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862 result(s) for "Chain scission"
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Thermal decomposition characteristics of polyvinyl chloride sheathing in MYJV-type mining cables
This study investigated the thermal decomposition characteristics of polyvinyl chloride (PVC) sheathing in MYJV-type mining cables. Firstly, thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) analysis was employed. The experimental results revealed that the thermal decomposition of PVC sheathing occurs in four stages, primarily yielding products, such as hydrogen chloride, carbon monoxide, carbon dioxide, and chlorinated hydrocarbons. Notably, carbon dioxide and carbon monoxide, emitted during PVC sheathing decomposition, exhibited prominent absorbance. Secondly, a comparative analysis of the thermal decomposition characteristics of chlorinated PVC (CPVC) sheathing in MYP-type mining cables was conducted. It was found that the residue rate of PVC sheathing was lower than that of CPVC sheathing, mainly because all chlorine in PVC was converted to hydrogen chloride during the first stage of decomposition, and CPVC sheathing demonstrated lower thermal stability and reaction rate compared to PVC sheathing. Finally, the study explored the kinetic parameters using the Kissinger and Ozawa methods. The results indicated that the primary chain scission reaction, occurring in the second stage of PVC decomposition, released a substantial amount of combustible and toxic gases, posing threats to fire spread and personal safety. This research provides a theoretical basis for assessing the fire hazard of mine cables by analyzing and comparing the thermal decomposition characteristics and thermokinetic parameters of PVC sheathing with CPVC sheathing.
Evaluation of cellulose paper degradation irradiated by an electron beam for conservation treatment
In this study, we investigate the chemical, physical and optical properties of cellulose paper irradiated by an electron beam for disinfection. Cellulose chain scission and oxidation induced by radiation increased considerably at 25 kGy irradiation, whereas folding endurance, morphology, and crystallinity did not undergo significant changes. The cellulose chain scission rate of paper irradiated under air-dried and wet conditions showed no difference; however, cellulose oxidation increased to a higher degree in paper irradiated under wet conditions than under air-dried conditions. Electron beam irradiation did not significantly affect changes in paper color, which is associated with oxidation. However, when irradiated papers were aged, the color difference increased according to the irradiation dose, as the oxidized functional groups of cellulose can act as a trigger for color change. A linear relationship between the cellulose chain scission rate and irradiation dose was found; thus, the cellulose chain scission rate can be predicted for a specific dose. The degree of polymerization was calculated from the predicted cellulose chain scission rate using the Ekenstam equation. According to the prediction, the degree of polymerization decreased to 74% at a dose of 5 kGy, a suitable dose for paper disinfection. In the low-dose range, electron beam irradiation did not adversely affect the physical properties of paper, but significant changes occurred in both the chemical and optical properties of paper. Thus, electron beam irradiation may be of use in disinfecting severely degraded paper due to biological factors; however, the irradiation process diminishes paper permanence.Graphic abstract
Advanced Oxidation Techniques and Hybrid Approaches for Microplastic Degradation: A Comprehensive Review
Microplastics (MPs) have emerged as persistent environmental pollutants with adverse effects on ecosystems and human health. Conventional removal methods, such as filtration and sedimentation, primarily rely on physical separation without addressing the degradation of MPs, leading to their accumulation and the risk of secondary pollution. This review explores the potential of advanced oxidation processes (AOPs), including photocatalysis, electrochemical oxidation, Fenton processes, sulfate radical-based oxidation, sonochemical treatment, ozonation, and plasma technologies, which generate reactive oxygen and nitrogen species capable of promoting polymer chain scission, microbial biodegradation, and the oxidative fragmentation and mineralization of MPs into non-toxic byproducts. Hybrid AOP systems combined with biological treatments or membrane-based filtration are also examined for their effectiveness in degrading MPs, as well as for scalability and the environmental impacts of their byproducts when integrated into existing wastewater treatment systems. The review further discusses challenges related to operational parameters, energy consumption, and the formation of secondary pollutants. By identifying current knowledge gaps and future research directions, this review provides insights into optimizing AOPs and integrations of AOPs with biological treatments or membrane-based processes for sustainable MP remediation and water treatment applications.
