食品模拟体系中淀粉基膜材增塑剂的迁移

本文采用酯化淀粉以三乙酸甘油酯为增塑剂,经流延法制备了酯化淀粉薄膜,并利用傅里叶红外光谱衰减全反射技术(ATR-FTIR)和热重分析仪(TGA)分析了淀粉基膜材与不同食品模拟体系接触后其表层增塑剂和整体增塑剂的变化情况。结果表明,基于与淀粉基膜材、增塑剂之间的亲和性差异,食品模拟体系对淀粉基膜材产生不同的溶胀作用,导致不同程度的增塑剂迁移;与淀粉基膜材亲和性越高的食品模拟体系,对淀粉基膜材表层和内部的溶胀更迅速,并可溶解更多的增塑剂分子,从而导致淀粉基膜材中更大程度的增塑剂迁移;表层增塑剂和整体增塑剂的迁移情况差异表明,溶剂溶胀和增塑剂迁移由膜材表层向内部发生。基于以上结果可推断,在实际应用过程中,选择合适的应用领域、设计调整材料结构可主动抑制增塑剂迁移,实现这类新型包装材料的安全使用。     

不同塑化剂对柠檬酸淀粉酯成膜性能的影响

以甘油、乙二醇、山梨醇和壳聚糖为塑化剂,机械活化柠檬酸淀粉酯为原料,以断裂伸长率为评价指标,通过SEM、FT-IR、TGA和接触角的分析,探讨不同塑化剂对淀粉酯成膜性能的影响。结果表明,不同塑化剂对淀粉酯的影响不同。不同塑化剂对淀粉酯膜的断裂伸长率影响为甘油>山梨醇>乙二醇>壳聚糖>原淀粉。添加塑化剂能使淀粉酯更好地成膜。SEM分析表明,以甘油和壳聚糖为塑化剂的淀粉酯膜具有更多网状结构,表面透气性好;以乙二醇和山梨醇为塑化剂的淀粉酯膜更为致密,表面相对光滑,气密性更好。FT-IR表明,淀粉酯膜均成功塑化且具有相同峰型,说明不同塑化剂的塑化机理基本相同。TGA显示,热分解温度与塑化剂分子大小及羟基含量存在密切关系。接触角分析表明,不同塑化剂对于淀粉酯膜的亲水性各不相同,其亲水性大小为山梨醇>甘油>壳聚糖>乙二醇。     

Composition and Film Properties of Temperature Responsive,Hydrophobically Modified Potato Starch

The film‐forming properties of hydrophobically modified potato starch were studied to optimize coating and surface sizing formulations for improvement of barrier properties of paper and paperboard. The spontaneous fractionation of a potato starch hydrophobically modified with a quaternary dodecylammonium chloride resulted in an amylose‐rich precipitate with properties differing from those of the original starch. Film formation was investigated in the presence of glycerol and poly(vinyl alcohol) plasticizers. Anti‐plasticization was found to occur at low and intermediate plasticizer levels but highly flexible, continuous films were obtained when 30 parts of plasticizer were added to 100 parts of dry starch. The highest transparency and greatest flexibility were obtained with glycerol, while the hydrophobic film properties were maintained with poly(vinyl alcohol). A study of the glass transition temperatures and melting behavior of starch‐plasticizer films by differential scanning calorimetry gave useful information about the crystallinity of the films.     

Effect of plasticizing sugars on rheological and thermal properties of zein resins and mechanical properties of zein films

Zein is the most important protein in corn. Zein has good film forming properties. One of the film forming methods is production of zein resin and then thermomolding by hot press. Pure zein film is very brittle. Plasticizers can improve mechanical and film making properties of zein. In this research, sugars (fructose, galactose and glucose) were used as plasticizers and rheological properties of zein resin were studied by dynamic oscillatory tests for determination of plasticization effectiveness. Effect of plasticizers on thermal properties of resins was investigated by DSC at −100 to 150 °C. No crystallization and melting peaks related to zein and plasticizers were observed. As well as there was not significant difference at glass transition temperature between zein resins containing various sugars. Zein films were prepared from zein resins by rolling and hot press and then mechanical properties of films were measured. Films containing galactose had better tensile properties than other films and showed higher tensile strength, strain at break, and Young modulus than films containing fructose and glucose.     

