A Comparison of Modified and Unmodified Cellulose Nanofiber Reinforced Polylactic Acid (PLA) Prepared by Twin Screw Extrusion

The goal of this work was to evaluate the effect of chemical modification of cellulose nanofibers (CNF) on the properties of polylactic acid (PLA) nanocomposites. Acetylated nanofibers (ACNF), with degree of substitution 1.07, were isolated from acetylated kenaf fibers by mechanical treatments. Acetylated nanofibers showed more hydrophobic properties compared to non-acetylated ones. The results showed that both crystallinity and thermal stability of acetylated nanofibers were lower than non-acetylated ones. The nanocomposites were prepared by premixing two PLA master batches, one with a high concentration of ACNF and the second with CNF. These were diluted to final concentrations (5?wt%) during the extrusion. The morphology studies of PLA and its nanocomposites showed nanofiber aggregates in both materials. The results showed that the tensile and dynamic mechanical properties were enhanced for both acetylated and non-acetylated nanocomposites compared to the neat PLA matrix while no significant improvement was observed for the acetylated nanocomposites compared to non-acetylated ones. However, the storage modulus increased slightly for acetylated nanocomposites compared to non-acetylated ones.     

Green Composites of Poly (Lactic Acid) and Sugarcane Bagasse Residues from Bio-refinery Processes

Twin-screw extrusion was used to prepare the composites consisting of PLA and three types of sugarcane bagasse residues (up to 30 wt%) derived from different steps of a biorefinery process. Each residue had different composition, particle size and surface reactivity due to chemical and biological (enzyme, microbes) treatments that the biomass was subjected to. The effects of different residue characteristics on properties, crystallization behaviors and morphologies of PLA composites were investigated. Besides, a small amount (2 wt%) of coupling agent, Desmodur^® VKS 20 (DVKS), was used to improve the interfacial bonding between PLA and bagasse residues. The results indicated that in the presence of 2 % DVKS, PLA composite with pretreated residue exhibited the maximum strength properties (98.94 % tensile strength and 93.91 % flexural strength of neat PLA), while PLA composite with fermentation residue exhibited the minimum strength properties (88.98 % tensile strength and 81.91 % flexural strength of neat PLA).     

Development of Cellulose from Sugarcane Bagasse and Polyacrylamide-Based Hydrogel Composites by Gamma Irradiation Technique: A Study of Controlled-Release Behavior of Urea

Journal of Polymers and the Environment - Cellulose was successfully purified from sugarcane bagasse by gamma irradiation technique. The crystallinity of cellulose was reduced by gamma irradiation....     

Comparative Study of Xylan Extracted by Sodium and Potassium Hydroxides (NaOH and KOH) from Bagasse Pulp: Characterization and Morphological Properties

Xylan is the second most abundant polysaccharide and the predominant hemicellulose component of soda bagasse pulp. The present endeavor focuses on increasing the value addition to underutilized agro-industrial residue such as bagasse. For this purpose, xylan was isolated by two conventional alkali extraction methods i.e. NaOH and KOH. The recovery rate and sugar composition of different reaction times and alkali consumptions were monitored with advanced method such as High Performance Liquid Chromatography (HPLC). The Fourier Transform Infrared Spectroscopy (FTIR) and Wide Angle X-ray spectroscopy (WAXS) were respectively employed to characterize the functional groups and Crystallinity Index (CrI) changes during the extraction process. It was explored that highest xylan recovery rates were obtained with 6% of NaOH at 120 min and 6% KOH at 45 min. The xylan morphology via WAXS was found that its structure to be amorphous. HPLC results also showed KOH had higher effectiveness than NaOH in terms of extracted xylan purity. Highest XGRs (Xylose to Glucose Ratios) were also achieved by KOH processes. Hence, this study contributes to the adequate utilization of agricultural residues, with promising potential for applications in the production of certain novel materials and chemical conversion industries.     

Orange Juice Processing Waste as a Biopolymer Base for Biodegradable Film Formation Reinforced with Cellulose Nanofiber and Activated with Nettle Essential Oil

Journal of Polymers and the Environment - Concerns about environmental problems have led to the development of biodegradable packaging. Food wastes as a byproduct could be a good source for...     

