Preparation and characterization of polychloroprene nanocomposites with cellulose nanofibers from oil palm empty fruit bunches as a nanofiller

Cellulose nanofibers (CNFs) from oil palm empty fruit bunches were chemically modified by acetylation with acetic anhydride and pyridine (as the solvent and catalyst). The acetylated CNFs showed good dispersion in a polychloroprene (PCR) matrix. The tensile strength and modulus of neat PCR were improved, whereas its elongation at break decreased with increasing nanofiber content. Above the glass‐transition temperature (T_g), the dynamic mechanical analysis profiles showed that the storage modulus of the PCR–cellulose nanocomposites was higher than that of neat PCR. Meanwhile, the thermal stability was still maintained, and the T_g was close to the neat PCR at the 5 wt % addition level of CNFs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40159.     

Preparation and characterization of antimicrobial films based on nanocrystalline cellulose

Nanocrystalline cellulose (NCC) has great potential in applications in medical and food packaging due to its abundance, high specific surface area, biodegradability, biocompatibility, and reproducibility. N-Halamine is one of the most effective antibacterial agents, with broad-spectrum efficacy against microorganisms, good stability, and reproducibility. Due to the nanosize effect and high specific surface area of NCC, N-halamine-modified NCC is potentially an excellent biocidal compound. In this paper, an N-halamine precursor 1-hydroxymethyl-5,5-dimethylhydantoin (HDH) was used to modify NCC with cyanuric chloride (cych) as the bonding agent. After chlorination, the produced NCC-cych-HDH-Cl became antibacterial. The synthesized NCC-cych-HDH-Cl was added to a chitosan (CS) and polyvinyl alcohol (PVA) solution to prepare antibacterial films. The optimum mixing ratio of PVA and CS in the PVA/CS films and concentration of NCC-cych-HDH-Cl were investigated. The surface morphologies and mechanical properties of the antibacterial films were characterized with scanning electron microscopy, transmission electron microscopy, and mechanical strength tests. The results indicated that the film with 90/10 PVA/CS and 7.0% loading of NCC-cych-HDH-Cl exhibited excellent tensile strength. The antibacterial film with 5.91 × 10¹⁷ atoms/cm² of active chlorine displayed an excellent antibacterial property against Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47101.     

Mechanical and barrier properties of cardboard and 3D packaging coated with microfibrillated cellulose

Microfibrillated cellulose (MFC) is increasingly used with cellulosic substrates and especially with paper materials. Its use with cardboard remains not reported and the study of mechanical and barrier properties of MFC‐coated cardboard has been investigated in this article. The influence of coating process as well as the effect of MFC have been highlighted by comparing different MFC‐coated cardboard samples with PE‐coated cardboard samples. MFC was coated using bar coating process. Their distribution and homogeneity onto cardboard was observed using techniques such as SEM and FE‐SEM. Tests such as oxygen and air permeability, bending stiffness, and compressive strength have been carried out. The coating process used impacts significantly cardboard properties by two opposite ways: on one hand it damages the structure cohesion of cardboard decreasing its compressive strength; on the other hand it increases its bending stiffness by increasing considerably the samples thickness. The addition of MFC counterbalances the negative effects of the coating process: bending stiffness and compressive strength are indeed improved by 30% in machine direction. On the contrary, MFC does not enhance much cardboard barrier properties, although it considerably increases their water absorption. Within a framework of packaging application, MFC will rather have consequent effects on cardboard's properties as blend or as part of the multilayer structure. Other applications have to be considered for its use as top layer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40106.     

Gelling of cellulose nanowhiskers in aqueous suspension

The gelling properties of a 0.46 wt % semi‐dilute aqueous suspension of well‐characterized nanocrystalline cellulose particles extracted from the tunic of marine animals were studied by measuring the time evolution of linear viscoelastic moduli at various frequencies. The results show the existence of a gel time characterized by a frequency‐independent loss angle, which suggests that gelling is due to the growth of self‐similar clusters, whose fractal dimension was determined. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40676.     

