Scalable production of hydrophobic starch/beeswax films by continuous solution casting

Starch is an appealing natural polymer for the scaled-up production of biodegradable plastics. However, the low water resistance of starch has made its broad applicability largely doubted. In this study, starch was combined with beeswax (BW) through a pilot scale continuous solution casting (CSC) technique to reduce water affinity while keeping the ensuing films totally biodegradable. The phase morphology, surface wettability, and water vapor permeability (WVP) of films were examined over a broad BW–starch mass ratio (0.3–0.7). Emulsified, surfactant-free starch/BW films were successfully obtained at a productivity of 0.55 m² film h⁻¹. The water contact angle increased nearly by 100% at 30 wt% BW, leading to remarkable reductions in WVP. BW droplets well distributed within the starch matrix played a key role in enhancing the water barrier properties of films. CSC of starch/BW films offers a basis to design new hydrophobic formulations for applications that require biodegradable plastics with high moisture resistance.     

All starch nanocomposite coating for barrier material

Starch nanocrystals (SNC) are nanofillers of growing interest for barrier and mechanical improvement of bio‐based polymers. However, their potential use as fillers for organic coating material of industrial packaging has never been investigated. In this study, SNC processability in coating is assessed and the final properties of coated papers are measured. Coating colors composed of plasticized starch show higher Brookfield viscosity when filled with SNC even with the addition of water but rod‐coating is still possible. These diluted water‐based coatings induce paper wetting and surface crackling issues during drying as proved by drying process analysis. However no gelatinization of the SNC is observed whichever the type of drying. SNC compensate some of the water induced loss of mechanical properties of the base paper and decrease the water vapor permeability (WVP) up to 40% compared with the base paper. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39826.     

Graft polymerization of acrylonitrile onto starch‐coated polyethylene film surfaces

Starch‐coated polyethylene (PE) films were prepared by immersing PE in a hot, jet cooked solution of starch. They were allowed to react with acrylonitrile (AN) in the presence of ceric ammonium nitrate initiator, and the graft polymerization that occurred produced starch‐g‐polyacrylonitrile (PAN) coatings that contained about 25 wt % grafted PAN. The starch‐g‐PAN coatings tightly adhered to the PE film surfaces. When grafted starch coatings were wetted with water and the surfaces vigorously rubbed, less than 20% of the coating was removed. The fact that PAN‐grafted coatings were not removed with boiling water provided further evidence for their strong adherence. When starch was removed from the coating by acid hydrolysis, the residual grafted PAN still remained adsorbed on the PE surface. Because the grafted coating was completely removed by treatment with refluxing 0.7N sodium hydroxide, there is apparently no chemical bonding between starch‐g‐PAN and PE. The dimensional changes associated with the evaporation of water from these PAN‐grafted coatings caused the films to curl during drying. Because the final shape of these coated films depends upon the presence or absence of water in the surrounding environment, these films may be considered to be a type of stimulus‐responsive polymer. Attempts to graft polymerize methyl methacrylate and methyl acrylate onto starch‐coated PE surfaces, under conditions similar to those used with AN, were unsuccessful. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3323–3328, 2003     

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.     

Cellulose/acrylic acid copolymer blends for films and coating applications

Enzymatically treated cellulose was dissolved in a NaOH/ZnO solvent system and mixed together with poly(ethylene‐co‐acrylic acid) (PE‐co‐AA) or poly(acrylamide‐co‐acrylic acid) (PAA‐co‐AA) polymers, in order to improve the properties of dissolved cellulose and to prepare homogeneous cellulose‐based blends for films and coatings. The solution stage properties of the blends were evaluated by rheological methods and the precipitated dry blends were characterized by dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy. Paperboard coating tests done at laboratory scale showed dissolved cellulose/acrylic acid copolymer‐based blends function well as coating materials. All of the tested blends showed a good resistance against grease in the coating trials, having grease resistance from 60 to 69 days despite a very thin (～2 µm) coating layer. In addition, cellulose/PE‐co‐AA coating showed improved water vapor and oxygen barrier properties when compared with neat dissolved cellulose‐coated paperboard. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40286.     

