Pub Date : 2025-01-25DOI: 10.1016/j.polymdegradstab.2025.111217
Alejandro Fonseca , Carlos Marquez , Nikolaos Giakoumakis , Ivica Duretek , Eleni Pachatouridou , Stylianos Stefanidis , Maarten Rubens , Angelos Lappas , Thomas Lucyshyn , Dirk De Vos
The search for non-halogenated, environmentally friendly flame retardants for plastics remains a major priority for industry. Current solutions rely mainly on the use of inorganic salts in high loading, which also alters the material properties. In this regard, phosphoramidate compounds have shown promising results at already low loadings in different polymeric materials; however, they still remain a relatively unexplored option. Here, we study the potential use of several phosphorus-based flame retardants (P-FR) for low density polyethylene (LDPE). Characterization of the prepared LDPE P-FR formulations showed minor differences between their physicochemical properties and those of the virgin LDPE polymer, while exhibiting a notable flame retardancy effect. Remarkably, the synthesized P-FR outperformed the commercially used inorganic salts when used at the same loadings. Finally, two potential methods for the valorization of waste LDPE were investigated to evaluate the effect of the P-FR on the chemical recyclability of the polymer.
{"title":"Phosphoramidates as promising low-loading flame retardants for low density polyethylene","authors":"Alejandro Fonseca , Carlos Marquez , Nikolaos Giakoumakis , Ivica Duretek , Eleni Pachatouridou , Stylianos Stefanidis , Maarten Rubens , Angelos Lappas , Thomas Lucyshyn , Dirk De Vos","doi":"10.1016/j.polymdegradstab.2025.111217","DOIUrl":"10.1016/j.polymdegradstab.2025.111217","url":null,"abstract":"<div><div>The search for non-halogenated, environmentally friendly flame retardants for plastics remains a major priority for industry. Current solutions rely mainly on the use of inorganic salts in high loading, which also alters the material properties. In this regard, phosphoramidate compounds have shown promising results at already low loadings in different polymeric materials; however, they still remain a relatively unexplored option. Here, we study the potential use of several phosphorus-based flame retardants (P-FR) for low density polyethylene (LDPE). Characterization of the prepared LDPE P-FR formulations showed minor differences between their physicochemical properties and those of the virgin LDPE polymer, while exhibiting a notable flame retardancy effect. Remarkably, the synthesized P-FR outperformed the commercially used inorganic salts when used at the same loadings. Finally, two potential methods for the valorization of waste LDPE were investigated to evaluate the effect of the P-FR on the chemical recyclability of the polymer.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111217"},"PeriodicalIF":6.3,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143095127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-24DOI: 10.1016/j.polymdegradstab.2025.111214
Shiya Wang , Miaojun Xu , Wei Huang , Yingke Zhu , Juan Li , Peng Chen
Polyamide 56 (PA56) is a polyamide based on bio-based chemical and has attracted widespread attentions. In this paper, a series of phosphomolybdates (POMs) with Keggin structure were incorporated into PA56 to modify its flame-retardant properties. Different POMs show different effects on the flame-retardant efficiency in PA56. A small amount of 3 wt% sodium phosphomolybdate (PMoNa) or nickel phosphomolybdate (PMoNi) enable PA56 to achieve the UL-94 V-0 rating, while the samples containing other POMs are not classified in the test. The POMs promote the degradation of PA56 at low temperature and char formation at high temperature, and improves the thermal stability in air. Especially, the PMoNa and PMoNi restrain the release of heat, flammable volatiles and toxic gas by forming more char and changing the pyrolysis pathway during combustion, thus modify the flame retardancy of PA56 effectively. The mechanical properties are deteriorated more or less which need to be modified further.