Polypropylene reinforced with nanocrystalline cellulose: Coupling agent optimization

Five different grades of maleic anhydride polypropylene (MAPP) having different molecular weight and acid value (AV) were used as coupler in PP‐nanocrystalline cellulose (NCC) composites. The main objective was to study the effect of MAPP structure (Mw, AV) and filler/coupler (F/C) ratio on mechanical properties in order to find optimum mechanical properties in tension, flexion, and impact. Results showed that both Mw and AV have direct effect on mechanical properties and a balance between both must be achieved to get the best performance. However, regardless of MAPP structure, optimum improvement was obtained for F/C = 7.5/1. Shear rheological data showed that at high MAPP content, MAPP acts as lubricant. DSC and AFM analysis showed small reduction in the size of PP crystals in the presence of NCC. Rheological data under large amplitude oscillatory shear showed that the nanocomposites used here are under percolation. Using these analyses, possible reinforcement mechanisms were investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42438.     

Physical and tensile properties of epoxy laminated magnetic bacterial cellulose nanocomposite films

Despite many potential applications, the adverse impacts of magnetic nanoparticles on the tensile properties of magnetic cellulose papers and films are well established. On the other hand, water absorption and thickness swelling of cellulose materials are important limiting factors in many engineering applications. These challenges caused limited applications of magnetic cellulose nanocomposites. The aim of this study is to examine the possibility of modifying the physical and mechanical behaviors of magnetic bacterial cellulose films by epoxy resin lamination. Results showed that the tensile modulus and strength of the magnetic bacterial cellulose film, respectively, increased about 280% and 240% after epoxy lamination while they maintained their desirable magnetic and flexibility properties. Furthermore, the water absorption and thickness swelling of the epoxy laminated magnetic nanocomposite films, respectively, improved about 43% and 42%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45118.     

The electrospun polyhydroxybutyrate fibers reinforced with cellulose nanocrystals: Morphology and properties

Polyhydroxybutyrate (PHB) has been used in the biomedical field. However, the poor mechanical properties of PHB have limited its application. Here, electrospun fibrous nanocomposite mats reinforced with cellulose nanocrystals (CNCs) were fabricated by using PHB as polymeric matrix. The morphological, thermal, mechanical properties, as well as cytotoxicity were characterized. Increasing the concentration of CNCs caused a decrease in diameter of the electrospun fibers. Moreover, thermal analysis indicated that melting temperature of PHB/CNCs electrospun fibers were improved with the increased CNCs content. The addition of CNCs gradually enhanced the tensile strength till 8 wt % content followed by a gradual decrease at higher CNCs content (12–22 wt %) in tensile strength. The PHB/CNCs electrospun fibers were nontoxic to L‐929 and capable of supporting cell proliferation in all conditions. This study demonstrates that fibrous PHB/CNCs electrospun fibers are cytocompatible and potentially useful mechanical properties for biomedical application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43273.     

Innovative preparation of bacterial cellulose/silver nanocomposite hydrogels: In situ green synthesis,characterization, and antibacterial properties

In this study, an innovative in situ green strategy was applied to prepare bacterial cellulose/silver nanocomposites using green tea as a substrate for the fermentation of Acetobacter xylinum bacteria and a reducing agent for the in situ synthesis of silver nanoparticles. The samples were analyzed by different characterization tests including field emission scanning electron microscopy (FESEM), X-ray diffraction analysis (XRD), UV–vis spectroscopy, atomic absorption spectroscopy, and ATR. The results indicated the excellent antibacterial activities with 100% bacterial reduction percentage and inhibition zones of 2.6 and 2.8 cm against S. aureus and E. coli, respectively. Moreover, water absorption percentage and vertical wicking measurements supported the hydrogel properties of the prepared bio-cellulose/silver nanocomposites. Finding of this research suggested the potential of the proposed green route for preparing antibacterial BC which can be regarded as a candidate for future wound healing applications.     

