High toughness poly (lactic acid) (PLA) formulations obtained by ternary blends with poly (3-hydroxybutyrate) (PHB) and flexible polyesters from succinic acid

[EN] This work reports the development of poly(lactic acid) (PLA) formulations with improved toughness by ternary blends with poly(3-hydroxybutyrate) (PHB) and two different flexible polyesters derived from succinic acid, namely poly(butylene succinate) (PBS) and a copolymer, poly(butylene succinate-co-adipate) (PBSA). The main aim of this work is to increase the low intrinsic toughness of PLA without compromising the thermal properties by manufacturing ternary blends using epoxidized vegetable oils as compatibilizer agents. The ternary blends were manufactured by reactive extrusion in a co-rotating extruder and were subjected to mechanical, thermal, thermos-mechanical and morphology characterization. The obtained results confirm that these two succinic acid-derived polymers, i.e., PBS and PBSA, positively contribute to increase ductile properties in ternary blends with PLA and PHB with a subsequent improvement on impact toughness. In addition, both epoxidized vegetable oils, ELO and ESBO, are responsible for somewhat compatibilization between all three polyesters in blends which gives improved ductile properties with regard to uncompatibilized ternary blends. In addition, the temperature range in which these materials can be used is broader than ternary blends with other flexible polyester such as poly(e-caprolactone), as both PBS and PBSA melt at about 100 °C. These PLA-based materials with improved impact properties offer interesting applications in the packaging industry.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).Garcia-Campo, M.; Quiles-Carrillo, L.; Sanchez-Nacher, L.; Balart, R.; Montanes, N. (2018). High toughness poly (lactic acid) (PLA) formulations obtained by ternary blends with poly (3-hydroxybutyrate) (PHB) and flexible polyesters from succinic acid. Polymer Bulletin. 76(4):1839-1859. https://doi.org/10.1007/s00289-018-2475-yS18391859764Arrieta MP, Samper MD, Aldas M, Lopez J (2017) On the use of PLA-PHB blends for sustainable food packaging applications. Materials 10(9):26. https://doi.org/10.3390/ma10091008Burgos N, Armentano I, Fortunati E, Dominici F, Luzi F, Fiori S, Cristofaro F, Visai L, Jimenez A, Kenny JM (2017) Functional properties of plasticized bio-based poly(lactic acid)_poly(hydroxybutyrate) (PLA_PHB) films for active food packaging. Food Bioprocess Technol 10(4):770–780. https://doi.org/10.1007/s11947-016-1846-3Moustafa H, El Kissi N, Abou-Kandil AI, Abdel-Aziz MS, Dufresne A (2017) PLA/PBAT bionanocomposites with antimicrobial natural rosin for green packaging. ACS Appl Mater Interfaces 9(23):20132–20141. https://doi.org/10.1021/acsami.7b05557Bergstrom JS, Hayman D (2016) An overview of mechanical properties and material modeling of polylactide (PLA) for medical applications. Ann Biomed Eng 44(2):330–340. https://doi.org/10.1007/s10439-015-1455-8Leroy A, Ribeiro S, Grossiord C, Alves A, Vestberg RH, Salles V, Brunon C, Gritsch K, Grosgogeat B, Bayon Y (2017) FTIR microscopy contribution for comprehension of degradation mechanisms in PLA-based implantable medical devices. J Mater Sci Mater Med 28(6):13. https://doi.org/10.1007/s10856-017-5894-7Ferreira RTL, Amatte IC, Dutra TA, Burger D (2017) Experimental characterization and micrography of 3D printed PLA and PLA reinforced with short carbon fibers. Compos Part B Eng 124:88–100. https://doi.org/10.1016/j.compositesb.2017.05.013Song Y, Li Y, Song W, Yee K, Lee KY, Tagarielli VL (2017) Measurements of the mechanical response of unidirectional 3D-printed PLA. Mater Des 123:154–164. https://doi.org/10.1016/j.matdes.2017.03.051Jandas PJ, Mohanty S, Nayak SK (2013) Surface treated banana fiber reinforced poly (lactic acid) nanocomposites for disposable applications. J Clean Prod 52:392–401. https://doi.org/10.1016/j.jclepro.2013.03.033Nagarajan V, Mohanty AK, Misratt M (2016) Perspective on polylactic acid (PLA) based sustainable materials for durable applications: focus on toughness and heat resistance. ACS Sustain Chem Eng 4(6):2899–2916. https://doi.org/10.1021/acssuschemeng.6600321Notta-Cuvier D, Odent J, Delille R, Murariu M, Lauro F, Raquez JM, Bennani B, Dubois P (2014) Tailoring polylactide (PLA) properties for automotive applications: effect of addition of designed additives on main mechanical properties. Polym Test 36:1–9. https://doi.org/10.1016/j.polymertesting.2014.03.007Raquez JM, Habibi Y, Murariu M, Dubois P (2013) Polylactide (PLA)-based nanocomposites. Prog Polym Sci 38(10–11):1504–1542. https://doi.org/10.1016/j.progpolymsci.2013.05.014Pozo Morales A, Guemes A, Fernandez-Lopez A, Carcelen Valero V, De La Rosa Llano S (2017) Bamboo–polylactic acid (PLA) composite material for structural applications. Materials 10(11):1286. https://doi.org/10.3390/ma10111286Gurunathan T, Mohanty S, Nayak SK (2015) A review of the recent developments in biocomposites based on natural fibres and their application perspectives. Compos Part A Appl Sci Manuf 77:1–25. https://doi.org/10.1016/j.compositesa.2015.06.007Balart JF, Fombuena V, Fenollar O, Boronat T, Sanchez-Nacher L (2016) Processing and characterization of high environmental efficiency composites based on PLA and hazelnut shell flour (HSF) with biobased plasticizers derived from epoxidized linseed oil (ELO). Compos Part B Eng 86:168–177. https://doi.org/10.1016/j.compositesb.2015.09.063Qiang T, Yu DM, Gao HH (2012) Impact strength and fractal characteristic of PLA-based wood plastic composites. In: Shao Y et al (eds) Advanced building materials and sustainable architecture, Pts 1–4. Trans Tech Publications Ltd, Durnten-Zurich, p 683Kfoury G, Hassouna F, Raquez JM, Toniazzo V, Ruch D, Dubois P (2014) Tunable and durable toughening of polylactide materials via reactive extrusion. Macromol Mater Eng 299(5):583–595. https://doi.org/10.1002/mame.201300265Li Z, Tan BH, Lin T, He C (2016) Recent advances in stereocomplexation of enantiomeric PLA-based copolymers and applications. Prog Polym Sci 62:22–72. https://doi.org/10.1016/j.progpolymsci.2016.05.003Qian W, Song T, Ye M, Xu P, Lu G, Huang X (2017) PAA-g-PLA amphiphilic graft copolymer: synthesis, self-assembly, and drug loading ability. Polym Chem 8(28):4098–4107. https://doi.org/10.1039/c7py00762kArrieta MP, Lopez J, Lopez D, Kenny JM, Peponi L (2015) Development of flexible materials based on plasticized electrospun PLA-PHB blends: structural, thermal, mechanical and disintegration properties. Eur Polym J 73:433–446. https://doi.org/10.1016/j.eurpolymj.2015.10.036Fortunati E, Puglia D, Iannoni A, Terenzi A, Kenny JM, Torre L (2017) Processing conditions, thermal and mechanical responses of stretchable poly (lactic acid)poly (butylene succinate) films. Materials 10(7):16. https://doi.org/10.3390/ma10070809Maiza M, Benaniba MT, Quintard G, Massardier-Nageotte V (2015) Biobased additive plasticizing polylactic acid (PLA). Polimeros-Ciencia E Tecnologia 25(6):581–590. https://doi.org/10.1590/0104-1428.1986Shirai MA, Olivera Mueller CM, Eiras Grossmann MV, Yamashita F (2015) Adipate and citrate esters as plasticizers for poly(lactic acid)/thermoplastic starch sheets. J Polym Environ 23(1):54–61. https://doi.org/10.1007/s10924-014-0680-9Hassouna F, Raquez J-M, Addiego F, Dubois P, Toniazzo V, Ruch D (2011) New approach on the development of plasticized polylactide (PLA): grafting of poly (ethylene glycol)(PEG) via reactive extrusion. Eur Polym J 47(11):2134–2144Zubir NHM, Sam ST, Zulkepli NN, Omar MF (2018) The effect of rice straw particulate loading and polyethylene glycol as plasticizer on the properties of polylactic acid/polyhydroxybutyrate-valerate blends. Polym Bull 75(1):61–76Pluta M, Piorkowska E (2015) Tough crystalline blends of polylactide with block copolymers of ethylene glycol and propylene glycol. Polym Test 46:79–87. https://doi.org/10.1016/j.polymertesting.2015.06.014Nazari T, Garmabi H (2018) The effects of processing parameters on the morphology of PLA/PEG melt electrospun fibers. Polym Int 67(2):178–188Burgos N, Martino VP, Jimenez A (2013) Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid. Polym Degrad Stab 98(2):651–658. https://doi.org/10.1016/j.polymdegradstab.2012.11.009Burgos N, Tolaguera D, Fiori S, Jimenez A (2014) Synthesis and characterization of lactic acid oligomers: evaluation of performance as poly(lactic acid) plasticizers. J Polym Environ 22(2):227–235. https://doi.org/10.1007/s10924-013-0628-5Ali F, Chang Y-W, Kang SC, Yoon JY (2009) Thermal, mechanical and rheological properties of poly (lactic acid)/epoxidized soybean oil blends. Polym Bull 62(1):91–98Ferri JM, Fenollar O, Jorda-Vilaplana A, García-Sanoguera D, Balart R (2016) Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends. Polym Int 65:453–463Ostafinska A, Fortelny I, Hodan J, Krejcikova S, Nevoralova M, Kredatusova J, Krulis Z, Kotek J, Slouf M (2017) Strong synergistic effects in PLA/PCL blends: impact of PIA matrix viscosity. J Mech Behav Biomed Mater 69:229–241. https://doi.org/10.1016/j.jmbbm.2017.01.015Ning Z, Liu J, Jiang N, Gan Z (2017) Enhanced crystallization rate and mechanical properties of poly (l-lactic acid) by stereocomplexation with four-armed poly (ϵ-caprolactone)-block-poly (d-lactic acid) diblock copolymer. Polym Int 66(6):968–976Fortelný I, Ostafińska A, Michálková D, Jůza J, Mikešová J, Šlouf M (2015) Phase structure evolution during mixing and processing of poly (lactic acid)/polycaprolactone (PLA/PCL) blends. Polym Bull 72(11):2931–2947Lai S-M, Liu Y-H, Huang C-T, Don T-M (2017) Miscibility and toughness improvement of poly(lactic acid)/poly(3-Hydroxybutyrate) blends using a melt-induced degradation approach. J Polym Res. https://doi.org/10.1007/s10965-017-1253-0Amor A, Okhay N, Guinault A, Miquelard-Garnier G, Sollogoub C, Gervais M (2018) Combined compatibilization and plasticization effect of low molecular weight poly(lactic acid) in poly(lactic acid)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blends. Exp Polym Lett 12(2):114–125. https://doi.org/10.3144/expresspolymlett.2018.10Gonzalez-Ausejo J, Sanchez-Safont E, Maria Lagaron J, Olsson RT, Gamez-Perez J, Cabedo L (2017) Assessing the thermoformability of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(acid lactic) blends compatibilized with diisocyanates. Polym Test 62:235–245. https://doi.org/10.1016/j.polymertesting.2017.06.026Huang XX, Tao XM, Zhang ZH, Chen P (2017) Properties and performances of fabrics made from bio-based and degradable polylactide acid/poly (hydroxybutyrate-co-hydroxyvalerate) (PLA/PHBV) filament yarns. Text Res J 87(20):2464–2474. https://doi.org/10.1177/0040517516671128Akrami M, Ghasemi I, Azizi H, Karrabi M, Seyedabadi M (2016) A new approach in compatibilization of the poly(lactic acid)/thermoplastic starch (PLA/TPS) blends. Carbohydr Polym 144:254–262. https://doi.org/10.1016/j.carbpol.2016.02.035Ibrahim N, Ab Wahab MK, Uylan DN, Ismail H (2017) Physical and degradation properties of polylactic acid and thermoplastic starch blends—effect of citric acid treatment on starch structures. BioResources 12(2):3076–3087Fernandes TMD, Leite MCAM, de Sousa AMF, Furtado CRG, Escócio VA, da Silva ALN (2017) Improvement in toughness of polylactide/poly (butylene adipate-co-terephthalate) blend by adding nitrile rubber. Polym Bull 74(5):1713–1726Luzi F, Fortunati E, Jimenez A, Puglia D, Pezzolla D, Gigliotti G, Kenny JM, Chiralt A, Torre L (2016) Production and characterization of PLA_PBS biodegradable blends reinforced with cellulose nanocrystals extracted from hemp fibres. Ind Crops Prod 93:276–289. https://doi.org/10.1016/j.indcrop.2016.01.045Supthanyakul R, Kaabbuathong N, Chirachanchai S (2017) Poly(L-lactide-b-butylene succinate-b-L-lactide) triblock copolymer: a multi-functional additive for PLA/PBS blend with a key performance on film clarity. Polym Degrad Stab 142:160–168. https://doi.org/10.1016/j.polymdegradstab.2017.05.029Hu X, Su T, Li P, Wang Z (2018) Blending modification of PBS/PLA and its enzymatic degradation. Polym Bull 75(2):533–546Ojijo V, Ray SS (2015) Super toughened biodegradable polylactide blends with non-linear copolymer interfacial architecture obtained via facile in-situ reactive compatibilization. Polymer 80:1–17. https://doi.org/10.1016/j.polymer.2015.10.038Pigatto C, Santos Almeida JH, Luiz Ornaghi H, Rodríguez AL, Mählmann CM, Amico SC (2012) Study of polypropylene/ethylene-propylene-diene monomer blends reinforced with sisal fibers. Polym Compos 33(12):2262–2270Liu L, Wang Y, Li Y, Wu J, Zhou Z, Jiang C (2009) Improved fracture toughness of immiscible polypropylene/ethylene-co-vinyl acetate blends with multiwalled carbon nanotubes. Polymer 50(14):3072–3078Samper-Madrigal M, Fenollar O, Dominici F, Balart R, Kenny J (2015) The effect of sepiolite on the compatibilization of polyethylene–thermoplastic starch blends for environmentally friendly films. J Mater Sci 50(2):863–872Pal P, Kundu MK, Malas A, Das CK (2014) Compatibilizing effect of halloysite nanotubes in polar–nonpolar hybrid system. J Appl Polym Sci 131(1):39587Si M, Araki T, Ade H, Kilcoyne A, Fisher R, Sokolov JC, Rafailovich MH (2006) Compatibilizing bulk polymer blends by using organoclays. Macromolecules 39(14):4793–4801Wang N, Yu J, Ma X (2007) Preparation and characterization of thermoplastic starch/PLA blends by one-step reactive extrusion. Polym Int 56(11):1440–1447Gonzalez-Ausejo J, Sanchez-Safont E, Maria Lagaron J, Balart R, Cabedo L, Gamez-Perez J (2017) Compatibilization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-poly(lactic acid) blends with diisocyanates. J Appl Polym Sci 134(20):44806. https://doi.org/10.1002/app.44806Sajna VP, Mohanty S, Nayak SK (2016) Effect of poly (lactic acid)-graft-glycidyl methacrylate as a compatibilizer on properties of poly (lactic acid)/banana fiber biocomposites. Polym Adv Technol 27(4):515–524. https://doi.org/10.1002/pat.3698Torres-Giner S, Montanes N, Boronat T, Quiles-Carrillo L, Balart R (2016) Melt grafting of sepiolite nanoclay onto poly(3-hydroxybutyrate-co-4-hydroxybutyrate) by reactive extrusion with multi-functional epoxy-based styrene-acrylic oligomer. Eur Polym J 84:693–707. https://doi.org/10.1016/j.eurpolymj.2016.09.057Darie-Nita RN, Vasile C, Irimia A, Lipsa R, Rapa M (2016) Evaluation of some eco-friendly plasticizers for PLA films processing. J Appl Polym Sci 133(13):11. https://doi.org/10.1002/app.43223Meng X, Bocharova V, Tekinalp H, Cheng S, Kisliuk A, Sokolov AP, Kunc V, Peter WH, Ozcan S (2018) Toughening of nanocelluose/PLA composites via bio-epoxy interaction: mechanistic study. Mater Des 139:188–197Yuryev Y, Mohanty AK, Misra M (2016) A new approach to supertough poly(lactic acid): a high temperature reactive blending. Macromol Mater Eng 301(12):1443–1453. https://doi.org/10.1002/mame.201600242Zhang K, Mohanty AK, Misra M (2012) Fully biodegradable and biorenewable ternary blends from polylactide, poly(3-hydroxybutyrate-co-hydroxyvalerate) and poly(butylene succinate) with balanced properties. ACS Appl Mater Interfaces 4(6):3091–3101. https://doi.org/10.1021/am3004522Carmona VB, Correa AC, Marconcini JM, Mattoso LHC (2015) Properties of a biodegradable ternary blend of thermoplastic starch (TPS), poly(epsilon-caprolactone) (PCL) and poly(lactic acid) (PLA). J Polym Environ 23(1):83–89. https://doi.org/10.1007/s10924-014-0666-7Ross S, Mahasaranon S, Ross GM (2015) Ternary polymer blends based on poly(lactic acid): effect of stereo-regularity and molecular weight. J Appl Polym Sci 132(14):8. https://doi.org/10.1002/app.41780Garcia-Campo MJ, Quiles-Carrillo L, Masia J, Reig-Perez MJ, Montanes N, Balart R (2017) Environmentally friendly compatibilizers from soybean oil for ternary blends of poly(lactic acid)-PLA, poly(epsilon-caprolactone)-PCL and Poly(3-hydroxybutyrate)-PHB. Materials (Basel, Switzerland) 10(11):1339. https://doi.org/10.3390/ma10111339García-Campo MJ, Boronat T, Quiles-Carrillo L, Balart R, Montanes N (2017) Manufacturing and characterization of toughened poly (lactic acid)(PLA) formulations by ternary blends with biopolyesters. Polymers 10(1):3Vijayarajan S, Selke SEM, Matuana LM (2014) Continuous blending approach in the manufacture of epoxidized soybean-plasticized poly(lactic acid) sheets and films. Macromol Mater Eng 299(5):622–630. https://doi.org/10.1002/mame.201300226Supthanyakul R, Kaabbuathong N, Chirachanchai S (2016) Random poly(butylene succinate-co-lactic acid) as a multi-functional additive for miscibility, toughness, and clarity of PLA/PBS blends. Polymer 105:1–9. https://doi.org/10.1016/j.polymer.2016.10.006Quiles-Carrillo L, Duart S, Montanes N, Torres-Giner S, Balart R (2018) Enhancement of the mechanical and thermal properties of injection-molded polylactide parts by the addition of acrylated epoxidized soybean oil. Mater Des 140:54–63Signori F, Boggioni A, Righetti MC, Escrig Rondan C, Bronco S, Ciardelli F (2015) Evidences of transesterification, chain branching and cross-linking in a biopolyester commercial blend upon reaction with dicumyl peroxide in the melt. Macromol Mater Eng 300(2):153–160. https://doi.org/10.1002/mame.201400187Ojijo V, Ray SS, Sadiku R (2012) Role of specific interfacial area in controlling properties of immiscible blends of biodegradable polylactide and poly (butylene succinate)-co-adipate. ACS Appl Mater Interfaces 4(12):6689–6700. https://doi.org/10.1021/am301842eNi CY, Luo RC, Xu KT, Chen GQ (2009) Thermal and crystallinity property studies of poly (L-Lactic Acid) blended with oligomers of 3-hydroxybutyrate or dendrimers of hydroxyalkanoic acids. J Appl Polym Sci 111(4):1720–1727. https://doi.org/10.1002/app.29182da Silva HSP, Ornaghi HL Jr, Santos Almeida JH Jr, Zattera AJ, Campos Amico S (2014) Mechanical behavior and correlation between dynamic fragility and dynamic mechanical properties of curaua fiber composites. Polym Compos 35(6):1078–1086Júnior JHSA, Júnior HLO, Amico SC, Amado FDR (2012) Study of hybrid intralaminate curaua/glass composites. Mater Des 42:111–11

