Thermodynamic and model-based kinetic analysis of natural rubber–silanised cellulose composites pyrolysis

Thermodynamic and model-based kinetic analysis of natural rubber–silanised cellulose composites pyrolysis | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Thermodynamic and model-based kinetic analysis of natural rubber–silanised cellulose composites pyrolysis Jana Dobrovská, Petra Skalková, Elizaveta Iudina, Sylva Holešová, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7964541/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Natural rubber (NR) composites filled with graded amount of silanised cellulose (CELS) were prepared by melting and vulcanisation. Thermogravimetric (TG) curves at six heating rates (2 to 20°C/min) were measured. Kinetic parameters were determined by using the Friedman model-free method and model-based methods. The following were studied: i) the effect of cellulose silanization on the thermal stability of the composites, ii) the mechanism of pyrolytic decomposition of the composites, and iii) the effect of the content of silanized cellulose on the decomposition mechanism. It was found that the pyrolysis process follows an autocatalytic mechanism. The results also show that silanisation of cellulose has a positive effect on thermal stability, but only up to a certain content of filler. An innovative method for determining the formal thermodynamic parameters was presented, based on the Eyring equation and knowledge of E α = f (α) and A α = f (α) from the model-free method; it makes it possible to obtain the thermodynamic parameters as a function of the entire conversion range. Another innovative approach, based on the results from multi-step kinetic analysis, makes it possible to determine thermodynamic parameters for individual steps of a multi-step model and thus to compare the energy demand, spontaneity, and change in disorder of the system in the transition state for individual steps. Natural rubber Cellulose Thermodymanics Kinetics Pyrolysis Model-based method Full Text Additional Declarations The authors declare no competing interests. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7964541","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":535977895,"identity":"58ff8e2e-aecc-48b5-8c3c-8b92f8f9e328","order_by":0,"name":"Jana Dobrovská","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA6UlEQVRIiWNgGAWjYBACxgYQycaQAOXYMDBIkKgljbAWCEBoOUxYC3P72YMfGMps8szbe4w/zqg5nzh/dgPjxx/4HNaTlyzBcC6tWObMGTPJDcduJ264c4BZAp9NjA05BhKMbYcTZ0ikpTE+YLttbCCRwMZggE9L/xvjH1AtyR8f/DtnLD8jAeo1XFpm5JhBbUk+ILmx7YAcww2glgN4tbwxs0gA+kWC5/AxyZl9yXIGdw42Szbg0WLYn2N84wMwxCTYG5s/9nyz45Gf3XwQb4gZgsxDczkjPjsYGOTxyo6CUTAKRsEoAAEA8FdPiLqCi/IAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-8586-8356","institution":"Faculty of Materials Science and Technology, VSB – Technical University of Ostrava, Czech Republic","correspondingAuthor":true,"prefix":"","firstName":"Jana","middleName":"","lastName":"Dobrovská","suffix":""},{"id":535977896,"identity":"ff75ee95-6b95-4b0d-ba09-d3b34c388e95","order_by":1,"name":"Petra Skalková","email":"","orcid":"https://orcid.org/0000-0003-0571-2237","institution":"Faculty of Industrial Technologies, A. 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pyrolysis\u003c/strong\u003e\u003c/p\u003e","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"VSB-Technical University of Ostrava","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Natural rubber, Cellulose, Thermodymanics, Kinetics, Pyrolysis, Model-based method","lastPublishedDoi":"10.21203/rs.3.rs-7964541/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7964541/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eNatural rubber (NR) composites filled with graded amount of silanised cellulose (CELS) were prepared by melting and vulcanisation. Thermogravimetric (TG) curves at six heating rates (2 to 20\u0026deg;C/min) were measured. Kinetic parameters were determined by using the Friedman model-free method and model-based methods. The following were studied: i) the effect of cellulose silanization on the thermal stability of the composites, ii) the mechanism of pyrolytic decomposition of the composites, and iii) the effect of the content of silanized cellulose on the decomposition mechanism. It was found that the pyrolysis process follows an autocatalytic mechanism. The results also show that silanisation of cellulose has a positive effect on thermal stability, but only up to a certain content of filler.\u003c/p\u003e\u003cp\u003eAn innovative method for determining the formal thermodynamic parameters was presented, based on the Eyring equation and knowledge of \u003cem\u003eE\u003c/em\u003e\u003csub\u003eα\u003c/sub\u003e = \u003cem\u003ef\u003c/em\u003e(α) and \u003cem\u003eA\u003c/em\u003e\u003csub\u003eα\u003c/sub\u003e = \u003cem\u003ef\u003c/em\u003e(α) from the model-free method; it makes it possible to obtain the thermodynamic parameters as a function of the entire conversion range. Another innovative approach, based on the results from multi-step kinetic analysis, makes it possible to determine thermodynamic parameters for individual steps of a multi-step model and thus to compare the energy demand, spontaneity, and change in disorder of the system in the transition state for individual steps.\u003c/p\u003e","manuscriptTitle":"Thermodynamic and model-based kinetic analysis of natural rubber–silanised cellulose composites pyrolysis","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-29 10:39:04","doi":"10.21203/rs.3.rs-7964541/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"3b46e284-984d-451a-808f-0ab3829c61db","owner":[],"postedDate":"October 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-10-29T10:39:04+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-29 10:39:04","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7964541","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7964541","identity":"rs-7964541","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}