Chain Scission Mechanism Research Articles

Ex-situ catalytic fast pyrolysis of waste polycarbonate for aromatic hydrocarbons: Utilizing HZSM-5/modified HZSM-5

Catalytic pyrolysis has been proven as a highly efficient process for transforming waste polycarbonate (PC) into valuable aromatic hydrocarbons, especially benzene, toluene, ethylbenzene, and xylene (BTEX). In the present work, the ex-situ catalytic fast pyrolysis of PC on metal- or alkali-modified HZSM-5 was investigated using the double micro-fixed bed system. Experimental results indicate that the rapid pyrolysis of PC may follow a homolytic chain scission mechanism, resulting in pyrolysis products dominated by phenols. Metal- or alkali-modified HZSM-5 significantly enhances the cleavage of C-OH bonds in phenols, improving the yield of aromatics. The yield of aromatics in the liquid product is 91 %, 72 %, and 77 % when loaded with nickel (Ni), iron (Fe), and cobalt (Co), respectively, all of which are higher than unmodified HZSM-5 with the yield of 43 %. Among them, the Ni/HZSM-5 has significantly enhanced the yield of BTEX reaching 81.64 %. When using alkali-modified HZSM-5 with a larger pore volume and higher specific surface area, the yield of aromatics can be increased to 60 %. Furthermore, the dual modification of alkali treatment and Ni loading on HZSM-5 simultaneously enhanced catalytic activity and resistance to coke formation. The yield of BTEX reaches 94.47 %. The BTEX formation mechanism can be explained by direct deoxygenation (DDO) of the pyrolytic volatiles of PC and the “phenol pool” mechanisms of primary products on the catalyst surface. This study enriches the understanding of catalytic pyrolysis of PC and provides a theoretical foundation for the harmless treatment of PC.

Pyrolysis of natural rubber–cellulose composites: isoconversional kinetic analysis based on thermogravimetric data

Despite the current growing interest in rubber composites with natural organic fillers, there is a lack of kinetic analyses that describe the decomposition of these materials during pyrolysis. For this reason, the main objective of this study was the kinetic analysis and determination of formal kinetic parameters for the pyrolytic decomposition of NR–CEL composites with different cellulose content (0, 30, 45, and 55 phr). Thermogravimetric measurements were made at heating rates of 2, 4, 6, 8, 10, and 20 °C min–1 in the temperature range of 20–600 °C. First, Friedman and KAS model-free methods were applied. Therefore, model-based methods and the model-fitting procedure were used to find the optimal multi-step kinetic model. The proposed final model consists of two parallel processes, which are kinetically independent: A → B → C and D → E → F. For each step, a kinetic triplet was calculated: the apparent activation energy, the pre-exponential factor, and the kinetic parameters of the extended empirical Prout–Tompkins model. The master plots method was used to determine the kinetic decomposition mechanism of the individual steps. It was found that step A → B has the shape of an nth-order model, step B → C mainly follows the diffusion model, the mechanism of step D → E transfers from a random scission kinetics model to an nth-order model with an increasing amount of CEL, and step E → F obeys the chain scission mechanism.

Low‐Volatile Binder Enables Thermal Shock‐Resistant Thin‐Film Cathodes for Thermal Batteries

Manufacturing thin‐film components is crucial for achieving high‐efficiency and high‐power thermal batteries (TBs). However, developing binders with low‐gas production at the operating temperature range of TBs (400–550 °C) has proven to be a significant challenge. Here, we report the use of acrylic acid derivative terpolymer (LA136D) as a low‐volatile binder for thin‐film cathode fabrication and studied the chain scission and chemical bond‐breaking mechanisms in pyrolysis. It is shown LA136D defers to random‐chain scission and cross‐linking chain scission mechanisms, which gifts it with a low proportion of volatile products (ψ, ψ = 39.2 wt%) at even up to 550 °C, well below those of the conventional PVDF (77.6 wt%) and SBR (99.2 wt%) binders. Surprisingly, LA136D contributes to constructing a thermal shock‐resistant cathode due to the step‐by‐step bond‐breaking process. This is beneficial for the overall performance of TBs. In discharging test, the thin‐film cathodes exhibited a remarkable 440% reduction in polarization and 300% enhancement in the utilization efficiency of cathode materials, while with just a slight increase of 0.05 MPa in gas pressure compared with traditional “thick‐film” cathode. Our work highlights the potential of LA136D as a low‐volatile binder for thin‐film cathodes and shows the feasibility of manufacturing high‐efficiency and high‐power TBs through polymer molecule engineering.

