Effect of Ca2+ induced crosslinking on the mechanical and barrier properties of cast alginate films

The use of alginate as a coating material for packaging applications is currently limited due to its difficult processability and high moisture sensitivity. Therefore, this study addresses the crosslinking and scale‐up to a continuous application. Three different crosslinking agents were applied: CaCl₂ with ethylene diamine tetraacetic acid and two low soluble salts (CaHPO₄ and CaCO₃). Those were incorporated by internal setting in an alginate matrix with varying Ca²⁺ concentration ( ) and ratio. With the addition of Ca²⁺, the tensile strength and elongation at break of the cast alginate films increased. This was optimal for a of 0.010–0.015 g (g alginate)^?1 dependent on the crosslinking agent. The decrease in water vapor and oxygen permeability due to crosslinking was independent of the crosslinking agent. However, the optimal aiming to decrease permeability was different for the crosslinking agents: CaHPO₄ showed best results at a of 0.010 g (g alginate)^?1, CaCl₂ at 0.012 g (g alginate)^?1, and CaCO₃ at 0.027 g (g alginate)^?1. Upon all analyzed properties CaHPO₄ was the most promising crosslinking agent for alginate. Moreover, selected alginate formulations were successfully processed in a continuous lacquering plant. The produced two‐layer systems have very low oxygen permeabilities which can be further reduced by crosslinking. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45754.     

Influence of processing on the mechanical properties and morphology of starch-based blends for film applications

This article describes the effect of processing on the properties and morphology of thermoplastic starch (TPS) and poly(butylene adipate-co-terephthalate) (PBAT) blends and films with high starch content. Different process parameters were modified during compounding of blends and extrusion of blown films. Morphology was examined through scanning electron microscopy. Mechanical and optical characterization of films was carried out as well. Decreasing specific throughput during compounding led to an increase in strain at break of the blends from 66 to 497%. The tensile strength increased from 6 to 22 MPa as well. The highest elastic modulus and tear resistance were achieved at intermediate specific throughputs, whereas the maximum TPS particle size and the lowest color difference were obtained at high specific throughputs. A decrease of color difference from 6.4 to 2.2 was observed by reducing the temperature profile in 5 °C. In the case of blown film extrusion, increasing the temperature profile resulted in a reduction of color difference of the films from 7.9 to 4.2. In addition, tensile strength and strain at break slightly increased. Color difference decreased with decreasing screw speed as well. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47990.     

Sophorolipid‐induced dimpling and increased porosity in solvent‐cast short‐chain polyhydroxyalkanoate films: Impact on thermomechanical properties

Sophorolipids (SL; microbial glycolipids) were used as additives in solvent‐cast short‐chain polyhydroxyalkanoate (sc‐PHA) films to enhance surface roughness and porosity. Poly‐3‐hydroxybutyrate (PHB), poly‐(6%)‐3‐hydroxybutyrate‐co‐(94%)‐3‐hydroxyvalerate (PHB/V), and poly‐(90%)‐3‐hydroxybutyrate‐co‐(10%)‐3‐hydroxyhexanoate (PHB/HHx) films were evaluated with up to 43 wt % of SL. Sophorolipid addition caused surface dimples with maximum diameters of 131.8 µm (PHB), 25.2 µm (PHB/V), and 102.8 µm (PHB/HHx). A rise in the size and number of pores in the polymer matrix also occurred in PHB and PHB/V films. Surface roughness and film porosity were visualized by scanning electron microscopy and quantitated using confocal microscopy by correlating the surface area (A′) to the scanned area (A) of the films. The phenotypic alterations of the films caused a gradual decline in tensile strength and modulus and increased the elongation to break. Reductions in the enthalpies of fusion (ΔH_f) in both the PHB (41% reduction) and PHB/HHx (36% reduction) films implied diminished crystallinity as SL concentrations increased. Over the same SL concentrations the Tan δ maxima shifted from 4 to 30°C and from 2 to 20°C in these respective films. These results provide a novel means by which sc‐PHA properties can be controlled for new/improved applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40609.     

