Physical and Mechanical Properties of Pea Starch Edible Films Containing Beeswax Emulsions

ABSTRACT:  Hydrophobic beeswax emulsions were incorporated into hydrophilic starch films to modify physical, mechanical, and thermal properties of the films. Beeswax was added in the film-forming solution of high-amylose pea starch (35% to 40% amylose w/w) at the level of 0%, 10%, 20%, 30%, and 40% w/w of starch with glycerol as a plasticizer (40/60 of glycerol/starch). Addition of beeswax affected mechanical properties, significantly reducing tensile strength and elongation and increasing elastic modulus. Beeswax addition decreased water vapor permeability and increased oxygen permeability. However, the addition of hydrophobic wax particles in starch films marginally affected these physical properties below 30% beeswax in the films. Beeswax addition at the 40% concentration formed amylose–lipid complex that caused the dramatic changes of physical and thermal properties of the films.     

Preparation and characterisation of films from xylose‐glycosylated peanut protein isolate powder

This work aimed at producing and characterising xylose‐glycosylated peanut protein isolate (PPI‐X) films by dissolving PPI‐X powder in water at ambient temperature and further plasticising with glycerol. The effect of powder dissolution temperature (20–100 °C) and glycerol concentration (15.0–45.0%, w/w) on mechanical properties and integrity of these films was quantified. The results showed that the powder dissolution temperature had no significant effect on the mechanical and water resistance properties of PPI‐X films within the temperature range tested. With increasing concentration of glycerol, the tensile strength and water resistance of PPI‐X films decreased and elongation increased. The films produced by dissolving the PPI‐X powder at 20 °C and plasticising with 25.0% glycerol had comparable mechanical properties and better water resistance compared to some other plant protein films plasticising with glycerol. The results suggested that PPI‐X films could potentially be used as biodegradable packaging materials.     

Physical and Swelling Properties of Spray‐Dried Powders made from Starch and Poly(vinyl alcohol)

The aim of this study was to investigate whether starch and poly(vinyl alcohol) could be compatible in a powder for coating. Free films of a mixture of the polymers were produced by casting and investigated with respect to their mechanical properties and moisture uptake. The moisture uptake was substantially higher when glycerol was added and the glycerol‐containing films had a lower failure stress under tension than the corresponding glycerol‐free films. At glycerol levels of 20 wt% or above, the glycerol content resulted in a high strain to failure. Dry powders with and without glycerol were made from the starch/poly(vinyl alcohol) solutions by spray drying. The powders were investigated by differential scanning calorimetry (DSC), to determine the degree of physical ageing or crystallinity. All powders showed a broad peak indicative of the melting of crystals at 100–150°C in the first scan, but this peak disappeared almost completely after rapid cooling. The glycerol‐free powder showed a small endothermic peak at about 45°C, indicating physical ageing of the powders during storage. Suspensions of the powders in a liquid plasticiser (glycerol or poly(ethylene glycol)) showed a sharp increase in storage modulus at a certain temperature, indicating the onset of swelling. The observed swelling meant that some of the powders are good candidates for plastisol coatings.     

How reactive extrusion with adipic acid improves the mechanical and barrier properties of starch/poly (butylene adipate‐co‐terephthalate) films

Blends of starch with polyesters have commonly been used in the production of biodegradable films. However, the components in the blend are not always miscible; therefore, the use of compatibilisers is recommended. The objective of the present work was to study the compatibilisation effect of adipic acid (0.5%; 1.0%; 1.5% (w/w)) on films consisting of starch/glycerol/poly (butylene adipate‐co‐terephthalate) (PBAT) produced by reactive extrusion. Films compatibilised with adipic acid exhibited statistically significant increase in tensile strength (from 7.28 to 8.45–9.13 MPa), elongation (in this case only with 0.5% of adipic acid) (516.51–679.10%), Young's modulus (21.72–28.75 MPa) and reduction in water vapour permeability (9.76–8.32 × 10^?11 g per s.m.Pa) compared with the control film, which lacked the compatibiliser. Films produced using the compatibiliser also presented a microstructure with fewer cracks. There were no differences in the thermal degradation and crystallinity profile of the films.     

