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.     

Compatibility improvement of poly(lactic acid)/thermoplastic starch blown films using acetylated starch

The present research aims to improve the compatibility between relatively hydrophobic poly(lactic acid) (PLA) and hydrophilic thermoplastic starch (TPS) and the properties of the PLA/TPS blends by replacing TPS from native cassava starch (TPSN) with TPS from acetylated starch (TPSA). The effects of the degree of acetylation (DA) of acetylated starch, that is, 0.021, 0.031, and 0.074, on the morphological characteristics and properties of PLA/TPS blend are investigated. The melt blends of PLA and TPS with a weight proportion of PLA:TPS of 50:50 are fabricated and then blown into films. Scanning electron microscopy confirms the dispersion of TPS phase in the PLA matrix. Better dispersion and smaller size of the TPS phase are observed for the PLA/TPSA blend films with low DA of acetylated starch, resulting in improved tensile and barrier properties and increased storage modulus, thermal stability, and T_g, T_cc, and T_m of PLA. Elongation at break of the PLA/TPSA blend increases up to 57%, whereas its water vapor permeability and oxygen permeability decrease about 15%. The obtained PLA/TPSA blend films have the potential to be applied as biodegradable flexible packaging.     

Development and characteristics of biodegradable Aloe‐gel/egg white films

The use of synthetic nonbiodegradable polymers has led to environmental damage. This has encouraged the interest to the development of new renewable and biodegradable matrices. The potential of egg white (EW) protein for the development of bioplastic materials has been published. However, the mixture of EW with Aloe‐gel (AG) for film formation has not been documented. In this study, films with different EW and AG combinations are manufactured and their properties are analyzed. In general, the AG/EW films are homogeneous, smooth, with no pores and with cumulus of protein on the surface with better extensibility, plasticity, and low tensile strength. In addition, they are yellow colored, UV‐light blocker, with high solubility (2.2 times) and high Water Vapor Permeability (4.17 times) compared with the control (EW film). The AG/EW films showed higher percentage of soluble protein and antibacterial activity than the control. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44067.     

Modification and extrusion coating of polylactic acid films

Polyethylene (PE) extrusion coating on paper substrates are the traditional packing material for coffee cups and take‐out food containers. It is difficult to recycle the PE/paper laminates and the thin polymer films remain in landfills after the decomposition of their paper substrates. Disposal of plastic materials is causing serious effects on our environment and wildlife. Demand for compostable or biodegradable plastic packaging products is increasing because of consumer pressure and legislation. Biodegradable polylactic acid (PLA) is regarded as one of the most promising biopolymers with a large market potential, but its applications are limited by poor thermal stability, mechanical properties and processibility. We utilize modified gelatin as additives to improve PLA's performance without compromizing the biomass origin and compostable properties of the material. Extrusion coating, or extrusion casting, of polylactic acid (PLA) films onto paper substrates to form PLA/paper laminates was achieved by modification of the polymer with a plant or animal gelatin. Various paper substrates with thin PLA coatings were prepared using a conventional extrusion coating equipment for the fabrication of take‐out food containers and coffee cups. Melt rheology of PLA and adhesion of the resulting thin film were greatly improved in the presence of a small amount of gelatin in the polymer matrices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42472.     

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.     

Utilization of ramon seeds (Brosimum alicastrum swarts) as a new source material for thermoplastic starch production

The development and characterization of biodegradable polymers deriving from renewable natural sources has attracted much attention. The aim of this work was to partially characterize a thermoplastic starch obtained from the starch of seeds from the ramon tree (TPS‐RS) as an option to substitute thermoplastic starch from corn (TPS‐CS), in some of its applications. At 55% of relative humidity (RH), TPS‐RS had higher tensile strength and deformation than TPS‐CS. X‐ray diffraction analysis showed similar values in residual crystallinity (percentage of crystallinity that remains after plasticization process) in both TPS. The SEM micrographs showed a few remnant granular structures in the TPS‐RS. The FTIR showed a greater intensity in band at 1016 cm^?1 in the TPS‐CS and TPS‐RS in comparison with their corresponding native starch, indicating an increase in the amorphous region after plasticization. The TGA analysis showed greater thermal stability in TPS‐CS (340 °C) compared with TPS‐RS (327 °C). In addition, the glass transition temperature in both TPS was 24 °C. The results obtained represent a starting point to potentialize the use of TPS‐RS instead of TPS‐CS for the development of new biodegradable materials for practical applications in different areas. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44235.     

