Desarrollo y optimización de 'green composites' basados en matrices derivadas de aceites vegetales modificados y refuerzos de fibras minerales

[EN] In recent years, the sensitiveness of society about the conservation of environment has increased; this has promoted the development of polymeric materials derived from renewable resources. These new polymeric materials have good properties and can be used for the development of 'green composites'. The main objective of thisdoctoral thesis is the development and optimization of 'green composites', using matrices derived from epoxidized vegetable oils and mineral fibers, which have similar properties to glass fibers. The matrices used are based on epoxidized linseed oil (ELO) and epoxidized soybean oil (ESBO), and two types of crosslinking agent. One is a eutectic system of phthalic anhydride (PA), 23.8 wt%, and maleic anhydride (MA), 76.2 wt%, with a melting temperature of 48.3 °C. The other crosslinking agent was methyl nadic anhydride (MNA) which is liquid at room temperature. Thermoset materials obtained show that MNA crosslinker provides materials with improved mechanical and thermomechanical properties when compared to thermoset materials obtained with the PA/MA system. Interface phenomena of composites based on ELO-MNA and ESBO-MNA with mineral fibers from basalt and slate was evaluated by the single fiber fragmentation test (SFFT) to assess fiber-matrix interactions on the selected composites Basalt fibers were modified with two amino-silanes ((3-aminopropyl) trimethoxysilane and [3-(2-aminoethylamino)propyl]trimethoxysilane) and two glycidyl-silanestrimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane and (3-glycidyloxypropyl) trimethoxysilane). SFFT determined that the interfacial shear stress (¿) of basalt fibers and ELO-MNA and ESBO-MNA matrices, is higher with basalt fibers treated with amino-silane [3-(2-aminoethylamino)propyl]trimethoxysilane and glycidyl silane trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane with both matrices. By considering the results obtained with the SFFT technique, composite laminates containing basalt fabrics modified with silanes [3-(2-aminoethylamino)propyl] trimethoxysilane and trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane were manufactured. These composite laminates offer good mechanical properties as expected on the base of SFFT results, with optimum results for composites with basalt fabric previously modified with([trimethoxy [2-(7-oxabicyclo [4.1.0] hept- 3-yl) ethyl] silane. Slate fibers were treated with an amino-silane[3-(2-aminoethylamino)propyl]trimethoxysilane, a glycidyl-silane trimethoxy[2-(7-oxabicyclo [4.1.0] hept-3-yl)]-silane, a zirconate (zirconium(IV)bis(dietilcitrato)dipropóxido) and a titanate (titanium (IV)(triethanolaminato)isopropoxide and ELO-MNAwas selected as matrix because it offers has good mechanical properties. The mechanical characterization of composites made from slate fabrics revealed that the best results are obtained using glycidyl silane and titanate coupling agents. Green composite made withslate fiber modified with trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane and ELO-MNA resin offers the best mechanical properties. This material has a flexural strength of 402.1 MPa, flexural modulus of 19.7 GPa, a tensile strength of 359.1 MPa and a Young's modulus of 25.6 GPa. These good properties allow it to compete with conventional composites manufactured with glass fiber.[ES] En los últimos años ha aumentado la sensibilidad de la sociedad ante la conservación del medio ambiente, lo que ha llevado al desarrollo de materiales poliméricos derivados de recursos renovables. Estos nuevos materiales poliméricos presentan propiedades tales que pueden usarse para el desarrollo de 'green composites'. El principal objetivo de esta tesis doctoral es el desarrollo y optimización de 'green composites', utilizando matrices derivadas de aceites vegetales epoxidados y fibras minerales, que presentan propiedades similares a las fibras de vidrio. Las matrices utilizadas se basan en aceite de linaza epoxidado (ELO) y aceite de soja epoxidado (ESBO), y se han utilizado dos tipos de agentes entrecruzantes. Uno es una mezcla de anhídrido ftálico (PA), 23,8% en peso, y anhídrido maleico (MA), 76,2 % en peso, que presenta una transformación eutéctica al porcentaje dado y cuya temperatura de fusión ocurre a 48,3 ºC. El otro agente entrecruzante utilizado es anhídrido metil nádico (MNA) que es líquido a temperatura ambiente. Los materiales termoestables obtenidos ponen de manifiesto que el agente entrecruzante MNA proporciona materiales con mejores propiedades mecánicas y termomecánicas que los obtenidos con la mezcla de PA/MA. A partir de las resinas basadas en ELO-MNA y ESBO-MNA y fibras de basalto y pizarra, se realiza la evaluación de la entrecara de los composites mediante el test de fragmentación de una sola fibra (SFFT) y posteriormente se realiza y evalúa los materiales compuestos seleccionados. Las fibras de basalto se modifican con dos amino-silano (3-aminopropil)trimetoxisilano y [3-(2-aminoetilamino)propil]trimetoxisilano) y dos glicidil-silano trimetoxi[2-(7-oxabiciclo[4.1.0]hept-3-il)etil]silano y (3-glicidiloxipropil) trimetoxisilano. El SFFT determina que el esfuerzo cortante en la entrecara (¿), de las fibras de basalto y las matrices ELO-MNA y ESBO-MNA, es más elevado con las fibras tratadas con el amino-silano [3-(2-aminoetilamino)propil]trimetoxisilano y con el glicidil-silano trimetoxi[2-(7-oxabiciclo[4.1.0]hept-3-il)etil]silano con ambas matrices. Debido