Effect of ionizing radiation on the physicochemical and functional properties of silicone rubber and silicone foley catheter

The utilization of ionizing radiation, such as gamma ray and electron beam, in medical product sterilization has seen significant growth in recent years, driven by concerns regarding the safety of ethylene oxide sterilization. This paper examines the effects of these radiation modalities on silicone rubber, and its applicability on a silicone rubber-containing medical device, specifically a silicone foley catheter, by assessing its functional properties before and after irradiation at varying absorbed doses.Analysis of the irradiated samples revealed the presence of carbonyl groups, indicating radiation-induced oxidation. Gamma irradiation did not exhibit fundamental changes in the polymer structure but showed degradation at higher temperatures due to oxidation mechanisms. Moreover, a significant decrease in elongation at break was observed indicating that the already highly crosslinked silicone rubber experienced additional crosslinking affecting its mechanical properties. In contrast, both irradiations led to degradation, as evidenced by a decrease in TG residue. However, the mechanical properties, including tensile strength and elongation at break, were less affected. This suggests limited crosslinking and fragmentation of the polymer backbone. At a lower dose, a decrease in both strength and elongation indicated the formation of branched structures, limiting mobility, introducing irregularities, and weakening the polymer's overall strength. Despite these effects, the functional properties of the silicone foley catheter were practically unaffected at low absorbed doses, except for the discoloration of the syringe ports. Overall, the study provides insights into the effects of ionizing radiation on silicone rubber, highlighting the complex interplay between crosslinking, chain scission, and oxidation mechanisms. The findings contribute to understanding the changes in the polymer's structure and properties under different radiation modalities and doses, facilitating the development of effective sterilization techniques for medical devices containing silicone rubber.

The Influence of Ionizing Radiation on Paclitaxel-Loaded Nanoparticles Based on PLGA

The effect of ionizing radiation (γ-rays and electron beam) on anticancer drug delivery systems (DDSs) properties was evaluated concerning potential sterilization. For this purpose, paclitaxel (PTX)-loaded nanoparticles were obtained using a biodegradable, self-developed copolymer of l-lactide and glycolide (PLGA), synthesized in the presence of bismuth 2-ethylhexanoate catalyst. The nanoparticles were obtained with a high encapsulation efficiency of PTX (EE = 94.2%). The average size of the nanoparticles was 253.5 nm. The influence of irradiation (sterilization dose, 25 kGy) on the microstructure and the physicochemical and thermal properties of the polymer matrix was investigated, as well as the effect of irradiation on the morphology and physicochemical properties of the pharmaceutical formulations of the nanoparticles. Additionally, an in vitro drug release study was conducted regarding any alterations in the kinetic profiles of drug release. It was confirmed that the irradiation with both types of ionizing radiation, i.e., γ-rays and electron-beam (EB), slightly decreased the average molecular weight of the polymer matrix. While only negligible changes in the microstructure and thermal properties of PLGA were observed after irradiation with EB, the average length of lactidyl blocks (lLL) in the copolymer chains irradiated with γ-rays decreased from 4.33 to 3.35. Moreover, the contribution of crystalline phase (Xc) in γ-irradiated samples decreased significantly from 35.1% to 22.7%, suggesting a dominant mechanism of chain scission over cross-linking in PLGA samples irradiated with γ-rays. In vitro drug release results demonstrate a sustained and controlled release of PTX from the nanoparticles based on PLGA. The kinetics of drug release was defined as first order with non-Fickian diffusion. Only negligible differences in the kinetic profiles of PTX release from PLGA drug carriers were observed after irradiation. The overall results suggest good resistance of PLGA nanoparticles to irradiation within the conditions used and the great potential of EB in the sterilization process of the polymeric DDSs.

