Supercritical Carbon Dioxide Isolation of Cellulose Nanofibre and Enhancement Properties in Biopolymer Composites

The physical properties, such as the fibre dimension and crystallinity, of cellulose nanofibre (CNF) are significant to its functional reinforcement ability in composites. This study used supercritical carbon dioxide as a fibre bundle defibrillation pretreatment for the isolation of CNF from bamboo, in order to enhance its physical properties. The isolated CNF was characterised through zeta potential, TEM, XRD, and FT-IR analysis. Commercial CNF was used as a reference to evaluate the effectiveness of the method. The physical, mechanical, thermal, and wettability properties of the bamboo and commercial CNF-reinforced PLA/chitin were also analysed. The TEM and FT-IR results showed the successful isolation of CNF from bamboo using this method, with good colloidal stability shown by the zeta potential results. The properties of the isolated bamboo CNF were similar to the commercial type. However, the fibre diameter distribution and the crystallinity index significantly differed between the bamboo and the commercial CNF. The bamboo CNF had a smaller fibre size and a higher crystallinity index than the commercial CNF. The results from the CNF-reinforced biocomposite showed that the physical, mechanical, thermal, and wettability properties were significantly different due to the variations in their fibre sizes and crystallinity indices. The properties of bamboo CNF biocomposites were significantly better than those of commercial CNF biocomposites. This indicates that the physical properties (fibre size and crystallinity) of an isolated CNF significantly affect its reinforcement ability in biocomposites. The physical properties of isolated CNFs are partly dependent on their source and production method, among other factors. These composites can be used for various industrial applications, including packaging.     

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.     

Cellulose nanofibril-reinforced biodegradable polymer composites obtained via a Pickering emulsion approach

Preparation of cellulose nanofibril (CNF)-reinforced, biodegradable polymer composites is challenging in that it’s hard to achieve good dispersion of the hydrophilic cellulose fibers in a hydrophobic polymer matrix. In this work, we developed a surfactant-free and efficient process to prepare CNF-reinforced poly (lactic acid) (PLA) composites from an aqueous dichloromethane Pickering emulsion self-emulsified by CNFs. CNF/PLA composites of homogeneous dispersion were obtained upon evaporation of CH₂Cl₂, filtration, drying and hot-pressing. Differential scanning calorimetry measurement revealed an enhanced crystallization capacity of the CNF/PLA composites. Thermogravimetric analysis indicated an increase of onset degradation temperature. The composites displayed an enhanced storage modulus compared with neat PLA throughout the testing temperature range, and especially in the high-temperature region (>70 °C). Enhancements of the flexural modulus and strength were also achieved.     

Processing-structure-property relationships of electrospun PLA-PEO membranes reinforced with enzymatic cellulose nanofibers

Three different solvent mixtures were used to prepare electrospun membranes based on polylactic acid (PLA), polyethylene oxide (PEO) and enzymatic cellulose nanofibers (CNF). The materials were characterized from a morphological, spectroscopic, mechanical and rheological point of view. Furthermore, swelling test were performed in order to assess the water uptake of each sample.The results put into evidence that the choice of the solvents affects the structure and the properties of the membranes. Among the protocols tested, using chloroform/acetone/ethanol mixture was found to allow a high degree of CNF dispersion and a good electrospinnability of polymer solutions. These features led to membranes with impressive improvement of mechanical properties (+350% in stiffness, +350% in tensile strength and +500% in toughness) with respect to those of PLA/PEO and dramatically increased the water uptake of these materials (up to +350% within 120 min).     

Cellulose nanofibre enabled natural rubber composites: Microstructure,curing behaviour and dynamic mechanical properties

Traditional rubber industries rely heavily on petroleum-based materials, such as carbon black (CB). The present study aims at mitigating the environmental challenges, through partial replacement of CB, while simultaneously consuming an easily accessible agricultural waste. Accordingly, cellulose nanofibre (CNF) was extracted from wheat-straw using chemo-mechanical process, which in-turn was used for fabrication of CNF enabled rubber nanocomposites. Microstructural observation of CNF confirmed nanometric defibrillation of cellulose. A variety of tests were performed on the nanocomposites towards exploring their structure-property correlations, curing-behaviour, thermal degradability and mechanical (static and dynamic) properties. Overall, considerable enhancement in properties such as tensile strength and strain energy density could be realized, owing to synergistic use of CNF and CB in rubber, allowing for replacement of up to 15 phr CB. These were further augmented by significant improvements in dynamic rolling-resistance, traction and stress-softening behaviour. The results were especially significant, considering that the improvements could be achieved without any modification of CNF surface, thereby establishing its potential for development of environment friendly rubber nanocomposites.     