Plasticizing effect of biobased epoxidized fatty acid esters on mechanical and thermal properties of poly(lactic acid)

Poly(lactic acid), PLA, is a polyester that can be produced from lactic acid derived from renewable resources. This polymer offers attracting uses in packaging industry due to its biodegradability and high tensile strength. However, PLA is quite brittle, which limits its applications. To overcome this drawback, PLA was plasticized with epoxy-type plasticizer derived from a fatty acid, octyl epoxy stearate (OES) at different loadings (1, 3, 5, 10, 15, and 20 phr). The addition of OES decreases the glass transition temperature and provides a remarkable increase in elongation at break and impact-absorbed energy. Plasticizer saturation occurs at relatively low concentrations of about 5 phr OES; higher concentration leads to phase separation as observed by field emission scanning electron microscopy (FESEM). Optimum balanced mechanical properties are obtained at relatively low concentrations of OES (5 phr), thus indicating the usefulness of this material as environmentally friendly plasticizer for PLA industrial formulations.This research was supported by the 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.Ferri Azor, JM.; Samper Madrigal, MD.; García Sanoguera, D.; Reig Pérez, MJ.; Fenollar Gimeno, OÁ.; Balart Gimeno, RA. (2016). Plasticizing effect of biobased epoxidized fatty acid esters on mechanical and thermal properties of poly(lactic acid). Journal of Materials Science. 51(11):5356-5366. https://doi.org/10.1007/s10853-016-9838-2S535653665111Alam J, Alam M, Raja M, Abduljaleel Z, Dass LA (2014) MWCNTs-reinforced epoxidized linseed oil plasticized polylactic acid nanocomposite and its electroactive shape memory behaviour. Int J Mol Sci 15(11):19924–19937. doi: 10.3390/ijms151119924Arrieta MP, Fortunati E, Dominici F, Lopez J, Kenny JM (2015) Bionanocomposite films based on plasticized PLA-PHB/cellulose nanocrystal blends. Carbohydr Polym 121:265–275. doi: 10.1016/j.carbpol.2014.12.056Dharmalingam S, Hayes DG, Wadsworth LC, Dunlap RN, DeBruyn JM, Lee J, Wszelaki AL (2015) Soil degradation of polylactic acid/polyhydroxyalkanoate-based nonwoven mulches. J Polym Environ 23(3):302–315. doi: 10.1007/s10924-015-0716-9Lin C-M, Lin C-H, Huang Y-T, Lou C-W, Lin J-H (2013) Mechanical and electrical properties of the polyaniline (PANI)/polylactic acid (PLA) nonwoven fabric. In: Kida K (ed), Machine design and manufacturing engineering II, Pts 1 and 2, vols 365–366. pp 1074–1077. doi: 10.4028/www.scientific.net/AMM.365-366.1074Serafini Immich AP, Lis Arias M, Carreras N, Luis Boemo R, Antonio Tornero J (2013) Drug delivery systems using sandwich configurations of electrospun poly(lactic acid) nanofiber membranes and ibuprofen. Mater Sci Eng C-Mater Biol Appl 33(7):4002–4008. doi: 10.1016/j.msec.2013.05.034Llorens E, Calderon S, del Valle LJ, Puiggali J (2015) Polybiguanide (PHMB) loaded in PLA scaffolds displaying high hydrophobic, biocompatibility and antibacterial properties. Mater Sci Eng C-Mater Biol Appl 50:74–84. doi: 10.1016/j.msec.2015.01.100Nainar SMM, Begum S, Ansari MNM, Hoque ME, Aini SS, Ng MH, Ruszymah BHI (2014) Effect of compatibilizers on in vitro biocompatibility of PLA-HA bioscaffold. Bioinspired Biomim Nanobiomater 3(4):208–216. doi: 10.1680/bbn.14.00014Huang R, Zhu X, Tu H, Wan A (2014) The crystallization behavior of porous poly(lactic acid) prepared by modified solvent casting/particulate leaching technique for potential use of tissue engineering scaffold. Mater Lett 136:126–129. doi: 10.1016/j.matlet.2014.08.044Yesid Gomez-Pachon E, Manuel Sanchez-Arevalo F, Sabina FJ, Maciel-Cerda A, Montiel Campos R, Batina N, Morales-Reyes I, Vera-Graziano R (2013) Characterisation and modelling of the elastic properties of poly(lactic acid) nanofibre scaffolds. J Mater Sci 48(23):8308–8319. doi: 10.1007/s10853-013-7644-7Zhang J, Yin H-M, Hsiao BS, Zhong G-J, Li Z-M (2014) Biodegradable poly(lactic acid)/hydroxyl apatite 3D porous scaffolds using high-pressure molding and salt leaching. J Mater Sci 49(4):1648–1658. doi: 10.1007/s10853-013-7848-xArmentano I, Fortunati E, Burgos N, Dominici F, Luzi F, Fiori S, Jimenez A, Yoon K, Ahn J, Kang S, Kenny JM (2015) Processing and characterization of plasticized PLA/PHB blends for biodegradable multiphase systems. Exp Polym Lett 9(7):583–596. doi: 10.3144/expresspolymlett.2015.55Patricia Arrieta M, del Mar Castro-Lopez M, Rayon E, Fernando Barral-Losada L, Manuel Lopez-Vilarino J, Lopez J, Victoria Gonzalez-Rodriguez M (2014) Plasticized poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends incorporated with catechin intended for active food-packaging applications. J Agric Food Chem 62(41):10170–10180. doi: 10.1021/jf5029812He Y, Hu Z, Ren M, Ding C, Chen P, Gu Q, Wu Q (2014) Evaluation of PHBHHx and PHBV/PLA fibers used as medical sutures. J Mater Sci-Mater Med 25(2):561–571. doi: 10.1007/s10856-013-5073-4Vieira AC, Vieira JC, Ferra JM, Magalhaes FD, Guedes RM, Marques AT (2011) Mechanical study of PLA-PCL fibers during in vitro degradation. J Mech Behav Biomed Mater 4(3):451–460. doi: 10.1016/j.jmbbm.2010.12.006K-y Zhang, X-h Ran, Y-g Zhuang, Yao B, L-s Dong (2009) Blends of poly(lactic acid) with thermoplastic acetylated starch. Chem Res Chin Univ 25(5):748–753Chieng BW, Ibrahim NA, Yunus WMZW, Hussein MZ (2013) Plasticized poly(lactic acid) with low molecular weight poly(ethylene glycol): mechanical, thermal, and morphology properties. J Appl Polym Sci 130(6):4576–4580. doi: 10.1002/app.39742Yu Y, Cheng Y, Ren J, Cao E, Fu X, Guo W (2015) Plasticizing effect of poly(ethylene glycol)s with different molecular weights in poly(lactic acid)/starch blends. J Appl Polym Sci 132(16). doi: 10.1002/app.41808Nazari T, Garmabi H (2014) Polylactic acid/polyethylene glycol blend fibres prepared via melt electrospinning: effect of polyethylene glycol content. Micro Nano Lett 9(10):686–690. doi: 10.1049/mnl.2013.0735Piorkowska E, Kulinski Z, Galeski A, Masirek R (2006) Plasticization of semicrystalline poly(l-lactide) with poly(propylene glycol). Polymer 47(20):7178–7188. doi: 10.1016/j.polymer.2006.03.115Burgos N, Martino VP, Jimenez A (2013) Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid. Polym Degrad Stab 98(2):651–658. doi: 10.1016/j.polymdegradstab.2012.11.009Dobircau L, Delpouve N, Herbinet R, Domenek S, Le Pluart L, Delbreilh L, Ducruet V, Dargent E (2015) Molecular mobility and physical ageing of plasticized poly(lactide). Polym Eng Sci 55(4):858–865. doi: 10.1002/pen.23952Hassouna F, Raquez J-M, Addiego F, Toniazzo V, Dubois P, Ruch D (2012) New development on plasticized poly(lactide): chemical grafting of citrate on PLA by reactive extrusion. Eur Polymer J 48(2):404–415. doi: 10.1016/j.eurpolymj.2011.12.001Tsou C-H, Suen M-C, Yao W-H, Yeh J-T, Wu C-S, Tsou C-Y, Chiu S-H, Chen J-C, Wang RY, Lin S-M, Hung W-S, De Guzman M, Hu C-C, Lee K-R (2014) Preparation and characterization of bioplastic-based green renewable composites from tapioca with acetyl tributyl citrate as a plasticizer. Materials 7(8):5617–5632. doi: 10.3390/ma7085617Jing J, Qa Qiao, Jin Y, Ma C, Cai H, Meng Y, Cai Z, Feng D (2012) Molecular and mesoscopic dynamics simulations on the compatibility of PLA/plasticizer blends. Chin J Chem 30(1):133–138. doi: 10.1002/cjoc.201180454Ljungberg N, Wesslen B (2003) Tributyl citrate oligomers as plasticizers for poly (lactic acid): thermo-mechanical film properties and aging. Polymer 44(25):7679–7688. doi: 10.1016/j.polymer.2003.09.055Notta-Cuvier D, Murariu M, Odent J, Delille R, Bouzouita A, Raquez J-M, Lauro F, Dubois P (2015) Tailoring polylactide properties for automotive applications: effects of co-addition of halloysite Nanotubes and selected plasticizer. Macromol Mater Eng 300(7):684–698. doi: 10.1002/mame.201500032Carbonell-Verdu A, Bernardi L, Garcia-Garcia D, Sanchez-Nacher L, Balart R (2015) Development of environmentally friendly composite matrices from epoxidized cottonseed oil. Eur Polymer J 63:1–10. doi: 10.1016/j.eurpolymj.2014.11.043Samper MD, Fombuena V, Boronat T, Garcia-Sanoguera D, Balart R (2012) Thermal and mechanical characterization of epoxy resins (ELO and ESO) cured with anhydrides. J Am Oil Chem Soc 89(8):1521–1528. doi: 10.1007/s11746-012-2041-ySamper MD, Petrucci R, Sanchez-Nacher L, Balart R, Kenny JM (2015) Properties of composite laminates based on basalt fibers with epoxidized vegetable oils. Mater Des 72:9–15. doi: 10.1016/j.matdes.2015.02.002Samper MD, Petrucci R, Sanchez-Nacher L, Balart R, Kenny JM (2015) New environmentally friendly composite laminates with epoxidized linseed oil (ELO) and slate fiber fabrics. Compos Part B Eng 71:203–209. doi: 10.1016/j.compositesb.2014.11.034Bueno-Ferrer C, Garrigos MC, Jimenez A (2010) Characterization and thermal stability of poly(vinyl chloride) plasticized with epoxidized soybean oil for food packaging. Polym Degrad Stab 95(11):2207–2212. doi: 10.1016/j.polymdegradstab.2010.01.027Bueno-Ferrer C, Jimenez A, Garrigos MC (2010) Migration analysis of epoxidized soybean oil and other plasticizers in commercial lids for food packaging by gas chromatography-mass spectrometry. Food Addit Contam Part a—Chem Anal Control Expo Risk Assess 27(10):1469–1477. doi: 10.1080/19440049.2010.502129Fenollar O, Garcia-Sanoguera D, Sanchez-Nacher L, Lopez J, Balart R (2010) Effect of the epoxidized linseed oil concentration as natural plasticizer in vinyl plastisols. J Mater Sci 45(16):4406–4413. doi: 10.1007/s10853-010-4520-6Fenollar O, Garcia-Sanoguera D, Sanchez-Nacher L, Lopez J, Balart R (2012) Characterization of the curing process of vinyl plastisols with epoxidized linseed oil as a natural-based plasticizer. J Appl Polym Sci 124(3):2550–2557. doi: 10.1002/app.34645Semsarzadeh MA, Mehrabzadeh M, Arabshahi SS (2005) Mechanical and thermal properties of the plasticized PVC-ESBO. Iran Polym J 14(9):769–773Chieng BW, Ibrahim NA, Then YY, Loo YY (2014) Epoxidized vegetable oils plasticized poly(lactic acid) biocomposites: mechanical, thermal and morphology properties. Molecules 19(10):16024–16038. doi: 10.3390/molecules191016024Prempeh N, Li J, Liu D, Das K, Maiti S, Zhang Y (2014) Plasticizing effects of epoxidized sun flower oil on biodegradable polylactide films: a comparative study. Polym Sci Ser A 56(6):856–863. doi: 10.1134/s0965545x14060182Santos EF, Oliveira RVB, Reiznautt QB, Samios D, Nachtigall SMB (2014) Sunflower-oil biodiesel-oligoesters/polylactide blends: plasticizing effect and ageing. Polym Test 39:23–29. doi: 10.1016/j.polymertesting.2014.07.010Li H, Huneault MA (2007) Effect of nucleation and plasticization on the crystallization of poly(lactic acid). Polymer 48(23):6855–6866. doi: 10.1016/j.polymer.2007.09.020Arrieta MP, Lopez J, Ferrandiz S, Peltzer MA (2013) Characterization of PLA-limonene blends for food packaging applications. Polym Test 32(4):760–768. doi: 10.1016/j.polymertesting.2013.03.016Arrieta MP, Samper MD, Lopez J, Jimenez A (2014) Combined effect of poly(hydroxybutyrate) and plasticizers on polylactic acid properties for film intended for food packaging. J Polym Environ 22(4):460–470. doi: 10.1007/s10924-014-0654-

