Catalytic degradation of a carbon fibre reinforced polymer for recycling applications
A range of alkaline and weak Lewis acid solutions were used in conjunction with an acetone / water solvent system in order to decompose a carbon fibre reinforced epoxy resin. The initial concentration of the additives in the mixture was varied between 0.01 to 0.40 M at temperatures and pressures of...
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Veröffentlicht in: | Polymer degradation and stability 2019-08, Vol.166, p.188-201 |
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description | A range of alkaline and weak Lewis acid solutions were used in conjunction with an acetone / water solvent system in order to decompose a carbon fibre reinforced epoxy resin. The initial concentration of the additives in the mixture was varied between 0.01 to 0.40 M at temperatures and pressures of 280 to 320 °C and 13 to 20 MPa. Under these conditions and a reaction time of 1 h, KOH and NaOH did not accelerate the decomposition of the matrix relative to the neat solvent, however, 0.05 M solutions of ZnCl2 and MgCl2 and a 0.005 M solution of AlCl3 facilitated the recovery of clean fibres at 300 °C. Under these conditions, the degradation achieved with acetone / water alone was just 33 wt%. By changing the process temperature and reaction time, the minimum necessary conditions for complete degradation were identified as 290 °C, 1.5 h or 300 °C, 45 min for all metal chlorides investigated. This represents a reduction in temperature of 40 °C when compared to a neat acetone / water solvent mixture. The reaction kinetics were studied through the application of a first order rate equation and a shrinking core model with the results demonstrating that 0.05 M ZnCl2 reduces the activation energy of the reaction by 30%. Analysis of the organic liquid fraction using infrared spectroscopy suggests that this is due to the cleavage of the CN bonds in the epoxy resin by the metal ions. Gas chromatography with mass spectrometry identified the presence of cyclic compounds and low concentrations of amine derivatives.
•The decomposition of a CFRP using an acetone/water solvent and various basic and weak-Lewis acid catalysts was studied.•Compared to the neat solvent, ZnCl2, MgCl2 and AlCl3 reduce the required reaction temperature by 40˚C.•A first order rate equation and shrinking core model was fitted to the decomposition data.•ZnCl2 enables EA to be reduced by 30% compared to the neat solvent mixture.•Analysis of the organic products demonstrated that the metal chlorides cleave the C–N bonds. |
doi_str_mv | 10.1016/j.polymdegradstab.2019.05.020 |
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•The decomposition of a CFRP using an acetone/water solvent and various basic and weak-Lewis acid catalysts was studied.•Compared to the neat solvent, ZnCl2, MgCl2 and AlCl3 reduce the required reaction temperature by 40˚C.•A first order rate equation and shrinking core model was fitted to the decomposition data.•ZnCl2 enables EA to be reduced by 30% compared to the neat solvent mixture.•Analysis of the organic products demonstrated that the metal chlorides cleave the C–N bonds.</description><identifier>ISSN: 0141-3910</identifier><identifier>EISSN: 1873-2321</identifier><identifier>DOI: 10.1016/j.polymdegradstab.2019.05.020</identifier><language>eng</language><publisher>London: Elsevier Ltd</publisher><subject>Acetone ; Additives ; Aluminum chloride ; Carbon fiber reinforced plastics ; Carbon fibers ; Carbon fibres ; Carbon-epoxy composites ; Catalysis ; Composites ; Cyclic compounds ; Decomposition ; Degradation ; Epoxy resins ; Fiber reinforced polymers ; Gas chromatography ; Infrared analysis ; Lewis acid ; Low concentrations ; Magnesium chloride ; Mass spectrometry ; Metal chlorides ; Organic liquids ; Reaction kinetics ; Reaction modelling ; Reaction time ; Recycling ; Shrinking core model ; Sodium hydroxide ; Solvents ; Solvolysis ; Temperature ; Thermosetting resin ; Zinc chloride</subject><ispartof>Polymer degradation and stability, 2019-08, Vol.166, p.188-201</ispartof><rights>2019 Elsevier Ltd</rights><rights>Copyright Elsevier BV Aug 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c398t-c9ae802446715e324aef23de136891612dcafc92908db40ad826d776e9c637383</citedby><cites>FETCH-LOGICAL-c398t-c9ae802446715e324aef23de136891612dcafc92908db40ad826d776e9c637383</cites><orcidid>0000-0002-1097-1797</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.polymdegradstab.2019.05.020$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3536,27903,27904,45974</link.rule.ids></links><search><creatorcontrib>Keith, Matthew J.</creatorcontrib><creatorcontrib>Leeke, Gary A.