a los resultados obtenidos con la técnica SFFT se realizan materiales compuestos utilizando tejidos de basalto modificados con los silanos [3-(2-aminoetilamino)propil]trimetoxisilano y trimetoxi[2-(7-oxabiciclo[4.1.0]hept-3-il)etil]silano. De esta forma se obtienen materiales compuestos con buenas propiedades mecánicas y se valida la técnica SFFT, ya que el material compuesto con mejores propiedades es realizado con los tejidos de basalto modificado con ([trimetoxi[2-(7-oxabiciclo[4.1.0]hept-3-il)etil]silano, tal y como se predijo con la técnica SFFT. Las fibras de pizarra fueron tratadas con un amino-silano ([3-(2-aminoetilamino)propil]trimetoxisilano), un glicidil-silano trimetoxi[2-(7-oxabiciclo[4.1.0]hept-3-il)etil]silano, un zirconato (zirconio(IV)bis(dietilcitrato)dipropóxido) y un titanato (titanio(IV)(trietanolaminato)isopropóxido y se seleccionó como matriz ELO-MNA debido a sus buenas propiedades mecánicas.La caracterización mecánica de los composites realizados con tejidos de pizarra reveló que los mejores resultados se obtienen utilizando los agentes de acoplamiento glicidil-silano y titanato. El 'green composite' que presenta las mejores propiedades mecánicas es el realizado con fibra de pizarra modificada con trimetoxi[2-(7-oxabiciclo[4.1.0]hept-3-il)etil]silano y la resina ELO-MNA. Este material presenta una resistencia a flexión de 402,1 MPa, un módulo a flexión de 19,7 GPa, la resistencia a tracción es de 359,1 MPa y el Módulo de Young es de 25,6 GPa. Las buenas propiedades resistentes que presenta le permite poder sustituir a composites tradicionales realizados con fibra de vidrio.[CA] En els últims anys ha augmentat la sensibilitat de la societat davant la conservació del medi ambient, el que ha portat al desenvolupament de materials polimèrics derivats de recursos renovables. Aquests nous materials polimèrics presenten propietats tals que poden usar-se per al desenvolupament de ''green composites''. El principal objectiu d'aquesta tesi doctoral és el desenvolupament i optimització de ''green composites'', utilitzant matrius derivades d'olis vegetals epoxidats i fibres minerals, que presenten propietats similars a les fibres de vidre. Les matrius utilitzades es basen en oli de llinosa epoxidat (ELO) i oli de soia epoxidat (ESBO), i s'han utilitzat dos tipus d'agents d'entrecreuament. Un és una barreja d'anhídrid ftàlic (PA), 23,8 % en pes, i anhídrid maleic (MA), 76,2 % en pes, que presenta una transformació eutèctica al percentatge donat i la seua temperatura de fusió passa a 48,3 ºC. L'altre agent d'entrecreuament utilitzat és anhídrid metil nàdic (MNA) que és líquid a temperatura ambient. Els materials termostables obtinguts posen de manifest que l'agent d'entrecreuament MNA proporciona materials amb millors propietats mecàniques i termomecàniques que els obtinguts amb la mescla de PA/MA. A partir de les resines basades en ELO-MNA i ESBO-MNA i fibres de basalt i llicorella, es va realitzar l'avaluació interfacial dels 'composites' utilizant el test de fragmentació d'una única fibra (SFFT) i posteriorment es van fabricar i avaluar els materials compostos seleccionats. Les fibres de basalt es van modificar amb dos amino-silans ((3-aminopropil)trimetoxisilà i [3-(2-aminoetilamino)propil]trimetoxisilà) i dos glicidil-silans trimetoxi[2-(7-oxabicicle[4.1.0]hept-3-il)etil]silà i 3-glicidiloxipropil)trimetoxisilà. El SFFT va determinar que l'esforç de tall interfacial (¿), de les fibres de basalt i les matrius ELO-MNA i ESBO-MNA, és més elevat amb les fibres tractades amb l'amino-silà [3-(2-aminoetilamino)propil]trimetoxisilà i amb el glicidil-silà ([trimetoxi[2-(7-oxabicicle[4.1.0]hept-3-il)etil]silà amb ambdues matrius. Degut als resultats obtinguts amb la tècnica SFFT es van realitzar materials compostos utilitzant teixits de basalt modificats amb els silans [3-(2-aminoetilamino)propil]trimetoxisilà i trimetoxi[2-(7-oxabicicle[4.1.0]hept-3-il)etil]silà. D'aquesta forma s'obtenen materials compostos amb bones propietats mecàniques i es va validar la tècnica SFFT, ja que el material compost amb millors propietats va ser realitzat amb els teixits de basalt modificat amb trimetoxi[2-(7-oxabicicle[4.1.0]hept-3-il)etil]silà, tal com es va predir amb la tècnica SFFT. Les fibres de llicorella van ser tractades amb un amino-silà ([3-(2-aminoetilamino)propil]trimetoxisilà), un glicidil-silà trimetoxi[2-(7-oxabicicle [4.1.0]hept-3-il)etil]silà, un zirconat (zirconi(IV)bis(dietilcitrat) dipropòxid) i un titanat (titani(IV)(trietanolaminato)isopropòxid i es va seleccionar com a matriu ELO-MNA a causa de les seues bones propietats mecàniques. La caracterització mecànica dels 'composites' realitzats amb teixits de llicorella va revelar que els millors resultats s'obtenen utilitzant els agents d'acoblament glicidil-silà i titanat. El 'green composite' que presenta les millors propietats mecàniques és el realitzat amb fibra de llicorella modificada amb trimetoxi[2-(7-oxabicicle[4.1.0]hept-3-il)etil]silà i la resina ELO-MNA. Aquest material presenta una resistència a flexió de 402,1 MPa, un mòdul a flexió de 19,7 GPa, la resistència a tracció és de 359,1 MPa i el mòdul de Young és de 25,6 GPa. Les bones propietats resistents que presenta li permeten poder substituir a 'composites' tradicionals realitzats amb fibra de vidre.Samper Madrigal, MD. (2015). Desarrollo y optimización de 'green composites' basados en matrices derivadas de aceites vegetales modificados y refuerzos de fibras minerales [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/52602TESISPremios Extraordinarios de tesis doctorale

