Synthesis and mechanical performance of thermoformable cellulose fatty acid esters using natural soap.

A cellulose fatty acid ester consisting solely of natural organic compounds is synthesized by heterogeneous esterification. Solid soap, a natural product-based compound, is used as a mixed fatty acid source. The synthesized cellulose ester can be readily processed into a semi-transparent film. Mechanical properties of the cellulose ester are also investigated.

Effect of cellulose materials on the mechanochemical-assisted reaction system with oleic acid.

As the most abundant natural polymer in nature, cellulose has become the promising alternative raw material to replace fossil-based polymer. Owing to the presence of innumerable hydroxyl groups, various approaches are employed to render processability of cellulose. Herein, a sustainable esterification strategy, mechanochemical-assisted esterification, was developed to produce cellulose oleate (CO) with only a small amount of solvent. The differences in reactivity between all types of cellulose were elucidated. According to thermal stability analysis, the degradation temperature decreased after modification due to the substitution of the long oleoyl group. High degree of substitution (DS) of CO also possessed glass transition temperature (Tg) based on differential scanning calorimetry (DSC) analysis. Herewith, the processability of cellulose was introduced after modification. In this study, bamboo waste cellulose nanofiber oleate (BW CNF-OA) showed the highest DS (2.28) among the COs. Its higher surface reactivity due to the high surface aspect ratio led to a higher quantity of fatty acids attached to the cellulose. For the mechanical properties, low DS of COs exhibited higher tensile strength values. In a nutshell, this greener approach is more favorable than conventional chemical esterification in terms of reduced solvent dosage and improved sustainability.

Surface Modification of a Regenerated Cellulose Film Using Low-Pressure Plasma Treatment with Various Reactive Gases.

There is a growing interest in the fabrication of membranes and packaging materials from natural resources for a sustainable society. A regenerated cellulose (RC) film composed solely of cellulose has outstanding advantages including biodegradability, transparency, mechanical strength, and thermal stability. To expand the application of the RC film, various surface modification methods have been proposed. However, conventional chemical methods have disadvantages such as environmental burden and difficulty in controlling the reaction. In this work, low-pressure plasma treatment, a green, solvent-free, and easily controllable approach, was performed for surface modification of the RC film. The effects of three different plasma species (O2, N2, and CF4) and treatment conditions on the surface properties of RC films were investigated based on water contact angle measurements, chemical composition analysis, and surface topography. O2 and N2 plasma treatment slightly enhanced the surface wettability of RC films due to the etching by the plasma reactive species and the formation of new hydrophilic functional groups. In CF4 plasma treatments, the hydrophobic surface with a contact angle of 120.6° was obtained in a short treatment time (60 s) owing to the deposition of fluorocarbon groups on the surface. However, the treated surface in a longer reaction time resulted in increased wettability due to the diffusion and degradation of fluorine-containing bonds. The new insights could be valuable for further studies of surface modification and functionalization of RC films.

Facile Preparation of Cellulose Fiber Reinforced Polypropylene Using Hybrid Filler Method.

Dried hybrid fillers comprised of silica/CNF were successfully synthesized in ethanol/water mixed solvents at room temperature without the usage of any precursor. The as-prepared fillers were incorporated with polypropylene (PP) as a polymer matrix through a twin-screw extruder. From surface morphology analysis, the agglomeration of the silica/CNF hybrid fillers was prevented in the PP matrix and they exhibited moderate transparency, around 17.9% and 44.6% T at 660 nm. Further, the chemical structures of the polymer composites were identified by Fourier transform infrared (FT-IR) analysis. According to thermogravimetric analysis (TGA), the insertion of silica as a co-filler to the PP matrix resulted in an increase in its degradation onset temperature and also thermal stability. In addition, the mechanical properties of the PP composites also increased after the blending process with the hybrid fillers. Overall, sample PP-SS/CNF exhibited the highest tensile strength, which was 36.8 MPa, or around 73.55% compared to the pristine PP. The improvements in tensile strength were attributed to good dispersion and enhanced efficiency of the stress transfer mechanism between the silica and the cellulose within the PP matrix. However, elongation of the sample was reduced sharply due to the stiffening effect of the filler.

Cu2O/TiO2 decorated on cellulose nanofiber/reduced graphene hydrogel for enhanced photocatalytic activity and its antibacterial applications.

