Catalytic Installation of Primary Amines Onto Polyolefins for Oligomer Valorization.

Polymerization of primary amine-containing monomers is challenging because the amine inhibits polymerization catalyst activity. An alternative approach to access primary amine functionalized polymers is postpolymerization modification. To this end, the hydroaminoalkylation of vinyl-terminated polyolefins with N-(trimethylsilyl)benzylamine is used to prepare primary amine-terminated polyolefins, with the free primary amine substituent being revealed upon hydrolytic work up. These materials are spectroscopically characterized, and an investigation of thermal properties by differential scanning calorimetry and thermogravimetric analysis is completed. These results show that the primary amine substituent increases the glass transition temperature and improves thermal stability. The reactive primary amine functionality is used in the photo-oxidative dimerization of polyolefins to demonstrate how this elusive functionality can be applied in oligomer valorization.

Ultra-Narrow Alkane Product Distribution in Polyethylene Waste Hydrocracking by Zeolite Micropore Diffusion Optimization.

Plastic pollution poses a pressing environmental challenge in modern society. Chemical catalytic conversion offers a promising solution for upgrading waste plastics into valuable liquid alkanes and other high value products. However, the current methods yield mixed products with a broad carbon distribution. To address this challenge, we introduce a tandem catalytic system that features matched acidic sites and confined metals for the conversion of low-density polyethylene (LDPE) into liquid alkanes. This system achieves a liquid alkane yield of 94.0%, with 84.8% of C5-C7 light alkanes. Combined with in situ FTIR and molecular dynamics simulation, the shape-selective mechanisms is elucidated, which ensures that only olefins of the appropriate size can diffuse to the encapsulated Pt sites within the zeolite for hydrogenation, resulting in an ultra-narrow product distribution. Furthermore, due to the rapid diffusion of olefins within the hierarchical zeolite, the catalyst exhibits higher catalytic efficiency and resistance to coking tendency. Our findings contribute to the design of efficient catalysts for plastic waste valorization.

Nickel-catalyzed in situ synthesis of UHMWPE/TiO2 composites with enhanced mechanical properties and adjustable photocatalytic degradabilities.

Expanding the application field of polyolefin materials through functionalization has been a research hotspot in the past three decades. Here, a TiO2-supported anilinenaphthoquinone nickel catalyst was assembled and applied for in situ ethylene polymerization with high activity (>2000 kg mol-1h-1) to produce ultra-high molecular weight polyethylene (UHMWPE)/TiO2 composites with unique physicochemical performance. The UHMWPE/TiO2 composite films and fibers prepared by in-situ ethylene polymerization are superior to the samples from the blend system in issues such as TiO2 dispersibility, mechanical property, and photocatalytic degradability. The mechanical properties (strength up to 26.8 cN/dtex, modulus up to 1248.8 cN/dtex) of the obtained UHMWPE/TiO2 composite fibers are significantly improved with a very low dosage of TiO2 (as low as 1.4 wt‰). Moreover, UHMWPE/TiO2 composites obtained by coating Al2O3 and SiO2 on the surface of TiO2 not only retain the strong absorption of ultraviolet rays, but also effectively weaken the photocatalytic degradation effect.

Aldehyde End-Capped Degradable Polyethylenes from Hydrogen-Controlled Ethylene/CO Copolymerization.

To access degradable polyolefin plastic, non-alternating copolymerization of ethylene (E) and carbon monoxide (CO) for producing polyethylene (PE) with in-chain ketones is particularly appealing; however, it still presents significant challenges such as molecular weight modulation (hydrogen response) and chain endgroup control (functional terminal). In this study, we achieved hydrogen-controlled E/CO non-alternating copolymerization using late transition metal catalysts. This process results in linear PEs containing the desired non-alternating in-chain keto groups (1.0-9.3 mol%) and with tunable molecular weights ranging from 43 to 195 kDa. In this reaction, H2 serves as a chain transfer agent, modulating the polymer's molecular weight, forming unique aldehyde endgroups and eliminating usual olefinic endgroups; CO undergoes non-alternating insertion into the PE chain, resulting in a strictly non-alternating structure (> 99%) for the keto-PE. The dispersed incorporation of in-chain keto groups retains bulk properties of PE and makes PE susceptible to photodegradation, which produces significantly lower molecular weight polymers and oligomers with unambiguous vinyl and acetyl terminals.