Polyester films obtained by noncatalyzed melt‐condensation polymerization of aleuritic (9,10,16‐trihydroxyhexadecanoic) acid in air

To mimic nontoxic and fully biodegradable biopolymers like the plant cutin, polyester films from a natural occurring fatty polyhydroxyacid like aleuritic (9,10,16‐trihydroxyhexadecanoic) acid have been prepared by noncatalyzed melt‐polycondensation at moderate temperature (150°C) directly in air. The course of the reaction has been followed by infrared spectroscopy, ¹³C magic angle spinning nuclear magnetic resonance spectroscopy, differential scanning calorimetry and X‐ray diffraction and well differentiated stages are observed. First, a high conversion esterification reaction leads to an amorphous rubbery, infusible, and insoluble material whose structure is made out of ester linkages mostly involving primary hydroxyls and partially branched by minor esterification with secondary ones. Following the esterification stage, the cleavage of vicinal secondary hydroxyls and further oxidation to carboxylic acid is observed at the near surface region of films. New carboxylic groups created also undergo esterification and generate cross‐linking points within the polymer structure. Additionally, and despite the harsh preparation conditions used, very little additional side reaction like peroxidation and dehydration are observed. Results demonstrate the feasibility of polyester films fabrication from a reference fatty polyhydroxyacid like aleuritic acid by noncatalyzed melt‐polycondensation directly in air. The methodology can potentially be extended to similar natural occurring hydroxyacids to obtain films and coatings to be used, for instance, as nontoxic and biodegradable food packaging material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41328.     

Compatibilization of starch/poly(butylene adipate‐co‐terephthalate) blown films using itaconic acid and sodium hypophosphite

Itaconic acid (IA) has potential as a compatibilizing agent in polymeric blends due to its unique chemical characteristics. Sodium hypophosphite (SHP) has been studied as a catalyst in esterifying reactions using multicarboxylic acids. Starch/poly(butylene adipate‐co‐terephthalate) blown films containing IA, with and without SHP, were produced. The film containing IA presented higher tensile strength (8.166 MPa) and elongation (891.473%) than the control film (5.548 MPa and 487.637%, respectively). When SHP was added (sample IA‐SHP), tensile strength increased even more (9.215 MPa); however, elongation (636.821%) was lower than in the IA film. This behavior was attributed to crosslinking between two starch itaconoate molecules intermediated by SHP. The increase in the compatibility between the polymeric phases justified the lower permeability to water vapor of the IA‐SHP films and was responsible for the production of films with a more compact and homogeneous structure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46629.     

Improving the toughening in poly(lactic acid)‐thermoplastic cassava starch reactive blends

Poly(lactic acid) (PLA), a physical blend of PLA and thermoplastic cassava starch (TPCS) (PLA‐TPCS), and reactive blends of PLA with TPCS using maleic anhydride as compatibilizer with two different peroxide initiators [i.e., 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane (L101) and dicumyl peroxide (DCP)] PLA‐g‐TPCS‐L101 and PLA‐g‐TPCS‐DCP were produced and characterized. Blends were produced using either a mixer unit or twin‐screw extruder. Films for testing were produced by compression molding and cast film extrusion. Morphological, mechanical, thermomechanical, thermal, and optical properties of the samples were assessed. Blends produced with the twin‐screw extruder resulted in a better grade of mixing than blends produced with the mixer. Reactive compatibilization improved the interfacial adhesion of PLA and TPCS. Scanning electron microscopy images of the physical blend showed larger TPCS domains in the PLA matrix due to poor compatibilization. However, reactive blends revealed smaller TPCS domains and better interfacial adhesion of TPCS to the PLA matrix when DCP was used as initiator. Reactive blends exhibited high values for elongation at break without an improvement in tensile strength. PLA‐g‐TPCS‐DCP provides promising properties as a tougher biodegradable film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46140.     

Conformational changes after foaming in a protein‐based thermoplastic

Novatein is a biopolymer produced from blood meal and can be foamed for use as a packaging material. The effect of foaming on protein ordered structures such as α‐helices and β‐sheets was investigated using synchrotron Fourier transform infrared (FTIR). Foaming caused a reduction in ordered structures due to an increase in random coils. FTIR also revealed a higher proportion of plasticizer (triethylene glycol, TEG) and β‐sheets toward the surface of enclosed bubbles. Increased TEG will assist foaming with greater plasticization aiding nucleation, while β‐sheets contribute to bubble stabilization. These structural changes occur as foaming takes place close to the degradation temperature of Novatein, and coincide with melting of α‐helices and/or β‐sheets. A more amorphous polymer is therefore produced which is subsequently easier to foam due to its increased elasticity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46005.     