Photocatalysis has gained attention as a viable wastewater remediation technique. However, the difficulty of recovering powder-based photocatalyst has often become a major limitation for their on-site practical application. Herein, we report on the successful in-situ preparation of a novel three-dimensional (3D) photocatalyst consisting of Cu2O/TiO2 loaded on a cellulose nanofiber (CNF)/reduced graphene hydrogel (rGH) via facile hydrothermal treatment and freeze-drying. The 3D macrostructure not only provides a template for the anchoring of Cu2O and TiO2 but also provides an efficient electron transport pathway for enhanced photocatalytic activity. The results showed that the Cu2O and TiO2 were uniformly loaded onto the aerogel framework resulting in the composites with large surface area with exposed actives sites. As compared to bare rGH, CNF/rGH, Cu2O/CNF/rGH and TiO2/CNF/rGH, the Cu2O/TiO2/CNF/rGH showed improved photocatalytic activity for methyl orange (MO) degradation. MO degradation pathway is proposed based on GC-MS analysis. The enhanced photoactivity can be attributed to the charge transfer and electron-hole separation from the synergistic effect of Cu2O/TiO2 anchored on CNF/rGH. In terms of their anti-bacterial activity towards Staphylococcus aureus and Escherichia coli, the synergistic effect of the Cu2O/TiO2 anchored on the CNF/rGH framework showed excellent activity towards the bacteria.

Esterification of Cellulose with Long Fatty Acid Chain through Mechanochemical Method.

Mechanochemical reaction, a green synthetic esterification route was utilized to prepare long-chain cellulose esters from microcrystalline cellulose. The influence of reaction conditions such as reaction temperature and time were elucidated. Only low dosage of oleic acid, 1-butyl-3-metylimidazolium acetate, and p-toluenesulfonyl chloride were required. The success of modification reaction was confirmed by Fourier transforms infrared spectroscopy as a new absorbance peak at 1731 cm-1 was observed, which indicated the formation of carbonyl group (C=O). Solid-state nuclear magnetic resonance was also performed to determine the structural property and degree of substitution (DS) of the cellulose oleate. Based on the results, increasing reaction temperature and reaction time promoted the esterification reaction and DS. DS values of cellulose oleates slightly decreased after 12 h reaction time. Besides, X-ray diffraction analysis showed the broadening of the diffraction peaks and thermal stability decreased after esterification. Hence, the findings suggested that grafting of oleic acid's aliphatic chain onto the cellulose backbone lowered the crystallinity and thermal stability.

The Relationship between Crystal Structure and Mechanical Performance for Fabrication of Regenerated Cellulose Film through Coagulation Conditions.

Cellulose films regenerated from aqueous alkali-urea solution possess different properties depending on coagulation conditions. However, the correlation between coagulant species and properties of regenerated cellulose (RC) films has not been clarified yet. In this study, RC films were prepared from cellulose nanofiber (CNF) and microcrystalline cellulose (MCC) under several coagulation conditions. Cellulose dissolved in aqueous LiOH-urea solution was regenerated using various solvents at ambient temperature to investigate the effects of their dielectric constant on the properties of RC film. The crystal structure, mechanical properties, and surface morphology of prepared RC films were analyzed using X-ray diffraction (XRD), tensile tester, and atomic probe microscopy (AFM), respectively. It is revealed that the preferential orientation of (110) and (020) crystal planes, which are formed by inter- and intramolecular hydrogen bonding in cellulose crystal regions, changed depending on coagulant species. Furthermore, we found out that tensile strength, elongation at break, and crystal structure properties of RC films strongly correlate to the dielectric constant of solvents used for the coagulation process. This work, therefore, would be able to provide an indicator to control the mechanical performance of RC film depending on its application and to develop detailed researches on controlling the crystal structure of cellulose.

Melt- vs. Non-Melt Blending of Complexly Processable Ultra-High Molecular Weight Polyethylene/Cellulose Nanofiber Bionanocomposite.

