R Laot , P-Y․Le Gac , M․Le Gall , M. Broudin , C. Ovalle , L. Laiarinandrasana
{"title":"氯化海水中使用的聚乙烯抗氧化剂损耗:从加速老化到建模","authors":"R Laot , P-Y․Le Gac , M․Le Gall , M. Broudin , C. Ovalle , L. Laiarinandrasana","doi":"10.1016/j.polymdegradstab.2025.111535","DOIUrl":null,"url":null,"abstract":"<div><div>This study focuses on the loss of stabilizers used in polyethylene (PE) formulations exposed to chlorinated seawater. A PE model containing antioxidants is aged in three different environments: deoxygenated water, oxygenated water and chlorinated seawater with oxygen. To elucidate slow-occurring phenomena, accelerated ageing experiments were performed across a range of chlorine concentrations and temperatures. Additionally, ageing tests are performed on samples of different thicknesses to distinguish between surface processes, reaction-based mechanisms and diffusion-involved mechanisms. In all cases, the loss of stabilizers is monitored by measuring the oxidation induction time. The results show that the physical extraction of stabilizers (leaching) can be described using existing theories from the literature, with the extraction constants identified based on tests in deoxygenated water at 60, 80 and 90 °C. It appears that the presence of oxygen in water leads to a faster decrease in stabilizers over time, explained by the reaction of these molecules with free radicals formed during the oxidation process. Kinetic rates associated with this process were determined at 40, 60, 80 and 90 °C. Finally, for the first time, the kinetics of stabilizer loss in chlorinated seawater are identified for two pro-oxidant concentrations at 21 °C. Based on theoretical considerations from the literature, a kinetic model of stabilizer loss is proposed to describe the results obtained in this study.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"241 ","pages":"Article 111535"},"PeriodicalIF":7.4000,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Antioxidant depletion in polyethylene used in chlorinated seawater: from accelerated ageing to modelling\",\"authors\":\"R Laot , P-Y․Le Gac , M․Le Gall , M. Broudin , C. Ovalle , L. Laiarinandrasana\",\"doi\":\"10.1016/j.polymdegradstab.2025.111535\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>This study focuses on the loss of stabilizers used in polyethylene (PE) formulations exposed to chlorinated seawater. A PE model containing antioxidants is aged in three different environments: deoxygenated water, oxygenated water and chlorinated seawater with oxygen. To elucidate slow-occurring phenomena, accelerated ageing experiments were performed across a range of chlorine concentrations and temperatures. Additionally, ageing tests are performed on samples of different thicknesses to distinguish between surface processes, reaction-based mechanisms and diffusion-involved mechanisms. In all cases, the loss of stabilizers is monitored by measuring the oxidation induction time. The results show that the physical extraction of stabilizers (leaching) can be described using existing theories from the literature, with the extraction constants identified based on tests in deoxygenated water at 60, 80 and 90 °C. It appears that the presence of oxygen in water leads to a faster decrease in stabilizers over time, explained by the reaction of these molecules with free radicals formed during the oxidation process. Kinetic rates associated with this process were determined at 40, 60, 80 and 90 °C. Finally, for the first time, the kinetics of stabilizer loss in chlorinated seawater are identified for two pro-oxidant concentrations at 21 °C. Based on theoretical considerations from the literature, a kinetic model of stabilizer loss is proposed to describe the results obtained in this study.</div></div>\",\"PeriodicalId\":406,\"journal\":{\"name\":\"Polymer Degradation and Stability\",\"volume\":\"241 \",\"pages\":\"Article 111535\"},\"PeriodicalIF\":7.4000,\"publicationDate\":\"2025-07-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Degradation and Stability\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0141391025003647\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Degradation and Stability","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0141391025003647","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Antioxidant depletion in polyethylene used in chlorinated seawater: from accelerated ageing to modelling
This study focuses on the loss of stabilizers used in polyethylene (PE) formulations exposed to chlorinated seawater. A PE model containing antioxidants is aged in three different environments: deoxygenated water, oxygenated water and chlorinated seawater with oxygen. To elucidate slow-occurring phenomena, accelerated ageing experiments were performed across a range of chlorine concentrations and temperatures. Additionally, ageing tests are performed on samples of different thicknesses to distinguish between surface processes, reaction-based mechanisms and diffusion-involved mechanisms. In all cases, the loss of stabilizers is monitored by measuring the oxidation induction time. The results show that the physical extraction of stabilizers (leaching) can be described using existing theories from the literature, with the extraction constants identified based on tests in deoxygenated water at 60, 80 and 90 °C. It appears that the presence of oxygen in water leads to a faster decrease in stabilizers over time, explained by the reaction of these molecules with free radicals formed during the oxidation process. Kinetic rates associated with this process were determined at 40, 60, 80 and 90 °C. Finally, for the first time, the kinetics of stabilizer loss in chlorinated seawater are identified for two pro-oxidant concentrations at 21 °C. Based on theoretical considerations from the literature, a kinetic model of stabilizer loss is proposed to describe the results obtained in this study.
期刊介绍:
Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology.
Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal.
However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.