Classification of gamma-irradiated aluminum-epoxy nanocomposites utilizing laser-induced breakdown spectroscopy and machine learning techniques
This study investigates the degradation characteristics of gamma-irradiated aluminum-filled epoxy nanocomposites through the integration of Laser-Induced Breakdown Spectroscopy (LIBS) and supervised machine learning techniques. To simulate prolonged aging in high-voltage insulation settings, epoxy-based composites containing 0 wt% and 5 wt% aluminum nanofillers were subjected to gamma radiation. The LIBS spectra exhibited distinct alterations in the elements of gamma-aged samples, including shifts in the emission lines of carbon and oxygen. This indicates that radiation induced chain scission and oxidation. Principal Component Analysis was employed to reduce spectral dimensionality and reveal underlying trends across four unique material states: unaged and aged, both with and without nanofillers. Principal Component Analysis (PCA) successfully reduced the spectral dimensionality, with the first three principal components (capturing 85.43% of variance) clearly separating the four material states of unaged/aged, with/without nanofillers. Seven machine learning classifiers were evaluated on the PCA-transformed data using a rigorous 5-fold cross-validation protocol. Linear Discriminant Analysis (LDA) and Support Vector Machine (SVM) achieved perfect classification accuracy, while K-Nearest Neighbors (KNN) also performed exceptionally (98.3% ± 3.7%). The results underscore the profound effectiveness of combining LIBS with ML for the non-destructive evaluation of insulation degradation and provide quantitative evidence for the stabilizing role of core–shell structured Al nanofillers. This methodological pipeline demonstrates significant potential for real-time, ML-enhanced condition monitoring of polymeric insulating materials in radiation-prone environments.
A New Kinetic Modeling Approach for Predicting the Lifetime of ATH-Filled Silane Cross-Linked Polyethylene in a Nuclear Environment
This study focuses on the degradation of a silane cross-linked polyethylene (Si-XLPE) matrix filled with three different contents of aluminum tri-hydrate (ATH): 0, 25, and 50 phr. These three materials were subjected to radiochemical ageing at three different dose rates (8.5, 77.8, and 400 Gy·h−1) in air at low temperatures close to ambient (47, 47, and 21 °C, respectively). Changes due to radio-thermal ageing were investigated according to both a multi-scale and a multi-technique approach. In particular, the changes in the chemical composition, the macromolecular network structure, and the crystallinity of the Si-XLPE matrix were monitored by FTIR spectroscopy, swelling measurements in xylene, differential scanning calorimetry, and density measurements. A more pronounced degradation of the Si-XLPE matrix located in the immediate vicinity of the ATH fillers was clearly highlighted by the swelling measurements. A very fast radiolytic decomposition of the covalent bonds initially formed at the ATH/Si-XLPE interface was proposed to explain the higher concentration of chain scissions. If, as expected, the changes in the elastic properties of the three materials under study are mainly driven by the crystallinity of the Si-XLPE matrix, in contrast, the changes in their fracture properties are also significantly impacted by the degradation of the interfacial region. As an example, the lifetime was found to be approximately halved for the two composite materials compared to the unfilled Si-XLPE matrix under the harshest ageing conditions (i.e., under 400 Gy·h−1 at 21 °C). The radio-thermal oxidation kinetic model previously developed for the unfilled Si-XLPE matrix was extended to the two composite materials by taking into account both the diluting effect of the ATH fillers (i.e., the ATH content) and the interfacial degradation.
Precursors of Majorana modes and their length-dependent energy oscillations probed at both ends of atomic Shiba chains
Isolated Majorana modes (MMs) are highly non-local quantum states with non-Abelian exchange statistics, which localize at the two ends of finite-size 1D topological superconductors of sufficient length. Experimental evidence for MMs is so far based on the detection of several key signatures: for example, a conductance peak pinned to the Fermi energy or an oscillatory peak splitting in short 1D systems when the MMs overlap. However, most of these key signatures were probed only on one of the ends of the 1D system, and firm evidence for an MM requires the simultaneous detection of all the key signatures on both ends. Here we construct short atomic spin chains on a superconductor—also known as Shiba chains—up to a chain length of 45 atoms using tip-assisted atom manipulation in scanning tunnelling microscopy experiments. We observe zero-energy conductance peaks localized at both ends of the chain that simultaneously split off from the Fermi energy in an oscillatory fashion after altering the chain length. By fitting the parameters of a low-energy model to the data, we find that the peaks are consistent with precursors of MMs that evolve into isolated MMs protected by an estimated topological gap of 50 μeV in chains of at least 35 nm length, corresponding to 70 atoms. Majorana modes are highly non-local quantum states with non-Abelian exchange statistics, which localize at the two ends of finite-size 1D topological superconductors of sufficient length. By precisely positioning magnetic atoms on a superconducting surface, their interaction is tailored such that the precursors of Majorana modes are simultaneously observed on both ends of linear atomic chains.