The major hurdle in melt-processing of ultra-high molecular weight polyethylene (UHMWPE) nanocomposite lies on the high melt viscosity of the UHMWPE, which may contribute to poor dispersion and distribution of the nanofiller. In this study, UHMWPE/cellulose nanofiber (UHMWPE/CNF) bionanocomposites were prepared by two different blending methods: (i) melt blending at 150 °C in a triple screw kneading extruder, and (ii) non-melt blending by ethanol mixing at room temperature. Results showed that melt-processing of UHMWPE without CNF (MB-UHMWPE/0) exhibited an increment in yield strength and Young's modulus by 15% and 25%, respectively, compared to the Neat-UHMWPE. Tensile strength was however reduced by almost half. Ethanol mixed sample without CNF (EM-UHMWPE/0) on the other hand showed slight decrement in all mechanical properties tested. At 0.5% CNF inclusion, the mechanical properties of melt-blended bionanocomposites (MB-UHMWPE/0.5) were improved as compared to Neat-UHMWPE. It was also found that the yield strength, elongation at break, Young's modulus, toughness and crystallinity of MB-UHMWPE/0.5 were higher by 28%, 61%, 47%, 45% and 11%, respectively, as compared to the ethanol mixing sample (EM-UHMWPE/0.5). Despite the reduction in tensile strength of MB-UHMWPE/0.5, the value i.e., 28.4 ± 1.0 MPa surpassed the minimum requirement of standard specification for fabricated UHMWPE in surgical implant application. Overall, melt-blending processing is more suitable for the preparation of UHMWPE/CNF bionanocomposites as exhibited by their characteristics presented herein. A better mechanical interlocking between UHMWPE and CNF at high temperature mixing with kneading was evident through FE-SEM observation, explains the higher mechanical properties of MB-UHMWPE/0.5 as compared to EM-UHMWPE/0.5.

Process Optimization of Ultra-High Molecular Weight Polyethylene/Cellulose Nanofiber Bionanocomposites in Triple Screw Kneading Extruder by Response Surface Methodology.

Incorporation of nanocellulose could improve wear resistance of ultra-high molecular weight polyethylene (UHMWPE) for an artificial joint application. Yet, the extremely high melt viscosity of the polymer may constrict the mixing, leading to fillers agglomeration and poor mechanical properties. This study optimized the processing condition of UHMWPE/cellulose nanofiber (CNF) bionanocomposite fabrication in triple screw kneading extruder by using response surface methodology (RSM). The effect of the process parameters-temperature (150-190 °C), rotational speed (30-60 rpm), and mixing time (30-45 min)-on mechanical properties of the bionanocomposites was investigated. Homogenous filler distribution, as confirmed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analysis, was obtained through the optimal processing condition of 150 °C, 60 rpm, and 45 min. The UHMWPE/CNF bionanocomposites exhibited improved mechanical properties in terms of Young's and flexural modulus by 11% and 19%, respectively, as compared to neat UHMWPE. An insignificant effect was observed when maleic anhydride-grafted-polyethylene (MAPE) was added as compatibilizer. The obtained results proved that homogenous compounding of high melt viscosity UHMWPE with CNF was feasible by optimizing the melt blending processing condition in triple screw kneading extruder, which resulted in improved stiffness, a contributing factor for wear resistance.

Well-Dispersed Cellulose Nanofiber in Low Density Polyethylene Nanocomposite by Liquid-Assisted Extrusion.

Two different liquid assisted processing methods: internal melt-blending (IMB) and twin-screw extrusion (TWS) were performed to fabricate polyethylene (PE)/cellulose nanofiber (CNF) nanocomposites. The nanocomposites consisted maleic anhydride-grafted PE (PEgMA) as a compatibilizer, with PE/PEgMA/CNF ratio of 97/3/0.5-5 (wt./wt./wt.), respectively. Morphological analysis exhibited that CNF was well-dispersed in nanocomposites prepared by liquid-assisted TWS. Meanwhile, a randomly oriented and agglomerated CNF was observed in the nanocomposites prepared by liquid-assisted IMB. The nanocomposites obtained from liquid-assisted TWS exhibited the best mechanical properties at 3 wt.% CNF addition with an increment in flexural strength by almost 139%, higher than that of liquid-assisted IMB. Results from this study indicated that liquid feeding of CNF assisted the homogenous dispersion of CNF in PE matrix, and the mechanical properties of the nanocomposites were affected by compounding method due to the CNF dispersion and alignment.

Development of Organo-Dispersible Graphene Oxide via Pseudo-Surface Modification for Thermally Conductive Green Polymer Composites.

