Improvement of mechanical and thermal properties of poly(3-hydroxybutyrate) (PHB) blends with surface-modified halloysite nanotubes (HNT)

[EN] The effect of two hydrophobic treatments on the hydrophilic nature of halloysite nanotubes (HNT) was studied in this research work: a silanization with (3-glycidyloxypropyl) trimethoxysilane (GLYMO) and a surface treatment with a natural aromatic compound, i.e. caffeic acid (CA). In addition, the effect of 3¿wt% of unmodified HNT, silanized HNT (HNTSIL) and caffeic acid-modified HNT (HNTCA) on mechanical, thermal and morphological properties of a binary blend of poly(3-hydroxybutyrate) (PHB) and poly(¿-caprolactone) (PCL) with a weight ratio of 75/25, respectively was evaluated. These blends and their corresponding composites with HNT were partially compatibilized by reactive extrusion with dicumyl peroxide (DCP) and further processed by injection molding. The effectiveness of the surface treatments on HNT was followed by Fourier transformed infrared spectroscopy (FTIT), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and contact angle measurements. The obtained results suggested a clear hydrophobizing effect of both surface treatments on HNT but the hydrophobic nature the caffeic acid treatment can provide to HNT is greater than silanization. FESEM study on HNT-loaded PHB/PCL blends showed increased compatibility between modified-HNT and the polymeric matrix, as well as a better particle dispersion. In particular, 3¿wt% HNTCA lead to an increase in tensile strength and elongation at break of 11.4% and 74%, respectively, with regard to composites with unmodified HNT. In addition, thermal analysis, evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), revealed a decrease in the melt peak temperature of 6.5¿°C for composites with 3¿wt% HNTCA as well a delay in the onset degradation temperature, thus leading to a broader processing window which enhances PHB processing by conventional techniques.This work was supported by the Ministry of Economy and Competitiveness (MINECO) [MAT2017-84909-C2-2-R]. D. Garcia-Garcia wants to thank the Spanish Ministry of Education, Culture and Sports for the financial support through a FPU grant [FPU13/06011].Garcia-Garcia, D.; Garcia-Sanoguera, D.; Fombuena, V.; López-Martínez, J.; Balart, R. (2018). Improvement of mechanical and thermal properties of poly(3-hydroxybutyrate) (PHB) blends with surface-modified halloysite nanotubes (HNT). Applied Clay Science. 162:487-498. https://doi.org/10.1016/j.clay.2018.06.042S48749816

Application of antimicrobial microcapsules on agrotextiles

[EN] The aim of this work was to develop a functional biodegradable nonwoven with antimicrobial microcapsules maintaining the stability and biodegradability of the nonwoven for use in agriculture applications. The nonwoven was obtained using hemp fibers by Wetlaid technology. Microcapsules were prepared by co-extrusion/gelling method with alginate as shell and oregano oil as core material. The microcapsules were developed to protect and control release of oregano oil. Microcapsules were incorporated on the nonwoven by coating method using a natural polymer as a graft material. After incorporating microcapsules, the nonwoven was subjected to several tests in order to determinate the microcapsules fixation and their functionality. The nonwovens were characterized for their antimicrobial activity against different kinds of bacteria and fungi. Nonwoven loaded with microcapsules was found to show good antimicrobial activity in comparison with nonwoven that was not loaded with microcapsules.The authors thank IVACE (Institut Valencià de Competitivitat Empresarial, Spain) and FEDER (Fondo Europeo de Desarrollo Regional, Europe) for the financial support.Ferrándiz, M.; Capablanca, L.; Garcia-Sanoguera, D.; Bonet-Aracil, M. (2017). Application of antimicrobial microcapsules on agrotextiles. Journal of Agricultural Chemistry and Environment. 6(1):62-82. doi:10.4236/jacen.2017.61004S62826

Development and characterization of environmentally friendly composites from poly(butylene succinate) (PBS) and almond shell flour with different compatibilizers

