Polymers, chemical attack

Isophthahc (y -phthahc) acid [121 -91 -5] (IPA) is selected to enhance thermal endurance as well as to produce stronger, more resiUent cross-linked plastics that demonstrate improved resistance to chemical attack. TerephthaUc (p-phthaUc) acid [100-21-0] (TA) provides somewhat similar properties as isophthahc acid but is only used in selective formulations due to the limited solubiUty of these polyester polymers in styrene [100-42-5] (see Phthalic acid AND OTHERBENZENEPOLYCARBOXYLIC ACIDS). 

Amines can also swell the polymer, lea ding to very rapid reactions. Pyridine, for example, would be a fairly good solvent for a VDC copolymer if it did not attack the polymer chemically. However, when pyridine is part of a solvent mixture that does not dissolve the polymer, pyridine does not penetrate into the polymer phase (108). Studies of single crystals indicate that pyridine removes hydrogen chloride only from the surface. Kinetic studies and product characterizations suggest that the reaction of two units in each chain-fold can easily take place further reaction is greatiy retarded either by the inabiUty of pyridine to diffuse into the crystal or by steric factors. 

Vinyl ester resins generally offer mechanical properties superior to those of polyester matrices but at an increased cost. Vinyl esters are chemically similar to epoxy resins but are manufactured via a cold-curing process similar to that used in the manufacture of polyester resins. Vinyl esters offer superior resistance to water and chemical attack and are used in such appHcations as underground pipes, tank liners, and storage tanks (see Vinyl polymers). 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

Membrane Limitations Chemical attack, fouling, and compaction are prominent problems with RO and NF membranes. Compaction is the most straightforward. It is the result of creep, slow cold flow of the polymer resulting in a loss of water permeability. It is measured by the slope of log flux versus log time in seconds. It is independent of the flux units used and is reported as a slope, sometimes with the minus sign omitted. A slope of—0.001, typical for noncelhilosic membranes, means that for every threefold increase in log(time), 10 seconds, a membrane looses 10 percent of its flux. Since membranes are rated assuming that the dramatic early decline in permeability has already occurred, the further decline after the first few weeks is veiy slow. Compaction is specific to pressure, temperature, and envi-... 

The chemical resistance of polyethylene is, to a large measure, that expected of an alkane. It is not chemically attacked by non-oxidising acids, alkalis and many aqueous solutions. Nitric acid oxidises the polymer, leading to a rise in power factor and to a deterioration in mechanical properties. As with the simple alkanes, halogens combine with the hydrocarbon by means of substitution mechanisms. 

Extruded applications of nylon, other than film and monofilcunent, are less commonly encountered because of the low melt viscosity of the polymers. Uses include cable sheathing which requires resistance to abrasion and/or chemical attack, flexible tubing for conveying petrol and other liquids, piping for chemical... 

The solubility parameter is about 19.2MPa and being amorphous they dissolve in such solvents as tetrahydrofuran, mesityl oxide, diacetone alcohol and dioxane. Since the main chain is composed of stable C—C and C—O—C linkages the polymer is relatively stable to chemical attack, particularly from acids and alkalis. As already mentioned, the pendant hydroxyl groups are reactive and provide a site for cross-linking. 

Acrylate polymers also have fully saturated polymer backbones free of any heteroatoms in the main chain. This makes the polymers highly resistant to oxidation, photo-degradation and chemical attack. The acrylate groups are esters, which could be hydrolyzed under severe conditions. However, the hydrophobic nature of most acrylic polymers minimizes the risk for hydrolysis and, even if this reaction happened to some extent, the polymer backbone would still be intact. Other desirable acrylate properties include the following ... 

Conductive Polymers Anodes currently available consist of a conductive-polymer graphite material coated on to a multistrand copper conductor. The polymer provides an active surface but shields the conductor from chemical attack. A non-conductive outer braid may be used to give abrasion resistance and avoid direct contact with the cathode. The finished anode has the appearance of an electric cable and is claimed to have applications for buried/immersed structures and for internal protection of tanks, etc. Anode current densities are typically given as 14-30mAm ... 

