This introductory article describes the various aspects of chemical structure that are important to an understanding of polymer properties and thus their eventual effect on the end-use performance of engineering plastics. The polymers covered include hydrocarbon polymers, carbon-chain polymers, heterochain polymers, and polymers containing aromatic rings. The article also includes some general information on the classification and naming of polymers and plastics. The most important properties of polymers, namely, thermal, mechanical, chemical, electrical, and optical properties, and the most significant influences of structure on those properties are then discussed. A variety of engineering thermoplastics, including some that are regarded as high-performance thermoplastics, are covered in this article. In addition, a few examples of commodity thermoplastics and biodegradable thermoplastics are presented for comparison. Finally, the properties and applications of six common thermosets are briefly considered.

A stamped coin exhibited visible discolored areas, seen as a tan haze on the surface. The discoloration was considered merely cosmetic. The nonstained and stained regions were studied using SEM/EDS. Greater amounts of aluminum and magnesium were found in the stained area as compared with the nonstained region. Some carbon and oxygen were detected in both areas, which may be suggestive of organic substances. Fourier transform infrared spectroscopy (FTIR) revealed traces of hydrocarbons and ether/alcohol materials in the stained area, suggesting that the stain was associated with a cellulose or carbohydrates (sugars). These findings, along with the appearance, suggest that a sugar-containing substance, such as coffee or a soft drink, dried onto the surface of this coin and caused the observed discoloration.

This article provides practical information and data on property development in engineering plastics. It discusses the effects of composition on submolecular and higher-order structure and the influence of plasticizers, additives, and blowing agents. It examines stress-strain curves corresponding to soft-and-weak, soft-and-tough, hard-and-brittle, and hard-and-tough plastics and temperature-modulus plots representative of polymers with different degrees of crystallinity, cross-linking, and polarity. It explains how viscosity varies with shear rate in polymer melts and how processes align with various regions of the viscosity curve. It discusses the concept of shear sensitivity, the nature of viscoelastic properties, and the electrical, chemical, and optical properties of different plastics. It also reviews plastic processing operations, including extrusion, injection molding, and thermoforming, and addresses related considerations such as melt viscosity and melt strength, crystallization, orientation, die swell, melt fracture, shrinkage, molded-in stress, and polymer degradation.

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.

A segment of a stainless steel clad bottom cone of an acid sulfite pulping batch digester failed from severe corrosion loss. The digester was fabricated of 19 mm ( 3 4 in.) low-carbon steel with 3.8 mm (0.15 in.) type 317L stainless steel cladding. The manufacturing method for the cladding was unknown. Visual and metallographic analyses indicated that the failure was from transgranular stress-corrosion cracking (TGSCC), which caused extensive cracking and spalling of the cladding and was localized in a segment of the bottom cone. The remainder of the digester cladding was unaffected. The TGSCC was attributed to high, locked-in residual stresses from the cladding process. It was recommended that the bottom cone replacement segment be stress relieved prior to installation.

A longeron assembly constructed of Alclad 2024, some parts being in the T3 condition, others in the T42 condition, failed at a rivet hole. Plastic deformation at the crack site was found, but no plastic deformation was found in similar failed components. It was concluded that the numerous hairline cracks in the Alclad layer adjacent to the main fracture were fatigue cracks. In another case, bonded samples of 2024-T3 sheet were fatigue tested at various stress levels. Failures could be separated into three groups: those that failed in the adhesive bond, those that failed in the base material, and those that exhibited a dual failure. The last category failed in the adhesive bond and also showed a type of pitting on one face of the base material. In a third case, a 2024-T4 extrusion section was found to exhibit blistering after chemical milling. The presence of interconnecting microcracks between adjacent discontinuities supported a hydrogen blistering diagnosis.

X-ray spectroscopy is generally accepted as the most useful ancillary technique that can be added to any scanning electron microscope (SEM), even to the point of being considered a necessity by most operators. While “stand-alone” x-ray detection systems are used less frequently in failure analysis than the more exact instrumentation employed in SEMs, the technology is advancing and is worthy of note due to its capability for nondestructive analysis and application in the field. This article begins with information on the basis of the x-ray signal. This is followed by information on the operating principles and applications of detectors for x-ray spectroscopy, namely energy-dispersive spectrometers, wavelength-dispersive spectrometers, and handheld x-ray fluorescence systems. The processes involved in x-ray analysis in the SEM and handheld x-ray fluorescence analysis are then covered. The article ends with a discussion on the applications of x-ray spectroscopy in failure analysis.

This article covers the three most popular techniques used to characterize the very outermost layers of solid surfaces: Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Some of the more important attributes are listed for preliminary insight into the strengths and limitations of these techniques for chemical characterization of surfaces. The article describes the basic theory behind each of the different techniques, the types of data produced from each, and some typical applications. Also discussed are the different types of samples that can be analyzed and the special sample-handling procedures that must be implemented when preparing to do failure analysis using these surface-sensitive techniques. Data obtained from different material defects are presented for each of the techniques. The examples presented highlight the typical data sets and strengths of each technique.