Influence of recycling of poly(lactic acid) on packaging relevant properties

The most promising representative of biodegradable plastics in packaging applications is polylactide (PLA). Despite this, there is only a small market of PLA in Europe. Reasons for that are the high price of PLA raw material and the lack of knowledge of the behavior in packaging applications. It has a number of peculiarities so producers of plastics packaging hesitate to use it. Like other polyesters, it can degrade at increased temperatures in the presence of moisture by hydrolysis whereby it loses its physical and chemical properties. In all production processes, production waste is generated (i.e., stamping grids or edge trim). In most cases, this waste is used. It is not known in detail, how an internal recycling process will influence the final product properties. One problem is hydrolysis by which the production waste is partially degraded. Target of this study is to analyze the recycling process of PLA within the context of necessary process adaptions and the effects upon ecological efficiency. Films for packaging containing multiple types and amounts of production waste will be produced by extrusion and tested concerning their mechanical properties. The analysis of the recycling behavior showed that internal PLA production waste is well suitable for recycling. The influence of the recycling on the molecular weight is negligible. The effect on the viscosity and thus on the extrusion process is higher. Packaging relevant properties like mechanical or optical properties are hardly influenced. Especially recycling with a recycling quota of up to 50% has an insignificant effect on the film properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41532.     

Antioxidant and physicochemical properties of blended films based on gelatin‐sodium caseinate activated with natural extracts

Blend films of pigskin gelatin (GEL) and sodium caseinate (SCas) with boldo (B), guarana (G), cinnamon (C), or rosemary (R) extracts added were studied. SCas and extracts addition in blend films significantly increased the gloss and better UV barrier of GEL100 films. Extracts incorporation significantly decreased the rigidity and elongation of GEL100 films, which were significantly improved in GEL75:SCas25 blend films with extracts (EM = 295.69 ± 21.75 MPa and EB = 11.60 ± 3.43%). SCas addition not affected the TS parameter. The water vapor permeability of GEL100 films was reduced in blended films with extracts, showing the lowest value for GEL75:SCas25 + R (0.99 ± 0.07 × 10¹⁰ g s^?1 m^?1 Pa^?1). FTIR and microstructure analyses showed good compatibility for all components. The antioxidant activity of GEL100 was significantly increased with SCas and extracts addition (GEL50:SCas50 + R = 4.31 ± 0.11 mM ), suggesting the application of these films as an active food packaging material. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44467.     

Mixture design applied for the development of films based on starch,polyvinyl alcohol,and glycerol

Starch and polyvinyl alcohol (PVA) are biodegradable materials with potentiality to replace the conventional polymers in some applications. The aim of this work was to produce biodegradable films of PVA, cassava starch, and glycerol by thermoplastic extrusion using a mixture design to evaluate the effects of each component in the blend properties. Six formulations were prepared using a twin‐screw extruder coupled with a calender. All the materials were visually homogeneous and presented good processability. Mechanical properties were dependent on both the relative humidity conditioning and the formulation; higher relative humidities detracted the mechanical properties, which was associated to plasticizer effect of the water. Furthermore, the mechanical properties were better when higher concentrations of PVA were used, resulting in films with lower opacity, lower water vapor permeability, and higher thermal stability, according to TGA. Biodegradable materials based on starch, PVA, and glycerol have adequate mechanical and processing properties for commercial production. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42697.     

Effect of different concentration of rapeseed‐oil‐based polyol and water on structure and mechanical properties of flexible polyurethane foams

Flexible polyurethane foams (FPURFs) with varied concentration of water from 3.2 to 4.2% and rapeseed oil based polyol (ROP) in the range of 13–22% in polyol premix were obtained. Effects of changes in polyurethane (PUR) formulation on the foaming process and mechanical properties of FPURFs were analyzed. It was found that the change of water content in PUR formulation influences its foaming process. Higher water content in the PUR formulation increases the growth velocity and the temperature of reaction mixture. In the case of foams modified with ROP, an opposite effect can be observed, where higher content of that component resulted in overall downturn of the foaming process and decreases of registered temperature inside the foams core. An addition of ROP beneficially influences on foams cellular structure favoring creation of finer cells. Such modification of PUR formulation with ROP increased apparent density, reduced hardness, and resilience of flexible foams. What is more the support factor of FPURFs with ROP was higher in comparison to the reference foam. Along with higher water content in the PUR formulation, apparent density and hardness has decreased and foams ability to absorb energy has been increased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42372.     

