The aggregation structure regulation of lignin by chemical modification and its effect on the property of lignin/styrene–butadiene rubber composites

The aggregation structure of lignin in aqueous solution had an important effect on the dispersion of lignin and the properties of lignin/styrene–butadiene rubber (SBR) composites. This article revealed the relationship between aggregation structure and chemical structure of modified lignin. Unmodified lignin was amorphous; however, our results showed that aldehyde‐modified lignin was transformed into spherical aggregates, while propylene‐oxide‐modified lignin self‐aggregated into supramolecular domains. The relationships between aggregation structure, filler dispersion, filler–rubber interaction, and performance were also studied by investigating the microstructure, viscoelastic behavior, and mechanical properties of lignin/SBR composites. Meanwhile, a solution to improve the coprecipitation efficiency of lignin and SBR latex was proposed. In this article, epoxidized natural rubber (ENR) was also used as compatibilizer to improve the interfacial adhesion between polar lignin and nonpolar SBR. The results showed better lignin dispersion for the ENR‐containing rubber composites, as well as superior wet skid resistance and lower rolling resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45759.     

Preparations,properties, and formation mechanism of novel cellulose hydrogel membrane based on ionic liquid

Cellulose hydrogel membranes were successfully produced by casting the cellulose/1‐butyl‐3‐methylimidazolium chloride (BmimCl) solution into assembling molds, and then coagulated in water. The morphological features and mechanical properties of the prepared hydrogel membranes were characterized by a series of techniques including X‐ray diffraction measurements, scanning electron microscopy measurements, UV–visible light absorption spectrum, and tensile testing. The formation mechanism and the effects of different pre‐gelation temperature, pre‐gelation time, and coagulation batch temperature on the morphology and property of prepared cellulose hydrogel membranes were explored. The result shows that the hydrogel membrane of cellulose with excellent performance can be prepared adopting novel ionic liquid (BmimCl) as solvent through suitable process; the prepared hydrogel membranes present good mechanical properties and excellent transparency. In addition, the model of the hydrogel formation is established. It is believed that this is a promising material in the application of biomedical engineering and medical material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45488.     

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.     

Characterization and mechanical properties of ultraviolet stimuli‐responsive functionalized cellulose nanocrystal alginate composites

The poor mechanical properties of alginate when exposed to aqueous solution have been a problem plaguing researchers within the biomedical field. In order to be able to improve the mechanical properties in a systematic manner functionalized cellulose nanocrystals (CNCs) were added to alginate and UV‐induced crosslinked following an azo‐initiated free radical polymerization. CNCs were functionalized with 4‐pentenoic acid (PA‐g‐CNCs) using a simple, environmentally friendly solvent‐free esterification. The dimensional and crystallinity properties of PA‐g‐CNCs remained unchanged following esterification. Thermogravimetric analysis, Fourier transform infrared spectroscopy, and ¹³C nuclear magnetic resonance indicated that 4‐pentenoic acid was present on the surface of CNCs through bulk analysis. These PA‐g‐CNCs were then used in the creation of composites with an azo‐initiator to induce UV‐dependent crosslinking for the improvement of the mechanical properties of alginate. It was shown that the properties of alginate can be enhanced with the addition of functionalized CNCs to nanocomposites in mechanical testing in wet and dry conditions. These results suggest that the addition of PA‐g‐CNCs and crosslinking by UV‐dependent free radical polymerization improves the performance of alginate when tested in dry conditions, but without any apparent dependence to azo‐initiated crosslinking when exposed to water in regards to mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45857.     

Preparation and characteristic of a sodium alginate/carboxymethylated bacterial cellulose composite with a crosslinking semi‐interpenetrating network

A novel ionic crosslinking sodium alginate (SA)/carboxymethylated bacterial cellulose (CM‐BC) composite with a semi‐interpenetrating polymer network (semi‐IPN) structure was developed in this study. The composite was prepared through the blending of an SA gel with CM‐BC then crosslinking by Ca²⁺ followed by a freeze‐drying process. Scanning electron microscopy showed the composite matrix organized in a three‐dimensional network of CM‐BC interpenetrated against SA molecular chains with a quantity of calcium alginate microspheres upon the surface. The swelling ratios of the composite were enhanced by 183, 198, and 212% with the supplementation of CM‐BC weight fractions of 25, 50, and 75%, respectively; the swelling ratios changed with changing pH. The tensile modulus, tensile strength, and elongation at break of SA were enhanced by 165, 152, and 188%, respectively, with the addition of 50 wt % CM‐BC. This study demonstrated that the semi‐IPN structure dramatically changed the swelling and mechanical properties of the composite, and the semi‐IPN will be a promising candidate for biomedical applications such as wound dressings and skin tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39848.     

