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      Improvement of Impact Strength of Polylactide Blends with a Thermoplastic Elastomer Compatibilized with Biobased Maleinized Linseed Oil for Applications in Rigid Packaging

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          Abstract

          This research work reports the potential of maleinized linseed oil (MLO) as biobased compatibilizer in polylactide (PLA) and a thermoplastic elastomer, namely, polystyrene -b-(ethylene -ran-butylene) -b-styrene (SEBS) blends (PLA/SEBS), with improved impact strength for the packaging industry. The effects of MLO are compared with a conventional polystyrene -b-poly(ethylene -ran-butylene) -b-polystyrene -graft-maleic anhydride terpolymer (SEBS -g-MA) since it is widely used in these blends. Uncompatibilized and compatibilized PLA/SEBS blends can be manufactured by extrusion and then shaped into standard samples for further characterization by mechanical, thermal, morphological, dynamical-mechanical, wetting and colour standard tests. The obtained results indicate that the uncompatibilized PLA/SEBS blend containing 20 wt.% SEBS gives improved toughness (4.8 kJ/m 2) compared to neat PLA (1.3 kJ/m 2). Nevertheless, the same blend compatibilized with MLO leads to an increase in impact strength up to 6.1 kJ/m 2, thus giving evidence of the potential of MLO to compete with other petroleum-derived compatibilizers to obtain tough PLA formulations. MLO also provides increased ductile properties, since neat PLA is a brittle polymer with an elongation at break of 7.4%, while its blend with 20 wt.% SEBS and MLO as compatibilizer offers an elongation at break of 50.2%, much higher than that provided by typical SEBS -g-MA compatibilizer (10.1%). MLO provides a slight decrease (about 3 °C lower) in the glass transition temperature ( T g ) of the PLA-rich phase, thus showing some plasticization effects. Although MLO addition leads to some yellowing due to its intrinsic yellow colour, this can contribute to serving as a UV light barrier with interesting applications in the packaging industry. Therefore, MLO represents a cost-effective and sustainable solution to the use of conventional petroleum-derived compatibilizers.

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          Physical and mechanical properties of PLA, and their functions in widespread applications - A comprehensive review.

          Poly(lactic acid) (PLA), so far, is the most extensively researched and utilized biodegradable aliphatic polyester in human history. Due to its merits, PLA is a leading biomaterial for numerous applications in medicine as well as in industry replacing conventional petrochemical-based polymers. The main purpose of this review is to elaborate the mechanical and physical properties that affect its stability, processability, degradation, PLA-other polymers immiscibility, aging and recyclability, and therefore its potential suitability to fulfill specific application requirements. This review also summarizes variations in these properties during PLA processing (i.e. thermal degradation and recyclability), biodegradation, packaging and sterilization, and aging (i.e. weathering and hygrothermal). In addition, we discuss up-to-date strategies for PLA properties improvements including components and plasticizer blending, nucleation agent addition, and PLA modifications and nanoformulations. Incorporating better understanding of the role of these properties with available improvement strategies is the key for successful utilization of PLA and its copolymers/composites/blends to maximize their fit with worldwide application needs.
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            Structure and reactivity of water at biomaterial surfaces.

            Molecular self association in liquids is a physical process that can dominate cohesion (interfacial tension) and miscibility. In water, self association is a powerful organizational force leading to a three-dimensional hydrogen-bonded network (water structure). Localized perturbations in the chemical potential of water as by, for example, contact with a solid surface, induces compensating changes in water structure that can be sensed tens of nanometers from the point of origin using the surface force apparatus (SFA) and ancillary techniques. These instruments reveal attractive or repulsive forces between opposing surfaces immersed in water, over and above that anticipated by continuum theory (DLVO), that are attributed to a variable density (partial molar volume) of a more-or-less ordered water structure, depending on the water wettability (surface energy) of the water-contacting surfaces. Water structure at surfaces is thus found to be a manifestation of hydrophobicity and, while mechanistic/theoretical interpretation of experimental results remain the subject of some debate in the literature, convergence of experimental observations permit, for the first time, quantitative definition of the relative terms 'hydrophobic' and 'hydrophilic'. In particular, long-range attractive forces are detected only between surfaces exhibiting a water contact angle theta > 65 degrees (herein defined as hydrophobic surfaces with pure water adhesion tension tau O = gamma O cos theta 30 dyn/cm). These findings suggest at least two distinct kinds of water structure and reactivity: a relatively less-dense water region against hydrophobic surfaces with an open hydrogen-bonded network and a relatively more-dense water region against hydrophilic surfaces with a collapsed hydrogen-bonded network. Importantly, membrane and SFA studies reveal a discrimination between biologically-important ions that preferentially solubilizes divalent ions in more-dense water regions relative to less-dense water regions in which monovalent ions are enriched. Thus, the compelling conclusion to be drawn from the collective scientific evidence gleaned from over a century of experimental and theoretical investigation is that solvent properties of water within the interphase separating a solid surface from bulk water solution vary with contacting surface chemistry. This interphase can extend tens of nanometers from a water-contacting surface due to a propagation of differences in self association between vicinal water and bulk-phase water. Physicochemical properties of interfacial water profoundly influence the biological response to materials in a surprisingly straightforward manner when key measures of biological activity sensitive to interfacial phenomena are scaled against water adhesion tension tau O of contacting surfaces. As examples, hydrophobic surfaces (tau O 30 dyn/cm) do not support adsorption because this mechanism is energetically unfavorable. Protein-adsorbing hydrophobic surfaces are inefficient contact activators of the blood coagulation cascade whereas protein-repellent hydrophilic surfaces are efficient activators of blood coagulation. Mammalian cell attachment is a process distinct from protein adsorption that occurs efficiently to hydrophilic surfaces but inefficiently to hydrophobic surfaces. (ABSTRACT TRUNCATED)
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              Review of recent advances in the biodegradability of polyhydroxyalkanoate (PHA) bioplastics and their composites