Graphene has attracted lots of researchers attention because of its remarkable conductivity in both electrically and thermally. However, it has poor dispersibility in organic solvents which limited its applications. Polymers with aromatic end group which act as an intercalator were prepared by ring-opening polymerization with ε-caprolactone by utilizing 1-naphthalene methanol (1-NM) as an initiator. These intercalators will exist between graphene oxide (GO) sheets to prevent aggregation via interactions. The attachment of 1-NM on polymer chains was supported by ultraviolet-visible spectra, size exclusion chromatography profiles, and 1H nuclear magnetic resonance spectra. Exfoliated structured functionalized GO (fGO)/polycaprolactone (PCL) (synthesized fGO) nanocomposites that dispersed well in acetone, chloroform, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and toluene were successfully synthesized. This agreed well with the enlarged interlayer spacing in the optimized fGO as compared to that of GO from density functional theory simulations using the DMol3 module that implemented in the Materials Studio 6.0. Furthermore, its potential to be applied as green electronics in electronics, aerospace, and automotive industries was presented, by trailering the thermal conductivity enhancement from the incorporation of fGO/PCL with commercialized biodegradable polymers, PCL, and poly[(R)-3-hydroxybutyric acid].

Simple Manufacture of Surface-Modified Nanolignocellulose Fiber via Vapor-Phase-Assisted Surface Polymerization.

This work tackles the disadvantages in the production of functionalized nanofibers from biomass and offers a new methodology to nanofiber-reinforced composite manufacturing. A vapor-phase-assisted surface polymerization (VASP) method has been used to develop surface-modified lignocellulosic nanofibers. Through the vaporized monomers during polymerization, the polymer chains can be introduced deep within oil palm mesocarp fibers (OPMFs) due to their unique porous structure. After OPMFs are modified with polymer chains, the simple Mortar grinder mill-ionic liquid (M-IL) method provides fibrillation from the macro- to nanoscale, retaining the grafted polymer chains. This approach for the functionalization of biomass could lead to the large-scale fabrication of surface-modified nanofibers for reinforced materials and promote innovative implementations of the renewable biomass resource.

Design of biodegradable PCL/PI films as a joining tape for grafting plant.

In this study, novel eco-friendly blends based on environmental-friendly polymers and compatibilizers, such as poly(ϵ-caprolactone) (PCL), cis-1,4-polyisoprene (PI), soybean lecithin (SOLE) and acrylated-epoxidized soybean oil (AESO), have been prepared in order to suggest a biodegradable joining tool used for plant grafting in agriculture, which will be competitive from the environment and economic points of view against conventional nonbiodegradable tools. PCL/PI blends, in which the portion of PCL was 75 and 50, were mixed with a compatibilizer by a melt-blending technique. The resulting blends were investigated by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy and also their mechanical properties were determined. Afterwards, the blend films were buried in the soil. Remarkable level of weight loss was achieved in 6 weeks, ∼46%. The results showed that the addition of SOLE helped to improve the compatibility between PCL and PI due to its amphipathic property, and, besides, accelerated the weight loss of the films in soil, increasing microorganism growth on the film.

Successful scaling-up of self-sustained pyrolysis of oil palm biomass under pool-type reactor.

An appropriate technology for waste utilisation, especially for a large amount of abundant pressed-shredded oil palm empty fruit bunch (OFEFB), is important for the oil palm industry. Self-sustained pyrolysis, whereby oil palm biomass was combusted by itself to provide the heat for pyrolysis without an electrical heater, is more preferable owing to its simplicity, ease of operation and low energy requirement. In this study, biochar production under self-sustained pyrolysis of oil palm biomass in the form of oil palm empty fruit bunch was tested in a 3-t large-scale pool-type reactor. During the pyrolysis process, the biomass was loaded layer by layer when the smoke appeared on the top, to minimise the entrance of oxygen. This method had significantly increased the yield of biochar. In our previous report, we have tested on a 30-kg pilot-scale capacity under self-sustained pyrolysis and found that the higher heating value (HHV) obtained was 22.6-24.7 MJ kg(-1) with a 23.5%-25.0% yield. In this scaled-up study, a 3-t large-scale procedure produced HHV of 22.0-24.3 MJ kg(-1) with a 30%-34% yield based on a wet-weight basis. The maximum self-sustained pyrolysis temperature for the large-scale procedure can reach between 600 °C and 700 °C. We concluded that large-scale biochar production under self-sustained pyrolysis was successfully conducted owing to the comparable biochar produced, compared with medium-scale and other studies with an electrical heating element, making it an appropriate technology for waste utilisation, particularly for the oil palm industry.

