豌豆淀粉/聚乳酸双层膜的制备与性能表征

采用溶液流延法以豌豆淀粉（PS）和聚乳酸（PLA）为原料制备了豌豆淀粉/聚乳酸（PS/PLA）双层薄膜。通过对双层薄膜的吸水性、溶解性、水蒸气透过性、拉伸性能、表面形貌等进行测试,研究了薄膜的力学性能、疏水性能以及水蒸气阻隔性能。结果表明：随着双层膜中聚乳酸层的比例增加,双层薄膜的吸水性、溶解性和水蒸气透过性逐渐降低,拉伸强度和拉伸模量逐渐增加,断裂伸长率逐渐下降,表明水蒸气阻隔效果明显,增加了膜的韧性,降低了膜的强度。当PLA和PS的质量比为50：50时,PS/PLA双层膜的拉伸强度为（13.47±0.75）MPa,拉伸模量为（0.848±0.002）GPa;断裂伸长率为（16.11±0.16）%,水蒸气透过系数为0.27×10^-10 g·cm/（cm²·s·Pa）。     

Performance of polyethylene/ethylene-vinyl alcohol copolymer/polyethylene multilayer films using maleated polyethylene blends

Blends of linear low density polyethylene (LLDPE) and linear low density polyethylene grafted with maleic anhydride (LLDPE-gMA) were used to promote adhesion between LLDPE and ethylene-vinyl alcohol copolymer (EVOH) in a coextruded three layer flat film, trying to avoid the use of a tie layer. These particular films could be an option when the equipment for a five layer system is not available. The effect of the modified polymer on the surface of cast films was characterized through contact angle measurements. T-peel strength, and oxygen and water vapor transmission rate of the multilayer films were measured as a function of LLDPE-gMA content. Compressed films with 0%, 0.03%, and 0.08% of maleic anhydride (MA) were also analyzed by infrared spectroscopy (FTIR). The increased T-peel strength observed when using MA contents higher than 0.08% suggests a good interfacial adhesion between layers. This increase could be associated with specific interactions between the LLDPE-gMA and the EVOH, as the development of covalent bonds through the reaction of the anhydride with the EVOH hydroxyl groups across the interface. This was proved by the FTIR analysis that showed an increase in the ester band absorbance with an increase on the maleated polymer content and bonding time indicating that a chemical reaction occurred, at the interface. The observed changes on the oxygen and water vapor barrier properties of the films were not significant.     

Gas barrier and wetting properties of whey protein isolate‐based emulsion films

The aim of this research was to investigate the effect of rapeseed oil concentration (1–3% w/w) on the water vapor, oxygen and carbon dioxide permeability, water vapor sorption and surface properties of whey protein isolate emulsion‐based films. The water contact angle as affected by oil content, film side and time was analyzed. The effect of temperature (5 and 25°C) on the water vapor permeability (WVP), water vapor sorption kinetics and diffusion coefficient was also studied. The results showed that the incorporation of a lipid phase to whey protein film‐forming solutions was able to decrease the WVP, water hydrophilicity (increasing water contact angle) and water transfer of whey protein films. However, the films containing oil were more permeable to oxygen and carbon dioxide. Significantly higher values of WVP and diffusion coefficient were obtained at 5°C than at 25°C, indicating that storage temperature should be taken into account when designing the composition of edible films and coatings for food applications. POLYM. ENG. SCI., 59:E375–E383, 2019. © 2018 Society of Plastics Engineers     

Barrier properties and abrasion resistance of biopolymer‐based coatings on biodegradable poly(lactic acid) films

Coated polylactic acid (PLA) films consisting of crosslinked‐chitosan/beeswax layer were prepared to improve barrier properties and abrasion resistance of the base substrate. The effect of crosslinking the chitosan layer on durability and barrier properties of the coatings was investigated. Crosslinked samples exhibited lower degree of swelling compared to uncrosslinked samples and 50% reduction in water vapor transmission rate (WVTR) compared to neat PLA films. The beeswax coating decreased the WVTR of chitosan‐coated PLA films significantly (by 100%). However, it had a marginal effect on the oxygen transmission rate. Water vapor transmission was less affected by abrasion than oxygen transmission for both uncrosslinked and crosslinked samples. The WVTR of crosslinked samples were retained even after being subjected to abrasion, whereas WVTR of uncrosslinked samples dropped by 50%. Results obtained using the Taber test method also show that the weight loss of crosslinked coatings are about 75% less than that of uncrosslinked samples and can withstand a greater number of cycles before rupture. These translucent‐coated films retained good barrier and mechanical properties along with providing improved abrasion resistance after crosslinking. This approach provides exciting new possibilities for expanding the use of biodegradable polymers in packaging applications. POLYM. ENG. SCI., 59:1874–1881, 2019. © 2019 Society of Plastics Engineers     