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). Effect of pine resin derivatives on the structural, thermal, and mechanical properties of Mater-Bi type bioplastic. Journal of Applied Polymer Science. 137(4):1-14. https://doi.org/10.1002/app.48236S1141374Plastics Europe Plastics – the Facts 2018. An analysis of European plastics production demand and waste data” [Online]. Available:https://www.plasticseurope.org/application/files/6315/4510/9658/Plastics_the_facts_2018_AF_web.pdf(accessed on July 1 2019).Arrieta, M. P., Peponi, L., López, D., & Fernández-García, M. (2018). Recovery of yerba mate (Ilex paraguariensis) residue for the development of PLA-based bionanocomposite films. Industrial Crops and Products, 111, 317-328. doi:10.1016/j.indcrop.2017.10.042Akrami, M., Ghasemi, I., Azizi, H., Karrabi, M., & Seyedabadi, M. (2016). A new approach in compatibilization of the poly(lactic acid)/thermoplastic starch (PLA/TPS) blends. Carbohydrate Polymers, 144, 254-262. doi:10.1016/j.carbpol.2016.02.035Arrieta, 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/ma10091008Elfehri Borchani, K., Carrot, C., & Jaziri, M. (2015). Biocomposites of Alfa fibers dispersed in the Mater-Bi® type bioplastic: Morphology, mechanical and thermal properties. Composites Part A: Applied Science and Manufacturing, 78, 371-379. doi:10.1016/j.compositesa.2015.08.023Ferri, 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.2016.03.082Arrieta, M. P., López, J., López, D., Kenny, J. M., & Peponi, L. (2016). Effect of chitosan and catechin addition on the structural, thermal, mechanical and disintegration properties of plasticized electrospun PLA-PHB biocomposites. Polymer Degradation and Stability, 132, 145-156. doi:10.1016/j.polymdegradstab.2016.02.027Fabra, M. J., López-Rubio, A., Cabedo, L., & Lagaron, J. M. (2016). Tailoring barrier properties of thermoplastic corn starch-based films (TPCS) by means of a multilayer design. Journal of Colloid and Interface Science, 483, 84-92. doi:10.1016/j.jcis.2016.08.021Makaremi, M., Pasbakhsh, P., Cavallaro, G., Lazzara, G., Aw, Y. K., Lee, S. M., & Milioto, S. (2017). Effect of Morphology and Size of Halloysite Nanotubes on Functional Pectin Bionanocomposites for Food Packaging Applications. ACS Applied Materials & Interfaces, 9(20), 17476-17488. doi:10.1021/acsami.7b04297Niu, X., Liu, Y., Song, Y., Han, J., & Pan, H. (2018). Rosin modified cellulose nanofiber as a reinforcing and co-antimicrobial agents in polylactic acid /chitosan composite film for food packaging. Carbohydrate Polymers, 183, 102-109. doi:10.1016/j.carbpol.2017.11.079Mujica‐Garcia A.;Sonseca A.;Arrieta M. P.;Yusef M.;López D.;Gimenez E.;Kenny J. M.;Peponi L.In Tiwari A. Wang R. Wei B.; Advanced Surface Engineering Materials; Wiley: Massachussets USA 2016.Sessini, 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.2016.02.026Ferri, 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.45751Trovatti, E., Carvalho, A. J. F., & Gandini, A. (2014). A new approach to blending starch with natural rubber. Polymer International, 64(5), 605-610. doi:10.1002/pi.4808Samper-Madrigal, M. D., Fenollar, O., Dominici, F., Balart, R., & Kenny, J. M. (2014). The effect of sepiolite on the compatibilization of polyethylene–thermoplastic starch blends for environmentally friendly films. Journal of Materials Science, 50(2), 863-872. doi:10.1007/s10853-014-8647-8Azevedo, V. M., Borges, S. V., Marconcini, J. M., Yoshida, M. I., Neto, A. R. S., Pereira, T. C., & Pereira, C. F. G. (2017). Effect of replacement of corn starch by whey protein isolate in biodegradable film blends obtained by extrusion. Carbohydrate Polymers, 157, 971-980. doi:10.1016/j.carbpol.2016.10.046Sessini, 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.201700388Correa, A. C., Carmona, V. B., Simão, J. A., Capparelli Mattoso, L. H., & Marconcini, J. M. (2017). Biodegradable blends of urea plasticized thermoplastic starch (UTPS) and poly(ε-caprolactone) (PCL): Morphological, rheological, thermal and mechanical properties. Carbohydrate Polymers, 167, 177-184. doi:10.1016/j.carbpol.2017.03.051Lendvai, L., Apostolov, A., & Karger-Kocsis, J. (2017). Characterization of layered silicate-reinforced blends of thermoplastic starch (TPS) and poly(butylene adipate-co-terephthalate). Carbohydrate Polymers, 173, 566-572. doi:10.1016/j.carbpol.2017.05.100Mikus, P.-Y., Alix, S., Soulestin, J., Lacrampe, M. F., Krawczak, P., Coqueret, X., & Dole, P. (2014). Deformation mechanisms of plasticized starch materials. Carbohydrate Polymers, 114, 450-457. doi:10.1016/j.carbpol.2014.06.087Sessini, V., Arrieta, M. P., Raquez, J.-M., Dubois, P., Kenny, J. M., & Peponi, L. (2019). Thermal and composting degradation of EVA/Thermoplastic starch blends and their nanocomposites. Polymer Degradation and Stability, 159, 184-198. doi:10.1016/j.polymdegradstab.2018.11.025Arrieta, M. P., Samper, M. D., Jiménez-López, M., Aldas, M., & López, J. (2017). Combined effect of linseed oil and gum rosin as natural additives for PVC. Industrial Crops and Products, 99, 196-204. doi:10.1016/j.indcrop.2017.02.009Narayanan, M., Loganathan, S., Valapa, R. B., Thomas, S., & Varghese, T. O. (2017). UV protective poly(lactic acid)/rosin films for sustainable packaging. International Journal of Biological Macromolecules, 99, 37-45. doi:10.1016/j.ijbiomac.2017.01.152Wilbon, P. A., Chu, F., & Tang, C. (2012). Progress in Renewable Polymers from Natural Terpenes, Terpenoids, and Rosin. Macromolecular Rapid Communications, 34(1), 8-37. doi:10.1002/marc.201200513Rodríguez-García, A., Martín, J. A., López, R., Sanz, A., & Gil, L. (2016). Effect of four tapping methods on anatomical traits and resin yield in Maritime pine (Pinus pinaster Ait.). Industrial Crops and Products, 86, 143-154. doi:10.1016/j.indcrop.2016.03.033Sharma, L., & Singh, C. (2016). Composite film developed from the blends of sesame protein isolate and gum rosin and their properties thereof. Polymer Composites, 39(5), 1480-1487. doi:10.1002/pc.24088Moustafa, H., El Kissi, N., Abou-Kandil, A. I., Abdel-Aziz, M. S., & Dufresne, A. (2017). PLA/PBAT Bionanocomposites with Antimicrobial Natural Rosin for Green Packaging. ACS Applied Materials & Interfaces, 9(23), 20132-20141. doi:10.1021/acsami.7b05557Yu, C., Chen, C., Gong, Q., & Zhang, F.-A. (2012). Preparation of polymer microspheres with a rosin moiety from rosin ester, styrene and divinylbenzene. Polymer International, 61(11), 1619-1626. doi:10.1002/pi.4249Gutierrez, J., & Tercjak, A. (2014). Natural gum rosin thin films nanopatterned by poly(styrene)-block-poly(4-vinylpiridine) block copolymer. RSC Advances, 4(60), 32024. doi:10.1039/c4ra04296dCavallaro, G., Lazzara, G., Milioto, S., Parisi, F., & Ruisi, F. (2017). Nanocomposites based on esterified colophony and halloysite clay nanotubes as consolidants for waterlogged archaeological woods. Cellulose, 24(8), 3367-3376. doi:10.1007/s10570-017-1369-8Marina P. Arrieta, Juan López, Santiago Ferrándiz, & Mercedes A. Peltzer. (2015). EFFECT OF D-LIMONENE ON THE STABILIZATION OF POLY (LACTIC ACID). Acta Horticulturae, (1065), 719-725. doi:10.17660/actahortic.2015.1065.90Arrieta, 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.2013.11.009Liu, X. Q., Huang, W., Jiang, Y. H., Zhu, J., & Zhang, C. Z. (2012). Preparation of a bio-based epoxy with comparable properties to those of petroleum-based counterparts. Express Polymer Letters, 6(4), 293-298. doi:10.3144/expresspolymlett.2012.32International Standards Organization ISO 527‐1:2012 ‐ Plastics ‐ Determination of tensile properties ‐ Part 1: General 2012.Sessini, V., Raquez, J.-M., Lo Re, G., Mincheva, R., Kenny, J. M., Dubois, P., & Peponi, L. (2016). Multiresponsive Shape Memory Blends and Nanocomposites Based on Starch. ACS Applied Materials & Interfaces, 8(30), 19197-19201. doi:10.1021/acsami.6b06618Samper, M., Bertomeu, D., Arrieta, M., Ferri, J., & López-Martínez, J. (2018). Interference of Biodegradable Plastics in the Polypropylene Recycling Process. Materials, 11(10), 1886. doi:10.3390/ma11101886International Standards Organization ISO 178:2010 ‐ Plastics ‐ Determination of flexural propertie 2010.International Standards Organization ISO 179:2010 ‐ Plastics ‐ Determination of charpy impact properties 2010.International Standards Organization ISO 868:2003 ‐ Plastics and ebonite ‐ Determination of indentation hardness by means of a durometer (Shore hardness) 2003.Jost, V. (2018). Packaging related properties of commercially available biopolymers – An overview of the status quo. Express Polymer Letters, 12(5), 429-435. doi:10.3144/expresspolymlett.2018.36International Standards Organization ISO 75‐1:2013 ‐ Plastics ‐ Determination of temperature of deflection under load ‐ Part 1: General test method 2013.Mok, S. L., Kwong, C. K., & Lau, W. S. (2001). A Hybrid Neural Network and Genetic Algorithm Approach to the Determination of Initial Process Parameters for Injection Moulding. The International Journal of Advanced Manufacturing Technology, 18(6), 404-409. doi:10.1007/s001700170050Al-Itry, R., Lamnawar, K., & Maazouz, A. (2012). Improvement of thermal stability, rheological and mechanical properties of PLA, PBAT and their blends by reactive extrusion with functionalized epoxy. Polymer Degradation and Stability, 97(10), 1898-1914. doi:10.1016/j.polymdegradstab.2012.06.028Bastioli, C., Cerutti, A., Guanella, I., Romano, G. C., & Tosin, M. (1995). Physical state and biodegradation behavior of starch-polycaprolactone systems. Journal of Environmental Polymer Degradation, 3(2), 81-95. doi:10.1007/bf02067484Esmaeili, M., Pircheraghi, G., & Bagheri, R. (2017). Optimizing the mechanical and physical properties of thermoplastic starch via tuning the molecular microstructure through co-plasticization by sorbitol and glycerol. Polymer International, 66(6), 809-819. doi:10.1002/pi.5319Mano, J. F., Koniarova, D., & Reis, R. L. (2003). Journal of Materials Science: Materials in Medicine, 14(2), 127-135. doi:10.1023/a:1022015712170Khan, G., Yadav, S. K., Patel, R. R., Kumar, N., Bansal, M., & Mishra, B. (2017). Tinidazole functionalized homogeneous electrospun chitosan/poly (ε-caprolactone) hybrid nanofiber membrane: Development, optimization and its clinical implications. International Journal of Biological Macromolecules, 103, 1311-1326. doi:10.1016/j.ijbiomac.2017.05.161Arrieta, M. P., & Peponi, L. (2017). Polyurethane based on PLA and PCL incorporated with catechin: Structural, thermal and mechanical characterization. European Polymer Journal, 89, 174-184. doi:10.1016/j.eurpolymj.2017.02.028Jindal, R., Sharma, R., Maiti, M., Kaur, A., Sharma, P., Mishra, V., & Jana, A. K. (2016). Synthesis and characterization of novel reduced Gum rosin-acrylamide copolymer-based nanogel and their investigation for antibacterial activity. Polymer Bulletin, 74(8), 2995-3014. doi:10.1007/s00289-016-1877-ySingh, V., Joshi, S., & Malviya, T. (2018). Carboxymethyl cellulose-rosin gum hybrid nanoparticles: An efficient drug carrier. International Journal of Biological Macromolecules, 112, 390-398. doi:10.1016/j.ijbiomac.2018.01.184Garcia-Garcia, D., Rayón, E., Carbonell-Verdu, A., Lopez-Martinez, J., & Balart, R. (2017). Improvement of the compatibility between poly(3-hydroxybutyrate) and poly(ε-caprolactone) by reactive extrusion with dicumyl peroxide. European Polymer Journal, 86, 41-57. doi:10.1016/j.eurpolymj.2016.11.018Peponi, L., Sessini, V., Arrieta, M. P., Navarro-Baena, I., Sonseca, A., Dominici, F., … Kenny, J. M. (2018). Thermally-activated shape memory effect on biodegradable nanocomposites based on PLA/PCL blend reinforced with hydroxyapatite. Polymer Degradation and Stability, 151, 36-51. doi:10.1016/j.polymdegradstab.2018.02.019Muthuraj, R., Misra, M., & Mohanty, A. K. (2015). Hydrolytic degradation of biodegradable polyesters under simulated environmental conditions. Journal of Applied Polymer Science, 132(27), n/a-n/a. doi:10.1002/app.42189Signori, F., Coltelli, M.-B., & Bronco, S. (2009). Thermal degradation of poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) and their blends upon melt processing. Polymer Degradation and Stability, 94(1), 74-82. doi:10.1016/j.polymdegradstab.2008.10.004Navarro-Baena, I., Arrieta, M. P., Sonseca, A., Torre, L., López, D., Giménez, E., … Peponi, L. (2015). Biodegradable nanocomposites based on poly(ester-urethane) and nanosized hydroxyapatite: Plastificant and reinforcement effects. Polymer Degradation and Stability, 121, 171-179. doi:10.1016/j.polymdegradstab.2015.09.002Salgado, C., Arrieta, M. P., Peponi, L., Fernández-García, M., & López, D. (2016). Influence of Poly(ε-caprolactone) Molecular Weight and Coumarin Amount on Photo-Responsive Polyurethane Properties. Macromolecular Materials and Engineering, 302(4), 1600515. doi:10.1002/mame.201600515Ferri, J. M., Fenollar, O., Jorda-Vilaplana, A., García-Sanoguera, D., & Balart, R. (2016). Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends. Polymer International, 65(4), 453-463. doi:10.1002/pi.5079Cerruti, P., Santagata, G., Gomez d’Ayala, G., Ambrogi, V., Carfagna, C., Malinconico, M., & Persico, P. (2011). Effect of a natural polyphenolic extract on the properties of a biodegradable starch-based polymer. Polymer Degradation and Stability, 96(5), 839-846. doi:10.1016/j.polymdegradstab.2011.02.00

