Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos

Detalhes bibliográficos
Ano de defesa: 2025
Autor(a) principal: Lopes, Henrique Solowej Medeiros
Orientador(a): Menezes, Aparecido Junior de lattes
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal de São Carlos
Câmpus Sorocaba
Programa de Pós-Graduação: Programa de Pós-Graduação em Ciência dos Materiais - PPGCM-So
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: https://hdl.handle.net/20.500.14289/22019
Resumo: Within the context of materials engineering, starch stands out as a sustainable source for the production of biofilms, due to its biodegradability and its renewable source of high produc-tion in several different climates and regions. However, pure starch materials have insuffi-cient properties for their wide application in industry and commerce, and hydroxypropyla-tion is a sustainable way to reduce the hydrophilic and fragile character of the material. In this study, cassava starch and açaí residue were chemically modified by hydroxypropylation. The combination of parameters for sample preparation was performed by a design of exper-iments 2³ full factorial. The substrates were previously activated with KOH in water and ethanol solution, modified in different molar ratios (0.4, 0.6 and 0.8 OHPO/OHglucose), tem-peratures (115, 125 and 135 °C) and açaí residue proportions (0, 5 and 10 wt%). The effects of each defined parameter were evaluated by analysis of variance (ANOVA), revealing that the molar ratio and the higher amount of açaí residue significantly increased the mass gain, while the temperature had the opposite effect. The structural characterization by FTIR and solid-state NMR confirmed the chemical modification through the identification of methyl bond peaks, with quantification of the degree of substitution by elemental analysis and sol-id-state NMR, varying between 0.1 and 0.4, as the molar ratio increases and the temperature decreases. Notably, complete gelatinization of starch was observed during the reaction, evi-denced by the absence of crystalline structures in XRD and SEM. However, homopolymeri-zation of propylene oxide (PPO) has been observed, resulting in the intermolecular presence of PPO in the polymer chains, significantly increasing the plasticization of the material. This plasticization can be observed by TG and DSC, which indicate a reduction in thermal stability, in addition to accelerated retrogradation with the formation of short- and long-range crystalline structures via XRD and FTIR, especially in samples containing açaí resi-due. Due to the previous plasticization of starch, films were obtained via casting at room temperature with significant lower amount of glycerol (7.5% starch weigh basis), resulting in materials with 470% high elongation at break, although with lower maximum tensile strength stress, greater hydrophilicity and tendency to retrogradation. The results demon-strate the potential of chemical modification of starch to expand its applications in sustaina-ble packaging, due to the success in the low use of synthetic plasticizers achieved.
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spelling Lopes, Henrique Solowej MedeirosMenezes, Aparecido Junior dehttp://lattes.cnpq.br/0484426340349483Komatsu, Danielhttp://lattes.cnpq.br/2620060426867863Dufresne, Alainhttp://lattes.cnpq.br/2836712749450886https://lattes.cnpq.br/5006391678583766orcid.org/0000-0002-8222-08882025-05-07T13:57:37Z2025-03-26LOPES, Henrique Solowej Medeiros. Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos. 2025. Tese (Doutorado em Ciência dos Materiais) – Universidade Federal de São Carlos, Sorocaba, 2025. Disponível em: https://repositorio.ufscar.br/handle/20.500.14289/22019.https://hdl.handle.net/20.500.14289/22019Within the context of materials engineering, starch stands out as a sustainable source for the production of biofilms, due to its biodegradability and its renewable source of high produc-tion in several different climates and regions. However, pure starch materials have insuffi-cient properties for their wide application in industry and commerce, and hydroxypropyla-tion is a sustainable way to reduce the hydrophilic and fragile character of the material. In this study, cassava starch and açaí residue were chemically