Review: Nanocomposites in Food Packaging

ABSTRACT:  The development of nanocomposites is a new strategy to improve physical properties of polymers, including mechanical strength, thermal stability, and gas barrier properties. The most promising nanoscale size fillers are montmorillonite and kaolinite clays. Graphite nanoplates are currently under study. In food packaging, a major emphasis is on the development of high barrier properties against the migration of oxygen, carbon dioxide, flavor compounds, and water vapor. Decreasing water vapor permeability is a critical issue in the development of biopolymers as sustainable packaging materials. The nanoscale plate morphology of clays and other fillers promotes the development of gas barrier properties. Several examples are cited. Challenges remain in increasing the compatibility between clays and polymers and reaching complete dispersion of nanoplates. Nanocomposites may advance the utilization of biopolymers in food packaging.     

表面酯化修饰纳米纤维素在聚乳酸复合膜中的应用

本文分别以纳米纤维素和酶促酯化改性后的纳米纤维素为增强材料,以聚乳酸为基质制备了聚乳酸-酯化纳米纤维素复合膜材料。通过对不同种类复合膜材料的透光性、拉伸性能、透湿率等各项性能指标的测定,对比研究了酯化改性前后纳米纤维素对聚乳酸膜、聚乳酸复合膜性能的影响;并探讨了脂肪酸链长对聚乳酸复合膜性能的影响。研究发现,纳米纤维素对聚乳酸的阻隔性能有一定的增强效果,但其不易分散于聚乳酸中,导致所制备的复合膜机械性能降低,膜表面出现明显的纳米纤维素聚团。经酯化疏水改性后所得到的纳米纤维素能分散良好于有机溶剂中,因而酯化改性对聚乳酸-酯化纳米纤维素复合膜的透明度影响甚小;同时,由于酯化纳米纤维素分散性良好,与聚乳酸具有更强的界面结合力,因此以酯化改性对酯化纳米纤维素-聚乳酸所制备的复合膜材料的机械性能、阻隔性能等较之未改性纳米纤维素-聚乳酸复合膜有了显著提高。这种新型复合膜可作为可降解性食品包装材料,在食品化工等领域有着良好的应用前景。     

熔融纺聚乳酸/聚丙烯纤维的制备及其性能

为提高聚乳酸(PLA)纤维的力学性能,采用聚丙烯(PP)与聚乳酸(PLA)通过熔融纺丝制备PLA/PP纤维,并借助差示扫描热量仪、热重分析仪、万能材料测试仪、纤维双折射仪对其热学性能、热稳定性、拉伸性能和纤维取向度进行表征。结果表明:PP的引入对PLA的玻璃化转变温度和熔融温度没有显著影响,但促进了PLA的结晶,结晶度提高了585.9%;随着PP质量分数的增加,PLA的热稳定性降低(特别是在初始分解阶段),但其残炭率提高,同时PLA/PP共混纤维的取向度提高,力学性能得到改善;当PP质量分数为20%时,PLA/PP共混纤维的取向度、断裂强度和断裂伸长率分别提高了55.6%,98.2%和44.4%。     

生物可降解聚（3-羟基丁酸-co-3-羟基戊酸共聚酯）/聚乳酸共混物的相容性和结晶性

针对聚（3-羟基丁酸-co-3-羟基戊酸共聚酯）（PHBV）热稳定性差、易分解的问题,通过与聚乳酸（PLA）采用熔融共混的方法制备了不同混合比例的的PHBV/PLA共混物,借助差示扫描量热仪、热重分析仪、动态热机械分析仪和X射线衍射仪研究了PHBV/PLA共混物的相容性、热学性能和结晶性等,并用热台偏光显微镜观察了PHBV/PLA共混物的动态热结晶过程。结果表明：PHBV/PLA共混物呈现分离的熔融温度和玻璃化转变温度,X射线衍射曲线上没有出现新的衍射峰,说明PHBV和PLA的相容性较差;PLA的加入提高了PHBV的热稳定性能,拓宽了PHBV的熔融加工窗口;随着共混物中PLA比例的增加,共混物的结晶相由“海-岛”相逐渐变成两聚合物分别连续成相。     

Effect of PLA lamination on performance characteristics of agar/κ-carrageenan/clay bio-nanocomposite film