Compatibilisation of starch/poly(butylene adipate co‐terephthalate) blends in blown films

Reactive extrusion was utilised for starch/poly(butylene adipate co‐terephthalate) (PBAT) blown film production, using maleic anhydride (MA) and citric acid (CA), alone or combined, as compatibilisers. These compounds (2% w/w) were added to the starch/PBAT (55:45) mixture after dispersion on glycerol. More rigid films, with greater tensile strength (9.82 ± 0.45 MPa), were produced when 2.0% CA was used. The opposite, little homogeneity and poor tensile strength (0.77 ± 0.12 MPa) and elongation (2.67 ± 0.67%) were found in films produced using 2.0% MA. Barrier properties to water vapour were improved by compatibilisers. FTIR analysis showed that CA and MA were able to promote esterification/transesterification reactions. Blends containing CA also showed better phase compatibilisation in the scanning electron microscopic images. It was found that in mixtures containing MA, the process and the concentration of this reagent need to be adapted to produce films with improved properties.     

Estimating the Specific Heat Capacity of Starch‐Water‐Glycerol Systems as a Function of Temperature and Compositions

Increasing interests in the use of starch as biodegradable plastic materials demand, amongst others, accurate information on thermal properties of starch systems particularly in the processing of thermoplastic starch (TPS), where plasticisers (water and glycerol) are added. The specific heat capacity of starch‐water‐glycerol mixtures was determined within a temperature range of 40‐120 °C. A modulated temperature differential scanning calorimeter (MTDSC) was employed and regression equations were obtained to predict the specific heat capacity as a function of temperature, water and glycerol content for four maize starches of differing amylose content (0—85%). Generally, temperature and water content are directly proportional to the specific heat capacity of the systems, but the influence of glycerol content on the thermal property varied according to the starch type.     

Rheological,mechanical and moisture sorption characteristics of cassava starch‐konjac glucomannan blend films

Cassava starch (ST)‐konjac glucomannan (KGM) blend films were prepared and their thermal, rheological, mechanical, moisture sorption properties and water vapour transmission rate were determined. Response surface methodology was employed for the preparation of films using different levels of ST, KGM and glycerol. All the filmogenic solutions exhibited shear thinning behaviour. Apparent viscosity and the dynamic rheological properties of filmogenic solutions varied considerably with KGM content. Rheological analysis revealed that the blend films are more appropriate than neat ST film for controlled drug release studies and for food coating. The melting temperature and enthalpy of fusion of the blend films were lower than that of neat ST film. When compared to neat starch film, the blend films showed broader peaks in DSC patterns, which suggests that incorporation of KGM decreased the crystallinity of ST. Mechanical properties, elongation at break and tensile strength of blend films were significantly higher (112.8% and 22.5 MPa, respectively) than those of neat ST film. Due to the more hydrophilic nature of KGM when compared to ST, the WVTR and moisture absorption of blend films were greater than that of neat ST film. Though KGM is more hydrophillic in nature, blend films with higher amount of KGM (0.643g) showed comparably lower values for both WVTR and moisture absorption than other blends. The solubility of the blend films was lower than that of neat starch film which also confirmed the strong intramolecular attraction between ST and KGM.     

Mechanical properties of pea starch films associated with xanthan gum and glycerol

The aim of this study was to evaluate the effect of the addition of xanthan gum and glycerol to the starch of green pea with high content of AM (cv. Utrillo) in the preparation of films and their physical characteristics. Filmogenic solution (FS) with different levels of pea starch (3, 4, and 5%), xanthan gum (0, 0.05, and 0.1%), and glycerol (glycerol–starch ratio of 1:5 w/w) were studied. The FS was obtained by boiling (5 min), followed by autoclaving for 1 h at 120°C. The films were prepared by casting. Films prepared only with pea starch were mechanically resistant when compared to other films, prepared with corn, cassava, rice, and even other pea cultivars (yellow, commercial). The tensile strength of these films is comparable to synthetic films prepared with high‐density polyethylene and linear low‐density polyethylene. However, they are films of low elasticity when compared to other films, such as rice starch films, and especially when compared to polyethylene films. The increased concentration of starch in the solution increased the puncture force. The increased concentration of glycerol slightly decreased the film crystallinity and interfered in the mechanical properties of the films, causing reduction of the maximum values of tensile strength, strain at break, and puncture force. The plasticizer also caused an increase of elongation at break. Xanthan gum was important to formation of films; however, it did not affect their mechanical properties.     

