淀粉成膜性和疏水性对表面施胶包装纸的影响

本文研究了添加甘油对疏水改性木薯淀粉膜力学性能及阻隔性能的影响,甘油的添加降低了疏水改性淀粉膜的玻璃转化温度、储能模量及水蒸气透过量.当温度低于临界温度上限时,疏水改性淀粉将会出现固态及液态两种形式.热的淀粉溶液中加入适量的甘油可以抑制淀粉微粒的沉淀.与羟丙基淀粉相比,疏水改性淀粉中添加不同量的甘油并涂覆干基材表面,对基材的阻隔性、水蒸气透过量、接触角及可勃吸水值均有一定影响.从表面施胶基材的可勃吸水值和水蒸气透过量的变化上可以看出,淀粉的成膜性对基材的性能有非常重要的影响.良好的成膜性可以改善基材的阻气、阻湿性,而对基材表面润湿性的影响不大.随着甘油含量的逐渐增加,基材的水蒸气透过量不断减少;但仍无法得到较好的阻湿性能.本文中所用的疏水改性淀粉具有较好的氧气阻隔性能和接触角,因此,表面施胶后的基材具有较好的疏水特性.同时在实验条件下研究了淀粉沉淀对基材性能的影响,利用淀粉沉淀对基材表面进行施胶后即使淀粉成膜性较差,也可以得到较低的水蒸气透过量和较高的接触角.通过增加疏水改性淀粉中甘油的含量,表面施胶基材的可勃吸水值可以得到显著改善.     

中心组合试验优化葛根淀粉-壳聚糖复合膜性能

利用玻璃板延流法制取葛根淀粉-壳聚糖复合膜,运用流变仪、质构仪等仪器测定葛根淀粉、壳聚糖、甘 油不同配比下复合膜的成膜特性,并通过响应面法分析和优化3种物料的配比。结果表明,以抗拉强度、延伸率、 水蒸气透过率和透明度为评价指标,通过Design-Expert软件分析得到在葛根淀粉质量分数1.5%,壳聚糖质量分数 1.29%,甘油质量分数24.27%时,葛根淀粉-壳聚糖复合膜的性能最好。     

甘油与甲基纤维素对高直链玉米淀粉- 壳聚糖复合膜性能的影响

以高直链玉米淀粉(HACS)和壳聚糖(CS)为基本材料,甘油为增塑剂,甲基纤维素(MC)为增强剂制备可食性复合膜,研究高直链玉米淀粉与壳聚糖的质量比,甘油的添加量以及甲基纤维素的添加量对复合膜物理性能的影响,包括抗拉强度(TS)、断裂伸长率(E)、水蒸气透过系数(WVP)和色度。结果表明,壳聚糖添加量的增大与甘油添加量的增加都使高直链玉米淀粉- 壳聚糖复合膜的抗拉强度降低,断裂伸长率和WVP 显著增大,膜颜色变黄;甲基纤维素的添加改善了复合膜的机械性能和WVP,随着甲基纤维素添加量的增加,复合膜的抗拉强度和断裂伸长率都随之增大,WVP 逐渐降低,且对膜的颜色没有显著影响。     

Acetylated and native corn starch blend films produced by blown extrusion

Thermoplastic starch (TPS) materials were developed from mixtures of native and acetylated corn starches with glycerol. To optimize the formulations an experimental design for multicomponent mixtures was used and the assayed formulations were determined by statistical software. Blends and pellets humidity content increased with glycerol concentration. Starch destructuration during the extrusion process was studied by thermal analysis. Films presented homogenous structure, rough surfaces and certain stickiness. They presented different properties, related mainly to the differential characteristics of native and acetylated starches and to hydrophilic character of glycerol. Their mechanical behavior indicated that they are a good option as a food packaging materials since TPS films resulted enough resistant to protect the product and flexible to resist moderate deformations. Besides, the use of acetylated starch in the formulations enhanced film resistance and reduced their WVP, despite of its low modification degree. The storage of the films under controlled conditions increased their stiffness, while their flexibility and WVP were reduced. Plasticizer migration towards the matrix surface was observed in stored films. Films resulted stable till a_w = 0.7 and due to their selective gaseous permeability they are useful to package products susceptible to oxidation or to control vegetable respiration and senescence.     