IFSS, TG, FT-IR spectra of impregnated sugar palm (Arenga pinnata) fibres and mechanical properties of their composites

This study aimed to investigate the effect of resin impregnation on the interfacial shear strength (IFSS), thermogravimetric (TG) and fourier transform infrared (FT-IR) of sugar palm (Arenga pinnata) fibres. In addition, the effect of resin impregnation on the mechanical properties of sugar palm fibre reinforced unsaturated polyester (UP) composites was also studied. The fibres were impregnated with UP via vacuum resin impregnation process at a pressure of 600 mmHg for 5 min. Composites of 10, 20, 30, 40 and 50 % fibre loadings were fabricated and tested for tensile and flexural properties. It was observed that the impregnation process caused the fibres to be enclosed by UP resin and this gave a strong influence to the increase of its interfacial bonding by the increase of its IFSS from single fibre pull-out test. It was also observed with TG and FT-IR spectra that the impregnated fibre had lower moisture uptake than the control and there was no significant increase in thermal stability of the impregnated fibre. The sequence of fibre decomposition started from the evaporation of moisture, hemicelluloses, cellulose, lignin and finally ash content and the presence of these components were proven by FT-IR spectra. For the composite specimens, due to the high interfacial bonding of the impregnated fibre and the matrix, the impregnated composites showed consistently higher tensile strength, tensile modulus, elongation at break, flexural strength, flexural modulus and toughness than the control samples. It was also observed that 30 % fibre loading gave optimum properties.     

Effects of Rice Straw Powder (RSP) Size and Pretreatment on Properties of FDM 3D-Printed RSP/Poly(lactic acid) Biocomposites

To develop a new kind of environment-friendly composite filament for fused deposition modeling (FDM) 3D printing, rice straw powder (RSP)/poly(lactic acid) (PLA) biocomposites were FDM-3D-printed, and the effects of the particle size and pretreatment of RSP on the properties of RSP/PLA biocomposites were investigated. The results indicated that the 120-mesh RSP/PLA biocomposites (named 120#RSP/PLA) showed better performance than RSP/PLA biocomposites prepared with other RSP sizes. Infrared results showed that pretreatment of RSP by different methods was successful, and scanning electron microscopy indicated that composites prepared after pretreatment exhibited good interfacial compatibility due to a preferable binding force between fiber and matrix. When RSP was synergistically pretreated by alkaline and ultrasound, the composite exhibited a high tensile strength, tensile modulus, flexural strength, and flexural modulus of 58.59, 568.68, 90.32, and 3218.12 MPa, respectively, reflecting an increase of 31.19%, 16.48%, 18.75%, and 25.27%, respectively, compared with unmodified 120#RSP/PLA. Pretreatment of RSP also improved the thermal stability and hydrophobic properties, while reducing the water absorption of 120#RSP/PLA. This work is believed to provide highlights of the development of cost-effective biocomposite filaments and improvement of the properties of FDM parts.     

Resin impregnation of cellulose nanofibril films facilitated by water swelling

Flexible composite films were produced by impregnating aqueous phenol formaldehyde (PF) resin into water-swollen cellulose nanofibril (CNF) films. CNF films were prepared using a pressurized filtration method in combination with freeze drying. The freeze-dried films were swollen with water then impregnated with PF resin by soaking in aqueous resin solutions of varying concentrations. Small amounts of PF slightly enhanced the tensile properties of CNF films. The formulation with the best mechanical properties was CNF/PF films with 8 wt % resin exhibiting tensile stress and toughness of 248 MPa and 26 MJ/m³, respectively. Resin concentrations higher than about 8 % resulted in composites with decreased tensile properties as compared to neat CNF films. The wet strength of the composite films was significantly higher than that of the neat CNF films. The resulting composites showed greater resistance to moisture absorption accompanied by reduced thickness swelling when soaked in water as compared to neat CNF films. The composites also showed decreased oxygen permeability at low humidity compared to neat films, but the composites did not show improved barrier properties at high humidity.     

