Reaction model describing antioxidant depletion in polyethylene-clay nanocomposites under thermal aging
Antioxidants are typically added to polyethylene to extend its durability, and recently clay nanoparticles have been blended into polyethylene to improve mechanical properties. However, the clay nanoparticles also accelerate the rate of antioxidant depletion in polyethylene. This paper uses a mathem...
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Veröffentlicht in: | Polymer degradation and stability 2014-12, Vol.110, p.318-335 |
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creator | AHMAD, Iftekhar LI, Christopher Y GRACE HSUAN, Y CAIRNCROSS, Richard A |
description | Antioxidants are typically added to polyethylene to extend its durability, and recently clay nanoparticles have been blended into polyethylene to improve mechanical properties. However, the clay nanoparticles also accelerate the rate of antioxidant depletion in polyethylene. This paper uses a mathematical model to describe the underlying mechanisms of antioxidant (hindered-phenol) depletion and to predict experimentally-measured antioxidant profiles in polyethylene-clay nanocomposites. The mathematical model uses a reaction kinetic scheme that includes free radical initiation and propagation reactions, antioxidant stabilization reactions and free radical termination reactions. In the model, alkyl free radicals oxidize rapidly. The role of antioxidants is to stabilize the oxidized free radicals to hydroperoxides, and interrupt propagation reactions. However, in nanocomposites, continuous depletion of antioxidant is caused by the clay acting as a catalyst to decompose hydroperoxides and regenerate alkyl free radicals. This cyclic hydroperoxide generation and decomposition leads to much faster antioxidant depletion in polyethylene nanocomposites. Phenoxyl radicals of antioxidants generated by stabilization reactions contribute to terminate polymeric free radicals and limit their accumulation. Predictions of antioxidant depletion are compared to experimental results for accelerated aging of polyethylene and nanocomposite samples. |
doi_str_mv | 10.1016/j.polymdegradstab.2014.09.002 |
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However, the clay nanoparticles also accelerate the rate of antioxidant depletion in polyethylene. This paper uses a mathematical model to describe the underlying mechanisms of antioxidant (hindered-phenol) depletion and to predict experimentally-measured antioxidant profiles in polyethylene-clay nanocomposites. The mathematical model uses a reaction kinetic scheme that includes free radical initiation and propagation reactions, antioxidant stabilization reactions and free radical termination reactions. In the model, alkyl free radicals oxidize rapidly. The role of antioxidants is to stabilize the oxidized free radicals to hydroperoxides, and interrupt propagation reactions. However, in nanocomposites, continuous depletion of antioxidant is caused by the clay acting as a catalyst to decompose hydroperoxides and regenerate alkyl free radicals. This cyclic hydroperoxide generation and decomposition leads to much faster antioxidant depletion in polyethylene nanocomposites. Phenoxyl radicals of antioxidants generated by stabilization reactions contribute to terminate polymeric free radicals and limit their accumulation. Predictions of antioxidant depletion are compared to experimental results for accelerated aging of polyethylene and nanocomposite samples.</description><identifier>ISSN: 0141-3910</identifier><identifier>EISSN: 1873-2321</identifier><identifier>DOI: 10.1016/j.polymdegradstab.2014.09.002</identifier><identifier>CODEN: PDSTDW</identifier><language>eng</language><publisher>Kidlington: Elsevier</publisher><subject>Antioxidants ; Applied sciences ; Clay (material) ; Composites ; Compounding ingredients ; Depletion ; Exact sciences and technology ; Forms of application and semi-finished materials ; Free radicals ; Mathematical models ; Nanocomposites ; Polyethylenes ; Polymer industry, paints, wood ; Stabilization ; Stabilizers (antioxydants, antiozonants, etc.) ; Technology of polymers</subject><ispartof>Polymer degradation and stability, 2014-12, Vol.110, p.318-335</ispartof><rights>2015 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c332t-36b505e0dece179d97f633789fb9a5f52ec615d8f61832d4a8dd94e8a2304f403</citedby><cites>FETCH-LOGICAL-c332t-36b505e0dece179d97f633789fb9a5f52ec615d8f61832d4a8dd94e8a2304f403</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27923,27924</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=29022295$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>AHMAD, Iftekhar</creatorcontrib><creatorcontrib>LI, Christopher Y</creatorcontrib><creatorcontrib>GRACE HSUAN, Y</creatorcontrib><creatorcontrib>CAIRNCROSS, Richard A</creatorcontrib><title>Reaction model describing antioxidant depletion in polyethylene-clay nanocomposites under thermal aging</title><title>Polymer degradation and stability</title><description>Antioxidants are typically added to polyethylene to extend its durability, and recently clay nanoparticles have been blended into polyethylene to improve mechanical properties. However, the clay nanoparticles also accelerate the rate of antioxidant depletion in polyethylene. This paper uses a mathematical model to describe the underlying mechanisms of antioxidant (hindered-phenol) depletion and to predict experimentally-measured antioxidant profiles in polyethylene-clay nanocomposites. The mathematical model uses a reaction kinetic scheme that includes free radical initiation and propagation reactions, antioxidant stabilization reactions and free radical termination reactions. In the model, alkyl free radicals oxidize rapidly. The role of antioxidants is to stabilize the oxidized free radicals to hydroperoxides, and interrupt propagation reactions. However, in nanocomposites, continuous depletion of antioxidant is caused by the clay acting as a catalyst to decompose hydroperoxides and regenerate alkyl free radicals. This cyclic hydroperoxide generation and decomposition leads to much faster antioxidant depletion in polyethylene nanocomposites. Phenoxyl radicals of antioxidants generated by stabilization reactions contribute to terminate polymeric free radicals and limit their accumulation. Predictions of antioxidant depletion are compared to experimental results for accelerated aging of polyethylene and nanocomposite samples.