[EN] This work reports the enhancement of the properties of poly (butylene succinate) (PBS) composites containing 30 wt% almond shell flour (ASF) by using different compatibilizer families: epoxy, maleic anhydride and acrylic. With regard to the epoxy compatibilizers, epoxidized linseed oil (ELO) and epoxidized soybean oil (ESBO) were used. Two maleic anhydride-derived compatibilizers, namely, maleinized linseed oil (MLO) and dodecenyl succinic anhydride (DDSA) were used. Finally, two acrylic monomers, namely methyl methacrylate (MMA) and acrylic acid (AA) were employed. Uncompatibilized and compatibilized PBS/ASF composites were characterized in terms of their mechanical properties, morphology, thermal behaviour and thermomechanical performance. The obtained results suggest that all three vegetable oil-derived compatibilizers (ELO, ESBO and MLO) give a remarkable increase in ductile properties while poor compatibilization is obtained with the acrylic monomers. These vegetable-oil derived compatibilizers could represents an interesting environmentally friendly solution to compatibilizing polyester-type polymers and their composites with lignocellulosic materials.This work was supported by the Ministry of Economy and Competitiveness (MINECO) grant numbers MAT2014-59242-C2-1-R and MAT2017-84909-C2-2-R. L. Quiles-Carrillo acknowledges Generalitat Valenciana (GV) for financial support through a FPI grant (ACIF/2016/182) and the Spanish Ministry of Education, Culture, and Sports (MECD) for his FPU grant (FPU15/03812).Liminana, P.; Garcia-Sanoguera, D.; Quiles-Carrillo, L.; Balart, R.; Montanes, N. (2018). Development and characterization of environmentally friendly composites from poly(butylene succinate) (PBS) and almond shell flour with different compatibilizers. Composites Part B Engineering. 144:153-162. https://doi.org/10.1016/j.compositesb.2018.02.031S15316214

Manufacturing and Characterization of Environmentally Friendly Wood Plastic Composites Using Pinecone as a Filler into a Bio-Based High-Density Polyethylene Matrix

[EN] The use of wood plastic composites (WPC) is growing very rapidly in recent years, in addition, the use of plastics of renewable origin is increasingly implemented because it allows to reduce the carbon footprint. In this context, this work reports on the development of composites of bio-based high density polyethylene (BioHDPE) with different contents of pinecone (5, 10, and 30 wt.%). The blends were produced by extrusion and injection-molded processes. With the objective of improving the properties of the materials, a compatibilizer has been used, namely polyethylene grafted with maleic anhydride (PE-g-MA 2 phr). The effect of the compatibilizer in the blend with 5 wt.% has been compared with the same blend without compatibilization. Mechanical, thermal, morphological, colorimetric, and wettability properties have been analyzed for each blend. The results showed that the compatibilizer improved the filler¿matrix interaction, increasing the ductile mechanical properties in terms of elongation and tensile strength. Regarding thermal properties, the compatibilizer increased thermal stability and improved the behavior of the materials against moisture. In general, the pinecone materials obtained exhibited reddish-brown colors, allowing their use as wood plastic composites with a wide range of properties depending on the filler content in the blend.Project with grant number PID2020-116496RB-C22 funded by the Ministry of Science and Innovation MCIN/AEI/10.13039/501100011033 and grant number AICO/2021/025 funded by Generalitat Valenciana.Morcillo, MDC.; Tejada, R.; Lascano-Aimacaña, DS.; Garcia-Garcia, D.; Garcia-Sanoguera, D. (2021). Manufacturing and Characterization of Environmentally Friendly Wood Plastic Composites Using Pinecone as a Filler into a Bio-Based High-Density Polyethylene Matrix. Polymers. 13(24):1-16. https://doi.org/10.3390/polym13244462S116132

Valorization of Linen Processing By-Products for the Development of Injection-Molded Green Composite Pieces of Polylactide with Improved Performance