Multilayer films composed of PLA and agar/κ-carrageenan/clay (Cloisite® Na⁺) nanocomposite films were prepared, and the effect of lamination of PLA layers on the performance properties such as optical, mechanical, gas barrier, water resistance, and thermal stability properties was determined. The tensile strength (TS) of the agar/κ-carrageenan/clay nanocomposite films (67.8 ± 2.1 MPa) was greater than that of PLA films (43.3 ± 3.6 MPa), and the water vapor permeability (WVP), water uptake ratio (WUR), and water solubility (WS) of the nanocomposite films were higher than those of PLA films. The film properties of the multilayer films exhibited better properties of the component film layers. Especially, the WVP and water resistance of the bionanocomposite film were improved significantly, while the OTR of the PLA film decreased profoundly after lamination with PLA layers. Thermal stability of the bionanocomposite also increased after lamination with PLA layers.     

高抗菌性聚乙烯醇/Ag@MOF食品包装膜的制备与表征

为分析银基金属有机框架(Ag@MOF)用于食品包装的可行性,采用流延法制备四种不同的聚乙烯醇(PVA)基食品包装膜(PVA/Ag@MOF、PVA/H₂PYDC、PVA/Ag、PVA),并研究它们的力学性能、热力学性能、水阻隔性、抗菌性、细胞毒性等。结果表明,与PVA、PVA/H₂PYDC膜相比,Ag@MOF的加入改善了薄膜的力学性能,使薄膜最大拉伸强度提高到36.21 MPa。与PVA、PVA/H₂PYDC、PVA/AgNPs膜相比,Ag@MOF的加入增强了膜的热稳定性。与PVA、PVA/H₂PYDC膜相比,AgNPs和Ag@MOF的刚性结构防止了水的扩散,提高了阻水性能。PVA/Ag@MOF膜对金黄色葡萄球菌和大肠杆菌的抗菌活性也很好,其抗菌活性远大于AgNPs和H₂PYDC复合膜,且具有较低的细胞毒性。因此,PVA/Ag@MOF薄膜是一种很有前景的食品包装材料,可以减少环境微生物对食品的干扰且细胞毒性较低,能够有效提高食品的安全性和储存周期。     

聚乳酸纺黏非织造布的性能测试和分析

为了探寻聚乳酸(PLA)纺黏非织造布的应用性能,对其力学、透气、透湿等6项性能进行测试。结果表明:PLA纺黏非织造布的断裂强度低于聚酯(PET)和聚丙烯(PP)(100%新料)纺黏非织造布;其透气性大于PET,但小于PP纺黏非织造布;PLA纺黏非织造布(60 g/m2)的透湿量为4 371.43 g/(m2·d),具有极好的透湿性;PLA纺黏非织造布的p H值为6.086,呈弱酸性,且具有一定的疏水性;PLA纺黏非织造布的耐热稳定性接近于PP纺黏非织造布。     

包装材料对贮藏期荔枝汁品质及非酶褐变的影响

研究了聚酯(PET)瓶、聚乳酸(PLA)瓶和聚酯/铝箔/聚乙烯(PET/Al/PE)复合袋装荔枝汁在25℃避光贮藏时的品质变化和非酶褐变情况,采用偏最小二乘法回归(PLSR)分析包装材料对荔枝汁非酶褐变的影响。结果表明:贮藏过程,PLA瓶装荔枝汁的L-抗坏血酸(L-AA)发生快速降解,PET瓶和复合袋中的L-AA降解缓慢;贮藏初期,溶解氧浓度(DOC)均急剧下降,贮藏后期,除PLA瓶中的DOC快速上升外,其它包装材料中的DOC均平缓下降并趋于稳定。包装材料阻隔性能对L-AA含量和DOC有显著(p<0.05)影响。蔗糖不断水解,果糖和葡萄糖含量在贮藏初期快速地增加,然后缓慢下降。氨基酸总量和总酚含量不断下降。可溶性固形物(TSS)含量缓慢上升,pH缓慢下降。5-HMF含量和褐变指数不断上升。包装材料阻隔性能使得荔枝汁中的溶解氧浓度差异,溶解氧能引起L-AA的降解和酚类物质氧化聚合,导致荔枝汁发生非酶褐变。     

