Tailored biodegradable films via extrusion blow molding using PBS,PBAT, and TPS

Research to replace synthetic polymers with biodegradable polymers is on the rise because common plastics have generated serious ecosystem problems. Films with thermoplastic starch (TPS), poly(butylene succinate) (PBS), poly(butylene adipate-co-butylene terephthalate (PBAT), and citric acid (CA) were produced by blown extrusion. They were characterized by blow-up ratio (BUR), water vapor permeability (WVP), soluble ratio (SR), water sorption isotherm, and thermogravimetric (TG) techniques. Films were uniform and showed BUR > 205%. The different proportions of PBS and PBAT significantly influenced the WVP of the films. All samples had WVP with an order of magnitude similar to other blends with high starch content (10⁻⁶ g m⁻¹ day⁻¹ Pa⁻¹). CA efficiently decreased the WVP of the PBS/PBAT/TPS formulations (15/15/70% and 20/10/70% by mass) by 25.2% and 24.7% compared to the acid-free formulations. There was no significant difference in SR (19.0%–20.1%). These materials were sensitive to moisture since the equilibrium moisture content increased pronouncedly from water activity of 0.5. Films showed good thermal stability, with a maximum decomposition temperature close to pure polyesters. CA did not increase the thermal stability of blends, probably because of the low content used (0.1%). Given the outcomes of this study, these films could be deemed appropriate for applications in food packaging.     

Self‐supporting‐film from starch,poly(vinyl alcohol), and glutaraldehyde: Optimization of composition using response surface methodology

Use of starch based biodegradable packaging film can partially reduce the landfilling problem from non‐biodegradable petroleum based alternatives. The aim of this work was to optimize raw material blend composition containing corn‐starch (CS), and low amount of poly(vinylalcohol) (PVA) and glutaraldehyde (GA) to produce self‐supporting‐film (SSF), using response surface methodology. Rotatable central composite design was used to evaluate the effect of CS (6.25–7.50), PVA (0.00–1.25), and GA (0.00–1.25), in g/100 mL of the blend, on tensile strength (TS), percent elongation (%El), and water vapor permeability (WVP) of the film. The most significant (p < 0.01/0.05) factors were: CS and GA for TS, CS and PVA for El, and PVA for WVP. The SSFs were thin, flexible and transparent; the optimum composition (g/100 mL) to maximize TS and El, and minimize WVP was 7.50 (CS), 0.875 (PVA), and 0.125 (GA), which produced SSF showing TS: 11.66 MPa, %El: 8.56, and WVP: 0.13 g mm/m² /kPa/h. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44436.     

Cassava starch‐based nanocomposites reinforced with cellulose nanofibers extracted from sisal

Cellulose nanofibers were extracted from sisal and incorporated at different concentrations (0–5%) into cassava starch to produce nanocomposites. Films' morphology, thickness, transparency, swelling degree in water, water vapor permeability (WVP) as well as thermal and mechanical properties were studied. Cellulose nanofiber addition affected neither thickness (56.637 ± 2.939 µm) nor transparency (2.97 ± 1.07 mm^?1). WVP was reduced until a cellulose nanofiber content of 3.44%. Tensile force was increased up to a nanocellulose concentration of 3.25%. Elongation was decreased linearly upon cellulose nanofiber addition. Among all films, the greatest Young's modulus was 2.2 GPa. Cellulose nanofibers were found to reduce the onset temperature of thermal degradation, although melting temperature and enthalpy were higher for the nanocomposites. Because cellulose nanofibers were able to improve key properties of the films, the results obtained here can pave the route for the development and large‐scale production of novel biodegradable packaging materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44637.     

Aging properties and hydrophilicity of maize starch plasticized by hyperbranched poly(citrate glyceride)

Hyperbranched poly(citrate glyceride)s (HBPETs) as plasticizers were mixed with maize starch (S) via cooking and film formation. The structure, aging properties, and hydrophilicity of the plasticized starches were studied by means of Fourier transform infrared spectroscopy, X-ray diffraction, tension testing, contact angle testing, solubility measurements, moisture absorption, and water vapor permeability (WVP). Compared with a glycerol–S plasticized film, the HBPET–S composite films had better mechanical properties in terms of both strength and elongation at break, better aging resistance, less moisture absorption, less WVP, and more hydrophobicity on the film surface. The mechanisms behind the performances resulted from stronger and more stable H bonds between the abundant active end groups of HBPET and hydroxyls of starch and the high branching degree of the HBPETs; this was helpful for effectively inhibiting the recrystallization of starch. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46899.     