Formation of hydrophilic starch coatings on polyethylene films

Thin starch coatings were deposited onto polyethylene (PE) film surfaces when PE films were immersed in 1% jet cooked starch solutions and the hot solutions were allowed to cool. Normal cornstarch, waxy cornstarch, high amylose cornstarch, and solvent‐extracted normal cornstarch (to remove native lipid) were used in these experiments. Amounts of adsorbed starch varied from about 0.03–0.05 mg per cm² of PE, and these starch coatings imparted hydrophilic properties to film surfaces, as evidenced by contact angle measurements. Although starch could be removed by gently rubbing water‐wet PE surfaces, air‐dried coatings were more firmly attached, and did not separate from the PE surface when films were bent or flexed. SEM images of starch‐coated film surfaces showed that starch was deposited as particles less than 1 μm in diameter, and also as aggregates of these submicron particles. Despite the fact that some starch samples contained only very small amounts of amylose and native lipid, surface‐deposited starch in all experiments contained 90–100% amylose; and exhibited the same V_h X‐ray diffraction pattern, indicative of helical inclusion complex formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1781–1788, 2002; DOI 10.1002/app.10589     

Hydrophobicity and Water Vapor Permeability of Ethylene-plasma-coated Whey,Chitosan and Starch Films

Abstract

Water vapor transmission rate was measured on uncoated and ethyfeae-plasma-coated whey (65-93.5% whey protein), on chitosan and starch films and on aluminum-coated chitosan. Surface hydrophobicity was assessed by contact angle measurements, and X-ray photoelectron spectroscopy was used to characterize the coatings. The water vapor transmission rate through the uncoated polymer films was highest for starch and lowest for chitosan. Whey showed intermediate water permeability, with the sample containing 65% whey-protein having the lowest water vapor transmission rate. An improvement in water vapor barrier properties was observed only for the aluminum-coated sample and not for any of the polyethylene-coated samples. It is observed that the penetrating water caused the substrate to swell and the polyethylene coating layer to crack. According to profilometry, the thickness of the polyethylene coating layer was 0.1-1 μm after 15 min exposure time. The coating was hydrophobic and contained almost exclusively carbons typical of linear or crosslinked hydrocarbons. It is suggested that the observed decrease in hydrophobicity with time during the contact angle measurements is due to the reorientation at the surface of carbonyls present in small amounts in the coating.     

Effect of unmodified and modified sago starch on properties of (sago starch)/silica/PVA plastic films

Sago starch was modified by crosslinking with sodium trimetaphosphate (STMP). Different formulations of films were prepared by a blending process and a casting method. A suitable plasticizer was added to the blend. Mechanical properties of plastic films with unmodified and modified sago starch were compared. From the results obtained, films with modified sago starch had better compatibility and interaction with polyvinyl alcohol than unmodified sago starch films. Thus, the tensile strength of modified films was higher, but lower in elongation at break than unmodified sago starch plastic films. Films with modified sago starch also showed lower water absorption, water vapor transmission, and degradation than unmodified sago starch plastic films. Chosen were 1 wt% and 2 wt% of silica as the optimum formulation that produced the best tensile properties for modified and unmodified sago starch plastic films. J. VINYL ADDIT. TECHNOL., 20:185–192, 2014. © 2014 Society of Plastics Engineers     

D‐isosorbide and 1,3‐propanediol as plasticizers for starch‐based films: Characterization and aging study

In the present work, D‐isosorbide and 1,3‐propanediol are proposed as alternative plasticizers obtained from renewable resources. Plasticized starch films were prepared by solvent casting method. The influence of using different “green” plasticizers in the final properties of starch‐based films was analyzed. Besides, the characterization of the films was also performed after storage time in order to evaluate the effect of the plasticizer on aging. UV‐spectrophotometry results showed better optical properties for both glycerol and D‐isosorbide films with higher transparency. The thermal and mechanical properties resulted influenced by the nature of the plasticizer. It was demonstrated that water vapor permeability was governed by the starch‐water interactions, whereas the oxygen permeability depended on the plasticizer's nature. The storage time affected the surface, mechanical, and thermal properties of the plasticized starch films. Atomic force microscopy results concluded that the topography of the films changed due to aging. The use of D‐isosorbide as plasticizer reduced the evolution of the mentioned properties and enhanced the reliability of the material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44793.     