Preparation and Characterization of Composites Based on Polylactic Acid and Beeswax with Improved Water Vapor Barrier Properties

Beeswax and a plasticizer (ATBC) were added to polylactic acid (PLA) films in order to enhance the water vapor barrier properties of the films. Beeswax improved the barrier properties; the water vapor permeability in the composite containing 1% beeswax was 58% lower than that of the neat PLA. Fourier transform infrared spectroscopy and X‐ray diffraction analysis revealed that the incorporation of beeswax and ATBC had so little effect on the PLA structure. In addition, the structure of PLA did not vary substantially with the additions. The surfaces of the composites were examined by using field emission scanning electron microscopy. Differential scanning calorimetry results showed that the degree of crystallinity of the PLA films increased with the addition of beeswax and ATBC. However, the tensile strength and elongation at break of the composites containing beeswax were up to approximately 50% lower than those of the neat PLA. Although further study is needed to improve the mechanical properties, the aforementioned results showed that the PLA barrier properties can be improved by the incorporation of a small amount of beeswax and ATBC.     

聚乳酸/乙酰化纳米纤维素薄膜制备及性能研究

为改善聚乳酸(PLA)薄膜的力学及阻隔性能,采用纳米纤维素(NCC)对其进行改性。以微晶纤维素(MCC)为原料,用硫酸法制备NCC,进而制备乙酰化纳米纤维素(ANCC),然后将PLA与ANCC按不同比例混合后制备复合薄膜。采用透射电子显微镜(TEM)、傅里叶红外光谱仪(FTIR)、扫描电子显微镜(SEM)对其微观结构和形态进行观测。采用拉伸仪和氧气透过率仪对其力学和气体阻隔性能进行分析。结果表明,使用酸法制备的纳米纤维素长度为100~200 nm,直径范围为10~20 nm。乙酰化处理对纳米纤维素的外观形态没有明显改变。与纯聚乳酸膜相比,ANCC添加量为1%时制备的复合薄膜的拉伸强度增加了29.09%,进一步增加ANCC含量则会导致复合薄膜力学性能下降。添加ANCC有效降低了复合薄膜的氧气透过量,ANCC添加量为0.5%时,薄膜的氧气透过率与纯PLA薄膜相比降低42%。添加ANCC对于薄膜的透光率和雾度没有明显影响。      

GEO添加量对PLA/GEO复合膜性能及双孢蘑菇保鲜效果的影响

本文研究了不同浓度（0%、5%、7.5%、10%和12.5%）的葡萄柚精油（GEO）对聚乳酸(PLA)/葡萄柚精油复合膜的热性能,结构性能,机械性能,气体阻隔性能和抗菌性能等方面的影响。GEO通过减少聚合物链段的分子间作用力,从而改善复合膜的柔韧性,对复合膜起到一定的增塑作用。GEO的添加降低了PLA相的结晶性。随着GEO浓度的增加,复合膜的水蒸汽阻隔性能显著降低。但是,复合膜的抗菌活性因GEO的加入得以提高。将聚乳酸/葡萄柚精油复合膜应用于双孢蘑菇保鲜。结果表明,聚乳酸/葡萄柚精油复合膜与纯聚乳酸膜、低密度聚乙烯膜相比较,更能有效地保持蘑菇的硬度,阻止微生物生长,维持较好的总体接受度。因此,聚乳酸/葡萄柚精油复合膜可作为一种有效的包装材料,用于延长双孢蘑菇的货架期。     

Effect of Type and Content of Modified Montmorillonite on the Structure and Properties of Bio-Nanocomposite Films Based on Soy Protein Isolate and Montmorillonite

