Preparation and analysis of poly(l-lactic acid) composites with oligo(d-lactic acid)-grafted cellulose

α-Cellulose extracted from jute fiber was grafted with oligo( d -lactic acid) (ODLA) via a graft polycondensation reaction in the presence of para-toluene sulfonic acid and potassium persulfate in toluene at 130 °C for 9 h under 380 mmHg. ODLA was synthesized by the ring-opening polymerization of d -lactides in the presence of stannous octoate (0.03 wt % lactide) and d -lactic acid at 140 °C for 10 h. Composites of poly( l -lactic acid) (PLLA) with the ODLA-grafted α-cellulose were prepared by the solution-mixing and film-casting methods. The grafting of ODLA onto α-cellulose was confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The analysis of the composites was performed with FTIR spectroscopy, SEM, wide-angle X-ray diffraction, and thermogravimetric analysis. The distribution of the grafted α-cellulose in the composites was uniform and showed better compatibility with PLLA through intermolecular hydrogen bonding. Only homocrystalline structures of PLLA were present in the composites, and the thermal stability increased with increasing percentage of grafted α-cellulose. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47424.     

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.     

Effects of biocide treatments on durability of wood and bamboo/high density polyethylene composites against algal and fungal decay

The main objective of this study was to investigate the algal and fungal resistance of biocide‐treated wood flour (WF)/high density polyethylene (HDPE) and bamboo flour (BF)/HDPE composites. The biocides included 4,5‐dichloro‐2‐octyl‐isothiazolone (DCOIT), zinc pyrithione (ZPT), and carbendazim (MBC). Resistance to algae and fungi was evaluated by artificially accelerated tests. Treated and untreated samples were exposed to algae (Chlorella vulgaris, Ulothrix sp., Scenedesmus quadricauda, and Oscillatoria sp.) and fungi (Coriolus versicolor and Poria placenta) for 21 days and 12 weeks, respectively. The volatile components of WF and BF extractives were analyzed by gas chromatography‐mass spectrometry (GC‐MS). The results indicated that incorporation of DCOIT, ZPT, and MBC effectively enhanced the durability of WF/HDPE and BF/HDPE composites against algal and fungal decay. Accordingly, DCOIT, ZPT, and MBC can be used as potential biocides for both WF/HDPE and BF/HDPE composites. GC‐MS analysis suggested that palmitic acid, oleic acid, stigmasta‐3,5‐dien‐7‐one, and vanillin in WF possibly provided some resistance to fungal attack, whereas di (2‐ethylhexyl) phthalate and linoleic acid in BF were responsible for algal resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45148.     

Nanocomposites of ethylene vinyl alcohol copolymer with thermally resistant cellulose nanowhiskers by melt compounding (I): Morphology and thermal properties

In this study, ethylene‐vinyl alcohol copolymer (EVOH) nanocomposites were prepared by melt compounding both plant cellulose nanowhiskers (CNW) and bacterial cellulose nanowhiskers (BCNW) as nanofillers. Electrospinning and a “dissolution precipitation” method were used as strategies for the incorporation of CNW in EVOH before melt compounding with the aim of enhancing the degree of dispersion of the nanocrystals when compared with direct melt‐mixing of the freeze‐dried product with the polymer. As revealed by morphological characterization, the proposed preincorporation methods led to a significant improvement in the dispersion of the nanofiller in the final nanocomposite films. Furthermore, it was possible to incorporate concentrations as high as 4 wt % BCNW without causing significant agglomeration of the nanofiller, whereas increasing the CNW concentration up to 3 wt % induced agglomeration. Finally, DSC studies indicated that the crystalline content was significantly reduced when the incorporation method led to a poor dispersion of the nanocrystals, whereas high‐nanofiller dispersion resulted in thermal properties similar to those of the neat EVOH. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel biocomposites based on wheat gluten and rubber wood sawdust