Advances in green solvents for production of polysaccharide-based packaging films: Insights of ionic liquids and deep eutectic solvents

The problems with plastic materials and the good film-forming properties of polysaccharides motivated research in the development of polysaccharide-based films. In the last 5 years, there has been an explosion of publications on using green solvents, including ionic liquids (ILs), and deep eutectic solvents (DESs) as candidates to substitute the conventional solvents/plasticizers for preparations of desired polysaccharide-based films. This review summarizes related properties and recovery of ILs and DESs, a series of green preparation strategies (including pretreatment solvents/reaction media, ILs/DESs as components, extraction solvents of bioactive compounds added into films), and inherent properties of polysaccharide-based films with/without ILs and DESs. Major reported advantages of these new solvents are high dissolving capacity of certain ILs/DESs for polysaccharides (i.e., up to 30 wt% for cellulose) and better plasticizing ability than traditional plasticizers. In addition, they frequently display intrinsic antioxidant and antibacterial activities that facilitate ILs/DESs applications in the processing of polysaccharide-based films (especially active food packaging films). ILs/DESs in the film could also be further recycled by water or ethanol/methanol treatment followed by drying/evaporation. One particularly promising approach is to use bioactive cholinium-based ILs and DESs with good safety and plasticizing ability to improve the functional properties of prepared films. Whole extracts by ILs/DESs from various byproducts can also be directly used in films without separation/polishing of compounds from the extracting agents. Scaling-up, including costs and environmental footprint, as well as the safety and applications in real foods of polysaccharide-based film with ILs/DESs (extracts) deserves more studies.     

Comparative study of film forming behaviour of low and high amylose starches using glycerol and xylitol as plasticizers

In this study, the film forming behaviour of low amylose (LA) and high amylose (HA) starches was studied. The starch-alone and a blend of plasticizer (polyol)-starch films were developed by gelatinising at various temperatures and casting at 25 °C. The starch-plasticizer films contained glycerol and xylitol either individually or in 1:1 combination. The concentration of plasticizer used was 15%, 20% and 30% for LA films while it was 20%, 30% and 40% for HA films on dry solid basis. The HA-glycerol films retained the highest moisture content among all the films. The HA films exhibited higher glass transition temperature, higher tensile strength, higher modulus of elasticity and lower elongation at break than those obtained from LA starch. The tensile strength and modulus of elasticity decreased and the elongation increased with increasing plasticizer concentrations above 15% on dry solid basis regardless the starch type. Low water vapour permeability was evident in LA and HA films plasticized by combined plasticizers at 20% plasticizer concentration. Rheological measurements showed that most of the suspensions exhibited Herschel-Bulkley behaviour and some of the HA suspensions exhibited Bingham plastic behaviour. At 15% (on dry solid basis) plasticizer concentration, the films obtained from both the starches were brittle due to the anti-plasticization behaviour.     

Effects of various plasticizers and nanoclays on the mechanical properties of red algae film

To manufacture red algae (RA) film, we used various plasticizers such as glycerol, sorbitol, sucrose, fructose, and polypropylene glycol (PPG), and then determined the mechanical properties of the RA films. The tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) of the films containing various plasticizers ranged between 0.43 to 9.10 MPa, 10.93% to 47.17%, and 1.28 to 1.42 ng m/m2sPa, respectively. RA films containing fructose as a plasticizer had the best mechanical properties of all the films evaluated. Incorporation of nanoclay (Cloisite Na+ and 30B) improved the mechanical properties of the films. RA film with 3% Cloisite Na+ had a TS of 10.89, while RA film with 30B had a TS of 10.85 MPa; these films also had better E and WVP values than the other RA films evaluated. These results suggest that RA/nanoclay composite films are suitable for use as food packaging materials. PRACTICAL APPLICATION: Edible RE/nanoclay composite films prepared in the present investigation can be applied in food packaging.     