modified by hydroxypropylation. The combination of parameters for sample preparation was performed by a design of exper-iments 2³ full factorial. The substrates were previously activated with KOH in water and ethanol solution, modified in different molar ratios (0.4, 0.6 and 0.8 OHPO/OHglucose), tem-peratures (115, 125 and 135 °C) and açaí residue proportions (0, 5 and 10 wt%). The effects of each defined parameter were evaluated by analysis of variance (ANOVA), revealing that the molar ratio and the higher amount of açaí residue significantly increased the mass gain, while the temperature had the opposite effect. The structural characterization by FTIR and solid-state NMR confirmed the chemical modification through the identification of methyl bond peaks, with quantification of the degree of substitution by elemental analysis and sol-id-state NMR, varying between 0.1 and 0.4, as the molar ratio increases and the temperature decreases. Notably, complete gelatinization of starch was observed during the reaction, evi-denced by the absence of crystalline structures in XRD and SEM. However, homopolymeri-zation of propylene oxide (PPO) has been observed, resulting in the intermolecular presence of PPO in the polymer chains, significantly increasing the plasticization of the material. This plasticization can be observed by TG and DSC, which indicate a reduction in thermal stability, in addition to accelerated retrogradation with the formation of short- and long-range crystalline structures via XRD and FTIR, especially in samples containing açaí resi-due. Due to the previous plasticization of starch, films were obtained via casting at room temperature with significant lower amount of glycerol (7.5% starch weigh basis), resulting in materials with 470% high elongation at break, although with lower maximum tensile strength stress, greater hydrophilicity and tendency to retrogradation. The results demon-strate the potential of chemical modification of starch to expand its applications in sustaina-ble packaging, due to the success in the low use of synthetic plasticizers achieved.Dentro do contexto de engenharia de materiais, o amido se destaca como uma fonte susten-tável para a produção de biofilmes, devido à sua biodegradabilidade e sua fonte renovável de alta produção em diversos climas e regiões diferentes. Entretanto, materiais de amido puro apresentam propriedades insuficientes para sua ampla aplicação na indústria e comércio, sendo a hidroxipropilação uma saída sustentável para diminuição do caráter hidrofílico e frágil do material. Neste estudo, amido de mandioca e resíduo de açaí foram quimicamente modificados por hidroxipropilação. A combinação de parâmetros para preparação das amos-tras foi realizada por um planejamento de experimentos do tipo fatorial completo 2³. Os substratos foram previamente ativados com KOH em solução de água e etanol, modificadas em diferentes razões molares (0,4, 0,6 e 0,8 OHOP/OHglicose), temperaturas (115, 125 e 135 °C) e proporções de resíduo de açaí (0, 5 e 10% em massa total). Os efeitos de cada parâme-tro definido foram avaliados por análise de variância (ANOVA), revelando que a razão mo-lar e a maior quantidade de resíduo de açaí aumentaram significativamente o ganho de mas-sa, enquanto a temperatura teve efeito inverso. A caracterização estrutural por FTIR e RMN no estado sólido confirmaram a modificação química por meio da identificação de picos de ligação metil, com quantificação do grau de substituição por análise elementar e RMN no estado sólido, variando entre 0,1 e 0,4, conforme aumenta-se a razão molar e diminui-se a temperatura. Notavelmente, observou-se a completa gelatinização do amido durante a rea-ção, evidenciada pela ausência de estruturas cristalinas em DRX e MEV. No entanto, a ho-mopolimerização do óxido de propileno (POP) foi observada, resultando na presença inter-molecular de poli(óxido de propileno) nas cadeias poliméricas, aumentando significativa-mente a plastificação do material. Essa plastificação pode ser observada por TG e DSC, que indicam redução da estabilidade térmica, além de retrogradação acelerada com formação de estruturas cristalinas de curto e longo alcance via DRX e FTIR, especialmente nas amostras contendo resíduo de açaí. Devido à plastificação prévia do amido, filmes foram obtidos via casting em temperatura ambiente com significativa menor quantidade de glicerol (7,5% em relação a massa de amido), resultando em um aumento de até 470% na elongação na ruptura, embora com menor tensão máxima de resistência à tração, maior hidrofilicidade e tendência à retrogradação. Os resultados demonstram o potencial da modificação química do amido para ampliar suas aplicações em embalagens sustentáveis, devido ao sucesso no baixo uso de plastificantes sintéticos atingido.