Embrittlement polymers

Polymer embrittlement was determined by 180° fold and/or pencil puncture tests. Elongation in the transverse direction of the LDPE samples was measured on an Instron TT-C tensile tester at 70°F and 65 relative humidity. The time to break was 25-50 sec. for 2 mm strips utilizing a gauge length of 0.5" and jaw-type clamps. 

Much work has already been done to unravel the complexities of photooxidative processes and to develop some highly effective light (UV) stabilizers which can delay the onset of polymer embrittlement. A good review has been presented by Carlsson et al.( ). Some polymer s-tems have also been e loited to fabricate plastics with controlled lifetimes in the short range(2,3). However, very little is known about the ultimate changes that occur in polymeric substances after very long periods such as the 20-year regime appropriate for economic photovoltaic power plants. 

Fig. 3.6 Found vs. calculated values for polymer embrittlement using the parameters in Table 3.1 and Eq. (3.7) with n=2 [15]...

Polyamides, like other macromolecules, degrade as a result of mechanical stress either in the melt phase, in solution, or in the soHd state (124). Degradation in the fluid state is usually detected via a change in viscosity or molecular weight distribution (125). However, in the soHd state it is possible to observe the free radicals formed as a result of polymer chains breaking under the appHed stress. If the polymer is protected from oxygen, then alkyl radicals can be observed (126). However, if the sample is exposed to air then the radicals react with oxygen in a manner similar to thermo- and photooxidation. These reactions lead to the formation of microcracks, embrittlement, and fracture, which can eventually result in failure of the fiber, film, or plastic article. 

Film or fibers derived from low molecular weight polymer tend to embrittle on immersion ia acetone those based on higher molecular weight polymer (>0.60 dL/g) become opaque, dilated, and elastomeric. When a dilated sample is stretched and dried, it retains orientation and is crystalline, exhibiting enhanced tensile strength. The tensile heat-distortion temperature of the crystalline film is iacreased by about 20°C, and the gas permeabiUty and resistance to solvent attack is iacreased. 

Antioxidants may be assessed in a variety of ways. For screening and for fundamental studies the induction period and rate of oxidation of petroleum fractions with and without antioxidants present provide useful model systems. Since the effect of oxidation differs from polymer to polymer it is important to evaluate the efficacy of the antioxidant with respect to some property seriously affected by oxidation. Thus for polyethylene it is common to study changes in flow properties and in power factor in polypropylene, flow properties and tendency to embrittlement in natural rubber vulcanisates, changes in tensile strength and tear strength. 

The polymer is not easy to process and in injection moulding melt temperatures of 300°C are employed. In order to prevent excess embrittlement by shock cooling of the melt, mould temperatures as high as 150°C may be used. The polymer may also be compression moulded at temperatures of 250-260°C. 

The polymers also have excellent resistance to oxidative degradation, most chemicals other than strong bases and high-energy radiation. Exposure for 1500 hours to a radiation of about 10 rads at 175°C led to embrittlement but the sample retained form stability. 

Weathering. This generally occurs as a result of the combined effect of water absorption and exposure to ultra-violet radiation (u-v). Absorption of water can have a plasticizing action on plastics which increases flexibility but ultimately (on elimination of the water) results in embrittlement, while u-v causes breakdown of the bonds in the polymer chain. The result is general deterioration of physical properties. A loss of colour or clarity (or both) may also occur. Absorption of water reduces dimensional stability of moulded articles. Most thermoplastics, in particular cellulose derivatives, are affected, and also polyethylene, PVC, and nylons. 

The mechanisms by which polymers undergo degradation in the human body are not yet completely understood. Examples of breakdown of these materials are illustrated by the embrittlement and excessive wear of polyester sockets exposed to the mechanical, biochemical and thermal stresses of the physiological milieu, as well as by the fatigue fractures, excessive wear and additional cross-linking (embrittlement) that have been observed in polyethylene sockets. 

Cellulosic They are tough, transparent, hard or flexible natural polymers made from plant cellulose feedstock. With exposure to light, heat, weather and aging, they tend to dry out, deform, embrittle and lose gloss. Molding applications include tool handles, control knobs, eyeglass frames. Extrusion uses include blister packaging, toys, holiday decorations, etc. Cellulosic types, each with their specialty properties, include cellulose acetates (CAs), cellulose acetate butyrates (CABs), cellulose nitrates (CNs), cellulose propionate (CAPs), and ethyl celluloses (EC). 

Relatively small changes in comonomer content can result in significant changes in physical or chemical properties. Polymer resin manufacturers exploit such relationships to control the properties of their products. The composition of a copolymer controls properties such as stiffness, heat distortion temperature, printability, and solvent resistance. For example, polypropylene homopolymer is brittle at temperatures below approximately 0 °C however, when a few percent ethylene is incorporated into the polymer backbone, the embrittlement temperature of the resulting copolymer is reduced by 20 °C or more. 

The nitroxide radical (from processes 5 and 6 and attack by other radicals on the parent piperidine) is found in photo-oxidizing PPH samples in concentrations of M. x 10 M (initial piperidine level 5 x 10-3M) up to the embrittlement point of the PPH film (7.). Nitroxides are well known to scavenge carbon centered radicals (but not peroxyl radicals) in both polymers and liquid alkanes (reaction 7) (10, 8). In the liquid phase k7 is... 

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