[EN] This work reports the development and characterization of green composites based on polylactide (PLA) containing fillers and additives obtained from by-products or waste-streams from the linen processing industry. Flaxseed flour (FSF) was first produced by the mechanical milling of golden flaxseeds. The resultant FSF particles were melt-compounded at 30 wt% with PLA in a twin-screw extruder. Two multi-functionalized oils derived from linseed, namely epoxidized linseed oil (ELO) and maleinized linseed oil (MLO), were also incorporated during melt mixing at 2.5 and 5 parts per hundred resin (phr) of composite. The melt-compounded pellets were thereafter shaped into pieces by injection molding and characterized. Results showed that the addition of both multi-functionalized linseed oils successfully increased ductility, toughness, and thermal stability of the green composite pieces whereas water diffusion was reduced. The improvement achieved was related to both a plasticizing effect and, more interestingly, an enhancement of the interfacial adhesion between the biopolymer and the lignocellulosic particles by the reactive vegetable oils. The most optimal performance was attained for the MLO-containing green composite pieces, even at the lowest content, which was ascribed to the higher solubility of MLO with the PLA matrix. Therefore, the present study demonstrates the potential use of by-products or waste from flax (Linum usitatissimum L.) to obtain renewable raw materials of suitable quality to develop green composites with high performance for market applications such as rigid food packaging and food-contact disposable articles in the frame of the Circular Economy and Bioeconomy.This research work was funded by the Spanish Ministry of Science, Innovation, and Universities (MICIU) project numbers RTI2018-097249-B-C21 and MAT2017-84909-C2-2-R.Agüero, Á.; Lascano-Aimacaña, DS.; Garcia-Sanoguera, D.; Fenollar, O.; Torres Giner, S. (2020). Valorization of Linen Processing By-Products for the Development of Injection-Molded Green Composite Pieces of Polylactide with Improved Performance. Sustainability. 12(2):1-24. https://doi.org/10.3390/su12020652S124122Fritsch, C., Staebler, A., Happel, A., Cubero Márquez, M., Aguiló-Aguayo, I., Abadias, M., … Belotti, G. (2017). 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A., Massoumi, I., & Hassan, A. (2010). Comparison of Polylactic Acid/Kenaf and Polylactic Acid/Rise Husk Composites: The Influence of the Natural Fibers on the Mechanical, Thermal and Biodegradability Properties. Journal of Polymers and the Environment, 18(3), 422-429. doi:10.1007/s10924-010-0185-0Quiles-Carrillo, L., Montanes, N., Garcia-Garcia, D., Carbonell-Verdu, A., Balart, R., & Torres-Giner, S. (2018). Effect of different compatibilizers on injection-molded green composite pieces based on polylactide filled with almond shell flour. Composites Part B: Engineering, 147, 76-85. doi:10.1016/j.compositesb.2018.04.017Montava-Jordà, S., Quiles-Carrillo, L., Richart, N., Torres-Giner, S., & Montanes, N. (2019). Enhanced Interfacial Adhesion of Polylactide/Poly(ε-caprolactone)/Walnut Shell Flour Composites by Reactive Extrusion with Maleinized Linseed Oil. Polymers, 11(5), 758. doi:10.3390/polym11050758Garcia-Garcia, D., Carbonell-Verdu, A., Jordá-Vilaplana, A., Balart, R., & Garcia-Sanoguera, D. (2016). Development and characterization of green composites from bio-based polyethylene and peanut shell. Journal of Applied Polymer Science, 133(37). doi:10.1002/app.43940Torres-Giner, S., Hilliou, L., Melendez-Rodriguez, B., Figueroa-Lopez, K. J., Madalena, D., Cabedo, L., … Lagaron, J. M. (2018). Melt processability, characterization, and antibacterial activity of compression-molded green composite sheets made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) reinforced with coconut fibers impregnated with oregano essential oil. Food Packaging and Shelf Life, 17, 39-49. doi:10.1016/j.fpsl.2018.05.002Quiles-Carrillo, L., Montanes, N., Lagaron, J. M., Balart, R., & Torres-Giner, S. (2018). 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Maleated coupling agents for natural fibre composites. Composites Part A: Applied Science and Manufacturing, 35(3), 357-362. doi:10.1016/j.compositesa.2003.09.014Yang, H.-S., Wolcott, M. P., Kim, H.-S., Kim, S., & Kim, H.-J. (2007). Effect of different compatibilizing agents on the mechanical properties of lignocellulosic material filled polyethylene bio-composites. Composite Structures, 79(3), 369-375. doi:10.1016/j.compstruct.2006.02.016Torres-Giner, S., Montanes, N., Fombuena, V., Boronat, T., & Sanchez-Nacher, L. (2016). Preparation and characterization of compression-molded green composite sheets made of poly(3-hydroxybutyrate) reinforced with long pita fibers. Advances in Polymer Technology, 37(5), 1305-1315. doi:10.1002/adv.21789Mathew, A. P., Oksman, K., & Sain, M. (2005). Mechanical properties of biodegradable composites from poly lactic acid (PLA) and microcrystalline cellulose (MCC). 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Optimization of Maleinized Linseed Oil Loading as a Biobased Compatibilizer in Poly(Butylene Succinate) Composites with Almond Shell Flour