Valorizing disposable face masks into non-condensable hydrocarbon gases via optimal reactor configurations in thermal pyrolysis

Pyrolysis studies often overlook the potential of pyrolytic gas as a valuable hydrocarbon resource, thereby hindering the production of advanced carbonaceous nanomaterials (CNM). This study aims to explore various configurations of a multi-zone tubular reactor to upcycle disposable face masks into non-condensable hydrocarbons as potential CNM precursors. The highest gas yield (56.2 wt%) was achieved using a 3-zone configuration (Z-1,3,4), attributed to the end chain scission mechanism. The increased abundance of light hydrocarbons (≤C10) in the resulting liquid confirms a greater extent of end chain scission in the optimum reactor configuration with cold zone retainment. Employing this configuration, different face mask types, including 3ply (polypropylene-based), KF94 (polypropylene-based) and N95 (polyester-based), were utilized as individual feedstocks or in various ratios as mixtures to investigate the resultant composition of hydrocarbon gases. This composition was compared with existing literature studies to identify suitable hydrocarbon gas compositions for CNM production. Mixing 3ply and KF94 face masks produced a consistent gas composition predominantly comprising propylene (62.3 – 66.9%) and ethane (15.4 – 16.8%) via thermal pyrolysis at 500 ℃ with a constant heating rate of 20 ℃/min. However, the inclusion of N95 face masks increased CO2 level fivefold, diminishing the gas quality as a CNM precursor. These findings underscore the necessity of segregating polyester face mask material from polypropylene face mask material prior to pyrolysis to ensure a consistent quality and yield of CNM precursors.

Analysis of photocatalytic degradation of polyamide microplastics in metal salt solution by high resolution mass spectrometry

Microplastic pollution has become one of the most concerned focuses in the world. Among many treatment methods, photocatalysis is considered to be one of the most environmentally friendly methods. In this work, the photodegradation behavior of polyamide microplastics is studied by using polyamide 6 PA6) as model microplastics and FeCl3 as catalyst. It is hoped that the PA6 fiber can be effectively degraded by utilizing the strong oxidizing active species that can be produced after FeCl3 is irradiated in water. The results shows that PA6 fiber can be almost completely degraded after 10 days of irradiation in FeCl3 aqueous solution, indicating that it is promising to use this new method to solve the problem of PA6 type microplastics. In addition, the chain scission mechanism and degradation process of PA6 are analyzed in detail by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS), which provides a new insight for the study of polymer degradation mechanism.

A reaction-diffusion framework for hydrolytic degradation of amorphous polymers based on a discrete chain scission model

Hydrolytic degradation of polymers involves the scission of long chain molecules, leading to molecular weight reduction and mass loss. The precise degradation response however depends on the scission probability of individual bonds along the polymer backbone. In particular, bonds near the chain ends are considered to be more susceptible to hydrolysis than inner bonds. In this paper, we incorporate a discrete chain scission model that can handle arbitrary bond scission probabilities within a continuum reaction-diffusion framework. Overall hydrolysis kinetics (including autocatalysis) is described independently of the chain scission model. By decoupling the description of the chain scission mechanism from kinetics, our framework enables the identification of the chain scission mechanism from molecular weight reduction and mass loss curves commonly reported in experimental degradation studies. We further propose a reduced continuum model which is better suited for large-scale simulations while retaining the predictive capability of the full discrete-continuum model. The model capability is illustrated in representative case studies based on experimental data from the literature for different materials and geometries. Statement of significanceMany models have been proposed to predict the evolution of molecular weight and mass loss in biodegradable polymers undergoing hydrolytic degradation. However, existing models remain limited in their ability to describe the degradation mechanism, autocatalytic kinetics and short chains diffusion simultaneously. Moreover, existing models often rely on empirical relations and a large number of fitting parameters. Here, we propose a conceptually simple discrete-continuum mathematical framework with a small number of parameters which all have a clear physical meaning. Model calibration against experimental data is simplified, and further provides insights into the degradation mechanisms at play, namely random scission, chain-end scission, or a combination of both. The framework can serve as a basis for future generalisations, including a description of evolving crystallinity, or other degradation mechanisms, such as thermal oxidation or photo-degradation.