Enhanced biocatalytic esterification with lipase-immobilized chitosan/graphene oxide beads.

In this work, lipase from Candida rugosa was immobilized onto chitosan/graphene oxide beads. This was to provide an enzyme-immobilizing carrier with excellent enzyme immobilization activity for an enzyme group requiring hydrophilicity on the immobilizing carrier. In addition, this work involved a process for the preparation of an enzymatically active product insoluble in a reaction medium consisting of lauric acid and oleyl alcohol as reactants and hexane as a solvent. This product enabled the stability of the enzyme under the working conditions and allowed the enzyme to be readily isolated from the support. In particular, this meant that an enzymatic reaction could be stopped by the simple mechanical separation of the "insoluble" enzyme from the reaction medium. Chitosan was incorporated with graphene oxide because the latter was able to enhance the physical strength of the chitosan beads by its superior mechanical integrity and low thermal conductivity. The X-ray diffraction pattern showed that the graphene oxide was successfully embedded within the structure of the chitosan. Further, the lipase incorporation on the beads was confirmed by a thermo-gravimetric analysis. The lipase immobilization on the beads involved the functionalization with coupling agents, N-hydroxysulfosuccinimide sodium (NHS) and 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC), and it possessed a high enzyme activity of 64 U. The overall esterification conversion of the prepared product was 78% at 60 °C, and it attained conversions of 98% and 88% with commercially available lipozyme and novozyme, respectively, under similar experimental conditions.

Modification of oil palm mesocarp fiber characteristics using superheated steam treatment.

In this study, oil palm mesocarp fiber (OPMF) was treated with superheated steam (SHS) in order to modify its characteristics for biocomposite applications. Treatment was conducted at temperatures 190-230 °C for 1, 2 and 3 h. SHS-treated OPMF was evaluated for its chemical composition, thermal stability, morphology and crystallinity. OPMF treated at 230 °C exhibited lower hemicellulose content (9%) compared to the untreated OPMF (33%). Improved thermal stability of OPMF was found after the SHS treatment. Moreover, SEM and ICP analyses of SHS-treated OPMF showed that silica bodies were removed from OPMF after the SHS treatment. XRD results exhibited that OPMF crystallinity increased after SHS treatment, indicating tougher fiber properties. Hemicellulose removal makes the fiber surface more hydrophobic, whereby silica removal increases the surface roughness of the fiber. Overall, the results obtained herewith suggested that SHS is an effective treatment method for surface modification and subsequently improving the characteristics of the natural fiber. Most importantly, the use of novel, eco-friendly SHS may contribute to the green and sustainable treatment for surface modification of natural fiber.

Biomass-based composites from poly(lactic acid) and wood flour by vapor-phase assisted surface polymerization.

To prepare biomass-based composites in an environmentally benign manner, vapor-phase assisted surface polymerization (VASP) was applied to prepare the composites from wood flour and poly(l-lactic acid) (PLLA) without solvent. VASP of l,l-lactide successfully proceeded on the wood flour surfaces, resulting in surface coverage by newly generated PLLA. For obtained PLLA/wood flour composites, it was clarified that grafting of PLLA on wood flour surfaces had occurred to form covalently bonded composites, with the accumulated PLLA layers having crystallized in situ during VASP. Resulting PLLA layers showed very high crystallinity of 79.2% and a high melting point close to the equilibrium melting point. Moreover, thermal degradation behavior of the composites suggested a cooperative degradation manner of the components.

Designed surface construction by photo-induced vapor-phase assisted surface polymerization of vinyl monomers using immobilized free radical initiators.

To build up finely designed patterns on solid surfaces, consecutive vapor-phase assisted surface photo-polymerization (VASP) of methyl methacrylate and styrene was carried out under UV-irradiation through a stripe-patterned photo-mask on Si-wafer and Au-plate surfaces, resulting in the reproduction of designed and multi-layered patterns made of block copolymer chains grafted from the surfaces.