The role of nanocellulose fibers, starch and chitosan on multipolysaccharide based films

Thin nanocomposite films of thermoplastic starch, chitosan and cellulose nanofibers (bacterial cellulose or nanofibrillated cellulose) were prepared for the first time by solvent casting of water based suspensions of the three polysaccharides. The role of the different bioploymers on the final properties (thermal stability, transparency, mechanical performance and antimicrobial activity) of the films was related with their intrinsic features, contents and synergic effects resulting from the establishment of interactions between them. Thermoplastic starch displays an important role on the thermal stability of the films because it is the most stable polysaccharide; however it has a negative impact on the mechanical performance and transparency of the films. The addition of chitosan improves considerably the transparency (up to 50 % transmittance for 50 % of chitosan, in respect to the amount of starch), mechanical performance and antimicrobial properties (at least 25 % of chitosan and no more than 10 % of cellulose nanofibers are required to observe bacteriostatic or bactericidal activity) but decrease their thermal stability. The incorporation of cellulose nanofibers had the strongest positive impact on the mechanical properties of the materials (increments of up to 15 and 30 MPa on the Young′s modulus and Tensile strength, respectively, for films with 20 % of BC or NFC). Nonetheless, the impact in thermal stability and mechanical performance of the films, promoted by the addition of chitosan and cellulose nanofibres, respectively, was higher than the expected considering their percentage contents certainly because of the establishment of strong and complex interactions between the three polysaccharides.     

Preparation and Characterization of Modified Cellulose Fiber-Reinforced Polyvinyl Alcohol/Polypyrrolidone Hybrid Film Composites

In this work, cellulose was modified by using 2-(trifluromethyl)benzoylchloride by base catalyzed reaction. Modification of cellulose was confirmed by IR studies. The biodegradable composite films were developed by a film casting method using modified cellulose with poly(vinyl alcohol) and polypyrrolidone in different compositions. Film composites showed good biodegradability. Better barrier and mechanical properties showed by film composites as the percentage of modified cellulose increased. This indicates the importance of modified cellulose as a reinforcing agent. After analyzing these properties of film composites we came to the conclusion that, these biocomposites can be used for membrane and packaging applications.     

Sustainable optically transparent composites based on epoxidized soy-bean oil (ESO) matrix and high contents of bacterial cellulose (BC)

Production of transparent composites from totally renewable resources with extraordinary potential for different applications can be made possible using cellulose. Composites of epoxidized soybean oil (ESO)/bacterial cellulose (BC) nanofibers have been prepared with high fiber content. Due to the nano-order scale network-like structure of BC nanofibers, composite films present high transparency even at high BC content. Transparency of films has been analyzed by UV–visible spectroscopy observing that only 15% of matrix transmittance is lost in the nanocomposites. ESO/BC composites show better mechanical properties with increasing BC content. Composites combine high stiffness and good ductility due to the incorporation of BC network structure in ESO matrix.     

Preparation and characterization of composites from starch with sugarcane bagasse nanofibres

This paper reports on the results of using unbleached sugar cane bagasse nanofibres (average diameter 26.5 nm; aspect ratio 247 assuming a dry fibre density of 1,500 kg/m³) to improve the physico-chemical properties of starch-based films. The addition of bagasse nanofibres (2.5 to 20 wt%) to modified potato starch (i.e. soluble starch) reduced the moisture uptake by up to 17 % at 58 % relative humidity. The film’s tensile strength and Young’s modulus increased by up to 100 % (3.1 to 6.2 MPa) and 300 % (66.3 to 198.3 MPa) respectively with 10 and 20 wt% fibre addition. However, the strain at yield dropped by 50 % for the film containing 10 wt% fibre. Models for composite materials were used to account for the strong interactions between the nanofibres and the starch matrix. The storage and loss moduli as well as the glass transition temperature (T_g) obtained from dynamic mechanical thermal analysis, were increased with the starch-nanofibre films indicating decreased starch chain mobility due to the interacting effect of the nanofibres. Evidence of the existence of strong interactions between the starch matrix and the nanofibres was revealed from detailed Fourier transform infra-red and scanning electron microscopic evaluation.     