Potential of Pinhão husk (Araucaria angustifolia) as a structural reinforcement agent in the properties of edible films of Pinhão flour and gelatin

In this study, the use of Pinhão husk as a source of reinforcement material for development of edible films, where the Pinhão seed flour and bovine gelatin were used as matrices for the films. Mechanical properties, water vapor permeability, solubility and opacity, microstructure, and thermal degradation characterized the films produced. The films presented homogeneous and cohesive structures. Pinhão husk content positively affected film properties by increasing tensile strength (TS) and decreasing water vapor permeability (WVP), with Pinhão flour film formulations (5.0% Pinhão flour, 1.2% glycerol, and 0.4% Pinhão husk) and gelatin (5.0% gelatin, 2.0% glycerol, and 0.4% Pinhão husk) those that presented the best results (5.06 MPa for TS and 0.14 g.mm/kPa.h.m² for WVP) and (3.88 MPa for TS and 0.28 g.mm/kPa.h.m² for WVP), respectively The thermal degradation study revealed that the films are stable at temperatures below 150°C, losing only free water and volatile compounds of low molecular weight. Pinhão husk can reinforce films, making them suitable as biodegradable and edible packaging materials for eco-friendly food products. This contributes to the circular economy, preserves biodiversity, and reduces plastic waste, offering promising sustainable packaging solutions.     

Morphological,barrier, and mechanical properties of cassava starch films reinforced with cellulose and starch nanoparticles

A comparative performance study of cellulose and starch nanoparticles on plasticized starch reinforcement has been presented. Starch nanoparticles were obtained by ultrasound and acid hydrolysis, and cellulose nanoparticles were extracted by acid hydrolysis from microcrystalline cellulose and sisal fibers. The nanoparticles were characterized according to the zeta potential, the particle-size distribution, transmission electron microscopy, X-ray diffraction, and thermogravimetric analysis. The influence of the addition of these nanoparticles to starch films on the morphology, water vapor permeability (WVP), and mechanical properties of the nanocomposites films were investigated. The cellulose nanoparticles exhibited higher electrical stability than those originating from starch. Acid hydrolysis produced starch nanoparticles with higher crystallinity than ultrasound. All the nanoparticles significantly reduced the WVP. The cellulose nanoparticles significantly increased the tensile strength of the starch films; however, they reduced the flexibility of the nanocomposites. The results of this work support the application of starch and cellulose nanostructures for the development of reinforced biodegradable materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47001.     

Water vapor and oxygen permeability of wax films

The water vapor (WVP) and oxygen (O₂P) permeabilities of beeswax (BW), candelilla wax (CnW), carnauba wax (CrW) and microcrystalline wax (MW), formed as freestanding films, were determined. CnW and CrW both had small values for O₂P (0.29 and 0.26 g·m⁻¹·sec⁻¹·Pa⁻¹ × 10⁻¹⁴, respectively), which are less than half the value for high-density polyethylene and about a decade greater than the value for polyethylene terephthalate. O₂P values for BW and MW were about 6−9× greater than those of CnW and CrW. WVP of CnW was 0.18 g·m⁻¹·sec⁻¹·Pa⁻¹ × 10⁻¹², which is about one-half the value for CrW and MW and about one-third the value for BW. The WVP of CnW was somewhat less than that of polypropylene and somewhat greater than that of high-density polyethylene. Differences in permeabilities among the wax films are attributed mainly to differences in chemical composition and crystal type as determined by X-ray diffraction.     

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.     