Biodegradation of four polyolefin plastics in superworms (Larvae of Zophobas atratus) and effects on the gut microbiome.

Recent studies have demonstrated superworms (larvae of Zophobas atratus) ability to degrade polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polypropylene (PP) within their digestive system. This study aimed to compare the ability of superworms to degrade the above four polyolefin plastics over a duration of 30 days. In this study, the degradation rate of PE was the highest, and the final average weight of superworms, as well as the final plastic mass loss consumed by them, significantly increased (73.38 % and 52.33 %, respectively) when PE was fed with wheat bran (1:1 [w/w]). FTIR and TGA indicated the occurrence of oxidation and biodegradation processes in the four polyolefin plastics when exposed to superworms. In addition, the molecular weights (Mw and Mn) of excreted polymer residues decreased by 3.1 % and 2.87 % in PE-fed superworms, suggesting that the depolymerization of PE was not entirely dependent on the gut microbial community. The analysis of the gut microbial communities revealed that the dominant microbial community were different for each type of plastic. The results indicate that the gut microbiome of superworms exhibited remarkable adaptability in degrading various types of plastics, and the intake preferences and efficiency of different plastics are associated with different dominant microbial community species.

Natural iron-containing minerals catalyze the degradation of polypropylene microplastics: a route to self-remediation learnt from the environment.

Virgin and environmentally aged polypropylene (PP) micropowders (V-PP and E-PP, respectively) were used as reference microplastics (MPs) in comparative photo- and thermo-oxidative ageing experiments performed on their mixtures with a natural ferrous sand (NS) and with a metal-free silica sand (QS). The ferrous NS was found to catalyze the photo-oxidative degradation of V-PP after both UV and simulated solar light irradiation. The catalytic activity in the V-PP/NS mixture was highlighted by the comparatively higher fraction of photo-oxidized PP extracted in dichloromethane, and the higher carbonyl index of the bulk polymer extracted with boiling xylene, when compared with the V-PP/QS mixture. Similarly, NS showed a catalytic effect on the thermal degradation (at T = 60 °C) of E-PP. The results obtained indicate that, under suitable environmental conditions (in this case, an iron-containing sediment or soil matrix, combined with simulated solar irradiation), the degradation of some types of MPs could be much faster than anticipated. Given the widespread presence of iron minerals (including the magnetite and iron-rich serpentine found in NS) in both coastal and mainland soils and sediments, a higher than expected resilience of the environment to the contamination by this class of pollutants is anticipated, and possible routes to remediation of polluted natural environments by eco-compatible iron-based minerals are envisaged.

Demystifying group-4 polyolefin hydrogenolysis catalysis. Gaseous propane hydrogenolysis mechanism over the same catalysts.

A kinetic/mechanistic investigation of gaseous propane hydrogenolysis over the single-site heterogeneous polyolefin depolymerization catalysts AlS/ZrNp2 and AlS/HfNp2 (AlS = sulfated alumina, Np = neopentyl), is use to probe intrinsic catalyst properties without the complexities introduced by time- and viscosity-dependent polymer medium effects. In a polymer-free automated plug-flow catalytic reactor, propane hydrogenolysis turnover frequencies approach 3,000 h-1 at 150 °C. Both catalysts exhibit approximately linear relationships between rate and [H2] at substoichiometric [H2] with rate law orders of 0.66 ± 0.09 and 0.48 ± 0.07 for Hf and Zr, respectively; at higher [H2], the rates approach zero-order in [H2]. Reaction orders in [C3H8] and [catalyst] are essentially zero-order under all conditions, with the former implying rapid, irreversible alkane binding/activation. This rate law, activation parameter, and DFT energy span analysis support a scenario in which [H2] is pivotal in one of two plausible and competing rate-determining transition states-bimolecular metal-alkyl bond hydrogenolysis vs. unimolecular ß-alkyl elimination. The Zr and Hf catalyst activation parameters, ΔH‡ = 16.8 ± 0.2 kcal mol-1 and 18.2 ± 0.6 kcal mol-1, respectively, track the relative turnover frequencies, while ΔS‡ = -19.1 ± 0.8 and -16.7 ± 1.4 cal mol-1 K-1, respectively, imply highly organized transition states. These catalysts maintain activity up to 200 °C, while time-on-stream data indicate multiday activities with an extrapolated turnover number ~92,000 at 150 °C for the Zr catalyst. This methodology is attractive for depolymerization catalyst discovery and process optimization.

