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Molecular degradation
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Book Chapter
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.homegoods.c0090424
EISBN: 978-1-62708-222-8
... 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. Brackets...
Abstract
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.
Book Chapter
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.auto.c0090451
EISBN: 978-1-62708-218-1
... process had exposed the resin to relatively high temperatures, which caused substantial molecular degradation, thus limiting the part's ability to withstand the stresses. The drying temperature was found to be significantly higher than the recommendation for the PET resin, and the testing itself exposed...
Abstract
Cracking occurred within the plastic jacket (injection molded from an impact-modified, 15% glass-fiber-reinforced PET resin.) of several assemblies used in a transportation application during an engineering testing regimen which involved cyclic thermal shock (exposing the parts to alternating temperatures of -40 and 180 deg C (-40 and 360 deg F)). Prior to molding, the resin had reportedly been dried at 135 deg C (275 deg F). The drying process usually lasted 6 h, but occasionally, the material was dried overnight. Comparison investigation (visual inspection, 20x SEM views, micro-FTIR, and analysis using DSC and TGA) with non-failed parts supported the conclusion that that the failure was via brittle fracture associated with the exertion of stresses that exceeded the strength of the resin as-molded caused by the disparity in the CTEs of the PET jacket and the mating steel sleeve. The drying process had exposed the resin to relatively high temperatures, which caused substantial molecular degradation, thus limiting the part's ability to withstand the stresses. The drying temperature was found to be significantly higher than the recommendation for the PET resin, and the testing itself exposed the parts to temperatures above the recognized limits for PET.
Book Chapter
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.modes.c0090460
EISBN: 978-1-62708-234-1
... 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...
Abstract
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.
Book Chapter
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.modes.c0090463
EISBN: 978-1-62708-234-1
... inserts. Investigation supported the conclusion that the switch housings failed via brittle fracture, likely through a creep mechanism. The failure was caused by severe embrittlement of the housing resin associated with massive molecular degradation produced during the molding process. A potential...
Abstract
A housing used in conjunction with an electrical switch failed shortly after being placed into service. A relatively high failure rate had been encountered, corresponding to a recent production lot of the housings, and the failed part was representative of the problem. The housing had been injection molded from a commercially available, medium-viscosity grade of PC, formulated with an ultraviolet stabilizer. In addition to the PC housing, the design of the switch included an external protective zinc component installed with a snap-fit and two retained copper press-fit contact inserts. Investigation supported the conclusion that the switch housings failed via brittle fracture, likely through a creep mechanism. The failure was caused by severe embrittlement of the housing resin associated with massive molecular degradation produced during the molding process. A potential contributing factor was the design of the part, which produced significant interference stresses between the contact and a mating retaining tab.
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.auto.c0090442
EISBN: 978-1-62708-218-1
... 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...
Abstract
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.
Series: ASM Handbook Archive
Volume: 11
Publisher: ASM International
Published: 01 January 2002
DOI: 10.31399/asm.hb.v11.a0003525
EISBN: 978-1-62708-180-1
..., including catastrophic mechanisms, such as brittle fracture, ductile overload, creep rupture, environmental stress cracking, molecular degradation, and fatigue. In the case of failure involving fracture, the determination of the failure mode involves identifying how the crack initiated and how...
Abstract
This article reviews the analytical techniques most commonly used in plastic component failure analysis. These include the Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, thermomechanical analysis, and dynamic mechanical analysis. The descriptions of the analytical techniques are supplemented by a series of case studies that include pertinent visual examination results and the corresponding images that aid in the characterization of the failures. The article describes the methods used for determining the molecular weight of a plastic resin. It explains the use of mechanical testing in failure analysis and also describes the considerations in the selection and use of test methods.
Image
in Characterization of Plastics in Failure Analysis
> Characterization and Failure Analysis of Plastics
Published: 15 May 2022
Fig. 17 Micrograph showing cracking on the failed housing boss. A localized zone of mud cracking and discoloration characteristic of molecular degradation is present.
