Transport and tensile properties of compression-molded wheat gluten films

Mechanical and transport properties were assessed on wheat gluten films with a glycerol content of 25-40%, prepared by compression molding for 5-15 min at temperatures between 90 and 130 degrees C. Effects of storing the films up to 24 days, in 0 and 50% relative humidity (RH), were assessed by tensile measurements. The films were analyzed with respect to methanol zero-concentration diffusivity, oxygen permeability (OP), water vapor permeability (WVP), Cobb60 and sodium dodecyl sulfate (SDS) solubility coupled with sonication. The SDS solubility and methanol diffusivity were lower at the higher molding temperature. Higher glycerol content resulted in higher OP (90-95% RH), WVP, and Cobb60 values, due to the plasticizing and hygroscopic effects. Higher glycerol contents gave a lower fracture stress, lower Young's modulus, lower fracture strain, and less strain hardening. The mold time had less effect on the mechanical properties than mold temperature and glycerol content. The fracture stress and Young's modulus increased and the fracture strain decreased with decreasing moisture content.     

Influence of thickness on the mechanical properties for starch films

The aim of the present study was to investigate some mechanical properties of starch films. Starch is a natural common polymer in nature and the use of natural materials is increasing in the industries. In this study, the mechanical properties of starch plasticized with 30 parts by weight, of glycerol, are investigated. For the mechanical testing films of different thickness were used, the thickness varied between 0.5 and 2.5 mm. T_g was measured with a differential scanning calorimeter and with a dynamical mechanical analysis. The starch films were tested in tension and characterised in terms of stiffness, strength and failure strain. Fracture toughness was measured by single edge notch tests. Both stiffness and strength showed a strong dependence on film thickness, stronger then expected from linear fracture mechanics. This can be due to the different molecule orientation in the films, and due to the crystallinity of the films.     

Extrusion of pectin/starch blends plasticized with glycerol

The microstructural and thermal dynamic mechanical properties of extruded pectin/starch/glycerol (PSG) edible and biodegradable films were measured by scanning electron microscopy (SEM) and thermal dynamic mechanical analysis (TDMA). SEM revealed that the temperature profile (TP) in the extruder and the amount of water present during extrusion could be used to control the degree to which the starch was gelatinized. TDMA revealed that moisture and TP during extrusion and by inference the amount of starch gelatinization had little effect on the mechanical properties of PSG films. Furthermore, TDMA revealed that PSG films underwent a glass transition commencing at about −50°C and two other thermal transitions above room temperature. Finally, it was concluded that the properties of extruded PSG films were comparable to those cast from solution.     

Aging properties of films of plasticized vital wheat gluten cast from acidic and basic solutions

In order to understand the mechanisms behind the undesired aging of films based on vital wheat gluten plasticized with glycerol, films cast from water/ethanol solutions were investigated. The effect of pH was studied by casting from solutions at pH 4 and pH 11. The films were aged for 120 days at 50% relative humidity and 23 degrees C, and the tensile properties and oxygen and water vapor permeabilities were measured as a function of aging time. The changes in the protein structure were determined by infrared spectroscopy and size-exclusion and reverse-phase high-performance liquid chromatography, and the film structure was revealed by optical and scanning electron microscopy. The pH 11 film was mechanically more stable with time than the pH 4 film, the latter being initially very ductile but turning brittle toward the end of the aging period. The protein solubility and infrared spectroscopy measurements indicated that the protein structure of the pH 4 film was initially significantly less polymerized/aggregated than that of the pH 11 film. The polymerization of the pH 4 film increased during storage but it did not reach the degree of aggregation of the pH 11 film. Reverse-phase chromatography indicated that the pH 11 films were to some extent deamidated and that this increased with aging. At the same time a large fraction of the aged pH 11 film was unaffected by reducing agents, suggesting that a time-induced isopeptide cross-linking had occurred. This isopeptide formation did not, however, change the overall degree of aggregation and consequently the mechanical properties of the film. During aging, the pH 4 films lost more mass than the pH 11 films mainly due to migration of glycerol but also due to some loss of volatile mass. Scanning electron and optical microscopy showed that the pH 11 film was more uniform in thickness and that the film structure was more homogeneous than that of the pH 4 film. The oxygen permeability was also lower for the pH 11 film. The fact that the pH 4 film experienced a larger and more rapid change in its mechanical properties with time than the pH 11 film, as a consequence of a greater loss of plasticizer, was presumably due to its initial lower degree of protein aggregation/polymerization. Consequently, the cross-link density achieved at pH 4 was too low to effectively retain volatiles and glycerol within the matrix.     

