Effects of plasticizers on the properties of oat starch films

Oat starch films were prepared by casting using glycerol, sorbitol, glycerol–sorbitol mixture, urea and sucrose as plasticizers. The effects of these plasticizers on the microstructure, moisture sorption, water vapor permeability (WVP) and mechanical properties were investigated using films stored under a range of relative humidities. The plasticizer type did not affect significantly (p ≤ 0.05) the equilibrium moisture content of films, except at 90% relative humidity (RH). Films without plasticizer adsorbed less water and showed higher WVP than plasticized ones, indicating the antiplasticizing effect observed in this work. In general, a decrease in stress at break and Young's modulus and an increase in strain at break were observed when RH increased in all film formulations. Films without plasticizer showed higher stress at break values than the plasticized ones and presented stable strain at break under a range of RH. Sucrose films were the most fragile at low RH while glycerol films were the most hygroscopic.     

Effects of glycerol and sorbitol on optical,mechanical, and gas barrier properties of potato peel‐based films

Potato peel is a by‐product of potato‐based food production and seen as a zero‐ or negative‐value waste of which millions of tons are produced every year. Previous studies showed that potato peel is a potential material for film development when plasticized with 10% to 50% glycerol (w/w potato peel). To further investigate potato peel as a film‐forming material, potato peel‐based films containing the plasticizer sorbitol were prepared and investigated on their physicochemical properties in addition to films containing glycerol. Due to sufficient producibility and handling of casted films in preliminary trials, potato peel‐based films containing 50%, 60%, or 70% glycerol (w/w potato peel) and films containing 90%, 100%, or 110% sorbitol (w/w potato peel) were prepared in this study. Generally, with increasing plasticizer concentration, water vapor and oxygen permeability of the films increased. Films containing glycerol showed higher water vapor and oxygen permeabilities than films containing sorbitol. Young's modulus, tensile strength, and elongation at break decreased with increasing sorbitol concentration, whereas no significant effect of plasticizer content on elongation at break was shown in films containing glycerol. Due to crystallization of films containing sorbitol as a plasticizer, potato peel‐based films containing 50% glycerol (w/w) were identified as the most promising films, characterized by a water vapor transmission rate of 268 g 100 μm m^?2 d^?1 and an oxygen permeability of 4 cm³ 100 μm m^?2 d^?1 bar^?1. Therefore, potato peel‐based cast films in this study showed comparable tensile properties with those of potato starch‐based films, comparable water vapor barrier with those of whey protein‐based films, and comparable oxygen barrier with those of polyamide films.     

增塑剂对马铃薯淀粉基复合膜物理机械性能的影响

以马铃薯淀粉、普鲁兰多糖、明胶为成膜物质,氯化钙为交联剂,甘油、山梨醇、聚乙二醇为增塑剂,采用流延法制备了马铃薯淀粉基复合膜,研究了3种增塑剂对复合膜物理机械性能的影响。结果表明:复合膜的抗拉强度和弹性模量均随增塑剂含量的增加而显著减小,断裂伸长率随甘油和山梨醇含量的增加而显著增加,聚乙二醇对其影响不显著;复合膜的水蒸气透过率和水溶性均随增塑剂含量的增加而增加;聚乙二醇能够显著降低复合膜的透光率。     

Effects of production process and plasticizers on stability of films and sheets of oat starch

The main disadvantage of biodegradable starch-based films is their hydrophilic character, which leads to low stability when these materials are submitted to different environmental conditions. The higher lipid content (1.36%) of oat starch compared to other traditional starches could impart more hydrophobic characteristics to its films, thereby increasing stability. The objective of this work was to investigate the behavior of oat starch films (produced by casting) and sheets (produced by extrusion), plasticized with urea, glycerol or sorbitol, and conditioned at 11, 57, 76 and 90% relative humidity (RH). In general, the increase of RH results in a decrease of stress and an increase of strain at break, independent of the type of plasticizer. The Tg of materials plasticized with polyols was similar. The extruded sheets were more permeable to water vapor than the casted films. Films containing urea presented a relative crystallinity (5.14%) four times lower when compared with the other films, but the same behavior was not observed for sheets. The lipid content of oat starch was not high enough to avoid altering of mechanical properties as a function of RH. When the two processes (casting and extrusion) applied for materials production were compared, similar trends were observed on the final effects.     

