Microbial degradation in the environment is initiated by abiotic (nonliving physical or chemical) processes. Mechanical weathering and other mechanical processes are the main drivers of the initial degradation. This article presents an overview of weathering and biodegradation. It summarizes the main synthetic polymers that are released and available for bacterial and fungal decomposition. The article also presents a detailed discussion on the enzymes that are involved in plastic degradation, and the measurement of polymer degradation.

With any polymeric material, chemical exposure may have one or more different effects. Some chemicals act as plasticizers, changing the polymer from one that is hard, stiff, and brittle to one which is softer, more flexible, and sometimes tougher. Often these chemicals can dissolve the polymer if they are present in large enough quantity and if the polymer is not crosslinked. Other chemicals can induce environmental stress cracking (ESC), an effect in which brittle fracture of a polymer will occur at a level of stress well below that required to cause failure in the absence of the ESC reagent. Finally, there are some chemicals that cause actual degradation of the polymer, breaking the macromolecular chains, reducing molecular weight, and diminishing polymer properties as a result. This article examines each of these effects. The discussion also covers the effects of surface embrittlement and temperature on polymer performance.

The susceptibility of plastics to environmental failure, when exposed to organic chemicals, can limit their use in many applications. A combination of chemical and physical factors, along with stress, usually leads to a serious deterioration in properties, even if stress or the chemical environment alone may not appreciably weaken a material. This phenomenon is referred to as environmental stress cracking (ESC). The ESC failure mechanism for a particular plastics-chemical environment combination can be quite complex and, in many cases, is not yet fully understood. This article focuses on two environmental factors that contribute to failure of plastics, namely chemical and physical effects.

This article describes the processes involved in photochemical aging and weathering of polymeric materials. It explains how solar radiation, especially in the UV range, combines with atmospheric oxygen, driving photooxidation and the development of unstable photoproducts that cause various types of damage when they decompose, including the scission of carbon bonds and polymer chains. The article illustrates some of the degradation reactions that occur in different polymers and presents an overview of the strategies used to prevent such reactions or otherwise mitigate their effects.

This article discusses pressure vessels, piping, and associated pressure-boundary items of the types used in nuclear and conventional power plants, refineries, and chemical-processing plants. It begins by explaining the necessity of conducting a failure analysis, followed by the objectives of a failure analysis. Then, the article discusses the processes involved in failure analysis, including codes and standards. Next, fabrication flaws that can develop into failures of in-service pressure vessels and piping are covered. This is followed by sections discussing in-service mechanical and metallurgical failures, environment-assisted cracking failures, and other damage mechanisms that induce cracking failures. Finally, the article provides information on inspection practices.

Six transformer brackets failed in service, sending a group of three pole-mounted transformers to the ground below. The brackets were made from acrylonitrile-butadiene-styrene (ABS) resin and had been in service for more than 30 years. Remnants of the fractured brackets were analyzed using optical and scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The exterior surfaces of all six brackets were alike and shared similar features, including witness marks, discoloration, mechanical deformation, and secondary cracking, along with crack networks. Both FTIR and TGA analyses indicated that the surface material was in a highly degraded state, likely due to weathering and thermal and ultraviolet exposure. This, in turn, led to the formation of cracks that propagated under the cyclic forces of vibration and wind. As the cracks grew larger, the weight of the transformer eventually overloaded the brackets, resulting in failure.

The crosslinked epoxy resin encapsulant protecting an electromagnetic valve coil failed during long-term storage and was examined to determine the cause. The investigation included fault-tree analysis, FTIR and EDX spectroscopy, and differential scanning calorimetry with thermogravimetric analysis. Based on test data, the epoxy resin had not been properly cured and was hydrolyzed in its compromised state because of humidity. Hence, the depolymerized material gradually softened to the point where the effect of creep caused it to flow, ultimately causing the failure.