Effect of five saturated fatty acids on the properties of sweet‐potato‐starch‐based films

To fully explore the influences of saturated fatty acids (SFAs) on the properties of sweet‐potato‐starch (SPS)‐based films, five SFAs were chosen to add to SPS. The SPS‐based films were prepared by casting. The microstructure, mechanical, optical, water vapor barrier, and thermal properties of the films were investigated. The 2.0% (w/w, on the basis of starch) SFA significantly changed the SPS pasting characteristics in the peak viscosity, breakdown, and other feature point viscosity values as determined by a Rapid Visco Analyser. The amylose molecular weights decreased as measured by high‐performance size exclusion chromatography. A thermal study with differential scanning calorimetry suggested that the addition of SFA increased the onset temperature and peak temperature. Scanning electronic microscope (SEM) images showed a continuous and uniform structure in the films with SFA. The SPS–SFA composite films showed lower light transmission and elongation at break than the control. Compared with the control films, the addition of SFA increased the tensile strength and decreased the water vapor permeability of the films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41380.     

Effect of dicumyl peroxide on biodegradable poly(lactic acid)/functionalized gum arabic based films

Blending of poly (lactic acid) (PLA)/functionalized gum arabic (FG) in presence of dicumyl peroxide (DCP) presents a simple process to produce film using melt extrusion (recycle time ~ 4 min, screw speed ~60 rpm) at 180°C with tailored characteristics. The FTIR investigation shows that the confirmation of grafting of PLA chains on FG through formation of new C─C linkage. Properties of fabricated films such as morphological, mechanical, UV barrier and contact angle are examined to develop film with improved interfacial interaction, increased toughness, UV–C blocking effect (~95%) and hydrophobicity (~14%). Polarized optical microscopy (POM) studies reveal that PLA/1FG with and without DCP has more crystal density as compared to PLA at 120°C. This melt extrusion permits straightforward, feasible bionanocomposite film and has great potential as a modification with DCP assists to overcome particular drawbacks of FG.     

Development of cross‐linked starch microcellular foam by solvent exchange and reactive supercritical fluid extrusion

Starch microcellular foams (SMCFs) are prepared by pore preserving drying or formation processes and contain pores in the micron size range. SMCFs have high specific surface area and are useful for applications such as opacifying pigments or as adsorbent materials. The objective of this research was to determine how the processing conditions and use of a crosslinking agent would affect the foam structure and properties. SMCFs (crosslinked and uncrosslinked) were prepared from molded aquagels and carbon dioxide extrusion processes separately and then solvent exchanged. Extruded samples showed macroscopic pores whereas samples from aquagels showed a much finer micropore structure. Aquagel‐based SMCF samples had lower density and higher brightness than did extruded samples. The starch foams with micropore structure had low density and high brightness. The solvent exchange process was the most important variable in generating a microcellular structure. Micropores and not macropores contributed to increased brightness of these materials. The brightness and density of the foams were found to be linearly related. Crosslinking with epichlorohydrin imparted significant water resistance to the extruded samples as evidenced in lower water swelling and higher contact angles. Equilibrium moisture content was correlated with the microporous structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of starch‐based composite films reinforced by corn and wheat hulls

Biodegradable films, with starch as a matrix, were developed and reinforced with wheat and corn hulls. The effect of the particle size of the filler on the microstructure and mechanical and barrier properties of starch‐based films was investigated. We observed that the addition of hulls enhanced the modulus, tensile strength, and impact strength of the starch matrix at the expense of its elongation. The water‐vapor transmission rate results show that corn starch was more efficient in reducing the water‐vapor permeability than wheat hulls. Scanning electron microscopy observations indicated that the compatibility of both fillers with the matrix was quite good; this was expected because all of the components used in this study were hydrophilic and exhibited polar behavior. Optical microscopy and X‐ray diffraction observations indicated that the processing conditions did not affect the crystalline and geometric structures of the hulls. Because all of the components used in this study were from food resources, the films could also be used for edible packaging. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45159.     

Fully bio‐based polyesters derived from 2,5‐furandicarboxylic acid (2,5‐FDCA) and dodecanedioic acid (DDCA): From semicrystalline thermoplastic to amorphous elastomer

A serials of fully bio‐based poly(ethylene dodecanedioate‐2,5‐furandicarboxylate) (PEDF) were synthesized from Dodecanedioic acid (DDCA), 2,5‐Furandicarboxylic acid (2,5‐FDCA), and ethylene glycol through a two‐step procedure consisted of transesterification and polycondensation. After their chemical structures were confirmed by Nuclear Magnetic Resonance and Fourier Transform Infrared Spectroscopy, their thermal, mechanical, and biodegradation properties were investigated in detail. Results showed that the chemical composition of PEDFs could be easily controlled by the feeding mole ratio of DDCA to FDCA and they possessed the characteristic of random copolyester with the intrinsic viscosity ranged from 0.82 to 1.2 dL/g. With the varied mole ratio of DDCA to FDCA, PEDFs could be changed from semicrystalline thermoplastic to the completely amorphous elastomer, indicated by the elongation at break ranged from 4 for poly(ethylene 2,5‐furandicarboxylate) to 1500% for amorphous PEDF‐40. The amorphous PEDF‐30 and PEDF‐40 showed satisfactory shape recovery after cyclic tensile test, which was the typical behavior for elastomer. Enzymatic degradation test indicated that all the PEDFs were biodegradable and the degradation rate was heavily affected by their chemical compositions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46076.     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Compatibilization of poly(lactic acid)/ethylene‐propylene‐diene rubber blends by using organic montmorillonite as a compatibilizer