High oxygen barrier materials from paper to regenerated cellulose films

A transparent, bendable, high oxygen barrier cellulose-based film was prepared, which has far better oxygen barrier properties than conventional polyethylene, polypropylene and cellophane materials. A series of regenerated cellulose films (RCs) were prepared from filter paper lacking oxygen barrier properties under different cellulose concentrations and gelation times. It was shown that the cellulose concentration and gel time had a greater effect on the oxygen barrier properties of RCs. When the cellulose concentration was 4 wt% and the gel time was 3 h, the RCs obtained the lowest oxygen permeability coefficient (OPC) down to 2.21 × 10⁻¹⁷ cm³ cm cm⁻² s⁻¹ Pa⁻¹. The films have a tensile strength of 109.5 MPa, an elongation at break of 27.3% and a light transmission rate of 89%. In further, molecular dynamics simulations showed that when the filter paper was converted to RCs, the increase in hydrogen bonding and the decrease in free volume between cellulose chains caused a decrease in the diffusion coefficient of oxygen. As a novel biobased high oxygen barrier material, the film has broad application prospect in packaging and chemical industry.     

Microcrystalline cellulose as reactive reinforcing fillers for epoxidized soybean oil polymer composites

Microcrystalline cellulose (MCC) and its oxidized product dialdehyde cellulose (DAC) were introduced as the reinforcing filler in epoxidized soybean oil (ESO) thermosetting polymer. The composites comprising up to 25 wt % cellulose fillers were obtained via a solution casting. The reinforcing effects of the cellulose were evaluated by microstructure analysis, dynamic mechanical analysis, and tensile and thermal stability tests. The results showed that at the same filler concentration, DAC led to higher stretching strength, modulus, and break elongation than MCC. The 5 wt % DAC loading in ESO polymer exhibits the highest toughness and thermal stability due to the good dispersion and interfacial interaction between DAC and ESO polymer matrix. The increased storage modulus and glass transition temperature also indicate the cellulose fillers impart stiffness to the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42488.     

Regenerated cellulose/layered double hydroxide nanocomposite films with improved mechanical property

Construction of environment-friendly biomass-based nanocomposites with high performance is in great demand for developing of a sustainable low-carbon society. Here, transparent and flexible regenerated cellulose (RC)/layered double hydroxide (LDH) nanocomposite films were prepared from aqueous NaOH/urea solutions. The obtained nanocomposite films were characterized using AFM, SEM, FTIR, XRD, tensile testing, water contact angle, and thermogravimetric analysis. The results show that LDH nanoplatelets were individually dispersed with a thickness of 1 nm and surface diameter of 100 nm after ultrasonic treatment. Strong interaction existed between LDH nanoplatelets and cellulose molecules, leading to the improved thermal stability and mechanical strength of RC together with the original good properties of LDH. In particular, the nanocomposite films with 10 wt% LDH showed a 135% and 234% increase in the tensile strength and Young's modulus than those of the neat RC film. Meanwhile, the nanocomposite films exhibited high transparency. Therefore, these RC/LDH nanocomposites are promising in the fields of high-performance packaging materials, flexible display panels, and high-temperature dielectric materials.     

Fabrication of natural cellulose microspheres via electrospraying from NaOH/Urea aqueous system

Regenerated cellulose microspheres (RCM) with controllable sizes and architectures are prepared via electrospraying from environmental‐friendly NaOH/Urea aqueous system. The particle size and shape of RCM is mainly dependent on the interplay among the electrical force, surface tension, and viscous force. Particle size can be reduced to a certain extent by increasing voltage and decreasing surface tension, electrode spacing, solution concentration, degree of polymerization, and flow rate. The deformation of droplets, which is peculiarly prone to occur for low viscosity and long electrode spacing, results in elongated spheres, tear‐shaped particles, wedge‐shaped particles, and banding shaped particles besides micorspheres. The sophericity and uniformity of particles generally become worse as a result of the deformation of droplets. RCM possess good porosity and large specific surface area after regeneration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40656.     

Preparation and characterization of transparent cellulose films using an improved cellulose dissolution process

Effective dissolution of cellulosic macromolecules is the first predominant step to prepare functional bio‐based materials with desirable properties. In this study, we developed an improved dissolution process using a freeze‐drying pretreatment to promote the dissolution of cellulose. Rheological measurements of cellulose solutions and physicochemical characterization of regenerated cellulose films (scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis) were performed. Cellulose solution prepared from 5% microcrystalline cellulose (w:v) in the solvent exhibits a Newtonian fluid character while cellulose solutions at higher concentrations show a pseudo‐plastic fluid behavior. Results from physicochemical characterization indicate that a freeze‐drying pretreatment step of cellulose leads to a complete dissolution at 5% concentration while only part of cellulose is dissolved at 10% and 15% concentrations. The results obtained indicated that the use of a freeze‐drying pretreatment step under mild conditions lead to a complete dissolution of cellulose at 5% concentration. The cellulose films prepared from 5% concentration exhibited desirable properties such as good optical transparency, crystallinity, and thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44871.     