Effect of structural characteristics of modified waxy corn starches on rheological properties,film‐forming solutions,and on water vapor permeability,solubility, and opacity of films

Waxy corn starch (amylopectin) and three of its chemical derivatives: acetylated cross‐linked (ACLS), oxidized (OS), and octenyl‐succinylated (OSA), were used together with additives such as Tween 80, sorbitol, and beeswax suspension or safflower oil to test their effect on film‐forming solutions (FFS) and films. The objectives of this study were the starch structure characterization, and its correlation with rheological properties of FFS and solubility, opacity, and water vapor permeability (WVP) of the produced films. Analysis of starch structure, rheological characterization, and films micrographs revealed that the starches contained predominantly low MW amylopectin molecules and film properties depended on their ability to reorganize. Additionally, the interaction among groups introduced in modified starches or with additive molecules can hinder or promote starch reorganization, resulting in films with increased or reduced WVP, solubility and transparency properties. Films were obtained by casting and showed a thickness less than 41 µm. Films prepared with OS and beeswax exhibited the best reorganizing capacity of FFS, resulting in less soluble (30.0 ± 1.6%), highly transparent (23.2 ± 3.3 UA × nm) and less permeable films (0.485 ± 0.016 g · mm · m⁻² · h⁻¹ · kPa⁻¹). On the other hand, ACLS showed an opposite trend which was attributed to a more open film structure. These results contribute to understand the molecular interactions of waxy starch molecules in FFS which may be useful to design tailored coatings.     

Dynamic Rheology of Rice Starch‐Galactomannan Mixtures in the Aging Process

The effect of galactomananns (guar gum and locust bean gum) at different concentrations (0, 0.2, 0.4, 0.6 and 0.8%, w/w) on the dynamic rheological properties of aqueous rice starch dispersions (5%, w/w) was investigated by small‐deformation oscillatory measurements during aging. Magnitudes of storage (G′) and loss (G′′) moduli measured at 4°C before aging increased with the increase in gum concentration in the range of 0.2–0.8%. G′ and G′′ values of rice starch‐locust bean gum (LBG) mixtures, in general, were higher than those of rice starch‐guar gum mixtures. G′ values of rice starch‐guar gum mixtures as a function of aging time (10 h) at 4°C increased rapidly at initial stage and then reached a plateau region at long aging times. However, G′ values of rice starch‐LBG mixtures increased steadily without showing a plateau region. Increasing the guar gum concentration resulted in an increase in plateau values. The rate constant (K) for structure development during aging was described by first‐order kinetics. K values in rice starch‐guar gum mixtures increased with the increase in guar gum concentration. G′ values of rice starch‐galactomannan mixtures after aging were greater than those before aging.     

Properties of Cast Films Made of HCl‐Methanol Modified Corn Starch

The molecular and physicochemical properties of the studied starches modified with 0.36% HCl in methanol at 25 °C and 45 °C were related to the film properties of these starches. The weight‐averaged molecular weight (M_w) and the number of long‐chain branches (DP 13‐36) of HCl‐methanol modified starch decreased with increasing degree of acid modification, but the number of short‐chain branches (DP < 6) increased. HCl‐methanol modification significantly decreased the ghost formation in gelatinized starch dispersions and the viscosity of starch film‐forming dispersions. Thus, the homogeneity of the produced starch films was improved and their opacity reduced. Proper HCl‐methanol modification produced corn starch films with lower moisture absorption rate and maximum moisture content under high relative humidity (RH = 97%) condition.     

