On the toughness of thermoplastic polymer nanocomposites as assessed by the essential work of fracture (EWF) approach

The essential work of fracture (EWF) approach is widely used to determine the plane stress fracture toughness of highly ductile polymers and related systems. To shed light on how the toughness is affected by nanofillers EWF-suited model polymers, viz. amorphous copolyester and polypropylene block copolymer were modified by multiwall carbon nanotube (MWCNT), graphene (GR), boehmite alumina (BA), and organoclay (MMT) in 1 wt% each. EWF tests were performed on deeply double-edge notched tensile-loaded specimens under quasistatic loading conditions. Data reduction occurred by energy partitioning between yielding and necking/tearing. The EWF prerequisites were not met with the nanocomposites containing MWCNT and GR by contrast to those with MMT and BA. Accordingly, the toughness of nanocomposites with homogeneously dispersed and low aspect ratio fillers may be properly determined using the EWF. Results indicated that incorporation of nanofillers may result in an adverse effect between the specific essential and non-essential EWF parameters

Heterogeneous Nucleation of Protein Crystals on Fluorinated Layered Silicate

Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface

In Situ Compatibilization of Biopolymer Ternary Blends by Reactive Extrusion with Low-Functionality Epoxy-Based Styrene Acrylic Oligomer

[EN] The present study reports on the use of low-functionality epoxy-based styrene¿acrylic oligomer (ESAO) to compatibilize immiscible ternary blends made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polylactide (PLA), and poly(butylene adipate-co-terephthalate) (PBAT). The addition during melt processing of low-functionality ESAO at two parts per hundred resin (phr) of biopolymer successfully changed the soften inclusion phase in the blend system to a thinner morphology, yielding biopolymer ternary blends with higher mechanical ductility and also improved oxygen barrier performance. The compatibilization achieved was ascribed to the in situ formation of a newly block terpolymer, i.e. PHBVb- PLA-b-PBAT, which was produced at the blend interface by the reaction of the multiple epoxy groups present in ESAO with the functional terminal groups of the biopolymers. This chemical reaction was mainly linear due to the inherently low functionality of ESAO and the more favorable reactivity of the epoxy groups with the carboxyl groups of the biopolymers, which avoided the formation of highly branched and/or cross-linked structures and thus facilitated the films processability. Therefore, the reactive blending of biopolymers at different mixing ratios with low-functionality ESAO represents a straightforward methodology to prepare sustainable plastics at industrial scale with different physical properties that can be of interest in, for instance, food packaging applications.This research was funded by the EU H2020 project YPACK (Reference number 773872) and by the Spanish Ministry of Science, Innovation, and Universities (MICIU) with project numbers MAT2017-84909-C2-2-R and AGL2015-63855-C2-1-R. L. Quiles-Carrillo wants to thank the Spanish Ministry of Education, Culture, and Sports (MECD) for financial support through his FPU Grant Number FPU15/03812. Torres-Giner also acknowledges the MICIU for his Juan de la Cierva contract (IJCI-2016-29675).Quiles-Carrillo, L.; Montanes, N.; Lagaron, J.; Balart, R.; Torres-Giner, S. (2019). 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. https://doi.org/10.1007/s10924-018-1324-2S8496271Babu RP, O’Connor K, Seeram R (2013) Prog Biomater 2:8Torres-Giner S, Torres A, Ferrándiz M, Fombuena V, Balart R (2017) J Food Saf 37:e12348Quiles-Carrillo L, Montanes N, Boronat T, Balart R, Torres-Giner S (2017) Polym Test 61:421Zakharova E, Alla A, Martínez A, De Ilarduya S, Muñoz-Guerra (2015) RSC Adv 5:46395Steinbüchel A, Valentin HE (1995) FEMS Microbiol Lett 128:219McChalicher CWJ, Srienc F (2007) J Biotechnol 132:296Reis KC, Pereira J, Smith AC, Carvalho CWP, Wellner N, Yakimets I (2008) J Food Eng 89:361Vink ETH, Davies S (2015) Ind