Hydrophobic nanocomposites of PBAT with Cl-fn-POSS nanofiller as compostable food packaging films

Antibacterial nanocomposite films of poly(butylene adipate-co-terephthalate) (PBAT) incorporated with different weight percentage of octakis(3-chloropropyl)octasilsesquioxane (chloropropyl functionalized POSS [Cl-fn-POSS]) nanofiller were prepared. The mechanical, thermal, morphological, barrier, and antimicrobial properties were examined. The mechanical properties of the nanocomposite films were enhanced by the addition of Cl-fn-POSS nanofiller. An optimum filler loading of 3 wt% is identified to be best suited for maximum enhancement in tensile strength (24 MPa for 3 wt% filled PBAT vs 11 MPa for neat PBAT) while a 1 wt% filler loading was adequate to double the tensile strength. The barrier properties (WVTR and oxygen transmission rate) of PBAT was improved by the presence of Cl-fn-POSS. A volume of 3 wt% filler loading results in 50% reduction of water permeation and 10% reduction in oxygen transmission. The thermogravimetric analyses of the nanocomposites indicated that the filler enabled the enhancement of thermal stability of PBAT. The nanocomposite films revealed antimicrobial activity with this activity increasing with increasing filler content. PBAT is compostable under suitable conditions and with a low weight percentage of filler that is largely made of silicon dioxide these nanocomposite films can find application as biodegradable food packaging material given their flexibility.     

Effects of plasticization conditions on the structures and properties of cellulose packaging films from ionic liquid [BMIM]Cl

By using natural softwood pulp with higher degree of polymerization (DP = 1460) as cellulose source, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid as solvent and glycerol as plasticizer, a novel cellulose packaging film was prepared. The effects of plasticization conditions on the structures, mechanical properties, permeability for oxygen and water vapor were measured by Wide-angle X-ray scattering, thermogravimetric analysis, scanning electron microscopy (SEM), and other techniques. The investigations suggested that the glycerol concentration and plasticizing time had great effect on the properties of the regenerated cellulose films. The crystal transformation of cellulose I to cellulose II occurred during the dissolution and regeneration process, combining with the decrease of thermal stability. The tensile strength decreased rapidly with the addition of glycerol and prolongation of plasticizing time. However, elongation at break of the regenerated cellulose films increased at first and then decreased with increasing of glycerol concentration and plasticizing time. The morphologies for the fracture surface obtained from SEM images showed transformation of typical brittle fracture to plastic deformation with increasing of glycerol concentrations. It was also found that both water vapor permeability and oxygen permeability of the regenerated cellulose films decreased slowly with increasing of glycerol concentrations and plasticizing time, but water vapor permeability and oxygen permeability presented an almost opposite trend. The films prepared by using ionic liquid technology would be used in food packaging or other fields as a kind of green packaging material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermo-mechanical and antioxidant properties of eugenol-loaded carrageenan-cellulose nanofiber films for sustainable packaging applications

This study aimed to investigate the thermomechanical and antioxidant properties of an active film composed of carrageenan and cellulose nanofibers incorporating (0.1%v/v–0.5%v/v) eugenol (Eu), intended for active packaging applications. The mechanical, physical, morphology, and thermal properties of the active film were extensively characterized, and the antioxidant activity was monitored over a 34-day-storage period. Broido's model was employed to assess the thermomechanical properties and activation energy of the films towards the Eu structure in carrageenan and cellulose nanofiber film. The findings revealed that the addition of Eu had a negative impact on the activation energy of the film's decomposition while positively affecting the release of antioxidants during storage. The film containing 0.4% Eu demonstrated optimal physical and mechanical characteristics, including a tensile strength of 38.08 ± 2.06 MPa and elongation at break of 21.95% ± 9.02%. Furthermore, the SGC-0.4% (SGC stand for Semi refined carragenan + Glycerol + Cellulose nanofiber) Eu film exhibited a higher activation energy (365.82 kJ/mol), suggesting enhanced stability and durability compared with other films. The film with 0.4% Eu content showed the highest release rate of polyphenols (614.9290 mg gallic acid/L sample) up to 28 days of storage. Additionally, it exhibited a 58% efficiency of radical scavenging activity. Overall, these results highlight the potential of the SGC-0.4% Eu film as a biodegradable packaging solution that offers prolonged food shelf life.     

