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This thesis work is devoted to the understanding of the structure-properties relationships of composite materials made from hybrid rovings composed of the thermoplastic matrix, polyphenylene sulphide, and reinforcements that can be either carbon or basalt. Thus, several lines of research have been pursued in this work: i) the impact of the commingling process on the final properties of composites, ii) the understanding of fiber-matrix interactions and iii) the optimization of those interactions in the interface. This work first demonstrated the link established between the mechanical and structural properties of the hybrid yarns and the mechanical properties of composite materials. The air commingling process degrades the resistance of the fibers and this is observed both on filaments tensile tests and commingled yarns. This degradation is not observed on twisted yarns. In the same time, composites based on commingled yarns show a better homogeneity, mechanical properties and a lower porosity rate. In a second step, the adhesion developped in all composite systems was evaluated at the micromechanical scale and correlated at the macroscopic scale. Accelerated ageing tests were also carried out to discriminate the most durable solutions. A final part of this work is devoted to the optimization of the interfacial properties of the systems studied. Two solutions were developed and gave interesting results: the use of a PPS / PE-EMA-GMA polymer mixture allowed to improve up to 56% the IFSS with basalt fibers and the use of an imidazolium salt as interfacial agent in the matrix allowed to improve by 25% the IFSS obtained with carbon fibers.; Ces travaux de thèse sont consacrés à la compréhension des relations structures-propriétés des matériaux composites réalisés à partir de mèches hybrides composées de la matrice thermoplastique, le polysulfure de phénylène et de renforts qui peuvent être soit du carbone soit du basalte. Plusieurs axes de recherche ont été approfondis dans ces travaux : i) l’impact des procédés de fabrication des mèches sur les propriétés finales des composites, ii) la compréhension des interactions fibres-matrice dans les systèmes étudiés et iii) l’optimisation de ces interactions à l’interphase. Ces travaux ont démontré le lien établi entre les propriétés mécaniques et structurelles des mèches hybrides et les propriétés finales des matériaux composites obtenus. Le procédé de comélage par air conditionne en partie les propriétés finales des composites en diminuant les propriétés mécaniques des fibres de renfort. Cette dégradation n’est pas observée pour le procédé de retordage. Dans le même temps, les composites obtenus par comélage sont de meilleure qualité en termes d’homogénéité, propriétés mécaniques et taux de porosité par rapport à ceux issus du procédé de retordage. Dans un second temps, l’adhérence de l’ensemble des systèmes étudiés a été évaluée à l’échelle micromécanique et corrélée à l’échelle macroscopique. Des essais de vieillissement accélérés ont également été conduits pour discriminer les solutions les plus durables. Une dernière partie de ces travaux est consacrée à l’optimisation des propriétés interfaciales des systèmes étudiés. Les deux voies explorées ont donné des résultats intéressants : l’utilisation d’un mélange polymère PPS / PE-EMA-GMA a permis d’améliorer jusqu’à 56 % l’IFSS avec les fibres de basalte et l’utilisation d’un sel imidazolium en tant qu’agent interfacial dans la matrice a permis d’améliorer de 25 % l’IFSS obtenu avec les fibres de carbone.