Abstract: The nonbiodegradable and nonrenewable nature of plastic packaging has led to a renewed interest in packaging materials based on bio-nanocomposites (biopolymer matrix reinforced with nanoparticles such as layered silicates). Bio-nanocomposite films based on soy protein isolate (SPI) and modified montmorillonite (MMT) were prepared using melt extrusion. The effect of different type (Cloisite 20A and Cloisite 30B) and content (0% to 15%) of modified MMT on the structure (degree of intercalation and exfoliation) and properties (color, mechanical, dynamic mechanical, thermal stability, and water vapor permeability) of SPI-MMT bio-nanocomposite films were investigated. Extrusion of SPI and modified MMTs resulted in bio-nanocomposites with exfoliated structures at lower MMT content (5%). At higher MMT content (15%), the structure of bio-nanocomposites ranged from intercalated for Cloisite 20A to disordered intercalated for Cloisite 30B. At an MMT content of 5%, bio-nanocomposite films based on modified MMTs (Cloisite 20A and Cloisite 30B) had better mechanical (tensile strength and percent elongation at break), dynamic mechanical (glass transition temperature and storage modulus), and water barrier properties as compared to those based on natural MMT (Cloisite Na⁺). Bio-nanocomposite films based on 10% Cloisite 30B had mechanical properties comparable to those of some of the plastics that are currently used in food packaging applications. However, much higher WVP values of these films as compared to those of existing plastics might limit the application of these films to packaging of high moisture foods such as fresh fruits and vegetables.     

Mechanical and barrier properties of biodegradable soy protein isolate-based films coated with polylactic acid

Polylactic acid (PLA)-coated soy protein isolate (SPI) films were prepared by dipping SPI film into PLA solution. The effects of coating on improvements in mechanical and water barrier properties of the film were tested by measuring selected film properties such as tensile strength (TS), elongation at break (E), water vapor permeability (WVP), and water solubility (WS). TS of SPI films increased from 2.8±0.3 up to 17.4±2.1 MPa, depending on the PLA concentration of the coating solution, without sacrificing the film's extensibility. In contrast, the extensibility of SPI film coated with solution containing more than 2 g PLA/100 ml solvent, increased. WVP of PLA-coated SPI films decreased from 20 to 60 fold, depending on the concentration of PLA coating solution. Water resistance of SPI films was greatly improved as demonstrated by the dramatic decrease in WS for PLA-coated films. The improvement in water barrier properties was mainly attributed to the hydrophobicity of PLA.     

Effect of High-Pressure Food Processing on the Physical Properties of Synthetic and Biopolymer Films

ABSTRACT:  The effect of high-pressure processing on 2 plastic food packaging films, a biopolymer (PLASiOx/PLA) and a synthetic polymer (PET-AlOx), was studied. Samples in direct contact with olive oil, as a fatty food simulant, and distilled water, as an aqueous simulant, were subjected to a pressure of 500MPa for 15 min at 50 °C. The mechanical, thermal, and gas barrier properties of both films were evaluated after the high-pressure processing (HPP) and compared to control samples that have not undergone this treatment. Significant changes in all properties were observed in both films after the HPP treatment and in contact with the food simulants. In both films an induced crystallization was noticed. In the PLASiOx/PLA film the changes were larger when in contact with water that probably acted as a plasticizer. In the PET-AlOx film the changes in properties were attributed to the formation of pinholes and cracks during the HPP treatment. In this film, most of the properties changed more in the presence of oil as the food simulant.     

Improving packaged food quality and safety. Part 2: Nanocomposites

This paper gathers a number of significant results where nanotechnology was satisfactorily applied to improve packaged food quality and safety by increasing the barrier properties to oxygen of an ethylene-vinyl alcohol copolymer (EVOH) in dry and under humid conditions and of a poly(lactic acid) (PLA) biopolymer. The nanodispersion in the polymer matrix of modified monolayers of clays included in positive lists for food-contact applications is an adequate methodology to increase packaged food shelf-life. In spite of the fact that, in principle, there is no reason to believe that 'adequately' modified nanocomposites making use of substances in positive lists can impose any immediate risk threat for food-contact applications, further studies concerning potential migration issues and life-cycle analysis have to still emerge within the overall field of nanotechnology to corroborate the fact.     