四种多元醇增塑剂对淀粉-壳聚糖复合膜的性能研究

目的探究多元醇作为增速剂对淀粉-壳聚糖薄膜材料性能的影响,评估4种多元醇的增塑效果,并选出最优。方法将4种不同的多元醇作为增塑剂,通过流延法制备壳聚糖-淀粉薄膜,分析增塑剂含量对材料力学性能的影响,并通过扫描电镜、傅里叶红外、X-射线衍射、静态接触角对复合膜的结构和性能进行表征。结果将单一多元醇作为增塑剂加入淀粉-壳聚糖溶液,当添加质量分数为15%的甘露醇时,拉伸强度为最大值,为53.39 MPa;当添加质量分数为60%的甘油时,断裂伸长率最大,为45.11%。当甘油质量分数为50%时,综合效果较好,拉伸强度为21.36 MPa,断裂伸长率为35.33%。结论复合膜中淀粉与壳聚糖具有良好的相容性,添加增塑剂有利于改善复合膜的力学性能。多元醇增塑剂处于低浓度或中等浓度范围时,不具有有效的增塑作用。在4种多元醇增塑剂中,甘油的综合效果最好,所制备的膜具有较优的综合性能。     

Combined Effects of Heat Treatment and Plasticizers on Polyvinyl Alcohol Films

The effects of heat treatment on PVA films containing water soluble plasticizers were investigated. Propylene glycol, glycerol and polyethylene glycol were used as plasticizers. There was synergism between heat treatment and the presence of plasticizers in enhancing the water resistance of PVA films. In the absence of heat treatment, however, the plasticizers increased the aqueous solubility of PVA films. The plasticized films further showed a lower permeability to propranolol HC1 compared to the unplasticized films following heat treatment.     

Properties of polysaccharide‐coated polypropylene films as affected by biopolymer and plasticizer types

Plasticized polysaccharide coatings on polypropylene (PP) film were prepared to evaluate the optical and tensile properties of the resulting coated films, as affected by biopolymer and plasticizer types, in order to develop a novel film structure of biopolymer coatings on common plastics intended for food packaging applications. Composite structures of PP film coated with several kinds of polysaccharides (MC, HPMC, chitosan, κ ‐carrageenan, dextrin) and plasticizers (PG, glycerol, PEG, sucrose, sorbitol) were obtained through a simple casting method. High glossy surfaces were observed on the coated films with chitosan and κ ‐carrageenan, with the sucrose‐plasticized chitosan coating giving the highest gloss of 142.7 GU. Biopolymers, but no plasticizers, exerted noticeable influence on the colour of the coated films. Chitosan‐ and κ ‐carrageenan‐coated PP films also showed greater transparency, tensile strength and elongation than the other coated films. Nisin‐incorporated κ ‐carrageenan coatings on PP film exhibited significant bacterial growth inhibition against Lactobacillus plantarum . The results suggest that coatings based on chitosan and κ ‐carrageenan with proper plasticizers possess excellent visual and mechanical characteristics and have great potential for acting efficiently as antimicrobial agent carriers in active packaging systems. Copyright © 2004 John Wiley & Sons, Ltd.     

Effects on Oxygen‐barrier Properties of Pretreating Paperboard with a Starch–Poly(Vinyl Alcohol) Blend before Polyethylene Extrusion

Polyethylene (PE) extrusion coating was performed on paperboard pre‐coated with water‐borne barrier coatings based on starch–poly(vinyl) (PVOH)–plasticizer blends in order to investigate that how the addition of a plasticizer to the pre‐coating affects the oxygen‐barrier properties of the board after PE extrusion coating. The plasticizers used were glycerol, polyethylene glycol (PEG) and citric acid (CA). Photomicrographs showed that the barrier coating layers were rather smooth, but defects were observed in the starch–PVOH layers when a plasticizer was added. Starch–PVOH layers had oxygen‐barrier properties similar to those of pure PVOH without plasticizers. When a sufficient number of layers (four layers) were applied to cover defects, the starch–PVOH layers containing CA showed oxygen transmission rate (OTR) values similar to those of starch–PVOH layers without plasticizer. The adhesion of PE to pre‐coated paperboard decreased when a plasticizer was added to the pre‐coating recipes. PE extrusion coating resulted in a reduction in the OTR in the case of pre‐coating formulations containing plasticizers. A lower OTR after polyethylene extrusion was observed with PEG as plasticizer than with CA as plasticizer. This could be explained by the increase in brittleness due to cross‐linking under the high temperature load during the extrusion process. Dynamic mechanical analysis of the films showed a substantial increase in storage modulus between 100°C and 200°C for CA‐containing starch–PVOH films. The contact angle of diiodomethane on the pre‐coating layer decreased when a plasticizer was added to the coating recipe indicating an increase in wetting of the PE melt. Addition of PEG to the pre‐coating led to a greater wetting than the addition of CA, and this may have sealed some defects in the pre‐coating leading to lower OTR values.     