Effect of plasticizing sugars on water vapor permeability, surface energy and microstructure properties of zein films

Sugars are natural plasticizers for food biopolymers and zein is the most important protein of corn. In this research, sugars (fructose, galactose and glucose) were used as plasticizers and the water vapor permeability (WVP), contact angle and microstructure of the zein films were studied. The pure zein film had high WVP and adding of sugars to 0.7 g/g zein caused to decrease of WVP. Films containing galactose had the lowest WVP.All samples had the lowest contact angle with ethanol and the highest contact angle with water. The zein films containing galactose had the highest water contact angle within the plasticized films. The pure zein films and the films containing fructose had higher critical surface tension of wetting (γ_c) than the films containing glucose and galactose. Adding sugar plasticizer to zein films increased the surface tension of zein films. In the unplasticized zein films, loose structures with a lot of cavities and voids were observed. The films plasticized by fructose had smooth surface and plasticizer particles distributed throughout of the films.     

Effects of Extrusion Temperature and Plasticizers on the Physical and Functional Properties of Starch Films

Cornstarch, at 20% moisture content (dry basis, d.b.), was mixed with glycerol at 3:1 ratio to form the base material for extruded starch films. Stearic acid, sucrose and urea, at varying concentrations, were tested as secondary plasticizers for the starch‐glycerol mixture. The ingredients were extruded at 110 and 120°C barrel temperatures to determine the effects of extrusion temperature, plasticizer type and their concentrations on the film‐forming characteristics of starch, as well as their effects on selected physical and functional properties of the films. The physical and mechanical properties of the films were studied by scanning electron microscopy (SEM) and tensile testing, while the glass transition and gelatinization properties were analyzed using differential scanning calorimetry (DSC). The interactions between the functional groups of starch and plasticizers were investigated using Fourier‐transform infrared (FTIR) spectroscopy. The water vapor permeability (WVP) properties of starch films were determined using ASTM standard E96‐95. Scanning electron micrographs exhibited the presence of native and partially melted starch granules in the extruded films. The tensile stress, strain at break and Young's modulus of starch films ranged from 0.9 to 3.2 MPa, 26.9 to 56.2% and 4.5 to 67.7 MPa, respectively. DSC scans displayed two glass transitions in the temperature ranges of 0.1 to 1°C and 9.6 to 12°C. Multiple melting endotherms, including that of amylose‐lipid complexes, were observed in the thermoplastic extrudates. The gelatinization enthalpies of the starch in the extruded films varied from 0 to 1.7 J/g, and were dependent largely on the extrusion temperature and plasticizer content. The shift in the FTIR spectral bands, as well as the appearance of double‐peaks, suggested strong hydrogen bonding interactions between the starch and plasticizers. The WVP of starch films ranged from 10.9 to 15.7 g mm h^‐1 m^‐2 kPa^‐1, depending on the extrusion temperature and the type of plasticizer used.     

Migration of plasticizers from printing inks into foods

It has been demonstrated that on storage of a tightly wound reel of polypropylene packaging film, specially printed for experimental purposes, transfer can occur of components from the ink on the outer surface of the film on to the inner food contact surface. For dicyclohexyl phthalate this transfer amounted to 6% of the total amount of plasticizer available in the printing ink system. It was subsequently shown for confectionery and snack food products wrapped in commercially printed polypropylene films that plasticizers only present in the printing ink migrated into the foods. The migration of plasticizer increased with storage time of the wrapped product; for dibutyl phthalate, for example, levels increased from 0.2 to 6.7 mg/kg over the period from 0 to 180 days storage of a chocolate-coated confectionery product. A small retail survey (47 samples) of confectionery, snack products and biscuits wrapped in printed polypropylene film showed the presence of one or more plasticizers at levels from 0.02 to 14.1 mg/kg for dibutyl phthalate, from less than 0.01 to 18.6 mg/kg for dicyclohexyl phthalate and from less than 0.01 to 1.8 mg/kg for di(2-ethylhexyl) phthalate. In all cases there was a good correlation between the plasticizers found in the printing ink from the film and those in the food. Wide variations were found, however, in the amounts and types of plasticizers used in printed packaging of the same brand of retail food product purchased from different regions of the country.     

