Thermosets characteristics

Hybrid versions of silicone-thermoplastic semi-IPNs have been developed (19). A hybrid interpenetrating network is one in which the cross-linked network is formed by the reaction of two polymers with structurally distinct backbones. Hydride-functionalized siloxanes can be reacted with organic polymers with pendant unsaturated groups such as polybutadienes (5) in the presence of platinum catalysts. Compared with the polysiloxane semi-IPNs discussed earlier, the hydride IPNs tend to maintain mechanical and morphologically derived properties, whereas properties associated with siloxanes are diminished. The probable importance of this technology is in cost-effective ways to induce thermoset characteristics in thermoplastic elastomers. 

Since the molecular backbone can be linear, branched, or network type, this aspect is also important for polymer structure. It is known that most polymers with a linear backbone are thermoplastics, while those with network backbone are thermosetting polymers. However, for classification from a chemical point of view, this differentiation is less significant. Many polymers with linear backbone are obtained from bifunctional monomers (e.g. terephthalic acid and glycol). If the polymer is obtained from similar monomers but with more than two functionalities (e g. terephthalic acid and ethylene glycerin), the polymer will have thermosetting characteristics. For this reason, this feature is not necessarily used for a classification from the chemical point of view. 

Another advantage of using IPNs involves its thermosetting characteristics. By definition, IPNs will not flow when heated. A partial exception is the thermoplastic IPNs, which behave crosslinked at ambient temperatures, but flow at elevated temperatures. While some IPNs are tough, impact-resistant plastics, the crosslinking permits many other types of applications, such as sound and vibration damping, biomedical, adhesives and coatings uses, etc. (see Section 6.5). 

The most harmful hydrolytic effect arises when the polymer contains an appreciable concentration of such hydrolyzable linkages as ester, urethane, or siloxane. Cleavage of hydrolyzable linkages manifests itself as a drop in tensile strength and an increase in ultimate elongation eventually leading to a loss of thermosetting characteristics. 

EPI adhesives are thermoplastic polymer dispersion adhesives combined with isocyanate cross-linking that gives a degree of thermosetting characteristics and properties. The adhesives are complex, multiphase systems with a number of physical processes and chemical reactions occurring in parallel during the gluing process. 

As a thermoplastic elastomer, these materials behave somewhat similarly to the triblock copolymers developed by Holden and Milkovich (see also Chapter 2). Above the melting point of the polypropylene plastic, the present material loses its thermoset characteristics. This compares to the glass transition softening of the polystyrene portion of the triblock copolymers. 

Heating alkali metal or alkaline earth metal dihydrogen phosphates produces polymeric salts (cyclic metaphosphates and linear polyphosphates) and cross-linked polyphosphates (ultraphosphates), depending on temperature and the presence of other ingredients (11,12). This complex group of polymers includes materials with crystalline, glass-like, fibrous, or ceramic properties as well as some with thermoplastic and thermoset characteristics some are useful as binders for metals, ceramics, and dental restorations. Reviews are available on glasses (12,13), crystalline compounds (14), and polyphosphate fibers (15). 

Polyamides and polyesters are used to produce fibers for different purposes, particularly for clothing. Different blends of these materials and conductive polymers have been developed in the form of films or fibers. Other types of materials are also used to make fibers, such as carbon fibers and Kevlar. In the latter case, however, the thermoset characteristic of the material permits obtaining only composites with conductive polymers. Materials used to produce fibers are discussed in this section in conjunction with their blends and composites with conductive polymers. 

Corrosion Resistant Fiber-Reinforced Plastic (FRP). Fiber glass reinforcement bonded with furfuryl alcohol thermosetting resias provides plastics with unique properties. Excellent resistance to corrosion and heat distortion coupled with low flame spread and low smoke emission are characteristics that make them valuable as laminating resins with fiber glass (75,76). Another valuable property of furan FRP is its strength at elevated temperature. Hand-layup, spray-up, and filament-win ding techniques are employed to produce an array of corrosion-resistant equipment, pipes, tanks, vats, ducts, scmbbers, stacks, and reaction vessels for industrial appHcations throughout the world. 

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). 