Sequential (anaerobic/aerobic) biological treatment of Dalaman SEKA Pulp and Paper Industry effluent

In the pulp and paper industry, lignin and other color compounds are removed by chemical agents in bleaching process. Use of chlorine-based agents results in production of degradation products which include various chloro-organic derivatives. Since these new compounds are highly chlorinated, they cause a problem in the treatment of pulp and paper industry wastewaters. Chemical precipitation, lagooning, activated sludge, and anaerobic treatment are the processes used for treating pulp and paper effluents. Furthermore, a combination of these processes is also applicable. In this study, the effluent of Dalaman SEKA Pulp and Paper Industry was examined for its toxic effects on anaerobic microorganisms by anaerobic toxicity assay. Additionally, this wastewater was applied to a sequential biotreatment process consisting of an upflow anaerobic sludge blanket as the anaerobic stage and a once-through completely mixed stirred tank as the aerobic stage. Results indicated that: (1) Dalaman SEKA Pulp and Paper Industry wastewater exerted no inhibitory effects on the anaerobic cultures under the studied conditions, and (2) application of a sequential biological (anaerobic/aerobic) system to treat the Dalaman SEKA Pulp and Paper Industry wastewater resulted in approximately 91% COD and 58% AOX removals at a HRT of 5 and 6.54 h for anaerobic and aerobic, respectively.     

Preparation and Properties of Carboxymethyl Cellulose (CMC)/Sodium alginate (SA) Blends Induced by Gamma Irradiation

Carboxymethyl Cellulose (CMC)/Sodium alginate (SA) blends have been prepared by casting solution method. The effect of different irradiation doses (2.5, 5, 10, 15, and 20 kGy) of gamma rays on the physical properties of the CMC/SA blend containing different ratios of SA (20, 30, and 40 %) such as gel fraction (%) and swelling (%) of CMC/SA blends were investigated. It was found that the gel fraction increases with increasing irradiation dose up to 20 kGy while the swelling of CMC/SA blend films tends to increase with increasing SA content and reduced with increasing irradiation doses. Mechanical and thermal properties of the blend films were improved when CMC content increased and with increasing irradiation dose up to 20 kGy. Morphology of the blend was examined by SEM, which indicates compatibility between CMC and SA. The blend rich in SA content possessed good antimicrobial activity against Gram +ve Bacteria (Bacillus subtilis).     

Enhanced Functional Properties of Biodegradable Polyvinyl Alcohol/Carboxymethyl Cellulose (PVA/CMC) Composite Films Reinforced with l-alanine Surface Modified CuO Nanorods

Journal of Polymers and the Environment - Herein, we described novel biogenic preparation of the CuO nanorods and its surface modification with l-alanine amino acid accelerated by microwave...     

Evaluation of Poly(lactic acid) and Sugar Beet Pulp Green Composites

Poly(lactic acid) (PLA) and sugar beet pulp (SBP) were compounded by twin-screw extrusion and injection molded into composite forms. Specific mechanical energy decreased with the addition of SBP during processing. PLA–SBP composites retained more tensile strength than expected based on the Nicolais–Narkis model especially at high levels of SBP suggesting adhesion between SBP and PLA. The thermal characteristics of PLA were not affected by thermo-mechanical processing or by the incorporation of SBP up to 30% weight basis. PLA and PLA–SBP composites had similar tensile properties to other thermoplastic resins and may be used as a cost-competitive replacement.

Interfaces in Cross-Linked and Grafted Bacterial Cellulose/Poly(Lactic Acid) Resin Composites

This article presents approaches to maximize the mechanical performance of bacterial cellulose/poly(lactic acid) composites through chemical modification of the interface. This is achieved by both cross-linking the layered bacterial cellulose structure and by grafting maleic anhydride to the matrix material. Unmodified and glyoxalized bacterial cellulose (BC) networks have been embedded in poly(lactic acid) (PLA) resin and then in maleated resin using a compression molding method. The effect of these chemical modifications on the physical properties of these composites is reported. The tensile properties of the composites showed that Young??s moduli can be increased significantly when both BC networks and PLA were chemically modified. Interface consolidation between layers in BC networks has been achieved by glyoxalization. The effect of these modifications on both stress-transfer between the fibers and between the matrix and the fibers was quantified using Raman spectroscopy. Two competitive deformation mechanisms are identified; namely the mobility between BC layers, and between BC and PLA. The coupling strength of these interfaces could play a key role for optimization of these composites?? mechanical properties.     