Effect of modified rubber powder on the morphology and thermal and mechanical properties of blown poly(lactic acid)–hydroxyl epoxidized natural rubber films for flexible film packaging

In this study, we prepared and used modified natural rubber powder to increase the toughness of poly(lactic acid) (PLA) films. We blended PLA and hydroxyl epoxidized natural rubber (HENR) via a melt-mixing process with twin-screw extruder and a blowing machine. We investigated the influence of the HENR content in the blend films on the microstructure, thermal, mechanical, and optical properties. The morphology of the blend showed a coarse surface and elongated fibrils of HENR in the PLA matrix. After blowing, the dispersion of small particles of HENR in the substrate was seen. The size of the remaining HENR particles was smaller than that of the starting powder. The compatibility of HENR and the remaining rubber particles may have synergistically contributed to improvements in the elongation at break, impact strength, and ultraviolet–visible transition protection of the PLA films. The elongation at break drastically increased from 3 to 228% after PLA was blended with 20 wt % HENR. On the other hand, all of the blends exhibited lower glass-transition temperatures and cold crystallization temperatures than the pure PLA films. We concluded that the blend was partially compatible and may have increased the flexibility of the PLA films. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47503.     

A statistical approach to engineer a biocomposite formulation from biofuel coproduct with balanced properties

A 3²‐full factorial design of experiment (DOE) and regression modeling were implemented together as a practical approach to attain a distillers' grains‐filled biocomposite with balanced mechanical and physical properties. The effects of compatibilizer and lubricant on tensile strength, flexural modulus, impact strength and melt flow index of the biocomposites were studied. Analysis of variance (ANOVA) was implemented to develop least square regression models containing statistically significant main effects (linear and quadratic) and interaction effect. The developed models showed good predictability for the new measurements. The statistical approach adopted in this work including overlaying contour plots of the response surfaces in the studied level domain was effective in highlighting an optimized region that leads to balanced mechanical and physical properties. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40443.     

Effect of bone ash fillers on mechanical and thermal properties of biobased epoxy nanocomposites

In this study, the fabrication and characterization of bone ash filled biobased epoxy resin (Super SAP 100/1000, contains 37% biobased carbon content) nanocomposites are presented. Biosource bone ash was modified by size reduction and surface modification processes using a combination of ball milling and sonochemical techniques and characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The modified bone ash particles were incorporated into biobased epoxy with noncontact mixing process. The as-fabricated nanocomposites were characterized using various thermal and mechanical analyses. The nanocomposites showed significant improvement in flexural strength (41.25%) and modulus (34.56%) for 2 wt% filler loading. Dynamic mechanical analysis (DMA) results showed improvement in both storage modulus and loss modulus. Additionally, DMA results showed a slight reduction in glass transition temperature which also complies with differential scanning calorimetry results. Thermomechanical analysis results showed a reduction in the coefficient of thermal expansion. Thermogravimetric analysis results showed improved thermal stability at both onset of degradation and the major degradation. These enhanced thermal and mechanical performances of the epoxy nanocomposites allows them to be suitable for lightweight aerospace, automotive, and biomedical applications.     

Mushroom polysaccharides‐incorporated cellulose nanofiber films with improved mechanical,moisture barrier,and antioxidant properties

Mushroom polysaccharides (MP), including white MP, brown MP, and enoki MP, were incorporated into cellulose nanofiber (CNF). Studies on thermal property, structure, crystallinity, and morphology of CNF‐MP films revealed that MP was well interacted with and adsorbed onto CNF. Incorporation of MP significantly (P < 0.05) increased tensile strength and reduced water vapor permeability of CNF film. CNF‐MP films possessed higher antioxidant activity than CNF only or CNF‐chitosan film, and the antioxidant activity of released components from CNF‐MP films immersed in water was higher than that released from films immersed in methanol. Radical scavenging activity and reducing ability were major antioxidant mechanisms of CNF‐MP films. These trends were consistent with the results of total phenolics content released from films and the antioxidant activity of MP themselves. This study demonstrated CNF‐MP films may be used as packaging material for preventing oxidation and/or dehydration of food during storage. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46166.     