Packaging‐related properties of alkyd‐coated,wax‐coated,and buffered chitosan and whey protein films

Packaging‐related properties of coated films of chitosan–acetic acid salt and whey protein concentrate (WPC) were studied. Chitosan (84.7% degree of deacetylation) and WPC (65–67% protein) were solution cast to films. These films are potential oxygen barriers for use in packaging. Coatings of wax or alkyds were used to enhance the water‐barrier properties. The packaging‐related properties of chitosan films treated in a buffering solution, with a pH of 7.8, were also investigated. The coated films were characterized with respect to Cobb absorbency, overall migration to water, water vapor transmission rate, and oxygen permeability. The creasability and bending toughness were determined. The wax was a more efficient barrier to liquid water and 90–95% relative humidity than the alkyd. However, the alkyd‐coated material had superior packaging‐converting properties. The alkyd‐coated WPC and chitosan–salt films were readily folded through 180° without any visible cracks or delamination. The overall migration from the alkyd‐coated materials was below the safety limit, provided the coat weight was higher than 7.5 mg/cm² on WPC and 2.1 mg/cm² on chitosan–salt. The barrier properties of chitosan film under moist conditions were improved by the buffer treatment. However, the buffering also resulted in shrinkage of the film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 60–67, 2004     

Characterization of Tri-Phasic Edible Films from Chitosan,Guar Gum,and Whey Protein Isolate Loaded with Plant-Based Antimicrobial Compounds

Essential oil containing tri-phasic films of chitosan, guar gum, and whey protein isolate were prepared. Eugenol, carvacrol, and citral were used as the oil phase, either alone or in combination. The addition of essential oils decreased the water vapor transmission rate and tensile strength of the films. CLSM confirmed the presence of essential oil droplets within the biopolymer matrix. XRD analysis indicated that the addition of essential oils altered biopolymer interactions. FTIR analysis suggested alterations within whey protein structure in the presence of essential oils. The essential oil containing films showed good antimicrobial activity, suggesting potential application in food packaging.     

Effects of graphene oxide on the formation,structure and properties of bionanocomposite films made from wheat gluten with chitosan

Graphene oxide (GO) was combined with wheat gluten (WG) and chitosan (CS) to prepare bionanocomposite films using a casting method. The films were characterized using a variety of techniques, including scanning and transmission electron microscopies, atomic force microscopy, X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, mechanical testing, water swelling, oxygen permeability and contact angle measurements, to determine the effects of GO on the formation, structure and properties of the bionanocomposites. Their formation and properties were found to be dependent on the mixing order of the three components. The added GO was found to strengthen the films, as well as to decrease water absorption and oxygen permeability. These effects were attributed to the good dispersion of GO in the WG/CS matrix enabled by hydrogen bonds. The decreased water absorption could be explained by the increased hydrophobicity. The notable improvement of the properties of the WG/CS films as a result of GO addition makes the films suitable as packaging materials. © 2016 Society of Chemical Industry     

Aging properties and hydrophilicity of maize starch plasticized by hyperbranched poly(citrate glyceride)

Hyperbranched poly(citrate glyceride)s (HBPETs) as plasticizers were mixed with maize starch (S) via cooking and film formation. The structure, aging properties, and hydrophilicity of the plasticized starches were studied by means of Fourier transform infrared spectroscopy, X-ray diffraction, tension testing, contact angle testing, solubility measurements, moisture absorption, and water vapor permeability (WVP). Compared with a glycerol–S plasticized film, the HBPET–S composite films had better mechanical properties in terms of both strength and elongation at break, better aging resistance, less moisture absorption, less WVP, and more hydrophobicity on the film surface. The mechanisms behind the performances resulted from stronger and more stable H bonds between the abundant active end groups of HBPET and hydroxyls of starch and the high branching degree of the HBPETs; this was helpful for effectively inhibiting the recrystallization of starch. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46899.     