Fully Recycled Polyolefin Elastomer-Based Vitrimers with Ultra-High, Universal, Stable, and Switchable Adhesion.

Achieving both robust adhesion to arbitrary surfaces and thermal-switchable/recyclable properties has proven challenging, particularly for commodity polyolefins. Herein, a simple and effective route is reported to transform polyolefins elastomer (POE) into a fully recycled epoxy-functionalized POE vitrimers (E-POE vit) with ultra-high, universal, stable, and switchable adhesion via facile free radical grafting and dynamic cross-linking. The resultant E-POE vit exhibits increase in adhesion strength on glass exceeding three to ten times compared to those commonly used polymers, due to the synergy of dense hydrogen (H)-bonds and strong interfacial affinity. In addition, E-POE vit also displays strong adhesion on diverse surfaces ranging from inorganic to organic while maintaining good stability in various harsh environments. More importantly, temperature-sensitive H-bonds allow E-POE vit to switch between attachment-detachment at alternating temperatures, resulting in reversible adhesion without adhesion loss, even after 10 cycles. Moreover, E-POE vit is able to be fully recycled and reused more than ten times via thermo-activated transesterification reactions with negligible change in structure and performance. This work may unlock strategies to fabricate high-performance commercial polymer-based adhesives with adhesion and recyclable features for intelligent and sustainable applications.

Upgrading Polyolefin Plastic Waste into Multifunctional Porous Graphene using Silicone-Assisted Direct Laser Writing.

The widespread use of plastics, especially polyolefin including polyethylene and polypropylene, has led to severe environmental crises. Chemical recycling, a promising solution for extracting value from plastic waste, however, is underutilized due to its complexity. Here, a simple approach, silicone-assisted direct laser writing (SA-DLW) is developed, to upgrade polyolefin plastic waste into multifunctional porous graphene, called laser-induced graphene (LIG). This method involves infiltrating polyolefins with silicone, which retards ablation during the DLW process and supplies additional carbon atoms, as confirmed by experimental and molecular dynamic results. A remarkable conversion yield of 38.3% is achieved. The upgraded LIG exhibited a porous structure and high conductivity, which is utilized for the fabrication of diverse energy and electronic devices with commendable performance. Furthermore, the SA-DLW technique is versatile for upgrading plastic waste in various types and forms. Upgrading plastic waste in the form of fabric has significantly simplified pre-treatment. Finally, a wearable flex sensor is fabricated on the non-woven fabric of a discarded medical mask, which is applied for gesture monitoring. This work offers a simple but effective solution to upgrade plastic waste into valuable products, contributing to the mitigation of environmental challenges posed by plastic pollution.

Recent Progresses in Pyrolysis of Plastic Packaging Wastes and Biomass Materials for Conversion of High-Value Carbons: A Review.

The recycling of plastic packaging wastes helps to alleviate the problems of white pollution and resource shortage. It is very necessary to develop high-value conversion technologies for plastic packaging wastes. To our knowledge, carbon materials with excellent properties have been widely used in energy storage, adsorption, water treatment, aerospace and functional packaging, and so on. Waste plastic packaging and biomass materials are excellent precursor materials of carbon materials due to their rich sources and high carbon content. Thus, the conversion from waste plastic packaging and biomass materials to carbon materials attracts much attention. However, closely related reviews are lacking up to now. In this work, the pyrolysis routes of the pyrolysis of plastic packaging wastes and biomass materials for conversion to high-value carbons and the influence factors were analyzed. Additionally, the applications of these obtained carbons were summarized. Furthermore, the limitations of the current pyrolysis technology are put forward and the research prospects are forecasted. Therefore, this review can provide a useful reference and guide for the research on the pyrolysis of plastic packaging wastes and biomass materials and the conversion to high-value carbon.

Shock absorption and dispersion capability of a novel five-layer mouthguard sheet material.

