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Control of crosslinking is critical for processing thermoset plastics, both the reaction prior to the gel point and that subsequent to the gel point The period after the gel point is usually referred to as the curing period Too slow or too rapid crosslinking can be detrimental to the properties of a desired product Thus, in the production of a thermoset foamed product, the foam structure may collapse if gelation occurs too slowly On the other hand, for reinforced and laminated products the bond strength of the components may be low if crosslinking occurs too quickly The fabrication techniques for producing objects from thermosetting and thermoplastic polymers are vastly different In the case of the thermoplastics the polymerization reaction is completed by the plastics manufacturer The fabricator takes the polymer and applies heat and pressure to produce a owable material that can be shaped into the desired nished object.

& ' GT GR sin2 w # dv exp 8p2 a2 c2 sin2 2 sin2 #=2 7:121

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The situation is quite different for thermosetting plastics A completely polymerized thermoset is no longer capable of ow and cannot be processed into an object Instead, the fabricator receives an incompletely polymerized polymer termed a prepolymer from the plastics manufacturer and polymerization (and crosslinking) is completed during the fabrication step For example, a prepolymer can be poured into an appropriate mold and then solidi ed to form the desired nished object by completing the polymerization The prepolymers are usually in the molecular weight range 500 5000 and may be either liquid or solid The molds used for thermosets must be hinged so that they can be opened after crosslinking to remove the nished product Thermoset polymers are classi ed as A-, B-, and C-stage polymers according to their extent of reaction p compared to the extent of reaction at gelation pc .

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The polymer is an A-stage polymer if p < pc , B-stage if the system is close to the gel point pc , and Cstage when it is well past pc The A-stage polymer is soluble and fusible The B-stage.

For the practical use of this formula, one must determine the parameters #, w and c at the center of each element of volume of scattering using the geometry and geophysical parameters of the radio trace and allow for the gain factors of the transmitting and receiving antennas for the corresponding directions. This procedure for the concrete middle-latitude radio trace is fully described in Reference [46]. We do not enter into details of the problem presented in Figure 7.20. To limit the working volume in the numerical integration, it is convenient to plot the isolines of the quantity of angle g c sin #=2 given in Figure 7.20, at the left side of each isoline. The numbers in decibel at the right side of each isoline in Figure 7.20 indicate the decrease of the power received due to p exponential factor the exp 8p2 a2 g2 . Here, the rst number is for a ljj =l 10 % 3:16, the second is for a 10. We can see that for a 3:16 integration can be con ned to within the volume of scattering between the isolines g 3 and for a 10 between the lines

polymer is still fusible but is barely soluble. The C-stage polymer is highly crosslinked and both infusible and insoluble. The prepolymer employed by a fabricator is usually a B-stage polymer, although it may be an A-stage one. The subsequent polymerization of the prepolymer takes it through to the C stage. Thermoset plastics can generally be grouped into two types depending on whether the same chemical reaction is used to both synthesize and crosslink the prepolymer. Generally, the older thermosetting materials involve the random crosslinking of bifunctional monomers with monomers of functionality greater than 2. The prepolymer is obtained in a rst step by stopping the reaction, usually by cooling, at the desired extent of conversion (either A- or Bstage). Polymerization with crosslinking is completed during a second-step fabrication process, usually by heating. The newer thermosets involve prepolymers of a more specially designed structure. These prepolymers undergo crosslinking in the second step by a chemical reaction different from that for the rst step. Because there is different chemistry in the two steps, one is not involved in any pc considerations in the rst step. The reactants are bifunctional with respect to the rst-step chemistry. However, one or more of the reactants has some functional group capable of reaction under other conditions. Such prepolymer systems are advantageous because they generally offer greater control of the polymerization and crosslinking reactions, and very importantly, of the structure of the nal product. The uses and markets for these newer thermosets are growing more rapidly than those of the older systems. 2-12a Polyesters, Unsaturated Polyesters, and Alkyds

a = 3.16

Polyesters formed from phthalic anhydride and glycerol were among the rst commercial crosslinked polyesters. Linear polyesters seldom are synthesized by the direct reactions of acids or acid anhydrides with alcohols because the higher temperatures requred for high conversions lead to side reactions, which interfere with obtaining high molecular weights. This consideration is not overwhelmingly important for crosslinking systems, since crosslinking is achieved at far lower extents of reaction than are needed to obtain high polymer in a linear polymerization. Crosslinked polyesters are typically synthesized by direct esteri cation of acid or acid anhydride with alcohol.

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