Kinetics and Thermodynamics of Ultrasound-Assisted Depolymerization of κ-Carrageenan
The ultrasound-assisted depolymerization of κ-carrageenan has been studied at various temperatures and times. The κ-carrageenan with initial molecular weight of 545 kDa was dispersed in water to form a 5 g/L solution, which was then depolymerized in an ultrasound device at various temperatures and times. The viscosity of the solution was measured using Brookfield viscometer, which was then used to find the number-average molecular weight by Mark-Houwink equation. To obtain the kinetics of κ-carrageenan depolymerization, the number-average molecular weight data was treated using midpoint-chain scission kinetics model. The pre-exponential factor and activation energies for the reaction are 2.683×10-7 mol g-1 min-1 and 6.43 kJ mol-1, respectively. The limiting molecular weight varies from 160 kDa to 240 kDa, and it is linearly correlated to temperature. The results are compared to the result of thermal depolymerization by calculating the half life. It is revealed that ultrasound assisted depolymerization of κ-carrageenan is faster than thermal depolymerization at temperatures below 72.2°C. Compared to thermal depolymerization, the ultrasound-assisted process has lower values of Ea, ΔG‡, ΔH‡, and ΔS‡, which can be attributed to the ultrasonically induced breakage of non-covalent bonds in κ-carrageenan molecules. 
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 O 2 /N 2 , CO 2 /CH 4 and H 2 /CH 4 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. Microporous polymers become increasingly attractive as materials for the fabrication of permeable and selective gas separation membranes but separation performance is often limited by broad pore size distribution. Here, the authors design a porous polymer membrane via multi-crosslinking of miscible blends of microporous polymers enabling simultaneous high permeability and selectivity.
A broadly applicable cross-linker for aliphatic polymers containing C–H bonds
Addition of molecular cross-links to polymers increases mechanical strength and improves corrosion resistance. However, it remains challenging to install cross-links in low-functionality macromolecules in a well-controlled manner. Typically, high-energy processes are required to generate highly reactive radicals in situ, allowing only limited control over the degree and type of cross-link. We rationally designed a bis-diazirine molecule whose decomposition into carbenes under mild and controllable conditions enables the cross-linking of essentially any organic polymer through double C–H activation. The utility of this molecule as a cross-linker was demonstrated for several diverse polymer substrates (including polypropylene, a low-functionality polymer of long-standing challenge to the field) and in applications including adhesion of low–surface-energy materials and the strengthening of polyethylene fabric.
Defining quality by quantifying degradation in the mechanical recycling of polyethylene
Polyolefins have a multitude of uses across packaging, automotive and construction sectors. Their resistance to degradation during reprocessing enables recyclability, but variability in recycled polymer feedstocks renders it difficult to assure their manufacturing suitability. The lack of quality control methods has disabled circular economy pathways; product failure is costly, wasteful and time-intensive. Using rheology-simulated and extrusion-based recycling experiments, we explore the degradation pathways of high-density polyethylene (HDPE). Chain scission dominates during the initial degradation of HDPE, and increasing exposure to O 2 shifts the dominant mechanism to long-chain branching. Importantly, extending this method to post-consumer recyclate (PCR), the results show potential as a methodology to assess recyclate quality to enable a circular plastics economy. In this study, we establish the validity of this rheology simulation to define a characteristic degradation parameter, relating it to the structural evolution under different environments defined for virgin HDPE and post-consumer recyclate (PCR). Polyolefins are used across packaging, automotive and construction but variability in recycled polymer feedstocks renders it difficult to assure a consistent manufacturing quality. Here, the authors use rheology-simulated and extrusion-based recycling experiments to explore the degradation pathways of high-density polyethylene and present a rheology-based method to assess the quality of the recycled material.