Formaldehyde cross-linking of gliadin films: effects on mechanical and water barrier properties

In this study, pioneering results on specific chemical modifications of wheat gluten gliadins and the corresponding impact on mechanical and water barrier properties of derived films are presented. Films were prepared from gliadins chemically treated with formaldehyde and subsequently mixed with different concentrations of glycerol as a plasticizing agent. Water vapor barrier and mechanical properties of the films were evaluated as a function of relative humidity and glycerol concentration. Formaldehyde treatment led to enhanced mechanical properties and, to a lesser extent, improved water barrier of the films, effects which point to the formation of new intermolecular bonds between monomeric gliadins. The occurrence of cross-linking was supported by SDS-PAGE analysis. Cross-linked films maintained their integrity after immersion in water and had similar optical properties to control films. The effect of glycerol and humidity on water vapor permeability and the mechanical properties of films was less acute when proteins were treated with formaldehyde. Thus, chemical treatment of proteins is shown to be a very effective route for optimizing the use of these films in packaging applications.     

Effect of glycerol on behaviour of amylose and amylopectin films

The effect of water and glycerol on sorption and calorimetric T_gs of amylose and amylopectin films were examined. The mechanical properties of the films were also analysed under varying glycerol content at constant RH and temperature. Based on changes observed in sorption and tensile failure behaviour glycerol was strongly interacted with both starch polymers. Even though water was observed to be more efficient plasticiser than glycerol, glycerol also affected the T_g. But in spite of the observed decrease in T_g under low glycerol contents brittleness of the films increased based on changes in elongation. The increase in brittleness of both polymers was also in agreement with their actual behaviour. At around 20% glycerol great change in the rheological properties occurred. Above 20% glycerol amylose film showed much larger elongation than the low glycerol content films and was still strong but the amylopectin produced a very week and non-flexible film.     

Stress relaxation in fine fibrin films: Comparison of films prepared with thrombin and ancrod

Measurements of stress relaxation in uniaxial extension have been made on fibrin film prepared from fine bovine fibrin clots (i.e., clots in which there is minimal lateral aggregation of protofibrils), both ligated and unligated, and polymerized with both thrombin and ancrod, plasticized with either aqueous buffer or glycerol. The stress 100 s after imposition of strain was approximately proportional to In λ, where λ is the stretch ratio. Ligated thrombin films showed comparatively little relaxation over a period of one day and almost complete recovery after release of stress. In unligated thrombin films, there was substantial relaxation in two stages, as previously observed for coarse films, and substantial irrecoverable deformation. The extent of relaxation and the proportion of strain that was irrecoverable increased with the magnitude of the strain. In ancrod films (unligated), there was much more relaxation (stress decaying by as much as a factor of 10) and much more irrecoverable deformation (about 70% of the initial deformation); these results did not depend on the magnitude of the strain. When an ancrod film was released after relaxation and submitted to a second stretch, the extent of the second relaxation was much less. These observations are discussed in relation to the structure of fine films and possible mechanisms for relaxation and irrecoverable deformation.     

Gliadins polymerized with cysteine: effects on the physical and water barrier properties of derived films

To study the effects of disulfide bonds on certain functional properties of films made from the wheat gluten proteins gliadin and glutenin, cysteine was used to promote the formation of interchain disulfide bridges between gliadins in 70% ethanolic solution. Disulfide-mediated polymerization of gliadins was confirmed by means of SDS-PAGE analysis. After chemical treatment of gliadins, films were solution cast and the effects of both glycerol (used as a plasticizer) and relative humidity were studied on water vapor permeability, moisture sorption isotherms at 23 degrees C, and the optical properties of the films. The results were compared with those obtained from analogous films made from untreated glutenin macromolecules. Cysteine-mediated polymerization of gliadins improved the water vapor resistance of films achieving values close to those obtained for glutenin films. Development of intra- and interchain disulfide bonds did not change the moisture sorption capacity of the films but transparency was slightly diminished.     