There is a growing need for a mouthguard sheet material with higher shock absorption and dispersion capacity than those obtained by conventional materials. A five-layer mouthguard sheet material was previously developed using laminated ethylene vinyl acetate and polyolefin copolymer resin. In this study, the shock absorption capacity and dispersion capability of the new sheet material were investigated and compared with those of other materials. Impact testing for the new sheet material showed that the force required to displace the sheet by 1 mm was significantly higher at all thicknesses (p<0.001), whereas the puncture energy and displacement were significantly lower than those for ethylene vinyl acetate (p<0.05). The five-layer mouthguard sheet material successfully absorbed and resisted shock. Therefore, the sheet material potentially increases resistance to applied deformation in teeth and alveolar bone and maintains structure. The five-layer sheet material could expand the range of mouthguard products and help prevent oral trauma.

Aqueous Coordination-Insertion Copolymerization for Producing High Molecular Weight Polar Polyolefins.

Hydrocarbons, when used as the medium for transition metal catalyzed organic reactions and olefin (co-)polymerization, are ubiquitous. Environmentally friendly water is highly attractive and long-sought, but is greatly challenging as coordination-insertion copolymerization reaction medium of olefin and polar monomers. Unfavorable interactions from both water and polar monomer usually lead to either catalyst deactivation or the formation of low-molecular-weight polymers. Herein, we develop well-behaved neutral phosphinophenolato nickel catalysts, which enable aqueous copolymerization of ethylene and diverse polar monomers to produce significantly high-molecular-weight linear polar polyolefins (219-549 kDa, 0.13-1.29 mol %) in a single-component fashion under mild conditions for the first time. These copolymerization reactions occur better in water than in hydrocarbons such as toluene. The dual characteristics of high molecular weight and the incorporation of a small amount of functional group result in improved surface properties while retain the desirable intrinsic properties of high-density polyethylene (HDPE).

Polyolefin-Based Smart Self-Healing Composite Coatings Modified with Calcium Carbonate and Sodium Alginate.

Corrosion-related damage incurs significant capital costs in many industries. In this study, an anti-corrosive pigment was synthesized by modifying calcium carbonate with sodium alginate (SA), and smart self-healing coatings were synthesized by reinforcing the anti-corrosive pigments into a polyolefin matrix. Structural changes during the synthesis of the anti-corrosive pigment were examined using scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. Moreover, thermal gravimetric analysis confirmed the loading of the corrosion inhibitor, and electrochemical impedance spectroscopic analysis revealed a stable impedance value, confirming the improved corrosion resistance of the modified polyolefin coatings. The incorporation of the anticorrosive pigment into a polyolefin matrix resulted in improved pore resistance properties and capacitive behavior, indicating a good barrier property of the modified coatings. The formation of a protective film on the steel substrate reflected the adsorption of the corrosion inhibitor (SA) on the steel substrate, which further contributed to enhancing the corrosion resistance of the modified coatings. Moreover, the formation of the protective film was also analyzed by profilometry and elemental mapping analysis.

Modulating Thermal Conductivity and Flame Retardancy of Polyolefin Composites via Distributed Structures of Magnesium Hydroxide and Hexagonal Boron Nitride.

Thermally conductive and flame-retardant polyolefin composites are facing great challenges in meeting the increasing demands for fire safety and thermal management. Aiming at simultaneously enhancing thermal conductivity and flame retardancy, hexagonal boron nitride (hBN) and magnesium hydroxide (MH) were adopted in ethylene-vinyl acetate copolymer/polyolefin elastomer (EVA/POE) blends to design composites with selective filler distributions and co-continuous networks via different processing schemes. The thermal conductivity and flame retardancy show strong dependence on the distributed structure of hBN and MH. The composites with hBN-rich centers and MH-rich edges in the filled POE phase show a thermal conductivity of 0.70 W/(m·K) and an LOI of 27.7%, which are very close to the thermal conductivity of EVA/POE/hBN and the LOI of EVA/POE/MH at the same total filler content. The composites with MH-rich centers and hBN-rich edges show pHRR, THR and TSP values of 169 kW/m2, 49.8 MJ/m2 and 1.8 m2, which are decreased by 40%, 33% and 62% in comparison with EVA/POE/MH, respectively. Modulating the filler structure distribution provides a strategy to co-enhance thermal conductivity and flame retardancy.