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)2022/11062-6porUniversidade Federal de São CarlosCâmpus SorocabaPrograma de Pós-Graduação em Ciência dos Materiais - PPGCM-SoUFSCarhttp://dx.doi.org/10.1021/acsomega.5c00246Attribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessAmidoAçaíHidroxipropilaçãoBiocompósitosStarchHydroxypropylationBiocompositesENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA::MATERIAIS NAO METALICOS::POLIMEROS, APLICACOESHidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitosHydroxypropylation of starch and fibers from açaí residue for biocomposites obtentioninfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARTEXTTese_vFINAL.pdf.txtTese_vFINAL.pdf.txtExtracted texttext/plain103033https://repositorio.ufscar.br/bitstreams/ae01744e-cdf7-465e-b632-87a4e9903180/download6045ee7bce587d4a1be15a9e42345021MD53falseAnonymousREADTHUMBNAILTese_vFINAL.pdf.jpgTese_vFINAL.pdf.jpgGenerated Thumbnailimage/jpeg3649https://repositorio.ufscar.br/bitstreams/709e0315-5642-4fc7-bc8c-29f306284525/download302d601943c2a8aa1f700aa786455675MD54falseAnonymousREADORIGINALTese_vFINAL.pdfTese_vFINAL.pdfapplication/pdf7114586https://repositorio.ufscar.br/bitstreams/d75c1815-0165-4a02-a92a-0de9a3f7f878/download90e4fd798f67b5ae02f42ca8cf01899aMD51trueAnonymousREADCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8905https://repositorio.ufscar.br/bitstreams/3f6d40a9-6fcb-450d-97b7-13c119d4e74e/download57e258e544f104f04afb1d5e5b4e53c0MD52falseAnonymousREAD20.500.14289/220192025-05-08 15:05:53.72http://creativecommons.org/licenses/by-nc-nd/3.0/br/Attribution-NonCommercial-NoDerivs 3.0 Brazilopen.accessoai:repositorio.ufscar.br:20.500.14289/22019https://repositorio.ufscar.brRepositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestrepositorio.sibi@ufscar.bropendoar:43222025-05-08T18:05:53Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
dc.title.alternative.eng.fl_str_mv Hydroxypropylation of starch and fibers from açaí residue for biocomposites obtention
title Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
spellingShingle Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
Lopes, Henrique Solowej Medeiros
Amido
Açaí
Hidroxipropilação
Biocompósitos
Starch
Hydroxypropylation
Biocomposites
ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA::MATERIAIS NAO METALICOS::POLIMEROS, APLICACOES
title_short Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
title_full Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
title_fullStr Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
title_full_unstemmed Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
title_sort Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos
author Lopes, Henrique Solowej Medeiros
author_facet Lopes, Henrique Solowej Medeiros
author_role author
dc.contributor.authorlattes.none.fl_str_mv https://lattes.cnpq.br/5006391678583766
dc.contributor.authororcid.none.fl_str_mv orcid.org/0000-0002-8222-0888
dc.contributor.author.fl_str_mv Lopes, Henrique Solowej Medeiros
dc.contributor.advisor1.fl_str_mv Menezes, Aparecido Junior de
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/0484426340349483
dc.contributor.advisor-co1.fl_str_mv Komatsu, Daniel
dc.contributor.advisor-co1Lattes.fl_str_mv http://lattes.cnpq.br/2620060426867863
dc.contributor.advisor-co2.fl_str_mv Dufresne, Alain
dc.contributor.advisor-co2Lattes.fl_str_mv http://lattes.cnpq.br/2836712749450886
contributor_str_mv Menezes, Aparecido Junior de
Komatsu, Daniel
Dufresne, Alain
dc.subject.por.fl_str_mv Amido
Açaí
Hidroxipropilação
Biocompósitos
topic Amido
Açaí
Hidroxipropilação
Biocompósitos
Starch
Hydroxypropylation
Biocomposites
ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA::MATERIAIS NAO METALICOS::POLIMEROS, APLICACOES
dc.subject.eng.fl_str_mv Starch