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Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006933
EISBN: 978-1-62708-395-9
... of contaminants is illustrated in Examples 3 and 8 in Ref 4 . Degradation Fourier transform infrared spectroscopy is a valuable tool in assessing a failed component material for degradation such as oxidation and hydrolysis. Molecular degradation, often involving molecular weight reduction, has...
Abstract
This article reviews analytical techniques that are most often used in plastic component failure analysis. The description of the techniques is intended to familiarize the reader with the general principles and benefits of the methodologies, namely Fourier transform infrared spectroscopy, energy-dispersive x-ray spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The article describes the methods for molecular weight assessment and mechanical testing to evaluate plastics and polymers. The descriptions of the analytical techniques are supplemented by a series of case studies to illustrate the significance of each method. The case studies also include pertinent visual examination results and the corresponding images that aided in the characterization of the failures.
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.homegoods.c0090448
EISBN: 978-1-62708-222-8
... had been degraded, producing a reduction in the molecular weight and reducing both the mechanical integrity and chemical-resistance properties of the parts. Crystallization Electrical appliances Grease Housings Injection molding Molding resins Undercrystallization Polycarbonate...
Abstract
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.
Book Chapter
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.chem.c0090454
EISBN: 978-1-62708-220-4
... of the vessel. The cracking extended transversely through the wall initially, and subsequently, circumferentially around the wall. Throughout the examination, no signs of postmolding molecular degradation or chemical attack were found. Fig. 1 Scanning electron image showing features associated...
Abstract
A chemical storage vessel failed while in service. The failure occurred as cracking through the vessel wall, resulting in leakage of the fluid. The tank had been molded from a high-density polyethylene (HDPE) resin. The material held within the vessel was an aromatic hydrocarbon-based solvent. Investigation (visual inspection, stereomicroscopic examination, 20x/100x SEM images, micro-FTIR in the ATR mode, and analysis using DSC and TGA) supported the conclusion that the chemical storage vessel failed via a creep mechanism associated with the exertion of relatively low stresses. The source of the stress was thought to be molded-in residual stresses associated with uneven shrinkage. This was suggested by obvious distortion evident on cutting the vessel. Relatively high specific gravity and the elevated heat of fusion indicated that the material had a high level of crystallinity. In general, increased levels of crystallinity result in higher levels of molded-in stress and the corresponding warpage. The significant reduction in the modulus of the HDPE material, which accompanied the saturation of the resin with the aromatic hydrocarbon-based solvent, substantially decreased the creep resistance of the material and accelerated the failure.
Series: ASM Failure Analysis Case Histories
Publisher: ASM International
Published: 01 June 2019
DOI: 10.31399/asm.fach.modes.c9001593
EISBN: 978-1-62708-234-1
... resins as a result of melt processing, where molecular weight can increase due to thermal induced crosslinking. The magnitude of the change, however, is low and the melt flow rate results suggest good retention of molecular weight through the molding process, without molecular degradation. Discussion...
Abstract
A failure analysis was conducted on a flow-sensing device that had cracked while in service. The polysulfone sensor body cracked radially, adjacent to a molded-in steel insert. This article describes the investigative methods used to conduct the failure analysis. The techniques utilized included scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermomechanical analysis, and melt flow rate determination. It was the conclusion of the investigation that the part failed via brittle fracture, with evidence also indicating low cycle fatigue associated with cyclic temperature changes from normal service. The design of the part and the material selection were significant contributing factors because of stresses induced during molding, physical aging of the amorphous polysulfone resin, and the substantial differential in coefficients of thermal expansion between the polysulfone and the mating steel insert.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006867
EISBN: 978-1-62708-395-9
... 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...
Abstract
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.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006916
EISBN: 978-1-62708-395-9
... be compared to the virgin resin to determine the extent of degradation due to the molding process, since degraded material would be lower in viscosity because of its reduced molecular weight. Figure 4 shows the results of a relative viscosity test conducted on normally ductile nylon wire ties that failed...