Biotechnol 11:167John RP, Nampoothiri KM, Pandey A (2006) Process Biochem 41:759Madhavan Nampoothiri K, Nair NR, John RP (2010) Biores Technol 101:8493Garlotta D (2001) J Polym Environ 9:63Lim LT, Auras R, Rubino M (2008) Prog Polym Sci 33:820Quiles-Carrillo L, Montanes N, Sammon C, Balart R, Torres-Giner S (2018) Ind Crops Prod 111:878Quiles-Carrillo L, Blanes-Martínez MM, Montanes N, Fenollar O, Torres-Giner S, Balart R (2018) Eur Polym J 98:402Witt U, Müller R-J, Deckwer W-D (1997) J Environ Polym Degrad 5:81Siegenthaler KO, Künkel A, Skupin G, Yamamoto M (2012) Ecoflex® and Ecovio®: biodegradable, performance-enabling plastics. In: Rieger B, Künkel A, Coates GW, Reichardt R, Dinjus E, Zevaco TA (eds) Synthetic biodegradable polymers. Springer, Berlin Heidelberg, p 91Jiang L, Wolcott MP, Zhang J (2006) Biomacromol 7:199Brandelero RPH, Yamashita F, Grossmann MVE (2010) Carbohyd Polym 82:1102Muthuraj R, Misra M, Mohanty AK (2014) J Polym Environ 22:336Porter RS, Wang L-H (1992) Polymer 33(10): 2019Koning C, Van Duin M, Pagnoulle C, Jerome R (1998) Prog Polym Sci 23:707Muthuraj R, Misra M, Mohanty AK (2017) J Appl Polym Sci 135:45726Ryan AJ (2002) Nat Mater 1:8Wu D, Zhang Y, Yuan L, Zhang M, Zhou W (2010) J Polym Sci Part B 48:756Kim CH, Cho KY, Choi EJ, Park JK (2000) J Appl Polym Sci 77:226Supthanyakul R, Kaabbuathong N, Chirachanchai S (2016) Polymer 105:1Na Y-H, He Y, Shuai X, Kikkawa Y, Doi Y, Inoue Y (2002) Biomacromolecules 3:1179Zeng J-B, Li K-A, Du A-K (2015) RSC Adv 5:32546Xanthos M, Dagli SS (1991) Polym Eng Sci 31:929Sundararaj U, Macosko CW (1995) Macromolecules 28:2647Milner ST, Xi H (1996) J Rheol 40:663Villalobos M, Awojulu A, Greeley T, Turco G, Deeter G (2006) Energy 31:3227Torres-Giner S, Montanes N, Boronat T, Quiles-Carrillo L, Balart R (2016) Eur Polym J 84:693Lehermeier HJ, Dorgan JR (2001) Polym Eng Sci 41:2172Liu B, Xu Q (2013) J Mater Sci Chem Eng 1:9Eslami H, Kamal MR (2013) J Appl Polym Sci 129:2418Loontjens T, Pauwels K, Derks F, Neilen M, Sham CK, Serné M (1997) J Appl Polym Sci 65:1813Ojijo V, Ray SS (2015) Polymer 80:1Frenz V, Scherzer D, Villalobos M, Awojulu AA, Edison M, Van Der Meer R (2008) Multifunctional polymers as chain extenders and compatibilizers for polycondensates and biopolymers. In: Technical papers, regional technical conference—society of plastics engineers, p. 3/1678Utracki LA (2002) Can J Chem Eng 80:1008Al-Itry R, Lamnawar K, Maazouz A (2012) Polym Degrad Stab 97:1898Lin S, Guo W, Chen C, Ma J, Wang B (2012) Mater Des (1980–2015) 36: 604Arruda LC, Magaton M, Bretas RES, Ueki MM (2015) Polym Test 43:27Wang Y, Fu C, Luo Y, Ruan C, Zhang Y, Fu Y (2010) J Wuhan Univ Technol Mater Sci Ed 25:774Wei D, Wang H, Xiao H, Zheng A, Yang Y (2015) Carbohyd Polym 123:275Abdelwahab MA, Taylor S, Misra M, Mohanty AK (2015) Macromol Mater Eng 300:299Sun Q, Mekonnen T, Misra M, Mohanty AK (2016) J Polym Environ 24:23Torres-Giner S, Gimeno-Alcañiz JV, Ocio MJ, Lagaron JM (2011) J Appl Polym Sci 122:914Miyata T, Masuko T (1998) Polymer 39:5515Muthuraj R, Misra M, Mohanty AK (2015) J Appl Polym Sci 132:42189Ren J, Fu H, Ren T, Yuan W (2009) Carbohyd Polym 77:576Torres-Giner S, Montanes N, Fenollar O, García-Sanoguera D, Balart R (2016) Mater Des 108:648Jamshidian M, Tehrany EA, Imran M, Jacquot M, Desobry S (2010) Compr Rev Food Sci Food Saf 9:552Savenkova L, Gercberga Z, Nikolaeva V, Dzene A, Bibers I, Kalnin M (2000) Process Biochem 35:573Costa ARM, Almeida TG, Silva SML, Carvalho LH, Canedo EL (2015) Polym Test 42:115Zhang K, Mohanty AK, Misra M (2012) ACS Appl Mater Interfaces 4:3091Zhang N, Wang Q, Ren J, Wang L (2009) J Mater Sci 44:250Chinsirikul W, Rojsatean J, Hararak B, Kerddonfag N, Aontee A, Jaieau K, Kumsang P, Sripethdee C (2015) Packag Technol Sci 28:741Auras R, Harte B, Selke S (2004) J Appl Polym Sci 92:1790Sanchez-Garcia MD, Gimenez E, Lagaron JM (2008) Carbohyd Polym 71:235Sanchez-Garcia MD, Gimenez E, Lagaron JM (2007) J Plast Film Sheeting 23:133Lagaron JM (2011) Multifunctional and nanoreinforced polymers for food packaging. In: Multifunctional and nanoreinforced polymers for food packaging. Woodhead Publishing, Cambridge, p