Effect of poly (lactic acid)‐graft‐glycidyl methacrylate as a compatibilizer on properties of poly (lactic acid)/banana fiber biocomposites

The main aim of this study was to synthesis of poly (lactic acid) (PLA)‐graft‐glycidyl methacrylate (GMA) as well as its influence on the properties of PLA/banana fiber biocomposites. PLA‐graft‐GMA graft copolymer (GC) was synthesized by melt blending PLA with GMA using benzoyl peroxide and dicumyl peroxide as initiators. Graft copolymerization was confirmed by FTIR and ¹H‐NMR spectroscopic studies. PLA/silane treated banana fiber (SiB) biocomposites with various GC concentrations were prepared by melt blending followed by injection molding techniques. The influence of GC content on the mechanical, thermal and moisture resistance properties of the composite was investigated. The addition of 15 wt% GC content in the biocomposite provided optimum tensile and flexural strength, which is attributed to the greater compatibility between fiber and PLA matrix. The thermal properties of biocomposites have been evaluated using thermogravimetric analysis which provided evidence of improved interfacial adhesion between SiB and PLA by the addition of GC. Additionally, GC enhanced the moisture absorption resistance of biocomposites. These results indicated that GC is indeed a good candidate as a compatibilizing agent to improve the compatibility in PLA/fiber biocomposites. Copyright © 2015 John Wiley & Sons, Ltd.     

Efficient barrier properties of mechanically enhanced agro-extracted cellulosic biocomposites

The objective of this work was to prepare the mechanically stable hydrophobic biocomposites by incorporating the cellulose fibers into the polymer matrices for their applications in biomedical and food packaging. Herein, two different types of biocomposites were prepared by mixing polylactic acid (PLA) and polyhydroxybutyrate (PHB) with the agro-extracted cellulose, separately at 170 °C. The influence of the cellulose fibers on the thermal, mechanical, and barrier properties of polymer matrices (PLA and PHB) was observed. With an increase in the cellulose content in PLA and PHB, the tensile strength of the biocomposite materials significantly improved with the enhancement of 24.45% and 32.08%, respectively, compared with the pure PLA and PHB. Furthermore, a decrease of 74.16% and 73.49% in the water vapor transmission rate and oxygen transmission rate, respectively, was observed for cellulose/PHB biocomposites. This study highlights that adding cellulose fibers significantly improves the mechanical and the barrier properties of PLA and PHB, suggesting their biocomposites for use in biodegradable polymer industries.     

Physicomechanical properties of nanocomposites based on cellulose nanofibre and natural rubber latex

Cellulose nanofibres (CNF) with diameter 10–60 nm were isolated from raw banana fibres by steam explosion process. These CNF were used as reinforcing elements in natural rubber (NR) latex along with cross linking agents to prepare nanocomposite films. The effect of CNF loading on the mechanical and dynamic mechanical (DMA) properties of NR/CNF nanocomposite was studied. The morphological, crystallographic and spectroscopic changes were also analyzed. Significant improvement of Young’s modulus and tensile strength was observed as a result of addition of CNF to the rubber matrix especially at higher CNF loading. DMA showed a change in the storage modulus of the rubber matrix upon addition of CNF which proves the reinforcing effect of CNF in the NR latex. A mechanism is suggested for the introduction of the Zn–cellulose complex and its three dimensional network as a result of the reaction between the cellulose and the Zinc metal which is originated during the composite formation.     

Three‐dimensional printing of poly(lactic acid) bio‐based composites with sugarcane bagasse fiber: Effect of printing orientation on tensile performance

The cellulose fiber was extracted from the abandoned crop sugarcane bagasse (SCB) by means of chemical treatment methods. Poly(lactic acid) (PLA) bio‐based composites with SCB were prepared through fused deposition modeling (FDM) 3D‐printing technology, and the morphologies, mechanical properties, crystallization properties, and thermal stability of 3D‐printed composites were investigated. Compared with the neat PLA, the incorporation of SCB into PLA reduces the tensile strength and flexural strength of 3D‐printed samples but increases the flexural modulus. The difference in tensile performance and bending performance is that the tensile strength of 3D‐printed samples is best when the SCB content is 6 wt%, while the flexural modulus continuously decreases as the SCB content increases. Furthermore, the effects of various printing methods on the tensile performance of 3D‐printed samples were explored via modifying G‐code of 3D models. The results indicate that the optimum SCB fiber content is identical for all printing methods except method “vertical.” Due to the fibers and molecular chains are oriented to varying degrees with altering raster angle in 3D‐printed samples, the fully oriented sample printed by method “parallel” has a better tensile strength. Besides, SCB exhibits enough high thermal decomposition temperature to meet requirements for melt extrusion processing of PLA composites, and SCB fiber is capable of promoting the crystallization of PLA.     