[EN] Green composites of poly(butylene succinate) (PBS) were manufactured with almond shell flour (ASF) by reactive compatibilization with maleinized linseed oil *MLO) by extrusion and subsequent injection molding. ASF was kept constant at 30 wt %, while the effect of different MLO loading on mechanical, thermal, thermomechanical, and morphology properties was studied. Uncompatibilized PBS/ASF composites show a remarkable decrease in mechanical properties due to the nonexistent polymer¿filler interaction, as evidenced by field emission scanning electron microscopy (FESEM). MLO provides a plasticization effect on PBS/ASF composites but, in addition, acts as a compatibilizer agent since the maleic anhydride groups contained in MLO are likely to react with hydroxyl groups in both PBS end chains and ASF particles. This compatibilizing effect is observed by FESEM with a reduction of the gap between the filler particles and the surrounding PBS matrix. In addition, the Tg of PBS increases from ¿28 °C to ¿12 °C with an MLO content of 10 wt %, thus indicating compatibilization. MLO has been validated as an environmentally friendly additive to PBS/ASF composites to give materials with high environmental efficiency.This work was supported by the Ministry of Economy and Competitiveness (MINECO) grant number MAT2017-84909-C2-2-R. L.Q.-C. wants to thank Generalitat Valenciana (GV) for his FPI grant (ACIF/2016/182) and the Spanish Ministry of Education, Culture, and Sports (MECD) for his FPU grant (FPU15/03812).Limiñana-Gregori, P.; Garcia-Sanoguera, D.; Quiles-Carrillo, L.; Balart, R.; Montanes, N. (2019). Optimization of Maleinized Linseed Oil Loading as a Biobased Compatibilizer in Poly(Butylene Succinate) Composites with Almond Shell Flour. Materials. 12(5):1-14. https://doi.org/10.3390/ma12050685S114125Liminana, P., Garcia-Sanoguera, D., Quiles-Carrillo, L., Balart, R., & Montanes, N. (2018). 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Manufacturing and Characterization of Hybrid Composites with Basalt and Flax Fabrics and a Partially Bio-based Epoxy Resin

[EN] This research is focused on manufacturing and characterization of hybrid composite laminates obtained different stacking sequences of basalt and flax fabrics with silane treatments embedded in a partially bio-sourced epoxy resin as matrix. They were manufactured by the vacuum-assisted resin infusion molding and mechanical properties were tested in tensile, flexural and impact conditions. The effect of the coupling agent on the fiber/matrix interface was studied by FESEM. The effect of temperature on mechanical properties was evaluated by DMTA and TMA. FESEM images revealed improved fiber/matrix interactions with silane treatment, having a more satisfactory effect on basalt fibers than on flax fibers because of its silica-based structure, leading to improved mechanical properties. It is worthy to note that the hybrid stacking sequence has no remarkable influence on the elongation at break. On the contrary, the hybrid stacking sequence offered a great influence on both the elastic modulus and the tensile strength.This research was funded by the Ministerio de Economía, Industria y Competitividad (MICINN) project number MAT2017-84909-C2-2-R. D. Lascano wants to thank UPV for the grant received though the PAID-01-18 program. Microscopy services at UPV are acknowledged for their help in collecting and analyzing FESEM images.Lascano-Aimacaña, DS.; Balart, R.; Garcia-Sanoguera, D.; Agüero-Rodríguez, Á.; Boronat, T.; Montanes, N. (2021). Manufacturing and Characterization of Hybrid Composites with Basalt and Flax Fabrics and a Partially Bio-based Epoxy Resin. Fibers and Polymers. 22(3):751-763. https://doi.org/10.1007/s12221-021-0209-5S751763223S. Yang, V. B. Chalivendra, and Y. K. Kim, Compos. Struct., 168, 120 (2017).R. Rahman and S. Z. F. S. 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Kinetic Analysis of the Thermal Degradation of Recycled Acrylonitrile-Butadiene-Styrene by non-Isothermal Thermogravimetry