Original article: Effect of sucrose and glycerol mixtures in the osmotic solution on characteristics of osmotically dehydrated mandarin cv. (Sai‐Namphaung)

This study investigated the effects of a series of osmotic solutions consisting of sucrose and glycerol on the quality of osmotically dehydrated mandarin, namely mandarin cv. (Sai‐Namphaung). Mandarin samples were peeled and osmotically dehydrated at 55 °C with agitation at 3.5776 × 10^?1g in five osmotic solutions containing various mixtures of 60% sucrose and 60% glycerol (9:1, 8:2, 7:3, 6:4 and 5:5 w/w, respectively). The osmotically dehydrated mandarin was further dried using hot‐air drying at 70 °C for 360 min. Increasing the glycerol ratio in the mixtures significantly (P ≤ 0.05) increased water loss and solid gain during osmotic dehydration, and significantly (P ≤ 0.05) affected kinetic rate constants during drying. An increase in the glycerol ratio in the mixtures caused a significant decrease in the quality factors of hardness, moisture content, water activity and reducing sugar. However, the increase resulted in an increase in the darkness of the dried mandarin, compared with increasing the sucrose ratio in the mixtures (P ≤ 0.05). The increase had an insignificant (P > 0.05) effect on vitamin C content.     

Hydrothermal Modifications of Tropical Tuber Starches. 1. Effect of Heat‐Moisture Treatment on the Physicochemical,Rheological and Gelatinization Characteristics

Cassava, sweet potato and arrowroot starches have been subjected to heat‐moisture treatment (HMT) under different conditions using a response surface design of the variables. A comparative study was performed on the pasting properties, swelling behaviour and the gelatinization properties of the modified starches and also on the rheological and textural properties of their pastes. X‐ray diffraction studies have shown that cassava starch exhibited a slight decrease in crystallinity, whereas sweet potato and arrowroot starches showed an increase in crystallinity after HMT at 120ºC for 14 h with 20% moisture. The swelling volume was reduced and the solubility was enhanced for all three starches after HMT, but both effects were more pronounced in the case of arrowroot starch. The decrease in paste clarity of the starch after HMT was higher in the case of cassava and sweet potato starches. Viscosity studies showed that the peak viscosity of all three starches decreased after HMT, but the paste stability increased as seen from the reduced breakdown ratio and setback viscosity. Studies on rheological properties have shown that storage and loss moduli were higher for the starches heat‐moisture treated at higher moisture and lower temperature levels than the corresponding native starches. Storage of the gel at ‐20ºC resulted in a significant increase in storage modulus for all the three starches. All the textural parameters of the gels were altered after the treatment which depended on the nature of the starch and also the treatment condition.     

In situ kinetic study of solid‐state crosslinking of potato starch

This work studies the solid‐state modification of potato starch using sodium trimetaphosphate (STMP) at elevated temperature (120°C). Kinetics for the reaction was investigated using an in situ technique based on attenuated total reflectance infrared spectroscopy for monitoring the extent of crosslinking. For tested STMP concentrations between 1.6 and 20% (w/w, dry starch basis), the degree of substitution varied between 0.015 and 0.106 mol P/mol anhydroglucose unit, respectively, within a reaction time of less than 10 min. The reaction data was found to follow a first‐order rate dependency and by examination using a phase‐boundary kinetic model was considered to be exterior diffusion limited. The extent of conversion always converged to an asymptotic value less than 100%. The inclusion of 1–2% hydrocolloidal xanthan gum were found to have no effect on the crosslinking of starch whereas 10–30% glycerol significantly lowered the rate of reaction.     

