Thermosetting polymers physical properties

Some of the common types of plastics that ate used ate thermoplastics, such as poly(phenylene sulfide) (PPS) (see Polymers containing sulfur), nylons, Hquid crystal polymer (LCP), the polyesters (qv) such as polyesters that ate 30% glass-fiber reinforced, and poly(ethylene terephthalate) (PET), and polyetherimide (PEI) and thermosets such as diaHyl phthalate and phenoHc resins (qv). Because of the wide variety of manufacturing processes and usage requirements, these materials ate available in several variations which have a range of physical properties. 

The chemistry of synthetic polymers is similar to the chemistry of small molecules with the same functional groups, but the physical properties of polymers are greatly affected by size. Polymers can be classified by physical property into four groups thermoplastics, fibers, elastomers, and thermosetting resins. The properties of each group can be accounted for by the structure, the degree of crystallinity, and the amount of cross-Jinking they contain. 

Composite Particles, Inc. reported the use of surface-modified rubber particles in formulations of thermoset systems, such as polyurethanes, polysulfides, and epoxies [95], The surface of the mbber was oxidized by a proprietary gas atmosphere, which leads to the formation of polar functional groups like —COOH and —OH, which in turn enhanced the dispersibility and bonding characteristics of mbber particles to other polar polymers. A composite containing 15% treated mbber particles per 85% polyurethane has physical properties similar to those of the pure polyurethane. Inclusion of surface-modified waste mbber in polyurethane matrix increases the coefficient of friction. This finds application in polyurethane tires and shoe soles. The treated mbber particles enhance the flexibility and impact resistance of polyester-based constmction materials [95]. Inclusion of treated waste mbber along with carboxyl terminated nitrile mbber (CTBN) in epoxy formulations increases the fracture toughness of the epoxy resins [96]. 

The final physical properties of thermoset polymers depend primarily on the network structure that is developed during cure. Development of improved thermosets has been hampered by the lack of quantitative relationships between polymer variables and final physical properties. The development of a mathematical relationship between formulation and final cure properties is a formidable task requiring detailed characterization of the polymer components, an understanding of the cure chemistry and a model of the cure kinetics, determination of cure process variables (air temperature, heat transfer etc.), a relationship between cure chemistry and network structure, and the existence of a network structure parameter that correlates with physical properties. The lack of availability of easy-to-use network structure models which are applicable to the complex crosslinking systems typical of "real-world" thermosets makes it difficult to develop such correlations. 

For the most part, plastics are man-made since very few plcistlcs are natural, i.e.- nature-made. Natural plastics include large molecular-wei t proteins and similar molecules. Man-made plastics can be classified as either thermoplastic or thermosetting. Each class derives its physical properties from the effects of application of heat, the former becoming "plastic" (that is- it becomes soft and tends to flow) while the latter becomes less "plastic" and tends to remain in a softened state. This difference in change of state derives from the actual nature of the chemical bonds in the polymer. Thermoplastic polymers generally consist of molecules composed of many monomeric units. A good example is that of polyethylene where the monomeric unit is -(CH2-CH2)-. The molecule is linear... 

This difference in spatial characteristics has a profound effect upon the polymer s physical and chemical properties. In thermoplastic polymers, application of heat causes a change from a solid or glassy (amorphous) state to a flowable liquid. In thermosetting polymers, the change of state occurs from a rigid solid to a soft, rubbery composition. The glass transition temperature, Tg, ... 

When a thermoplastic polyurethane elastomer is heated above the melting point of its hard blocks, the chains can flow and the polymer can be molded to a new shape. When the polymer cools, new hard blocks form, recreating the physical crosslinks. We take advantage of these properties to mold elastomeric items that do not need to be cured like conventional rubbers. Scrap moldings, sprues, etc. can be recycled directly back to the extruder, which increases the efficiency of this process. In contrast, chemically crosslinked elastomers, which are thermosetting polymers, cannot be reprocessed after they have been cured. 

A thermosetting resin converts to an infusible, cross-linked plastic which is insoluble in any solvent after curing. Because of this irreversible cross-linking reaction, excellent physical properties such as heat resistance, creep resistance, mechanical strength, etc., are obtainable through design of the polymer structure. 

In the previous chapter we talked about linear polymers and have mentioned the concept of cross-linking only in passing. Linear polymers are usually thermoplastic they soften or melt when heated and will dissolve in suitable solvents. They can be remelted and shaped into their finished product with no further chemical reactions. Thermoset resins, those having elaborately cross-linked three-dimensional structures, set or harden by undergoing a chemical reaction during the manufacture of finished products. They decompose on heating and are infusible and insoluble. Their chemistry and physical properties are quite different from thermoplastic polymers. The important ones are now discussed. 