Hydroxypropylation
Biocomposites
dc.subject.cnpq.fl_str_mv ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA::MATERIAIS NAO METALICOS::POLIMEROS, APLICACOES
description Within the context of materials engineering, starch stands out as a sustainable source for the production of biofilms, due to its biodegradability and its renewable source of high produc-tion in several different climates and regions. However, pure starch materials have insuffi-cient properties for their wide application in industry and commerce, and hydroxypropyla-tion is a sustainable way to reduce the hydrophilic and fragile character of the material. In this study, cassava starch and açaí residue were chemically modified by hydroxypropylation. The combination of parameters for sample preparation was performed by a design of exper-iments 2³ full factorial. The substrates were previously activated with KOH in water and ethanol solution, modified in different molar ratios (0.4, 0.6 and 0.8 OHPO/OHglucose), tem-peratures (115, 125 and 135 °C) and açaí residue proportions (0, 5 and 10 wt%). The effects of each defined parameter were evaluated by analysis of variance (ANOVA), revealing that the molar ratio and the higher amount of açaí residue significantly increased the mass gain, while the temperature had the opposite effect. The structural characterization by FTIR and solid-state NMR confirmed the chemical modification through the identification of methyl bond peaks, with quantification of the degree of substitution by elemental analysis and sol-id-state NMR, varying between 0.1 and 0.4, as the molar ratio increases and the temperature decreases. Notably, complete gelatinization of starch was observed during the reaction, evi-denced by the absence of crystalline structures in XRD and SEM. However, homopolymeri-zation of propylene oxide (PPO) has been observed, resulting in the intermolecular presence of PPO in the polymer chains, significantly increasing the plasticization of the material. This plasticization can be observed by TG and DSC, which indicate a reduction in thermal stability, in addition to accelerated retrogradation with the formation of short- and long-range crystalline structures via XRD and FTIR, especially in samples containing açaí resi-due. Due to the previous plasticization of starch, films were obtained via casting at room temperature with significant lower amount of glycerol (7.5% starch weigh basis), resulting in materials with 470% high elongation at break, although with lower maximum tensile strength stress, greater hydrophilicity and tendency to retrogradation. The results demon-strate the potential of chemical modification of starch to expand its applications in sustaina-ble packaging, due to the success in the low use of synthetic plasticizers achieved.
publishDate 2025
dc.date.accessioned.fl_str_mv 2025-05-07T13:57:37Z
dc.date.issued.fl_str_mv 2025-03-26
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dc.identifier.citation.fl_str_mv LOPES, Henrique Solowej Medeiros. Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos. 2025. Tese (Doutorado em Ciência dos Materiais) – Universidade Federal de São Carlos, Sorocaba, 2025. Disponível em: https://repositorio.ufscar.br/handle/20.500.14289/22019.
dc.identifier.uri.fl_str_mv https://hdl.handle.net/20.500.14289/22019
identifier_str_mv LOPES, Henrique Solowej Medeiros. Hidroxipropilação de amido e fibras de resíduo de açaí para obtenção de biocompósitos. 2025. Tese (Doutorado em Ciência dos Materiais) – Universidade Federal de São Carlos, Sorocaba, 2025. Disponível em: https://repositorio.ufscar.br/handle/20.500.14289/22019.
url https://hdl.handle.net/20.500.14289/22019
dc.language.iso.fl_str_mv por
language por
dc.relation.uri.none.fl_str_mv http://dx.doi.org/10.1021/acsomega.5c00246
dc.rights.driver.fl_str_mv Attribution-NonCommercial-NoDerivs 3.0 Brazil
http://creativecommons.org/licenses/by-nc-nd/3.0/br/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivs 3.0 Brazil
http://creativecommons.org/licenses/by-nc-nd/3.0/br/
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Universidade Federal de São Carlos
Câmpus Sorocaba
dc.publisher.program.fl_str_mv Programa de Pós-Graduação em Ciência dos Materiais - PPGCM-So
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