Mechanical and barrier properties of edible starch–protein‐based films

The present investigation dealt with the mechanical properties, water‐vapor transmission behavior at different relative humidity conditions, and DSC thermograms of edible films formulated using various proteins (casein, gelatin, albumin) in combination with starch and nonthermal as well as intense thermal blending. Nonthermal blended film showed in the DSC thermogram a double T_g, indicating poor miscibility of the components and, hence, a poor film‐forming property. However, the DSC thermogram of all the films based on intense thermal blending showed a single T_g, indicating the complete molecular miscibility of the components. Casein‐based film showed a lower water‐vapor transmission rate, water gain at different relative humidity conditions, and higher tensile strength compared to its counterparts containing gelatin and albumin. Since the casein–starch blend gave better film properties, a blend of hydrophobic carnauba wax and casein was prepared to compare the properties of hydrophilic–hydrophilic and hydrophobic–hydrophilic blends. Both these blends compared well with respect to the water‐vapor transmission rate. Wax‐based film showed multiphased behavior in the DSC thermograms and the percent elongation was lower as compared to the casein–starch blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 64–71, 2003     

DRYING CHARACTERISTICS OF OSMOTICALLY DEHYDRATED FRUITS COATED WITH SEMIPERMEABLE EDIBLE FILMS

This paper deals with key issues of the coating technology applied to plant materials prior to osmotic dehydration and convective drying. Coatings created with solutions of starch products and pectin were examined. It was shown that coating of foods to be dehydrated influences mass transfer in a plant tissue during osmotic pre-treatment as well as during convective drying. Each coating should be individually examined. The properties of coatings depend on their composition and the method used for the fabrication of a coating. Coating of foods with an artificial barrier on the surface may efficiently hinder the penetration of solute inside the food, not affecting much the rate of water removal. The coated plant materials had a greater water loss/solids gain ratio then the uncoated ones. Osmotic dehydration seems to be one of possible pre-treatment methods before drying. The conditions of convective drying are changed upon osmotic dehydration of plant materials. It was shown that changes in drying rate depend on the kind of coating substance. Bigger differences were observed at higher water content and these differences narrowed as water content in dried material decreased. The positive effect of coatings on the physical properties of dried fruits was found.     

DRYING CHARACTERISTICS OF OSMOTICALLY DEHYDRATED FRUITS COATED WITH SEMIPERMEABLE EDIBLE FILMS

This paper deals with key issues of the coating technology applied to plant materials prior to osmotic dehydration and convective drying. Coatings created with solutions of starch products and pectin were examined. It was shown that coating of foods to be dehydrated influences mass transfer in a plant tissue during osmotic pre-treatment as well as during convective drying. Each coating should be individually examined. The properties of coatings depend on their composition and the method used for the fabrication of a coating. Coating of foods with an artificial barrier on the surface may efficiently hinder the penetration of solute inside the food, not affecting much the rate of water removal. The coated plant materials had a greater water loss/solids gain ratio then the uncoated ones. Osmotic dehydration seems to be one of possible pre-treatment methods before drying. The conditions of convective drying are changed upon osmotic dehydration of plant materials. It was shown that changes in drying rate depend on the kind of coating substance. Bigger differences were observed at higher water content and these differences narrowed as water content in dried material decreased. The positive effect of coatings on the physical properties of dried fruits was found.     

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.     

Influence of MA‐g‐HDPE compatibilizer content on quality and adhesion/bending strength of polyethylene/O‐MMT coating films

High density polyethylene/organo‐modified montmorillonite composites whit various concentrations of maleic anhydride grafted high density polyethylene (MA‐g‐HDPE) as compatibilizer (5–20 wt %) have been prepared by melt process. The extruded composite powders are applied on the treated steel surfaces using spray electrostatic powder technique, followed by oven curing at various temperatures (180°C–220°C) and times (15–45 min). The surface uniformity of produced coating films is studied by scanning electron microscopy. Comparison of micrographs of the coatings shows the composite coating films are measured using standard methods. The uniformity, adhesion, and bending strength of the coating films are compared to select high performance coatings. The results indicate that the presence of 15 wt % MA‐g‐HDPE in the coatings shows the highest properties (adhesion and bending strength) and more surface uniformity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40926.     