Nanocomposite films based on TEMPO-mediated oxidized bacterial cellulose and chitosan

Nanobacterial cellulose (BC) and chitosan (CH) have similar molecular structures. In the present work, nanocomposite films based on BC and CH were prepared by stepwise modification instead of by conventional physical blending. First, surface C6-carboxylated BC was prepared in a bromide-free system using 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO) as a catalyst. The carboxylate groups of oxidised BC could couple to the amine groups of CH. The composite films were characterised by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Carbon-13 solid nuclear magnetic resonance ¹³C NMR. The results showed that a cross-linking reaction occurred between TEMPO-mediated oxidised BC and CH. Even in the absence of cross-linkers, these two biopolymers could interact with each other because of their structural similarity. SEM images and tensile tests showed that the TEMPO-oxidized BC and CH composite film prepared at a 0.5:1 ratio was an exception. The mechanical properties of the composite films decreased with increasing CH content, passed through a minimum, and then increased. To explain this phenomenon, we propose that the hydrogen bonding in the original BC microstructure plays a decisive role in the modified nanocomposites. However, BC/CH composites with excellent properties could be synthesised at appropriate reactant ratios.     

Investigation of cross-linked PVA/starch biocomposites reinforced by cellulose nanofibrils isolated from aspen wood sawdust

In this study, a bio-based composite prepared from cross-linked polyvinyl alcohol/starch/cellulose nanofibril (CNF) was developed for film packaging applications. For this purpose, CNF, as reinforcing phase, was initially isolated from aspen wood sawdust (AWS) using chemo-mechanical treatments, and during these treatments, hydrolysis conditions were optimized by experimental design. Morphological and chemical characterizations of AWS fibers were studied by transmission electron microscopy, scanning electron microscopy, Kappa number, and attenuated total reflectance-Fourier transform infrared spectroscopy, as well as National Renewable Energy Laboratory and ASTM procedures. Morphological images showed that the diameter of the AWS fibers was dramatically decreased during the chemo-mechanical treatments, proving the successful isolation of CNF. Moreover, chemical composition results indicated the successful isolation of cellulose, and Kappa number analysis demonstrated a dramatic reduction in lignin content. Mechanical, morphological, biodegradability, and barrier properties of biocomposites were also investigated to find out the influence of CNF on the prepared biocomposite properties. The mechanical results obtained from tensile analysis revealed that Young’s modulus and ultimate tensile strength of biocomposite films were enhanced with increasing CNF concentration, while a significant decrease was observed in elongation at break at the same concentration of CNF. Furthermore, with adding CNF, barrier properties and resistance to biodegradability were increased in films, whereas film transparency gradually declined.     

Mechanical,thermal and barrier properties of pectin/cellulose nanocrystal nanocomposite films and their effect on the storability of strawberries (Fragaria ananassa)

In this work, two formulations of pectin/cellulose nanocrystals/glycerol nanocomposites were employed as packaging to extend storage life of strawberries. The effects of incorporating cellulose nanocrystals extracted from bleached Kraft wood pulp on the mechanical, thermal, and barrier properties of pectin‐based nanocomposites were evaluated. Nanocomposite films with different filler levels of cellulose nanocrystals (1, 2, 4 and 8% w/w) were prepared by casting. Compared with the neat film of pectin, improvements in the mechanical properties of the nanocomposites were observed, but these films became fragile. To improve the film flexibility, glycerol was added as a plasticizer and then new variations in the mechanical, thermal, and barrier properties of these nanocomposites were evaluated. The effects of nanocomposite films on storability of strawberries were compared with Poly vinyl chloride packaging films. The Poly vinyl chloride film and the nanocomposites showed similar behavior regarding weight loss by the strawberries, especially in the initial days of storage. The results show that pectin/cellulose nanocrystals/glycerol nanocomposites could be considered as a viable packaging alternative for replaced the Poly vinyl cloride film. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface only modification of bacterial cellulose nanofibres with organic acids

Bacterial cellulose (BC) nanofibres were modified only on their surface using an esterification reaction with acetic acid, hexanoic acid or dodecanoic acid. This reaction rendered the extremely hydrophilic surfaces of BC nanofibres hydrophobic. The hydrophobicity of BC increased with increasing carbon chain length of the organic acids used for the esterification reaction. Streaming (zeta-) potential measurements showed a slight shift in the isoelectric point and a decrease in ζ_plateau was also observed after the esterification reactions. This was attributed to the loss of acidic functional groups and increase in hydrophobicity due to esterification of BC with organic acids. A method based on hydrogen/deuterium exchange was developed to evaluate the availability of surface hydroxyl groups of neat and modified BC. The thermal degradation temperature of modified BC sheets decreased with increasing carbon chain length of the organic acids used. This is thought to be a direct result of the esterification reaction, which significantly reduces the packing efficiency of the nanofibres because of a reduction in the number of effective hydrogen bonds between them.     