This thesis work is devoted to the understanding of the structure-properties relationships of composite materials made from hybrid rovings composed of the thermoplastic matrix, polyphenylene sulphide, and reinforcements that can be either carbon or basalt. Thus, several lines of research have been pursued in this work: i) the impact of the commingling process on the final properties of composites, ii) the understanding of fiber-matrix interactions and iii) the optimization of those interactions in the interface. This work first demonstrated the link established between the mechanical and structural properties of the hybrid yarns and the mechanical properties of composite materials. The air commingling process degrades the resistance of the fibers and this is observed both on filaments tensile tests and commingled yarns. This degradation is not observed on twisted yarns. In the same time, composites based on commingled yarns show a better homogeneity, mechanical properties and a lower porosity rate. In a second step, the adhesion developped in all composite systems was evaluated at the micromechanical scale and correlated at the macroscopic scale. Accelerated ageing tests were also carried out to discriminate the most durable solutions. A final part of this work is devoted to the optimization of the interfacial properties of the systems studied. Two solutions were developed and gave interesting results: the use of a PPS / PE-EMA-GMA polymer mixture allowed to improve up to 56% the IFSS with basalt fibers and the use of an imidazolium salt as interfacial agent in the matrix allowed to improve by 25% the IFSS obtained with carbon fibers., Ces travaux de thèse sont consacrés à la compréhension des relations structures-propriétés des matériaux composites réalisés à partir de mèches hybrides composées de la matrice thermoplastique, le polysulfure de phénylène et de renforts qui peuvent être soit du carbone soit du basalte. Plusieurs axes de recherche ont été approfondis dans ces travaux : i) l’impact des procédés de fabrication des mèches sur les propriétés finales des composites, ii) la compréhension des interactions fibres-matrice dans les systèmes étudiés et iii) l’optimisation de ces interactions à l’interphase. Ces travaux ont démontré le lien établi entre les propriétés mécaniques et structurelles des mèches hybrides et les propriétés finales des matériaux composites obtenus. Le procédé de comélage par air conditionne en partie les propriétés finales des composites en diminuant les propriétés mécaniques des fibres de renfort. Cette dégradation n’est pas observée pour le procédé de retordage. Dans le même temps, les composites obtenus par comélage sont de meilleure qualité en termes d’homogénéité, propriétés mécaniques et taux de porosité par rapport à ceux issus du procédé de retordage. Dans un second temps, l’adhérence de l’ensemble des systèmes étudiés a été évaluée à l’échelle micromécanique et corrélée à l’échelle macroscopique. Des essais de vieillissement accélérés ont également été conduits pour discriminer les solutions les plus durables. Une dernière partie de ces travaux est consacrée à l’optimisation des propriétés interfaciales des systèmes étudiés. Les deux voies explorées ont donné des résultats intéressants : l’utilisation d’un mélange polymère PPS / PE-EMA-GMA a permis d’améliorer jusqu’à 56 % l’IFSS avec les fibres de basalte et l’utilisation d’un sel imidazolium en tant qu’agent interfacial dans la matrice a permis d’améliorer de 25 % l’IFSS obtenu avec les fibres de carbone.

金沢大学ナノマテリアル研究所 / 金沢大学理工研究域生命理工学系, Lignin is a renewable resource, but it is also considered a waste or a very-low-value material. Herein, we propose a lignin-derived compatibilizing agent as an alternative to the current compatibilizing agents. We prepared a polypropylene-based carbon fiber-reinforced plastic (CFRP) with butylated lignin (C4 lignin). Upon the addition of C4 lignin, the dispersion of carbon fiber into the matrix, and the adhesion between the carbon fiber and the matrix were greatly improved. As a result, the tensile strength of the CFRP prepared with C4 lignin was greater than that of the CFRP without lignan lignin (37.1 compared to 40.2 MPa). This value is close to that of CFRPs prepared with maleic anhydride-modified polypropylene (40.9 MPa), an existing compatibilizing agent. C4 lignin is a promising candidate for biomass-derived compatibilizing agents for polypropylene-based CFRPs., Embargo Period 6 months, This paper has supplementary information.

金沢大学ナノマテリアル研究所 / 金沢大学理工研究域生命理工学系, As an alternative to petroleum-based compatibilizing agents, we developed lignin derivatives for compatibilizing agents of carbon fiber-reinforced plastics that have thermoplasticity. In this study, alkyl chains were introduced into alkali lignin at various ratios to optimize the compatibility of the lignin derivatives with both polypropylene and carbon fiber. The interfacial shear strength between the two materials was improved from 8.2 to 17.2 MPa by mixing with the optimized lignin derivative. The value is comparable to that achieved with a typical petroleum-based compatibilizing agent (18.3 MPa)., Embargo Period 6 months, This paper has supplementary information.