Increasing the elongation at break of polyhydroxybutyrate biopolymer: Effect of cellulose nanowhiskers on mechanical and thermal properties

Bionanocomposites based on polyhydroxybutyrate (PHB) and cellulose nanowhiskers (CNWs) were prepared by dispersing CNWs in poly(ethylene glycol) (PEG) plasticizer subsequently incorporating the CNWs/PEG suspensions in the matrix. The thermal properties of the nanocomposites indicate an enlargement in the processing window in comparison to the neat PHB. The nanocomposites showed a remarkable increase in the strain level (50 times related to the neat PHB), without a significant loss of the tensile strength with the incorporation of small concentrations of CNWs in the final nanocomposite (up to 0.45 wt %). This behavior was explained in terms of a considerable chain orientation promoted by the presence of CNWs in the same direction of the applied load, which activated shear flow of the polymer matrix. The results described here can be explored to extend the applications of this biopolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Multilayer coextrusion of graphene polymer nanocomposites with enhanced structural organization and properties

A potential advantage of platelet‐like nanofillers as nanocomposite reinforcements is the possibility of achieving two‐dimensional (2D) stiffening through planar orientation of the platelets. Forced assembly by multilayer coextrusion, which enables the in‐plane orientation of platelet‐like fillers in alternating layers, was used in this work to produce poly(lactic acid) (PLA)/graphene multilayer films. These films exhibited a multilayer structure made of alternating layers of neat PLA and PLA containing graphite nanoplatelets (GNPs). Electron microscopy revealed information on the orientation of the individual GNPs. X‐ray diffraction results indicated that the thickness of the individual GNPs was reduced during the multilayer coextrusion process. A significant reinforcement of 120% at an overall GNP loading of 1 wt % in PLA was achieved. This high effective reinforcement was attributed to the high degree of planar alignment, improved dispersion and exfoliation and increased aspect ratio of the GNPs in the composite layers after multilayer coextrusion. Improved water vapor barrier properties were also achieved as a result of the highly organized 2D nanofillers in the multilayer films. These industrial scalable multilayer nanocomposite films open up possibilities for lightweight and strong packaging materials for food and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46041.     

Effect of montmorillonite clay addition on the morphological and physical properties of Jatropha curcas L. and Glycine max L. protein concentrate films

Protein concentrates from jatropha (JPC) and soy seeds (SPC) were obtained by solubilization and acid precipitation of proteins. JPC and SPC films were prepared by the casting method, using two different montmorillonite (MMT) clay concentrations and plasticized with glycerol. Film properties were evaluated by scanning electron microscopy, transmission electron microscopy, X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis, tensile properties, water retention, and water vapor transmission rate (WVRT). Typical tactoid microcomposite structures were found to be heterogeneously dispersed in the films containing MMT. A small XRD peak was found in films with MMT. Slight improvements in thermal stability and tensile strength were observed in the films with MMT. Reductions in water retention and WVRT were obtained when MMT was added into the films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44459.     

Polyhydroxyalkanoate coatings restrict moisture uptake and associated loss of barrier properties of thermoplastic starch films

This work investigates the use of polyhydroxyalkanoate (PHA) films as moisture barriers for thermoplastic starch (TPS) films, to produce biodegradable, multi‐layer materials with high gas barrier properties. This is a necessary extension to the limited work available on this topic and confirms that PHAs are suitable coating materials for TPS films intended for use in food packaging. Under storage conditions of up to 75% relative humidity (RH) for 2 weeks, a PHA coating maintained the moisture content (MC) of the TPS below the point at which its barrier properties were detrimentally affected. Furthermore, for PHBV coating thicknesses of 91–115 μm, the MC of the TPS remains significantly lower than uncoated TPS for the duration of the experiment (>25 days). The flux of water into the coated TPS fit to a model based on Fick's law. However, when the multi‐layered films were stored at 95% RH delamination occurred within 24 h. Preliminary investigation into possible material design improvements showed that the addition of a small amount of PHA to the TPS layer prolonged the time to delamination. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46379.     

Potato protein isolate‐based biopolymers

Thermal processing of two potato protein isolates (PPIs) with glycerol as a plasticizer was explored in this study. The PPIs were pretreated by alkali or alkali under reducing conditions. The PPIs before and after pretreatment were analyzed by sodium dodecyl sulfate polyacrylamide gel electrophoresis, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The effects of plasticizer content and pretreatment on mechanical and thermo‐mechanical properties of the compression‐molded biopolymers were studied. The highest tensile strengths obtained were 20–25 MPa and the biopolymer can be brittle or ductile depending on the plasticizer contents. The molecular weight and protein structure of the PPIs markedly affected the resultant biopolymers’ static and dynamic mechanical properties. The pretreatment of PPIs caused distinctly different changes in the mechanical properties of the two PPIs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42723.     

