Shrinkage thermosets

Dershem, S. Yang, K. Low Shrinkage Thermosetting Resin Compositions and use in Low Shrinkage Die Attach Pastes. Patent WO 2002028813, 2002. 

A.STM D1299, Test Methodfor Shrinkage of Molded and Eaminated Thermosetting Plastics at ElevatedTemperatures, Vol. 8.01, ASTM, Philadelphia, Pa., 1979. 

Poly(methyl methacrylate) and poly(vinyl acetate) precipitate from the resin solution as it cures. This mechanism offsets the contraction in volume as the polyester resin cross-links, resulting in a nonshrinking thermoset. Other polymer additives such as poly(butylene adipate) provide similar shrinkage... 

A variety of thermosetting resins are used in SMC. Polyesters represent the most volume and are available in systems that provide low shrinkage and low surface profile by means of special additives. Class A automotive surface requirements have resulted in the development of sophisticated systems that commercially produce auto body panels that can be taken direcdy from the mold and processed through standard automotive painting systems, without additional surface finishing. Vinyl ester and epoxy resins (qv) are also used in SMC for more stmcturaHy demanding appHcations. 

Such reactions allow chain extension and/or cross-linking to occur without the elimination of small molecules such as water, i.e. they react by a rearrangement polymerisation type of reaction. In consequence these materials exhibit a lower curing shrinkage than many other types of thermosetting plastics. 

Low-profile additives, which control shrinkage, have emerged as a distinct science and class of additive. Unsaturated polyester resins, as do all thermosetting polymers, shrink when cured. Low-profile additives are a major class of additives used to control shrinkage, which vastly improves surface quality. This science is credited with the opening of automotive markets where surface quality is of prime importance. In exterior automotive body panels, Class A surfaces are required for market acceptance. 

The primary resin of interest is epoxy. Carbon-fiber-epoxy composites represent about 90% of CFRP production. The attractions of epoxy resins are that they polymerize without the generation of condensation products that can cause porosity, they exhibit little volumetric shrinkage during cure which reduces internal stresses, and they are resistant to most chemical environments. Other matrix resins of interest for carbon fibers include the thermosetting phenolics, polyimides, and polybismaleimides, as well as high-temperature thermoplastics such as polyether ether ketone (PEEK), polyethersulfone (PES), and polyphenylene sulfide. 

The characteristics of the three most common thermoset resin systems used in pultrusion are compiled in Table 11.2 [3]. It is noteworthy that unreinforced polyesters and vinylesters shrink 7-9% upon crosslinking, whereas epoxies shrink much less and tend to adhere to the die. These epoxy characteristics translate into processing difficulties, reduced processing speed, and inferior component surface finish. It is normal practice to use resin additives to improve processability, mechanical properties, electrical properties, shrinkage, environmental resistance, temperature tolerance, fire tolerance, color, cost, and volatile evaporation. It is normally the resin, or rather its reactivity, that determines the pulling speed. Typical pulling speeds for polyesters tend to be on the order of 10-20 mm/s, whereas speeds may exceed lOOmm/s under certain circumstances. Apart from the resins characterized in Table 11.2, several other thermosets, such as phenolics, acrylics, and polyurethanes, have been tried, as have several thermoplastics (as will be discussed in Sec. 11.2.6). 

Common thermosets are cured by a free radical addition mechanism. These types of composites are cured by heat initiators, such as peroxides, or by photo initiators, such as a-diketones. A characteristic of cured acrylates is large shrinkage in the course of polymerization, which is undesirable for many uses. Another undesirable characteristic of acrylates is the formation of an oxygen-inhibited layer on the surface upon curing. 

Another type of thermoset polymers is based on epoxy monomers. These thermosets are cured by use of a two-component system or by photo initiators. Disadvantages of epoxies are high water uptake in service and polymerization shrinkage (22). 

Compositions that are curing by the principle of ROMP have been added to the spectrum of thermosets. These may be either one part compositions and two part compositions. The materials have a remarkably low shrinkage on curing. Therefore, typical applications are in the fields of dental applications or in automotive and electronic applications. 

Very often particles are blended into polymers, in thermoplasts as well as in thermosets and in synthetic rubbers. This is done for various reasons the aim may be stiffness, strength, hardness, softening temperature, a reduction of shrinkage in processing, reduction of thermal expansion or electric resistance, or, simply, to reduce the price of the material. The fillers used are wood flour, carbon black, glass powder, chalk, quartz powder, mica, molybdene sulphide, various metal oxides, etc. etc. 

Since the epoxy resin cures primarily by a ring-opening mechanism, it exhibits a smaller degree of cure shrinkage than other thermosetting resins. In these reaction processes, the epoxy group may react in one of two different ways anionically and cationically. Both are of importance in epoxy resin chemistry. In the anionic mechanism, the epoxy group may be opened in various fashions to produce an anion, as shown in Fig. 2.10. 

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