Crazes and crazing

Different methods of measuring the scatter function of corpuscular as well as wave radiations are used for indirect measurements of microscopic heterogeneities or changes in morphology, which develop under the action of load, especially development, distribution and size of crazes and craze fibrils in amorphous and ruhher-toughened polymers, and change of lamellae in semiciystalline polymers. 

Plastic Sheet. Poly(methyl methacrylate) plastic sheet is manufactured in a wide variety of types, including cleat and colored transparent, cleat and colored translucent, and colored semiopaque. Various surface textures ate also produced. Additionally, grades with improved weatherabiUty (added uv absorbers), mat resistance, crazing resistance, impact resistance, and flame resistance ate available. Selected physical properties of poly(methyl methacrylate) sheet ate Hsted in Table 12 (102). 

In general, polycarbonate resins have fair chemical resistance to aqueous solutions of acids or bases, as well as to fats and oils. Chemical attack by amines or ammonium hydroxide occurs, however, and aUphatic and aromatic hydrocarbons promote crazing of stressed molded samples. Eor these reasons, care must be exercised in the choice of solvents for painting and coating operations. Eor sheet appHcations, polycarbonate is commonly coated with a sihcone—sihcate hardcoat which provides abrasion resistance as well as increased solvent resistance. Coated films are also available. 

Polystyrene. Polystyrene [9003-53-6] is a thermoplastic prepared by the polymerization of styrene, primarily the suspension or bulk processes. Polystyrene is a linear polymer that is atactic, amorphous, inert to acids and alkahes, but attacked by aromatic solvents and chlorinated hydrocarbons such as dry cleaning fluids. It is clear but yellows and crazes on outdoor exposure when attacked by uv light. It is britde and does not accept plasticizers, though mbber can be compounded with it to raise the impact strength, ie, high impact polystyrene (HIPS). Its principal use in building products is as a foamed plastic (see Eoamed plastics). The foams are used for interior trim, door and window frames, cabinetry, and, in the low density expanded form, for insulation (see Styrene plastics). 

Figure 3.9. Rubber particle straddling craze perpendicular to stress is subjected to triaxial stresses and because of its high bulk modulus becomes load bearing. (After Bucknall )...

The rubber particles should not be so small that they are completely embedded in a craze. It is interesting to note that in high-impact polystyrene crazes tend to be about 2 p.m thick and the optimum particle sizes observed as a result of experience are quoted in the range 1-10 p.m. For ABS the figures are about 0.5 p.m and 0.1-l.Op.m respectively. 

As may be expected of an amorphous polymer in the middle range of the solubility parameter table, poly(methyl methacrylate) is soluble in a number of solvents with similar solubility parameters. Some examples were given in the previous section. The polymer is attacked by mineral acids but is resistant to alkalis, water and most aqueous inorganic salt solutions. A number of organic materials although not solvents may cause crazing and cracking, e.g. aliphatic alcohols. 

Internal stresses occur because when the melt is sheared as it enters the mould cavity the molecules tend to be distorted from the favoured coiled state. If such molecules are allowed to freeze before they can re-coil ( relax ) then they will set up a stress in the mass of the polymer as they attempt to regain the coiled form. Stressed mouldings will be more brittle than unstressed mouldings and are liable to crack and craze, particularly in media such as white spirit. They also show a characteristic pattern when viewed through crossed Polaroids. It is because compression mouldings exhibit less frozen-in stresses that they are preferred for comparative testing. 

Notch sensitivity and susceptibility to crazing under strain. 

Provided due care is taken with respect to predrying and to crazing tendencies, polycarbonates may also be thermoformed, used for fluidised bed coating and machined and cemented. Like metals, but unlike most thermoplastics, polycarbonates may be cold formed by punching and cold rolling. Cold rolling can in fact improve the impact resistance of the resin. 

Isophthalic acid (m.p. 347°C), made by oxidation of /w-xylene, has also been introduced for resins. The resins have higher heat distortion temperatures and flexural moduli and better craze resistance. They are also useful in the preparation of resilient gel coats. 

The mechanical properties, especially the internal stresses set up by interaction of substrate and deposit, have a close bearing on the behavior of metallic interconnects (electrical conductors) in integrated circuits. Such interconnects suffer from more diseases than does a drink-sodden and tobacco-crazed invalid, and stress-states play roughly the role of nicotine poisoning. A very good review specifically of stresses in films is by Nix (1989). 

Whereas coiTosion of metals is due to chemical or substantial electrochemical attack, the deterioration of plastics and other non-metals which are susceptible to swelling, cracking, crazing, softening etc. is essentially physicochemical rather than electrochemical. 

Processes that occur at a size scale larger than the individual chain have been studied using microscopy, mainly transmission electron microscopy (TEM), but optical microscopy has been useful to examine craze shapes. The knowledge of the crazing process obtained by TEM has been ably summarised by Kramer and will not be repeated here [2,3]. At an interface between two polymers a craze often forms within one of the materials, typically the one with lower crazing stress. 

When the stress that can be bom at the interface between two glassy polymers increases to the point that a craze can form then the toughness increases considerably as energy is now dissipated in forming and extending the craze structure. The most used model that describes the micro-mechanics of crazing failure was proposed by Brown [8] in a fairly simple and approximate form. This model has since been improved and extended by a number of authors. As the original form of the model is simple and physically intuitive it will be described first and then the improvements will be discussed. 

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