Properties and interfacial bonding of regenerated cellulose films coated with polyurethane–chitosan IPN coating

Water-resistant films were prepared by coating a castor oil-based polyurethane–chitosan (PU–CH), in which grafted interpenetrating polymer networks (IPNs) were produced, on a regenerated cellulose (RC) film. The tensile strengths of the coated films cured at 90°C for 5 min reached 853 kg cm⁻² (dry state) and 503 kg cm⁻² (wet state) and were obviously higher than those of the films of uncoated and coated with PU coating. Moreover, the coated films have excellent water resistivity, low vapor permeability, and good size stability, and their optical transmittance is even better than that of the RC film in the range of 400–800 nm. The interfacial structure of the coated films was investigated by using spectroscopy infrared, ultraviolet spectroscopy, transmission electron microscopy, and electron probe microanalysis. It was shown that the strong interfacial bonding with chemical and hydrogen bonds between the RC film and the coating exists. The PU prepolymer in the IPN coating penetrated through the interface into the RC film and partly crosslinked with the cellulose, forming a semi-IPNs. The chitosan in the PU–CH coating plays an important role not only in accelerating the cure of the coating but also in improving the mechanical properties and biodegradability of the coated film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1313–1319, 1998     

Effects of molding surfaces on the wettability of compression-molded polypropene films

Contact angles were measured for a series of compression-molded polypropene films blended with acrylic acid (AA) or maleic anhydride (MAH)/polyethylene oxide (PEO) (1 : 1) additives. The influence of different molding conditions concerning time and temperature as well as a coating of the aluminium foils used for the processing with polyethylene oxide (PEO) or polyvinyl pyrrolidone (PVP) were investigated. Films processed with uncoated aluminium foils showed, with one exception, no influence on contact angles with increasing molding temperatures and longer processing times. Upon coating the aluminium foils with hydrophilic substances the receding contact angles decrease by up to 60° with constant contact angle hysteresis. This behaviour corresponding to a permanent hydrophilization is attributed to chemical reactions of the coating with the functional groups of the additives.     

壳聚糖对玉米淀粉可食膜性能的影响

以玉米淀粉为原料,结合壳聚糖在增塑剂甘油的作用下通过溶液浇铸法制备了玉米淀粉/壳聚糖复合可食薄膜,采用红外光谱和扫描电子显微镜对薄膜结构和微观形貌进行了表征,研究了壳聚糖的含量对薄膜力学性能、水蒸气透过性、阻油性及抗菌性能的影响.结果表明,适量的壳聚糖可以较明显地改善薄膜的力学性能,提高其隔水和阻油性能;壳聚糖与淀粉质...     

Effects of graphene on the behavior of chitosan and starch nanocomposite films

The objective of this study was to prepare chitosan and starch composite films by the addition of 0–3 wt% graphene nanosheets. The film's tensile strength (TS), tensile modulus (TM), elongation at break (E), moisture uptake (Mu), and water vapor transmission rate (WVTR) were investigated. The surface morphology of the composite films was studied using scanning electron microscopy (SEM). Regardless of biopolymer type, both the TS and TM of the composite films first increased and then decreased with graphene loading. Composite film made with native (unmodified) starch showed lower TS and TM than those with chitosan. Composite films exhibit lower E values than pure chitosan and starch; this is attributed to the increase in the hardness of the films. SEM micrographs indicated that, the surface roughness and phase separation increased with increasing graphene content. This is due to the aggregation of graphene nanosheets, leading to the reduced compatibility of biopolymers. The addition of graphene considerably decreased WVTR and Mu of the composite films. These results indicated that graphene is a promising reinforcing agent for biopolymer composite films. POLYM. ENG. SCI., 54:2258–2263, 2014. © 2013 Society of Plastics Engineers     

Performance of multilayer films using maleated linear low-density polyethylene blends

Blends of linear low-density polyethylene (LLDPE) and linear low-density polyethylene grafted maleic anhydride (LLDPE-gMA) were prepared by melt mixing and then coextruded as external layers, with a central layer of polyamide (PA) on three-layer coextruded flat films. Blends with contents of 0% to 55 wt% of maleated LLDPE, on the external layers, were analyzed. The T-peel strength and oxygen and water vapor transmission rate of the films were measured. The surfaces of the peeled films were characterized using attenuated total reflection infrared spectroscopy (FTIR-ATR) and scanning electron microscopy (SEM). The observed increase in T-peel strength of the films with 10% and higher levels of maleated LLDPE in the blend suggests good interfacial adhesion between layers. This sharp increase in peel strength appears to be associated, besides interdiffusion, with specific interactions between polymers, as the bond formation between maleic anhydride and the polyamide end groups by in situ block copolymer formation across the interface. No significant modifications in oxygen barrier properties of the films were observed; however, the use of higher contents of LLDPEgMA, even though it increases the adhesion performance, also increases the water vapor transmission rate by a reduction in the degree of crystallinity.     