Material properties of plasticized hardwood xylans for potential application as oxygen barrier films

Free films based on glucuronoxylan isolated from aspen wood were prepared by casting from aqueous solutions and drying in a controlled environment. Addition of xylitol or sorbitol facilitated film formation and thus examination of the material properties of these films. The mechanical properties of the films were evaluated using tensile testing and dynamic mechanical analysis in a controlled ambient relative humidity. The strain at break increased, and the stress at break and Young's modulus of the films decreased with increasing amounts of xylitol and sorbitol due to plasticization. At high amount of plasticizer, it was found that films with xylitol gave lower extensibility. Wide-angle X-ray scattering analysis showed that xylitol crystallized in a distinct phase, which we believe contributes to the more brittle behavior of these films. The effect of the plasticizers on the glass transition temperature was determined using dynamic mechanical analysis and differential scanning calorimetry. An increased amount of plasticizer shifted the glass transition to lower temperatures. The effect of moisture on the properties of plasticized films was investigated using water vapor sorption isotherms and by humidity scans in dynamic mechanical analysis. Sorption isotherms showed a transition from type II to type III when adding plasticizer. The films showed low oxygen permeability and thus have a potential application in food packaging.     

Permeation of volatile compounds through starch films

The aim of this study was to gain insight into the factors that affect the permeation of volatiles through starch films. These films were obtained by casting gelatinized starch/water/glycerol mixtures. The films were dried and conditioned under different conditions (temperature and relative humidity) resulting in films that vary in the degree of starch crystallinity and glycerol and water content. The permeation of two model volatiles (carvone and diacetyl) at 20 degrees C and at 30, 60, or 90% relative humidity (RH) was analyzed gravimetrically. Further, the solubility of the two model compounds (under conditions where the permeation experiments were carried out) was determined. From the obtained permeation and solubility data, the diffusion coefficients of these compounds in the different starch films were calculated. The crystallinity in the starch films increased with increasing water content of the films during preparation. The water content of the resulting films in turn increased with increasing glycerol and when the films were exposed to a higher RH during drying or conditioning. For films with the same composition, the flux for diacetyl was greater than for carvone. The solubilities of diacetyl and carvone were slightly dependent on the properties of the films. It was found that with increasing starch crystallinity the diffusion coefficient for both compounds decreases, which is probably due to the impermeability of starch crystallites. Interestingly, in films with about the same extent of crystallinity, the diffusion can be described with the free volume model, with water and glycerol determining the amount of free volume.     

Preparation and characteristics of oxidized potato starch films

Starch films were developed from oxidized potato starch (OPS) with glycerol as a plasticizer at different contents. The OPS films were transparent and flexible. The mechanical properties of these films were measured, and the results indicated that the film with 19.4% glycerol exhibited the desirable mechanical properties. X-ray diffraction study showed that the increase of glycerol content led to a decrease in the crystallinity for OPS films, and storage conditions such as storage time, storage temperature and relative humidity also had certain effects on the retrogradation of starch owing to re-crystallization. Anti-leakage, anti-crosslinking, and stability in acid or alkali solutions of the OPS films were also studied, and the results indicated that the OPS films had excellent anti-leakage ability for vegetable oil, good anti-crosslinking ability in saturated formaldehyde vapor, and good stability in acid aqueous medium, but poor stability in alkali aqueous medium.     

Some effects of processing on the molecular structure and morphology of thermoplastic starch

Hydroxypropylated and oxidised potato starch (HONPS) was used together with glycerol and water to produce thermoplastic starch. The amount of glycerol was kept constant at 22 parts by weight per 100 parts of dry starch. The thermoplastic starch was converted into films/sheets using three different processing techniques; casting, compression moulding and film blowing. The last two methods represent typical thermoplastic conversion techniques requiring elevated processing temperatures. By means of size-exclusion chromatography, it was found that compression moulding and film blowing led to some degradation of high-molecular weight amylopectin as well as of high-molecular weight amylose-like molecules. The degradation was significantly less pronounced for the cast films. The morphology of the specimens was quite complex and phase separations on different levels were identified. In the cast films and, to a lesser extent, in the compression-moulded specimens, a fine network structure could be distinguished. Such a structure could however not be ascertained in the film-blown material and this is discussed in terms of the thermo-mechanical treatment of the starch materials.     

Structure–properties relationship in cross-linked high amylose starch cast films

Cross-linked high amylose starch cast films were prepared to study the effect of cross-linking degree on various properties in normal environmental conditions. Mechanical tensile properties (Young's modulus, elongation at break, tensile strength), water vapour transmission rate (WVTR) and oxygen permeability coefficients of cast films were determined as a function of cross-linking degree and percentage of free humidity. Cross-linking degree and degree of crystallinity are closely related and seem to have non-negligible opposite effect on the properties of interest. By using increased amounts of cross-linking agents, the effect of cross-linking degree tends to reduce the degree of crystallinity modulating thus mechanical properties, water vapour permeability and oxygen permeability coefficients. Yield strength, tensile strength at break, WVTR versus cross-linking degree showed a non-monotonous behaviour. Maximal values for these properties were reached for moderate cross-linking degree. Optimal crystalline/amorphous ratio in the films may induce interactions and balanced effects, which would be responsible for the non-linear behaviour of some of the investigated properties. By cross-linking with epichlorohydrin in the range 1–10 g crosslinker/100 g polymer, the mechanical properties of films are still related to water content and water vapour permeability remains high compared to some synthetic polymeric materials.     