单糖对玉米淀粉基复合膜性能的影响

目的研究D-果糖和葡萄糖作为增塑剂对玉米淀粉-壳聚糖复合膜性能的影响。方法糊化后的玉米淀粉溶液与壳聚糖溶液混合,分别添加5%,20%,35%,50%,65%(质量分数)的D-果糖及葡萄糖,均质后流延成膜;测定膜的力学性能,并通过扫描电镜、接触角、傅里叶红外扫描和X-衍射对复合膜相关特性进行表征。结果成膜物质之间相容性好,增塑剂用量由5%增加至65%,膜的厚度增加,经D-果糖和葡萄糖增塑的复合膜抗拉强度分别由73.99,70.88 MPa减至18.08,40.53 MPa。经D-果糖增塑的复合膜断裂伸长率呈递增趋势,在添加量为65%时达到19.03%,经葡萄糖增塑的复合膜呈现递减趋势。结论同一含量下,2种复合膜的厚度相近,抗拉强度相差不大,但经D-果糖增塑的复合膜断裂伸长率高,亲水性较好,更适合作为增塑剂应用在复合膜的制备中。     

Whey protein isolate coating on LDPE film as a novel oxygen barrier in the composite structure

To examine the feasibility of whey protein isolate (WPI) coating as an alternative oxygen barrier for food packaging, heat‐denatured aqueous solutions of WPI with various levels of glycerol as a plasticizer were applied on corona‐discharge‐treated low‐density polyethylene (LDPE) films. The resulting WPI‐coated LDPE films showed good appearance, flexibility and adhesion between the coating and the base film, when an appropriate amount of plasticizer was added to the coating formulations. WPI‐coated LDPE films showed significant decrease in oxygen permeability (OP) at low to intermediate relative humidity, with an Arrhenius behaviour and an activation energy of 50.26 kJ/mol. The OP of the coated films increased significantly with increasing relative humidity, showing an exponential function. Although the coated films showed a tendency to have less oxygen barrier and more glossy surfaces with increasing plasticizer content, differences in the OP and gloss values were not significant. Haze index and colour of the coated films were also little influenced by WPI coating and plasticizer content. The results suggest that whey protein isolate coating could work successfully as an oxygen barrier and have potential for replacing synthetic plastic oxygen‐barrier layers in many laminated food packaging structures. Copyright © 2004 John Wiley & Sons, Ltd.     

Morphology and antibacterial properties of plasticized chitosan/metallocene polyethylene blends

In this work, plasticized chitosan-based materials were produced through a molten process. A thermo-mechanical treatment was used to achieve chitosan plasticization in the presence of water, acetic acid, and glycerol. Water and glycerol acted as plasticizers, while acetic acid was used as a solvent and plasticizer for chitosan. The influence of acetic acid total content, chitosan/acetic acid solution ratio, and chitosan/glycerol ratio were examined in this study. The various plasticized compounds were blended with a metallocene polyethylene (mPE) and the morphology, rheological, and antibacterial properties of this novel blend system were examined. It was found that an increase in acetic acid content allowed better chitosan dissolution, while a higher glycerol concentration resulted in improved dispersion of the plasticized chitosan phase in the mPE. Following thermo-mechanical treatment, blends presented good antibacterial properties with a reduction of the number of bacteria (non-pathogenic Escherichia coli) by 2 log(CFU/mL) for the chitosan-containing systems with respect to neat mPE. Mechanical properties of the mPE/plasticized chitosan blends were improved by compatibilization with ethylene vinyl acetate, while antibacterial properties were not affected.     

The Effect of Plasticizers on the Properties of Polyvinyl Alcohol Films

Abstract

The effect of water-soluble plasticizers viz propylene glycol (PG), glycerol and polyethylene glycol 600 (PEG) on the morphology and water resistance of polyvinyl alcohol (PVA) films was investigated. Polyvinyl alcohol films were cast from aqueous solutions, and their morphology studied using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Water resistance was characterized by the extent of film dissolution and the water uptake capacity of remnant films after immersion of the films in distilled water for 3 days at 37° C. DSC thermograms showed that crystallite formation in the PVA films was affected to different extent by addition of the three plasticizers. The plasticizers not only reduced the degree of crystallinity in the films, but also lowered the crystalline melting temperatures probably by introducing defects into the crystal lattice. This factor, coupled with leaching of the water-soluble plasticizers from the films when immersed in distilled water, lowered the water resistance of the plasticized PVA films. The influence of plasticizers on the properties of PVA films was further related to the degree of compatibility between the plasticizers and PVA.     