塑化剂对玉米醇溶蛋白膜表面及机械性质的影响

研究了塑化剂种类(甘油、油酸和聚乙二醇)、用量对玉米醇溶蛋白(zein)膜表面和机械特性的影响及塑化剂对zein成膜液黏度、成膜后表面形貌、水分吸附特性的影响。结果表明:含油酸的成膜液黏度最大,含甘油的成膜液黏度最小,成膜后表面呈现不同的形貌图;蛋白膜的水分吸附特性与塑化剂亲水性变化趋势一致,随甘油、聚乙二醇和油酸顺序而下降;油酸和聚乙二醇塑化的zein膜的表观接触角随塑化剂含量的增加而增加,甘油膜却呈相反趋势;蛋白膜表面润湿动力学可用指数方程模型表征,动态接触角变化速率表现为甘油膜聚乙二醇膜油酸膜;随塑化剂含量增加,聚乙二醇蛋白膜抗拉强度(TS值)下降,延伸率(EB值)却急剧增加,甘油和油酸蛋白膜的TS值和EB值具有相同的变化趋势但效果不明显。     

Surface and mechanical properties of an organic-inorganic super- hydrophobic coating using modified nano-SiO2 and mixing polyurethane emulsion as raw materials

A series of organic-inorganic super-hydrophobic coatings were prepared using nano-SiO₂ particles modified by fluorine and silicone coupling agents, and a mixing polyurethane emulsion as main raw materials. The mixing polyurethane emulsion was consisted of the polyurethane emulsion end-terminated by double bond (WPUD) and polyurethane emulsion modified by silicone (WPUS). The influence of content of modified nano-SiO₂ particles and the weight ratio of WPUS to WPUD on microstructure and hydrophobicity of the coating surface were studied. The morphologies of coating surface were examined using SEM and AFM, hydrophobicity of the coating was researched by examining static water contact angle and so on. It was found that modified nano-SiO₂ particle was an indispensable factor during the preparation of super-hydrophobic coating. The roughness and hydrophobicity of the coating surface were enhanced obviously with an increase of the content of the modified nano-SiO₂ particles. When the content of the modified nano-SiO₂ particles increased up to 1.5%, the surface of coating possessed good super-hydrophobicity, and static water contact angle reached 169.1°. It was also noticed that the weight ratio of WPUS to WPUD in the base layer has also an important influence on the hydrophobicity and mechanical property of coating surface. With an increase of the ratio of WPUS to WPUD the hydrophobicity of the coating was enhanced, the tensile strength and peel strength reduced, but the elongation at break increased. When the weight ratio of WPUS to WPUD reaches up to 9/100, the static water contact angle reaches the maximum value of 169.1°.     

Effect of starch on thermal,mechanical, and barrier properties of low density polyethylene film

Low‐density polyethylene (LDPE) with different quantities of starch was compounded using a twin screw extruder and blown into films by a Konar K, blow‐film machine. Mechanical properties, namely percent elongation, tensile, bursting, and tear strength, as well as barrier properties, such as water vapor and oxygen transmission rate, of the filled LDPE film were studied. Thermal properties of the films were studied using DSC and DMA. Master curves at reference temperature of 30°C were obtained using software linked to DMA. Incorporation of 1% starch in LDPE has marginally affected the thermal, barrier, and mechanical properties; however, that of 5% starch filled LDPE has affected the properties to a great extent. The mechanical properties, such as percent elongation, tensile, tear, bursting, and seal strength, decreased by 19.2, 33.6, 3.60, 10.8, and 22.12%, respectively. Similarly, water vapor and oxygen transmission rate increased to 32.5 and 18.3%, respectively. Other physical properties, namely migration and thermal properties, were also affected in 5% starch filled LDPE; however, the film can still be used as packaging material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3355–3364, 2006     