Production and characterization of starch-based films reinforced by ramie nanofibers (Boehmeria nivea)

In this study, the use of cellulose nanofibers from ramie, a plant species with important characteristics of reinforcement, was investigated in the production of bio-based polymer films. A central composite rotatable design was applied to produce the films, analyze the effects of cassava starch, glycerol, and nanofibers content on their properties, obtain mathematical models, response surface plots, and determine an optimum composition. The films produced were characterized by mechanical properties, water vapor permeability (WVP), solubility, and opacity. Microstructure and thermal behavior were also evaluated. The ramie nanofibers content had a positive effect on mechanical and barrier properties, as it increased tensile strength by 207.9%, and decreased WVP and solubility by 52.9 and 72.9%, respectively. Furthermore, the obtained films exhibited homogeneous and cohesive structures, which encourages the use of ramie nanofibers as a reinforcement material in the production of green plastics. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47919.     

乙酰化淀粉/聚己内酯共混物的制备和性能研究

分别采用淀粉(TPS)、乙酰化淀粉(TPAS)与聚己内酯(PCL)进行熔融共混，制备了可生物降解的塑料，探讨了淀粉乙酰化改性后对共混物力学性能、耐水性、熔融流动性、相容性及生物降解性的影响。共混物的拉伸强度均随PCL用量的增加而增大，TPAS／PCL体系的拉伸强度低于TPS／PCL体系，而断裂伸长率高于TPS／PCL体系。PCL可以明显改善淀粉基材料的耐水性，淀粉乙酰化后共混体系的相容性及熔体流动性得到一定的改善，生物降解性略微下降。     

Mechanical properties and water vapor permeability of thin film from corn hull arabinoxylan

Isolated corn hull arabinoxylan was dissolved in water and provided a clear solution. Plasticizer (glycerol, propylene glycol, or sorbitol) was added to the arabinoxylan solution at 0–20 wt % (film dry weight), which was cast into stable films. Film thickness ranged from 22 to 32 μm. Mechanical properties, moisture content, and water vapor permeability (WVP) were studied for the arabinoxylan‐based films as a function of plasticizer concentration. Measured data for the corn hull arabinoxylan–based films were 13–18 wt % moisture content, 10–61 MPa tensile strength, 365–1320 MPa modulus, 6–12% elongation, and 0.23–0.43 × 10^?10 g m^?1 Pa^?1 s^?1 water vapor permeability. Plasticized arabinoxylan films produced in this study had lower WVPs than those of unplasticized films, which is likely attributable to the phenomenon known as antiplasticization. Scanning electron micrographs showed a homogeneous structure on film surfaces. Films containing sorbitol had the best moisture barrier properties. When grapes were coated with arabinoxylan and arabinoxylan/sorbitol films, weight loss rates of the fruit decreased by 18 and 41%, respectively, after 7 days. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2896–2902, 2004     

Development of sulfated polysaccharide-based film reinforced with seaweed biomass-derived nanofillers

Cling films and single-use plastics are difficult to recycle and cause major environmental pollution, leading to an increase in microplastics in nature. To overcome this issue, biodegradable films are being explored more extensively. Seaweed is gaining prominence in the food packaging sector since it is beneficial in all aspects. Two fractions of Indian brown seaweed Sargassum wightii, biopolymer (sulfated polysaccharide [SP]) as base material and nanofillers (cellulose nanocrystals [CNC]) as reinforced filler are employed to develop a sustainable cling film for food packaging. This cellulose filler can be isolated from solid seaweed biomass after the polysaccharide extraction and converted into nanoform using the response surfaces method (RSM) to maximize the yield of CNC. The objective of this research is to construct seaweed-based biodegradable nanocomposite films and to examine their improved properties. It exhibited a gradual decrease in water absorption and water vapor permeability (WVP), along with better wettability, mechanical, and antioxidant properties, and thermal analysis compared with the control SP film. The degradation rates of the films were analyzed using the soil-burial method. According to the results obtained, it is suggested that CNC can be utilized as a functional filler to improve the qualities of seaweed-based cling films.     

Improvement of water barrier properties of soybean protein isolate films by poly(3-hydroxybutyrate) thin coating

The aim of this work was to study the preparation of bilayer films formed by soy protein isolate (SPI) and polyhydroxybutyrate (PHB). This was done using the lowest possible concentration of PHB to improve the functionality of SPI films as food packaging or for agricultural uses, specially reducing their water vapor permeability (WVP). SPI films are environmentally friendly since they are biodegradable and come from renewable sources but they are brittle and have high water permeability. Even for the lowest concentration analyzed, PHB managed to form a homogeneous layer that successfully covered up the SPI film surface. All bilayers films showed a significant reduction of WVP of SPI films, and those with the highest PHB content showed the highest elastic Young's modulus and mechanical strength while maintaining a good elongation and low T_g value, similar to that of SPI. Despite of their hydrophobicity differences, a good adherence of both layers was achieved, which allowed to improve the mechanical and barrier properties of the SPI coated films with respect to films formed by both biopolymers separately. The combination of both SPI and PHB seems to be a good alternative to prepare a biodegradable material taking advantages of the best properties of each component.     