[EN] This work presents an in-depth kinetic study of the thermal degradation of recycled acrylonitrile-butadiene-styrene (ABS) polymer. Non-isothermal thermogravimetric analysis (TGA) data in nitrogen atmosphere at different heating rates comprised between 2 and 30 K min¿1 were used to obtain the apparent activation energy (Ea) of the thermal degradation process of ABS by isoconversional (differential and integral) model-free methods. Among others, the differential Friedman method was used. Regarding integral methods, several methods with different approximations of the temperature integral were used, which gave different accuracies in Ea. In particular, the Flynn-Wall-Ozawa (FWO), the Kissinger-Akahira-Sunose (KAS), and the Starink methods were used. The results obtained by these methods were compared to the Kissinger method based on peak temperature (Tm) measurements at the maximum degradation rate. Combined Kinetic Analysis (CKA) was also carried out by using a modified expression derived from the general Sestak-Berggren equation with excellent results compared with the previous methods. Isoconversional methods revealed negligible variation of Ea with the conversion. Furthermore, the reaction model was assessed by calculating the characteristic "y(¿)" and "z(¿)" functions and comparing them with some master plots, resulting in a nth order reaction model with n = 1.4950, which allowed calculating the pre-exponential factor (A) of the Arrhenius constant. The results showed that Ea of the thermal degradation of ABS was 163.3 kJ mol¿1, while ln A was 27.5410 (A in min¿1). The predicted values obtained by integration of the general kinetic expression with the calculated kinetic triplet were in full agreement with the experimental data, thus giving evidence of the accuracy of the obtained kinetic parameters.This research was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) program numbers MAT2017-84909-C2-2-R. L.Q.-C. wants to thank the Generalitat Valenciana (GVA) for his FPI grant (ACIF/2016/182) and the Spanish Ministry of Education, Culture, and Sports (MECD) for his FPU grant (FPU15/03812), while S.T.-G. is a recipient of a Juan de la Cierva - Incorporacion contract (IJCI-2016-29675) from MINECO.Balart, R.; Garcia-Sanoguera, D.; Quiles-Carrillo, L.; Montanes, N.; Torres-Giner, S. (2019). Kinetic Analysis of the Thermal Degradation of Recycled Acrylonitrile-Butadiene-Styrene by non-Isothermal Thermogravimetry. Polymers. 11(2). https://doi.org/10.3390/polym11020281S112Scaffaro, R., Botta, L., & Di Benedetto, G. (2012). Physical properties of virgin-recycled ABS blends: Effect of post-consumer content and of reprocessing cycles. European Polymer Journal, 48(3), 637-648. doi:10.1016/j.eurpolymj.2011.12.018Tiganis, B. ., Burn, L. ., Davis, P., & Hill, A. . (2002). Thermal degradation of acrylonitrile–butadiene–styrene (ABS) blends. Polymer Degradation and Stability, 76(3), 425-434. doi:10.1016/s0141-3910(02)00045-9Niemczyk, A., Dziubek, K., Sacher-Majewska, B., Czaja, K., Czech-Polak, J., Oliwa, R., … Szołyga, M. (2018). Thermal Stability and Flame Retardancy of Polypropylene Composites Containing Siloxane-Silsesquioxane Resins. Polymers, 10(9), 1019. doi:10.3390/polym10091019Chieng, B., Ibrahim, N., Yunus, W., & Hussein, M. (2013). Poly(lactic acid)/Poly(ethylene glycol) Polymer Nanocomposites: Effects of Graphene Nanoplatelets. Polymers, 6(1), 93-104. doi:10.3390/polym6010093Zhang, X., Wu, Y., Chen, X., Wen, H., & Xiao, S. (2017). Theoretical Study on Decomposition Mechanism of Insulating Epoxy Resin Cured by Anhydride. Polymers, 9(12), 341. doi:10.3390/polym9080341Ramesh, V., Biswal, M., Mohanty, S., & Nayak, S. K. (2014). Compatibilization effect of EVA-g-MAH on mechanical, morphological and rheological properties of recycled PC/ABS blend. Materials Express, 4(6), 499-507. doi:10.1166/mex.2014.1198Kuram, E., Ozcelik, B., Yilmaz, F., Timur, G., & Sahin, Z. M. (2014). The effect of recycling number on the mechanical, chemical, thermal, and rheological properties of PBT/PC/ABS ternary blends: With and without glass-fiber. Polymer Composites, 35(10), 2074-2084. doi:10.1002/pc.22869Balart, R., López, J., García, D., & Dolores Salvador, M. (2005). Recycling of ABS and PC from electrical and electronic waste. Effect of miscibility and previous degradation on final performance of industrial blends. 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Utilización de plataformas multimedia para la docencia no presencial en el campo de las ingenierías