Synthesis and Assessment of Novel Sustainable Antioxidants with Different Polymer Systems.

Antioxidants are essential to the polymer industry. The addition of antioxidants delays oxidation and material degradation during their processing and usage. Sustainable phenolic acids such as 4-hydroxybenzoic acid or 3,4-dihydroxybenzoic acid were selected. They were chemically modified by esterification to obtain various durable molecules, which were tested and then compared to resveratrol, a biobased antioxidant, and Irganox 1076, a well-known and very efficient fossil-based antioxidant. Different sensitive matrices were used, such as a thermoplastic polyolefin (a blend of PP and PE) and a purposely synthesized thermoplastic polyurethane. Several formulations were then produced, with the different antioxidants in varying amounts. The potential of these different systems was analyzed using various techniques and processes. In addition to antioxidant efficiency, other parameters were also evaluated, such as the evolution of the sample color. Finally, an accelerated aging protocol was set up to evaluate variations in polymer properties and estimate the evolution of the potential of different antioxidants tested over time and with aging. In conclusion, these environmentally friendly antioxidants make it possible to obtain high-performance materials with an efficiency comparable to that of the conventional ones, with variations according to the type of matrix considered.

Recent Advancements in Mechanistic Studies of Palladium- and Nickel-Catalyzed Ethylene Copolymerization with Polar Monomers.

The introduction of polar functional groups into polyolefin chain structures creates opportunities to enhance specific properties, such as adhesion, dyeability, printability, compatibility, thermal stability, and electrical conductivity, which widen the range of potential applications for these modified materials. Transition metal catalysts, especially late transition metals, have proven to be highly effective in copolymerization processes due to their reduced Lewis acidity and electrophilicity. However, when compared to the significant progress and summary of synthetic methods, there is a distinct lack of a comprehensive summary of mechanistic studies pertaining to the catalytic systems involved in ethylene copolymerization catalyzed by palladium and nickel catalysts. In this review, we have provided a comprehensive summary of the latest developments in mechanistic studies of ethylene copolymerization with polar monomers catalyzed by late-transition-metal complexes. Experimental and computational methods were employed to conduct a detailed investigation of these organic and organometallic systems. It is mainly focused on ligand substitution, changes in binding modes, ethylene/polar monomer insertion, chelate opening, and ß-H elimination. Factors that control the catalytic activity, molecular weight, comonomer incorporation ratios, and branch content are analyzed, these include steric repulsions between ligands and monomers, electronic effects arising from both ligands and monomers, and so on.

Comparative Life Cycle Assessment (LCA) of Porous Asphalt Mixtures with Sustainable and Recycled Materials: A Cradle-to-Gate Approach.

The road and construction sectors consume a large number of natural resources and energy, contributing significantly to waste generation and greenhouse gas emissions (GHG). The use of recycled aggregate from construction and demolition waste as a substitute for virgin aggregate is a current practice in the construction of new road sections. Additionally, in recent years, there has been an increasing focus on finding alternatives to bitumen for binders used in asphalt mixes. This study investigates and compares the impacts associated with two porous asphalt mixtures produced with CDW aggregates, virgin aggregates, and a polyolefin-based synthetic transparent binder through an LCA methodology. A cradle-to-gate approach was employed. Model characterization for calculating the potential environmental impacts of each porous asphalt mixture was performed using the ReCipe 2016 assessment method at the midpoint and endpoint levels. The results are presented with reference to a baseline scenario corresponding to a porous asphalt mixture, confirming the benefits associated with the use of recycled aggregates and in some cases the benefits of not using bitumen-based binders. This work contributes to the understanding of the importance of choosing the least environmentally damaging solution during the production or rehabilitation of road pavement infrastructure.

Entropy Confinement Promotes Hydrogenolysis Activity for Polyethylene Upcycling.