Abstract
This article focuses on manufacturing-related failures of injection-molded plastic parts, although the concepts apply to all plastic manufacturing processes It provides detailed examples of failures due to improper material handling, drying, mixing of additives, and molecular packing and orientation. It also presents examples of failures stemming from material degradation improper use of metal inserts, weak weld lines, insufficient curing of thermosets, and inadequate mixing and impregnation in the case of thermoset composites.
Image
Published: 15 May 2022
Fig. 1 General concept of plastic degradation by microorganisms. (a) Enzymes from bacteria attached to high-molecular-weight fibers. (b) Assumed transport of mono- and oligomers into the cell and microbial metabolism. Today, only a few enzymes involved in plastic degradation have been
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Series: ASM Handbook Archive
Volume: 11
Publisher: ASM International
Published: 01 January 2002
DOI: 10.31399/asm.hb.v11.a0003550
EISBN: 978-1-62708-180-1
... on plastics is to actually degrade the polymer; that is, to break down the polymer chains into lower molecular weight compounds that no longer have the desirable strength or toughness properties of the original. Certain polymer types are more susceptible than others to specific degradation mechanisms, but all...
Abstract
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.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006920
EISBN: 978-1-62708-395-9
... the mechanism and rate of the subsequent degradation reactions are typically not influenced. Temperature Influences Even though the formation of excited molecular states is initiated by the absorption of photons, the subsequent deactivation and degradation reactions are influenced by the temperature...
Abstract
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.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006917
EISBN: 978-1-62708-395-9
... semicrystalline polymers, as mentioned previously, molding has a direct effect on the level of chain entanglement and the molecular weight of the molded article. If the material undergoes molecular degradation during processing, the polymer chains can be substantially shortened, which reduces inherent...
Abstract
While there are many fracture mechanisms that can lead to the failure of a plastic component, environmental stress cracking (ESC) is recognized as one of the leading causes of plastic failure. This article focuses on unpacking the basic concepts of ESC to provide the engineer with a better understanding of how to evaluate and prevent it. It then presents factors that affect and contribute to the susceptibility of plastic to ESC: material factors, chemical factors, stress, and environmental factors. The article includes the collection of background information to understand the circumstances surrounding the failure, a fractographic evaluation to assess the cracking, and analytical testing to evaluate the material, design, manufacturing, and environmental factors.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006866
EISBN: 978-1-62708-395-9
... degradation by microorganisms. (a) Enzymes from bacteria attached to high-molecular-weight fibers. (b) Assumed transport of mono- and oligomers into the cell and microbial metabolism. Today, only a few enzymes involved in plastic degradation have been characterized. It is not clear if native plastic binding...
Abstract
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.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006915
EISBN: 978-1-62708-395-9
... effect on solubility, chemical resistance, and softening point. Silicon Silicon is found primarily in silicones, where it imparts low surface energy and resistance to oxidation. Phosphorus Low-molecular-weight phosphorus-containing additives or co-monomers are used as flame retardants...
Abstract
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.
Series: ASM Handbook
Volume: 11B
Publisher: ASM International
Published: 15 May 2022
DOI: 10.31399/asm.hb.v11B.a0006931
EISBN: 978-1-62708-395-9
... a particular analytical technique. Practical information derived from polymer analysis methods Table 2 Practical information derived from polymer analysis methods Test method Property Practical information provided Gel permeation chromatography (GPC); molecular weight distribution...
Abstract
This article presents tools, techniques, and procedures that engineers and material scientists can use to investigate plastic part failures. It also provides a brief survey of polymer systems and the key properties that need to be measured during failure analysis. It describes the characterization of plastics by infrared and nuclear magnetic resonance spectroscopy, differential scanning calorimetry, differential thermal analysis, thermogravimetric analysis, thermomechanical analysis, and dynamic mechanical analysis. The article also discusses the use of X-ray diffraction for analyzing crystal phases and structures in solid materials.
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