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Thermal degradation of polyoxypropylene glycol- toluene 2, 4-diisocyanate polymer /POPG-TDI/ OCCURS by random scission of urethane linkages to regenerate hydroxyl and isocyanate
Polymer degradation to small fragments is treated as a rate controlling step in hybrid rocket combustion. Both numerical and approximate analytical solutions of the complete energy and polymer chain bond conservation equations for the condensed phase are obtained. Comparison with inert atmosphere data is very good. It is found that the intersect of curves of pyrolysis rate versus interface temperature for hybrid combustors, with the thermal degradation theory, falls at a pyrolysis rate very close to that for which a pressure dependence begins to be observable. Since simple thermal degradation cannot give sufficient depolymerization at higher pyrolysis rates, it is suggested that oxidative catalysis of the process occurs at the surface, giving a first order dependence on reactive species concentration at the wall. Estimates of the ratio of this activation energy and interface temperature are in agreement with best fit procedures for hybrid combustion data. Requisite active species concentrations and flux are shown to be compatible with turbulent transport. Pressure dependence of hybrid rocket fuel regression rate is thus shown to be describable in a consistent manner in terms of reactive species catalysis of polymer degradation.
Polymer degradation dosimeter of polyisobutylene in heptane noting viscosity range effects, concentration change and molecular weight
An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.
Column elution fractionation and thermal degradation of polyoxypropylene glycol-toluene diisocyanate /PPG-TDI/ polymers of molecular weight of about 100,000
Polymer thermal degradation theory of pressure sensitive hybrid combustion, calculating linear regression rates
A new family of water-degradable elastic polymers prepared by oxidative crosslinking of the parent polythionolactones shows promise in a broad range of applications, but the compositions of these materials elude conventional analytical methods. Here, in this work, we use sulfur K-edge X-ray absorption spectroscopy to quantify the amounts of thioether, disulfide, sulfone, sulfate ester, and thionoester in each polymer and to rule out the presence of several other functional groups, including sulfonate, thiosulfonate, sulfate, and sulfoxide. We rationalize this speciation as a function of linker flexibility in the context of sulfinyl cycloaddition reactions and propose a mechanism of aggregation for the oxidized polymers. Our results correlate with swelling ratios but not with porosity nor crosslink density measurements, demonstrating the importance of pairing mechanical and chemical techniques when characterizing heterogeneous organic polymers. Finally, we take advantage of the proximity of the gold M 4,5 -edges to the sulfur K-edge to analyze the binding and reactivity of Au(III) with the crosslinked polymers.
Most students enter college without any exposure to polymer science, which leads to the poor understanding and slow implementation of plastic recycling programs in the United States. Here, to address the knowledge gap in chemical recycling, we introduce a 2-part laboratory experiment that was conducted in multiple high schools and public outreach events to demonstrate the depolymerization of PET via aminolysis and the remanufacturing of cleaved PET fragments into a new aramid polymer. Student experiences were evaluated with two postlab assignments.
To test the hypothesis that exposure to ultrafine particles results in an increased interstiatilization of the particles which is accompanied by an acute pathological inflammation, rats were exposed to titanium dioxide (TiO2) particles by intratracheal instillation and by inhalation. Both acute intratracheal instillation and subchronic inhalation studies on rats show that ultrafine TiO2 particles access the pulmonary interstitium to a larger extent than fine particles and that they elicit an inflammatory response as indicated by PMN increase in lavaged cells. The release of ultrafine particles into the air of an enclosed environment from a thermodegradation event or from other sources is a potential hazard for astronauts. Knowing the mechanisms of action is a prerequisite for technical or medical countermeasures.
There is a need to simulate the near-Earth-orbit environmental conditions, and it is useful to be able to monitor the changes in physical properties of spacecraft materials. Two different methods for simulating the vacuum-ultraviolet (VUV) and soft X-ray near-Earth-orbit flux are presented. Also, methods for monitoring the changes in optical ultraviolet transmission and mass loss are presented. The results of exposures to VUV photons and charged particles on these materials are discussed.