表面接枝聚乙烯吡咯烷酮的聚乳酸纤维改性

针对聚乳酸（PLA）纤维的强疏水性,对聚乳酸纤维表面接枝聚乙烯吡咯烷酮进行研究。通过万能强力仪、红外光谱仪,扫描电子显微镜对改性聚乳酸纤维进行力学性能和结构的表征,并对纤维水解质量减少率、改性纤维吸水率和接枝率进行测定。结果显示,碱水解和酸水解之后的PLA纤维均成功地接枝聚乙烯吡咯烷酮（PVP）;但是碱水解的聚乳酸纤维接枝PVP的接枝率低于酸水解的聚乳酸纤维;2种接枝PVP的聚乳酸纤维吸水率明显提高,分别是未改性聚乳酸纤维吸水率6.44倍和8.97倍,但是接枝的聚乳酸纤维的力学性能均下降。     

Development of multifunctional cotton fabric using atmospheric pressure plasma and nano-finishing

The possibility of using atmospheric pressure dielectric barrier discharge plasma treatment for textile surface activation to facilitate deposition of nano TiO₂/SiO₂ onto cotton fabric is investigated. It is aimed to develop a multifunctional cotton textile using plasma and nanotechnology. The treated fabric is evaluated through measuring the ultraviolet protection factor, antimicrobial activity, and flame retardancy as functional finishes. Surface morphology (Scanning electron microscopy, SEM), thermogravimetric analysis, and mechanical properties were also studied. SEM shows deposition of nanoparticles onto the fabric. He–O₂ plasma pretreatment improves the flame retardancy, antibacterial activity, and thermal stability of the samples were compared with the untreated samples.     

聚乳酸纤维耐热收缩改性增塑剂的选择

在聚乳酸纤维耐热改性的前期研究中增塑剂的种类及用量是非常重要的,以PEG聚乙二醇4000、PEG2000、PEG600、柠檬酸三丁酯作为增塑剂,对聚乳酸纤维进行增塑改性;用综合热分析仪对改性PLA的热性能进行了表征,讨论了不同增塑剂及其用量对改性PLA性能的影响。使用适当剂量的增塑剂,聚乳酸纤维的强度下降很少,伸长率明显增加。柠檬酸三丁酯用量为10%时增塑效果较好。     

PEG/SiC对PLA材料改性研究及其在加热卷烟中的应用

  目的  加热卷烟烟支结构较短,入口烟气温度相对传统卷烟较高,需添加降温材料以降低烟气温度。通过对聚乳酸（PLA）材料进行改性处理,以开发出适用于加热卷烟用的降温材料。  方法  采用熔融挤出方法制备聚乙二醇（PEG）/碳化硅（SiC）改性PLA复合材料,利用拉伸机、热重（TG）、差示扫描量热仪（DSC）与加热卷烟吸烟机考察复合材料力学性能、热特性以及对烟气降温效果、关键成分释放的影响。  结果  （1）较纯相PLA而言,添加PEG后复合材料拉伸强度、冲击强度明显下降,熔融指数与断裂延伸率增大,韧性增强;进一步添加SiC后,复合材料断裂延伸率与熔融指数减小。（2）添加PEG后,复合材料起始热分解温度降低,20%添加量下DSC曲线在53.32℃处出现主吸热峰,热焓变化值为48.63 J/g;加入SiC后,该峰热焓变化值减小,主吸热峰转至PLA熔融吸热峰处。（3）逐口烟气温度随PEG含量增加呈明显降低趋势,加入SiC后,复合材料导热系数增大,对烟气降温效果进一步提高;添加改性复合材料后,主流烟气中总粒相物、烟碱、水分、甘油含量降低,CO释放量变化不明显,不同改性样品间各成分释放差异较小。  结论  利用PEG、SiC对PLA进行改性处理,可有效提升对烟气的降温效果。      

大豆蛋白-聚乙烯醇-层状硅酸盐粘土复合薄膜的性能研究

通过溶液流延法制备了大豆蛋白/聚乙烯醇/层状硅酸盐黏土(Laponite RD)共混物薄膜,研究了纳米黏土的添加量对薄膜的热性能、机械性能以及水蒸气阻隔性能的影响。随着Laponite RD的添加,薄膜熔融峰首先向低温方向偏移(0%~10%Laponite RD),然后随着Lapontite RD含量的继续增加,熔融峰又向高温方向偏移。Laponite RD的添加增强了薄膜的水蒸汽阻隔性能,对比不同相对湿度(RH)下的水蒸气透过性(WVP),75%RH下的WVP要高于50%RH下的WVP。随着Laponite RD添加量的增加,拉伸强度和断裂伸长率同样呈现先升后降的趋势。在较高的相对湿度下(75%RH),由于水分子的塑化作用,薄膜的拉伸强度和断裂伸长率相对50%RH下更低。