Surface properties,thermal, and mechanical characteristics of poly(vinyl alcohol)–starch‐bacterial cellulose composite films

Nanocomposite films for food packaging applications were developed using bacterial cellulose (BC) nanofibers in different amount in a poly(vinyl alcohol)/starch (PVA/St) matrix. In search of a better method to reduce the harmful ingredients in food packaging, the cellulose nanofibers were obtained by the mechanical defibrillation of BC pellicles thus avoiding the addition of chemicals in the final packaging material. Improved mechanical performances were obtained starting from just 1% BC nanofibers in PVA/St. Atomic force microscopy images showed a uniform dispersion of BC nanofibers on the surface of nanocomposites. A twofold increase of both tensile strength and modulus was obtained for 2 wt % BC in the composite. BC nanofibers have greatly improved the barrier properties of PVA/St matrix, a twofold increase of water vapor permeability being obtained for only 2 wt % BC nanofibers in the composite film. PVA/St/2BC was proposed as a high potential material for food packaging applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45800.     

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.     

Effect of the dissolution time on the structure and properties of lyocell‐fabric‐based all‐cellulose composite laminates

In this study, all‐cellulose composite laminates were prepared from lyocell fabric with ionic liquid (1‐butyl‐3‐methyl imidazolium chloride), a conventional hand layup method, and compression molding. Eight layers of lyocell fabric, which were impregnated with ionic liquid, were stacked symmetrically and hot‐pressed under compression molding for various times; this resulted in the partial dissolution of the surface of the lyocell fibers. The dissolved cellulose held the laminas together and resulted in a consolidated laminate. Finally, the prepared laminate was impregnated in water to remove the ionic liquid and to regenerate a matrix phase in situ; this was followed by hot‐press drying. Optical microscopy and scanning electron microscopy studies were used to analyze composite structures. With increasing dissolution time, the void content in the composites decreased, and the interlaminar adhesion improved. For LC‐2h and LC‐3h, the highest tensile strength and modulus values obtained were 48.2 MPa and 1.78 GPa, respectively. For LC‐4h, the highest flexural strength and modulus values obtained were 53.96 MPa and 1.2 GPa, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43398.     

Homogeneous synthesis and characterization of polyacrylamide‐grafted cationic cellulose flocculants

In this work, cationic cellulose (CC) with different degrees of substitution (DS) was successfully synthesized by the reaction between cellulose and 3‐chloro‐2‐hydroxypropyl‐trimethylammonium chloride (CHPTAC) in a 7 wt % NaOH and 12 wt % urea aqueous solution. The structure of the CC was characterized by using elemental analysis, ¹H‐NMR, and FTIR. The DS values of CC ranged between 0.18 and 0.50, which could be obtained by adjusting the reaction temperature, reaction time, and molar ratio of CHPTAC to anhydroglucose unit of cellulose. The cationic cellulose–graft–polyacrylamide flocculant (CC‐g‐PAM) based on CC and polyacrylamide (PAM) was also synthesized in a homogeneous aqueous solution. The flocculation characteristics of CC and CC‐g‐PAM were evaluated in a kaolin suspension. The results showed that CC‐g‐PAM was an effective flocculant for the kaolin suspension under acidic or neutral conditions, and the flocculation efficiency was over 90%, while the CC showed better flocculation performance under alkaline conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43106.     

Silicified microcrystalline cellulose based pellets and their physicochemical properties

Silicified microcrystalline cellulose (SMCC), Prosolv SMCC 50 was used as spheronization aid to manufacture pellets by extrusion and spheronization. Different ratios of SMCC to lactose were used to manufacture pellets using appropriate levels of water as liquid binder. Avicel PH101 based pellets were also manufactured for comparison of their physical properties. The ratio of liquid binder to spheronization aid was critical to produce pellets of desired size and shape. Extrudates composed of 20% aid could withstand only smaller spheronization force in order to be shaped into pellets. The successful products fulfilled the quality of pellets such as narrow size distribution and spherical in shape. The highest surface tensile strength was observed in pellets with equal ratio of lactose to SMCC while pellets having 20% aid disintegrated rapidly within 15 min. Furthermore, Prosolv SMCC 50 based pellets possessed a stronger surface tensile strength when compared with Avicel PH101 based pellets. In conclusion, Prosolv SMCC 50 has showed to be a good spheronization aid for extrusion and spheronization when used in the range of 20 to 80% content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43829.     