Effects of co‐plasticization of acetyl tributyl citrate and glycerol on the properties of starch/PVA films

Starch/polyvinyl alcohol (PVA) nanocomposite films by film blowing process were successfully obtained. Starch (1700 g), PVA (300 g), and organically modified montmorillonite (OMMT, 200 g) were blended and plasticized with acetyl tributyl citrate (ATBC) and glycerol (GLY) at weight ratios of 0/100, 5/95, 10/90, 15/85, 20/80, and 25/75. The structural, morphology, barrier, mechanical, and thermal properties of the films, as well as molecular interactions in the nanocomposites were analyzed. The 3.98 nm d‐spacing was the highest in starch/PVA nanocomposite films plasticized with ATBC/GLY ratio of 10/90. The film with ATBC/GLY (5/95) had the lowest WVP (3.01 × 10^?10 g m^?1 s^?1 Pa^?1). The longitudinal tensile strength (TS) of starch/PVA nanocomposite films gradually increased from 4.46 to 6.81 MPa with the increase of ATBC/GLY ratios. The T_g steadily increased from 49.2°C to 55.2°C and the ΔH of the nanocomposite films decreased from 81.77 to 51.43 J/g at the presence of ATBC. The addition of ATBC into GLY plasticized starch/PVA/OMMT system enhanced the intermolecular interaction in the nanocomposites. This study proved that ATBC was an excellent compatibilizer in the preparation of starch/PVA/OMMT nanocomposite films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42544.     

Films from oat spelt arabinoxylan plasticized with glycerol and sorbitol

The development of packaging films based on renewable materials is an important and active area of research today. This is the first extensive study focusing on film‐forming properties of an agrobiomass byproduct, namely, oat spelt arabinoxylan. A plasticizer was needed for cohesive film formation, and glycerol and sorbitol were compared. The tensile properties of the films varied with the type and amount of the polyol. With a 10% (w/w) plasticizer content, the films containing glycerol had higher tensile strength than the films containing sorbitol, but with a 40% plasticizer content, the result was the opposite. Sorbitol‐plasticized films retained their tensile properties better than films with glycerol during 5 months of storage. The films were semicrystalline with similar crystallinity indices of 0.20–0.26. The largest crystallites (9.5 nm) were observed in the film with 40% glycerol. The softening of films with 40% (w/w) glycerol started at a significantly lower relative humidity (RH) than that of the corresponding sorbitol‐containing films. The films with sorbitol also had lower water vapor permeability (WVP) than the films with glycerol. The films plasticized with 10% (w/w) sorbitol had a WVP value of 1.1 g mm/(m²·d·kPa) at the RH gradient of 0/54%. The oxygen permeability of films containing 10% (w/w) glycerol or sorbitol was similar: 3 cm³·μm/(m²·d·kPa) at 50–75% RH. A higher plasticizer content resulted in more permeable films. Permeation of sunflower oil through the films was not detected. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of the incorporation of saturated fatty acids on the mechanical and barrier properties of biodegradable films

The effects of saturated fatty acids at a concentration of 1.5% on the mechanical and barrier properties of starch‐based films were evaluated in films prepared with two concentrations of glycerol, 20 and 25%. The water vapor permeability (WVP) was determined at three ranges of relative humidity, RH, (0–33, 33–64 and 64–97%). In all cases, an increase in WVP values was observed with increasing RH. SEM images showed a more homogeneous and compact structure in the films with caproic and lauric acids. The films with fatty acids showed higher elongation and maximum stress, and they had Young's modulus values close to those of the control; thus, the addition of fatty acids did not impair the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical and water binding properties of carboxymethyl cellulose/multiwalled carbon nanotube nanocomposites