响应面试验优化玉米淀粉-壳聚糖可食膜的制备工艺

通过响应面法优化玉米淀粉、壳聚糖和甘油的质量分数来制备可食膜,以机械性能（伸长率、抗拉强度）和透湿性（water vapor permeability,WVP）为评价指标,得出二次响应预测模型。结果表明：玉米淀粉、壳聚糖和甘油的质量分数分别为3.71%、0.95%和0.64%时,抗拉强度最大;3 种物料质量分数分别为3.82%、0.50%和1.00%时,伸长率最大;3 种物料质量分数分别为3.52%、0.52%和0.50%时,WVP最小。综合考虑,玉米淀粉、壳聚糖和甘油质量分数分别为3.50%、0.50%和0.67%时,可食膜的性能最优。     

Combined effect of plasticizers and surfactants on the physical properties of starch based edible films

Films made of potato starch were developed and glycerol as plasticizer and Tween 20, Span 80, and soy lecithin as surfactants were included in the formulation. Films were characterized with respect to water vapor permeability (WVP) and mechanical properties. The wettability of the film solutions was quantified by measuring their surface tension.The incorporation of plasticizers resulted in more flexible and manageable films and higher WVP. At low concentration, Tween 20 was the surfactant that reduced surface tension the most, while at high concentration it was lecithin. In the absence of glycerol, surfactants had a significant effect on mechanical properties, but they did not modify significantly WVP of the films. It was observed a synergistic behavior between the plasticizer and the surfactants. Films with glycerol and high level of any of the surfactants behaved as films with larger amount of plasticizer (with lower tensile strength, higher elongation, and higher WVP). Tween 20 was the surfactant that showed the most intense synergistic effect with glycerol.     

Effect of the presence of glycerol and Tween 20 on the chemical and physical properties of films based on chitosan with different degree of deacetylation

Chitosans with two different deacetylation degree (DD) (60.9% and 96%) were used to elaborate edible films. The influence of the degree of deacetylation and the presence of glycerol and Tween 20 in the formulation on the surface tension of the film forming solutions as well as on the chemical structure, optical and mechanical properties and water vapor permeability (WVP) of the resulting films were studied.IR spectra showed no significant differences on the chemical structures of chitosan of the different films. However, X-ray diffraction analysis indicated that the use of chitosan with higher DD and the use of glycerol as additive resulted in higher crystallinity. Films made of chitosan with the lower DD (60.9%) were found to have higher tensile strength (TS) and elongation (E) in a tensile test. Degree of deacetylation did not have any effect on WVP. The presence of glycerol resulted in less resistant, more elastic and more permeable films.The presence of Tween 20 improved the wettability of film solutions and affected significatively mechanical, optical and barrier properties of the films. A positive interaction between glycerol and Tween 20 was observed for WVP.     

Preparation and properties of rice starch–chitosan blend biodegradable film

Biodegradable blend films from rice starch–chitosan were developed by casting film-solution on leveled trays. The influence of the ratio of starch and chitosan (2:1, 1.5:1, 1:1, and 0.5:1) on the mechanical properties, water barrier properties, and miscibility of biodegradable blend films was investigated. The biodegradable blend film from rice starch–chitosan showed an increase in tensile strength (TS), water vapor permeability (WVP), lighter color and yellowness and a decreasing elongation at the break (E), and film solubility (FS) after incorporation of chitosan. The introduction of chitosan increased the crystalline peak structure of starch film; however, too high chitosan concentration yielded phase separation between starch and chitosan. The amino group band of the chitosan molecule in the FTIR spectrum shifted from 1541.15 cm⁻¹ in the chitosan film to 1621.96 cm⁻¹ in the biodegradable blend films. These results pointed out that there was a molecular miscibility between these two components. The properties of rice starch–chitosan biodegradable blend film and selected biopolymer and synthetic polymer films were compared; the results demonstrated that rice starch–chitosan biodegradable blend film had mechanical properties similar to the other chitosan films. However, the water vapor permeability of rice starch–chitosan biodegradable blend film was characterized by relatively lower water vapor permeability than chitosan films but higher than polyolefin.     

玉米淀粉/壳聚糖/魔芋葡甘露聚糖复合膜的制备及物性研究

以玉米淀粉、壳聚糖、魔芋葡甘露聚糖(KGM)为成膜基材。通过研究成膜配方中壳聚糖与KGM质量比、玉米淀粉、甘油、吐温-80等材料的质量分数对复合抗拉强度(TS)、断裂伸长率(EAB)、水蒸气透过系数(WVP)和不透明度(Opacity)的影响,以主成分分析法计算复合膜综合分为评价指标,利用正交实验对复合膜成膜配方进行优化。结果表明:当壳聚糖与KGM质量比1.0∶0.6、玉米淀粉质量分数10%、甘油质量分数0.50%、吐温-80质量分数0.30%时,复合膜TS为(22.53±0.16)MPa,EAB为(20.07±1.18)%,WVP为(1.87±0.01)×10~(-12)g·cm~(-1)·s~(-1)·Pa~(-1),不透明度为(4.13±0.07)mm~(-1),复合膜性能最优。     