Chemical upcycling that catalyzes waste plastics back to high-purity chemicals holds great promise in end-of-life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state. This approach involves the synthesis of p-Ru/SBA catalysts, in which Ru nanoparticles are uniformly distributed within the channels of an SBA-15 support, using a precise impregnation method. The unique design of the p-Ru/SBA catalyst has demonstrated significant improvements in catalytic performance for the conversion of polyethylene into high-value liquid fuels, particularly diesel. The catalyst achieved a high solid conversion rate of 1106 g ⋅ gRu -1 ⋅ h-1 at 230 °C. Comparatively, this catalytic activity is 4.9 times higher than that of a control catalyst, Ru/SiO2 , and 14.0 times higher than that of a commercial catalyst, Ru/C, at 240 °C. This remarkable catalytic activity opens up immense opportunities for the chemical upcycling of waste plastics.

Influence of the Print Envelope Temperature on the Morphology and Tensile Properties of Thermoplastic Polyolefins Fabricated by Material Extrusion and Material Jetting Additive Manufacturing.

Additive manufacturing (AM) nowadays has become a supportive method of traditional manufacturing. In particular, the medical and healthcare industry can profit from these developments in terms of personalized design and batches ranging from one to five specimens overall. In terms of polymers, polyolefins are always an interesting topic due to their low prices, inert chemistry, and crystalline structure resulting in preferable mechanical properties. Their semi-crystalline nature has some advantages but are challenging for AM due to their shrinkage and warping, resulting in geometrical inaccuracies or even layer detaching during the process. To tackle these issues, process parameter optimization is vital, with one important parameter to be studied more in detail, the print envelope temperature. It is well known that higher print envelope temperatures lead to better layer adhesion overall, but this investigation focuses on the mechanical properties and resulting morphology of a semi-crystalline thermoplastic polyolefin. Further, two different AM technologies, namely material jetting (ARBURG plastic freeforming-APF) and filament-based material extrusion, were studied and compared in detail. It was shown that higher print envelope temperatures lead to more isotropic behavior based on an evenly distributed morphology but results in geometrical inaccuracies since the material is kept in a molten state during printing. This phenomenon especially could be seen in the stress and strain values at break at high elongations. Furthermore, a different crystal structure can be achieved by setting a specific temperature and printing time, also resulting in peak values of certain mechanical properties. In comparison, better results could be archived by the APF technology in terms of mechanical properties and homogeneous morphology. Nevertheless, real isotropic part behavior could not be managed which was shown by the specimen printed vertically. Hence, a sweet spot between geometrical and mechanical properties still has to be found.

Numerical Simulation of PFRC Fracture Subjected to High Temperature by Means of a Trilinear Softening Diagram.

Fibre-reinforced concrete (FRC) has been used for decades in certain applications in the construction industry, such as tunnel linings and precast elements, but has experienced important progress in recent times, boosted by the inclusion of guidelines for its use in some national and international standards. Traditional steel fibres have been studied in depth and their performance is well-known, although in recent years new materials have been proposed as possible alternatives. Polyolefin macro-fibres, for instance, have been proven to enhance the mechanical properties of concrete and the parameters that define their behaviour (fibre length, fibre proportion or casting method, for instance) have been identified. These fibres overcome certain traditional problems related to steel fibres, such as corrosion or their interaction with magnetic fields, which can limit the use of steel in some applications. The behaviour of polyolefin fibre-reinforced concrete (PFRC) has been numerically reproduced with success through an embedded cohesive crack formulation that uses a trilinear softening diagram to describe the fracture behaviour of the material. Furthermore, concrete behaves well under high temperatures or fire events, especially when it is compared with other construction materials, but the behaviour of PFRC must be analysed if the use of these fibres is to be extended. To this end, the degradation of PFRC fracture properties has been recently experimentally analysed under a temperature range between 20 °C and 200 °C. As temperature increases, polyolefin fibres modify their mechanical properties and their shape, which reduce their performance as reinforcements of concrete. In this work, those experimental results, which include results of low (3 kg/m3) and high (10 kg/m3) proportion PFRC specimens, are used as reference to study the fracture behaviour of PFRC exposed to high temperatures from a numerical point of view. The experimental load-deflection diagrams are reproduced by modifying the trilinear diagram used in the cohesive model, which helps to understand how the trilinear diagram parameters are affected by high temperature exposure. Finally, some expressions are proposed to adapt the initial trilinear diagram (obtained with specimens not exposed to high temperature) in order to numerically reproduce the fracture behaviour of PFRC affected by high temperature exposure.