Copolymer brittleness

Examination of oven-aged samples has demonstrated that substantial degradation is limited to the outer surface (34), ie, the oxidation process is diffusion limited. Consistent with this conclusion is the observation that oxidation rates are dependent on sample thickness (32). Impact property measurements by high speed puncture tests have shown that the critical thickness of the degraded layer at which surface fracture changes from ductile to brittle is about 0.2 mm. Removal of the degraded layer restores ductiHty (34). Effects of embrittled surface thickness on impact have been studied using ABS coated with styrene—acrylonitrile copolymer (35). 

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

The dynamic mechanical properties of VDC—VC copolymers have been studied in detail. The incorporation of VC units in the polymer results in a drop in dynamic modulus because of the reduction in crystallinity. However, the glass-transition temperature is raised therefore, the softening effect observed at room temperature is accompanied by increased brittleness at lower temperatures. These copolymers are normally plasticized in order to avoid this. Small amounts of plasticizer (2—10 wt %) depress T significantly without loss of strength at room temperature. At higher levels of VC, the T of the copolymer is above room temperature and the modulus rises again. A minimum in modulus or maximum in softness is usually observed in copolymers in which T is above room temperature. A thermomechanical analysis of VDC—AN (acrylonitrile) and VDC—MMA (methyl methacrylate) copolymer systems shows a minimum in softening point at 79.4 and 68.1 mol % VDC, respectively (86). 

In cases where the copolymers have substantially lower glass-transition temperatures, the modulus decreases with increasing comonomer content. This results from a drop in crystallinity and in glass-transition temperature. The loss in modulus in these systems is therefore accompanied by an improvement in low temperature performance. However, at low acrylate levels (< 10 wt %), T increases with comonomer content. The brittle points in this range may therefore be higher than that of PVDC. 

Another polyolefin of interest is polystyrene, a clear, brittle plastic that, by itself, is rarely used in composites. However, several copolymers and alloys of polystyrene with acrylonitrile or butadiene have been used with fiber glass or glass spheres to form composites (7). 

Fig. 24.1. (a) A copolymer of vinyl chloride and vinyl acetate the "alloy" pocks less regularly, has a lower Tg, and is less brittle than simple polyvinylchloride (PVC). (b) A block copolymer the two different molecules in the alloy ore clustered into blocks along the chain. 

One unfortunate characteristic property of polypropylene is the dominating transition point which occurs at about 0°C with the result that the polymer becomes brittle as this temperature is approached. Even at room temperature the impact strength of some grades leaves something to be desired. Products of improved strength and lower brittle points may be obtained by block copolymerisation of propylene with small amounts (4-15%) of ethylene. Such materials are widely used (known variously as polyallomers or just as propylene copolymers) and are often preferred to the homopolymer in injection moulding and bottle blowing applications. 

In the early stages of development of polypropylene rubbers, particularly butyl rubber, were used to reduce the brittleness of polypropylene. Their use declined for some years with the development of the polypropylene copolymers but interest was greatly renewed in the 1970s. This interest has been centred largely around the ethylene-propylene rubbers which are reasonably compatible in all proportions with polypropylene. At first the main interest was with blends in which the rubber content exceeded 50% of the blend and such materials have been designated as thermoplastic polyolefin elastomers (discussed in Section 11.9.1). There is also increasing interest in compounds with less than 50% rubber, often referred to as elastomer-modified thermoplastics. It is of interest to note... 

For reasons explained below, the effect of increasing the vinyl alcohol content in EVOH is quite different to that of increasing the vinyl acetate content in EVA. In the case of ethylene-vinyl acetate (EVA) copolymers, increasing the vinyl acetate content up to about 50% makes the materials less crystalline and progressively more flexible and then rubbery. In the range 40-70% vinyl acetate content the materials are amorphous and rubbery, whilst above 70% the copolymers become increasingly rigid and brittle. 

Vulcanisation can be effected by diamines, polyamines and lead compounds such as lead oxides and basic lead phosphite. The homopolymer vulcanisate is similar to butyl rubber in such characteristics as low air permeability, low resilience, excellent ozone resistance, good heat resistance and good weathering resistance. In addition the polyepichlorohydrins have good flame resistance. The copolymers have more resilience and lower brittle points but air impermeability and oil resistance are not so good. The inclusion of allyl glycidyl ether in the polymerisation recipe produces a sulphur-curable elastomer primarily of interest because of its better resistance to sour gas than conventional epichlorhydrin rubbers. 

Photodegradation may involve use of inherently photo-unstable polymers or the use of photodegradant additives. An example of the former are ethylene-carbon monoxide polymers in which absorption of light by the ketone group leads to chain scission. The polymer becomes brittle and forms a powder. Such materials are marketed by Dow and by Du Pont. Other examples are the copolymers of divinyl ketone with ethylene, propylene or styrene marketed by Eco Atlantic. 

The homopolymers, which are formed from alkyl cyanoacrylate monomers, are inherently brittle. For applications which require a toughened adhesive, rubbers or elastomers can be added to improve toughness, without a substantial loss of adhesion. The rubbers and elastomers which have been used for toughening, include ethylene/acrylate copolymers, acrylonitrile/butadiene/styrene (ABS) copolymers, and methacrylate/butadiene/styrene (MBS) copolymers. In general, the toughening agents are incorporated into the adhesive at 5-20 wt.% of the monomer. 

In the late 1940s, the demand for styrene homopolymers (PS) and styrene-acrylonitrile copolymers (SAN) was drastically reduced due to their inherent brittleness. Thus, the interest was shifted to multiphase high-impact polystyrene (HIPS) and rubber-modified SAN (ABS). In principle, both HIPS and ABS can be manufactured by either bulk or emulsion techniques. However, in actual practice, HIPS is made only by the bulk process, whereas ABS is produced by both methods [132,133]. 

Plastics are susceptible to brittle crack-growth fractures as a result of cyclic stresses in much the same way as metals. In addition, because of their high damping and low thermal conductivity, plastics are prone to thermal softening if the cyclic stress or cyclic rate is high. Examples of the TPs with the best fatigue resistance include PP and ethylene-propylene copolymers. 

In a block copolymer, a long segment made from one monomer is followed by a segment formed from the other monomer. One example is the block copolymer formed from styrene and butadiene. Pure polystyrene is a transparent, brittle material that is easily broken polybutadiene is a synthetic rubber that is very resilient, but soft and opaque. A block copolymer of the two monomers produces high-impact polystyrene, a material that is a durable, strong, yet transparent plastic. A different formulation of the two polymers produces styrene-butadiene rubber (SBR), which is used mainly for automobile tires and running shoes, but also in chewing gum. 

Mixtures of two or more monomers can polymerize to form copolymers. Many copolymers have been developed to combine the best features of each monomer. For example, poly(vinyl chloride) (called a homopolymer because it is made from a single monomers) is brittle. By copolymerizing vinyl chloride with vinyl acetate, a copolymer is obtained that is flexible. Arrangement of the monomer units in a copolymer depends on the rates at which the monomers react with each other. Graft copolymers are formed when a monomer is initiated by free radical sites created on an already-formed polymer chain. 

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