Effect of Molecular Weight,Acid, and Plasticizer on the Physicochemical and Antibacterial Properties of β‐Chitosan Based Films

Abstract: Effects of chitosan molecular weight (1815 and 366 kDa), type of acid (1% acetic, formic, and propionic acid, or 0.5% lactic acid) and plasticizer (0, 25% glycerol or sorbital w/w chitosan) on the mechanical, water barrier, and antibacterial properties of β‐chitosan films were investigated. Tensile strength (TS) of high molecular weight (Hw) films was 53% higher than that of low molecular weight (Lw) ones, acetate, and propionate films had the highest TS (43 and 40 MPa) among tested acids, and plasticizer‐reduced film TS 34%. Film elongation at break (EL) was higher in Hw films than in Lw ones, in which formate and acetate films were the highest (9% and 8%, respectively), and plasticizer increased the film EL 128%. Molecular weight of chitosan did not influence water vapor permeability (WVP) of the films. Acetate and propionate films had lower WVP than other acid types of films, and plasticizer increased film WVP about 35%. No difference was found between glycerol and sorbitol films in terms of film mechanical and water barrier properties. Lw β‐chitosan films showed significant antibacterial activity against E. coli and L. innocua. This study demonstrated that β‐chitosan films are compatible to α‐chitosan films in physicochemical properties and antibacterial activity, yet with simple sample preparation. Practical Application: β‐chitosan based edible films at molecular weight of about 300 kDa showed great antibacterial activity against Gram‐positive and Gram‐negative bacteria. The films have similar mechanical and water barrier properties to α‐chitosan based films at the similar molecular weight, but simple sample preparation procedures and more attractive color. The release of active chitosan fragment from the film matrix acts as an antibacterial agent, making β‐chitosan films suitable as intelligent food wraps or coatings for a wide range of food products to control moisture loss and prevent surface bacterial growth.     

Mechanical and water vapor barrier properties of tapioca starch/decolorized hsian-tsao leaf gum films in the presence of plasticizer

The objectives of this research were to examine the mechanical and water vapor barrier properties of the starch/decolorized hsian-tsao leaf gum (dHG) films as a function of dHG and glycerol concentration. Edible film-forming solutions were prepared by mixing tapioca starch with dHG at different starch/dHG ratios to make a total solid content of 2%. In total, 15–40% glycerol was then added based on the dry film matter. Starch/dHG films were obtained by casting. It was found that the puncture strength, tensile strength, and modulus as well as the inverse of relaxation coefficient of starch/dHG films pronouncedly increased with increasing dHG, accompanied with a decreasing tendency in puncture deformation and tensile strain at break. Such results implied that starch interacted with dHG synergistically, resulting in the formation of a new network to improve the mechanical properties of tapioca starch/dHG films. Mechanical strengths of starch/dHG films decreased and water vapor permeability (WVP) at 75% RH increased with increasing glycerol concentration. However, the plasticizing effect of glycerol became less significant at high dHG concentration, particularly for the puncture deformation and tensile strain at break of the films. Water sorption isotherm results indicated that significant water sorption would only occur at high water activity (about 0.75), and generally became more pronounced with increasing glycerol and dHG concentration, but to a lesser extent for the latter. Dynamic mechanical analysis revealed that the major glass transition of starch/dHG films occurred at about −50 °C.     

Mechanical and Thermal Characteristics of Pea Starch Films Plasticized with Monosaccharides and Polyols

Edible starch films were produced from pea starch and various plasticizers (mannose, glucose, fructose, and glycerol and sorbitol) at the ratio of 4.34, 6.50, 8.69, and 10.87 mmol plasticizer per gram of starch. After film specimens were conditioned at 50% relative humidity, mechanical properties (tensile strength, elongation, and modulus of elasticity), water vapor permeability (WVP), moisture content, and thermomechanical properties (G’ and tan8) were determined as a function of plasticizer concentration. At all concentration levels, monosaccharides (mannose, glucose, and fructose) made the starch films stronger (higher tensile strength) and more stretchable than polyols (glycerol and sorbitol), while WVP of monosaccharide‐plasticized starch films were lower than those of polyol‐plasticized starch films, especially at higher plasticizer concentration levels. Except for 4.34 mmol/g of mannose‐plasticized film, all the other films showed similar modulus of elasticity at the same plasticizer concentration. Polyol‐plasticized films had lower T than the monosaccharide‐plasticized films. Glucose‐ and sorbitol‐plasticized films needed more activation energy to go through glass transition than others. After all, research results showed that not only the polyols but also the monosaccharides were effective in plasticizing starch films. It is concluded that molecular size, configuration, total number of functional hydroxyl group of the plasticizer as well as its compatibility of the plasticizers with the polymer could affect the interactions between the plasticizers and starch molecules, and consequently the effectiveness of plasticization.     

