosetting to describe these cross-linked polymeric materials. Because their mechanical properties are largely unaffected by temperature variations-in contrast to thermoplastic materials which become more fluid on heating-step-growth polymers that exceed the gel point are widely used as engineering materials. 

SAN resins possess many physical properties desked for thermoplastic appHcations. They are characteristically hard, rigid, and dimensionally stable with load bearing capabiHties. They are also transparent, have high heat distortion temperatures, possess exceUent gloss and chemical resistance, and adapt easily to conventional thermoplastic fabrication techniques (7). 

Cyanoacrylate adhesives (Super-Glues) are materials which rapidly polymerize at room temperature. The standard monomer for a cyanoacrylate adhesive is ethyl 2-cyanoacrylate [7085-85-0], which readily undergoes anionic polymerization. Very rapid cure of these materials has made them widely used in the electronics industry for speaker magnet mounting, as weU as for wire tacking and other apphcations requiring rapid assembly. Anionic polymerization of a cyanoacrylate adhesive is normally initiated by water. Therefore, atmospheric humidity or the surface moisture content must be at a certain level for polymerization to take place. These adhesives are not cross-linked as are the surface-activated acryhcs. Rather, the cyanoacrylate material is a thermoplastic, and thus, the adhesives typically have poor temperature resistance. 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

Thermal Properties. Fibers are not thermoplastic and stable to temperatures below 150°C, with the possible exception of slight yellowing. They begin to lose strength gradually above 170°C, and decompose more rapidly above 300°C. They ignite at 420°C and have a heat of combustion of 14,732 J/g (3.5 kcal/g). 

Polyester sheet products may be produced from amorphous poly(ethylene terephalate) (PET) or partiaHy crystallized PET. Acid-modified (PETA) and glycol modified (PETG) resins are used to make ultraclear sheet for packaging. Poly(butylene terephthalate) (PBT) has also been used in sheet form. Liquid-crystal polyester resins are recent entries into the market for specialty sheet. They exhibit great strength, dimensional stabHity, and inertness at temperatures above 250°C (see Polyesters,thermoplastic). 

Physical or chemical vapor-phase mechanisms may be reasonably hypothesized in cases where a phosphoms flame retardant is found to be effective in a noncharring polymer, and especially where the flame retardant or phosphoms-containing breakdown products are capable of being vaporized at the temperature of the pyrolyzing surface. In the engineering of thermoplastic Noryl (General Electric), which consists of a blend of a charrable poly(phenylene oxide) and a poorly charrable polystyrene, experimental evidence indicates that effective flame retardants such as triphenyl phosphate act in the vapor phase to suppress the flammabiUty of the polystyrene pyrolysis products (36). 

As a tme thermoplastic, FEP copolymer can be melt-processed by extmsion and compression, injection, and blow molding. Films can be heat-bonded and sealed, vacuum-formed, and laminated to various substrates. Chemical inertness and corrosion resistance make FEP highly suitable for chemical services its dielectric and insulating properties favor it for electrical and electronic service and its low frictional properties, mechanical toughness, thermal stabiUty, and nonstick quaUty make it highly suitable for bearings and seals, high temperature components, and nonstick surfaces. 

The typical mechanical properties that qualify PCTFE as a unique engineering thermoplastic are provided ia Table 1 the cryogenic mechanical properties are recorded ia Table 2. Other unique aspects of PCTFE are resistance to cold flow due to high compressive strength, and low coefficient of thermal expansion over a wide temperature range. 

Stabilization of the Cellular State. The increase in surface area corresponding to the formation of many ceUs in the plastic phase is accompanied by an increase in the free energy of the system hence the foamed state is inherently unstable. Methods of stabilizing this foamed state can be classified as chemical, eg, the polymerization of a fluid resin into a three-dimensional thermoset polymer, or physical, eg, the cooling of an expanded thermoplastic polymer to a temperature below its second-order transition temperature or its crystalline melting point to prevent polymer flow. 

Poly(vinylchloride). Cellular poly(vinyl chloride) is prepared by many methods (108), some of which utili2e decompression processes. In all reported processes the stabili2ation process used for thermoplastics is to cool the cellular state to a temperature below its second-order transition temperature before the resia can flow and cause coUapse of the foam. 

Phase Separation. Microporous polymer systems consisting of essentially spherical, intercoimected voids, with a narrow range of pore and ceU-size distribution have been produced from a variety of thermoplastic resins by the phase-separation technique (127). If a polyolefin or polystyrene is insoluble in a solvent at low temperature but soluble at high temperatures, the solvent can be used to prepare a microporous polymer. When the solutions, containing 10—70% polymer, are cooled to ambient temperatures, the polymer separates as a second phase. The remaining nonsolvent can then be extracted from the solid material with common organic solvents. These microporous polymers may be useful in microfiltrations or as controlled-release carriers for a variety of chemicals. 

Plastic packagiag materials are thermoplastic, ie, reversibly fluid at high temperatures and soHd at ambient temperatures. These materials may be modified by copolymerization, additives ia the blead, aHoyiag, and surface treatment and coating. Properties of principal plastic packagiag materials are givea ia Table 1. 

Polyester. Poly(ethylene terephthalate) [25038-59-9] (PET) polyester film has intermediate gas- and water- vapor barrier properties, very high tensile and impact strengths, and high temperature resistance (see Polyesters, thermoplastic). AppHcations include use as an outer web in laminations to protect aluminum foil. It is coated with PVDC to function as the flat or sealing web for vacuum/gas flush packaged processed meat, cheese, or fresh pasta. 

Free mono- and multilayer films may be adhesive- or extmsion-bonded in the laminating process. The bonding adhesive may be water- or solvent-based. Alternatively, a temperature-dependent polymer-based adhesive without solvent may be heated and set by cooling. In extmsion lamination, a film of a thermoplastic such as polyethylene is extmded as a bond between the two flat materials, which are brought together between a chilled and backup roU. 

Unsaturated resias based on 1,4-cyclohexanedimethanol are useful ia gel coats and ia laminating and molding resias where advantage is taken of the properties of very low water absorption and resistance to boiling water (6). Thermal stabiHty is imparted to molding resias, both thermoplastic (71,72) and thermoset (73—76), enabling retention of physical and electrical properties at elevated temperatures (77). Additionally, resistance to chemical and environmental exposure is characteristic of products made from these resias (78). 

Jippliance wires require a higher temperature rating (105°C or higher). Therefore, the insulation is made of duorinated thermoplastics, such as poly-tetrafluoroethylene (PTEE) or duorinated ethylene—propjdene (EEP). 

Ja.cketingMa.teria.ls. Besides the metallic protective coverings (based on aluminum, copper and copper alloys, lead, steel, and zinc), the most popular jacketing materials are based on polymeric materials that can be either thermoplastic (with limited high temperature use) or thermosetting. 

Butadiene—Methacrylic Acid Ionomers. Carboxyl groups can readily be introduced into butadiene elastomers by copolymerization, and the effects of partial neutralization have been reported (63—66). The ionized polymers exhibit some degree of fluidity at elevated temperatures, but are not thermoplastic elastomers, and are very deficient in key elastomer properties such as compression set resistance. 

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