Rubber wood sawdust (RWS) was used as a reinforcement for wheat gluten based bioplastics. The RWS content was varied from 0, 5, 10, 15–20 wt %. Effects of the RWS content on the morphology, water absorption, mechanical, thermal, and biodegradation properties of the wheat gluten based bioplastic were investigated. An addition of RWS caused an improvement of the tensile strength and water resistance of the wheat gluten based bioplastics. Scanning electron micrograph of the wheat gluten/RWS composites with a 10 wt % of RWS revealed a good dispersion and uniform embedding of the RWS within the wheat gluten matrix. Agglomeration of RWS was observed when the RWS loads were increased (15 and 20 wt %). The biodegradation process of the composites depended on the amount of RWS. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43705.     

Modification of the wood-plastic composite for enhancement of formaldehyde clearance and the 3D printing application

As the formaldehyde is one of the main indoor pollutants, the purpose of this study is to effectively remove indoor formaldehyde pollution by using environmentally friendly 3D printing ornaments. The wood 3D printing filaments cellulose/polylactic acid composite (Cellu/P) was selected as the starting material, and 3-aminopropyltriethoxysilane (APTES) was used for chemical modification to obtain a series of cellulose composite materials with amino groups. The modified composite materials (APTES@Cellu/P) were characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy, thermogravimetric analysis, and mechanical tests, and a formaldehyde removal experiment was performed. The feasibility of 3D printing was evaluated, and the process of 3D printing-functionalized customized ornaments was proposed, and then a school emblem was used for modeling, printing, and surface modification. Compared with the commercially traditional activated carbon, 3D printing-customized ornaments of APTES@Cellu/P material has a better formaldehyde removal effect, and can even avoid the secondary pollution that is common to the activated carbon.     

In-depth material characterization of polyhydroxybutyrate from a forest biorefinery

Large-scale replacement of petroplastics with compostable plastics, like polyhydroxybutyrates (PHB) will contribute to elimination plastic pollution, decrease greenhouse gas emissions, and valorize local biomass resources. Lignocellulose hydrolysates have emerged as potentially sustainable carbon sources for PHB production. For industrial processing, it is necessary to know the polymer properties. Yet, most studies on PHB samples from lignocellulose report few material properties. PHB samples produced from a pilot scale hardwood holocellulose hydrolysate conversion process were characterized and compared with PHB from a sugar hydrolysate and a commercial PHB powder. PHB from hardwood holocellulose hydrolysate was found to be comparable with commercial PHB in all properties. Differential scanning calorimetry and thermal gravimetric analysis showed that all samples had similar thermal behavior, where the melting temperature was 176°C and the decomposition temperature was 293°C. From the melting enthalpy, all samples showed 63% crystallinity. Dynamic mechanical analysis showed a glass transition temperature at 5°C and a crystallization temperature of 57°C. Fourier transform infrared spectroscopy and nuclear magnetic resonance confirmed that the samples were homopolymers comprised of hydroxybutyrate units. The difference among the samples was the number average molecular mass, being lower for wood hydrolysate (246.4 kDa) than sugar hydrolysate (670.3 kDa).     

Alkaline extraction of xylan from wood using microwave and conventional heating

This study aims to investigate the effect of microwave heating versus conventional heating for the alkaline hydrolysis of xylan from birch wood to understand the effect of the heating process on the dissolution of wood, the yield of xylan, and the degree of polymerization of the isolated xylan. The results indicate that the rate of wood dissolution is significantly higher (0.020/s) during microwave extraction than the conventional extraction (0.001/s). Wood solubilization, after an initial rapid removal of damaged fibers, is linear with time for both conventional and microwave extraction, with microwave showing a rate 20 times faster. The yield of xylan reaches a limit of about 60% for both processes but then declines slowly as thermal degradation become significant. Microwave heating provides 60% yield in 1/10th the time of the conventional process. This is found to be associated with the rapid temperature rise, and also with local “hot spots” generated during microwave treatment. The results indicated that xylan degradation was significant above 95°C. The nature of the isolated xylan was different for the two heating methods: the xylan isolated using microwave extraction for 20 min exhibits higher molecular weight (i.e., a greater degree of polymerization, about 150) than the xylan isolated using conventional extraction for the same duration (degree of polymerization, about 124) demonstrating the effectiveness of microwave heating for extraction of xylan from wood. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41330.     