{"title":"Roles of degradation and charring in the flame retardancy of polyamide 56 induced by phosphomolybdates with different cations","authors":"Shiya Wang , Miaojun Xu , Wei Huang , Yingke Zhu , Juan Li , Peng Chen","doi":"10.1016/j.polymdegradstab.2025.111214","DOIUrl":"10.1016/j.polymdegradstab.2025.111214","url":null,"abstract":"<div><div>Polyamide 56 (PA56) is a polyamide based on bio-based chemical and has attracted widespread attentions. In this paper, a series of phosphomolybdates (POMs) with Keggin structure were incorporated into PA56 to modify its flame-retardant properties. Different POMs show different effects on the flame-retardant efficiency in PA56. A small amount of 3 wt% sodium phosphomolybdate (PMoNa) or nickel phosphomolybdate (PMoNi) enable PA56 to achieve the UL-94 V-0 rating, while the samples containing other POMs are not classified in the test. The POMs promote the degradation of PA56 at low temperature and char formation at high temperature, and improves the thermal stability in air. Especially, the PMoNa and PMoNi restrain the release of heat, flammable volatiles and toxic gas by forming more char and changing the pyrolysis pathway during combustion, thus modify the flame retardancy of PA56 effectively. The mechanical properties are deteriorated more or less which need to be modified further.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111214"},"PeriodicalIF":6.3,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-23DOI: 10.1016/j.polymdegradstab.2025.111213
Chao Yan , Yiqun Fang , Ruofan Yang , Mengfan Yan , Weihong Wang , Yongming Song , Qingwen Wang
The development of efficient, eco-friendly and cost-effective transparent fire-retardant coatings is crucial for maximizing the value of wood resources. In this study, an all-biobased flame retardant (PA-CS) was synthesized from corn starch (CS) and phytic acid (PA). A modified melamine resin (MFGT) with intrinsic flame-retardant properties was prepared by incorporating melamine, formaldehyde, allyl glycidyl ether, and tannic acid. The resulting MFGT@xPA-CS system demonstrated excellent thermal stability and low curing activation energy. Additionally, the system was used on the surface of wood and demonstrated good transparency, outstanding flame retardancy, smoke suppression, and char-forming ability. Cone calorimeter tests revealed that the peak heat release rate (PHRR) of [email protected] decreased by 31.12%, and total smoke production was reduced by 48.03%. Additionally, the residual char increased from 34.93% (c-MFGT) to 43.25% ([email protected]), and the ID/IG ratio of the residual char decreased by 40.58% from 3.08 (c-MFGT) to 1.83 ([email protected]). Gas-phase and condensed-phase pyrolysis products revealed synergistic effects between the phosphorus in PA-CS and the nitrogen in MFGT. Based on these results, a potential flame-retardant mechanism was proposed. This study presents a novel strategy for developing transparent intumescent flame-retardant coatings and broadens the application of biomass-based flame retardants.
{"title":"Preparation of amino wood coatings with superior flame retardancy, smoke suppression, and transparency using fully bio-based flame retardants","authors":"Chao Yan , Yiqun Fang , Ruofan Yang , Mengfan Yan , Weihong Wang , Yongming Song , Qingwen Wang","doi":"10.1016/j.polymdegradstab.2025.111213","DOIUrl":"10.1016/j.polymdegradstab.2025.111213","url":null,"abstract":"<div><div>The development of efficient, eco-friendly and cost-effective transparent fire-retardant coatings is crucial for maximizing the value of wood resources. In this study, an all-biobased flame retardant (PA-CS) was synthesized from corn starch (CS) and phytic acid (PA). A modified melamine resin (MFGT) with intrinsic flame-retardant properties was prepared by incorporating melamine, formaldehyde, allyl glycidyl ether, and tannic acid. The resulting MFGT@xPA-CS system demonstrated excellent thermal stability and low curing activation energy. Additionally, the system was used on the surface of wood and demonstrated good transparency, outstanding flame retardancy, smoke suppression, and char-forming ability. Cone calorimeter tests revealed that the peak heat release rate (PHRR) of [email protected] decreased by 31.12%, and total smoke production was reduced by 48.03%. Additionally, the residual char increased from 34.93% (c-MFGT) to 43.25% ([email protected]), and the I<sub>D</sub>/I<sub>G</sub> ratio of the residual char decreased by 40.58% from 3.08 (c-MFGT) to 1.83 ([email protected]). Gas-phase and condensed-phase pyrolysis products revealed synergistic effects between the phosphorus in PA-CS and the nitrogen in MFGT. Based on these results, a potential flame-retardant mechanism was proposed. This study presents a novel strategy for developing transparent intumescent flame-retardant coatings and broadens the application of biomass-based flame retardants.