Polymers amorphous, solvent cracking

Of the instances of so-called solvent cracking of amorphous polymers known to the author, the liquid involved is not usually a true solvent of the polymer but instead has a solubility parameter on the borderline of the solubility range. Examples are polystyrene and white spirit, polycarbonate and methanol and ethyl acetate with polysulphone. The propensity to solvent stress cracking is however far from predictable and intending users of a polymer would have to check on this before use. 

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. 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

In the case of crystalline polymers it may be that solvents can cause cracking by activity in the amorphous zone. Examples of this are benzene and toluene with polyethylene. In polyethylene, however, the greater problem is that known as environmental stress cracking , which occurs with materials such as soap, alcohols, surfactants and silicone oils. Many of these are highly polar materials which cause no swelling but are simply absorbed either into or on to the polymer. This appears to weaken the surface and allows cracks to propagate from minute flaws. 

Aryl-aliphatic copolyamides (Ar-Al-PA) are industrial technical polymers whose uses as transparent plastics require performances in terms of temperature behaviour, or resistance to solvents and stress cracking. The transparency of materials necessitates a completely amorphous structure, which is obtained by using not only para-substituted phenyl rings, but also meta-substituted phenyl rings that decrease the chain regularity. 

PSF/PET blends show a dispersed morphology. The combination of crystalline PET and amorphous polysulfone provides chemical resistance and warp-free properties. The amount of crystalline polymer is varied to meet requirements in thermal properties and the level of reinforcement is varied to tailor the modulus. The blends have electrical and mechanical properties similar to PET but only a third of its shrinkage and warpage. Also, stress crack resistance to common solvents is improved. Similarly, the service T is upgraded compared to PET. The blends are formed by injection molding and extrusion. 

The dissolution of a polymer in a penetrant involves two transport processes, namely penetration of the solvent into the polymer, followed by disentanglement of the macromolecular chains. When an uncrosslinked, amorphous, glassy polymer is in contact with a thermodynamically compatible liquid (solvent), the latter diffuses into the polymer. A gel-like layer is formed adjacent to the solvent-polymer interface due to plasticization of the polymer by the solvent. After an induction time, the polymer is dissolved. A schematic diagram of solvent diffusion and polymer dissolution is shown in Fig. 1. However, there also exist cases where a polymer cracks when placed in a solvent. 

Chemical Resistance - PBS is an amorphous aromatic polymer and as such tends to bestable towards aqueous solutions but susceptible to attack from certain polar organic solvents. PBS resists attack from acids, alkalis, oils, fats, greases, petroleum and aliphatic hydrocarbons and alcohols. It does however suffer from stress cracking in certain ketones, esters and aromatic hydrocarbons, and dissolves in the more polar solvents such as dimethyl farmamide and some chlorinated hydrocarbons. Because of the solubility of the material it can be applied as a lacquer or solvent cast into thin film. 

The amorphous character of polyarylates renders this class of polymer susceptible to stress-cracking tendencies in solvents such as ketones, aromatic hydrocarbons, esters, and chlorinated hydrocarbons. In applications where chemical resistance is critical, alloying polyarylate with other high performance materials can often meet the requirement. 

Poly(methyl methacrylate) prepared by free radical polymerization is amorphous and is therefore soluble in solvents of similar solubility parameter. Effective solvents include aromatic hydrocarbons such as benzene and toluene chlorinated hydrocarbons such as chloroform and ethylene dichloride and esters such as ethyl acetate and amyl acetate. Some organic materials, although not solvents for the polymer, cause crazing and cracking, e.g., aliphatic alcohols and amines. Poly(methyl methacrylate) has very good resistance to attack by water, alkalis, aqueous inorganic salts and most dilute acids. Some dilute acids such as hydrocyanic and hydrofluoric acids, however, do attack the polymer, as do concentrated oxidizing acids. Poly(methyl methacrylate) has much better resistance to hydrolysis than poly(methyl acrylate), probably by virtue of the... 

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