A bond-based peridynamics modeling of polymeric material fracture under finite deformation

We have developed a bond-based peridynamics model to study the fracture of polymer networks under finite deformation. Our approach is based on the Kuhn–Grün model of randomly jointed polymers with extensible chains, which allows the rupture of polymers through the chain scission mechanism. We introduced a novel mesoscale potential function that intrinsically incorporates an Arruda–Boyce type model into a nonlocal continuum framework with the purpose of modeling the mechanical response of general polymeric materials and the fracture of polymers. We have demonstrated through a series of numerical examples, both two-dimensional and three-dimensional, that the proposed model is robust and efficient in modeling crack growth in polymeric materials. The model is carefully validated with experimental data and numerical results obtained on the basis of existing continuum mechanics polymer models. We have shown that the proposed peridynamic model is accurate and stable in various configurations and loading modes, such as mode I and shear crack opening. In comparison to existing continuum polymer models and fracture modeling methods, our present technique has the advantages of being theoretically simple, rigorous, and computationally fast. The numerical results show that the nonlocal polymer model can easily capture the fracture process in polymeric materials without complex ad hoc modeling parameters under finite deformation, and it has the potential to become a convenient simulation tool for modeling the polymer failure process in the design and optimization of polymeric materials.

Sewage sludge induces changes in the surface chemistry and crystallinity of polylactic acid and polyethylene films

Plastic pollution is a major threat facing our environment. To understand the full effects, we must first characterize how plastics break down in environmental systems. Heretofore, there has been little work examining how exposure to sewage sludge facilitates the degradation of plastics, particularly of plastics that have been previously weathered. Herein, we characterize how the crystallinity, surface chemistry, and morphology of polylactic acid (PLA) and polyethylene (PE) films change due to sludge exposure. In this work, sludge-induced changes in carbonyl index were found to depend on the level of prior exposure to ultraviolet (UV) irradiation. The carbonyl indices of un-irradiated films increased while those of UV-aged films decreased after 35 days of sludge exposure. In addition, the carbon‑oxygen and hydroxyl bond indices of PE films increased with sludge exposure, suggesting the surface oxidation of PE. As for PLA, crystallinity was found to increase with sludge exposure, consistent with a chain scission mechanism. This work will help to predict the behavior of plastic films after transfer from wastewater to sewage sludge.

A Simple, Selective, and General Catalyst for Ring Closing Depolymerization of Polyesters and Polycarbonates for Chemical Recycling

AbstractThe ability to efficiently and selectively process mixed polymer waste is important to address the growing plastic waste problem. Herein, we report that the combination of ZnCl2 and an additive amount of poly(ethylene glycol) under vacuum can readily and selectively depolymerize polyesters and polycarbonates with high ceiling temperatures (Tc>200 °C) back to their constitute monomers. Mechanistic experiments implicate a random chain scission mechanism and a catalyst structure containing one equivalent of ZnCl2 per ethylene glycol repeat unit in the poly(ethylene glycol). In addition to being general for a wide variety of polyesters and polycarbonates, the catalyst system could selectively depolymerize a polyester in the presence of other commodity plastics, demonstrating how reactive distillation using the ZnCl2/PEG600 catalyst system can be used to separate mixed plastic waste.

A Simple, Selective, and General Catalyst for Ring Closing Depolymerization of Polyesters and Polycarbonates for Chemical Recycling.

The ability to efficiently and selectively process mixed polymer waste is important to address the growing plastic waste problem. Herein, we report that the combination of ZnCl2 and an additive amount of poly(ethylene glycol) under vacuum can readily and selectively depolymerize polyesters and polycarbonates with high ceiling temperatures (Tc >200 °C) back to their constitute monomers. Mechanistic experiments implicate a random chain scission mechanism and a catalyst structure containing one equivalent of ZnCl2 per ethylene glycol repeat unit in the poly(ethylene glycol). In addition to being general for a wide variety of polyesters and polycarbonates, the catalyst system could selectively depolymerize a polyester in the presence of other commodity plastics, demonstrating how reactive distillation using the ZnCl2 /PEG600 catalyst system can be used to separate mixed plastic waste.