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111213"},"PeriodicalIF":6.3,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-23DOI: 10.1016/j.polymdegradstab.2025.111198
Wenyue Guo, Guangyong Jiang, Jing Gao, Jiajun Li, Weiyi Xing, Zhou Gui, Lei Song, Yuan Hu
To meet the demands for fire safety and environmental sustainability, developing solvent-free, flame-retardant polyurethane adhesives with high bonding strength is crucial. In this work, a novel intrinsically flame-retardant phosphorus-containing polyester polyol (ADHE) is synthesized and combined with the flame retardant aluminum diethylphosphinate (ADP) to enhance the flame-retardant properties of the bio-based polyurethane adhesive APUx (where x denotes the mass fraction of ADP). The results show excellent synergistic flame-retardant effects. When the mass fraction of ADP is 10 %, APU10 exhibits good anti-dripping and self-extinguishing performance. It achieves a vertical combustion test (UL-94) V-0 rating, with a limiting oxygen index (LOI) increasing from 20 % for the pure sample to 29 %, and a 50.4 % reduction in total heat release (THR). Hydrogen bonding in the matrix improves the interface bond to the substrate, resulting in a shear strength of 21.7 MPa on the aluminum substrate. This study proposes an integrated strategy for developing flame-retardant polyurethane adhesives with high adhesion performance.
{"title":"Flame-retardant and solvent-free polyurethane adhesive via synergistic phosphorus-containing polyol and ammonium dihydrogen phosphate","authors":"Wenyue Guo, Guangyong Jiang, Jing Gao, Jiajun Li, Weiyi Xing, Zhou Gui, Lei Song, Yuan Hu","doi":"10.1016/j.polymdegradstab.2025.111198","DOIUrl":"10.1016/j.polymdegradstab.2025.111198","url":null,"abstract":"<div><div>To meet the demands for fire safety and environmental sustainability, developing solvent-free, flame-retardant polyurethane adhesives with high bonding strength is crucial. In this work, a novel intrinsically flame-retardant phosphorus-containing polyester polyol (ADHE) is synthesized and combined with the flame retardant aluminum diethylphosphinate (ADP) to enhance the flame-retardant properties of the bio-based polyurethane adhesive APUx (where x denotes the mass fraction of ADP). The results show excellent synergistic flame-retardant effects. When the mass fraction of ADP is 10 %, APU10 exhibits good anti-dripping and self-extinguishing performance. It achieves a vertical combustion test (UL-94) V-0 rating, with a limiting oxygen index (LOI) increasing from 20 % for the pure sample to 29 %, and a 50.4 % reduction in total heat release (THR). Hydrogen bonding in the matrix improves the interface bond to the substrate, resulting in a shear strength of 21.7 MPa on the aluminum substrate. This study proposes an integrated strategy for developing flame-retardant polyurethane adhesives with high adhesion performance.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111198"},"PeriodicalIF":6.3,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143095128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-22DOI: 10.1016/j.polymdegradstab.2025.111211
Thayri Khaled , Agustín Rios de Anda , Emmanuel Richaud
Three room temperature-vulcanized PDMS rubbers were thermally aged under air at 250 °C or submitted to aminolysis at room temperature. Ageing was followed by uniaxial tensile testing, sol gel measurements in toluene, and Time Domain Double Quantum NMR characterization. Mechanical tests were exploited to identify the parameters of the Ogden model so as to describe the hyperelastic behavior of PDMS. Sol gel and Double Quantum NMR were used to track and quantify macromolecular changes within the samples. A multiscale correlation between the results of each technique was proposed to highlight the understanding of multiscale analysis in rubber ageing.