Influence of Ultraviolet Radiation Exposure Time on Styrene-Ethylene-Butadiene-Styrene (SEBS) Copolymer

[EN] The effect of ultraviolet radiation on styrene-ethylene-butadiene-styrene (SEBS) has been studied at different exposures times in order to obtain a better understanding of the mechanism of ageing. The polymer materials were mechanically tested and then their surfaces were analyzed using a scanning electron microscope (SEM) and atomic force microscopy (AFM). Moreover, the optical analysis of contact angle (OCA) was used to evaluate the surface energy (gamma(s)) and the yellowing index (YI) and attenuated total reflectance infrared spectroscopy (ATR-FTIR) were used to observe structural and physical changes in aging SEBS. The results obtained for the SEBS, in relation to the duration of exposure, showed superficial changes that cause a decrease in the surface energy (gamma(s)) and, therefore, a decrease in surface roughness. This led to a reduction in mechanical performance, decreasing the tensile strength by about 50% for exposure times of around 200 hours.This work was supported by the Ministry of Economy and Competitiveness (MINECO) grant number MAT2017-84909-C2-2-R). Daniel Garcia-Garcia acknowledges Generalitat Valenciana (GVA) for financial support through a postdoctoral contract (APOSTD/2019/201).Garcia-Garcia, D.; Crespo, J.; Parres, F.; Samper, M. (2020). Influence of Ultraviolet Radiation Exposure Time on Styrene-Ethylene-Butadiene-Styrene (SEBS) Copolymer. Polymers. 12(4):1-14. https://doi.org/10.3390/polym12040862S114124Picchioni, F., Giorgi, I., Passaglia, E., Ruggeri, G., & Aglietto, M. (2001). Blending of styrene-block-butadiene-block-styrene copolymer with sulfonated vinyl aromatic polymers. Polymer International, 50(6), 714-721. doi:10.1002/pi.692Zhu, J., Birgisson, B., & Kringos, N. (2014). Polymer modification of bitumen: Advances and challenges. 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Characterization of the surface changes and the aging effects of low-pressure nitrogen plasma treatment in a polyurethane film. Polymer Testing, 27(1), 75-83. doi:10.1016/j.polymertesting.2007.09.002Sheikhy, H., Shahidzadeh, M., Ramezanzadeh, B., & Noroozi, F. (2013). Studying the effects of chain extenders chemical structures on the adhesion and mechanical properties of a polyurethane adhesive. Journal of Industrial and Engineering Chemistry, 19(6), 1949-1955. doi:10.1016/j.jiec.2013.03.008Švab, I., Musil, V., Šmit, I., & Makarovič, M. (2007). Mechanical properties of wollastonite-reinforced polypropylene composites modified with SEBS and SEBS-g-MA elastomers. Polymer Engineering & Science, 47(11), 1873-1880. doi:10.1002/pen.20897Sanchis, M. R., Blanes, V., Blanes, M., Garcia, D., & Balart, R. (2006). Surface modification of low density polyethylene (LDPE) film by low pressure O2 plasma treatment. European Polymer Journal, 42(7), 1558-1568. doi:10.1016/j.eurpolymj.2006.02.001Ganguly, A., & Bhowmick, A. K. (2009). Effect of polar modification on morphology and properties of styrene-(ethylene-co-butylene)-styrene triblock copolymer and its montmorillonite clay-based nanocomposites. Journal of Materials Science, 44(3), 903-918. doi:10.1007/s10853-008-3183-

Are Women More Empathetic than Men? A Longitudinal Study in Adolescence

Since the 1970s there has been a growing interest in analysing sex differences in psychological variables. Empirical studies and meta-analyses have contributed evidence on the differences between male and female individuals. More recently, the gender similarities hypothesis has supported the similarity of men and women in most psychological variables. This study contributes information on women's greater empathic disposition in comparison with men by means of a longitudinal design in an adolescent population. 505 male and female adolescents aged between 13 and 16 years were evaluated at two different moments (grade 2 and grade 3, lower secondary education). They completed the Index of Empathy for Children and Adolescents by Bryant and the Interpersonal Reactivity Index by Davis. The results confirm a greater empathic response in females than in males of the same age, differences growing with age. The sizes of the effect estimated in the second evaluation (average age 14 years) are large for emotional empathy and medium for cognitive [email protected]; [email protected]; [email protected]; [email protected]