PBAT/PLA/cellulose nanocrystals biocomposites compatibilized with polyethylene grafted maleic anhydride (PE-g-MA)

The use of biodegradable polymers has grown exponentially due to their lower environmental impact when compared to conventional polymers. In this sense, biocomposites are an alternative due to their promising properties, maintaining biodegradability. For this purpose, in the present study, a biodegradable biocomposite of PBAT (poly [butylene adipate co-terephthalate]) and PLA (polylactide) blend containing cellulose nanocrystals (CNC) were obtained, using polyethylene grafted with maleic anhydride (PE-g-MA) as a coupling agent. Seven formulations were produced by extrusion and had their structure, morphology, thermal, and rheological properties analyzed. The results showed a significant improvement of adhesion among the components using PE-g-MA as a coupling agent. Moreover, CNC and PE-g-MA increased the PLA crystallinity degree and reduced the complex viscosity. These results are unprecedented in the literature using these compositions and extrusion processing conditions. Therefore, these new insights provide a vast horizon for the use of biodegradable mixtures using PBAT/PLA and CNC.     

不同形貌纳米纤维素对天然橡胶力学性能的影响

将两种纳米纤维素[纤维素纳米丝(CNF)和纤维素纳米晶(CNC)]与天然胶乳通过溶液共混和浇注成膜制备CNF/天然橡胶(NR)和CNC/NR复合材料,考察CNF和CNC对NR的补强效果。结果表明:CNF与CNC对NR都具有补强效果,当二者用量相同时,CNF对NR的补强效果更显著;在成膜过程中,CNC发生沉降,在底部形成CNC富集层;当CNC用量大于5份时,CNC/NR复合材料在拉伸过程中CNC富集层发生滑脱分层;纳米纤维素与NR的极性相差较大,提高二者的相容性和界面结合力需进一步研究。     

Preparation of Spherical Cellulose Nanocrystals from Microcrystalline Cellulose by Mixed Acid Hydrolysis with Different Pretreatment Routes

Spherical cellulose nanocrystal (CNC), as a high value cellulose derivative, shows an excellent application potential in biomedicine, food packaging, energy storage, and many other fields due to its special structure. CNC is usually prepared by the mixed acid hydrolysis method from numerous cellulose raw materials. However, the pretreatment route in preparing spherical CNC from cellulose fiber is still used when choosing microcrystalline cellulose (MCC) as the raw material, which is not rigorous and economical. In this work, pretreatment effects on the properties of spherical CNC produced from MCC by mixed acid hydrolysis were systematically studied. Firstly, the necessity of the swelling process in pretreatment was examined. Secondly, the form effects of pretreated MCC (slurry or powder form) before acid hydrolysis in the preparation of spherical CNC were carefully investigated. The results show that the swelling process is not indispensable. Furthermore, the form of pretreated MCC also has a certain influence on the morphology, crystallinity, and thermal stability of spherical CNC. Thus, spherical CNC with different properties can be economically prepared from MCC by selecting different pretreatment routes through mixed acid hydrolysis.     

Surface properties,thermal, and mechanical characteristics of poly(vinyl alcohol)–starch‐bacterial cellulose composite films

Nanocomposite films for food packaging applications were developed using bacterial cellulose (BC) nanofibers in different amount in a poly(vinyl alcohol)/starch (PVA/St) matrix. In search of a better method to reduce the harmful ingredients in food packaging, the cellulose nanofibers were obtained by the mechanical defibrillation of BC pellicles thus avoiding the addition of chemicals in the final packaging material. Improved mechanical performances were obtained starting from just 1% BC nanofibers in PVA/St. Atomic force microscopy images showed a uniform dispersion of BC nanofibers on the surface of nanocomposites. A twofold increase of both tensile strength and modulus was obtained for 2 wt % BC in the composite. BC nanofibers have greatly improved the barrier properties of PVA/St matrix, a twofold increase of water vapor permeability being obtained for only 2 wt % BC nanofibers in the composite film. PVA/St/2BC was proposed as a high potential material for food packaging applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45800.     

Starch nanocomposite films incorporating grape pomace extract and cellulose nanocrystal

The objectives of this study were to prepare starch nanocomposite films incorporating grape pomace extract (GPE) and cellulose nanocrystal (CNC) using a solvent‐casting method, and to characterize the mechanical properties, color, water vapor transmission rate (WVTR), crystalline structure, morphology, thermal stability, phenolic compound release profile and antibacterial activity of the films. Incorporating CNC and GPE significantly (P < 0.05) increased the films’ thickness, mechanical properties, and opacity. Brightness and color were mainly influenced by GPE level, while CNC had a great impact on the reduction of WVTR values of the film. Three characteristic cellulose I crystalline peaks were observed using X‐ray diffraction in CNC‐containing nanocomposite films. However, the effect of CNC levels on thermal stability was not significant. Phenolic compound releases were time and film dependent, and the nanocomposite films incorporating with GPE and CNC exhibited stronger inhibitory effect against Staphylococcus aureus ATCC 29213 compared to Listeria monocytogenes ATCC 7644. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44438.     