Recyclable and transparent bacterial cellulose/hemiaminal dynamic covalent network polymer nanocomposite films

Recyclable and transparent nanocomposite films based on bacterial cellulose (BC) and hemiaminal dynamic covalent network polymer (HDCN) have been synthesized by in situ polymerization of 4,4′-diaminodiphenyl ether (ODA) with paraformaldehyde. Transparency and structural and mechanical properties of such nanocomposite films are investigated. It was found that BC/HDCN nanocomposite films exhibits a high optical transparency (86 % at 550 nm). Scanning electron microscopy reveals excellent compatibility of the reinforcement of BC nanofibers and HDCN matrix, which leads to the improvement of 20 and 200 % in tensile strength and storage modulus, respectively, as compared to neat HDCN films. BC hydrogels are readily recoverable from nanocomposite films by the sulphuric acid treatment and ODA monomer is deposited and also recycled.     

Roles of xyloglucan and pectin on the mechanical properties of bacterial cellulose composite films

Xyloglucan and pectin are major non-cellulosic components of most primary plant cell walls. It is believed that xyloglucan and perhaps pectin are functioning as tethers between cellulose microfibrils in the cell walls. In order to understand the role of xyloglucan and pectin in cell wall mechanical properties, model cell wall composites created using Gluconacetobacter xylinus cellulose or cellulose nanowhiskers (CNWs) derived there from with different amounts of xyloglucan and/or pectin have been prepared and measured under extension conditions. Compared with pure CNW films, CNW composites with lower amounts of xyloglucan or pectin did not show significant differences in mechanical behavior. Only when the additives were as high as 60 %, the films exhibited a slightly lower Young’s modulus. However, when cultured with xyloglucan or pectin, the bacterial cellulose (BC) composites produced by G. xylinus showed much lower modulus compared with that of the pure BC films. Xyloglucan was able to further reduce the modulus and extensibility of the film compared to that of pectin. It is proposed that surface coating or tethering of xyloglucan or pectin of cellulose microfibrils does not alone affect the mechanical properties of cell wall materials. The implication from this work is that xyloglucan or pectin alters the mechanical properties of cellulose networks during rather than after the cellulose biosynthesis process, which impacts the nature of the connection between these compounds.     

Bacterial cellulose films with controlled microstructure–mechanical property relationships

Bacterial cellulose (BC) films with different porosities have been developed in order to obtain improved mechanical properties. After 13 days of incubation of Gluconobacter xylinum bacteria in static culture, BC pellicles have been set. BC films have been compression molded after water dispersion of BC pellicles and filtration by applying different pressures (10, 50, and 100 MPa) to obtain films with different porosities. Tensile behavior has been analyzed in order to discuss the microstructure–property relationships. Compression pressure has been found as an important parameter to control the final mechanical properties of BC films where slightly enhanced tensile strength and deformation at break are obtained increasing mold compression pressure, while modulus also increases following a nearly linear dependence upon film porosity. This behavior is related to the higher densification by increasing mold compression pressure that reduces the interfibrillar space, thus increasing the possibility of interfibrillar bonding zones. Network theories have been applied to relate film elastic properties with individual nanofiber properties.     

Improving the mechanical properties of CNF films by NMMO partial dissolution with hot calender activation

Reinforcing of cellulose nanofibril (CNF) films by partial dissolution with N-methylmorpholine-N-oxide (NMMO) was investigated. The method investigated is composed of impregnation of CNF film with liquid solution of NMMO followed by dry heat activation. The heat activation of the impregnated film was carried out using a heated calendering nip, which enabled simultaneous heating and compression. The partial dissolution of cellulose by NMMO caused a significant increase in the transparency of CNF film due to the decrease of film porosity and increased surface smoothness. The dry strength of the reinforced film was increased from 122 up to 195 MPa. Furthermore, the wet strength of the reinforced film was up to 70% greater than the dry strength of pure CNF film. The changes in the fibrillar structure were investigated with topographical imaging (SEM and AFM) and spectroscopically using NMR and FTIR. No significant changes in the fibril structure or cellulose morphology were observed. Moreover, the treated film resisted significant water pressure, highlighting CNF film’s permanent water resistance. The partial dissolution process with NMMO was also capable of reinforcing a CNF composite film with macro scale structural elements (lyocell short-cut fibres). The strategy investigated is a robust and fast method to improve the mechanical properties of fibrillary cellulose films, allowing them utilization in applications where improved water resistance and fully cellulosic character are required properties.     