{"title":"Macromolecular and mechanical changes in aged silicones","authors":"Thayri Khaled , Agustín Rios de Anda , Emmanuel Richaud","doi":"10.1016/j.polymdegradstab.2025.111211","DOIUrl":"10.1016/j.polymdegradstab.2025.111211","url":null,"abstract":"<div><div>Three room temperature-vulcanized PDMS rubbers were thermally aged under air at 250 °C or submitted to aminolysis at room temperature. Ageing was followed by uniaxial tensile testing, sol gel measurements in toluene, and Time Domain Double Quantum NMR characterization. Mechanical tests were exploited to identify the parameters of the Ogden model so as to describe the hyperelastic behavior of PDMS. Sol gel and Double Quantum NMR were used to track and quantify macromolecular changes within the samples. A multiscale correlation between the results of each technique was proposed to highlight the understanding of multiscale analysis in rubber ageing.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111211"},"PeriodicalIF":6.3,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-22DOI: 10.1016/j.polymdegradstab.2025.111203
Giada Lo Re , Angelica Avella , Daniela Pappalardo , Rosica Mincheva
Polyesters synthesised from renewable monomers via intensified and industrially relevant processes provide nowadays a science-to-technology breakthrough, especially if they offer a suitable end-of-life scenario for a circular economy. In this work bio-based macrolactone ethylene brassylate was polymerized by reactive extrusion and the properties of the polyester and its end-of-life options were studied. The ring-opening polymerization was tested with several catalytic systems, among which the organic base 1,5,7-triazabicyclo[4.4.0]dec-5-en (TBD) and the immobilized enzymes Lipase B from Candida antarctica and Lipase from Pseudomonas cepacia successfully synthesised poly(ethylene brassylate) (PEB). TBD served as both catalyst and initiator, yielding PEB with a molar mass of 8000 g/mol, melting temperature around 70 °C and main degradation temperature of 440 °C. Tensile tests showed that PEB had a brittle behaviour with Young's modulus of 290 MPa and elongation at break of 4 %. PEB lost 93 % of its initial weight after 90 days in compost, degrading through surface erosion. Lipase B from Candida antarctica was demonstrated successful for the enzymatic depolymerization. Therefore, enzymatic depolymerization and disintegration in compost were suggested as feasible pathways for PEB circular design.
{"title":"Ring-opening polymerization of ethylene brassylate in reactive extrusion and its end-of-life options","authors":"Giada Lo Re , Angelica Avella , Daniela Pappalardo , Rosica Mincheva","doi":"10.1016/j.polymdegradstab.2025.111203","DOIUrl":"10.1016/j.polymdegradstab.2025.111203","url":null,"abstract":"<div><div>Polyesters synthesised from renewable monomers via intensified and industrially relevant processes provide nowadays a science-to-technology breakthrough, especially if they offer a suitable end-of-life scenario for a circular economy. In this work bio-based macrolactone ethylene brassylate was polymerized by reactive extrusion and the properties of the polyester and its end-of-life options were studied. The ring-opening polymerization was tested with several catalytic systems, among which the organic base 1,5,7-triazabicyclo[4.4.0]dec-5-en (TBD) and the immobilized enzymes Lipase B from <em>Candida antarctica</em> and Lipase from <em>Pseudomonas cepacia</em> successfully synthesised poly(ethylene brassylate) (PEB). TBD served as both catalyst and initiator, yielding PEB with a molar mass of 8000 g/mol, melting temperature around 70 °C and main degradation temperature of 440 °C. Tensile tests showed that PEB had a brittle behaviour with Young's modulus of 290 MPa and elongation at break of 4 %. PEB lost 93 % of its initial weight after 90 days in compost, degrading through surface erosion. Lipase B from <em>Candida antarctica</em> was demonstrated successful for the enzymatic depolymerization. Therefore, enzymatic depolymerization and disintegration in compost were suggested as feasible pathways for PEB circular design.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111203"},"PeriodicalIF":6.3,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-21DOI: 10.1016/j.polymdegradstab.2025.111210