胶原蛋白/海藻酸/羧甲基纤维素共混膜的结构与性能

利用溶液共混法成功制备了新型生物膜材料—胶原蛋白/海藻酸/羧甲基纤维素共混膜(blend film),通过红外光谱、X-射线衍射、原子吸收光谱、扫描电镜对共混膜的结构进行了表征,同时测定了不同配比共混膜的透光率、拉伸强度(tensile strength)、断裂伸长率(breaking elonga-tion)、吸水率和水蒸汽透过率;对共混膜进行了热重和差示量热扫描分析。结果表明:共混膜中胶原蛋白、海藻酸钠和羧甲基纤维素之间具有较强的相互作用和良好的相容性,Ca2+交联、氢键以及静电引力等强烈相互作用使三元共混膜力学性能等得到了显著改善,其拉伸强度明显高于胶原蛋白膜、海藻酸膜和胶原蛋白/海藻酸二元共混膜、海藻酸钠/羧甲基纤维素二元共混膜,胶原蛋白质量分数为18.1%、海藻酸质量分数为45.5%和羧甲基纤维素为36.4%的三元共混膜中抗张强度最大,达102MPa。三元共混膜具有良好的力学性能,较好的热稳定性,作为一种新型生物材料可望在生物医学和食品材料领域得到应用。     

酰胺化纳米晶纤维素提高乙烯-醋酸乙烯酯共聚物薄膜阻透性的研究

合成了三种酰胺化纳米晶纤维素,并采用溶液共混成膜法制备了酰胺化纳米晶纤维素（CNC）/乙烯醋酸乙烯醋共聚物(EVA)复合膜材料。通过紫外-可见分光光度计、电子万能试验机和透湿仪研究了酰胺化CNC/ EVA复合膜的光学性能、力学性能以及水蒸气阻隔性,并通过原子力显微镜研究热压处理的EVA复合膜的表面形貌。结果表明,添加三种不同碳链的酰胺化CNC都使 EVA膜的透光率有所降低,当添加量为5 %时,EVA膜透光率仍高达90%。一定程度的热压能够让酰胺化纳米晶纤维素在EVA基体中分散更均匀,使EVA复合膜的透光率提高了2%～3%;随着纳米晶纤维素含量的逐渐增加,三种酰胺化CNC/EVA膜的拉伸强度均逐渐增强,透湿率（WVTR值）均减小;酰胺化CNC含量相同时, 十六胺改性的纳米晶纤维素(CNC-N16)/EVA复合膜的力学性能和水蒸气阻隔效果优于相应的十二胺和正辛胺。     

Microstructural,Thermal, Crystallization,and Water Absorption Properties of Films Prepared from Never-Dried and Freeze-Dried Cellulose Nanocrystals

In this paper, the microstructural, optical, thermal, crystallization, and water absorption properties of films prepared from never-dried (ND) and freeze-dried (FD) cellulose nanocrystals (CNCs) are reported. Morphology of the ND CNCs reveals a needle-like structure, while after freeze-drying, they show a flake-like morphology. Microstructural analysis of ND and FD CNCs are further studied via small angle X-ray scattering to probe interactions. ND CNCs yield a transparent film with a low surface roughness (14 ± 4 nm), while the FD CNC film evidence a significant reduction of their transparency due to their higher surface roughness (134 ± 20 nm). Although Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy analyses reveal no chemical change occurs during the freeze-drying process, yet a more intense thermal degradation profile is observed for FD CNC film, probably due to the higher oxygen ingress within the gaps created between the stacked flakes. This, in turn, results in a greater loss of crystallinity at a higher temperature (300 °C) compared to the ND CNC film. A rapid decrease in water contact angle of the FD CNC film proves that the morphology of flakes and their orientation within the film has a strong influence in increasing water absorption capacity.     