碳纳米管/聚乙烯复合材料薄膜紫外线透过性能的研究

阳光中的紫外线是引起高分子材料老化的最主要因素,高分子材料被紫外线照射后发生一系列的光化学反应,导致材料变色、变脆、透明度下降和力学性能降低,缩短了其使用寿命,长期以来,围绕紫外光对高分子材料老化作用的问题,科学工作者进行了广泛的观测和研究。结果表明,在高     

Cationic wood cellulose films with high strength and bacterial anti-adhesive properties

In this work, periodate oxidized birch wood pulp and microfibrillated cellulose (MFC) were cationized using Girard’s reagent T or aminoguanidine. Cationic celluloses were used to obtain films via solvent-casting method, and the effects of the cationization route and the cellulose fiber source on the properties of the films were studied. Thermal and optical properties of the films were measured using differential scanning calorimetry and UV–Vis spectrometry, and the morphology of the films was examined using an optical microscope and a field emission scanning electron microscope. Bacterial anti-adhesive properties of the films were also studied using a modified leaf print method and against Staphylococcus aureus and Escherichia coli. Both cationizing agents exhibited similar reactivity with periodate oxidized celluloses, however, MFC had significantly higher reactivity compared to birch pulp. The films with high tensile strength (39.1–45.3 MPa) and modulus (3.5–7.3 GPa) were obtained from cationized birch pulp, aminoguanidine modification producing a film with slightly better mechanical properties. Modulus of the films was significantly increased (up to 14.0 GPa) when MFC was used as a cellulose fiber source. Compared to the unmodified MFC films, the cationic MFC films were less porous and significantly more transparent; however, they had slightly lower tensile strength values. It was found that aminoguanidine modified celluloses had no culturable bacteria on its surface and also exhibited resistance to microbial degradation, whereas there were culturable bacteria on the surface of Girard’s reagent modified films and they were partially degraded by the bacteria.     

Comparison of hydroxypropyl and carboxymethyl guar for the preparation of nanocellulose composite films

The gas barrier and mechanical properties are crucial parameters for packaging materials, and they are highly correlated to the molecular interactions in the polymer matrix. To improve these properties of TEMPO-oxidized cellulose nanofibers (TOCNs) composite films, we studied the effect using hydroxypropyl guar (HPG) or carboxymethyl guar (CMG) in the preparation of TOCN composite films, which were made by following the solution-casting method. The subsequent film characterizations were carried out by UV–Vis spectra, scanning electron microscopy, oxygen and water vapor permeability measurements, tensile and thermogravimetric analyses. SEM results showed that CMG-based films had denser structures than their HPG counterparts. Moreover, the improved hydrogen bonding of the CMG-based films was partially responsible for the improved gas barrier performance, tensile strength and thermal stability. These results support the conclusion that CMG had advantages over HPG when used in the preparation of TOCNs packaging composite films.     

Development and thermal behaviour of ternary PLA matrix composites

Biodegradable PLA composites were prepared using microcrystalline cellulose (MCC) and silver (Ag) nanoparticles. The main objective of the present study is to develop new biopolymer composites with good mechanical properties, thermal stability, maintaining the optical transparency and also providing antimicrobial properties through silver nanoparticle introduction. Composites were prepared with 1%wt of Ag nanoparticles and 5%wt of MCC using a twin-screw microextruder; film parameters were optimized in order to obtain a thickness range between 20 and 60 μm.PLA composites maintained optical transparency properties of the matrix, while MCC was able to reduce polymer permeability. Thermal analysis revealed that MCC increased PLA crystallinity and the mechanical properties of the composites demonstrated that tensile modulus was improved by microcrystalline cellulose.     