增塑剂对改性纤维素膜性能的影响及其机理研究

研究增塑剂对羧甲基纤维素(CMC)膜、甲基纤维素(MC)膜性能的影响,并利用扫描电镜、红外光谱仪和X 射线衍射仪探讨增塑剂对膜的作用机理。实验结果表明：0.2% 甘油对CMC 膜的增塑效果较好,而0.4% 聚乙二醇对MC 膜的增塑效果较好。增塑剂对膜性能的影响由增塑剂与膜材的相容性决定。     

THE EFFECTS of PLASTICIZERS ON CRYSTALLINITY, PERMEABILITY, and MECHANICAL PROPERTIES of METHYLCELLULOSE FILMS

The effects of plasticizers (polyethylene glycols [PEG] 400, 1,450, 8,000 and 20,000, glycerol [G] and propylene glycol [PG]), 30% dry basis, on the physical properties of methylcellulose (MC) films were investigated. With the exception of PG, plasticizers with low molecular weights (G and PEG 400) caused the largest increase in the d₁₀₁ spacing of the crystal lattice. All plasticizers significantly (α= 0.05) increased oxygen (O₂P) and water vapor permeabilities (WVP) of the films as compared to that of unplasticized MC, with PEG 400 having the greatest effect on O₂P and G having the greatest effect on WVP. With the exception of PG, all plasticizers decreased the tensile strength of MC films, with PEG 400 causing the largest decrease. With the exception of PG and PEG 400, all plasticizers increased percent elongation values of MC films, with PEG 1,450 having the greatest effect. Glycerol and PEG were the most effective plasticizers for MC. the higher molecular weight plasticizers do provide some plasticizing properties and may be more suitable for applications that require a lower permeability to water vapor than can be achieved with glycerol.     

Water Vapor Permeability and Mechanical Properties of Soy Protein Isolate Edible Films Composed of Different Plasticizer Combinations

Water barrier and mechanical properties were measured for soy protein isolate (SPI) films plasticized with glycerol (GLY) and 1 of the plasticizers (propylene glycol [PG], polyethylene glycol [PEG], sorbitol [SOR], or sucrose [SUC]) at a ratio of 25:75, 50:50, 75:25, and 0:100. Plasticizer type as well as the plasticizer ratio in the GLY: plasticizer mixtures affected the film water barrier and mechanical properties. An addition of as little as 25% of a less hygroscopic plasticizer in the mixture induced significant reduction in water vapor permeability (WVP) of SPI films. However, at least 50% of the mixture needs to be GLY to show significant improvement in tensile strength (TS). From our experimental design, 50:50 GLY:SOR was the recommended combination because of its comparatively low WVP value and relatively high flexibility and strength. Incompatibility of GLY:PEG plasticizer mixture in SPI film was observed by surface migration of PEG from the film matrix.     

不同增塑剂对大豆蛋白包装薄膜机械性能稳定性的影响

大豆蛋白膜是以大豆分离蛋白（soybean protein isolate,SPI）为主料,添加适量增塑剂形成具有一定机 械性能的包装薄膜,但其在贮藏过程中机械性能的不稳定是制约其在实际中应用的主要因素。因此本实验选取甘 油、山梨醇、油酸3 种增塑剂制备SPI膜,以贮藏期间抗拉强度、断裂延伸率、水蒸气透过率、水溶失率的变化为 评价指标,探讨添加不同增塑剂的SPI膜在贮藏期间机械性能变化规律。结果表明,以甘油、山梨醇和油酸组合 （2∶1∶1,m/m）作为增塑剂制备SPI膜时,SPI膜机械性能稳定性最佳,与空白组（单独由甘油增塑的SPI膜）相 比,抗拉强度稳定性提高了64%,断裂延伸率稳定性提高了65%,水蒸气透过率稳定性提高了27%,对水的稳定性 提高了20%。本实验可为SPI包装薄膜在实际中更广泛的应用提供一定的理论依据。     