              Poly(hydroxyalkanoate)s (PHAs) represent a promising solution to allay climate change and plastic waste pollution. Being both completely bio-based and biodegradable, PHAs can approach a carbon neutral platform whereas petroleum-based plastics cannot. The detrimental impact of single-use plastics on the environment is daily news across the globe. Single-use plastic packaging materials and other plastic waste originating from petroleum-based sources are continuously building up in landfills and leaching into the environment. Managing plastic waste remains an urgent crisis in the environment and switching to biodegradable plastics can help mitigate some of these issues. This review will summarize recent advances and opportunities to utilize polyhydroxyalkanoates (PHAs) as a biodegradable substitute in some applications where non-biodegradable and petroleum-based plastics are currently used. PHAs are a well-known family of bacteria-based biodegradable plastics and offer an approach to carbon neutrality and support a more sustainable industry. PHAs such as poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) show biodegradable behaviour in all aerobic and anaerobic environments defined by ASTM standards, and can be used to make completely compostable, and soil and marine biodegradable products – a strong positive compared to the negativity associated with the landfilling of plastics. However, PHAs are relatively expensive compared to petroleum-based alternatives. To reduce the cost, PHAs can be used in biocomposite materials, where bio-based agro-residues are incorporated, while maintaining the performance in certain applications. Organic fillers and fibres composed of cellulosic material can improve the properties of polymers, however, their effect on the marine biodegradable properties of the composite matrix remains an unexplored area. When used in biocomposites with PHAs, they improve biodegradation rates in all environments. In addition to cellulose, other bio-based fillers such as proteins ( i.e. distillers dried grains with solubles) and starch have been reported to significantly improve soil and marine biodegradability rates compared to other fibres and fillers. Other components that affect biodegradability are additives ( i.e. chain extenders) and compatibilizers ( i.e. maleic anhydride etc. ) that are added to optimize the service life properties, but are reported to inhibit the biodegradation properties by impacting the hydrophilicity of the polymer and enzyme activity. The multitude of possible combinations of polymers and fillers and fibres, and their effect on the biodegradation of PHA-based biocomposites are a largely unexplored frontier. The potential benefits of PHA-based biocomposites make a strong case for further research into this area.
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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                05 January 2021
                January 2021
                : 26
                : 1
                : 240
                Affiliations
                Technological Institute of Materials (ITM), Universitat Politècnica de València (UPV), Plaza Ferrándiz y Carbonell 1, 03801 Alcoy, Spain; rateol@ 123456epsa.upv.es (R.T.-O.); juaivmar@ 123456doctor.upv.es (J.I.-M.); jaugoca@ 123456epsa.upv.es (J.G.-C.); nesmonmu@ 123456upvnet.upv.es (N.M.)
                Author notes
                [* ]Correspondence: rbalart@ 123456mcm.upv.es (R.B.); luiquic1@ 123456epsa.upv.es (L.Q.-C.); Tel.: +34-966-528-433 (L.Q.-C.)
                Author information
                https://orcid.org/0000-0001-5670-7126
                https://orcid.org/0000-0001-8968-4899
                https://orcid.org/0000-0001-8037-2215
                Article
                molecules-26-00240
                10.3390/molecules26010240
                7796501
                625fbed5-9faa-4906-a67a-228250e6d3ec
                © 2021 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 17 December 2020
                : 01 January 2021
                Categories
                Article

                polylactide,thermoplastic elastomer,impact strength,rigid packaging,mechanical properties

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