RESUMO O crescente desperdício de materiais plásticos no meio ambiente juntamente com a preocupação com a futura escassez do petróleo tem aumentado o interesse por polímeros biodegradáveis, como o amido. Nos últimos anos, o amido tem sido utilizado em misturas com diferentes polímeros sintéticos. Essas misturas têm sido compatibilizadas por meio do uso de agentes compatibilizantes do tipo copolímeros. O presente trabalho tem como objetivo avaliar a influência da adição do copolímero graftizado (PP-g-MA) nas propriedades mecânicas, térmicas e morfológicas de misturas de polipropileno (PP) e amido termoplástico (TPS). O TPS foi obtido em uma extrusora monorosca com 20 % (m/m) de glicerol, usado como plastificante. Posteriormente, misturas PP/TPS 80:20 % (m/m) foram processadas em uma extrusora de rosca dupla corotacional, na presença de 3, 5 e 7% (m/m) do PP-g-MA. A morfologia das misturas foi avaliada através de microscopia eletrônica de varredura. Os resultados mostraram uma redução significativa da fase dispersa de amido, com a adição do compatibilizante. As misturas processadas em presença do PP-g-MA apresentaram uma distribuição mais homogênea da fase de amido na matriz de PP. Os resultados dos ensaios de resistência à tração mostraram que o módulo do PP sofre um ligeiro aumento, com a adição do amido e do compatibilizante. A resistência das misturas no ponto de escoamento apresentou valores similares aos do PP. Apesar disso, a deformação na ruptura diminui drasticamente com a incorporação do amido. A adição de amido ao polipropileno, entretanto, aumenta significativamente a resistência ao impacto do polímero sintético. Com a adição de PP-g-MA à mistura PP/TPS, a resistência ao impacto sofre uma queda, que pode ser atribuída a redução da fase de amido na mistura. A estabilidade térmica das misturas PP/TPS sofre um ligeiro aumento com a incorporação do agente compatibilizante. Os materiais obtidos podem ser utilizados em substituição ao PP. ABSTRACT The growing waste of plastics in the environment coupled with concerns about future oil shortages has increased interest in biodegradable polymers such as starch. In recent years, starch has been used in blends with different synthetic polymers. Such blends have been compatibilized by the use of compatibilizing agents of the copolymer type. In this study, the morphological, mechanical and thermal properties of polypropylene (PP)/thermoplastic starch (TPS) blends obtained in the presence of the compatibilizing agent (PP-g-MA) were evaluated. The thermoplastic starch was obtained in a single screw extruder with 20% (mass/mass) of glycerol used as plasticizer. PP/TPS blends were prepared by melt mixing in a co-rotating twin-screw extruder. The concentration of the compatibilizing agent was 3, 5 and 7% (mass/mass). The morphology of the blends was evaluated by scanning electron microscopy. The results showed a significant reduction of the dispersed starch phase with the addition of the PP-g-MA. The blends obtained in the presence of PP-g-MA showed a more homogeneous distribution of the starch phase in the PP matrix. The results obtained with the tensile tests showed that the elastic modulus of PP undergoes a slight increase with the addition of the starch and the compatibilizer. The tensile strength of the PP was not significantly affected. However, there was a significant decrease of the elongation at break with the incorporation of starch. The starch incorporated in the PP matrix led to a significant increase in the impact strength of the final material. However, with the addition of PP-g-MA to the PP/TPS blend, the impact strength falls. This result can be attributed to the reduction of the starch phase in the PP matrix. The thermal stability of the PP/TPS blends was slightly increased with the incorporation of the compatibilizing agent. The materials obtained can be used instead of PP.