Kefiran films plasticized with sugars and polyols: water vapor barrier and mechanical properties in relation to their microstructure analyzed by ATR/FT-IR spectroscopy

Kefiran, an exopolysaccharide produced by microorganisms present in kefir grains, is a glucogalactan that has several health promoting properties. In the present work the effect of different sugars (glucose, galactose, sucrose) and polyols (glycerol and sorbitol) as plasticizers on kefiran film properties was evaluated. Kefiran films were brittle and rigid and all the tested plasticizers improved film properties. They were all transparent with low opacity. Unplasticized kefiran films X-ray diffraction patterns were similar to those of plasticized ones, showing an amorphous-crystalline structure with low crystallinity degree. All films presented low a_w values (below 0.5) conferring protection properties against microorganism growth. The lowest permeability value was obtained with glucose as plasticizer whereas the best mechanical properties were obtained with glycerol addition.     

Plasticization of Pea Starch Films with Monosaccharides and Polyols

ABSTRACT:  Monosaccharides have several hydroxyl groups and a compatible structure with starch polymers resulting in effective plasticization in starch films. Two groups of plasticizers (polyols and monosaccharides) were used to compare their plasticizing efficiency. Fructose, glucose, mannose, galactose, glycerol, sorbitol, ethylene glycol, and maltitol were selected at 13.031 mmol per 100 g of pea starch. Edible starch films were produced after heat gelatinization and dehydration of the 3% starch dispersion. The microstructure, attenuated total reflection foorier transform infrared (ATR-FTIR) characteristics, thickness, moisture content, tensile strength, modulus of elasticity, elongation-at-break, water vapor permeability, and transparency of films were determined. Microstructure of the film solutions showed that some swollen starch granules and their remnants existed in the film. Compared to the FTIR spectra of pure starch films, the spectra of plasticized films showed that more hydrogens bound hydroxyl groups and more water molecules were attracted around starch polymer chains. Ethers were produced in glycerol-plasticized films. Monosaccharide-plasticized films were comparable to the polyol-plasticized films in tensile test, but more resistant in moisture permeation than the polyol-plasticized films. It was assumed that the structural compatibility of monosaccharides with starch might result in denser polymer-plasticizer complex, smaller size of free volume, and less segmental motions of starch chains. In conclusion, monosaccharides were identified as effective plasticizers for starch film.     

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.     

Preparation and mechanical properties of edible rapeseed protein films

Edible films were manufactured from rapeseed oil extraction residues. To prepare rapeseed protein (RP) films, various concentrations of plasticizers and emulsifiers were incorporated into the preparation of a film-forming solution. The optimal conditions for the preparation of the RP film were 2% sorbitol/0.5% sucrose as plasticizer and 1.5% polysorbate 20 as an emulsifier. In addition, RP blend films were prepared. Gelidium corneum or gelatin was added to improve the physical properties of the RP film, and the highest tensile strength value of the films was 53.45 MPa for the 3% RP/4% gelatin film. Our results suggest that the RP-gelatin blend film is suitable for applications in food packaging. PRACTICAL APPLICATION: Edible RP films prepared in the present investigation can be applied in food packaging.     

琼脂-麦芽糊精共混物的成膜特性研究

将琼脂与不同水解程度的麦芽糊精按一定比例分别混合,考察共混液的黏度以及所成膜的透明度、机械性能和透湿性。结果表明:琼脂-麦芽糊精共混液的黏度主要取决于琼脂的质量分数,琼脂质量分数小于3%,有利于流延成膜。低DE值的麦芽糊精与琼脂共混膜的机械性能、阻湿性优于高DE值的麦芽糊精与琼脂形成的共混膜,但高DE值的麦芽糊精-琼脂共混膜的透明度较高,并且膜面较为光滑平整。     

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.