</creatorcontrib><creatorcontrib>Khan, Palvisha</creatorcontrib><creatorcontrib>Ingram, Andrew</creatorcontrib><title>Catalytic degradation of a carbon fibre reinforced polymer for recycling applications</title><title>Polymer degradation and stability</title><description>A range of alkaline and weak Lewis acid solutions were used in conjunction with an acetone / water solvent system in order to decompose a carbon fibre reinforced epoxy resin. The initial concentration of the additives in the mixture was varied between 0.01 to 0.40 M at temperatures and pressures of 280 to 320 °C and 13 to 20 MPa. Under these conditions and a reaction time of 1 h, KOH and NaOH did not accelerate the decomposition of the matrix relative to the neat solvent, however, 0.05 M solutions of ZnCl2 and MgCl2 and a 0.005 M solution of AlCl3 facilitated the recovery of clean fibres at 300 °C. Under these conditions, the degradation achieved with acetone / water alone was just 33 wt%. By changing the process temperature and reaction time, the minimum necessary conditions for complete degradation were identified as 290 °C, 1.5 h or 300 °C, 45 min for all metal chlorides investigated. This represents a reduction in temperature of 40 °C when compared to a neat acetone / water solvent mixture. The reaction kinetics were studied through the application of a first order rate equation and a shrinking core model with the results demonstrating that 0.05 M ZnCl2 reduces the activation energy of the reaction by 30%. Analysis of the organic liquid fraction using infrared spectroscopy suggests that this is due to the cleavage of the CN bonds in the epoxy resin by the metal ions. Gas chromatography with mass spectrometry identified the presence of cyclic compounds and low concentrations of amine derivatives.
•The decomposition of a CFRP using an acetone/water solvent and various basic and weak-Lewis acid catalysts was studied.•Compared to the neat solvent, ZnCl2, MgCl2 and AlCl3 reduce the required reaction temperature by 40˚C.•A first order rate equation and shrinking core model was fitted to the decomposition data.•ZnCl2 enables EA to be reduced by 30% compared to the neat solvent mixture.•Analysis of the organic products demonstrated that the metal chlorides cleave the C–N bonds.</description><subject>Acetone</subject><subject>Additives</subject><subject>Aluminum chloride</subject><subject>Carbon fiber reinforced plastics</subject><subject>Carbon fibers</subject><subject>Carbon fibres</subject><subject>Carbon-epoxy composites</subject><subject>Catalysis</subject><subject>Composites</subject><subject>Cyclic compounds</subject><subject>Decomposition</subject><subject>Degradation</subject><subject>Epoxy resins</subject><subject>Fiber reinforced polymers</subject><subject>Gas chromatography</subject><subject>Infrared analysis</subject><subject>Lewis acid</subject><subject>Low concentrations</subject><subject>Magnesium chloride</subject><subject>Mass spectrometry</subject><subject>Metal chlorides</subject><subject>Organic liquids</subject><subject>Reaction kinetics</subject><subject>Reaction modelling</subject><subject>Reaction time</subject><subject>Recycling</subject><subject>Shrinking core model</subject><subject>Sodium hydroxide</subject><subject>Solvents</subject><subject>Solvolysis</subject><subject>Temperature</subject><subject>Thermosetting resin</subject><subject>Zinc chloride</subject><issn>0141-3910</issn><issn>1873-2321</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqNkE1LxDAQhoMouK7-h4B4bM1Hv3LwIEVXYcGLew5pMl1Suk1NukL_vdmtJ0_OHCYZ5n2HeRB6oCSlhBaPXTq6fj4Y2HtlwqSalBEqUpKnhJELtKJVyRPGGb1EK0IzmnBByTW6CaEjMbKcrtCuVpPq58lqvPioyboBuxYrrJVv4ru1jQfswQ6t8xoMPm8Fj-M3tvWsezvssRrH3uqzPNyiq1b1Ae5-6xrtXl8-67dk-7F5r5-3ieaimhItFFSEZVlR0hw4yxS0jBugvKgELSgzWrVaMEEq02REmYoVpiwLELrgJa_4Gt0vvqN3X0cIk-zc0Q9xpWSsFOdkceppmdLeheChlaO3B-VnSYk8kZSd_ENSnkhKkstIMuo3ix7iKd8WvAzawhBR2Hj-JI2z_3T6AbTihto</recordid><startdate>20190801</startdate><enddate>20190801</enddate><creator>Keith, Matthew J.</creator><creator>Leeke, Gary A.