Chloé Jost , Maxime Lacuve , Servane Haller , Eliane Espuche , Xavier Colin
Ethylene Propylene Diene Monomer (EPDM) was sulfur-crosslinked and aged in air at 130°C to study the impact of thermo-oxidative aging on the polymer structure and water sorption properties. The oxidized functions formed during aging were identified and titrated by infrared spectroscopy. Density and swelling measurements performed on aged samples showed an increase in polymer density due to oxygen grafting, and a decrease in swelling assigned to a cross-linking phenomenon. This last phenomenon was confirmed by an increase in the glass transition temperature. Concerning water transport properties, it was evidenced that, with the creation of oxidized functions and the decrease in molecular mobility, the water diffusion slowed down, while the amount of sorbed water increased. Finally, the sorption isotherms obtained for EPDM before and after aging were modelled with a good accuracy by the Park's and the GAB's models. Both models led to the conclusion that aging mainly affects the polymer affinity with water, without modifying the mean size of the water clusters evidenced at high water activity.
{"title":"Influence of thermo-oxidative aging on the structure and the water transport properties of sulfur-crosslinked EPDM","authors":"Chloé Jost , Maxime Lacuve , Servane Haller , Eliane Espuche , Xavier Colin","doi":"10.1016/j.polymdegradstab.2025.111210","DOIUrl":"10.1016/j.polymdegradstab.2025.111210","url":null,"abstract":"<div><div>Ethylene Propylene Diene Monomer (EPDM) was sulfur-crosslinked and aged in air at 130°C to study the impact of thermo-oxidative aging on the polymer structure and water sorption properties. The oxidized functions formed during aging were identified and titrated by infrared spectroscopy. Density and swelling measurements performed on aged samples showed an increase in polymer density due to oxygen grafting, and a decrease in swelling assigned to a cross-linking phenomenon. This last phenomenon was confirmed by an increase in the glass transition temperature. Concerning water transport properties, it was evidenced that, with the creation of oxidized functions and the decrease in molecular mobility, the water diffusion slowed down, while the amount of sorbed water increased. Finally, the sorption isotherms obtained for EPDM before and after aging were modelled with a good accuracy by the Park's and the GAB's models. Both models led to the conclusion that aging mainly affects the polymer affinity with water, without modifying the mean size of the water clusters evidenced at high water activity.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111210"},"PeriodicalIF":6.3,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.polymdegradstab.2025.111206
Shuang Liu , Song Liu , Ziming Feng , Linchen Hu , Shaohua Zeng , Jun Guan , Pengpeng Chen , Ying Xu , Hang Liu , Wangyan Nie , Yifeng Zhou
Polymer-matrix composites with superior fire safety, thermal conductivity, and mechanical performance are increasingly in demand due to the rapid development of advanced electronic devices. Herein, a nitrogen/phosphorus-functionalized carbon nanotubes-montmorillonite (CNTs-N,P-Mt) hybrid was constructed and self-assembled in polydimethylsiloxane (PDMS) to form a three-dimensional (3D) interconnected network structure, based on the geometrical constraint of sheet-like Mt. The 3D CNTs-N,P-Mt network enabled the PDMS-based composite with enhanced mechanical properties, thermal conductivity and flame retardancy simultaneously. When 10.0 wt.% CNTs-N,P-Mt hybrids were incorporated, tensile strength and thermal conductivity of the obtained PDMS-based composites were 225.0 % and 70.4 % higher than those of pure PDMS; meanwhile, such composite exhibited the smoke production rate of 0.04 m2▪s−1 and peak total smoke production of 3.51 m2, which were 48.1 % and 30.3 % lower than those of pure PDMS (suggesting superb smoke suppression properties). This work provides valuable insight into developing multifunctional polymer-based packaging materials for application in advanced electronic devices.