Properties desired in cable insulation and flexible circuit substrate materials include mechanical flexibiUty, fatigue endurance, and resistance to chemicals, water absorption, and abrasion. Both thermoplasts and thermosets are used as cable-insulating materials. Thermoplastic materials possess excellent electrical characteristics and are available at relatively low cost. 

Softening and cure is examined with the help of a torsional pendulum modified with a braid (65), which supports thermosets such as phenoHcs and epoxies that change from a Hquid to a soHd on curing. Another method uses vibrating arms coupled to a scrim-supported sample to measure storage and loss moduH as a function of time and temperature. An isothermal analytical method for phenoHc resins provides data regarding rate constants and activation energies and allows prediction of cure characteristics under conditions of commercial use (47). 

Polymeric Ma.teria.Is, The single-ply membranes are made from a wide variety of polymers. The following is a brief description of those polymers and their characteristics. There are three thermosetting-type elastomeric membranes as of this writing (1996) neoprene, CSPE, and EPDM. Neoprene is stiU used where oil resistance is needed. Eor instance. Hydrotech uses neoprene flashings, the base of which is hot-set in mbberized asphalt (see ElASTOL RS, SYNTHETIC-POLYCm.OROPRENE). 

CSPE. Chlorosulfonated polyethylene (CSPE), a synthetic mbber manufactured by DuPont, is marketed under the name Hypalon. It can be produced as a self-curing elastomer designed to cure on the roof. The membrane is typically reinforced with polyester and is available in finished thicknesses of 0.75 to 1.5 mm. Because CSPE exhibits thermoplastic characteristics before it cures, it offers heat-weldable seams. After exposure on the roof, the membrane cures offering the toughness and mechanical set of a thermoset. The normal shelf life of the membrane for maintaining this thermoplastic characteristic is approximately six months. After the membrane is fully cured in the field, conventional adhesives are needed to make repairs. 

In addition to fiber and fabric influences on abrasion resistance, chemical finishes must also be considered. Many thermosetting resins used to impart durable press characteristics to ceUulosic fabrics reduce their resistance to abrasion as a result of fiber embrittlement. 

Poly(vinyl alcohol) is employed as a modifier of thermosetting resins used as adhesives in plywood and particle board manufacture (314,315). The polymer is added to urea-formaldehyde or urea—melamine—formaldehyde resins to improve initial grab, to increase viscosity, and, in general, to improve the characteristics of the board. 

Plastics. Almost all commercial plastics find some use both dry and lubricated for sliding at low speeds and light loads the most commonly used thermoplastics are nylon, acetal resins, and polytetrafluoroethylene (PTFE). Typical thermosetting resins for bearing appHcations are phenoHcs, polyesters, and polyimides. Table 8 compares the characteristics of plastic bearing materials with those of graphite, wood, and mbber which find use in somewhat similar appHcations. 

The use of calcium carbonate in thermosets continues to grow as these plastics replace alternative materials, especially in automotive appHcations. Increased loadings of calcium carbonate in thermosets reduce cost and provide better surface characteristics. 

Thermoplastic polyesters achieved some commercial success during the mid-1980s however, these were eventually replaced by nylon coating powders in functional coatings and thermosetting polyester powders in decorative appHcations because of lack of any unique characteristics or price advantages (see Polyesters, thermoplastic). 

Specification for 600/1000V and 1900/3300 V armoured electric cables having thermosetting insulation Fire resisting characteristics of electric cables Performance requirements, sample and lest conditions - BS 5467/1997... 

In September 1964 the Du Pont company announced materials that had characteristics of both thermoplastics and thermosetting materials. These materials, known as ionomers, are prepared by copolymerising ethylene with a small amount (1-10 % in the basic patent) of an unsaturated carboxylic acid such as acrylic acid using the high-pressure process. Such copolymers are then treated... 

The heat and flame resistance coupled with good electrical insulation characteristics, which includes in some grades good arcing and arc tracking resistance, has led to PPS replacing some of the older thermosets in electrical parts. These include connectors, coil formers, bobbins, terminal blocks, relay components, moulded bulb sockets for electric power station control panels, brush holders, motor housings, thermostat parts and switch components. 

Since the cross-linking of molecules is by strong chemical bonds, thermosetting materials are characteristically quite rigid materials and their... 

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