Interference of biodegradable plastics in the polypropylene recycling process

[EN] Recycling polymers is common due to the need to reduce the environmental impact of these materials. Polypropylene (PP) is one of the polymers called commodities polymers' and it is commonly used in a wide variety of short-term applications such as food packaging and agricultural products. That is why a large amount of PP residues that can be recycled are generated every year. However, the current increasing introduction of biodegradable polymers in the food packaging industry can negatively affect the properties of recycled PP if those kinds of plastics are disposed with traditional plastics. For this reason, the influence that generates small amounts of biodegradable polymers such as polylactic acid (PLA), polyhydroxybutyrate (PHB) and thermoplastic starch (TPS) in the recycled PP were analyzed in this work. Thus, recycled PP was blended with biodegradables polymers by melt extrusion followed by injection moulding process to simulate the industrial conditions. Then, the obtained materials were evaluated by studding the changes on the thermal and mechanical performance. The results revealed that the vicat softening temperature is negatively affected by the presence of biodegradable polymers in recycled PP. Meanwhile, the melt flow index was negatively affected for PLA and PHB added blends. The mechanical properties were affected when more than 5 wt.% of biodegradable polymers were present. Moreover, structural changes were detected when biodegradable polymers were added to the recycled PP by means of FTIR, because of the characteristic bands of the carbonyl group (between the band 1700-1800 cm(-1)) appeared due to the presence of PLA, PHB or TPS. Thus, low amounts (lower than 5 wt.%) of biodegradable polymers can be introduced in the recycled PP process without affecting the overall performance of the final material intended for several applications, such as food packaging, agricultural films for farming and crop protection.This research was funded by Conselleria d'Educacio, Investigacio, Cultura y Esport de la Generalitat Valenciana, grant number APOSTD/2018/209.Samper, M.; Bertomeu, D.; Arrieta, MP.; Ferri, JM.; López-Martínez, J. (2018). Interference of biodegradable plastics in the polypropylene recycling process. Materials. 11(10):1-18. https://doi.org/10.3390/ma11101886S1181110Plastics Europe, Plastics—The Facts 2017https://www.plasticseurope.org/application/files/5715/1717/4180/Plastics_the_facts_2017_FINAL_for_website_one_page.pdfAres, A., Bouza, R., Pardo, S. G., Abad, M. J., & Barral, L. (2010). Rheological, Mechanical and Thermal Behaviour of Wood Polymer Composites Based on Recycled Polypropylene. Journal of Polymers and the Environment, 18(3), 318-325. doi:10.1007/s10924-010-0208-xBodar, C., Spijker, J., Lijzen, J., Waaijers-van der Loop, S., Luit, R., Heugens, E., … Traas, T. (2018). Risk management of hazardous substances in a circular economy. Journal of Environmental Management, 212, 108-114. doi:10.1016/j.jenvman.2018.02.014Alam, O., Wang, S., & Lu, W. (2018). Heavy metals dispersion during thermal treatment of plastic bags and its recovery. Journal of Environmental Management, 212, 367-374. doi:10.1016/j.jenvman.2018.02.034Bucci, D. Z., Tavares, L. B. B., & Sell, I. (2005). PHB packaging for the storage of food products. Polymer Testing, 24(5), 564-571. doi:10.1016/j.polymertesting.2005.02.008Siracusa, V., Rocculi, P., Romani, S., & Rosa, M. D. (2008). Biodegradable polymers for food packaging: a review. Trends in Food Science & Technology, 19(12), 634-643. doi:10.1016/j.tifs.2008.07.003Claro, P. I. C., Neto, A. R. S., Bibbo, A. C. C., Mattoso, L. H. C., Bastos, M. S. R., & Marconcini, J. M. (2016). Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films. Journal of Polymers and the Environment, 24(4), 363-371. doi:10.1007/s10924-016-0785-4Avérous, L. (2004). Biodegradable Multiphase Systems Based on Plasticized Starch: A Review. Journal of Macromolecular Science, Part C: Polymer Reviews, 44(3), 231-274. doi:10.1081/mc-200029326Armentano, I., Fortunati, E., Burgos, N., Dominici, F., Luzi, F., Fiori, S., … Kenny, J. M. (2015). Processing and characterization of plasticized PLA/PHB blends for biodegradable multiphase systems. Express Polymer Letters, 9(7), 583-596. doi:10.3144/expresspolymlett.2015.55Arrieta, M. P., López, J., Rayón, E., & Jiménez, A. (2014). Disintegrability under composting conditions of plasticized PLA–PHB blends. Polymer Degradation and Stability, 108, 307-318. doi:10.1016/j.polymdegradstab.2014.01.034Garcia-Garcia, D., Ferri, J. M., Montanes, N., Lopez-Martinez, J., & Balart, R. (2016). Plasticization effects of epoxidized vegetable oils on mechanical properties of poly(3-hydroxybutyrate). Polymer International, 65(10), 1157-1164. doi:10.1002/pi.5164Russo, M. A. L., O’Sullivan, C., Rounsefell, B., Halley, P. J., Truss, R., & Clarke, W. P. (2009). The anaerobic degradability of thermoplastic starch: Polyvinyl alcohol blends: Potential biodegradable food packaging materials. Bioresource Technology, 100(5), 1705-1710. doi:10.1016/j.biortech.2008.09.026Neumann, I. A., Flores-Sahagun, T. H. S., & Ribeiro, A. M. (2017). Biodegradable poly (l-lactic acid) (PLLA) and PLLA-3-arm blend membranes: The use of PLLA-3-arm as a plasticizer. Polymer Testing, 60, 84-93. doi:10.1016/j.polymertesting.2017.03.013Khalid, S., Yu, L., Meng, L., Liu, H., Ali, A., & Chen, L. (2017). Poly(lactic acid)/starch composites: Effect of microstructure and morphology of starch granules on performance. Journal of Applied Polymer Science, 134(46), 