Inducing surface porosity in aqueous‐quenched,microporous Nylon 11 and Nylon 12 films

Nylon 11 and Nylon 12 have been studied for many years for the purpose of fabricating microporous films. Unfortunately, these polymers have somewhat unique properties that prevent the films from exhibiting porous surfaces when their solutions undergo thermally induced phase separation by quenching in water. Without surface pores, these films have limited utility as water purification membranes. In this work, application of high temperature diluent coatings to the surface prior to quenching is shown to enable the formation of surface porosity in Nylon 11 and Nylon 12 films. Furthermore, the pore sizes achieved are suitable for ultrafiltration applications. Following successful lab‐scale coating experiments, the effects of coating thickness, temperature, and solvent type on surface morphology are demonstrated over five film extrusion trials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44695.     

Effect of starch on thermal,mechanical, and barrier properties of low density polyethylene film

Low‐density polyethylene (LDPE) with different quantities of starch was compounded using a twin screw extruder and blown into films by a Konar K, blow‐film machine. Mechanical properties, namely percent elongation, tensile, bursting, and tear strength, as well as barrier properties, such as water vapor and oxygen transmission rate, of the filled LDPE film were studied. Thermal properties of the films were studied using DSC and DMA. Master curves at reference temperature of 30°C were obtained using software linked to DMA. Incorporation of 1% starch in LDPE has marginally affected the thermal, barrier, and mechanical properties; however, that of 5% starch filled LDPE has affected the properties to a great extent. The mechanical properties, such as percent elongation, tensile, tear, bursting, and seal strength, decreased by 19.2, 33.6, 3.60, 10.8, and 22.12%, respectively. Similarly, water vapor and oxygen transmission rate increased to 32.5 and 18.3%, respectively. Other physical properties, namely migration and thermal properties, were also affected in 5% starch filled LDPE; however, the film can still be used as packaging material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3355–3364, 2006     

Gas barrier and wetting properties of whey protein isolate‐based emulsion films

The aim of this research was to investigate the effect of rapeseed oil concentration (1–3% w/w) on the water vapor, oxygen and carbon dioxide permeability, water vapor sorption and surface properties of whey protein isolate emulsion‐based films. The water contact angle as affected by oil content, film side and time was analyzed. The effect of temperature (5 and 25°C) on the water vapor permeability (WVP), water vapor sorption kinetics and diffusion coefficient was also studied. The results showed that the incorporation of a lipid phase to whey protein film‐forming solutions was able to decrease the WVP, water hydrophilicity (increasing water contact angle) and water transfer of whey protein films. However, the films containing oil were more permeable to oxygen and carbon dioxide. Significantly higher values of WVP and diffusion coefficient were obtained at 5°C than at 25°C, indicating that storage temperature should be taken into account when designing the composition of edible films and coatings for food applications. POLYM. ENG. SCI., 59:E375–E383, 2019. © 2018 Society of Plastics Engineers     

Effect of dual chemical modification on the properties of biodegradable films from achira starch

The objective of this study was to evaluate the effect of a dual modification (acid hydrolysis and succination) on the structural, mechanical, thermomechanical, and permeability properties of films from achira starch. Micrographs of films revealed a smooth surface and some remnants of starch granules, indicating a partial gelatinization. Tensile strength and percentage of elongation increased in films from double modified starch (10.50 MPa and 42.83%, respectively). The OH groups formed in the amylose and amylopectin chains during the hydrolysis and the alkoxide groups (R O⁻) generated during the succination resulted in high values of water vapor permeability (3.215 × 10⁻¹⁰ g/s m Pa). The glass transition temperature (T_g) of films from hydrolyzed–succinated starch was decreased due to the reduction of the molecular weight of the polymeric chains and the presence of succinate groups that reduced the molecular interactions of the polymeric chains, increasing the mobility and therefore decreasing the softening temperature.     

Physicochemical properties of edible films from chitosan composites obtained by microwave heating

Summary  Chitosan films were prepared by casting, using microwave and dried by air convection. No scientific literature covers the use of microwave heating in the preparation of chitosan films by casting technique. Effects of heating time, molecular weight and plasticizer on structure, thermal behavior, surface, barrier properties and light transmission were investigated. Heating time showed that the microwave heating did not affect the structural composition and thermal decomposition of chitosan films. UV-vis light barrier properties, equilibrium moisture content and water vapor permeability varied significantly with the heating treatment. Surface film analysis revealed no captured differences between different heating treatments.     

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.