Enhancement of basic properties of polysaccharide-based composites with organic and inorganic fillers: A review

The global shift towards biodegradable composite has made polysaccharides a green alternative to synthetic polymers owing to their biocompatibility, sustainability, and ecofriendly biomaterials. Despite the limitations in their applications, many studies have validated the effectiveness of using organic or inorganic fillers to ameliorate their mechanical and barrier properties. However, the understanding of how polysaccharides matrix is enhanced by fillers is still inexplicit. Hence, it is imperative to review the effects of using inorganic and organic fillers in some prominent polysaccharides in terms of mechanical and water barrier properties while taking into account the function of filler morphology, size and loading. Although it is intricate to indicate the best filler used for each of the polysaccharides matrices, this review served as a “food for thought” on the established works of enhanced-matrix filler combinations aimed at improving the mechanical and barrier properties of biodegradable films based on neutral or negatively charged polysaccharides-based composite films for potential application in food packaging, agriculture, biomedicine and constructions sector. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47251.     

Nanocellulose-Polymer Composites for Applications in Food Packaging: Current Status,Future Prospects and Challenges

Nanocellulose has potential applications across the several industrial sectors and addresses a lot of issues related to environmental concern. As biodegradable filler in composite manufacturing, coating, and self-standing thin films, it offers novel and promising properties. Very few available reviews report on nanocellulose-impregnated composite materials for food packaging. Nanocellulose reinforcement is found to be promising for mechanical and barrier properties of composite for biopolymer and synthetic polymer. In this paper, we provide a thorough review of recent advances of nanocellulose synthesis and its application as a filler material for production of nanocomposites to be used for food packaging.     

Palmitoylated cellulose nanocrystal/polycarbonate composite with high mechanical performance and good transparency

To fabricate polycarbonate (PC) composites with high mechanical and optical properties, PC composite films reinforced by cellulose nanocrystals esterified using palmitoyl chloride (palmitoylated cellulose nanocrystal [PAL-CNCs]) were fabricated by casting-evaporation and characterized by several techniques. It was shown that the PAL-CNCs with a substitution degree of 0.43 and the crystalline index of 53.3% were better dispersed in chloroform and tetrahydrofuran, and achieved a water contact angle of 81.0°. The crystallite size and crystalline index of the PC in the composite film significantly increased to more than 5.2 nm and 51.5%, respectively, after the incorporation of the PAL-CNCs. The PC composite film had an increase of 91.4% in tensile strength, 84.1% in Young's modulus, and a decrease of 5% in impact strength. Meanwhile, its UV–Vis-light transmittance was above 90%. Therefore, the palmitoylated -CNCs were a better candidate for engineering PC composites with high mechanical performance and transparency.     

Improvement of polyvinyl alcohol/casein blend film properties by adding cellulose nanocrystals

This study aims to prepare and examine the properties of poly(vinyl alcohol)/casein (PVA/CAS) based films reinforced with cellulose nanocrystals (NC), which can be presented as an alternative to petroleum-based polymer packaging materials. PVA/CAS and 0.5–1–3–5 wt% NC containing PVA/CAS biocomposite films were prepared by solution casting method. Afterward, the 1NC film, which exhibited the best mechanical properties, was crosslinked with various amounts of glyoxal. Structural, morphological (polarized optical microscope), mechanical (tensile), thermal (differential scanning calorimetry, thermogravimetric analysis), contact angle, and water vapor transmission rate (WVTR) properties of the samples were investigated. The 1NC film exhibited the highest tensile strength (TS) and elongation values in PVA/CAS/NC films, and its mechanical properties decreased due to agglomeration with increasing NC amount. As expected, crosslinking improved the TS. The thermal stability of the PVA/CAS film was generally improved with the addition of NC and crosslinking. The high WVTR value of the PVA/CAS film decreased with the addition of NC and the 1NC film presented the lowest value. Thanks to the complex structure formed as a result of crosslinking and the reduced free volume, the WVTR of the 1NC film has reduced. The results showed that PVA/CAS-based films with good mechanical properties and water vapor barrier are promising as packaging materials.     

Biodegradable Blown Film Composites from Bioplastic and Talc: Effect of Uniaxial Stretching on Mechanical and Barrier Properties

As public awareness about climate change grows, there is an increase in the research on bioplastic packaging films. This is the first-ever scientific report on uniaxially stretched biobased-polybutylene succinate-co-adipate (BioPBSA) and talc (15 and 25 wt%) based blown film composites at different stretch ratios (SR). The water vapor barrier properties of BioPBSA+25%Talc film at SR 4 shows an improvement of 40% compared to its unstretched counterpart, while an overall improvement of 48% is observed compared to the unstretched BioPBSA film. The successful dispersion of talc in the BioPBSA matrix, the orientation of talc filler during stretching, and the polymer chains orientation are responsible for such improvement. Additionally, XRD analysis shows that during uniaxial stretching, the crystallinity of the films increases by up to 26% as a result of strain-induced crystallization, with BioPBSA+25%Talc at SR 4 having the highest crystallinity (≈75%). Furthermore, the inclusion of 25% talc in BioPBSA considerably enhances the tensile modulus by 246% compared to its unstretched counterpart. Hence biodegradable films with balanced barrier and tensile properties may be promising alternatives to petroleum-based plastic materials used in flexible packaging applications.     