Long-term degradation of high molar mass poly(ethylene oxide) in a turbulent pilot-scale pipe flow

The long-term drag reduction capability of poly(ethylene oxide) with a nominal molar weight of Mw=4×106 g/mol dissolved in water was investigated in a pilot-scale pipe flow device (inner diameter of test section 26 mm) at a Reynolds number of 105. A total loss of the initially high (75%) drag reduction capability was observed over a flow distance of several ∼10 km while the molar weight of the polymer was still Mw∼5×105 g/mol. Mechanical degradation in the turbulent flow as well as ageing of the polymer dissolved in water caused this loss in drag reduction capability. A simple ansatz of two independent, statistical polymer chain scission mechanisms was used to describe the polymer degradation empirically using a modified Brostow model. This empirical description was applied successfully and suggested that the polymer exhibited at least 15 cleavage points for mechanical degradation.

Degradation mechanism of FKM during thermo-oxidative aging from mechanical and network structure correlations

The thermal weak point of a peroxide-cured fluoroelastomer (FKM) in presence of triallylisocyanurate (TAIC) has been identified. To that purpose, the thermal stability was assessed by TGA measurements. In parallel, thermo-oxidative degradation was characterized after the aging of several samples at 250 °C for various durations. Specific attention has been directed to the structural evolution, evaluated by both FTIR and equilibrium swelling experiments. Experimental results highlight that TAIC, the system's crosslink node, is the thermal weak point of a peroxide-cured fluoroelastomer (FKM). Nonetheless, crosslinks are not entirely broken since the crosslinking density decreases with aging time before stabilizing for one week at 250 °C. This allows the material to retain some of its mechanical properties such as good elongation at break. For longest exposure times at 250 °C (beyond one week), chain scission mechanism becomes predominant leading to a loss of the mechanical properties. Regarding the degradation mechanism, TGA-FTIR results are rather in favor of a dehydrofluorination mechanism as hydrogen fluoride (HF) is detected upon the first times of thermo-oxidative aging. In a second step, chain scission starts to occur. Recombination reactions between double bonds provided by dehydrofluorination and macroradicals formed during chain scission could explain that FKM is still crosslinked after one week at 250 °C under air.

Investigation of Abortiporus biennis lignocellulolytic toolbox, and the role of laccases in polystyrene degradation

White-rot basidiomycetes are the only microorganisms able to produce both hydrolytic (cellulases and hemicellulases) and oxidative (ligninolytic) enzymes for degrading all lignocellulose constituents. Their enzymatic machinery makes them ideal for the discovery of novel enzymes with desirable properties. In the present work, Abortiporus biennis, a white-rot fungus, was studied in regard to its lignocellulolytic potential. Secretomics and biochemical analyses were employed to study the strain's enzymatic arsenal, after growth in corn stover cultures and xylose-based defined media. The results revealed the presence of all the necessary enzymatic activities for complete breakdown of biomass, while the prominent role of oxidative enzymes in the lignocellulolytic strategy of the strain became evident. Two novel laccases, AbiLac1 and AbiLac2, were isolated from the culture supernatant with ion-exchange chromatography. Characterization of purified laccases revealed their ability to oxidize a wide variety of phenolic and non-phenolic substrates. AbiLac1 was found to oxidize polystyrene powder, showing high depolymerization potential, based on radical chain scission mechanism as evidenced by molecular weight decrease. The results of the present study demonstrate the biotechnological potential of the unexplored enzymatic machinery of white-rot basidiomycetes, including the design of improved lignocellulolytic cocktails, as well as the degradation and/or valorization of plastic waste materials.

Thermal Degradation of Fluorosilicone Elastomers

AbstractThis paper explores the structure‐relationships involved in the degradation of fluorosilicones (FVMQs). For that purpose, FVMQs are thermally aged at 280 °C under various atmospheres (nitrogen, atmospheric air, pure oxygen). It seems that FVMQs undergo a strong mass loss irrespectively of the atmosphere. Under nitrogen, a chain scission (unzipping) mechanism is suspected whereas under air, a crosslinking mechanisms leads to an increase in tensile modulus. A degradation mechanism is proposed as a basis for lifetime prediction.