Carboxymethyl cellulose (CMC) composite films were prepared from CMC solutions (2% w/v) containing multiwalled carbon nanotubes (MWCNT) as nanofiller and glycerol (25% w/w CMC) as plasticizer. Tensile strength, elongation at break (EAB), young's modulus, water solubility, water swelling, water uptake, and water vapor permeability (WVP) for CMC films were 27.5 ± 2.5 MPa, 11.2 ± 0.8%, 198 ± 18 MPa, 57 ± 1.5%, 738 ± 25%, 124 ± 4%, and 0.55 ± 0.036 g.mm/m².kPa.h, respectively. By increasing the relative humidity from 11.4 to 85.5%, the moisture absorption (MA) of CMC films was increased from 4 to 38%. Incorporation of MWCNT into the matrix caused a significant increase in the tensile strength, decrease in EAB, increase in young's modulus, decrease in water solubility, decrease in water swelling, decrease in water uptake, and decrease in MA. CMC/MWCNT films containing 1% MWCNT showed the lowest WVP. Scanning electron microscopy showed a good dispersion of MWCNT in the CMC matrix. CMC/MWCNT films containing >1% MWCNT showed significant antibacterial activities against both Gram‐positive and Gram‐negative bacteria in a dose‐dependent manner. Thus, good mechanical properties and water resistance along with strong antibacterial activities make CMC films grafted with MWCNT as a suitable packaging material. POLYM. COMPOS., 36:145–152, 2015. © 2014 Society of Plastics Engineers     

Influence of preparation conditions on the physical properties of zein films

Zein is a hydrophobic protein produced from maize. Biodegradable zein films without additional reagents were prepared using various controlled drying conditions. The zein films were transparent. Mechanical properties (tensile strength and puncture strength), gas permeability, and water vapor permeability (WVP) of the zein films were measured. The tensile strengths of the zein films were between 7 and 30 MPa and the puncture strengths between 37 and 191 MPa. The zein films had higher oxygen permeability than carbon dioxide permeability. The lowest WVP of the zein film was 0.012×10⁻⁹ g·m/m²·s·Pa. We found differences in the WVP between the sides of the zein films; i.e., the air side of the zein film had a higher WVP than the basal side of the zein film when the films were exposed to high humidity during testing. This indicates a relationship between the WVP of the zein film and the contact angle of the zein film. The mechanical properties of the zein film depended on the drying conditions during preparation. Zein films with various useful physical mechanical properties were produced.     

A starch‐based biodegradable film modified by nano silicon dioxide

The purpose of this work was to improve the properties of the starch/poly(vinyl alcohol) (PVA) films with nano silicon dioxide (nano SiO₂). Starch/PVA/nano‐SiO₂ biodegradable blend films were prepared by a solution casting method. The characteristics of the films were assessed by Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray photoelectron spectroscopy (XPS). The results obtained in this study indicated that the nano‐SiO₂ particles were dispersed evenly within the starch/PVA coating and an intermolecular hydrogen bond and a strong chemical bond C? O? Si were formed in the nano‐SiO₂ and starch/PVA. That the blending of starch, PVA and nano‐SiO₂ particles led to uniform starch/PVA/nano‐SiO₂ blend films with better mechanical properties. In addition, the nano‐SiO₂ particles can improve the water resistance and light transmission of the blend films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water vapor barrier and mechanical properties of konjac glucomannan–chitosan–soy protein isolate edible films

The effects of polymer composition, glycerol concentration and pH of film-forming solution on water vapor permeability (WVP), tensile strength (TS) and percentage elongation at break (%E) of composite edible film based on konjac glucomannan (KGM), chitosan and soy protein isolate (SPI) were investigated. Of the plasticizers tested, glycerol was found to be a suitable plasticizer regarding mechanical properties and WVP. The WVPs of the films were determined to be (3.29–9.63) × 10^?11 g m^?1 s^?1 Pa^?1, TS between 16.77 and 51.07 MPa, and %E between 1.29% and 10.73%, depending on film composition. Incorporation of SPI to the polymer matrix decreased both WVP and mechanical properties. Increase in both glycerol concentration and the pH of film-forming solution decreased WVP and TS but increased %E. The results suggest that film composition and the pH of film-forming solution are the major factors influencing the film properties.