Maleic anhydride (MA) grafted with poly(trimethylene terephthalate) (PTT)&mdash, abbreviated as PTT-g-MA&mdash, can be used as a compatibilizing agent to improve the compatibility and dispersion of nanofillers and a dispersed polymer phase into PTT matrix. This work suggests the preparation of PTT-g-MA using a mixture of PTT, MA, and benzoyl peroxide (BPO) by a reactive extrusion process. PTT-g-MA was characterized to confirm the grafting reaction of maleic anhydride on PTT chains by Fourier transform infrared (FTIR) spectroscopy. Thermal properties (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)) and rheological analysis (parallel plates rheology) were used to prove the changes that occurred after the graphitization reaction. The reactive processing route allowed the production of the compatibilizing agent (PTT-g-MA) with good thermal properties and with lower viscosity compared to neat PTT, and this could be an alternative for the compatibilization of polymer blends, as example for PTT/ABS (acrylonitrile butadiene styrene) blends and nanocomposites based on PTT matrix.

Polipropileno (PP) ha sido funcionalizado en solución mediante injerto de monometil itaconato (MMI) usando xileno y decalina como solventes y 2,5-dimetil- 2,5-bis(ter-butilperoxi)hexano (Lup. 101) como iniciador radical. La existencia de injerto de MMI en PP fue confirmada mediante espectroscopia FT-IR. La presencia de bandas de absorción en la zona de grupos carbonilos provenientes de MMI muestran que el PP esta funcionalizado. Estas bandas de absorción están ausentes en el espectro de FT-IR del PP sin modificar. La extensión de injerto de MMI fue evaluada tanto mediante retrotitulación volumétrica de los grupos carboxilos como también por análisis FT-IR, donde para éste último se utilizó una curva de calibración. Para ambos casos la cantidad de monómero incorporado en las cadenas del PP fue expresada como porcentaje de injerto. Se realizó un estudio sistemático de las variables más importantes de reacción sobre el porcentaje de injerto. Este estudio permitió optimizar el proceso de funcionalización obteniendo un valor máximo cercano a 0,4% de injerto cuando xileno fue utilizado como solvente. Al usar decalina, se obtuvieron menores porcentajes de injerto. Se encontró que la extensión del injerto depende de la concentración inicial de monómero y de iniciador así como también del tiempo y la temperatura de reacción. Se observó la ciclación parcial del monómero durante la reacción de injerto. Esto fue atribuido al uso del peróxido orgánico como iniciador. El peso molecular del PP injertado disminuye con el aumento de la concentración inicial del peróxido utilizado como iniciador. Esto fue evaluado mediante determinación de valores del índice de fluencia (MFI) (masa de polímero fundido que tarda de fluir a través de un tubo capilar durante un determinado tiempo) de muestras de PP funcionalizado bajo diferentes condiciones de reacción Polypropylene (PP) was functionalized in solution by grafting with monomethyl itaconate (MMI) by using xylene and decalin as solvents and 2,5-dimethyl-2,5-bis(tert-buthylperoxy)hexane (Lup. 101) as radical initiator. The existence of grafted MMI in PP was confirmed by FT-IR spectroscopy. Carbonyl absorption bands from MMI was observed in the FT-IR spectrum of the functionalized polypropylene. These absorption bands are absent in the FT-IR spectrum of the unmodified polypropylene. The percentage of grafted MMI was estimated by volumetric titration as well as FT-IR analysis. The amount of monomer incorporated in polypropylene by the latter method was determined from a FT-IR calibration curve established for this monomer. A systematic study of the reaction variables allowed the optimisation of the grafting process where a maximum of nearly 0.4% of grafting was achieved when xylene was used as solvent. When decalin was used as solvent, the percentage of grafting attained was lower. It was found that the percentage of grafting depends on the initial concentration of monomer and initiator as well as reaction time and reaction temperature. The grafted MMI was partially cyclized during the grafting reaction. This was attributed to the presence of the organic peroxide used as initiator for grafting reactions. It was also found that the molecular weight of the grafted polymer decreased with increasing initial concentration of the peroxide as was estimated by measuring the melt flow index (MFI) of modified polypropylene samples