Cassava starch‐based nanocomposites reinforced with cellulose nanofibers extracted from sisal

Cellulose nanofibers were extracted from sisal and incorporated at different concentrations (0–5%) into cassava starch to produce nanocomposites. Films' morphology, thickness, transparency, swelling degree in water, water vapor permeability (WVP) as well as thermal and mechanical properties were studied. Cellulose nanofiber addition affected neither thickness (56.637 ± 2.939 µm) nor transparency (2.97 ± 1.07 mm^?1). WVP was reduced until a cellulose nanofiber content of 3.44%. Tensile force was increased up to a nanocellulose concentration of 3.25%. Elongation was decreased linearly upon cellulose nanofiber addition. Among all films, the greatest Young's modulus was 2.2 GPa. Cellulose nanofibers were found to reduce the onset temperature of thermal degradation, although melting temperature and enthalpy were higher for the nanocomposites. Because cellulose nanofibers were able to improve key properties of the films, the results obtained here can pave the route for the development and large‐scale production of novel biodegradable packaging materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44637.     

Reducing the environmental load of triacetyl cellulose film production using wood pulp

Triacetyl cellulose (TAC) films, which are currently produced mainly from cotton linter, are widely used for liquid crystalline display (LCD) applications. However, cotton linter is an expensive source of cellulose and the environmental load related with cotton cultivation is notoriously heavy. Herein, the replacement of cotton linter by wood pulp was systematically investigated to explore the possibility of TAC production using a less expensive source. The mechanical and thermal properties of TAC films made from wood (wTAC) were outstanding compared to those of TAC films made from cotton (cTAC). The optical transparency of wTAC was also excellent. While Tinuvin (a UV stabilizer) produced more isotropic structures in cTAC films, it produced more anisotropic structures in wTAC films. Overall, the optical films of wTAC showed good performance for LCD applications, comparable to that of cTAC. These results could be used to develop more environmentally friendly production methods for optical TAC films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42146.     

Surface modification of microcrystalline cellulose (MCC) and its application in LDPE‐based composites

Microcrystalline cellulose (MCC) was modified by grafting onto its surface ferulic acid, methacryloyl chloride and oleoyl chloride. The efficacy of the chemical modification was confirmed by X‐ray photoelectron spectroscopy. In addition, the size distribution of the cellulosic particles was investigated by optical microscopy and laser granulometry and its hydrophobicity was evaluated using a contact angle method. Finally, to investigate the affinity of modified MCC with a nonpolar polymer and to assess its potential as a biobased reinforcing filler, the modified MCC was compounded into low‐density polyethylene. An organic peroxide, dicumyl peroxide, was added at selected formulations to see if it could further enhance mechanical bonding between the polymer and the particulates. The dispersion was assessed by scanning electron microscopy. Mechanical properties were investigated through tensile testing while the melt rheology of the composites was monitored by small angle oscillatory shear rheology. The acylation modification of the MCC improved the dispersion within LDPE and enhanced the mechanical properties of the composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44348.     

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.     

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.     

Processing–morphology–property relationships of polypropylene–graphene nanoplatelets nanocomposites

Polypropylene (PP) nanocomposites reinforced with graphene nanoplatelets (GNPs) were prepared via melt extrusion. A special sheet die containing with two shunt plates was designed. The relationships among the flow field of the special die, exfoliation, and dispersion morphology of the GNPs in PP and the macroscopic properties of the nanocomposites were analyzed. Flow field simulation results show that the die with shunt plates provided a high shear stress, high pressure, and high velocity. The differential scanning calorimetry, X‐ray scattering, and electron microscopy results reveal that the nanocomposites prepared by the die with the shunt plates had higher crystallinity values and higher exfoliation degrees of GNPs. The orientation of the GNPs parallel with the extrusion direction was also observed. The nanocomposites prepared by the die with shunt plates showed a higher electrical volume conductivity, thermal conductivity, and tensile properties. This indicated that the high shear stress exfoliated the GNPs effectively to a thinner layer and then enhanced the electrical, thermal, and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44486.     

