Polymer Degradation through Chemical Change: A Quantum-based Test of Inferred Reactions in Irradiated Polydimethylsiloxane

Chemical reaction schemes are key conceptual tools for interpreting the results of experiments and simulations, but often carry implicit assumptions that remain largely unverified for complicated systems. Established schemes for chemical damage through crosslinking in irradiated silicone polymers comprised of polydimethylsiloxane (PDMS) date to the 1950's and correlate small-molecule off-gassing with specific crosslink features. In this regard, we use a somewhat reductionist model to develop a general conditional probability and correlation analysis approach that tests these types of causal connections between proposed experimental observables to reexamine this chemistry through quantum-based molecular dynamics (QMD) simulations. Analysis of the QMD simulations suggests that the established reaction schemes are qualitatively reasonable, but lack strong causal connections under a broad set of conditions that would enable making direct quantitative connections between off-gassing and crosslinking. Further assessment of the QMD data uncovers a strong (but nonideal) quantitative connection between exceptionally hard-to-measure chain scission events and the formation of silanol (Si-OH) groups. Our analysis indicates that conventional notions of radiation damage to PDMS should be further qualified and not necessarily used ad hoc. In addition, our efforts enable independent quantum-based tests that can inform confidence in assumed connections between experimental observables without the burden of fully elucidating entire reaction networks.

Fully Biobased Reactive Extrusion of Biocomposites Based on PLA Blends and Hazelnut Shell Powders (HSP)

The production of biocomposites based on natural fiber waste and biopolymers is constantly increasing because of their renewability, biodegradability, and the accordance with the circular economy principles. The aim of this work is to contrast the disadvantages in the production of biocomposites, such as reduction of molecular weight through the use of biobased chain extenders. For this purpose, epoxidized soybean oil (ESO) and dicarboxylic acids (DCAs) were used to contrast the slight chain scission observed in a poly(lactic acid) (PLA)/poly(butylene succinate-co-adipate) (PBSA) binary blend caused by the melt mixing with hazelnut shell powder (HSP). Two different dimensions of HSPs were considered in this study as well as different concentrations of the ESO/DCA system, comparing succinic acid and malic acid as dicarboxylic acids. Melt viscosity parameters, such as torque and melt volume rate (MVR), were measured to investigate the chain extender effect during the extrusion. In addition, the reactivity of the ESO/DCA system was investigated through infrared spectroscopy. The effect of chain extenders on thermal properties, in particular on the crystallinity of PLA, and on mechanical properties of final biocomposites was investigated to understand their potentialities in industrial application. Results of this study evidenced a modest increase in melt viscosity due to ESO/malic acid chain extension system, but only for the HSP with the lower dimension (so the higher surface area) and adding 0.5 wt.% of ESO/malic acid. Thus, the slight chain scission of polyesters, not significantly affecting the final properties of these biocomposites, is the most relevant effect that was revealed in this complex reactive system.

Insights on the Molecular Behavior of Polypropylene in the Process of Ultrasonic Injection Molding

Product miniaturization is a constant trend in industries that demand ever-smaller products that can be mass produced while maintaining high precision dimensions in the final pieces. Ultrasonic micro injection molding (UMIM) technology has emerged as a polymer processing technique capable of achieving the mass production of polymeric parts with micro-features, while still assuring replicability, repeatability, and high precision, contrary to the capabilities of conventional processing technologies of polymers. In this study, it is shown that the variation of parameters during the UMIM process, such as the amplitude of the ultrasound waves and the processing time, lead to significant modification on the molecular structure of the polymer. The variation of both the amplitude and processing time contribute to chain scission; however, the processing time is a more relevant factor for this effect as it is capable of achieving a greater chain scission in different areas of the same specimen. Further, the presence of polymorphism within the samples produced by UMIM is demonstrated. Similarly to conventional processes, the UMIM technique leads to some degree of chain orientation, despite the fact that it is carried out in a relatively small time and space. The results presented here aim to contribute to the optimization of the use of the UMIM process for the manufacture of polymeric micro parts.