{"title":"Mechanically robust, thermally conductive and flame retardant polydimethylsiloxane composites decorated with a nitrogen/phosphorus-functionalized carbon nanotubes-montmorillonite interconnected network","authors":"Shuang Liu , Song Liu , Ziming Feng , Linchen Hu , Shaohua Zeng , Jun Guan , Pengpeng Chen , Ying Xu , Hang Liu , Wangyan Nie , Yifeng Zhou","doi":"10.1016/j.polymdegradstab.2025.111206","DOIUrl":"10.1016/j.polymdegradstab.2025.111206","url":null,"abstract":"<div><div>Polymer-matrix composites with superior fire safety, thermal conductivity, and mechanical performance are increasingly in demand due to the rapid development of advanced electronic devices. Herein, a nitrogen/phosphorus-functionalized carbon nanotubes-montmorillonite (CNTs-N,P-Mt) hybrid was constructed and self-assembled in polydimethylsiloxane (PDMS) to form a three-dimensional (3D) interconnected network structure, based on the geometrical constraint of sheet-like Mt. The 3D CNTs-N,P-Mt network enabled the PDMS-based composite with enhanced mechanical properties, thermal conductivity and flame retardancy simultaneously. When 10.0 wt.% CNTs-N,P-Mt hybrids were incorporated, tensile strength and thermal conductivity of the obtained PDMS-based composites were 225.0 % and 70.4 % higher than those of pure PDMS; meanwhile, such composite exhibited the smoke production rate of 0.04 m<sup>2</sup>▪s<sup>−1</sup> and peak total smoke production of 3.51 m<sup>2</sup>, which were 48.1 % and 30.3 % lower than those of pure PDMS (suggesting superb smoke suppression properties). This work provides valuable insight into developing multifunctional polymer-based packaging materials for application in advanced electronic devices.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111206"},"PeriodicalIF":6.3,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143095254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.polymdegradstab.2025.111208
Xinliang Liu , Menghe Zhu , Jianhao Zhu , Zhihui Liu , Yiwei Geng , Chuanxin Xie , Xilei Chen , Lei Liu , Pingan Song
Lightweight and thermally insulating rigid polyurethane foam (RPUF) features various important industrial applications, but intrinsic flammability extremely restricts its practical use. The development of multifunctional coating that combines traditional passive fire retardancy and active fire alarm response has been proven to be a promising method to improve the fire safety of RPUF. Herein, we rationally construct organic-inorganic hybrid coatings with a flame-retardant layer and a temperature-sensitive layer by using poly (vinyl alcohol) (PVA), TiO2, graphite nanoplates (GNs), glass powders (GPs), and copper phytate modified mica (MP) as building blocks. The resultant RPUF achieves a V-0 rating during vertical burning with a limiting oxygen index of up to 31.5 vol.%, in addition to reduced heat and CO yield by 24.0 % and 77.0 %. Moreover, the coated foam shows a rapid fire-alarm response of ∼8 s upon flame attack and displays a good fire cyclic warning performance. Furthermore, the thermal insulation property is well-preserved even when exposed to ∼1100 °C flame due to the good ceramic charring capability. This work provides a promising strategy for the creation of fire-proof coatings for RPUF, which hold great promise for many industrial applications.