Properties of wheat starch film-forming dispersions and films as affected by chitosan addition

In order to evaluate the impact of chitosan on the physical properties of wheat starch–glycerol films, part of the wheat starch was replaced by chitosan, and the effect of composition on the properties of both the films and the film-forming dispersions was studied. The latter became more stable and viscous as the chitosan proportion was increased in the mixture. Both polymers appeared to integrate homogeneously in the film matrix. The combined effect of the glycerol and chitosan proportions affected the mechanical and barrier properties of the films. The tensile strength and elastic modulus of the films were improved as chitosan ratio increased. The oxygen and water vapor permeability slightly increased in line with the amount of chitosan in the blend although the induced differences were very small. Chitosan ratio directly affected the antimicrobial properties of the films, which showed a significant bactericide activity when the chitosan–starch ratio in the film was 50%. Nevertheless, at a starch:chitosan ratio of 80:20, counts of coliforms did not exceed the initial value in the meat after 7 storage days.     

Extrusion parameters related to starch/chitosan active films properties

Despite the increased use of extrusion technology in the production of biodegradable films, a better understanding of its effects on the several biopolymers is required. Therefore, the influence of extrusion temperature (120, 130 and 140 °C) and screw speed (25, 35 and 45 r.p.m.) on the properties of an active film formulated with starch, chitosan and oregano essential oil was investigated. Mechanical and barrier properties, apparent opacity and blow‐up ratio (BUR) of films were determined. The increase in screw speed had a positive effect on BUR and water vapour permeability (WVP) and a negative effect on opacity, tensile strength and elongation at break of the films. Low die temperatures resulted in decreased tensile strength, elongation at break, Young’s modulus and WVP of the films. Sorption isotherms of films were directly influenced by the extrusion conditions and films produced at 130 °C and 35 r.p.m. were less hydrophilic.     

Nanocellulose Reinforced Chitosan Composite Films as Affected by Nanofiller Loading and Plasticizer Content

ABSTRACT: Chitosan is a biopolymer obtained by N-deacetylation of chitin, produced from shellfish waste, which may be employed to elaborate edible films or coatings to enhance shelf life of food products. This study was conducted to evaluate the effect of different concentrations of nanofiller (cellulose nanofibers, CNF) and plasticizer (glycerol) on tensile properties (tensile strength—TS, elongation at break—EB, and Young's modulus—YM), water vapor permeability (WVP), and glass transition temperature (T_g) of chitosan edible films, and to establish a formulation to optimize their properties. The experiment was conducted according to a central composite design, with 2 variables: CNF (0 to 20 g/100 g) and glycerol (0 to 30 g/100 g) concentrations in the film (on a dry basis), which was produced by the so-called casting technique. Most responses (except by EB) were favored by high CNF concentrations and low glycerol contents. The optimization was based on maximizing TS, YM, and T_g, and decreasing WVP, while maintaining a minimum acceptable EB of 10%. The optimum conditions were defined as: glycerol concentration, 18 g/100 g; and CNF concentration, 15 g/100 g. AFM imaging of films suggested good dispersion of the CNF and good CNF-matrix interactions, which explains the good performance of the nanocomposite films. Practical Application: Chitosan is a biodegradable polymer which may be used to elaborate edible films or coatings to enhance shelf life of foods. This study demonstrates how cellulose nanofibers (CNF) can improve the mechanical and water vapor barrier properties of chitosan films. A nanocomposite film with 15% CNF and plasticized with 18% glycerol was comparable to some synthetic polymers in terms of strength and stiffness, but with poorer elongation and water vapor barrier, indicating that they can be used for applications that do not require high flexibility and/or water vapor barrier. The more important advantage of such films when compared to synthetic polymer films is their environmentally friendly properties.     