Empirical investigations on the effects of ionizing radiation on epoxy structural adhesives and resins: An overview

Depending on the type of application, ageing effects can highly influence the properties of adhesives. Radiation environment as it can be found in space missions, nuclear reactors – both fusion and fission and particle detectors represents hazardous conditions for adhesives due to the polymer chains of which it is composed. Ionizing radiation interacts through the mechanism of chain scission and crosslinking with these chains resulting in a change of physical properties. In the present study, a comprehensive literature review is conducted regarding the influence of ionizing radiation on the mechanical properties of epoxy adhesives. Radiation damage tests are expensive and complex in terms of operational safety. Therefore, it is desirable to screen the results of previously conducted experiments. 126 data sets collected from about 46 articles are analysed, homogenised, and visualised to provide an overview of the current state of this field of research. The data is categorised according to the performed test and the type of applied load. Mechanical properties are plotted over irradiation dose. Since conducting irradiation tests are often costly and includes hazards, the collection of data sets presented in this study brings huge benefit to the adhesive community. In the future, high demand for such data is becoming apparent due to the recent boom in the space industry and the major efforts made in the field of nuclear fusion development. The provided data can be used by designers, engineers, and scientists for sizing adhesives joints under radiation environment by taking this particular ageing effect into account.

The first quantitative investigation of compounds generated from PFAS, PFAS-containing aqueous film-forming foams and commercial fluorosurfactants in pyrolytic processes

Pyrolysis as a thermochemical technology is commonly used in waste management and remediation of organic-contaminated soil. This study, for the first time, investigated fluorinated and non-fluorinated compounds emitted from per- and polyfluoroalkyl substances (PFAS) and relevant products upon pyrolysis (200–890 °C) and their formation mechanisms. Approximately 30 non-fluorinated compounds were detected from PFAS-containing aqueous film-forming foams (AFFFs) and commercial surfactant concentrates (SCs) after heating, including glycols and glycol ethers that were predominant at 200 °C. Oxygen (e.g., 1,4-dioxane) and nitrogen heterocycles and benzene were unexpectedly observed at higher temperatures (300–890 °C), which were likely formed as a consequence of the thermal dehydration, dehydrogenation, and intermolecular cyclization of glycols and glycol ethers. Fluorinated volatiles in six major classes were detected at low and moderate temperatures (200–500 °C), including perfluoroalkenes, perfluoroalkyl aldehydes, fluorotelomer alcohols, and polyfluorinated alkanes/alkenes. Several features of the pyrolyses of PFAS suggest that the underlying decomposition mechanism is radical-mediated. Perfluoroheptene thermally decomposed at 200 °C to shorter-chain homologues following a radical chain-scission mechanism. Most of these volatiles observed at low/moderate temperatures were not detected at 890 °C. Ultra-short-chain fluorinated greenhouse gases (e.g., perfluoromethane) were not found.

The Mechanochemistry of Carboranes

AbstractWe developedo‐carborane as a new mechanophore by showing that theo‐carborane cluster is the preferred scission site in chain‐centered polymers through ultrasonication mechanochemistry. Mechanistic studies are consistent with a predominately homolytic mechanism of chain scission. The mechanically generated monocarbaborane fragments are highly reactive toward alcohol nucleophiles. By contrast, carborane with a different regiochemistry (m‐carborane) maintained its high mechanical stability. DFT simulations provide insights into the origins of carborane's mechanical lability. This fundamental research provides a new stimulus for carborane cage activation.

The Mechanochemistry of Carboranes.

We developed o-carborane as a new mechanophore by showing that the o-carborane cluster is the preferred scission site in chain-centered polymers through ultrasonication mechanochemistry. Mechanistic studies are consistent with a predominately homolytic mechanism of chain scission. The mechanically generated monocarbaborane fragments are highly reactive toward alcohol nucleophiles. By contrast, carborane with a different regiochemistry (m-carborane) maintained its high mechanical stability. DFT simulations provide insights into the origins of carborane's mechanical lability. This fundamental research provides a new stimulus for carborane cage activation.