A Deeper Microscopic Study of the Interaction between Gum Rosin Derivatives and a Mater-Bi Type Bioplastic

[EN] The interaction between gum rosin and gum rosin derivatives with Mater-Bi type bioplastic, a biodegradable and compostable commercial bioplastic, were studied. Gum rosin and two pentaerythritol esters of gum rosin (Lurefor 125 resin and Unik Tack P100 resin) were assessed as sustainable compatibilizers for the components of Mater-Bi® NF 866 polymeric matrix. To study the influence of each additive in the polymeric matrix, each gum rosin-based additive was compounded in 15 wt % by melt-extrusion and further injection molding process. Then, the mechanical properties were assessed, and the tensile properties and impact resistance were determined. Microscopic analyses were carried out by field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and atomic force microscopy with nanomechanical assessment (AFM-QNM). The oxygen barrier and wettability properties were also assayed. The study revealed that the commercial thermoplastic starch is mainly composed of three phases: A polybutylene adipate-co-terephthalate (PBAT) phase, an amorphous phase of thermoplastic starch (TPSa), and a semi-crystalline phase of thermoplastic starch (TPSc). The poor miscibility among the components of the Mater-Bi type bioplastic was confirmed. Finally, the formulations with the gum rosin and its derivatives showed an improvement of the miscibility and the solubility of the components depending on the additive usedThis research was funded by Spanish Ministry of Economy and Competitiveness (MINECO), project: PROMADEPCOL (MAT2017-84909-C2-2-R) and M.P.A. s contract: Juan de la Cierva-Incorporación (FJCI-2017-33536).Aldas-Carrasco, MF.; Rayón, E.; López-Martínez, J.; Arrieta, MP. (2020). A Deeper Microscopic Study of the Interaction between Gum Rosin Derivatives and a Mater-Bi Type Bioplastic. Polymers. 12(1):1-17. https://doi.org/10.3390/polym12010226S117121Keshavarz, T., & Roy, I. (2010). Polyhydroxyalkanoates: bioplastics with a green agenda. Current Opinion in Microbiology, 13(3), 321-326. doi:10.1016/j.mib.2010.02.006Aldas, M., Paladines, A., Valle, V., Pazmiño, M., & Quiroz, F. (2018). Effect of the Prodegradant-Additive Plastics Incorporated on the Polyethylene Recycling. International Journal of Polymer Science, 2018, 1-10. doi:10.1155/2018/2474176Arrieta, M. P., Peponi, L., López, D., & Fernández-García, M. (2018). Recovery of yerba mate (Ilex paraguariensis) residue for the development of PLA-based bionanocomposite films. Industrial Crops and Products, 111, 317-328. doi:10.1016/j.indcrop.2017.10.042Akrami, M., Ghasemi, I., Azizi, H., Karrabi, M., & Seyedabadi, M. (2016). A new approach in compatibilization of the poly(lactic acid)/thermoplastic starch (PLA/TPS) blends. Carbohydrate Polymers, 144, 254-262. doi:10.1016/j.carbpol.2016.02.035Elfehri Borchani, K., Carrot, C., & Jaziri, M. (2015). Biocomposites of Alfa fibers dispersed in the Mater-Bi® type bioplastic: Morphology, mechanical and thermal properties. Composites Part A: Applied Science and Manufacturing, 78, 371-379. doi:10.1016/j.compositesa.2015.08.023Sessini, V., Arrieta, M. P., Fernández-Torres, A., & Peponi, L. (2018). Humidity-activated shape memory effect on plasticized starch-based biomaterials. Carbohydrate Polymers, 179, 93-99. doi:10.1016/j.carbpol.2017.09.070Arrieta, 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/ma10091008Aldas, M., Ferri, J. M., Lopez‐Martinez, J., Samper, M. D., & Arrieta, M. P. (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), 48236. doi:10.1002/app.48236Sessini, V., Navarro-Baena, I., Arrieta, M. P., Dominici, F., López, D., Torre, L., … Peponi, L. (2018). Effect of the addition of polyester-grafted-cellulose nanocrystals on the shape memory properties of biodegradable PLA/PCL nanocomposites. Polymer Degradation and Stability, 152, 126-138. doi:10.1016/j.polymdegradstab.2018.04.012Sessini, V., Arrieta, M. P., Raquez, J.-M., Dubois, P., Kenny, J. M., & Peponi, L. (2019). Thermal and composting degradation of EVA/Thermoplastic starch blends and their nanocomposites. Polymer Degradation and Stability, 159, 184-198. doi:10.1016/j.polymdegradstab.2018.11.025Kaseem, M., Hamad, K., & Deri, F. (2012). Thermoplastic starch blends: A review of recent works. Polymer Science Series A, 54(2), 165-176. doi:10.1134/s0965545x1202006xOlivato, J. B., Nobrega, M. M., Müller, C. M. O., Shirai, M. A., Yamashita, F., & Grossmann, M. V. E. (2013). Mixture design applied for the study of the tartaric acid effect on starch/polyester films. Carbohydrate Polymers, 92(2), 1705-1710. doi:10.1016/j.carbpol.2012.11.024Yoshida, Y., & Uemura, T. (1994). Properties and Applications of «Mater-Bi». Biodegradable Plastics and Polymers, 443-450. doi:10.1016/b978-0-444-81708-2.50049-xNainggolan, H., Gea, S., Bilotti, E., Peijs, T., & Hutagalung, S. D. (2013). Mechanical and thermal properties of bacterial-cellulose-fibre-reinforced Mater-Bi® bionanocomposite. Beilstein Journal of Nanotechnology, 4, 325-329. doi:10.3762/bjnano.4.37Ferri, 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.2016.03.082Morreale, M., Scaffaro, R., Maio, A., & La Mantia, F. P. (2008). Effect of adding wood flour to the physical properties of a biodegradable polymer. Composites Part A: Applied Science and Manufacturing, 39(3), 503-513. doi:10.1016/j.compositesa.2007.12.002Nayak, S. K. (2010). Biodegradable PBAT/Starch Nanocomposites. Polymer-Plastics Technology and Engineering, 49(14), 1406-1418. doi:10.1080/03602559.2010.496397González Seligra, P., Eloy Moura, L., Famá, L., Druzian, J. I., & Goyanes, S. (2016). Influence of incorporation of starch nanoparticles in PBAT/TPS composite films. Polymer International, 65(8), 938-945. doi:10.1002/pi.5127Arrieta, M. P., Samper, M. D., Jiménez-López, M., Aldas, M., & López, J. (2017). Combined effect of linseed oil and gum rosin as natural additives for PVC. Industrial Crops and Products, 99, 196-204. doi:10.1016/j.indcrop.2017.02.009Gutierrez, J., & Tercjak, A. (2014). Natural gum rosin thin films nanopatterned by poly(styrene)-block-poly(4-vinylpiridine) block copolymer. RSC Advances, 4(60), 32024. doi:10.1039/c4ra04296dWilbon, P. A., Chu, F., & Tang, C. (2012). Progress in Renewable Polymers from Natural Terpenes, Terpenoids, and Rosin. Macromolecular Rapid Communications, 34(1), 8-37. doi:10.1002/marc.201200513Rodríguez-García, A., Martín, J. A., López, R., Mutke, S., Pinillos, F., & Gil, L. (2015). Influence of climate variables on resin yield and secretory structures in tapped Pinus pinaster Ait. in central Spain. Agricultural and Forest Meteorology, 202, 83-93. doi:10.1016/j.agrformet.2014.11.023Davis, G., & Song, J. H. (2006). Biodegradable packaging based on raw materials from crops and their impact on waste management. Industrial Crops and Products, 23(2), 147-161. doi:10.1016/j.indcrop.2005.05.004Yadav, B. K., Gidwani, B., & Vyas, A. (2015). Rosin: Recent advances and potential applications in novel drug delivery system. Journal of Bioactive and Compatible Polymers, 31(2), 111-126. doi:10.1177/0883911515601867Butt, H.-J., Cappella, B., & Kappl, M. (2005). Force measurements with the atomic force microscope: Technique, interpretation and applications. Surface Science Reports, 59(1-6), 1-152. doi:10.1016/j.surfrep.2005.08.003J. Roa, J., Rayon, E., Morales, M., & Segarra, M. (2012). Contact Mechanics at Nanometric Scale Using Nanoindentation Technique for Brittle and Ductile Materials. Recent Patents on Engineering, 6(2), 116-126. doi:10.2174/187221212801227130Hernández‐Fernández, J., Rayón, E., López, J., & Arrieta, M. P. (2019). Enhancing the Thermal Stability of Polypropylene by Blending with Low Amounts of Natural Antioxidants. Macromolecular Materials and Engineering, 304(11), 1900379. doi:10.1002/mame.201900379Taguet, A., Huneault, M. A., & Favis, B. D. (2009). Interface/morphology relationships in polymer blends with thermoplastic starch. Polymer, 50(24), 5733-5743. doi:10.1016/j.polymer.2009.09.055Zhang, S., He, Y., Lin, Z., Li, J., & Jiang, G. (2019). Effects of tartaric acid contents on phase homogeneity, morphology and properties of poly (butyleneadipate-co-terephthalate)/thermoplastic starch bio-composities. Polymer Testing, 76, 385-395. doi:10.1016/j.polymertesting.2019.04.005Mohammadi Nafchi, A., Moradpour, M., Saeidi, M., & Alias, A. K. (2013). Thermoplastic starches: Properties, challenges, and prospects. Starch - Stärke, 65(1-2), 61-72. doi:10.1002/star.201200201Van Soest, J. J. G., De Wit, D., & Vliegenthart, J. F. G. (1996). Mechanical properties of thermoplastic waxy maize starch. Journal of Applied Polymer Science, 61(11), 1927-1937. doi:10.1002/(sici)1097-4628(19960912)61:113.0.co;2-lZhang, Y., Rempel, C., & Liu, Q. (2014). Thermoplastic Starch Processing and Characteristics—A Review. Critical Reviews in Food Science and Nutrition, 54(10), 1353-1370. doi:10.1080/10408398.2011.636156Yu, J., Gao, J., & Lin, T. (1996). Biodegradable thermoplastic starch. Journal of Applied Polymer Science, 62(9), 1491-1494. doi:10.1002/(sici)1097-4628(19961128)62:93.0.co;2-1Zullo, R., & Iannace, S. (2009). The effects of different starch sources and plasticizers on film blowing of thermoplastic starch: Correlation among process, elongational properties and macromolecular structure. Carbohydrate Polymers, 77(2), 376-383. doi:10.1016/j.carbpol.2009.01.007Sousa, F. M., Costa, A. R. M., Reul, L. T. A., Cavalcanti, F. B., Carvalho, L. H., Almeida, T. G., & Canedo, E. L. (2018). Rheological and thermal characterization of PCL/PBAT blends. Polymer Bulletin, 76(3), 1573-1593. doi:10.1007/s00289-018-2428-5Mittal, V., Akhtar, T., Luckachan, G., & Matsko, N. (2014). PLA, TPS and PCL binary and ternary blends: structural characterization and time-dependent morphological changes. Colloid and Polymer Science, 293(2), 573-585. doi:10.1007/s00396-014-3458-7Arrieta, 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.2013.11.009Burgos, N., Martino, V. P., & Jiménez, A. (2013). Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid. Polymer Degradation and Stability, 98(2), 651-658. doi:10.1016/j.polymdegradstab.2012.11.009Armentano, 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., Peltzer, M. A., López, J., Garrigós, M. del C., Valente, A. J. M., & Jiménez, A. (2014). Functional properties of sodium and calcium caseinate antimicrobial active films containing carvacrol. Journal of Food Engineering, 121, 94-101. doi:10.1016/j.jfoodeng.2013.08.015Hambleton, A., Fabra, M.-J., Debeaufort, F., Dury-Brun, C., & Voilley, A. (2009). Interface and aroma barrier properties of iota-carrageenan emulsion–based films used for encapsulation of active food compounds. Journal of Food Engineering, 93(1), 80-88. doi:10.1016/j.jfoodeng.2009.01.00