Mechanical, thermal, and moisture absorption properties of nano-clay reinforced nano-cellulose biocomposites

In this research, fully environment-friendly, sustainable and biodegradable ‘green’ composites were fabricated. A novel material comprised of microfibrillated cellulose and laponite clay with different inorganic/organic ratios (m/m) was prepared. The composites were characterized by tensile, bending and water absorption tests as well as dynamic mechanical analysis. The morphologies of these nanocomposites were evaluated through scanning electron microscopy. Results showed considerable improvement of mechanical properties; specifically in elastic modulus, tensile strength and flexural modulus with the addition of nanoclay up to 7.5 wt% nano-clay. The modulus of elasticity increased significantly by about 26 % at 5 wt% nanocaly. The flexural modulus increased by about 90 % at 7.5 wt% nanoclay. However, with an increased load of clay in the nanocomposite, the mechanical properties decreased due to the agglomeration of excessive nanoclay. The storage modulus was significantly increased at high temperature with increasing the load of nanoclay.     

Poly(lactic acid)/poly(butylene succinate)/calcium sulfate whiskers biodegradable blends prepared by vane extruder: Analysis of mechanical properties,morphology, and crystallization behavior

Ternary blends of PLA/PBS/CSW with different weight fractions were prepared using a vane extruder. The mechanical properties, morphology, crystallization behavior and thermal stability of the blends were investigated. For the PLA/CSW blend, the tensile strength decreased, the flexural strength and modulus increased compared with pure PLA. For PBS, the addition of CSW had little influence on the mechanical properties. For the ternary blends PLA/PBS/CSW, the tensile strength, flexural strength and modulus decreased compared with pure PLA, while the elongation at break and the impact strength increased significantly. The brittle-ductile transition of the blends took place when the PBS weight fraction reaching 30 wt%. As a soft component in the blends, PBS was beneficial to improve the tensile ductility and the toughness of PLA. SEM measurements reveal that PLA/PBS/CSW blends were immiscible. When the weight fraction of PBS was 50 wt%, significant phase separation was observed, and CSW had preferential location in the PBS phase of the blend. DSC measurement and POM observation reveal that CSW had a heterogeneous nucleation effect on PLA and PBS matrix. The addition of PBS improved the crystallization of PLA and the thermal resistance of the PLA/PBS/CSW blends significantly.     

Hydrophobic cellulose nanopaper through a mild esterification procedure

Films of cellulose nanofibrils (CNF) (referred to as nanopaper) present a great potential in many applications due to the abundance, low environmental impact, excellent oxygen barrier properties and good mechanical performance of CNF. However, the strong hygroscopic character of the natural nanofibers limits their use in environments with high relative humidity. In this paper, we introduce a simple route for the esterification and processing of CNF with the aim of reducing their hydrophilicity, and producing hydrophobic cellulose nanopaper with reduced moisture sensitivity. The preparation steps of hydrophobic nanopapers involve vacuum filtration, solvent exchange from water to acetone, and reaction with anhydride molecules bearing different hydrophobic alkyl chains by hot pressing. Porous films having a surface area between 38 and 47 g/m² and pore sizes in the 3–200 nm range are obtained. This method preserves the crystalline structure of native cellulose, and successfully introduces hydrophobic moieties on CNF surface as confirmed by FTIR, XPS and elemental analysis. As a result, modified nanopapers have a reduced moisture uptake, both higher surface water contact angle and wet tensile properties as compared with reference non-modified nanopaper, thus illustrating the benefit of the modification for the use of cellulose nanopaper in humid environments.     

A novel polyacrylamide nanocomposite hydrogel reinforced with natural chitosan nanofibers

Polyacrylamide (PAM) was used as a matrix material for fabricating novel nanocomposite hydrogels reinforced with natural chitosan nanofibers (CNFs) via in situ free-radical polymerization. The nanocomposite's structure, strength, morphology and rheological properties were investigated. The results showed that the CNFs had a strong interaction with PAM through hydrogen and covalent bondings. The CNFs acted as a multifunctional cross-linker and a reinforcing agent in the hydrogel system. The compression strength and storage modulus of the nanocomposite hydrogels were significantly higher than those of the pure PAM hydrogels and the corresponding PAM/chitosan semi-interpenetrating polymer network (PAM-SIPN) hydrogels. The swelling ratio (SR) of the nanocomposite hydrogels was lower than that of the PAM hydrogel, but was similar to that of the PAM-SIPN hydrogel. Among the CNF contents used, the 1.5 wt% CNF loading level showed the best combined swelling and mechanical properties for the hydrogels.     

Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils

Cellulose nanofibrils (CNF) were isolated from cotton microfibrils (CM) by acid hydrolysis and coated with polyaniline (PANI) by in situ polymerization of aniline onto CNF in the presence of hydrochloride acid and ammonium peroxydisulfate to produce CNF/PANI. Nanocomposites of natural rubber (NR) reinforced with CNF and CNF/PANI were obtained by casting/evaporation method. TG analyses showed that coating CNF with PANI resulted in a material with better thermal stability since PANI acted as a protective barrier against cellulose degradation. Nanocomposites and natural rubber showed the same thermal profiles to 200 °C, partly due to the relatively lower amount of CNF/PANI added as compared to conventional composites. On the other hand, mechanical properties of natural rubber were significantly improved with nanofibrils incorporation, i.e., Young’s modulus and tensile strength were higher for NR/CNF than NR/CNF/PANI nanocomposites. The electrical conductivity of natural rubber increased five orders of magnitude for NR with the addition of 10 mass% CNF/PANI. A partial PANI dedoping might be responsible for the low electrical conductivity of the nanocomposites.     

Preparation and modification of collagen-based porous scaffold for tissue engineering

In the effort to generate cartilage tissues using mesenchymal stem cells, porous scaffolds with prescribed biomechanical properties were prepared. Scaffolds with interconnected pores were prepared via lyophilisation of frozen hydrogels made from collagen modified with chitosan nanofibres, hyaluronic acid, copolymers based on poly(ethylene glycol) (PEG), poly(lactic-co-glycolic acid) (PLGA), and itaconic acid (ITA), and hydroxyapatite nanoparticles. The modified collagen compositions were cross-linked using N-(3-dimethylamino propyl)-N′-ethylcarbodiimide hydrochloride (EDC) combined with N-hydroxysuccinimide (NHS) in water solution. Basic physicochemical and mechanical properties were measured and an attempt to relate these properties to the molecular and supermolecular structure of the modified collagen compositions was carried out. Scaffolds containing hydrophilic chitosan nanofibres showed the highest swelling ratio (SR = 20–25) of all the materials investigated, while collagen modified with an amphiphilic PLGA-PEG-PLGA copolymer or functionalised with ITA exhibited the lowest swelling ratio (SR = 5–8). The best resistance to hydrolytic degradation was obtained for hydroxyapatite containing scaffolds. On the other hand, the fastest degradation rate was observed for synthetic copolymer-containing scaffolds. The results showed that the addition of hydroxyapatite or hyaluronic acid to the collagen matrix increases the rigidity in comparison to the collagen-chitosan scaffold. Collagen scaffold modified with hyaluronic acid presented reduced deformation at break while the presence of hydroxypatatite enhanced the scaffold deformation under tensile loading. The tensile elastic modulus of chitosan nanofibre collagen scaffold was the lowest but closest to the articular cartilage; however, the strength and deformation to failure increased up to 200 %. Presented at the 1st Bratislava Young Polymer Scientists Workshop, Bratislava, 20–23 August 2007.     

Assessing the effect of PLA,cellulose microfibers and CaCO3 on the properties of starch-based foams using a factorial design

The effect of polylactic acid (PLA), cellulose microfibers (CEL), and calcium carbonate (CaCO₃) on the equilibrium moisture content (EMC), density and flexural mechanical properties of starch-based bio-foams was studied using a full factorial design 2³. Also, a moisture aging study was carried out. The results show the three factors studied changed the bio-foams morphology, contribute to density increment, enhance dimensional stability and improve both the moisture resistance and the mechanical flexural properties. The moisture aging studies show that, although the flexural mechanical properties decrease with increasing humidity, the bio-foams exceed the mechanical properties of commercial expanded polystyrene (EPS) trays. These findings suggest the bio-composites could be used in regions where the humidity conditions are moderate to very humid, guaranteeing their dimensional stability and functional properties. Thus, these new bio-foams are an attractive and sustainable option to replace the non-biodegradable EPS commercial trays.     

Tensile Properties and Morphology of Oil Palm Empty Fruit Bunch Regenerated Cellulose Biocomposite Films

The regenerated cellulose (RC)biocomposite films were prepared using casting method where oil palm empty fruit bunch (OPEFB) and microcrystalline cellulose (MCC) were dissolved in N-dimethylacetamide/lithium chloride (DMAc/LiCl)solution. The increasing of OPEFB contents up to 2 wt% increased the tensile strength and modulus of elasticity of RC biocomposite films while the elongation at break decreased. However, at 3 and 4 wt% of OPEFB content, the tensile strength and modulus of elasticity decreased with increases OPEFB content, but elongation at break increased. The increment of tensile strength and modulus of elasticity at 2 wt% is due to the OPEFB fiber that partially dissolved and dispersed with the OPEFB matrix. The morphology studies illustrate that at 2 wt% of OPEFB content of biocomposite films surface consists less voids and agglomerations than at 4 wt%. This can be considered the RC filler was partially dispersed with the RC matrix in the biocomposite films.