Preparation and characterization of liquid natural rubber through oxidative degradation with phenyl hydrazine and benzoyl peroxide-oxygen

The aim of this research was to synthesize liquid natural rubber (LNR) from Natural rubber (SIR-20) by chain scission method in the presence of oxygen gas and difference of peroxides, phenyl hydrazine and benzoyl peroxide. The chain scission reaction was conducted in solution of xylene in close system. SIR-20 was diluted xylene before flushing with oxygen and the addition of the peroxide. The degradation oxidation by the oxygen and the peroxides was processed at 60°C for 24 hours. The degradative oxidation product was re-precipitated by adding the excess of methanol and filtrated before dried in vacuum oven 60°C for 24 hours. The dried product was characterized by Fourier Transform Infra Red (FTIR). It was found that the liquid natural rubber product successfully degraded by chain scission process as shown the change of the peak area intensity of infrared absorption. It was showed the peaks area intensity of O-H and carbonyl group of liquid natural rubber spectra increased.

Ultra-selective molecular-sieving gas separation membranes enabled by multi-covalent-crosslinking of microporous polymer blends

High-performance membranes exceeding the conventional permeability-selectivity upper bound are attractive for advanced gas separations. In the context microporous polymers have gained increasing attention owing to their exceptional permeability, which, however, demonstrate a moderate selectivity unfavorable for separating similarly sized gas mixtures. Here we report an approach to designing polymeric molecular sieve membranes via multi-covalent-crosslinking of blended bromomethyl polymer of intrinsic microporosity and Tröger’s base, enabling simultaneously high permeability and selectivity. Ultra-selective gas separation is achieved via adjusting reaction temperature, reaction time and the oxygen concentration with occurrences of polymer chain scission, rearrangement and thermal oxidative crosslinking reaction. Upon a thermal treatment at 300 °C for 5 h, membranes exhibit an O2/N2, CO2/CH4 and H2/CH4 selectivity as high as 11.1, 154.5 and 813.6, respectively, transcending the state-of-art upper bounds. The design strategy represents a generalizable approach to creating molecular-sieving polymer membranes with enormous potentials for high-performance separation processes.

Volume Dependence of Hydrogen Sorption and Desorption Diffusion in Cylindrical Polymers

We have investigated the volume effects on hydrogen diffusion properties in both sorption and desorption processes by employing a volumetric analysis technique. The total uptake (𝐶∞), total desorbed content (𝐶0), sorption diffusion coefficient (Ds), desorption diffusion coefficient (Dd), sorption and desorption equilibrium time of hydrogen in two rubbery polymers are determined relative to the diameter and thickness of the cylindrical sample in the two processes. 𝐶∞ and 𝐶0 do not demonstrate the appreciable volume dependence for all rubbers. The identical values in 𝐶∞ and 𝐶0 indicate the reversibility between sorption and desorption, which is interpreted by the occurrence of physisorption rather than chemisorption by introducing hydrogen molecules. The larger Dd values in the desorption process than Ds may be attributed to increased amorphous phase and volume swelling caused by increased hydrogen voids and polymer chain scission after decompression. The time to reach equilibrium in both sorption and desorption processes was found to be linearly proportional to the square of thickness above an aspect ratio of 3.7, which is consistent with the numerical simulations based on the solution of Fick’s law. This finding could be used to predict the equilibrium adsorption time depending on the sample size in the polymer.

Natural Aging of Ethylene-Propylene-Diene Rubber under Actual Operation Conditions of Electrical Submersible Pump Cables

Ethylene-propylene-diene monomer (EPDM) rubbers used in electric submersible pump (ESP) cables were analyzed after being aged in actual operation conditions in oil wellbores. These rubbers constitute the insulation and jacket layers of the ESP cables. EPDM rubbers from four different cables operating during different time intervals (2 and 4.8 years) at different depths (from 760 to 2170 m) below sea level were studied. To verify the effects of the long exposure on the rubber performance, thermal analysis was performed to determine the thermal stability and activation energy of degradation. In addition, structural analysis, through vibrational spectroscopy and crosslinking fraction assessment, was carried out. The mechanical properties of the aged rubbers were inferred through the measurement of hardness, while the absorption of a service fluid was studied by gravimetry. The results showed only minor changes in the thermal, structural, mechanical and barrier properties of the EPDM-based ESP cable layers. It is suggested that the thermo-oxidation mechanism followed by chain scission does not have a role in the degradation of EPDM within the aged ESP cables, and no sign of variation of crosslink fractions has been encountered. Therefore, it was concluded that EPDM-based layers seem not to be weak links in the configuration of modern ESP systems.