Effect of the viscosity ratio on the PLA/PA10.10 bioblends morphology and mechanical properties

PLA bio-blends with a predominantly biosourced PA10.10 in the composition range 10-50wt.% were prepared by melt blending in order to overcome the advanced brittleness of PLA. Due to the inherent immiscibility of the blends, 30 wt.% of PA was needed to achieve a brittle-to-ductile transition and a co-continuous morphology was predicted at 58 wt.% of PA. The initial enhancement of the PLA rheological behaviour through the environmentally friendly reactive extrusion process yielded a finer and more homogeneous microstructure and hence enhanced the mechanical properties of the bio-blends at much lower PA contents. The brittle-to-ductile transition could be achieved with only 10 wt.% and co-continuity was observed already at 44 wt.% of PA. Results indicate the significant potential of modifying PLA flow behaviour as a promising green manufacturing method toward expanding PLA-based bio-blends applications.Peer ReviewedPostprint (published version

Study of thermal and rheological properties of PLA loaded with carbon and halloysite nanotubes for additive manufacturing

[EN] Purpose This paper aims to propose using polylactic acid (PLA) as an alternative to nanocomposites in additive manufacturing processes in fusion deposition modelling (FDM) systems and describe its thermal and rheological conditions with multi-wall carbon nanotube (PLA/MWCNT) and halloysite nanotube (PLA/HNT) composites for possible applications in additive manufacturing processes. Design/methodology/approach PLA/MWCNTs and PLA/HNTs were obtained through fusion in a co-rotating twin-screw extruder. PLA was mixed with different percentages of MWCNTs and HNTs at concentrations of 0.5 Wt.%, 0.75 Wt.% and 1 Wt.%. Differential scanning calorimetry (DSC) and capillary rheometry were used to characterise these products, together with an analysis of the melt flow index (MFI). Findings The DSC data revealed that the nanocomposites had a glass transition temperature T-g = 65 +/- 2 degrees C and a melting temperature T-m = 169 +/- 1 degrees C. The crystallisation temperature of PLA/MWCNTs and PLA/HNTs was between 107 +/- 2 degrees C and 129 degrees C, respectively. The viscosity data of PLA/MWCNTs and PLA/HNTs obtained by capillary rheometry indicated that the viscosity of the materials is the same as that of neat PLA. These results were confirmed by the higher fluidity index in the MFI analysis. Originality/value This paper presents an alternative for the applications of nanocomposites in additive manufacturing processes in FDM systems.Cobos, CM.; Garzón, L.; López-Martínez, J.; Fenollar, O.; Ferrándiz Bou, S. (2019). Study of thermal and rheological properties of PLA loaded with carbon and halloysite nanotubes for additive manufacturing. Rapid Prototyping Journal. 25(4):738-743. https://doi.org/10.1108/RPJ-11-2018-0289S738743254Altınkaynak, A., Gupta, M., Spalding, M. A., & Crabtree, S. L. (2011). Melting in a Single Screw Extruder: Experiments and 3D Finite Element Simulations. International Polymer Processing, 26(2), 182-196. doi:10.3139/217.2419Berber, S. Kwon, Y.-K. and Tománek, D. (2000), “Unusually high thermal conductivity of carbon nanotubes”, available at: https://pdfs.semanticscholar.org/6595/44a005ba8d622c272d4bf737f12e26f8c415.pdf (accessed 23 February 2019).Carrasco, F., Pagès, P., Gámez-Pérez, J., Santana, O. O., & Maspoch, M. L. (2010). Processing of poly(lactic acid): Characterization of chemical structure, thermal stability and mechanical properties. Polymer Degradation and Stability, 95(2), 116-125. doi:10.1016/j.polymdegradstab.2009.11.045Dong, Y., Chaudhary, D., Haroosh, H., & Bickford, T. (2011). Development and characterisation of novel electrospun polylactic acid/tubular clay nanocomposites. Journal of Materials Science, 46(18), 6148-6153. doi:10.1007/s10853-011-5605-6Ferri Azor, J.M., Balart Gimeno, R.A. and Fenollar Gimeno, O. (2017), Desarrollo de formulaciones derivadas de ácido poliláctico (PLA), mediante plastificación e incorporación de aditivos de origen natural, Doctoral Thesis, Universitat Politècnica de València, Alcoy.Gao, Y., Picot, O. T., Bilotti, E., & Peijs, T. (2017). Influence of filler size on the properties of poly(lactic acid) (PLA)/graphene nanoplatelet (GNP) nanocomposites. European Polymer Journal, 86, 117-131. doi:10.1016/j.eurpolymj.2016.10.045Hamad, K., Kaseem, M., & Deri, F. (2011). Melt Rheology of Poly(Lactic Acid)/Low Density Polyethylene Polymer Blends. Advances in Chemical Engineering and Science, 01(04), 208-214. doi:10.4236/aces.2011.14030Harris, A. M., & Lee, E. C. (2007). Improving mechanical performance of injection molded PLA by controlling crystallinity. Journal of Applied Polymer Science, 107(4), 2246-2255. doi:10.1002/app.27261Kim, S. Y., Shin, K. S., Lee, S. H., Kim, K. W., & Youn, J. R. (2010). Unique crystallization behavior of multi-walled carbon nanotube filled poly(lactic acid). Fibers and Polymers, 11(7), 1018-1023. doi:10.1007/s12221-010-1018-4Li, T., Turng, L.-S., Gong, S., & Erlacher, K. (2006). Polylactide, nanoclay, and core–shell rubber composites. Polymer Engineering & Science, 46(10), 1419-1427. doi:10.1002/pen.20629López, J., Navarro, R., Gallego, J. M., Parres, F., & Ferrandiz, S. (2009). Analysis weld seam weak in blow molding large parts made of commodity plastics. Engineering Failure Analysis, 16(3), 856-862. doi:10.1016/j.engfailanal.2008.07.007Murariu, M., & Dubois, P. (2016). PLA composites: From production to properties. Advanced Drug Delivery Reviews, 107, 17-46. doi:10.1016/j.addr.2016.04.003Richard, T. (2008), “Preparación y caracterización de nanocompuestos en base PLA”, Universitat Politècnica de Catalunya. available at: http://upcommons.upc.edu/handle/2099.1/4791 (accessed 26 July 2017).Singh, V. P., Vimal, K. K., Kapur, G. S., Sharma, S., & Choudhary, V. (2016). High-density polyethylene/halloysite nanocomposites: morphology and rheological behaviour under extensional and shear flow. Journal of Polymer Research, 23(3). doi:10.1007/s10965-016-0937-1Song, Y., Li, Y., Song, W., Yee, K., Lee, K.-Y., & Tagarielli, V. L. (2017). Measurements of the mechanical response of unidirectional 3D-printed PLA. Materials & Design, 123, 154-164. doi:10.1016/j.matdes.2017.03.051Suriñach, S., Baro, M.D., Bordas, S., Clavaguera, N. and Clavaguera-mora, M.T. (1992), “La calorimetría diferencial de barrido y su aplicación a la ciencia de materiales”, Vol. 31, available at: http://boletines.secv.es/upload/199231011.pdf (accessed: 26 July 2017).Wu, W., Cao, X., Zhang, Y., & He, G. (2013). Polylactide/halloysite nanotube nanocomposites: Thermal, mechanical properties, and foam processing. Journal of Applied Polymer Science, 130(1), 443-452. doi:10.1002/app.39179Yuan, P., Tan, D., & Annabi-Bergaya, F. (2015). Properties and applications of halloysite nanotubes: recent research advances and future prospects. Applied Clay Science, 112-113, 75-93. doi:10.1016/j.clay.2015.05.00

Thermal and mechanical characterization of epoxy resins (ELO and ESO) cured with anhydrides

In this work we have developed polymeric materials from epoxidized vegetable oils in order to obtain materials with excellent mechanical properties for use as green matrix composites. Epoxidized soybean oil (ESO), epoxidized linseed oil (ELO) and different mixtures of the two oils were used to produce the polymers. Phthalic anhydride (17 mol%) and maleic anhydride (83 mol%) which has a eutectic reaction temperature of 48 °C were used as crosslinking agents while benzyl dimethyl amine (BDMA) and ethylene glycol were used as the catalyst and initiator, respectively. The results showed that samples 100ELO and 80ELO20ESO could be used as a matrix in green composites because they demonstrated good mechanical properties. © 2012 AOCS (outside the USA).This work is part of the project IPT-310000-2010-037,''ECOTEXCOMP: Research and development of textile structures useful as reinforcement of composite materials with marked ecological character'' funded by the "Ministerio de Ciencia e Innovacion", with financial aid of 189,540.20 EUR, within the "Plan Nacional de Investigacion Cientifica, Desarrollo e Innovacion Tecnologica 2008-2011" and funded by the European Union through FEDER funds, Technology Fund 2007-2013, Operational Programme on R + D + i for and on behalf of the companies.Samper Madrigal, MD.; Fombuena Borrás, V.; Boronat Vitoria, T.; García Sanoguera, D.; Balart Gimeno, RA. (2012). Thermal and mechanical characterization of epoxy resins (ELO and ESO) cured with anhydrides. Journal of the American Oil Chemists' Society. 89(8):1521-1528. https://doi.org/10.1007/s11746-012-2041-yS15211528898Averous L (2004) Biodegradable multiphase systems based on plasticized starch: a review. J Macromol Sci Polym Rev C44:231–274Bledzki AK, Jaszkiewicz A (2010) Mechanical performance of biocomposites based on PLA and PHBV reinforced with natural fibres—a comparative study to PP. Compos Sci Technol 70:1687–1696Raquez JM, Deleglise M, Lacrampe MF, Krawczak P (2010) Thermosetting (bio)materials derived from renewable resources: a critical review. Prog Polym Sci 35:487–509Charlet K, Jernot JP, Gomina M, Bizet L, Breard J (2010) Mechanical properties of flax fibers and of the derived unidirectional composites. J Compos Mater 44:2887–2896Barreto ACH, Esmeraldo MA, Rosa DS, Fechine PBA, Mazzetto SE (2010) Cardanol biocomposites reinforced with jute fiber: microstructure, biodegradability, and mechanical properties. Polym Compos 31:1928–1937Thakur VK, Singha AS (2010) Physico-chemical and mechanical characterization of natural fibre reinforced polymer composites. Iran Polym J 19:3–16Schmitz WR, Wallace JG (1954) Epoxidation of methyl oleate with hydrogen peroxide. J Am Oil Chem Soc 31:363–365La Scala J, Wool RP (2002) Effect of FA composition on epoxidation kinetics of TAG. J Am Oil Chem Soc 79:373–378de Espinosa LM, Ronda JC, Galia M, Cadiz V (2008) A new enone-containing triglyceride derivative as precursor of thermosets from renewable resources. J Polym Sci Pol Chem 46:6843–6850Gerbase AE, Petzhold CL, Costa APO (2002) Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil. J Am Oil Chem Soc 79:797–802Boquillon N, Fringant C (2000) Polymer networks derived from curing of epoxidised linseed oil: influence of different catalysts and anhydride hardeners. Polymer 41:8603–8613Montserrat S, Flaque C, Calafell M, Andreu G, Malek J (1995) Influence of the accelerator concentration on the curing reaction of an epoxy-anhydride system. Thermochim Acta 269:213–229Zacharuk M, Becker D, Coelho LAF, Pezzin SH (2011) Study of the reaction between polyethylene glycol and epoxy resins using N,N-dimethylbenzylamine as catalyst. Polimeros 21:73–77Lozada Z, Suppes GJ, Tu YC, Hsieh FH (2009) Soy-based polyols from oxirane ring opening by alcoholysis reaction. J Appl Polym Sci 113:2552–256