Surface modified graphene oxide/poly(vinyl alcohol) composite for enhanced hydrogen gas barrier film

A series of novel polyethyleneimine (PEI) modified graphene oxide (PEI-mGO) filled poly(vinyl alcohol) (PVA) nanocomposite (PEI-mGO/PVA) films were prepared by solution-casing for hydrogen gas barrier applications. Hydrophilic PEI was used to simultaneously reduce and modify graphene oxide sheets, thereby facilitating a homogeneous dispersion of PEI-mGO in the PVA matrix. The effects of PEI-mGO on the morphology and properties of the nanocomposite films were examined by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and field emission scanning electron microscopy. Analogous GO/PVA composites were also prepared and characterized for comparative purposes. The PEI-mGO/PVA nanocomposites showed higher thermal and mechanical stability as well as remarkable improvement in hydrogen gas barrier properties compared to the PVA film; specifically, the PEI-mGO/PVA film having 3.0 wt% of PEI-mGO content exhibited almost 95% decrease in GTR and permeability values compared to PVA film.     

Susceptibility of never-dried and freeze-dried bacterial cellulose towards esterification with organic acid

The susceptibility of (1) never-dried and (2) freeze-dried bacterial cellulose (BC) towards organic acid esterification is reported in this work. When never-dried BC (BC which was solvent exchanged from water through methanol into pyridine) was modified with hexanoic acid, it was found that the degree of substitution (DS) was significantly lower than that of hexanoic acid modified freeze-dried BC. The crystallinity of freeze-dried BC hexanoate was found to be significantly lower compared to neat BC and never-dried BC hexanoate. This result, along with the high DS indicates that significant bulk modification occurred during the esterification of freeze-dried BC. Such results were not observed for never-dried BC hexanoate. All these evidence point towards to fact that freeze-dried BC was more susceptible to organic acid esterification compared to never-dried BC. A few hypotheses were explored to explain the observed behaviour and further investigated to elucidate our observation; the effect of residual water in cellulose, the accessibility of hydroxyl groups and the crystal structure of never-dried and freeze-dried BC on the susceptibility of cellulose fibrils to esterification, respectively. However, the investigation of these hypotheses raised more questions and we are still left with the main question; why do BC nanofibres behave differently when modifying freeze-dried BC or never-dried BC?     

Comparison of nano- and microfibrillated cellulose films

Nanocellulose is an interesting building block for functional materials and has gained considerable interest due to its mechanical robustness, large surface area and biodegradability. It can be formed into various structures such as solids, films and gels such as hydrogels and aerogels and combined with polymers or other materials to form composites. Mechanical, optical and barrier properties of nanofibrillated cellulose (NFC) and microfibrillated cellulose (MFC) films were studied in order to understand their potential for packaging and functional printing applications. Impact of raw material choice and nanocellulose production process on these properties was evaluated. MFC and NFC were produced following two different routes. NFC was produced using a chemical pretreatment followed by a high pressure homogenization, whereas MFC was produced using a mechanical treatment only. TEMPO-mediated oxidation followed by one step of high pressure (2,000 bar) homogenization seems to produce a similar type of NFC from both hardwood and softwood. NFC films showed superior mechanical and optical properties compared with MFC films; however, MFC films demonstrated better barrier properties against oxygen and water vapor. Both the MFC and NFC films were excellent barriers against mineral oil used in ordinary printing inks and dichlorobenzene, a common solvent used in functional printing inks. Barrier properties against vegetable oil were also found to be exceptionally good for both the NFC and MFC films.     

Improved thermal and mechanical properties of bacterial cellulose with the introduction of collagen

Composite films comprised of bacterial cellulose (BC) and collagen (COL) were developed using BC hydrogel membranes as the base material and COL as the reinforcing material. Glutaraldehyde (GT) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC·HCl) were then used as cross-linking agents to prepare cross-linked BC/COL composite films by a wet chemical method. The effects of chemical cross-linking on the thermal and mechanical properties of composite films were investigated in detail. The COL molecules were adsorbed and deposited inside of 3D nanofiber networks of BC, coated on the surface of BC fibers. Chemical bonds formed between BC molecules, and between BC and COL molecules after cross-linking. Compared with BC, the obtained composite films showed 57.9 and 70.8% improvement in tensile strength after being cross-linked by GT and EDC·HCl, respectively. Cross-linking also enhanced the thermal stability of the specimens.