Synthesis,Characterization and Nanocomposite Formation of Poly(glycerol succinate-co-maleate) with Nanocrystalline Cellulose

A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with nanocrystalline cellulose. This glycerol-based polymer is thermally stable as a consequence of its targeted cross-linked structure. To broaden its range of properties, it was specifically formulated with nanocrystalline cellulose (NCC) at concentrations of 1, 2 and 4 wt%, and showed improved mechanical properties with NCC. Specifically, the effect of reinforcement on mechanical properties, thermal stability, structure, and biodegradability was evaluated, respectively, by tensile tests and thermogravimetric analyses, X-ray diffraction and respirometry. The neat poly(GlySAMA) polymer proved flexible, exhibiting an elongation-to-break of 8.8 % while the addition of nanowhiskers (at 4 wt%) caused tensile strength and Young’s modulus to increase, 20 and 40 %, respectively. Stiffness improved without significantly decreasing thermal stability as measured by thermogravimetric analysis. Biodegradation tests indicated that all samples were degradable but NCC reduced the rate of biodegradation.     

Dispersion and Reinforcing Potential of Carboxymethylated Nanofibrillated Cellulose Powders Modified with 1-Hexanol in Extruded Poly(Lactic Acid) (PLA) Composites

Bionanocomposites of poly(lactic acid) (PLA) and chemically modified, nanofibrillated cellulose (NFC) powders were prepared by extrusion, followed by injection molding. The chemically modified NFC powders were prepared by carboxymethylation and mechanical disintegration of refined, bleached beech pulp (c-NFC), and subsequent esterification with 1-hexanol (c-NFC-hex). A solvent mix was then prepared by precipitating a suspension of c-NFC-hex and acetone-dissolved PLA in ice-cold isopropanol (c-NFC-hex_sm), extruded with PLA into pellets at different polymer/fiber ratios, and finally injection molded. Dynamic mechanical analysis and tensile tests were performed to study the reinforcing potential of dried and chemically modified NFC powders for PLA composite applications. The results showed a faint increase in modulus of elasticity of 10?% for composites with a loading of 7.5?% w/w of fibrils, irrespective of the type of chemically modified NFC powder. The increase in stiffness was accompanied by a slight decrease in tensile strength for all samples, as compared with neat PLA. The viscoelastic properties of the composites were essentially identical to neat PLA. The absence of a clear reinforcement of the polymer matrix was attributed to poor interactions with PLA and insufficient dispersion of the chemically modified NFC powders in the composite, as observed from scanning electron microscope images. Further explanation was found in the decrease of the thermal stability and crystallinity of the cellulose upon carboxymethylation.     

Study of Fatigue Life and Filler Interaction of Paper Sludge Filled Epoxidized Natural Rubber (ENR) and Maleated Natural Rubber (MNR) Composites

An investigation on the effect of epoxidation and maleated natural rubber (MNR) on fatigue and rubber-filler interaction properties of paper sludge filled natural rubber composites was elucidated. Paper sludge loading was varied from 0 to 40 phr and conventional vulcanisation system was used while compounding was carried out on a laboratory sized two roll mill. Two different types of natural rubber, SMR L and ENR 50 having 0 and 50 mole% of epoxidation were used in order to investigate the effect of epoxidation on the composites. Results indicate that, at a fixed filler loading, ENR 50 vulcanizates exhibit higher fatigue life than SMR L vulcanizates especially at filler loading below 20 phr which might be associated with better rubber-filler interaction. In the case of composites with the addition of maleated natural rubber (MNR), a higher fatigue life was observed due to presence of physical and/or chemical linkages, which increases the interfacial adhesion. Scanning electron microscopy (SEM) micrographs of fatigue fracture surfaces and rubber-filler interaction study supported the observed result on fatigue life.     