Influence of Aging on the Physical-Mechanical Properties of Acrylic Resin Films Cast from Aqueous Dispersions and Organic Solutions

The physical-mechanical properties of the enteric copolymers, poly(methacrylic acid, ethyl acrylate) Eudragit® L100-55, and Eudragit® L30D have been investigated. Free films of the copolymer containing varying levels of glyceryl triacetate (triacetin) and citrate ester (Citroflex®) plasticizers were prepared by both aqueous and solvent casting techniques. Conditioned films were stored at different humidities and temperatures for predetermined time periods prior to testing. Free films with plasticizer concentration ranging from 0 to 30% by weight of the polymer demonstrated that physical aging at room temperature resulted in physical-mechanical changes as the stress-strain curves indicated a decrease in the percent elongation with increases in the tensile strength. Films prepared from the aqueous latex approached a constant state of equilibrium at a faster rate than films prepared from isopropyl alcohol, where the mechanical properties approach a relatively constant value. Free films containing varying amounts of the plasticizer, triethyl citrate, were stored under different humidity and temperature conditions. In addition, a headspace-gas chromatography (HSGC) method was developed to correlate solvent residues with mechanical properties. The results indicated that an increase in temperature and humidity accelerated the rate of solvent evaporation as a function of time. High vacuum and low humidity conditions were demonstrated to be ineffective conditions for solvent removal. Solvent residues were found in all films after 48 hours of exposure to temperatures up to 60°C and/or exposure to relatively high humidity conditions. A direct relationship between plasticizer content and rate of solvent evaporation from the film was established. Higher concentrations of the plasticizer were found to augment the evaporation of the solvents. This enhanced evaporation was due to the stronger molecular interaction forces between the polymer and the plasticizer than between the polymer and the solvent.     

Mechanical and Water Vapor Transmission Properties of Polysaccharide Films

The film-forming properties of chitosan, chitosan glutamate, sodium alginate, and hydroxypropyl methylcellulose (HPMC) were investigated. Films were produced by a casting/solvent evaporation method from plasticizer-free and plasticizer-containing aqueous solutions. The water vapor transmission and mechanical properties (puncture strength and % elongation) of the films were investigated as a function of the polymer type and viscosity, plasticizer type (glycerin, propylene glycol, polyethylene glycol, triethyl citrate), plasticizer concentration, and type and concentration of acid used to dissolve chitosan. The effect of storage humidity was also examined. Glycerin and water were good plasticizers for chitosan glutamate. The chitosan film properties were dependent on the type and concentration of acid used to dissolve it, citric acid being a good plasticizer. The mechanical and water vapor transmission properties of alginate and HPMC films were less influenced by the investigated variables.     

Incorporation of organic acids turns classically brittle zein films into flexible antimicrobial packaging materials

This study aimed to turn classically brittle zein films into flexible antimicrobial ones by the use of lactic (LA), malic (MA) and tartaric acids (TA). The most effective plasticizer was LA (400% elongation at break [EB] at 4%), while MA (189% EB at 4.5%) and TA (68% EB at 5%) showed moderate and limited plasticizing effects, respectively. The LA- and MA-loaded films maintained their flexibility during 30-day storage at 4°C or 25°C. Fourier transform infrared (FTIR) analysis suggested that the plasticization of LA and MA could be related to secondary structural changes in zein such as increased α-helix and random coils (mainly by MA) and spaced/modified intermolecular (only by LA) and intramolecular (mainly by MA) β-sheets. Atomic force and scanning electron microscopy showed that LA and MA gave more homogenous and smoother films than TA. Films with LA showed the highest water vapour permeability followed by those of control, MA- and TA-loaded films. Films with 3%–4% LA or MA formed clear zones on Listeria innocua and Klebsiella pneumonia, but only films with LA formed clear zones on Escherichia coli. All OA-loaded films gave unclear zones on Staphylococcus aureus in disc-diffusion tests, but this bacterium was inactivated rapidly in antimicrobial tests based on surface inoculation tests. LA is the best OA to develop flexible antimicrobial films from zein, an industrial by-product that films could not have been utilized as a widespread packaging material due to their brittleness.     