45504. doi:10.1002/app.45504Arrieta, M., Samper, M., Aldas, M., & López, J. (2017). On the Use of PLA-PHB Blends for Sustainable Food Packaging Applications. Materials, 10(9), 1008. doi:10.3390/ma10091008Cosate de Andrade, M. F., Souza, P. M. S., Cavalett, O., & Morales, A. R. (2016). Life Cycle Assessment of Poly(Lactic Acid) (PLA): Comparison Between Chemical Recycling, Mechanical Recycling and Composting. Journal of Polymers and the Environment, 24(4), 372-384. doi:10.1007/s10924-016-0787-2Navarro, R., Ferrándiz, S., López, J., & Seguí, V. J. (2008). The influence of polyethylene in the mechanical recycling of polyethylene terephtalate. Journal of Materials Processing Technology, 195(1-3), 110-116. doi:10.1016/j.jmatprotec.2007.04.126Navarro, R., López, J., Parres, F., & Ferrándiz, S. (2011). Process behavior of compatible polymer blends. Journal of Applied Polymer Science, 124(3), 2485-2493. doi:10.1002/app.35260Sánchez-Jiménez, P. E., Pérez-Maqueda, L. A., Crespo-Amorós, J. E., López, J., Perejón, A., & Criado, J. M. (2010). Quantitative Characterization of Multicomponent Polymers by Sample-Controlled Thermal Analysis. Analytical Chemistry, 82(21), 8875-8880. doi:10.1021/ac101651gAlaerts, L., Augustinus, M., & Van Acker, K. (2018). Impact of Bio-Based Plastics on Current Recycling of Plastics. Sustainability, 10(5), 1487. doi:10.3390/su10051487Pivsa-Art, S., Kord-Sa-Ard, J., Pivsa-Art, W., Wongpajan, R., O-Charoen, N., Pavasupree, S., & Hamada, H. (2016). Effect of Compatibilizer on PLA/PP Blend for Injection Molding. Energy Procedia, 89, 353-360. doi:10.1016/j.egypro.2016.05.046Yoo, T. W., Yoon, H. G., Choi, S. J., Kim, M. S., Kim, Y. H., & Kim, W. N. (2010). Effects of compatibilizers on the mechanical properties and interfacial tension of polypropylene and poly(lactic acid) blends. Macromolecular Research, 18(6), 583-588. doi:10.1007/s13233-010-0613-yRosa, D. S., Guedes, C. G. F., & Carvalho, C. L. (2007). Processing and thermal, mechanical and morphological characterization of post-consumer polyolefins/thermoplastic starch blends. Journal of Materials Science, 42(2), 551-557. doi:10.1007/s10853-006-1049-9Sadi, R. K., Kurusu, R. S., Fechine, G. J. M., & Demarquette, N. R. (2011). Compatibilization of polypropylene/ poly(3-hydroxybutyrate) blends. Journal of Applied Polymer Science, 123(6), 3511-3519. doi:10.1002/app.34853Parres, F., Balart, R., López, J., & García, D. (2008). Changes in the mechanical and thermal properties of high impact polystyrene (HIPS) in the presence of low polypropylene (PP) contents. Journal of Materials Science, 43(9), 3203-3209. doi:10.1007/s10853-008-2555-8Fekete, E., Földes, E., & Pukánszky, B. (2005). Effect of molecular interactions on the miscibility and structure of polymer blends. European Polymer Journal, 41(4), 727-736. doi:10.1016/j.eurpolymj.2004.10.038Macaúbas, P. H. P., & Demarquette, N. R. (2002). Time-temperature superposition principle applicability for blends formed of immiscible polymers. Polymer Engineering & Science, 42(7), 1509-1519. doi:10.1002/pen.11047Polymer Properties Databasehttps://polymerdatabase.com/polymer%20classes/Intro.htmlGoonoo, N., Bhaw-Luximon, A., & Jhurry, D. (2015). Biodegradable polymer blends: miscibility, physicochemical properties and biological response of scaffolds. Polymer International, 64(10), 1289-1302. doi:10.1002/pi.4937Arrieta, M. P., López, J., López, D., Kenny, J. M., & Peponi, L. (2015). Development of flexible materials based on plasticized electrospun PLA–PHB blends: Structural, thermal, mechanical and disintegration properties. European Polymer Journal, 73, 433-446. doi:10.1016/j.eurpolymj.2015.10.036Ferri, J. M., Garcia-Garcia, D., Carbonell-Verdu, A., Fenollar, O., & Balart, R. (2017). Poly(lactic acid) formulations with improved toughness by physical blending with thermoplastic starch. Journal of Applied Polymer Science, 135(4), 45751. doi:10.1002/app.45751Sessini, V., Arrieta, M. P., Kenny, J. M., & Peponi, L. (2016). Processing of edible films based on nanoreinforced gelatinized starch. Polymer Degradation and Stability, 132, 157-168. doi:10.1016/j.polymdegradstab.2016.02.026Fan, Y., Nishida, H., Shirai, Y., Tokiwa, Y., & Endo, T. (2004). Thermal degradation behaviour of poly(lactic acid) stereocomplex. Polymer Degradation and Stability, 86(2), 197-208. doi:10.1016/j.polymdegradstab.2004.03.001Sessini, V., Raquez, J.-M., Lourdin, D., Maigret, J.-E., Kenny, J. M., Dubois, P., & Peponi, L. (2017). Humidity-Activated Shape Memory Effects on Thermoplastic Starch/EVA Blends and Their Compatibilized Nanocomposites. Macromolecular Chemistry and Physics, 218(24), 1700388. doi:10.1002/macp.201700388Gerard, T., Budtova, T., Podshivalov, A., & Bronnikov, S. (2014). Polylactide/poly(hydroxybutyrate-co-hydroxyvalerate) blends: Morphology and mechanical properties. Express Polymer Letters, 8(8), 609-617. doi:10.3144/expresspolymlett.2014.64Lanzotti, A., Grasso, M., Staiano, G., & Martorelli, M. (2015). The impact of process parameters on mechanical properties of parts fabricated in PLA with an open-source 3-D printer. Rapid Prototyping Journal, 21(5), 604-617. doi:10.1108/rpj-09-2014-0135Arrieta, M. P., López, J., Hernández, A., & Rayón, E. (2014). Ternary PLA–PHB–Limonene blends intended for biodegradable food packaging applications. European Polymer Journal, 50, 255-270. doi:10.1016/j.eurpolymj.2013.11.009Du, Y.-L., Cao, Y., Lu, F., Li, F., Cao, Y., Wang, X.-L., & Wang, Y.-Z. (2008). Biodegradation behaviors of thermoplastic starch (TPS) and thermoplastic dialdehyde starch (TPDAS) under controlled composting conditions. Polymer Testing, 27(8), 924-930. doi:10.1016/j.polymertesting.2008.08.00