Regenerated cellulose aerogel: Morphology control and the application as the template for functional cellulose nanoparticles

This article focuses on controlling the morphology of regenerated cellulose aerogel (RCA) and its application as a template for the preparation of functional cellulose nanoparticles (FCNPs). RCA is prepared by lyophilizing cellulose hydrogel which is fabricated through a sol–gel method in sodium hydroxide (NaOH)/urea aqueous solution. The morphology of RCA is adjusted by varying the gelation temperature and time. With the gelation temperature and time increasing, lamellar RCA transforms into strings of cellulose nanoparticles. Subsequently, RCA with the morphology of "strings of nanoparticles" is modified through the bulk condensation of l -lactic acid and RCA. Eventually, the prepared functionalized RCA (FRCA) is dispersed in an organic solvent to obtain purified FCNPs. The results demonstrate that single FCNP can be obtained by dispersing FRCA in dimethyl sulfoxide. Moreover, the prepared FCNPs have uniform size, good thermal-stability, and increasing hydrophobicity, which are ideal candidates for polymer composites in terms of fillers.     

Effect of dimethyl sulfoxide on synthesis of thermoplastic cellulose‐Graft‐poly(l‐lactide) copolymer using ionic liquid as reaction media

In this study, ring‐opening graft polymerization of l ‐lactide onto cellulose was carried out homogeneously in ionic liquid (IL)/dimethyl sulfoxide (DMSO) co‐solvent as a reaction media. Through the effective control of high viscosity and steric hindrance caused by the interaction between the IL and the hydroxyl group of cellulose by adding DMSO as a co‐solvent, cellulose‐graft‐poly(l ‐lactide) (Cell‐g‐PLLA) copolymer with higher substitution efficiency was successfully prepared, at relatively low concentration of l ‐lactide. The maximum values of molar substitution, degree of lactyl substitution, and degree of polymerization of poly(l ‐lactide) in the copolymer were 3.76, 1.74, and 2.16, respectively, determined by ¹H‐NMR. The prepared cell‐g‐PLLA copolymers showed thermal plasticization with a glass transition temperature of 155°C. In addition, the thermal processibility could be improved as the amount of grafted PLLA in the copolymer increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41331.     

Thermoplastic composites of polyamide‐12 reinforced by cellulose nanofibers with cationic surface modification

Cellulose nanofibers (CNFs) have many useful properties, including high strength and low thermal expansion, and are also environmentally friendly, readily renewable, safe, and biodegradable. The focus of this study was the development of lightweight thermoplastic polymer composites with good mechanical properties based on the incorporation of CNFs that have undergone surface pretreatment with a cationic reagent. The polyamide (PA12) was mixed with surface‐treated CNFs using a twin screw extruder and the resulting pellets were injection molded. The Izod impact strength without notch of CNF‐based composites exceeded that of composites incorporating organophilic montmorillonite (OMMT), a representative nanocomposite material. When the Izod impact test without notch, the impact hammer was stopped by the specimen with incorporation of surface treated CNF. Furthermore, the bending modulus and strength were equal to or greater than that of OMMT composites. The heat distortion temperature was improved as 33°C from neat PA12, and moreover improved as 29°C from OMMT composites. Cationic pretreatment of the CNF surfaces was found to increase the dispersion of the fibers and also to greatly improve the mechanical and thermal properties of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40920.     

Morphological investigation of cellulose acetate/cellulose nanocrystal composites obtained by melt extrusion

Composites were prepared from cellulose acetate (CA) and cellulose nanocrystals (CNC) by melt extrusion using two methods for the introduction of CNC: direct mixing and predispersion in CA solution. CNC were isolated using hydrochloric acid to increase thermal stability allowing the composites to be processed above 150 °C. The effect of CNC dispersion on the composites morphology, thermal, and mechanical properties was investigated. Field emission scanning electron microscopy and transmission electron microscopy results indicated that the predispersion method allows better CNC dispersion and distribution when compared to the direct mixture method. In addition, predispersion promotes preferential CNC orientation in relation to the injection flow. The predispersion method also showed a 14% Young's modulus increase in composites containing 15 wt % CNC while no significant change was observed when using the direct mixing. The results obtained in this work show that, to achieve the percolation threshold, nanoparticle distribution is as important as their content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44201.