Films made from poly(vinyl alcohol‐co‐ethylene) and soluble biopolymers isolated from municipal biowaste

Blends were obtained from poly(vinyl alcohol‐co‐ethylene) and water‐soluble biopolymers isolated from the alkaline hydrolysate of two materials sampled from an urban waste treatment plant: that is, an anaerobic fermentation digestate and a compost. The digestate biopolymers contained more lipophilic and aliphatic C and less acidic functional groups than the compost biopolymers. Evidence was obtained for a condensation reaction occurring between the biopolymers and the synthetic polymer. The thermal, rheological, and mechanical properties of the blends were studied. Films containing a low concentration (ca. 6–7%) of biopolymers exhibited up to three times higher yield strength than the neat synthetic polymer. The films' properties were found to be dependent on the concentration and nature of the biopolymers. The results offer a scope for investigating biopolymers sourced from other biowastes and for a better understanding of the reasons for the observed effects and exploiting their full potential for modifying or replacing synthetic polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41359.     

Bio-based sustainable films from the Algerian Opuntia ficus-indica cladodes powder: Effect of plasticizer content

The present study investigated the fabrication and characterization of bio-based sustainable films composed of a terrestrial plant raw material, namely Opuntia ficus-indica (OFI) cladodes powder (CP) and a marine seaweed derivative, namely agar (A). The effect of glycerol concentration on the properties of the casted films was evaluated at four different contents, namely 30, 40, 50 and 60 wt%. The films present UV-blocking properties, as well as moderate mechanical performance, thermal stability, and water vapor transmission rate (WVTR). The results point to an increase in thickness, elongation at break, moisture content, water solubility, and WVTR with increasing glycerol content. On the contrary, Young's modulus, tensile strength, and water contact angle decreased as glycerol concentration increased. The best combination is obtained for the film with 30% glycerol, based on an intermediate compromise between physical, mechanical, thermal, and barrier properties. All these outcomes express the potentiality of the powder obtained from grinding the OFI cladodes as raw material to produce low-cost films for the development of sustainable packaging materials.     

Antioxidant films based on gelatin capsules and minimally processed beet root (Beta vulgaris L. var. Conditiva) residues

Biocomposite films were prepared by incorporating different concentrations of beet root residue powder (BRP) (2, 4, 8, and 12 g BRP/100 g water) into films based on residues of gelatin capsules (GCR) (40 g GCR/100 g water). Control films had no BRP added. A complete mechanical, physicochemical, barrier, optical, and antioxidant characterization of all films was performed. Among all the films considered, BRP12 was found to present the most adequate properties and was further investigated. SEM micrographs showed that BRP12 presented a less homogeneous surface in comparison with the control film, but they showed similar thermal stability. After 15 days of soil degradation, the films lost over 75% of weight. The films were effective on protecting sunflower oil from primary oxidation process, and BRP12 showed higher protection than control film. Therefore, this study suggests that the formulated films could act as promising antioxidant materials and contribute to environmentally friendly technologies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43094.     

Impact of the starch source on the physicochemical properties and biodegradability of different starch‐based films

Concern about environmental issues has motivated research into the development of biodegradable packaging from renewable sources. Natural polymers such as starch constitute a good alternative for diminishing the use of nonbiodegradable and nonrenewable components in the packaging industry. However, depending on the botanical source, films with different properties are formed. The aim of this study was to evaluate the film‐forming capacity of different starch sources (cassava, corn, potato, and wheat) by casting with starch contents from 2 to 6%. Principal component analysis methodology was used to evaluate the correlation between the formulations and their physicochemical and mechanical properties. It was not possible to produce continuous films based on potato starch, probably because of its very low amylose content (10%). The corn‐, cassava‐, and wheat‐starch‐based films were characterized by their thicknesses (0.06–0.22 mm), moisture contents (19–26%), water solubilities (13.7–26.5%), water‐vapor permeabilities (WVPs; 0.19–0.48 g mm h^?1 m^?2 kPa^?1), wettabilities (35–106°), biodegradabilities in soil, and thermal and mechanical properties (tensile strength = 1.9–6.7 MPa, elongation = 41–166%, and Young's modulus = 8–127 MPa). The wheat starch films presented higher WVPs and lower mechanical properties. The cassava starch films presented lower wettabilities and good mechanical properties; this suggested that their use in packaging for products, such as fruits and vegetables, with higher water activities could be feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46564.