Sustainable bionanocomposite from d,l‐lactide/δ‐valerolactone triblock and bionanowhiskers: Preparation,characterization, and properties

Bionanocomposites were prepared using d ,l ‐lactide–δ‐valerolactone–d ,l ‐lactide triblock and unmodified and modified cellulose nanowhiskers (CNs) at different loadings (0, 2, 4, 8 wt %). Poly(δ‐valerolactone) chains were grafted on CNs for modification. These were characterized by various techniques. The broadening of OH (hydroxyl) stretching region and the presence of low‐intensity peaks at 1064 cm^?1 for C? O/C? C stretching vibration and 1426 cm^?1 for bending vibration of CH₂ group_, were evident in Fourier transform infrared spectra of the nanocomposites. The increase in crystallinity was noticed as the amount of nanowhiskers was increased. The nanowhiskers having the width in the range of 80–300 nm were uniformly dispersed in the triblock matrix. The tensile strength and modulus increased by 130% and 50% respectively at 8 wt % of filler loading. The storage modulus, loss modulus, complex viscosity, and tan δ values increased with increased filler loading. Further improvement in mechanical properties was observed with the modified CNs. The modulus mapping from atomic force microscopy confirmed the effective reinforcement behavior of the nanowhiskers. Scaffold fabrication using the bionanocomposite exhibited porous nature, having a homogeneous dispersion of CNs on the surface of the scaffold. The 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay confirmed the suitability of the composite material for scaffold application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 135, 46035.     

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.     

Hydrolysis of birch wood by simultaneous ball milling,dilute citric acid,and fungus Penicillium simplicissimum treatment at room temperature

In this study, birch wood chips were treated in one‐step ball milling (BM) hydrolysis with dilute citric acid and fungus Penicillium simplicissimum at room temperature and atmospheric pressure. An efficient conversion process for the production of fermentable sugars from woody biomasses using wet BM system was developed, in which wood lignocellulose was hydrolyzed into reducing sugars with the total yield of 245.3 mg/g wood. The concentrations of several major substances in the hydrolyzate were discussed in detail. The yields of the monomeric sugars were notably increased in the presence of fungus P. simplicissimum. Corresponding structure transformations before and after milling were analyzed by X‐ray diffraction, UV spectroscopy, transmission Fourier transform infrared spectroscopy, and environmental scanning electron microscopy clearly indicated that this combined treatment could be attributed to the crystalline and chemical structure changes of wood lignocellulose during BM. When compared with traditional method of BM, this work showed a more simple, novel, and environmental friendly way in mechanochemical treatment of lignocellulosic biomass, especially woody biomass. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanomechanical properties and thermal stability of recycled cellulose reinforced starch–gelatin polymer composite

Samples of starch?gelatin polymer reinforced with 5% of recycled cellulose were prepared using an extrusion‐compression molding process. Nanoindentation and atomic force acoustic microscopy (AFAM) techniques were used to study the effect of reinforcement at nanoscale level. Nanoindentation tests show a 163% increase in hardness and 123% of elastic modulus enhancement after recycled cellulose inclusion. AFAM shows that distribution of recycled cellulose into the polymer matrix is rather homogeneous at nanoscale which improves load transfer. Thermogravimetric analysis indicates an increase in thermal stability of the cellulose reinforced polymer matrix samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41787.     