Leaching of water-soluble plasticizers from polymeric films prepared from aqueous colloidal polymer dispersions

The leaching of water-soluble plasticizers from polymeric films prepared by casting and drying of plasticized colloidal polymer dispersions was investigated with respect to the type and concentration of plasticizer (triethyl citrate or triacetin), film thickness, type of colloidal polymer dispersions (acrylic: Eudragit RS30D, RL30D, or L30D; cellulosic: Aquacoat), Eudragit RS30D/RL30D ratio, and method of film preparation (solvent- or pseudolatex-casting). The leaching increased with increasing level of plasticizer as indicated by an increase in the release rate constant while the release rate constant was independent of the film thickness. The leaching was more rapid from Aquacoat films than from Eudragit RS30D films at all plasticizer concentrations. Increasing the amount of the more hydrophilic polymer dispersion, Eudragit RL30D, in mixed Eudragit RS/RL films increased the rate of leaching. The incorporation of propranolol HCl into the polymeric films significantly increased the leaching rate constant when compared to drug-free films. The leaching from pseudolatex-cast films was faster when compared to the leaching from solvent-cast films due to the denser structure of the solvent-cast films.     

聚酯增塑剂的合成及对PVC的增塑

通过熔融缩聚的方法,合成了己二酸丙二醇型聚酯增塑剂,将其作为辅助增塑剂用于软质PVC的制备,期望达到降低聚氯乙烯(PVC)主增塑剂邻苯二甲酸二辛酯(DOP)迁移和抽出的目的。通过引入第三单体三羟甲基丙烷,并控制第三单体的加入量,合成了具有不同支化度的聚酯,并对PVC进行增塑试验,考察了聚酯的支化度及相对分子质量对PVC增塑效果的影响。实验结果表明,所合成的不同分子量聚酯增塑剂与PVC树脂的相容性均良好,当采用较高分子量聚酯或较低支化度聚酯时,其增塑PVC材料的玻璃化转变温度较低,所显示的增塑效率较高,材料的热稳定性能较好。     

Mechanical and Water Vapor Transmission Properties of Polysaccharide Films

Abstract

The film-forming properties of chitosan, chitosan glutamate, sodium alginate, and hydroxypropyl methylcellulose (HPMC) were investigated. Films were produced by a casting/solvent evaporation method from plasticizer-free and plasticizer-containing aqueous solutions. The water vapor transmission and mechanical properties (puncture strength and % elongation) of the films were investigated as a function of the polymer type and viscosity, plasticizer type (glycerin, propylene glycol, polyethylene glycol, triethyl citrate), plasticizer concentration, and type and concentration of acid used to dissolve chitosan. The effect of storage humidity was also examined. Glycerin and water were good plasticizers for chitosan glutamate. The chitosan film properties were dependent on the type and concentration of acid used to dissolve it, citric acid being a good plasticizer. The mechanical and water vapor transmission properties of alginate and HPMC films were less influenced by the investigated variables.     

Surface evaluation of whey protein films by atomic force microscopy and water vapour permeability analysis

The atomic force microscopy (AFM) technique is a powerful tool for studying surfaces and has been used to provide qualitative and quantitative information about nanometer‐scale matter properties that are often inaccessible by any other experimental technique. In this work AFM was used to evaluate the surfaces of edible films produced with whey protein concentrate (WPC). The morphology and the roughness of the films were analysed. The effects of WPC and plasticizer concentration were characterized in terms of water vapour permeability (WVP) and roughness parameters. Roughness was calculated through the images captured with AFM. AFM can be useful to identify structural changes of the film resulting from sample preparation. The results showed a relation between water vapour permeability and area roughness, through different sample preparation. The analyses of topography through roughness obtained with AFM, demonstrated the correlation between the morphology of the film, obtained with nanometer resolution and WVP. Copyright © 2004 John Wiley & Sons, Ltd.     

Evaluation of the film-forming property of hydrogenated rosin

The film-forming and coating properties of a new biomaterial, hydrogenated rosin (HR), is investigated in the present communication. Films produced by casting method are studied for mechanical, (tensile strength, elongation, and Young's modulus), water vapor transmission, and moisture absorption characteristics. Type of plasticizer and its concentration were observed to play an important role in modifying the film characteristics. Dibutyl sebacate (DBS), a hydrophobic plasticizer, was found to be suitable for development of flexible and smooth films. Film formulations plasticized with DBS were investigated for coating the drug layered nonpareil seeds where plasticization facilitated development of smooth and uniformly coated pellets. The increase in coat buildup, however, did not sustain the drug release significantly. The studies conclude that HR films promise utility as moisture-protective hydrophobic, film-coating materials.