Ductility and Toughness Improvement of Injection-Molded Compostable Pieces of Polylactide by Melt Blending with Poly(e-caprolactone) and Thermoplastic Starch

[EN] The present study describes the preparation and characterization of binary and ternary blends based on polylactide (PLA) with poly("-caprolactone) (PCL) and thermoplastic starch (TPS) to develop fully compostable plastics with improved ductility and toughness. To this end, PLA was first melt-mixed in a co rotating twin-screw extruder with up to 40 wt % of different PCL and TPS combinations and then shaped into pieces by injection molding. The mechanical, thermal, and thermomechanical properties of the resultant binary and ternary blend pieces were analyzed and related to their composition. Although the biopolymer blends were immiscible, the addition of both PCL and TPS remarkably increased the flexibility and impact strength of PLA while it slightly reduced its mechanical strength. The most balanced mechanical performance was achieved for the ternary blend pieces that combined high PCL contents with low amounts of TPS, suggesting a main phase change from PLA/TPS (comparatively rigid) to PLA/PCL (comparatively flexible). The PLA-based blends presented an ¿island-and-sea¿ morphology in which the TPS phase contributed to the fine dispersion of PCL as micro-sized spherical domains that acted as a rubber-like phase with the capacity to improve toughness. In addition, the here-prepared ternary blend pieces presented slightly higher thermal stability and lower thermomechanical stiffness than the neat PLA pieces. Finally, all biopolymer pieces fully disintegrated in a controlled compost soil after 28 days. Therefore, the inherently low ductility and toughness of PLA can be successfully improved by melt blending with PCL and TPS, resulting in compostable plastic materials with a great potential in, for instance, rigid packaging applications.This research was supported by the Ministry of Science, Innovation, and Universities (MICIU) program numbers MAT2017-84909-C2-2-R and AGL2015-63855-C2-1-R, and by the EU H2020 project YPACK (reference number 773872).Quiles-Carrillo, L.; Montanes, N.; Pineiro, F.; Jorda-Vilaplana, A.; Torres-Giner, S. (2018). Ductility and Toughness Improvement of Injection-Molded Compostable Pieces of Polylactide by Melt Blending with Poly(e-caprolactone) and Thermoplastic Starch. Materials. 11(11):1-20. https://doi.org/10.3390/ma11112138S1201111Hopewell, J., Dvorak, R., & Kosior, E. (2009). Plastics recycling: challenges and opportunities. Philosophical Transactions of the Royal Society B: Biological Sciences, 364(1526), 2115-2126. doi:10.1098/rstb.2008.0311Quiles-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.2018.04.017Madhavan Nampoothiri, K., Nair, N. R., & John, R. P. (2010). An overview of the recent developments in polylactide (PLA) research. Bioresource Technology, 101(22), 8493-8501. doi:10.1016/j.biortech.2010.05.092Kumar, N., & Das, D. (2017). Fibrous biocomposites from nettle (Girardinia diversifolia) and poly(lactic acid) fibers for automotive dashboard panel application. Composites Part B: Engineering, 130, 54-63. doi:10.1016/j.compositesb.2017.07.059Garcés, J. M., Moll, D. J., Bicerano, J., Fibiger, R., & McLeod, D. G. (2000). Polymeric Nanocomposites for Automotive Applications. Advanced Materials, 12(23), 1835-1839. doi:10.1002/1521-4095(200012)12:233.0.co;2-tLasprilla, A. J. R., Martinez, G. A. R., Lunelli, B. H., Jardini, A. L., & Filho, R. M. (2012). Poly-lactic acid synthesis for application in biomedical devices — A review. Biotechnology Advances, 30(1), 321-328. doi:10.1016/j.biotechadv.2011.06.019Torres-Giner, S., Gimeno-Alcañiz, J. V., Ocio, M. J., & Lagaron, J. M. (2011). Optimization of electrospun polylactide-based ultrathin fibers for osteoconductive bone scaffolds. Journal of Applied Polymer Science, 122(2), 914-925. doi:10.1002/app.34208Muller, J., González-Martínez, C., & Chiralt, A. (2017). Combination of Poly(lactic) Acid and Starch for Biodegradable Food Packaging. Materials, 10(8), 952. doi:10.3390/ma10080952Kakroodi, A. R., Kazemi, Y., Nofar, M., & Park, C. B. (2017). Tailoring poly(lactic acid) for packaging applications via the production of fully bio-based in situ microfibrillar composite films. Chemical Engineering Journal, 308, 772-782. doi:10.1016/j.cej.2016.09.130Kao, C.-T., Lin, C.-C., Chen, Y.-W., Yeh, C.-H., Fang, H.-Y., & Shie, M.-Y. (2015). Poly(dopamine) coating of 3D printed poly(lactic acid) scaffolds for bone tissue engineering. Materials Science and Engineering: C, 56, 165-173. doi:10.1016/j.msec.2015.06.028Chen, Q., Mangadlao, J. D., Wallat, J., De Leon, A., Pokorski, J. K., & Advincula, R. C. (2017). 3D Printing Biocompatible Polyurethane/Poly(lactic acid)/Graphene Oxide Nanocomposites: Anisotropic Properties. ACS Applied Materials & Interfaces, 9(4), 4015-4023. doi:10.1021/acsami.6b11793Quiles-Carrillo, L., Duart, S., Montanes, N., Torres-Giner, S., & Balart, R. (2018). Enhancement of the mechanical and thermal properties of injection-molded polylactide parts by the addition of acrylated epoxidized soybean oil. Materials & Design, 140, 54-63. doi:10.1016/j.matdes.2017.11.031Mooney, D. J., Breuer, C., McNamara, K., Vacanti, J. P., & Langer, R. (1995). Fabricating Tubular Devices from Polymers of Lactic and Glycolic Acid for Tissue Engineering. Tissue Engineering, 1(2), 107-118. doi:10.1089/ten.1995.1.107Elsawy, M. A., Kim, K.-H., Park, J.-W., & Deep, A. (2017). Hydrolytic degradation of polylactic acid (PLA) and its composites. Renewable and Sustainable Energy Reviews, 79, 1346-1352. doi:10.1016/j.rser.2017.05.143Pluta, M., & Piorkowska, E. (2015). Tough crystalline blends of polylactide with block copolymers of ethylene glycol and propylene glycol. Polymer Testing, 46, 79-87. doi:10.1016/j.polymertesting.2015.06.014Maiza, M., Benaniba, M. T., Quintard, G., & Massardier-Nageotte, V. (2015). Biobased additive plasticizing Polylactic acid (PLA). Polímeros, 25(6), 581-590. doi:10.1590/0104-1428.1986Ljungberg, N., & Wesslén, B. (2002). The effects of plasticizers on the dynamic mechanical and thermal properties of poly(lactic acid). Journal of Applied Polymer Science, 86(5), 1227-1234. doi:10.1002/app.11077Darie-Niţă, R. N., Vasile, C., Irimia, A., Lipşa, R., & Râpă, M. (2015). Evaluation of some eco-friendly plasticizers for PLA films processing. Journal of Applied Polymer Science, 133(13), n/a-n/a. doi:10.1002/app.43223Quiles-Carrillo, L., Blanes-Martínez, M. M., Montanes, N., Fenollar, O., Torres-Giner, S., & Balart, R. (2018). Reactive toughening of injection-molded polylactide pieces using maleinized hemp seed oil. European Polymer Journal, 98, 402-410. doi:10.1016/j.eurpolymj.2017.11.039Ferri, J. M., Garcia-Garcia, D., Montanes, N., Fenollar, O., & Balart, R. (2017). The effect of maleinized linseed oil as biobased plasticizer in poly(lactic acid)-based formulations. Polymer International, 66(6), 882-891. doi:10.1002/pi.5329Carbonell-Verdu, A., Garcia-Garcia, D., Dominici, F., Torre, L., Sanchez-Nacher, L., & Balart, R. (2017). PLA films with improved flexibility properties by using maleinized cottonseed oil. European Polymer Journal, 91, 248-259. doi:10.1016/j.eurpolymj.2017.04.013Quiles-Carrillo, L., Montanes, N., Sammon, C., Balart, R., & Torres-Giner, S. (2018). Compatibilization of highly sustainable polylactide/almond shell flour composites by reactive extrusion with maleinized linseed oil. Industrial Crops and Products, 111, 878-888. doi:10.1016/j.indcrop.2017.10.062Gerard, T., & Budtova, T. (2012). Morphology and molten-state rheology of polylactide and polyhydroxyalkanoate blends. European Polymer Journal, 48(6), 1110-1117. doi:10.1016/j.eurpolymj.2012.03.015Yu, L., Dean, K., & Li, L. (2006). Polymer blends and composites from renewable resources. Progress in Polymer Science, 31(6), 576-602. doi:10.1016/j.progpolymsci.2006.03.002Gug, J.-I., Tan, B., Soule, J., Downie, M., Barrington, J., & Sobkowicz, M. J. (2017). Analysis of Models Predicting Morphology Transitions in Reactive Twin-Screw Extrusion of Bio-Based Polyester/Polyamide Blends. International Polymer Processing, 32(3), 363-377. doi:10.3139/217.3351Stoclet, G., Seguela, R., & Lefebvre, J.-M. (2011). Morphology, thermal behavior and mechanical properties of binary blends of compatible biosourced polymers: Polylactide/polyamide11. Polymer, 52(6), 1417-1425. doi:10.1016/j.polymer.2011.02.002Al-Itry, R., Lamnawar, K., & Maazouz, A. (2012). Improvement of thermal stability, rheological and mechanical properties of PLA, PBAT and their blends by reactive extrusion with functionalized epoxy. Polymer Degradation and Stability, 97(10), 1898-1914. doi:10.1016/j.polymdegradstab.2012.06.028Wu, N., & Zhang, H. (2017). Mechanical properties and phase morphology of super-tough PLA/PBAT/EMA-GMA multicomponent blends. Materials Letters, 192, 17-20. doi:10.1016/j.matlet.2017.01.063Sarazin, P., Li, G., Orts, W. J., & Favis, B. D. (2008). Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch. Polymer, 49(2), 599-609. doi:10.1016/j.polymer.2007.11.029Valerio, O., Misra, M., & Mohanty, A. K. (2018). Statistical design of sustainable thermoplastic blends of poly(glycerol succinate-co-maleate) (PGSMA), poly(lactic acid) (PLA) and poly(butylene succinate) (PBS). Polymer Testing, 65, 420-428. doi:10.1016/j.polymertesting.2017.12.018Ostafinska, A., Fortelný, I., Hodan, J., Krejčíková, S., Nevoralová, M., Kredatusová, J., … Šlouf, M. (2017). Strong synergistic effects in PLA/PCL blends: Impact of PLA matrix viscosity. Journal of the Mechanical Behavior of Biomedical Materials, 69, 229-241. doi:10.1016/j.jmbbm.2017.01.015Wu, D., Lin, D., Zhang, J., Zhou, W., Zhang, M., Zhang, Y., … Lin, B. (2011). Selective Localization of Nanofillers: Effect on Morphology and Crystallization of PLA/PCL Blends. Macromolecular Chemistry and Physics, 212(6), 613-626. doi:10.1002/macp.201000579Liu, H., Song, W., Chen, F., Guo, L., & Zhang, J. (2011). Interaction of Microstructure and Interfacial Adhesion on Impact Performance of Polylactide (PLA) Ternary Blends. Macromolecules, 44(6), 1513-1522. doi:10.1021/ma1026934Wokadala, O. C., Ray, S. S., Bandyopadhyay, J., Wesley-Smith, J., & Emmambux, N. M. (2015). Morphology, thermal properties and crystallization kinetics of ternary blends of the polylactide and starch biopolymers and nanoclay: The role of nanoclay hydrophobicity. Polymer, 71, 82-92. doi:10.1016/j.polymer.2015.06.058Zolali, A. M., & Favis, B. D. (2017). Partial to complete wetting transitions in immiscible ternary blends with PLA: the influence of interfacial confinement. Soft Matter, 13(15), 2844-2856. doi:10.1039/c6sm02386jMatzinos, P., Tserki, V., Kontoyiannis, A., & Panayiotou, C. (2002). Processing and characterization of starch/polycaprolactone products. Polymer Degradation and Stability, 77(1), 17-24. doi:10.1016/s0141-3910(02)00072-1Maglio, G., Malinconico, M., Migliozzi, A., & Groeninckx, G. (2004). Immiscible Poly(L-lactide)/Poly(ɛ-caprolactone) Blends: Influence of the Addition of a Poly(L-lactide)-Poly(oxyethylene) Block Copolymer on Thermal Behavior and Morphology. Macromolecular Chemistry and Physics, 205(7), 946-950. doi:10.1002/macp.200300150Forssell, P., Mikkilä, J., Suortti, T., Seppälä, J., & Poutanen, K. (1996). Plasticization of Barley Starch with Glycerol and Water. Journal of Macromolecular Science, Part A, 33(5), 703-715. doi:10.1080/10601329608010888Raquez, J.-M., Nabar, Y., Srinivasan, M., Shin, B.-Y., Narayan, R., & Dubois, P. (2008). Maleated thermoplastic starch by reactive extrusion. Carbohydrate Polymers, 74(2), 159-169. doi:10.1016/j.carbpol.2008.01.027Averous, L. (2000). Properties of thermoplastic blends: starch–polycaprolactone. Polymer, 41(11), 4157-4167. doi:10.1016/s0032-3861(99)00636-9Odelius, K., Ohlson, M., Höglund, A., & Albertsson, A. (2012). Polyesters with small structural variations improve the mechanical properties of polylactide. Journal of Applied Polymer Science, 127(1), 27-33. doi:10.1002/app.36842Zhen, Z., Ying, S., Hongye, F., Jie, R., & Tianbin, R. (2011). Preparation, Characterization and Properties of Binary and Ternary Blends with Thermoplastic Starch, Poly(Lactic Acid) and Poly(Butylene Succinate). Polymers from Renewable Resources, 2(2), 49-62. doi:10.1177/204124791100200201Ren, J., Fu, H., Ren, T., & Yuan, W. (2009). Preparation, characterization and properties of binary and ternary blends with thermoplastic starch, poly(lactic acid) and poly(butylene adipate-co-terephthalate). Carbohydrate Polymers, 77(3), 576-582. doi:10.1016/j.carbpol.2009.01.024Ferri, 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.2016.03.082García-Campo, M., Boronat, T., Quiles-Carrillo, L., Balart, R., & Montanes, N. (2017). Manufacturing and Characterization of Toughened Poly(lactic acid) (PLA) Formulations by Ternary Blends with Biopolyesters. Polymers, 10(1), 3. doi:10.3390/polym10010003Chen, C.-C., Chueh, J.-Y., Tseng, H., Huang, H.-M., & Lee, S.-Y. (2003). Preparation and characterization of biodegradable PLA polymeric blends. Biomaterials, 24(7), 1167-1173. doi:10.1016/s0142-9612(02)00466-0Ferri, J. M., Fenollar, O., Jorda-Vilaplana, A., García-Sanoguera, D., & Balart, R. (2016). Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends. Polymer International, 65(4), 453-463. doi:10.1002/pi.5079Tang, L., Wang, L., Chen, P., Fu, J., Xiao, P., Ye, N., & Zhang, M. (2017). Toughness of ABS/PBT blends: The relationship between composition, morphology, and fracture behavior. Journal of Applied Polymer Science, 135(13), 46051. doi:10.1002/app.46051Muthuraj, R., Misra, M., & Mohanty, A. K. (2017). Biodegradable compatibilized polymer blends for packaging applications: A literature review. Journal of Applied Polymer Science, 135(24), 45726. doi:10.1002/app.45726Carmona, V. B., Corrêa, A. C., Marconcini, J. M., & Mattoso, L. H. C. (2014). Properties of a Biodegradable Ternary Blend of Thermoplastic Starch (TPS), Poly(ε-Caprolactone) (PCL) and Poly(Lactic Acid) (PLA). Journal of Polymers and the Environment, 23(1), 83-89. doi:10.1007/s10924-014-0666-7Kim, H.-Y., Park, S. S., & Lim, S.-T. (2015). Preparation, characterization and utilization of starch nanoparticles. Colloids and Surfaces B: Biointerfaces, 126, 607-620. doi:10.1016/j.colsurfb.2014.11.011Bordes, C., Fréville, V., Ruffin, E., Marote, P., Gauvrit, J. Y., Briançon, S., & Lantéri, P. (2010). Determination of poly(ɛ-caprolactone) solubility parameters: Application to solvent substitution in a microencapsulation process. International Journal of Pharmaceutics, 383(1-2), 236-243. doi:10.1016/j.ijpharm.2009.09.023Small, P. A. (2007). Some factors affecting the solubility of polymers. Journal of Applied Chemistry, 3(2), 71-80. doi:10.1002/jctb.5010030205Navarro-Baena, I., Sessini, V., Dominici, F., Torre, L., Kenny, J. M., & Peponi, L. (2016). Design of biodegradable blends based on PLA and PCL: From morphological, thermal and mechanical studies to shape memory behavior. Polymer Degradation and Stability, 132, 97-108. doi:10.1016/j.polymdegradstab.2016.03.037Averous, L., & Boquillon, N. (2004). Biocomposites based on plasticized starch: thermal and mechanical behaviours. Carbohydrate Polymers, 56(2), 111-122. doi:10.1016/j.carbpol.2003.11.015Zhang, Y., Rempel, C., & Liu, Q. (2014). Thermoplastic Starch Processing and Characteristics—A Review. Critical Reviews in Food Science and Nutrition, 54(10), 1353-1370. doi:10.1080/10408398.2011.636156Patrício, T., & Bártolo, P. (2013). Thermal Stability of PCL/PLA Blends Produced by Physical Blending Process. Procedia Engineering, 59, 292-297. doi:10.1016/j.proeng.2013.05.124Mofokeng, J. P., & Luyt, A. S. (2015). Morphology and thermal degradation studies of melt-mixed poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) biodegradable polymer blend nanocomposites with TiO2 as filler. Polymer Testing, 45, 93-100. doi:10.1016/j.polymertesting.2015.05.007Quiles-Carrillo, L., Montanes, N., Lagaron, J. M., Balart, R., & Torres-Giner, S. (2018). In Situ Compatibilization of Biopolymer Ternary Blends by Reactive Extrusion with Low-Functionality Epoxy-Based Styrene–Acrylic Oligomer. Journal of Polymers and the Environment, 27(1), 84-96. doi:10.1007/s10924-018-1324-2Garcia-Campo, M., Quiles-Carrillo, L., Masia, J., Reig-Pérez, M., Montanes, N., & Balart, R. (2017). Environmentally Friendly Compatibilizers from Soybean Oil for Ternary Blends of Poly(lactic acid)-PLA, Poly(ε-caprolactone)-PCL and Poly(3-hydroxybutyrate)-PHB. Materials, 10(11), 1339. doi:10.3390/ma10111339Torres-Giner, S., Montanes, N., Fenollar, O., García-Sanoguera, D., & Balart, R. (2016). Development and optimization of renewable vinyl plastisol/wood flour composites exposed to ultraviolet radiation. Materials & Design, 108, 648-658. doi:10.1016/j.matdes.2016.07.037Martin, O., & Avérous, L. (2001). Poly(lactic acid): plasticization and properties of biodegradable multiphase systems. Polymer, 42(14), 6209-6219. doi:10.1016/s0032-3861(01)00086-6Mittal, V., Akhtar, T., & Matsko, N. (2015). Mechanical, Thermal, Rheological and Morphological Properties of Binary and Ternary Blends of PLA, TPS and PCL. Macromolecular Materials and Engineering, 300(4), 423-435. doi:10.1002/mame.201400332Di Franco, C. R., Cyras, V. P., Busalmen, J. P., Ruseckaite, R. A., & Vázquez, A. (2004). Degradation of polycaprolactone/starch blends and composites with sisal fibre. Polymer Degradation and Stability, 86(1), 95-103. doi:10.1016/j.polymdegradstab.2004.02.009Iovino, R., Zullo, R., Rao, M. A., Cassar, L., & Gianfreda, L. (2008). Biodegradation of poly(lactic acid)/starch/coir biocomposites under controlled composting conditions. Polymer Degradation and Stability, 93(1), 147-157. doi:10.1016/j.polymdegradstab.2007.10.011Thakore, I. ., Desai, S., Sarawade, B. ., & Devi, S. (2001). Studies on biodegradability, morphology and thermo-mechanical properties of LDPE/modified starch blends. European Polymer Journal, 37(1), 151-160. doi:10.1016/s0014-3057(00)00086-0Sikorska, W., Musiol, M., Nowak, B., Pajak, J., Labuzek, S., Kowalczuk, M., & Adamus, G. (2015). Degradability of polylactide and its blend with poly[(R,S)-3-hydroxybutyrate] in industrial composting and compost extract. International Biodeterioration & Biodegradation, 101, 32-41. doi:10.1016/j.ibiod.2015.03.02