Plasticization effect of epoxidized cottonseed oil (ECSO) on poly(lactic acid)

[EN] In this work, the use of an environmentally friendly plasticizer derived epoxidized cottonseed oil (ECSO) for poly(lactic acid) (PLA) is proposed. Melt extrusion was used to plasticize PLA formulations with different ECSO contents in the 0 - 10 wt.%. PLA formulation with 10 wt.% shows a remarkable increase in mechanical ductile properties with a percentage increase in elongation at break of more than 1100% and a noticeable increase in the impact absorbed energy. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) revealed a clear decrease in the glass transition temperature of neat PLA as the ECSO content increased. Field emission scanning electron microscopy (FESEM) of fractured surfaces from impact tests showed an improvement of ductility with typical rough and porous topographies. Migration tests in n-hexane at different temperatures revealed very low migration properties thus leading to new interesting plasticizers for improved PLA industrial formulations.This research was supported by the Spanish Ministry of Economy and Competitiveness - MINECO, Ref: MAT2014-59242-C2-1-R. Authors also thank to "Conselleria d'Educacio, Cultura i Esport" - Generalitat Valenciana, Ref: GV/2014/008 for financial support. A. Carbonell-Verdu wants to thank Universitat Politecnica de Valencia for financial support through an FPI grant. D. Garcia-Garcia wants to thanks the Spanish Ministry of Education, Culture and Sports for their financial support through an FPU grant (FPU13/06011).Carbonell-Verdu, A.; Samper, M.; Garcia-Garcia, D.; Sanchez-Nacher, L.; Balart, R. (2017). Plasticization effect of epoxidized cottonseed oil (ECSO) on poly(lactic acid). Industrial Crops and Products. 104:278-286. https://doi.org/10.1016/j.indcrop.2017.04.050S27828610

Development and characterization of a new natural fiber reinforced thermoplastic (NFRP) with Cortaderia selloana (Pampa grass) short fibers

[EN] In this work, fully bio-based thermoplastic composites are manufactured with bio-based polyethylene (from sugarcane) and short fibers coming from Cortaderia selloana (CS) wastes. These wastes are characterized by high cellulose content, which can provide high stiffness to the polymeric matrix. The effect of Cortaderia selloana short fibers on thermal properties has been evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The effect of the filler load on mechanical properties has also been evaluated by tensile and impact tests as well as the effects of different coupling agents. Fiber-matrix interactions have been studied by scanning electron microscopy (SEM). The addition of 15-30 wt% Cortaderia selloana short fiber leads to high elastic and flexural modulus without remarkable changes in thermal degradation of the polymer composite. (C) 2017 Elsevier Ltd. All rights reserved.This work was funded by the Conselleria d'Educacio, Cultura i Esport (Generalitat Valenciana) Ref: GV/2014/008. The authors declare that they have no conflict of interest.Jorda-Vilaplana, A.; Carbonell-Verdu, A.; Samper, M.; Pop, A.; García Sanoguera, D. (2017). Development and characterization of a new natural fiber reinforced thermoplastic (NFRP) with Cortaderia selloana (Pampa grass) short fibers. Composites Science and Technology. 145:1-9. https://doi.org/10.1016/j.compscitech.2017.03.036S1914