Selected Applications of Chitosan Composites

Chitosan is one of the emerging materials for various applications. The most intensive studies have focused on its use as a biomaterial and for biomedical, cosmetic, and packaging systems. The research on biodegradable food packaging systems over conventional non-biodegradable packaging systems has gained much importance in the last decade. The deacetylation of chitin, a polysaccharide mainly obtained from crustaceans and shrimp shells, yields chitosan. The deacetylation process of chitin leads to the generation of primary amino groups. The functional activity of chitosan is generally owed to this amino group, which imparts inherent antioxidant and antimicrobial activity to the chitosan. Further, since chitosan is a naturally derived polymer, it is biodegradable and safe for human consumption. Food-focused researchers are exploiting the properties of chitosan to develop biodegradable food packaging systems. However, the properties of packaging systems using chitosan can be improved by adding different additives or blending chitosan with other polymers. In this review, we report on the different properties of chitosan that make it suitable for food packaging applications, various methods to develop chitosan-based packaging films, and finally, the applications of chitosan in developing multifunctional food packaging materials. Here we present a short overview of the chitosan-based nanocomposites, beginning with principal properties, selected preparation techniques, and finally, selected current research.     

Beyond waste: Transforming wheat straw into oxygen and UV-resistant cellulose films

Regenerated cellulose membrane is a biomaterial obtained by activating, dissolving, solidifying, and regenerating cellulose powder using solvents of different polarities. It has the characteristics of high oxygen resistance and high strength. However, its low water vapor barrier and single function limit its application. In order to improve the water resistance of regenerated cellulose membranes and endow them with UV resistance, lignin was extracted from waste wheat straw using formic acid method. The extracted formic acid lignin (FAL) was added to the cellulose solution to prepare a series of regenerated lignocellulosic membranes (RC-FAL) with different lignin contents. The results indicate that lignin can not only improve the water vapor barrier, tensile strength, and water resistance of the film, but also enhance the oxygen barrier and UV absorption of the film. Compared with pure cellulose film, the contact angle of lignocellulose film can be increased by 66.2%, the UV absorption rate can reach 100%, and the oxygen transmission coefficient has no significant effect. In this paper, a new kind of biological packaging material with high oxygen resistance, strong ultraviolet absorption, and water resistance was prepared by recycling waste wheat straw, it has a broad application prospect in the industrial production of packaging materials.     

Full Bio-Based Soy Protein Isolate Film Enhanced by Chicken Feather Keratin

Soy protein isolate (SPI) film is considered a promising biomaterial for the replacement of petroleum-based food packaging plastics. However, current SPI films are still replying on petroleum-based crosslink agents. In this paper, a green and effective approach is developed to prepare a full biomass-based sustainable film with high strength and toughness by incorporating feather keratin (FK, extracted from the waste chicken feathers) into the SPI via the reaction of disulfide bonds. The broken disulfide bonds in FK are recombined with the sulfhydryl group on the SPI molecular chains to form a cross-linked network. Compared to the SPI film, the tensile strength of the SPI/FK composite film is increased by 242% to 8.2 MPa and the toughness is increased by 152% to 9.18 MJ m⁻³. The thermal stability and the water resistance of the SPI/FK composite films are also improved. The replacement rate of FK-modified SPI is up to 40%. Since the film is 100% made from bio-based materials, it would be biodegradable. This research provides a green and economic approach to improve the performance of protein-based food packaging films by introducing FK as an enhancer and constructing disulfide bonds cross-linked network structure in the protein system.     

Evaluation of Structural Properties of Cellulose Ether-Corn Starch Based Biodegradable Films

The object of this study was to investigate the physicochemical interactions between starch and cellulose ethers when they were blended to obtain biodegradable films. Fourier transform infrared spectroscopy results revealed the hydrogen bond formation between polymer chains and/or plasticizer molecules and hence good compatibility of the film constituents. X-ray diffraction (XRD) patterns indicated that cellulose ethers could be used to increase the strength and stiffness of the starch films due to their improvement on crystallinity. Simultaneous evaluation of XRD and optical microscopy results revealed that methylcellulose films had three-dimensional ordered crystalline structure and starch and carboxymethylcellulose films showed randomly distributed small crystallites and amorphous regions.