Mechanical and Barrier Properties of Films from Millet Protein Pennisetin

Plastics are one of the most commonly used materials today in an immense range of applications. Since plastics originate from petroleum, which is not a renewable resource, we need to find alternatives to achieve environmentally sustainable goals. One of our most abundant renewable resources is cereals; wheat gluten is recognized as a replacement for synthetic plastics. Another cereal protein is pennisetin from pearl millet, which can grow in more arid areas and is therefore an important crop in times of climate change. In contrast to gluten, the material properties of pennisetin have as yet been relatively unexplored. This work evaluated the mechanical and barrier properties of pennisetin films, including three different plasticizers (glycerol only, glycerol/citric acid mixture, and glycerol/lactic acid/polyethylene glycol mixture). The films were cast from ethanol solutions. It was found that all of the three plasticizers resulted in approximately equal thermomechanical properties in the pennisetin films. However, the glycerol/citric acid mixture seemed to give more beneficial tensile and barrier properties. The advantage of this plasticizer mixture was believed to be due to the altered microstructure of the films. The material properties of pennisetin were found to be fully comparable to those of other cereal protein materials.     

Physical properties of emulsion-based hydroxypropyl methylcellulose films: Effect of their microstructure

The initial characteristics of emulsions and the rearrangement of the oil droplets in the film matrix during film drying, which defines its microstructure, has an important role in the physical properties of the emulsion-based films. The objective of this work was to study the effect of the microstructure (two droplet size distributions) and stability (with or without surfactant) of HPMC oil-in-water emulsions over physical properties of HPMC emulsion-based edible films. HPMC was used to prepare sunflower oil-in-water emulsions containing 0.3 or 1.0% (w/w) of oil with or without SDS, as surfactant, using an ultrasonic homogenizer. Microstructure, rheological properties and stability of emulsions (creaming) were measured. In addition, microstructure, coalescence of oil droplets, surface free energy, optical and mechanical properties and water vapor transfer of HPMC films were evaluated. Image analysis did not show differences among droplet size distributions of emulsions prepared at different oil contents; however, by using SDS the droplet size distributions were shifted to lower values. Volume mean diameters were 3.79 and 3.77μm for emulsions containing 0.3 and 1.0% without surfactant, respectively, and 2.72 and 2.71μm for emulsions with SDS. Emulsions formulated with 1.0% of oil presented higher stability, with almost no change during 5 and 3 days of storage, for emulsions with and without SDS, respectively. Internal and surface microstructure of emulsion-based films was influenced by the degree of coalescence and creaming of the oil droplets. No effect of microstructure over the surface free energy of films was found. The incorporation of oil impaired the optical properties of films due to light scattering of light. Addition of oil and SDS decreased the stress at break of the emulsion-based films. The replace of HPMC by oil and SDS produce a lower "amount" of network structure in the films, leading to a weakening of their structure. The oil content and SDS addition had an effect over the microstructure and physical properties of HPMC-based emulsions which lead to different microstructures during film formation. The way that oil droplets were structured into the film had an enormous influence over the physical properties of HPMC films.     

Compression molding and tensile properties of thermoplastic potato starch materials

The mechanical and melt flow properties of two thermoplastic potato starch materials with different amylose contents were evaluated. The materials were prepared by mixing starch, glycerol, and water, mainly in the weight proportions of 10:3:4.5. Compression molding was used to produce sheets/films with a thickness in the range of 0.3-1 mm. After conditioning at 53% relative humidity (RH) and 23 C, the glycerol-plasticized sheets with a higher amylose content (HAP) were stronger and stiffer than the normal thermoplastic starch (NPS) with an amylose content typical for common potato starch. The tensile modulus at 53% RH was about 160 MPa for the high-amylose material and about 120 MPa for the plasticized NPS. The strain at break was about 50% for both materials. The stress at break was substantially higher for the HAP materials than for the NPS materials, 9.8 and 4.7 MPa, respectively. Capillary viscometry at 140 C showed that the high-amylose material had a higher melt viscosity and was more shear-thinning than the NPS. Dynamic mechanical measurements indicated a broad transition temperature range for both types of starch material. The main transition peaks for glycerol-plasticized starch were located at about room temperature with the transition for the HAP material being at a somewhat higher temperature than that of the NPS material with a lower amylose content. It was also noted that the processing conditions used during the compression molding markedly affected the mechanical properties of the starch material.     