{"title":"A ceramifiable organic-inorganic fire extinguishing hybrid coating capable of cyclic fire-warning","authors":"Xinliang Liu , Menghe Zhu , Jianhao Zhu , Zhihui Liu , Yiwei Geng , Chuanxin Xie , Xilei Chen , Lei Liu , Pingan Song","doi":"10.1016/j.polymdegradstab.2025.111208","DOIUrl":"10.1016/j.polymdegradstab.2025.111208","url":null,"abstract":"<div><div>Lightweight and thermally insulating rigid polyurethane foam (RPUF) features various important industrial applications, but intrinsic flammability extremely restricts its practical use. The development of multifunctional coating that combines traditional passive fire retardancy and active fire alarm response has been proven to be a promising method to improve the fire safety of RPUF. Herein, we rationally construct organic-inorganic hybrid coatings with a flame-retardant layer and a temperature-sensitive layer by using poly (vinyl alcohol) (PVA), TiO<sub>2</sub>, graphite nanoplates (GNs), glass powders (GPs), and copper phytate modified mica (MP) as building blocks. The resultant RPUF achieves a V-0 rating during vertical burning with a limiting oxygen index of up to 31.5 vol.%, in addition to reduced heat and CO yield by 24.0 % and 77.0 %. Moreover, the coated foam shows a rapid fire-alarm response of ∼8 s upon flame attack and displays a good fire cyclic warning performance. Furthermore, the thermal insulation property is well-preserved even when exposed to ∼1100 °C flame due to the good ceramic charring capability. This work provides a promising strategy for the creation of fire-proof coatings for RPUF, which hold great promise for many industrial applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111208"},"PeriodicalIF":6.3,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.polymdegradstab.2025.111209
Jiajun Li , Bin Zou , Amirbek Bekeshev , Marzhan Akhmetova , Raigul Orynbassar , Xin Wang , Yuan Hu
The traditional trial-and-error method for developing organophosphorus flame retardants is time-consuming and expensive. This work constructed machine learning models for limiting oxygen index (LOI), peak heat release rate (PHRR), and UL-94 for epoxy resin on the basis of the collected multifactor database, including the structure of organophosphorus flame retardants, addition amounts, matrix combustion performance, and flux. The training and test sets were divided on the basis of molecular groups to avoid data leakage within the same molecule group, in contrast to conventional random splitting. The best results for LOI and PHRR prediction were achieved via the XGBoost algorithm and ECFP4 fingerprints, with mean absolute errors of 1.61% and 125.5 kW/m2 on the test set, respectively. For UL-94 classification, the MACCS with XGBoost achieved 79% accuracy. The Shapley additive explanation for the model indicated that the addition amount and matrix combustion performance data were the two most important features. This work could help develop a more accurate and reliable prediction model for flame retardancy.
{"title":"Practical machine learning model selection and interpretation for organophosphorus flame retardancy in Epoxy resin","authors":"Jiajun Li , Bin Zou , Amirbek Bekeshev , Marzhan Akhmetova , Raigul Orynbassar , Xin Wang , Yuan Hu","doi":"10.1016/j.polymdegradstab.2025.111209","DOIUrl":"10.1016/j.polymdegradstab.2025.111209","url":null,"abstract":"<div><div>The traditional trial-and-error method for developing organophosphorus flame retardants is time-consuming and expensive. This work constructed machine learning models for limiting oxygen index (LOI), peak heat release rate (PHRR), and UL-94 for epoxy resin on the basis of the collected multifactor database, including the structure of organophosphorus flame retardants, addition amounts, matrix combustion performance, and flux. The training and test sets were divided on the basis of molecular groups to avoid data leakage within the same molecule group, in contrast to conventional random splitting. The best results for LOI and PHRR prediction were achieved via the XGBoost algorithm and ECFP4 fingerprints, with mean absolute errors of 1.61% and 125.5 kW/m<sup>2</sup> on the test set, respectively. For UL-94 classification, the MACCS with XGBoost achieved 79% accuracy. The Shapley additive explanation for the model indicated that the addition amount and matrix combustion performance data were the two most important features. This work could help develop a more accurate and reliable prediction model for flame retardancy.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"234 ","pages":"Article 111209"},"PeriodicalIF":6.3,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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