Overload failures refer to the ductile or brittle fracture of a material when stresses exceed the load-bearing capacity of a material. This article reviews some mechanistic aspects of ductile and brittle crack propagation, including a discussion on mixed-mode cracking, which may also occur when an overload failure is caused by a combination of ductile and brittle cracking mechanisms. It describes the general aspects of fracture modes and mechanisms. The article discusses some of the material, mechanical, and environmental factors that may be involved in determining the root cause of an overload failure. It also presents examples of thermally and environmentally induced embrittlement effects that can alter the overload fracture behavior of metals.

This article provides an overview of the classification of hydrogen damage. Some specific types of the damage are hydrogen embrittlement, hydrogen-induced blistering, cracking from precipitation of internal hydrogen, hydrogen attack, and cracking from hydride formation. The article focuses on the types of hydrogen embrittlement that occur in all the major commercial metal and alloy systems, including stainless steels, nickel-base alloys, aluminum and aluminum alloys, titanium and titanium alloys, copper and copper alloys, and transition and refractory metals. The specific types of hydrogen embrittlement discussed include internal reversible hydrogen embrittlement, hydrogen environment embrittlement, and hydrogen reaction embrittlement. The article describes preservice and early-service fractures of commodity-grade steel components suspected of hydrogen embrittlement. Some prevention strategies for design and manufacturing problem-induced hydrogen embrittlement are also reviewed.

In a HyL III heat exchanger's radiant pipes, metal dusting reduced the pipe thickness from 8.5 to 3 mm in just nine months, leaving craters on the inner surface. The pipes are fabricated from HK 40 alloy. The heated gas (400 to 800 deg C) consisted of CO, CO2, and H2, with a 4:1 CO/CO2 ratio. Metallographic investigations revealed that the surface of the attacked pipes consisted of (Cr, Fe) carbide. The metal dusting was the result of a decomposition process (CO to CO2 + C) that deposited C on the pipe surface. Because of the high temperature, the C subsequently diffused through the surface oxide layer (Cr2O3), triggering a succession of reactions that led to pitting and the formation of craters.

This article discusses the operating principles, advantages, and limitations of scanning electron microscopy, atomic force microscopy, x-ray photoelectron spectroscopy, and secondary ion mass spectroscopy that are used to analyze the surface chemistry of plastics.

Hydrogen damage is a term used to designate a number of processes in metals by which the load-carrying capacity of the metal is reduced due to the presence of hydrogen. This article introduces the general forms of hydrogen damage and provides an overview of the different types of hydrogen damage in all the major commercial alloy systems. It covers the broader topic of hydrogen damage, which can be quite complex and technical in nature. The article focuses on failure analysis where hydrogen embrittlement of a steel component is suspected. It provides practical advice for the failure analysis practitioner or for someone who is contemplating procurement of a cost-effective failure analysis of commodity-grade components suspected of hydrogen embrittlement. Some prevention strategies for design and manufacturing problem-induced hydrogen embrittlement are also provided.

This article provides information on the chemical characterization of surfaces by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). It describes the basic theory behind each of these techniques, the types of data produced from each, and some typical applications. The article explains the strengths of AES, XPS, and TOF-SIMS based on data obtained from the surface of a slightly corroded stainless steel sheet.

Several large-diameter type 304L stainless steel impeller/propeller blades in a circulating water pump failed after approximately 8 months of operation. The impeller was a single casting that had been modified with a fillet weld buildup at the blade root. Visual examination indicated that the fracture originated near the blade-to-hub attachment in the area of the weld buildup. Specimens from four failed castings and from an impeller that had developed cracks prior to design modification were subjected to a complete analysis. A number of finite-element-method computer models were also constructed. It was determined that the blades failed by fatigue that had been accelerated by stress-corrosion cracking. The mechanism of failure was flow-induced vibration, in which the vortex-shedding frequencies of the blades were attuned to the natural frequency of the blade/hub configuration. A number of solutions involving material selection and impeller redesign were recommended.

This article aims to identify and illustrate the types of overload failures, which are categorized as failures due to insufficient material strength and underdesign, failures due to stress concentration and material defects, and failures due to material alteration. It describes the general aspects of fracture modes and mechanisms. The article briefly reviews some mechanistic aspects of ductile and brittle crack propagation, including discussion on mixed-mode cracking. Factors associated with overload failures are discussed, and, where appropriate, preventive steps for reducing the likelihood of overload fractures are included. The article focuses primarily on the contribution of embrittlement to overload failure. The embrittling phenomena are described and differentiated by their causes, effects, and remedial methods, so that failure characteristics can be directly compared during practical failure investigation. The article describes the effects of mechanical loading on a part in service and provides information on laboratory fracture examination.

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.

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.

This article describes some of the common elemental composition analysis methods and explains the concept of referee and economy test methods in failure analysis. It discusses different types of microchemical analyses, including backscattered electron imaging, energy-dispersive spectrometry, and wavelength-dispersive spectrometry. The article concludes with information on specimen handling.