Psychometric properties and factorial structure of the Spanish version of the Children’s Beliefs About Parental Divorce Scale (CBAPS)

Abstract: The purpose of this study was to examine for the first time the factor structure and psychometric properties of the Children’s Beliefs About Parental Divorce Scale (CBAPS) in a community Spanish-speaking sample. Participants were 341 Spanish children and adolescents aged 10–17 years. Item analysis and exploratory and confirmatory factor analysis suggested an 18-item shortened version of the scale, maintaining the same six subscales as the original measure. Internal consistency was acceptable (α = .78) and convergent validity was supported through correlation between CBAPS and a measure of depression. Gender and age effects on CBAPS scores were found. Overall, the shortened version of the CBAPS obtained was shown to have good psychometric properties for use with Spanish children and adolescents to assess problematic beliefs regarding their parents' divorce.Keywords: problematic beliefs; parental divorce; children; adolescents; depression; assessmentPropiedades psicométricas y estructura factorial de la versión española de la Escala de Creencias de los Niños Sobre el Divorcio de los Padres (CBAPS)Resumen: El propósito de este estudio fue examinar por primera vez la estructura factorial y las propiedades psicométricas de la Escala de Creencias de los Niños Sobre el Divorcio de los Padres (CBAPS) en una muestra comunitaria de niños hispanohablantes. Participaron 341 niños y adolescentes españoles de 10 a 17 años. El análisis de ítems y el análisis factorial exploratorio y confirmatorio sugirieron una versión abreviada de 18 ítems de la escala, manteniendo las seis subescalas de la medida original. La consistencia interna fue aceptable (α = .78) y la validez convergente se apoyó mediante la correlación entre la CBAPS y una medida de depresión. Se encontraron efectos de género y edad en las puntuaciones de la CBAPS. En general, la versión abreviada de la CBAPS obtenida mostró tener buenas propiedades psicométricas para su uso con niños y adolescentes españoles para evaluar creencias problemáticas con respecto al divorcio de sus padres.Palabras clave: creencias problemáticas; divorcio parental; niños; adolescentes; depresión; evaluació

Compatibilization and Characterization of Polylactide and Biopolyethylene Binary Blends by Non-Reactive and Reactive Compatibilization Approaches

[EN] In this study, different compatibilizing agents were used to analyze their influence on immiscible blends of polylactide (PLA) and biobased high-density polyethylene (bioPE) 80/20 (wt/wt). The compatibilizing agents used were polyethylene vinyl acetate (EVA) with a content of 33% of vinyl acetate, polyvinyl alcohol (PVA), and dicumyl peroxide (DPC). The influence of each compatibilizing agent on the mechanical, thermal, and microstructural properties of the PLA-bioPE blend was studied using different microscopic techniques (i.e., field emission electron microscopy (FESEM), transmission electron microscopy (TEM), and atomic force microscopy with PeakForce quantitative nanomechanical mapping (AFM-QNM)). Compatibilized PLA-bioPE blends showed an improvement in the ductile properties, with EVA being the compatibilizer that provided the highest elongation at break and the highest impact-absorbed energy (Charpy test). In addition, it was observed by means of the different microscopic techniques that the typical droplet-like structure is maintained, but the use of compatibilizers decreases the dimensions of the dispersed droplets, leading to improved interfacial adhesion, being more pronounced in the case of the EVA compatibilizer. Furthermore, the incorporation of the compatibilizers caused a very marked decrease in the crystallinity of the immiscible PLA-bioPE blendThis research was funded by the Spanish Ministry of Science, Innovation, and Universities (MICIU), project numbers MAT2017-84909-C2-2-R.Ferri Azor, JM.; Garcia-Garcia, D.; Rayón Encinas, E.; Samper, M.; Balart, R. (2020). Compatibilization and Characterization of Polylactide and Biopolyethylene Binary Blends by Non-Reactive and Reactive Compatibilization Approaches. Polymers. 12(6):1-20. https://doi.org/10.3390/polym12061344S120126Nofar, M., Sacligil, D., Carreau, P. J., Kamal, M. R., & Heuzey, M.-C. (2019). Poly (lactic acid) blends: Processing, properties and applications. International Journal of Biological Macromolecules, 125, 307-360. doi:10.1016/j.ijbiomac.2018.12.002Farto-Vaamonde, X., Auriemma, G., Aquino, R. P., Concheiro, A., & Alvarez-Lorenzo, C. (2019). Post-manufacture loading of filaments and 3D printed PLA scaffolds with prednisolone and dexamethasone for tissue regeneration applications. European Journal of Pharmaceutics and Biopharmaceutics, 141, 100-110. doi:10.1016/j.ejpb.2019.05.018Fajardo, J., Valarezo, L., López, L., & Sarmiento, A. (2013). Experiencies in obtaining polymeric composites reinforced with natural fiber from Ecuador. Ingenius, (9). doi:10.17163/ings.n9.2013.04Ferri, J. M., Garcia-Garcia, D., Carbonell-Verdu, A., Fenollar, O., & Balart, R. (2017). Poly(lactic acid) formulations with improved toughness by physical blending with thermoplastic starch. Journal of Applied Polymer Science, 135(4), 45751. doi:10.1002/app.45751Ferri, J. M., Garcia-Garcia, D., Sánchez-Nacher, L., Fenollar, O., & Balart, R. (2016). The effect of maleinized linseed oil (MLO) on mechanical performance of poly(lactic acid)-thermoplastic starch (PLA-TPS) blends. Carbohydrate Polymers, 147, 60-68. doi:10.1016/j.carbpol.2016.03.082Gao, H., Hu, S., Su, F., Zhang, J., & Tang, G. (2011). Mechanical, thermal, and biodegradability properties of PLA/modified starch blends. Polymer Composites, 32(12), 2093-2100. doi:10.1002/pc.21241Arrieta, M. P., López, J., Ferrándiz, S., & Peltzer, M. A. (2013). Characterization of PLA-limonene blends for food packaging applications. Polymer Testing, 32(4), 760-768. doi:10.1016/j.polymertesting.2013.03.016Arrieta, M. P., López, J., Hernández, A., & Rayón, E. (2014). Ternary PLA–PHB–Limonene blends intended for biodegradable food packaging applications. European Polymer Journal, 50, 255-270. doi:10.1016/j.eurpolymj.2013.11.009Iglesias Montes, M. L., Cyras, V. P., Manfredi, L. B., Pettarín, V., & Fasce, L. A. 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Effect of pine resin derivatives on the structural, thermal, and mechanical properties of Mater-Bi type bioplastic