Preparation of treelike and rodlike carboxymethylated nanocellulose and their effect on carboxymethyl cellulose films

In this work, carboxymethyl cellulose (CMC) with low substitution degree, followed by different posttreatments, was applied to prepare treelike CMC nanofibrils (CMCNFs) and rodlike CMC nanocrystals (CMCNCs), and their performance in CMC composite film was evaluated simultaneously. From transmission electron microscopy results, it was found that the treelike CMCNCFs exhibited a lager aspect ratio compared to the rodlike CMCNCs. As for reinforcing CMC film, 4 wt% was the best adding amount, at this time, the tensile strength of CMC/CMCNFs and CMC/CMCNCs composite films was increased by 72.1% and 47.3%, respectively. Moreover, adding these nanofillers to CMC also could enhance the thermal stability of composite films slightly, while the transmittance of composite films was reduced at the same time. In addition, CMC/CMCNFs film was designed as a packaging box to determine its performance. Therefore, this study could reveal the differences of properties for composites with different types of nanocellulose and provide a foundation for further application of nanocellulose.     

Development and characterization of chitosan bionanocomposites containing oxidized cellulose nanocrystals

In this research, cellulose nanocrystals (CNs) were extracted from corn cobs by 2,2,6,6,‐tetramethylpiperidine‐1‐oxyl radical‐mediated oxidation combined with ultrasonic treatment for the first time. These CNs were then used as a mechanical reinforcement agent and barrier in chitosan‐based bionanocomposite films. Birefringence analyses under crossed polarizers indicated the presence of isolated nanocrystals in suspension, which was later confirmed by TEM analysis. The crystallinity index obtained from X‐ray diffraction was 92.4%. The incorporation of these nanoparticles into a filmogenic matrix of chitosan made it possible to obtain bionanocomposite films with improved properties. The water‐vapor permeability was reduced by 70%, whereas the tensile strength and Young's modulus increased by up to 136 and 224% respectively. The developed films were applied as interleaving of sliced cheese, and the efficiency was assessed by investigation of adhesion between the surfaces and by comparing its properties with two commercial interleaving products (polyethylene (PE), and Greasepel paper (GP)). Concluding, the developed films showed a substantial potential to be exploited as an interleaving film, owing to its excellent mechanical properties, permeability, hydrophobicity, and low surface adhesion compared to pure chitosan, PE, and GP films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43033.     

Thermomechanical properties of poly(lactic acid) films reinforced with hydroxyapatite and regenerated cellulose microfibers

Novel composite films constituted of poly(lactic acid) (PLA), hydroxyapatite (HAp), and two types of regenerated cellulose fillers—particulate and fibrous type—were produced by melt extrusion in a twin‐screw micro‐compounder. The effect of the film composition on the tensile and dynamic mechanical behavior and the HAp dispersion in the PLA matrix were investigated thoroughly. Appearance of crazed regions and prevention of HAp aggregation in the PLA matrix were elucidated in the composites with up to 15 wt % particulate cellulose content, which was the main reason for only slight reduction in the tensile properties, and consequently trivial degradation of their pre‐failure energy absorption as compared to neat PLA films. Superior dynamical energy storage capacities were obtained for the particulate cellulose modified composites, while their fibrous counterparts had not as good properties. Additionally, the anisotropic mechanical behavior obtained for the extruded composites should be favorable for use as biomaterials aimed at bone tissue engineering applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40911.     