[ES] En los últimos años, se ha producido un incremento importante en la demanda de formación no presencial. La Universidad Politécnica de Valencia, consciente de este nuevo marco docente, ha realizado un gran esfuerzo en el desarrollo de nuevas plataformas multimedia que permitan desarrollar el proceso de enseñanza-aprendizaje no presencial en el campo de las ingenierías, con un óptimo rendimiento. Una de las plataformas que ofrece en este atractivo proyecto, es la herramienta Polimedia, que consiste en una extensa base de videos en los que una presentación y una grabación del docente, se sincronizan para llevar a cabo la explicación de conceptos individuales relacionados con algún aspecto de la ingeniería (son los denominados Objetos de Aprendizaje). Esta herramienta es de gran utilidad para la docencia no presencial, al igual que el portal de Open Course Ware de la UPV donde se ofrece material de libre acceso relacionado con diversas asignaturas en el campo de la ingeniería. Este material de acceso libre contiene información necesaria para realizar un seguimiento de la asignatura (sesiones teóricas, material de apoyo, sesiones prácticas,¿) en situaciones no presenciales. Ambas herramientas ofrecen una serie de plataformas de gran interés para la docencia en ingeniería.Balart, R.; Garcia-Sanoguera, D.; Fenollar, O.; Boronat, T.; Sanchez-Nacher, L. (2011). Utilización de plataformas multimedia para la docencia no presencial en el campo de las ingenierías. Instituto de Ciencias de la Educación de la Universidad de Alicante. 1-8. http://hdl.handle.net/10251/178220S1

Aplicación docente para el cálculo de sistemas de alimentación de fundición. Fundisa 1.0

[ES] Se ha desarrollado una herramienta informática que permite a los estudiantes de ingeniería el cálculo de sistemas de alimentación del fundición. Esta herramienta permite a los estudiantes comprobar y comparar rápidamente los resultados de fabricación en diversos escenarios. Esto permite reducir de manera significativa el tiempo de estudio, lo que mejora el aprendizaje. Los programas informáticos disponibles para el cálculo de los sistemas de alimentación de fundición no son útiles en un ambiente académico porque no están diseñados para la enseñanza y que se caracterizan por su alto costo económico y alta complejidad. La aplicación Fundisa 1.0 ha sido desarrollada utilizando Visual Basic. La aplicación incluye todas las variantes de sistemas de alimentación, dividido en diferentes secciones. Además de facilitar el proceso de enseñanza-aprendizaje de la aplicación tiene una ayuda completa a fin de que este programa sea un instrumento útil, versátil y fácil de utilizar por los estudiantes. Hoy en día los estudiantes de estudios técnicos valoran altamente el uso de herramientas que les da autonomía en su proceso educativo, que se adapte al ritmo de aprendizaje particular de cada estudiante, y además el uso de herramientas informáticas les proporciona, una mayor motivación para aumentar el conocimiento de la materia.Boronat, T.; Garcia-Sanoguera, D.; Fenollar, O.; Balart, R.; Sanchez-Nacher, L. (2011). Aplicación docente para el cálculo de sistemas de alimentación de fundición. Fundisa 1.0. Instituto de Ciencias de la Educación de la Universidad de Alicante. 1086-1094. http://hdl.handle.net/10251/178199S1086109