Effect of Glycerol on Water Vapor Sorption and Mechanical Properties of Starch/Clay Composite Films

Plasticized starch/clay composite films were prepared by casting aqueous solutions containing oxidized corn starch, different concentrations of glycerol as a plasticizer and 5% clay (sodium montmorillonite, Na⁺‐MMT) on the basis of dry starch. The water‐binding properties of the composite films were evaluated by water vapor sorption isotherms at room temperature and various relative humidities (RHs). Mechanical properties and abrasion resistance were also analyzed for the films with varying glycerol contents at 68% RH and room temperature. Changes in water sorption isotherms suggested that glycerol interacted with both water and starch in a complicated way. A saturation phenomenon of glycerol, depending on RH, was observed based on the isotherms. Above this saturation content, phase separation of the system occurred with the appearance of free glycerol. According to mechanical performance and abrasion resistance, as well as water vapor sorption of the starch blend films, the three‐stage transition was presented to be related to the state of glycerol in the blend system, i.e. adsorption of glycerol onto H‐bonding sites of starch, supersaturation of glycerol as plasticizer and further supersaturation of glycerol. Only above the supersaturation content can glycerol play a plasticizer role in starch‐based composites.     

Effect of Plasticizers on Mechanical and Barrier Properties of Rice Starch Film

The effect of plasticizers, glycerol, sorbitol and poly(ethylene glycol) 400 (PEG 400), on mechanical and barrier properties of rice starch film has been investigated. Sorbitol‐ and glycerol‐plasticized starch films appeared homogeneous, clear, smooth, and contained less insoluble particles compared to unplasticized rice starch films. PEG 400 did not form plasticized films of suitable characteristics. The softness and stickiness of films improved with increasing concentrations of glycerol and sorbitol. In general, films plasticized with glycerol and sorbitol displayed a better solubility in water than unplasticized films, i.e. 35% (w/w) glycerol and 45% w/w (sorbitol) (optimum solubility). The tensile strength of films decreased especially in the high concentration regime of plasticizers, between 20–45% (w/w) of plasticizer/rice starch film. Through the entire concentration regime, the tensile strength of glycerol‐plasticized films was significantly lower than that of sorbitol‐plasticized films, but their elongation was larger. The water vapor transmission rate (WVTR) through plasticized films and the oxygen transmission rate (OTR) increased with glycerol and sorbitol concentrations, however, glycerol was revealed to be significantly more effective in reducing the tensile strength as well as increasing the WVTR and the OTR compared to sorbitol. With the higher tensile strength and the smaller OTR and WVTR, the 30% sorbitol‐plasticized film reveals an improved coating performance in terms of a reduction of coating failures.     

Physical properties of edible films made from mixtures of sodium caseinate and WPI

The physical properties of thin films (25–30 μm) made from mixtures of sodium caseinate (NaCas) and whey protein isolate (WPI) were investigated. Films were formed by mixing solutions of NaCas (2.5% w/w protein), plasticised with glycerol (NaCas–gly) at a glycerol:protein ratio of 0.32, with WPI solutions (2.3% w/w protein), plasticised (WPI-gly) at a glycerol:protein ratio 0.37. Tensile and water barrier properties of films formed from mixtures of NaCas–gly and WPI-gly were similar to films containing NaCas–gly only. Films containing only WPI-gly had higher maximum load and elastic modulus values than the mixed films. Increasing the NaCas–gly content of the films from 25 to 100% greatly increased solubility. This increased film solubility may increase the number of food applications for protein-based films.     

Response Surface Methodology for the Optimization and Characterization of Cassava Starch‐graft‐Poly(acrylamide)

Response surface methodology (RSM) was employed for the synthesis of cassava starch‐graft‐poly(acrylamide) using ceric ammonium nitrate as free radical initiator. Concentration of acrylamide, concentration of ceric ammonium nitrate, reaction temperature and duration of reaction were optimized using a 4‐factor 3‐level Box‐Behnken design. The dependent variables were percentage grafting (%G) and grafting efficiency (GE). Second order polynomial relationships were obtained for %G and GE, which explained the main, quadratic and interaction effects of factors. The highest%G and GE obtained were 174.8% and 90.7%, respectively. The optimum values of parameters predicted through RSM were 20 g acrylamide/10 g dry starch, 3.3 g/L ceric ammonium nitrate, 180 min reaction duration and 45ºC temperature with a %G of 190.0. For GE, the predicted levels of factors for the optimum value of 90.8% were 17.5 g acrylamide/10 g dry starch, 4.1 g/L ceric ammonium nitrate, 180 min reaction duration and 55ºC temperature. The graft reaction was confirmed by FTIR analysis, where the absorption bands corresponding to the C=O stretching and N‐H bending of the –CONH₂ group were observed. Scanning electron microscopic studies on grafted starches revealed that the granular structure of the starch was affected by the reaction. X‐ray diffraction analysis showed that the crystallinity of starch was decreased as a result of grafting and the reduction was higher for the grafted starches with higher percentage grafting.     