It is essential to appreciate that such plasticisers will considerably modify the chemical properties of the plastics material since the plasticiser may be readily extracted by certain chemicals and chemically attacked by others whilst the base polymer may be unaffected. 

Resistance of a polymer to chemical attack resulting in breakdown of some covalent bonds and formation of new ones. This could involve breakdown initiated by heat and radiation including u.v. light. 

Expressed simply the resistance of a polymer to chemical attack may be said to be determined by the following factors ... 

Polytetrafluorethylene (p.t.f.e.) This polymer does not absorb water, has no solvents and is almost completely inert to chemical attack molten alkali metals and sodium in liquid ammonia are the rare exceptions. Furthermore it does not soften below 320°C, is electrically inert and has a very low coefficient of friction. It is more expensive than general purpose plastics, requires special fabrication techniques, is degraded by high energy radiation, and has a low creep resistance. 

Teflon (C2F2) , where n is of the order of 104 to 10s, is a versatile but expensive polymer ( 10-20/kg). It is virtually impervious to chemical attack, even at high temperatures. Apparently the fluorine atoms form a protective shield around the central carbon chain ... 

Both share more or less the same merits but also the same disadvantages. The beneficial properties are high OCV (2.12 and 1.85 V respectively) flexibility in design (because the active chemicals are mainly stored in tanks outside the (usually bipolar) cell stack) no problems with zinc deposition in the charging cycle because it works under nearly ideal conditions (perfect mass transport by electrolyte convection, carbon substrates [52]) self-discharge by chemical attack of the acid on the deposited zinc may be ignored because the stack runs dry in the standby mode and use of relatively cheap construction materials (polymers) and reactants. 

Report 130 Failure of Polymer Products Due to Chemical Attack,... 

Among elastomers, artificial rubbers have replaced natural rabber for many uses because of their high resistance to chemical attack by ozone, an atmospheric pollutant. When ozone reacts with polymer chains, it breaks CUCn bonds and introduces additional cross-linking. Breaking 7r bonds causes the rabber to sofien, and cross-linking makes it more brittle. Both changes eventually lead to rupture of the polymer structure. 

Portland cement is susceptible to corrosion by CO2 and H2S. The chemical attack by CO2 is called carbonation. A microsample technique has been developed to study the CO2 corrosion in cements, because the corrosion is difficult to monitor with common test procedures [264]. This technique is also advantageous as an accelerated testing method. A polymer-modified cement has been tested in field studies [694]. The addition of silica also improves chemical resistance [146], in particular brine corrosion. 

A comprehensive review of compositional and failure analysis of polymers, which includes many further examples of analysis of contaminants, inclusions, chemical attack, degradation, etc., was published in 2000 [2], It includes details on methodologies, sampling, and sample preparation, and microscopy, infrared spectroscopy, and thermal analysis techniques. 

A wax-like polymer with resistance to a wide range of temperatures, high resistance to chemical attack and very low frictional resistance. It is widely used in O-rings, seals and gaskets it may also be sintered on to a mould surface to assist the release of the product. Polythene... 

The effect of heat, whether generated externally or by other mechanisms within the polymer itself, will be to raise the temperature. An increase in temperature will accelerate most of the degradation mechanisms listed, such as oxidation, chemical attack or mechanical creep. Temperature alone can cause thermal expansion, while at very high temperatures polymers will decompose, although this may be masked by the effects of oxidation. 

Because commercial synthetic thermoplastic polymers are either addition polymers or condensation polymers, depolymerization occurs by different routes. Addition polymers, for which the synthesis reactions are essentially not reversible, depolymerize by pyrolysis or such severe chemical attack that few useful monomers can be practically recovered. With pyrolysis, a wide spectrum of species are created, which offers little in the way of valuable reaction products without costly separation processes. The overall yield to desired products can be unattractively low. 

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