Bio‐hybrid nanocomposite coatings from sonicated chitosan and nanoclay

Nanocomposite films and coatings with improved properties were produced from ultrasonic dispersed chitosan and hydrophilic bentonite nanoclay. Bio‐hybrid coatings were applied onto argon–plasma‐activated LDPE coated paper. The intercalation of chitosan in the silicate layers was confirmed by the decrease of diffraction angles as the chitosan/nanoclay ratio increased. Nanocomposite films and multilayer coatings had improved barrier properties against oxygen, water vapor, grease, and UV‐light transmission. Oxygen transmission was significantly reduced under all humidity conditions. In dry conditions, over 99% reduction and at 80% relative humidity almost 75% reduction in oxygen transmission rates was obtained. Hydrophilic chitosan was lacking the capability of preventing water vapor transmission, thus total barrier effect of nanoclay containing films was not more than 15% as compared with pure chitosan. Because to very thin coatings (≤1 μm), nanoclay containing chitosan did not have antimicrobial activity against test strains. All coating raw materials were “generally recognized as safe” (GRAS) and the calculated total migration was in all cases ≤6 mg/dm², thus the coatings met the requirements set by the packaging legislation. Processing of the developed bio‐hybrid nanocomposite coated materials was safe as the amounts of released particles under rubbing conditions were comparable with the particle concentrations in a normal office environment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

取向TS-1分子筛膜的合成与结构引导机理

通过壳聚糖的引导作用, 采用水热法在氧化铝载体上原位合成了b-轴取向的钛硅分子筛(TS-1)膜. 使用XRD、SEM等手段对所合成的TS-1膜进行了表征. 通过漫反射FT-IR和接触角的测定描述了壳聚糖薄膜的表面官能团、壳聚糖薄膜表面与合成液的相互作用. SEM结果表明, 在壳聚糖的引导下可得到b-轴取向的TS-1膜, 而直接在氧化铝载体上只能得到无序的TS-1膜层. XRD的测量结果表现了典型的TS-1结构. 漫反射FT-IR和接触角的测试结果表明, 由于壳聚糖表面官能团的作用, 其表面形成过渡层, 经过成核, 晶核生长得到片状TS-1晶体颗粒, 最后获得多层b-轴取向的TS-1膜.     

Orange peel‐derived pectin jelly and corn starch‐based biocomposite film with layered silicates

Orange peel‐derived pectin jelly/corn starch‐based biocomposite films with and without layered silicates (LSs) were prepared using melt extrusion followed by film die casting. To enhance interfacial compatibility, corn starch and LSs were chemically modified. Regardless of chemical modification or LS weight content, different pectin jelly‐to‐starch weight ratios (63/37, 60/40, 57/43, and 54/46) were considered to formulate the ingredients of biocomposite films in light of Taguchi‐based predictions. X‐ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), scanned electron microscopy (SEM) and transmission electron microscopy (TEM) were systematically used to characterize corn starch, LSs, and biocomposite films. Among all the films considered, pectin jelly/modified (15%) starch‐based biocomposite film (54/46 w/w) containing 0.25 wt % of pristine LSs was found to be the most promising in terms of texture structure and mechanical integrity. Furthermore, creep recovery, hydrophobicity, and water vapor and oxygen gas transmission rates of the most promising biocomposite film were experimentally determined. Based on the findings obtained, the overall performance of the biocomposite film was evaluated and weighed against the overall performance of a low‐density polyethylene film. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40654.     

磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能

以甲苯二异氰酸酯（TDI）、聚乙二醇（PEG）为单体,二羟甲基丙酸（DMPA）和磷-硼杂化预聚物PBHP为扩链剂,通过逐步加聚制备不同组分的含磷、硼元素的阻燃水性聚氨酯（FRWPU）。FRWPU与聚磷酸铵（APP）、季戊四醇（PER）、三聚氰胺（MEL）膨胀阻燃体系复配制备阻燃纸张施胶剂。采用红外光谱（FTIR）、核磁共振波谱（NMR）、热重分析（TGA）、扫描电镜（SEM）、接触角测定、X射线光电子能谱（XPS）和垂直燃烧测试对FRWPU分散体、FRWPU薄膜、未施胶纸样和施胶纸样进行了表征。研究表明,随着PBHP加入量的提高,薄膜的疏水性增强,FRWPU40的接触角为85.4°,较FRWPU0提高了35.3%;同时,薄膜的最大热分解速率下降,800℃的残留质量从0上升到7.80%;施胶纸样的最大热分解速率下降,残留质量提高,平均炭化长度减小。当PBHP含量为50%时,残炭量为27.84%,较FPU0/IFR提高了30.6%;平均炭化长度为5.9cm,较FPU0/IFR降低了30%。SEM结果表明,施胶纸样燃烧后表面生成更加致密的炭层,阻燃性能提高。