Modified natural halloysite/potato starch composite films

Halloysite/potato starch composites were prepared by adding modified natural halloysite nanotubes into potato starch matrices to reenforce the mechanical properties of potato starch films. The halloysite/potato starch films were characterized by X-ray diffraction, scanning electron microscope and infrared spectrometry. Meanwhile, the mechanical properties and transparency of the films were studied. The results show that the modified halloysite nanotubes can be well distributed in the starch matrix and thus the tensile strength of the films was clearly enhanced. The flexibility of the films could be improved through adding glycerol although at the cost of reducing tensile strength. But incorporation of PVA could further improve the tensile strength of the halloysite/potato starch films.     

Effects of extrusion and glycerol content on properties of oxidized and acetylated corn starch-based films

Oxidized and acetylated corn starch-based films were prepared by casting with glycerol as a plasticizer. The present study investigated the effects of extrusion prior to film-making and glycerol content on the properties of starch films. The films with extrusion exhibited lower tensile strength, higher elongation at break, higher water vapor permeability and higher oil permeability than those without extrusion. Extrusion reduced heat sealability of the films. With the increase of glycerol content, the films became more flexible with higher elongation at break and lower tensile strength. Water vapor permeability, oil permeability and the range between the onset temperature and the melt peak temperature rose as glycerol content increased. The thermograms indicated that plasticizers and biopolymers were compatible. These results suggested that extrusion did no good to starch films while glycerol content had apparent effect on the mechanical and barrier properties of the films.     

Glycerol-plasticized films prepared from starch—poly(vinyl alcohol) mixtures: effect of poly(ethylene-co-acrylic acid)

Equations were obtained from response surface models to show how the ultimate tensile strength (UTS) and percent elongation at break (%E) of solution-cast films vary with relative amounts of starch, poly(vinyl alcohol) (PVA), poly(ethylene-co-acrylic acid) (EAA) and glycerol in the formulation. Equations found from the response surface methodology were used to optimize the relative amounts of the four components with respect to the physical properties of cast films. The model showed that only glycerol content was important to predict the UTS of the films. The model for %E was more complicated, since there was a three-way interaction between EAA, PVA and glycerol. This model also contained two other terms: a two-way interaction evolving glycerol and EAA. and a (PVA)³ term. In general, %E increased as EAA, PVA and glycerol were increased together. However, increased amounts of EAA could decrease %E if EAA was the only component increased. It is believed that EAA forms complexes with both starch and PVA, thereby increasing compatibility of the two polyhydroxy polymers. As %E increases, UTS of the films decreases. All the films produced in this paper were made with starch contents above 50% to insure an optimum film formulation with at least 50% starch. A mixture of 55·6% starch, 2·8% EAA, 28·3% PVA and 13·3% glycerol is believed to be close to the optimum formulation to obtain films having at least 100%E and UTS of 25 MPA, while still maintaining starch concentrations above 50%.     

Enhanced film forming and film properties of amylopectin using micro-fibrillated cellulose

This work describes a novel approach to produce amylopectin films with enhanced properties by the addition of microfibrillated cellulose (MFC). Aqueous dispersions of gelatinized amylopectin, glycerol (0–38 wt%) and MFC (0–10 wt%) were cast at ambient temperature and 50% relative humidity and, after 10 days of storage, the tensile properties were investigated. The structure of the composite films was revealed by optical, atomic force and transmission electron microscopy. The moisture content was determined by thermogravimetry and the temperature-dependent film rigidity was measured by thermal mechanical analysis. Synchrotron simultaneous small- and wide-angle X-ray measurements revealed that the solutions had to be heated to above 85 °C in order to achieve complete gelatinization. Optical microscopy and atomic force microscopy revealed uniformly distributed MFC aggregates in the films, with a length of 10–90 μm and a width spanning from a few hundred nanometers to several microns. Transmission electron microscopy showed that, in addition to aggregates, single MFC microfibrils were also embedded in the amylopectin matrix. It was impossible to cast amylopectin films of sufficient quality with less than 38 wt% glycerol. However, when MFC was added it was possible to produce high quality films even without glycerol. The film without glycerol was stiff and strong but not brittle. It was suggested that this remarkable effect was due to its comparatively high moisture content. Consequently MFC acted both as a “conventional” reinforcement because of its fibrous structure and also indirectly as a plasticiser because its presence led to an increase in film moisture content.