</creator><creator>Khan, Palvisha</creator><creator>Ingram, Andrew</creator><general>Elsevier Ltd</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0002-1097-1797</orcidid></search><sort><creationdate>20190801</creationdate><title>Catalytic degradation of a carbon fibre reinforced polymer for recycling applications</title><author>Keith, Matthew J. ; Leeke, Gary A. ; Khan, Palvisha ; Ingram, Andrew</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c398t-c9ae802446715e324aef23de136891612dcafc92908db40ad826d776e9c637383</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Acetone</topic><topic>Additives</topic><topic>Aluminum chloride</topic><topic>Carbon fiber reinforced plastics</topic><topic>Carbon fibers</topic><topic>Carbon fibres</topic><topic>Carbon-epoxy composites</topic><topic>Catalysis</topic><topic>Composites</topic><topic>Cyclic compounds</topic><topic>Decomposition</topic><topic>Degradation</topic><topic>Epoxy resins</topic><topic>Fiber reinforced polymers</topic><topic>Gas chromatography</topic><topic>Infrared analysis</topic><topic>Lewis acid</topic><topic>Low concentrations</topic><topic>Magnesium chloride</topic><topic>Mass spectrometry</topic><topic>Metal chlorides</topic><topic>Organic liquids</topic><topic>Reaction kinetics</topic><topic>Reaction modelling</topic><topic>Reaction time</topic><topic>Recycling</topic><topic>Shrinking core model</topic><topic>Sodium hydroxide</topic><topic>Solvents</topic><topic>Solvolysis</topic><topic>Temperature</topic><topic>Thermosetting resin</topic><topic>Zinc chloride</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Keith, Matthew J.</creatorcontrib><creatorcontrib>Leeke, Gary A.</creatorcontrib><creatorcontrib>Khan, Palvisha</creatorcontrib><creatorcontrib>Ingram, Andrew</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer degradation and stability</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Keith, Matthew J.</au><au>Leeke, Gary A.</au><au>Khan, Palvisha</au><au>Ingram, Andrew</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalytic degradation of a carbon fibre reinforced polymer for recycling applications</atitle><jtitle>Polymer degradation and stability</jtitle><date>2019-08-01</date><risdate>2019</risdate><volume>166</volume><spage>188</spage><epage>201</epage><pages>188-201</pages><issn>0141-3910</issn><eissn>1873-2321</eissn><abstract>A range of alkaline and weak Lewis acid solutions were used in conjunction with an acetone / water solvent system in order to decompose a carbon fibre reinforced epoxy resin. The initial concentration of the additives in the mixture was varied between 0.01 to 0.40 M at temperatures and pressures of 280 to 320 °C and 13 to 20 MPa. Under these conditions and a reaction time of 1 h, KOH and NaOH did not accelerate the decomposition of the matrix relative to the neat solvent, however, 0.05 M solutions of ZnCl2 and MgCl2 and a 0.005 M solution of AlCl3 facilitated the recovery of clean fibres at 300 °C. Under these conditions, the degradation achieved with acetone / water alone was just 33 wt%. By changing the process temperature and reaction time, the minimum necessary conditions for complete degradation were identified as 290 °C, 1.5 h or 300 °C, 45 min for all metal chlorides investigated. This represents a reduction in temperature of 40 °C when compared to a neat acetone / water solvent mixture. The reaction kinetics were studied through the application of a first order rate equation and a shrinking core model with the results demonstrating that 0.05 M ZnCl2 reduces the activation energy of the reaction by 30%. Analysis of the organic liquid fraction using infrared spectroscopy suggests that this is due to the cleavage of the CN bonds in the epoxy resin by the metal ions. Gas chromatography with mass spectrometry identified the presence of cyclic compounds and low concentrations of amine derivatives.
•The decomposition of a CFRP using an acetone/water solvent and various basic and weak-Lewis acid catalysts was studied.•Compared to the neat solvent, ZnCl2, MgCl2 and AlCl3 reduce the required reaction temperature by 40˚C.•A first order rate equation and shrinking core model was fitted to the decomposition data.•ZnCl2 enables EA to be reduced by 30% compared to the neat solvent mixture.•Analysis of the organic products demonstrated that the metal chlorides cleave the C–N bonds.</abstract><cop>London</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.polymdegradstab.2019.05.020</doi><tpages>14</tpages><orcidid>https://orcid.org/0000-0002-1097-1797</orcidid></addata></record> |
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subjects | Acetone Additives Aluminum chloride Carbon fiber reinforced plastics Carbon fibers Carbon fibres Carbon-epoxy composites Catalysis Composites Cyclic compounds Decomposition Degradation Epoxy resins Fiber reinforced polymers Gas chromatography Infrared analysis Lewis acid Low concentrations Magnesium chloride Mass spectrometry Metal chlorides Organic liquids Reaction kinetics Reaction modelling Reaction time Recycling Shrinking core model Sodium hydroxide Solvents Solvolysis Temperature Thermosetting resin Zinc chloride |
title | Catalytic degradation of a carbon fibre reinforced polymer for recycling applications |
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