Effect of Epoxidized and Maleinized Corn Oil on Properties of Polylactic Acid (PLA) and Polyhydroxybutyrate (PHB) Blend

[EN] The present work analyzes the influence of modified, epoxidized and maleinized corn oil as a plasticizing and/or compatibilizing agent in the PLA¿PHB blend (75% PLA and 25% PHB wt.%). The chemical modification processes of corn oil were successfully carried out and different quantities were used, between 0 and 10% wt.%. The different blends obtained were characterized by thermal, mechanical, morphological, and disintegration tests under composting conditions. It was observed that to achieve the same plasticizing effect, less maleinized corn oil (MCO) is needed than epoxidized corn oil (ECO). Both oils improve the ductile properties of the PLA¿PHB blend, such as elongation at break and impact absorb energy, however, the strength properties decrease. The ones that show the highest ductility values are those that contain 10% ECO and 5% MCO, improving the elongation of the break of the PLA¿PHB blend by more than 400% and by more than 800% for the sample PLA.This work was supported by the Spanish Ministry of Science and Innovation, NANOCIRCOIL (PID2021-123753NA-C33)Sempere-Torregrosa, J.; Ferri, J.; Rosa-Ramírez, HDL.; Pavón-Vargas, CP.; Samper, M. (2022). Effect of Epoxidized and Maleinized Corn Oil on Properties of Polylactic Acid (PLA) and Polyhydroxybutyrate (PHB) Blend. Polymers. 14(19):1-16. https://doi.org/10.3390/polym14194205116141