"This is the peer reviewed version of the following article: Aldas, M., J. M. Ferri, J. Lopez-Martinez, M. D. Samper, and M. P. Arrieta. 2019. Effect of Pine Resin Derivatives on the Structural, Thermal, and Mechanical Properties of Mater-Bi Type Bioplastic. Journal of Applied Polymer Science 137 (4). Wiley: 48236. doi:10.1002/app.48236, which has been published in final form at https://doi.org/10.1002/app.48236. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] The effect of three additives derived from pine resin, namely, gum rosin (GR) and two pentaerythritol ester of GR, Lurefor (LF) and Unik Tack (UT), in 5, 10, and 15 wt %, on the properties of Mater-Bi, based on plasticized starch, poly(butylene adipate-co-terephthalate), and poly(epsilon-caprolactone) (PCL), obtained by injection molding processes, was studied. The mechanical, microstructural, and thermal properties were evaluated. LF had a cohesive behavior with the components of Mater-Bi, increasing the toughness of the material up to 250% accompanied by an increase of tensile modulus and tensile strength. UT had an intermediate behavior, conferring cohesive and plasticizing effects, allowing an increase of 105% in impact resistance. GR had a more marked plasticizing effect. This allows processing temperatures of about 50 degrees C lower than those used for neat Mater-Bi. In addition, an increase of the elongation at break, toughness, and impact resistance in 370, 480, and 250%, respectively, was achieved.This work was supported by the Spanish Ministry of Economy and Competitiveness, PROMADEPCOL (MAT2017-84909-C2-2-R). M. P. Arrieta thanks Complutense University of Madrid for "Ayudas para la contratacion de personal postdoctoral en formacion en docencia e investigacion en departamentos de la UCM."Aldas-Carrasco, MF.; Ferri, JM.; López-Martínez, J.; Samper, M.; Arrieta, MP. (2020). 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Properties of composite laminates based on basalt fibers with epoxidized vegetable oils

This paper deals with the development of polymeric materials derived from epoxidized vegetable oils which have been used in the manufacture of laminated composite materials with basalt fabrics. Epoxidized linseed oil (ELO) and epoxidized soybean oil (ESBO) were used as biobased matrices. The basalt fabrics were modified with amino-silane and glycidyl-silane to increase fiber-matrix interactions. The curing behaviour of both resins was evaluated by differential scanning calorimetry (DSC) and oscillatory rheometry (OR). The evaluation of mechanical properties was made by tensile, flexural and Charpy tests. The extent of the fiber-matrix interactions among interface was evaluated by scanning electron microscopy (SEM). The obtained results revealed that surface modification of basalt fibers with glycidyl-silane clearly improves the mechanical properties of the composites. The use of the ELO resin as matrix for composite laminates improved substantially the mechanical performance compared to composites made with ESBO. (C) 2015 Elsevier Ltd. All rights reserved.This study was funded by the "Conselleria d'Educacio, Cultura i Esport" - Generalitat Valenciana (reference number: GV/2014/008).Samper Madrigal, MD.; Petrucci, R.; Sánchez Nacher, L.; Balart Gimeno, RA.; Kenny, JM. (2015). Properties of composite laminates based on basalt fibers with epoxidized vegetable oils. Materials and Design. 72:9-15. doi:10.1016/j.matdes.2015.02.002S9157