</description><subject>Antioxidants</subject><subject>Applied sciences</subject><subject>Clay (material)</subject><subject>Composites</subject><subject>Compounding ingredients</subject><subject>Depletion</subject><subject>Exact sciences and technology</subject><subject>Forms of application and semi-finished materials</subject><subject>Free radicals</subject><subject>Mathematical models</subject><subject>Nanocomposites</subject><subject>Polyethylenes</subject><subject>Polymer industry, paints, wood</subject><subject>Stabilization</subject><subject>Stabilizers (antioxydants, antiozonants, etc.)</subject><subject>Technology of polymers</subject><issn>0141-3910</issn><issn>1873-2321</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNpdkEtLxDAUhYMoOD7-QzcDblrzaDvNwoWILxgQRNfhTnI7kyFNatIB59-bUXHh3Ry499zvwCFkzmjFKGuvt9UY3H4wuI5g0gSrilNWV1RWlPIjMmPdQpRccHZMZvnASiEZPSVnKW1pnrphM7J-RdCTDb4YgkFXGEw62pX16wJ83n9akzWvR4ffNuuLQypOm71Dj6V2sC88-KDDMIZkJ0zFzhuMxbTBOIArYJ1pF-SkB5fw8lfPyfvD_dvdU7l8eXy-u12WWgg-laJdNbRBalAjW0gjF30rxKKT_UpC0zccdcsa0_Ut6wQ3NXTGyBo74ILWfU3FObn64Y4xfOwwTWqwSaNz4DHskmJtww48WWfrzY9Vx5BSxF6N0Q4Q94pRdShYbdW_gtWhYEWlygXn__lvFCQNro_gtU1_EC4p51w24gvBNoSV</recordid><startdate>20141201</startdate><enddate>20141201</enddate><creator>AHMAD, Iftekhar</creator><creator>LI, Christopher Y</creator><creator>GRACE HSUAN, Y</creator><creator>CAIRNCROSS, Richard A</creator><general>Elsevier</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20141201</creationdate><title>Reaction model describing antioxidant depletion in polyethylene-clay nanocomposites under thermal aging</title><author>AHMAD, Iftekhar ; LI, Christopher Y ; GRACE HSUAN, Y ; CAIRNCROSS, Richard A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c332t-36b505e0dece179d97f633789fb9a5f52ec615d8f61832d4a8dd94e8a2304f403</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Antioxidants</topic><topic>Applied sciences</topic><topic>Clay (material)</topic><topic>Composites</topic><topic>Compounding ingredients</topic><topic>Depletion</topic><topic>Exact sciences and technology</topic><topic>Forms of application and semi-finished materials</topic><topic>Free radicals</topic><topic>Mathematical models</topic><topic>Nanocomposites</topic><topic>Polyethylenes</topic><topic>Polymer industry, paints, wood</topic><topic>Stabilization</topic><topic>Stabilizers (antioxydants, antiozonants, etc.)</topic><topic>Technology of polymers</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>AHMAD, Iftekhar</creatorcontrib><creatorcontrib>LI, Christopher Y</creatorcontrib><creatorcontrib>GRACE HSUAN, Y</creatorcontrib><creatorcontrib>CAIRNCROSS, Richard A</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Polymer degradation and stability</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>AHMAD, Iftekhar</au><au>LI, Christopher Y</au><au>GRACE HSUAN, Y</au><au>CAIRNCROSS, Richard A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reaction model describing antioxidant depletion in polyethylene-clay nanocomposites under thermal aging</atitle><jtitle>Polymer degradation and stability</jtitle><date>2014-12-01</date><risdate>2014</risdate><volume>110</volume><spage>318</spage><epage>335</epage><pages>318-335</pages><issn>0141-3910</issn><eissn>1873-2321</eissn><coden>PDSTDW</coden><abstract>Antioxidants are typically added to polyethylene to extend its durability, and recently clay nanoparticles have been blended into polyethylene to improve mechanical properties. However, the clay nanoparticles also accelerate the rate of antioxidant depletion in polyethylene. This paper uses a mathematical model to describe the underlying mechanisms of antioxidant (hindered-phenol) depletion and to predict experimentally-measured antioxidant profiles in polyethylene-clay nanocomposites. The mathematical model uses a reaction kinetic scheme that includes free radical initiation and propagation reactions, antioxidant stabilization reactions and free radical termination reactions. In the model, alkyl free radicals oxidize rapidly. The role of antioxidants is to stabilize the oxidized free radicals to hydroperoxides, and interrupt propagation reactions. However, in nanocomposites, continuous depletion of antioxidant is caused by the clay acting as a catalyst to decompose hydroperoxides and regenerate alkyl free radicals. This cyclic hydroperoxide generation and decomposition leads to much faster antioxidant depletion in polyethylene nanocomposites. Phenoxyl radicals of antioxidants generated by stabilization reactions contribute to terminate polymeric free radicals and limit their accumulation. Predictions of antioxidant depletion are compared to experimental results for accelerated aging of polyethylene and nanocomposite samples.</abstract><cop>Kidlington</cop><pub>Elsevier</pub><doi>10.1016/j.polymdegradstab.2014.09.002</doi><tpages>18</tpages></addata></record> |
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subjects | Antioxidants Applied sciences Clay (material) Composites Compounding ingredients Depletion Exact sciences and technology Forms of application and semi-finished materials Free radicals Mathematical models Nanocomposites Polyethylenes Polymer industry, paints, wood Stabilization Stabilizers (antioxydants, antiozonants, etc.) Technology of polymers |
title | Reaction model describing antioxidant depletion in polyethylene-clay nanocomposites under thermal aging |
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