Natural Fiber Reinforced Poly(vinyl chloride) Composites: Effect of Fiber Type and Impact Modifier

Poly(vinyl chloride) (PVC) and natural fiber composites were prepared by melt compounding and compression molding. The influence of fiber type (i.e., bagasse, rice straw, rice husk, and pine fiber) and loading level of styrene-ethylene-butylene-styrene (SEBS) block copolymer on composite properties was investigated. Mechanical analysis showed that storage modulus and tensile strength increased with fiber loading at the 30% level for all composites, but there was little difference in both properties among the composites from various fiber types. The use of SEBS decreased storage moduli, but enhanced tensile strength of the composites. The addition of fiber impaired impact strength of the composites, and the use of SEBS led to little change of the property for most of the composites. The addition of fiber to PVC matrix increased glass transition temperature (T_g), but lowered degradation temperature (T_d) and thermal activation energy (E_a). After being immersed in water for four weeks, PVC/rice husk composites presented relatively smaller water absorption (WA) and thickness swelling (TS) rate compared with other composites. The results of the study demonstrate that PVC composites filled with agricultural fibers had properties comparable with those of PVC/wood composite.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Biodegradation of Poly(vinyl alcohol) and Bacterial Cellulose Composites by <Emphasis Type="Italic">Aspergillus niger</Emphasis>

The ability of fungal strains to attack a composite material obtained from poly(vinyl alcohol) (PVA) and bacterial cellulose (BC) is investigated. The fungal strain tested was Aspergillus niger. This fungal strain was able to change not only the polymer surface from smoother to rougher, but also to disrupt the polymer. The degradation results were confirmed by visual observations, scanning electron microscopy (SEM) analyses, X-ray diffraction analyses and FTIR spectra of the film samples. SEM micrographs confirmed the growth of fungi on the composite film surface. The degree of microbial degradation depends on culture medium and on composition of polymeric materials, especially on PVA content. The biodegradation process is accelerated by the presence of glucose in the culture medium as an easily available carbon source.     

Study of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/Bamboo Pulp Fiber Composites: Effects of Nucleation Agent and Compatibilizer

In this study, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/bamboo pulp fiber (BPF) composites were prepared by melt compounding and injection molding. The crystallization ability, tensile strength and modulus, flexural strength and modulus, and impact strength were found substantially increased by the addition of BPF. Tensile and flexural elongations were also moderately increased at low fiber contents (<20%). BPF demonstrated not only higher strength and modulus, but also higher failure strain than the PHBV8 matrix. Boron nitride (BN) was also investigated as a nucleation agent for PHBV8 and maleic anhydride grafted PHBV8 (MA-PHBV8) as a compatibilizer for the composite system. BN was found to increase the overall properties of the neat polymer and the composites due to refined crystalline structures. MA-PHBV8 improved polymer/fiber interactions and therefore resulted in increased strength and modulus. However, the toughness of the composites was substantially reduced due to the hindrance to fiber pullout, a major energy dissipation source during the composite deformation.     

Preparation and Characterization of Hybrids of Cellulose Acetate Membranes Blended with Polysulfone and Embedded with Silica for Copper(II), Iron(II) and Zinc(II) Removal from Contaminated Solutions

Journal of Polymers and the Environment - With the objective to assess the suitability of cellulose acetate (CA), polysulfone (PSF) and silica (SiO2) for wastewater treatment, this work presents...     

Mechanical Property Characterization of Plasticized Sugar Beet Pulp and Poly(Lactic Acid) Green Composites Using Acoustic Emission and Confocal Microscopy

Sorbitol and glycerol were used to plasticize sugar beet pulp-poly(lactic acid) green composites. The plasticizer was incorporated into sugar beet pulp (SBP) at 0%, 10%, 20%, 30% and 40% w/w at low temperature and shear and then compounded with poly(lactic acid) (PLA) using twin-screw extrusion and injection molding. The SBP:PLA ratio was maintained at 30:70. As expected, tensile strength decreased by 25% and the elongation increased. Acoustic emission (AE) showed correlated debonding and fracture mechanisms for up to 20% w/w plasticizer and uncorrelated debonding and fracture for 30–40% sorbitol and 30% glycerol content in SBP–PLA composites. All samples had a well dispersed SBP phase with some aggregation in the PLA matrix. However, at 40% glycerol plasticized SBP–PLA composites exhibited unique AE behavior and confocal microscopy revealed the plasticized SBP and PLA formed a co-continuous two phase system.