Gelatine–starch films: Physicochemical properties and their application in extending the post‐harvest shelf life of avocado (Persea americana)

BACKGROUND: Several storage techniques have been developed to extend the post‐harvest shelf life of horticultural products. One method involves the use of edible or biodegradable coatings. Such coatings are made of biological materials that are used to coat fresh products, providing a semi‐permeable barrier to water vapour and gases, e.g. O₂ and CO₂. The influence of starch concentration, glycerol content and pH on the carbon dioxide permeability (CO₂P) and mechanical properties of gelatine–starch edible films were evaluated. RESULTS: Results showed that increments in the starch concentration and pH resulted in higher CO₂P values. Film puncture strength increased when the starch concentration decreased and the maximum resistance value (32.6 N) was obtained at pH 6. Deformation was mainly affected by glycerol and starch content. Some films were chosen in order to evaluate their effect, as coatings, in the post‐harvest shelf life of avocados (Persea americana Mill c.v. Hass). Fruits were immersed in the coating solutions, air dried and stored at two temperatures. Changes in colour, weight loss and pulp firmness were determined in fruits stored at 6 °C. In addition, respiration rate was measured in avocados kept at 20 °C. CONCLUSION: The application of gelatine–starch coatings delayed the ripening process of avocados, as indicated by a better pulp firmness and retention of skin colour, and lower weight loss of coated fruits in comparison with control avocados. The coatings also resulted in a delayed respiratory climacteric pattern, by 3 days, for coated fruits. Copyright © 2007 Society of Chemical Industry     

Macromolecular Changes in Extruded Starch‐Films Plasticized with Glycerol,Water and Stearic Acid

Native corn starch, plasticized with water, glycerol and stearic acid, was extruded in a conical twin‐screw extruder and sheeted into 0.4–0.6 mm thick films. The effects of extrusion and plasticizers on gelatinization, as well as the molecular and structural changes, in thermoplastic starch were analyzed. The onset and peak gelatinization temperatures of extruded starch varied from 42–46°C and 52.9–56.9°C, respectively, depending on the glycerol content. The enthalpy of gelatinization of extruded thermoplastic starch in excess water varied from 3.6–7.6 J/g, which also increased with plasticizer content. Amylose‐lipid complexes were formed during extrusion, and their enthalpies depended on the initial stearic acid and moisture contents. High‐performance size‐exclusion chromatography (HPSEC) data revealed that the starch underwent fragmentation during extrusion even under highly plasticized conditions, but the degradation was not severe as compared to previous findings. The relative percentages of amylopectin and amylose in native starch were 76.9 and 23.1%, respectively, which were changed to 71.3–76.6% and 23.4–28.7% in the extrudates. The average molecular weights of amylopectin and amylose in the extrudates ranged from 1.55×10⁷–2.07×10⁷ and 4.35×10⁵–7.39×10⁵, respectively. On the other hand, the molecular weights of amylopectin and amylose in native corn starch were observed as 2.27×10⁷ and 4.68×10⁵, respectively. Cross‐polarization magical angle spinning (CP/MAS) and high‐power decoupling (HP‐DEC) nuclear magnetic resonance (NMR) spectra of thermoplastic starch revealed the characteristics of amylomaize starch, confirming HPSEC results that the amylopectin macromolecules underwent fragmentation into amylose‐like fractions. In the extrudates, glycerol was found to be less mobile and entrained within the starch network.