This work focuses on phase morphology and properties of immiscible poly(lactic acid)/ethylene‐propylene‐diene rubber (PLA/EPDM) blends compatibilized with organic montmorillonite (OMMT). Effect of OMMT loading on phase morphology, mechanical properties, and blown film bubble stability was investigated. Transmission electron micrographs show that a large number of OMMT nanolayers locate at interfacial region between PLA and EPDM phase, as well as in EPDM phase due to higher affinity of OMMT with EPDM. Scanning electron micrographs show that EPDM domain size decreases largely with increasing OMMT loading, which is associated with reduction of interfacial energy and inhibition of coalescence by the OMMT locating at the interface, acting as an emulsifier to enwrap the discrete domains. As OMMT loading increases from 0 to 1 phr, elongation at break increases from 20.4 to 151.7% and notched impact strength is enhanced from 8.2 to 31.7 kJ?m^?2. The reduced EPDM domain is the main reason for enhanced toughness of PLA/EPDM/OMMT samples according to crazing with shear yielding mechanism. However, with more than 2 phr of OMMT, the toughness decreases largely due to excessive stress concentration and OMMT aggregation. Attempts were made to produce ductile films from the PLA/EPDM/OMMT nanocomposites by using blown film extrusion. Improvement in blown film bubble stability and tensile ductility of PLA/EPDM/OMMT films also shows that OMMT is an efficient compatibilizer, as well as a processing aid for PLA/EPDM blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44192.     

Surface and degradation properties of thermoplastic blends from albumin and zein‐based plastics

The use of traditional petroleum‐based thermoplastics in food packaging applications pose an environmental hazard, as their lack of biodegradability creates waste that environmental systems are unable to cope with. To address this issue, the investigation of surface, biodegradation, and water solubility properties of the albumin and zein thermoplastic blends plasticized with glycerol and mixed with varying amounts of low‐density polyethylene (LDPE) is conducted. When subjected to soil burial, albumin as a bioplastic completely biodegrades within two months, while a zein‐based bioplastic is more resilient to attacks from microbes within the soil (4.34% of intial mass remains). If albumin and zein proteins are used in the production of thermoplastics in tandem with LDPE, it could be possible to produce a plastic that will naturally biodegrade over time, decreasing the environmental impact of the use of thermoplastics in medical and food packaging applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44646.     

Ultra‐microstructural features of perborate oxidized starch

Ultrafine structures of low, medium, and highly oxidized starches, symbolized as LOS, MOS, and HOS, respectively, were thoroughly investigated. These oxidized starches were obtained by treatment of native starch (NS) with three different concentrations of sodium perborate (SPB). Thus, obtained products were studied with respect to major chemical and fine physical characteristics vis‐a‐vis these of NS (a) acidic and reduced groups creation along with mode of association, (b) significant increase in solubility, and (c) outstanding decrease in apparent viscosity. Thermogravimetric analysis (TGA) revealed thermal stability of the said substrates follows order: HOS > MOS > LOS > NS. Scanning electron micrographs (SEM) showed polygonal or irregular shape with particle size ranging from 2 to 20 μ. After oxidation, the starch surface became rough and the edges lost their definiteness completely. In conclusion, SPB is an efficient oxidant to produce oxidized starches with useful characteristics, which advocate them to wide applications in textile sizing and medicinal domains. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40170.     

Polyurethane‐functionalized starch nanoparticles for the purification of biodiesel

Polyurethane‐functionalized starch nanoparticles (PUFSNPs) have been synthesized by chemical modification of polyhydroxylated starch nanocrystals (SNC) with aliphatic and aromatic diisocyanates. The covalent attachment of the diisocyanates to the backbone of SNC for the formation of starch‐derived nanopolyurethane polymers was unambiguously determined by FTIR and NMR spectroscopy. PUFSNPs were entirely obtained from SNC with yields ranging from 41.5 to 86.0 wt % and their size distribution, size, porosity and morphology were determined by dynamic light scattering (DLS), high resolution transmission electron microscopy (HRTEM) and Brunauer–Emmett–Teller (BET) adsorption techniques. The size and surface area of the cyclic aliphatic‐based PUFSNP (NPU4) is 27 nm and 52.64 m² g^?1, respectively, indicating one of the potential and promising biodegradable materials for the adsorption of acid impurities and contaminants that are found in crude biodiesel. The acid content of the biodiesel is remarkably reduced by 32–39% with PUFSNPs while 7–18% with their corresponding bulk materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44463.