Poly(lactic acid)–thermoplastic starch–cotton composites: Starch-compatibilizing effects and composite biodegradability

Poly(lactic acid) (PLA) is a biodegradable, brittle, and high-cost polymer, which can be applied over structural components and green packaging. In this study, we reinforced PLA with natural cotton (10 wt %) and thermoplastic starch (TPS; 3 wt %) to obtain a biodegradable and lower cost composite. TPS was incorporated in three distinct ways: it was blended, coated, and blended and coated. In this study, we investigated the compatibilization of TPS in the improvement of matrix-reinforcement adhesion and increase in the tensile behavior without a compromise in biodegradation. The samples were investigated with thermal analysis, dynamic mechanical thermal analysis, tensile testing, scanning electron microscopy, confocal laser scanning microscopy, and hydrolytic degradation. The results show that the coupling effect was more pronounced in the PLA_TPS–cotton_TPS (hybrid system with PLA and cotton) hybrid system. This formulation presented a higher glass-transition temperature, thermal stability, storage modulus, wettability, and ductility. The TPS addition improved the adhesion between the matrix and starched cotton fiber and retarded abiotic biodegradation. These properties will allow for green applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47490.     

Controlling lignin particle size for polymer blend applications

Softwood lignin produced by the LignoForce System^TM was physically processed using different milling approaches to ascertain effective and scalable means to yield micro to submicron particles of controllable and uniform size. Our work suggests that wet ball‐milling using a small milling medium is the most reliable method in terms of processing efficiency and particle‐size controllability. Controllable particle size reduction would permit lignin to be used as an effective filler in polymer blends. We show that wet‐milled lignin could, subsequently, be oven‐ or spray‐dried, and, subsequently, blended with, for instance, polypropylene (PP) through co‐extrusion. The spray‐drying method produced spherical lignin aggregates smaller and more uniform than oven‐dried ones. As a consequence, spray‐dried lignin demonstrated a more uniform distribution within the polymer melt, leading to noticeable improvement in the strain—or flexibility—of the lignin‐PP polymer blends. Furthermore, it is confirmed that the investigated drying methods had no effect on the thermal stability of the resulting lignin‐PP blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44669.     

Modifying biodegradable plastics with additives based on condensed tannin esters

Condensed tannins derived from Pinus radiata bark have been esterified and added to biodegradable plastics as extrusion compounded functional plastic additives. The presence of longer alkyl chain hexanoate esters promoted tannin miscibility in the commercial polyesters Bionolle? and Biopol? whereas short chain acetate esters tended to remain as discrete domains, acting as fillers in the processed plastics. In the aliphatic polyester Bionolle the presence of tannin esters at typical plastic additive loadings did not alter plastic mechanical properties whereas at 5% content in Biopol the tannin‐additives reduced both flexural and tensile properties. Similarly tannin esters do not alter the melt or glass transition temperatures of the polyesters, but tannin hexanoate at 5% can influence the crystallization temperatures. Artificially aging plastics realized the functionality these plant extracts can impart to plastics in acting to reduce ultraviolet (UV)‐induced plastic degradation. Results indicate the tannin‐additives likely provide a stabilising role through inhibiting UV penetration into the plastic, with color analysis suggesting the tannin moiety itself was sacrificial and preferentially degrading. The imparted UV stability was linked to the dissolution of tannin esters in the plastic with longer chain esters providing greater protection against UV degradation. Tannin esters showed potential as functional additives for biodegradable polymers enhancing the UV stability of the plastic. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41626.     

Preparation and properties of cotton stalk bark fibers using combined steam explosion and laccase treatment

Cotton stalk bark fibers (CSBF) were prepared using combined steam explosion and laccase treatment (explosion–laccase). CSBF have been applied to reinforce thermoplastic composites, but were difficult to be spun into yarns due to their inferior fineness and high stiffness. In order to improve the fineness and flexibility with a green method, explosion–laccase treatment was used to separate bark of cotton stalks. The results indicated that steam explosion at 1.7 MPa for 3 min effectively facilitated laccase penetration into the lignocellulose complex to enhance delignification without negative effects on activity of laccase. Compared with CSBF after explosion, CSBF after explosion–laccase had better fineness (31 dtex), higher aspect ratio (1110), higher tensile strength (2.81 cN/dtex), higher flexibility (321 twist/(m·dtex)), and better thermal stability, which meets the requirement of textile fibers. CSBF had higher water retention (127%) and moisture regain (10.3%) than cotton. Explosion–laccase is an effective and eco‐friendly method of preparing CSBF for textiles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45058.     