Cellulose nanocrystals extracted from okra fibers in PVA nanocomposites

Cellulose nanocrystals (CNC) were extracted from okra bahmia (Abelmoschus Esculentus) bast fibers and inserted in different tenors (1, 2, 5, and 10 wt %) as the reinforcement of a poly(vinyl alcohol) (PVA) matrix. The extraction of cellulose was carried out in a two‐step procedure: the first chemical treatment led to the production of holocellulose by the gradual removal of lignin, while the subsequent sulphuric acid hydrolysis process allowed obtaining cellulose nanocrystals in an aqueous suspension. The dispersion of CNC in the composite appeared effective at low cellulose content (1 wt %), while it presented more problems for higher contents. However, a 5 wt % cellulose content proved ideal to promote a direct mechanical interaction between the PVA and cellulose structures. Thermal analysis demonstrated that the presence of okra did not have a large effect on glass transition temperature, while it sensibly modified the melting temperature of the PVA matrix, as well as the crystallization temperature, due to the nucleating action of the nanofillers. FTIR spectroscopy performed during the exposure to UV light underlined that no oxidative reactions occur after a short‐time exposure and that a longer irradiation times are required to produce oxidation on neat matrix and PVA/CNC nanocomposites. The results confirmed that the presence of CNC does not affect the stability of the neat PVA matrix to the photodegradation after UV irradiation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crosslinked PVA nanofibers reinforced with cellulose nanocrystals: Water interactions and thermomechanical properties

Acid‐catalyzed vapor phase esterification with maleic anhydride was used to improve the integrity and thermo‐mechanical properties of fiber webs based on poly(vinyl alcohol), PVA. The fibers were produced by electrospinning PVA from aqueous dispersions containing cellulose nanocrystals (CNCs). The effect of esterification and CNC loading on the structure and solvent resistance of the electrospun fibers was investigated. Chemical characterization of the fibers (FTIR, NMR) indicated the formation of ester bonds between hydroxyl groups belonging to neighboring molecules. Thermomechanical properties after chemical modification were analyzed using thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. An 80% improvement in the ultimate strength was achieved for CNC‐loaded, crosslinked PVA fiber webs measured at 90% air relative humidity. Besides the ultra‐high surface area, the composite PVA fiber webs were water resistant and presented excellent mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40334.     

Melt extruded nanocomposites of polybutylene adipate‐co‐terephthalate (PBAT) with phenylbutyl isocyanate modified cellulose nanocrystals

Traditional commodity polymers are widely used in several disposable or short‐life items and take hundreds of years to decompose in nature. These polymers could be replaced in several uses by biodegradable polymers, like polybutylene adipate‐co‐terephthalate (PBAT) studied in this work. For this, nonetheless, it is necessary to improve some of the PBAT properties, like mechanical resistance and barrier properties. In this work, cellulose nanocrystals (CNC) were incorporated in PBAT with this intention, through melt extrusion. Aiming to avoid CNC aggregation during the drying and extrusion process, a CNC chemical modification with phenylbutyl isocyanate was done. It was possible to obtain PBAT‐CNC melt extruded composites with an elastic modulus 55% higher and water vapor permeability 63% lower than the values of the pure polymer, without compromising PBAT biodegradation. Therefore, the composites prepared with these enhanced properties have great potential as substitutes for traditional commodity polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43678.     

Development of active cassava starch films reinforced with waste from industrial wine production and enriched with pink pepper extract

This study investigated the influence of grape stalk (GS) from the Bordo grape variety (Vittis labrusca L.) as a reinforcing agent, and pink pepper (Schinus terebinthifolius Raddi) extract (PPE) as an antioxidant, in cassava starch (CS)-glycerol (GLY) films. The developed biodegradable films were characterized according to structural, barrier, mechanical, antioxidant and optical properties, as well as biodegradability and compared to both the control and blank films. Films containing a high GS content exhibited a significant increase in tensile strength (TS) values by 73%, whereas the films containing a high PPE content exhibited an important increase elongation (ELO) values by 20%, comparing to the control film (CO). The films containing 5.52% v/v of PPE presented an improving on antioxidant activity and barrier properties, leading DPPH and ABTS percentual radical scavenging activity by 51.79% and 58.18%, and decreasing water vapor permeability and solubility by expressive values of 34.11% and 79.43%, respectively. According to the results obtained in this study, the films using GS and PPE exhibited valuable characteristics and are an alternative for applications as a promising biodegradable packaging material.