Ultraviolet degradation of polymer films
Degradable, nanocrystalline semiconducting polymers lacking long-range order are able to degrade orders of magnitude faster than their semicrystalline counterparts.
Polymeric encapsulants are essential materials in photovoltaic modules, protecting sensitive electronics from the environment while providing mechanical integrity to the multilayered assembly. However, these polymeric materials are susceptible to degradation processes driven by the ingress of environmental species, ultraviolet radiation, thermal stresses, and mechanical loading. In this study, we employ a combined atomistic simulation and accelerated aging experimental approach to study the molecular-scale mechanisms of encapsulant degradation. Classical molecular dynamics simulations quantify the diffusion of environmental and degradation species through the polymer matrix, producing composition-specific diffusion coefficients. Reactive simulations characterize activation energy barriers and reaction rate constants for key chemical pathways. In parallel, thermal-desorption analyses coupled with mass spectrometry monitor the emergence and concentration profiles of degradation products under controlled stressor conditions. By integrating simulation and experiment, we establish quantitative correlations between polymer composition, species diffusivity, and chemical reactivity. We anticipate that these relations and quantitative values could serve as high-fidelity inputs to reaction-diffusion models, enabling physics-informed lifetime predictions and guiding the design of more durable encapsulant materials for solar energy applications.
Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.
Electron-spin-resonance (ESR) spectroscopy and Arrhenius plots used to determine maximum safe temperature for accelerated testing of photothermal degradation of polymers. Aging accelerated by increasing illumination, temperature, or both. Results of aging tests at temperatures higher than those encountered in normal use valid as long as mechanism of degradation same throughout range of temperatures. Transition between different mechanisms at some temperature identified via transition between activation energies, manifesting itself as change in slope of Arrhenius plot at that temperature.
The effects of cavitating flow on the polymeric additives used in functional fluids are described. A comparison of thermal and mechanical stability tests for these polymer solutions show distinct differences in the machanism of the polymer degradation. The thermal degradation tests appear to cause an unzippering or depolymerization type of reaction in which there is no particular selectivity based on molecular weight. The mechanical degradation of these fluids appears to be based on molecular weight. Measurements of molecular weight distributions during mechanical degradation show that for a given level of intensity only molecules above a certain minimum size are degraded. The effects of ultrasonic radiation on polymer degradation are reported. Tests were conducted to demonstrate the mechanism of mechanical polymer degradiation in an orifice. A more severe test than the orifice test in which two tapered roller bearings loaded against each other produce the mechanical breakdown is discussed.
Polymer nanocomposites with high concentrations of nanoparticles (NPs) possess exceptional mechanical, transport, and thermal properties. To enable their widespread use in structural applications and functional coatings, it is crucial to understand how nanoconfinement and the polymer-NP interface influence polymer degradation under various environmental conditions, including prolonged UV exposure. In this study, we investigate the photooxidative degradation of polystyrene (PS)-confined in the interstices of SiO 2 NP films. These nanocomposite films are prepared by the capillary rise infiltration (CaRI) of PS into interstices of SiO 2 NP packings, and subsequently subjected to UV irradiation. Our investigation reveals that PS degradation progresses uniformly across the thickness, with degradation initiating from the center of the NP interstitial pores and extending towards the NP surface. We rationalize this degradation mechanism based on the disparity in the surface energies of PS and the NP surface, as well as slow oxygen diffusion through confined PS. Here, we also demonstrate that packing smaller NPs at a given thickness or thicker packing of a specific NP size facilitates photooxidative degradation, highlighting the critical role of the number of interstitial pores in influencing degradation processes.
Group of phthalocyanine polymers resist thermal degradation. Polymers expected semiconducting. Principal applications probably in molded or laminated parts that have to withstand high temperatures. Polymers made from either of two classes of monomer: Bisphthalonitriles with imide linkages or Bisphthalonitriles with ester-imide linkages.