PBAT/PLA/cellulose nanocrystals biocomposites compatibilized with polyethylene grafted maleic anhydride (PE-g-MA)

The use of biodegradable polymers has grown exponentially due to their lower environmental impact when compared to conventional polymers. In this sense, biocomposites are an alternative due to their promising properties, maintaining biodegradability. For this purpose, in the present study, a biodegradable biocomposite of PBAT (poly [butylene adipate co-terephthalate]) and PLA (polylactide) blend containing cellulose nanocrystals (CNC) were obtained, using polyethylene grafted with maleic anhydride (PE-g-MA) as a coupling agent. Seven formulations were produced by extrusion and had their structure, morphology, thermal, and rheological properties analyzed. The results showed a significant improvement of adhesion among the components using PE-g-MA as a coupling agent. Moreover, CNC and PE-g-MA increased the PLA crystallinity degree and reduced the complex viscosity. These results are unprecedented in the literature using these compositions and extrusion processing conditions. Therefore, these new insights provide a vast horizon for the use of biodegradable mixtures using PBAT/PLA and CNC.     

Mechanical recycling of nanocellulose containing multilayer packaging films

The aim of this study was to demonstrate mechanical recycling of low density polyethylene (LDPE) films coated with a thin layer of cellulose nanofibrils (CNFs). CNF acts as an effective barrier against oxygen and mineral oil residues. Two different CNF grades were tested, and both were applied onto plasma activated LDPE film using a pilot coating line. The coated films were shredded with the help of liquid nitrogen, compacted and compounded with virgin LDPE and compatibilizer, and processed into cast films and injection molded test specimens. The CNF coatings were completely blent as microscale agglomerates in the LDPE matrix. The effect of these agglomerates on the barrier and heat sealing properties was statistically insignificant compared to recycled uncoated LDPE. The mechanical properties were only moderately changed. CNF‐coated LDPE films can therefore be recycled back into films without sacrificing the characteristic properties of the base polymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46237.     

Fire retardant cellulose aerogel with improved strength and hydrophobic surface by one-pot method

Bio-based materials with multifunctional performance are getting immense attention nowadays for their environment friendly and renewable character. Inspired by toughening effect of graphene nanosheets and borate chemistry, a simple in-situ borate crosslinking in water and freeze-drying method was employed to fabricate a fire retarded bio-based aerogel. The structure of the material was evaluated and analysis by SEM, XRD, FTIR, Raman and XPS. Importantly, the bio-based aerogel has improved strength and adsorption properties due to unique structure. The compressive strength of rGO(reduced graphene oxide) + CMC (carboxymethyl cellulose) aerogel could reach 128 ± 2.1 kPa which is five times that of neat CMC aerogel. The bio-based aerogel can load more than 2500 times of self-weight. The adsorption capacity for organic solvents and oil of rGO+CMC aerogel is also greatly improved by a little rGO (1%) introducing due to its unique porous structure and hydrophobic nature of rGO. Additionally, rGO+CMC aerogel is also found fire resistant with relatively low thermal conductivity due to the borate and GO introduction.     

Recycling of wood fiber‐reinforced HDPE by multiple reprocessing

The mechanical recycling of high‐density polyethylene (HDPE) reinforced with wood fiber was studied by means of repeated injection moulding. The change in properties during the recycling was monitored by tensile and flexural tests, Charpy impact tests, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), FTIR spectroscopy, and by measuring the fiber lengths. Tests were also done where injection moulding was combined with subsequent accelerated thermo‐oxidative ageing and thereafter repeated numerous times. The results showed that the HDPE composites were relatively stable toward both the ageing conditions and the repeated injection moulding. The change of the mechanical properties was mainly observed as an increased elongation at max. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43877.