Polystyrene brittleness

More expensive than commodities such as polyolefins, PVC and polystyrene brittle when dry, sensitive to water (swelling up to 10%, decrease in mechanical and electrical properties) opaque or translucent require UV and weathering protection significant shrinkage after moulding inherent flammability (but FR grades are marketed). 

Polystyrene Brittle, hard, rigid Toys, food containers... 

Impact polystyrene contains polybutadiene added to reduce brittleness. The polybutadiene is usually dispersed as a discrete phase in a continuous polystyrene matrix. Polystyrene can be grafted onto rubber particles, which assures good adhesion between the phases. 

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). 

As with other rigid amorphous thermoplastic polymers such as PVC and polystyrene (see the next chapter) poly(methyl methacrylate) is somewhat brittle and, as with PVC and polystrene, efforts have been made to improve the toughness by molecular modification. Two main approaches have been used, both of which have achieved a measure of success. They are copolymerisation of methyl methacrylate with a second monomer and the blending of poly(methyl methacrylate) with a rubber. The latter approach may also involve some graft copolymerisation. 

Because of such desirable characteristics as low cost, good mouldability, excellent colour range, transparency, rigidity and low water absorption, polystyrene became rapidly developed. For many purposes, however, it was considered to be unacceptably brittle and this led to the development of the rubber-modified high-impact polystyrene (HIPS) and to the complex ABS, AMBS and... 

Because of the chain-stiffening effect of the benzene ring the TgS of commercial materials are in the range 90-100°C and isotactic polymers have similar values (approx. 100°C). A consequence of this Tg value plus the amorphous nature of the polymer is that we have a material that is hard and transparent at room temperature. Isotactic polystyrenes have been known since 1955 but have not been of commercial importance. Syndiotactic polystyrene using metallocene catalysis has recently become of commercial interest. Both stereoregular polymers are crystalline with values of 230°C and 270°C for the isotactic and syndiotactic materials respectively. They are also somewhat brittle (see Section 16.3). 

For many applications polystyrene might be considered to be too brittle a polymer. Because of this, polystyrene manufacturers have made a number of attempts to modify their products. 

The use of stabilisers (antioxidants) may, however, have adverse effects in that they inhibit cross-linking of the rubber. The influence of phenolic antioxidants on polystyrene-SBR alloys blended in an internal mixer at 180°C has been studied. It was found that alloys containing 1% of certain phenolic antioxidants were gel-deficient in the rubber phase.The gel-deficient blends were blotchy in appearance, and had lower flow rates compared with the normal materials, and mouldings were somewhat brittle. Substantial improvements in the impact properties were achieved when the antioxidant was added later in the mixing cycle after the rubber had reached a moderate degree of cross-linking. 

In the crystalline region isotactic polystyrene molecules take a helical form with three monomer residues per turn and an identity period of 6.65 A. One hundred percent crystalline polymer has a density of 1.12 compared with 1.05 for amorphous polymer and is also translucent. The melting point of the polymer is as high as 230°C. Below the glass transition temperature of 97°C the polymer is rather brittle. 

The brittleness of isotactic polystyrenes has hindered their commercial development. Quoted Izod impact strengths are only 20% that of conventional amorphous polymer. Impact strength double that of the amorphous material has, however, been claimed when isotactic polymer is blended with a synthetic rubber or a polyolefin. 

The polymers are, however, more brittle than polystyrene and not suitable for applications which are to be subject to mechanical shock. 

It may be prepared in two stereo-regular forms, cis- and trans-. The cii-polymer, which crystallises in zig-zag form, has a of 235°C, whilst the fran -polymer, which crystallises in helical form, melts at the much lower temperature of 145°C. Tensile strengths of both forms are reportedly similar to that of Penton whilst the tensile modulus of 2300 MPa is about twice as high. Unfortunately the material is rather brittle with an impact strength only about half that of polystyrene although this may be improved by orientation. 

Polystyrene (PS). Polystyrene is available in a range of grades which generally vary in impact strength from brittle to very tough. The non-pigmented... 

At low strains there is an elastic region whereas at high strains there is a nonlinear relationship between stress and strain and there is a permanent element to the strain. In the absence of any specific information for a particular plastic, design strains should normally be limited to 1%. Lower values ( 0.5%) are recommended for the more brittle thermoplastics such as acrylic, polystyrene and values of 0.2-0.3% should be used for thermosets. 

With plastics there is a certain temperature, called the glass transition temperature, Tg, below which the material behaves like glass i.e. it is hard and rigid. As can be seen from Table 1.8 the value for Tg for a particular plastic is not necessarily a low temperature. This immediately helps to explain some of the differences which we observe in plastics. For example, at room temperature polystyrene and acrylic are below their respective Tg values and hence we observe these materials in their glassy state. Note, however, that in contrast, at room temperature, polyethylene is above its glass transition temperature and so we observe a very flexible matoial. When cooled below its Tg it then becomes a hard, brittle solid. Plastics can have several transitions. 

Polycarbonate is perhaps the most notoriously notch-sensitive of all thermoplastics, although nylons arc also susceptible to ductileAjrittle transitions in failure behaviour caused by notch sharpening. Other plastics such as acrylic, polystyrene and thermosets are always brittle - whatever the crack condition. 

This diagram also helps to illustrate why the inherent fracture toughness of a material is not the whole story in relation to brittle fracture. For example. Table 2.2 shows that polystyrene, which is known to be a brittle material, has a K value of about 1 MN However, LDPE which has a very high... 

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]. 

Polystyrene One of the high volume plastics, is relatively low in cost, easy to process, has sparkling clarity, and low water absorption. But basic form (crystal PS) is brittle, with low heat and chemical resistance, poor weather resistance. High impact polystyrene is made with butadiene modifiers provides significant improvements in impact strength and elongation over crystal polystyrene, accompanied by a loss of transparency and little other property improvement. PS is used in many different formulations. 

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. 

About half of the styrene produced is polymerized to polystyrene, an easily molded, low-cost thermoplastic that is somewhat brittle. Foamed polystyrene can be made by polymerizing it in the presence of low-boiling hydrocarbons, which cause bubbles of gas in the solid polymer after which it migrates out and evaporates. Modification and property enhancement of polystyrene-based plastics can be readily accomplished by copolymerization with other substituted ethylenes (vinyl monomers) for example, copolymerization with butadiene produces a widely used synthetic rubber. 

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