Thermal stability as measured by these ramped TGA experiments of the sort previously described are not the definitive test of a polymer s utility at elevated temperature. Rather, for a polymer to be useful at elevated temperatures, it must exhibit some significant retention of useful mechanical properties over a predetermined lifetime at the maximum temperature that will be encountered in its final end use application. While many of the bisbenzocyclobutene polymers have been reported in the literature, only a few have been studied in detail with regards to their thermal and mechanical performance at both room and elevated temperatures. Tables 7-10 show some of the preliminary mechanical data as well as some other physical properties of molded samples of polymers derived from amide monomer 32, ester monomer 40, diketone monomer 14 and polysiloxane monomer 13. The use of the term polyamide, ester etc. with these materials is not meant to imply that they are to be regarded as merely modified linear thermoplastics. Rather, these polymers are for the most part highly crosslinked thermosets. 

The effect (or lack of effect) of crosslinks on basic physical properties of thermosetting polymers is discussed in Chapter 10, while the effect on elastic and viscoelastic properties is analyzed in Chapter 11. Yielding and fracture of neat and modified thermosetting polymers are discussed in Chapters 12 and 13. Finally, the very important problem of the durability of polymer networks is presented in Chapter 14. 

Figure 3.3 Evolution of physical properties of the thermosetting polymer as a function of conversion of reactive groups (a) zero-shear viscosity and elastic modulus, (b) sol fraction.

As in linear polymers, the relative influence of the molecular structure (scale of nanometers and monomers), and the macromolecular structure (crosslink density), on network properties, depends on temperature, as shown in Fig. 10.9. In the glassy state, the physical behavior is essentially controlled by cohesion and local molecular mobility, both properties being mainly under the dependence of the molecular scale structure. As expected, there are only second-order differences between linear and network polymers. Here, most of the results of polymer physics, established on linear polymers, can be used to predict the properties of thermosets. Open questions in this domain concern the local mobility (location and amplitude of the (3 transition). 

The most common advanced composites are made of thermosetting resins, such as epoxy polymers (the most popular singlematrix material), polyesters, vinyl esters, polyurethanes, polyimids, cianamids, bismaleimides, silicones, and melamine. Some of the most widely used thermoplastic polymers are polyvinyl chloride (PVC), PPE (poly[phenylene ether]), polypropylene, PEEK (poly [etheretherketone]), and ABS (acrylonitrile-butadiene-styrene). The precise matrix selected for any given product depends primarily on the physical properties desired for that product. Each type of resin has its own characteristic thermal properties (such as melting point... 

So many kinds of polymers exist that scientists have developed ways of categorizing them to make it easier to study and describe them. Polymers formed by addition or condensation reactions, for example, are placed in the same category because they are formed by a common chemical reaction and, in many cases, have common physical and chemical properties. Similarly, thermoplastic and thermosetting polymers are grouped together primarily because of their behaviors when exposed to heat, and, hence, applications for which they are likely to he most suitable. 

Thermoset polyurethanes are cross-linked polymers, which are produced by casting or reaction injection molding (RIM). For cast elastomers, TDI in combination with 3,3,-dichloro-4,4,-diphen5lmethanediamine (MOCA) are often used. In the RIM technology, aromatic diamine chain extenders, such as diethyltoluenediamine (DETDA), are used to produce poly(urethane ureas) (47), and replacement of the polyether polyols with amine-terminated polyols produces polyureas (48). The aromatic diamines are soluble in the polyol and provide fast reaction rates. In 1985, internal mold release agents based on zinc stearate compatibilized with primary amines were introduced to the RIM process to minimize mold preparation and scrap from parts tom at demold. Some physical properties of RIM systems are listed in Table 7. 

First, a common method of forming polymers by a radical reaction is discussed. After the structures of the addition polymers made by this method are examined, several other procedures that can be used to prepare these or similar polymers are presented. Next, the effect of the structure of a polymer on its physical properties is discussed. This provides a basis for understanding the properties and uses of a number of other addition polymers. Rubbers (elastomers) are then discussed followed by condensation polymers and thermosetting polymers. The chapter concludes with a brief examination of the chemical properties of polymers. 

Epoxy resins are high-performance thermosetting resins, which display a unique combination of properties. Epoxy resins have been commercially available for almost a half-century. Epoxy resins are arguably one of the most versatile polymers with uses across an enormously wide variety of industries. The outstanding physical properties exhibited by epoxy resins include... 

Curing of epoxy thermosets requires a knowledge of the chemical kinetics and the crosslinking reactions. This information is necessary to optimize the cure cycle. The parameters that define the cure cycle ultimately determine the crosslink density and the final physical properties of the polymer. In addition to temperature, these parameters include the rate of temperature increase, the number of stages in the cure, the hold temperature at each stage, the pressure at which cure takes place, and the time allotted for the cure cycle. These parameters are usually determined empirically. Once the kinetics are understood and the actual chemistry behind the cure is established, these cure cycle parameters can be chosen based on the desired end properties. Usually the cure cycle seeks to establish a certain degree of cure that is in line with the expected final properties. 

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