A component of a water filtration unit failed while being used in service for approximately eight months. The filter system had been installed in a commercial laboratory, where it was stated to have been used exclusively in conjunction with deionized water. The failed part had been injection molded from a 30% glass-fiber and mineral-reinforced nylon 12 resin. Investigation, including visual inspection, 118x SEM images, 9x micrographs, energy-dispersive x-ray spectroscopy, micro-FTIR in the ATR mode, and TGA, supported the conclusion that the filter component failed as a result of molecular degradation caused by the service conditions. Specifically, the part material had undergone severe chemical attack, including oxidation and hydrolysis, through contact with silver chloride. The source of the silver chloride was not established, but one potential source was photographic silver recovery.

Housings (being tested as part of a material conversion) from an electrical appliance failed during an engineering evaluation. They had been injection molded from a commercial polycarbonate/PET blend. Parts produced from the previous material, a nylon 6/6 resin, had consistently passed the testing regimen. Grease was applied liberally within the housing assembly during production. Investigation included visual inspection, 24x SEM images, micro-FTIR in the ATR mode, and analysis using DSC. No signs of material contamination were found, but the thermograms showed a crystallization of the PET resin. The grease present within the housing assembly, analyzed using micro-FTIR, was composed of a hydrocarbon-based oil, a phthalate-based oil, lithium stearate, and an amide-based additive. The conclusion was that the appliance housings failed through environmental stress cracking caused by a phthalate-based oil that was not compatible with the PC portion of the resin blend. Thus, the resin conversion was the root cause of the failures. Additionally, during the injection molding process the molded parts had been undercrystallized, reducing their mechanical strength. More importantly, the resin had been degraded, producing a reduction in the molecular weight and reducing both the mechanical integrity and chemical-resistance properties of the parts.

A set of plastic grips from an electric consumer product failed while in service. The grips had been injection molded from a general-purpose grade of ABS resin. The parts had cracked while in use after apparent embrittlement of the material. Investigation (visual inspection, SEM imaging, and micro-FTIR in the ATR mode) showed that the spectrum representing the grip surface contained absorption bands associated with ABS as well as additional bands of significant intensity. A spectral subtraction removed the bands associated with the ABS resin resulting in a very good match with glyceride derivatives of fats and oils. This supported the conclusion that the grips failed via brittle fracture associated with severe chemical attack of the ABS resin. A significant level of glyceride derivatives of fatty acids, known to degrade ABS resins, was found on the part surface.

A plastic bracket exhibited relatively brittle material properties, which ultimately led to catastrophic failure. The part had been injection molded from a medium-viscosity polycarbonate resin and had been in service for a short duration prior to the failure. Investigation (visual inspection and analysis using micro-FTIR in the ATR mode) revealed the spectrum showed changes in the relative intensities of several bands, as compared to the results representing the base material. A spectral subtraction was performed, and the results produced a good match with diphenyl carbonate, which is a common breakdown product produced during the decomposition of polycarbonate. The conclusion was that the most likely cause of the molecular degradation was improper drying and/or exposure to excessive heat during the injection molding process that in turn caused the material degradation.

A number of plastic sleeves used in an automotive application cracked after assembly but prior to installation into the mating components. The sleeves were specified to be injection molded from a 20% glass-fiber-reinforced polybutylene terephthalate (PBT) resin. After molding, electronic components are inserted into the sleeves, and the assembly is filled with a potting compound. Investigation of the cracked parts and some reference parts available for testing included visual inspection, micro-FTIR in the ATR mode, and analysis using DSC. Subtle spectrum differences suggested degradation of the failed part material, and the thermograms supported this. The conclusion was that the failed sleeves had cracked due to embrittlement associated with severe degradation and the corresponding molecular weight reduction. The reduction in molecular weight significantly reduced the mechanical properties of the sleeves. The cause of the degradation was not evident, but the likely source appears to be the molding operation and exposure to elevated temperature for an extended period of time.

The article commences with an overview of short-term and long-term mechanical properties of polymeric materials. It discusses plasticization, solvation, and swelling in rubber products. The article further describes environmental stress cracking and degradation of polymers. It illustrates how surface degradation of a plain strain tension specimen alters the ductile brittle transition in polyethylene creep rupture. The article concludes with information on the effects of temperature on polymer performance.