乳清浓缩蛋白可食用膜成膜工艺的研究

研究了乳清浓缩蛋白可食用膜的成膜工艺,分析了蛋白质浓度、甘油浓度和加热温度对可食用膜透水性和透氧性的影响,并确定了可食用膜阻隔性能的优化工艺参数。研究结果表明,可食用膜的阻水性随蛋白质浓度和甘油浓度的增大而下降,阻氧性随甘油浓度增大而下降。加热温度为70℃时,膜的阻水性和阻氧性达到最佳。响应面分析表明,当蛋白质浓度为100 g/L,甘油浓度为27 g/L,加热温度为69℃时,乳清浓缩蛋白可食用膜的综合通透性能为最佳,其透湿系数为0.004 35 g·mm/(m~2·h·kPa),透氧系数为0.134 cm~3·mm/(m~2·min·kPa)。     

Effect of glycerol on the physicochemical properties of films based on legume protein concentrates: A comparative study

The overall goal of this research was to examine the mechanical, water vapor barrier properties and opacity of films prepared using legume protein concentrates (faba bean, pea, lupin, lentil, and soy) as a function of glycerol concentration (50, 75, or 100% [wt/wt]—relative to the protein weight). Overall, tensile strength (TS) decreased with increasing glycerol concentration, whereas tensile elongation (TE) and water vapor permeability (WVP) increased with increasing glycerol concentration. Film opacity was independent of glycerol concentration. The effect of protein‐type varied considerably depending on the functional property of the film being measured; TS was greatest with faba bean and lowest with lupin, whereas TE was highest for pea, and lowest for soy. Lentil protein films had considerably higher WVP, at the 100% glycerol concentration, as compared to the other protein concentrates. Findings from this study indicate that legume protein concentrates are capable of forming biodegradable, edible films. Overall, pea protein concentrate films showed the most promise for application in terms of strength, elongation, and moisture barrier properties.     

Mechanical Properties, Water Vapor Permeabilities and Solubilities of Highly Carboxymethylated Starch-Based Edible Films

ABSTRACT: Tensile strength (TS), elongation (E), water vapor permeabilities (WVP) and solubilities were determined for highly carboxymethylated starch (HCMS)-based edible films plasticized with sorbitol (S), xylitol (X), mannitol (M) and glycerol (G). TS and E of HCMS-based film increased as the concentration of plasticizer S, M or × increased. TS of the HCMS-based film containing combined plasticizers were higher than those of films containing single plasticizer. The WVP of HCMS-based films seemed to decreased as the concentration of M, X or G plasticizer increased. Increasing plasticizer concentrations in HCMS-based film resulted in decreasing solubility of the films.     

Water Solubility, Mechanical, Barrier, and Thermal Properties of Cross-linked Whey Protein Isolate-based Films

Water solubility, hermal properties, tensile strength, percent elongation, oxygen permeability (OP), water‐vapor permeability (WVP) of cross‐linked glycerol plasticized whey protein isolate films were studied to determine the effect of cross‐linkers (glutaraldehyde, formaldehyde, dialdehyde starch, carbonyldiimidazole, and UV irradiation) on film properties. With the exception of UV treatment, solubility of the films decreased (P>0.05) upon treatment of the film‐forming solutions with chemical cross‐linkers. Tensile strength increased (P>0.05), whereas percent elongation was not affected by cross‐linking. Chemical cross‐linking increased (P>0.05) WVP and decreased (P>0.05) OP of the films. UV treatment had no effect on WVP and O P. With the exception of UV‐treated films, both onset temperature and degradation temperatures, as determined by differential scanning calorimetry, were increased upon cross‐linking.     

Effects of pH and Salts on Physical and Mechanical Properties of Pea Starch Films

To identify the significant contribution of intermolecular hydrogen bonds of starch molecules to the film structure formation, pH of film‐forming solutions was adjusted and also various salts (NaCl, CaCl₂, CaSO₄, and K₂SO₄) were mixed into the glycerol‐plasticized pea starch film. The film made from pH 7 possessed the highest tensile strength‐at‐break (2 times) and elastic modulus (4 to 15 times) and the lowest elongation‐at‐break compared with those of the films made from acid and alkali environments. The pH 7 film also has the highest film density and the lowest total soluble matter. At the level of 0.01 to 0.1 M of CaSO₄ and 0.1 M of K₂SO₄ in a kilogram of starch, the water solubility of the film increased, while chloride salts slightly lowered the solubility. NaCl and CaSO₄ reduced water vapor permeability (WVP), while CaCl₂ slightly increased WVP at 0.01 and 0.06 M concentrations, and K₂SO₄ significantly increased WVP at 0.03 and 0.15 M. Presence of salts increased tensile strength (5 to 14 times than the control films) and elastic modulus (35 to 180 times) of starch film at 0.01 to 0.03 M of CaSO₄ and K₂SO₄. Elongation‐at‐break increased significantly as salt concentration increases to an optimal level. However, when the concentration exceeded above the optimal level, the E of starch films decreased and showed no significant difference from the control film. Overall, the addition of salts modified physical and mechanical properties of pea starch films more than pH adjustment without any salt addition.