Miscible raw lignin/nylon 6 blends: Thermal and mechanical performances

Environmentally friendly bio‐filled composites of various proportions of polyamide 6 (PA6) and technical lignin have been prepared using a twin‐screw extruder. Transmission electron microscopy has been used to investigate the morphology of the composites. It reveals homogeneous single phase system, indicating the miscibility of PA6 and lignin. The glass transition temperature of the blends, determined by DMA, was shifted systematically to higher temperature with increasing concentration of lignin which highlights the miscibility of both components. In addition, Fourier Transform Infrared analyses have shown that new specific hydrogen‐bonding interactions are formed between hydroxyl groups of lignin and amine groups of the PA6. The presence of these intermolecular interactions between PA6 and lignin strongly influenced the thermal stability of the blends by lowering the onset of the blend's degradation process. However, the blends exhibit good mechanical properties whatever the lignin content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42963.     

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.     

Effect of processing conditions on wood and glass fiber length attrition during twin screw composite compounding

In this study, we compare the effect of twin-screw extrusion processing on the attrition of wood fibers (WFs) with glass fiber. The effects of process variables and screw design on fiber length were investigated by performing a range of dead-stop experiments where the extruder was stopped, opened-up, and compound removed from the screw elements. Fibers, chemically extracted from the polypropylene matrix, were analyzed for length and width using a commercial fiber analyzer. It was found that WF length attrition and composite properties were less affected by screw design and twin-screw processing conditions (feed rate and screw speed) than glass fiber. Length weighted fiber length and X50 length (a measure used in particle size analysis) were equally correlated with process conditions and composite performance for both fiber types. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48551.     

Alfa fiber/polypropylene composites: Influence of fiber extraction method and chemical treatments

Alfa fiber/polypropylene composites were manufactured using twin-screw extrusion. Fibers were extracted using alkaline and steam explosion methods. Three chemical treatments were also applied to the alkaline-extracted fibers: stearic acid (SA), and potassium permanganate dissolved in water (KW) and in acetone (KA). Finally, thermal annealing was applied to the composites. The results indicate that composites with steam-exploded fibers had a significantly higher melt flow index than composites with alkaline-extracted fibers. Moreover, the incorporation of fibers into the matrix increased the Young's modulus, where the optimum results were obtained utilizing the alkaline-extracted fibers. Both extraction methods also significantly decreased the water uptake, especially the steam explosion. The three chemical treatments increased the melt flow index and conversely decreased the tensile strength and Young's modulus. In addition, KW treatment decreased the water uptake. Finally, thermal annealing increased the tensile strength and Young's modulus of composites with SA-treated fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47392.     

The rheology and extrusion processing performance of wood/melamine composites

A modified melamine resin that exhibits both thermoplastic and thermoset behaviors was used as a matrix for wood plastic composites (WPCs). The thermoplastic melamine (TPM) resin exhibits a glass transition at approximately 34°C and continues to be thermally malleable until a crosslinking reaction develops with additional heating and an acid catalyst. Varying blends of TPM and wood flour were evaluated for their rheology and curing behavior using torque rheometry. WPC composites were manufactured with extrusion methods and final product properties determined. The torque rheometry results showed a highly dependent relationship of the curing behavior to the amount of wood flour utilized and temperature. Based upon the torque rheometry results, two extrusion platforms were developed to initiate the curing process; (1) cure within the die land and (2) post‐cure of the extrudate. The post‐cure procedure provided composites with higher mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39858.     

Valorization of pineapple peel waste and sisal fiber: Study of cellulose nanocrystals on polypropylene nanocomposites

The present study focuses on the isolation and characterization of the cellulose nanocrystals (CNCs) from the pineapple peel waste (PPW) (agro-waste) and sisal fiber (SiF) (natural fiber) employing the acid hydrolysis method, and its comparison with the commercially available CNCs (CNC-C). Furthermore, the CNCs from PPW, SiF, and CNC-C were subjected to transmission electron microscopy (TEM), Fourier transform electron microscopy, X-ray diffraction, particle size distribution, and zeta potential analysis. The studied properties of the isolated CNCs are considerably different from the PPW and SiF. The CNCs so formed have been estimated by TEM to be around 10–40 nm wide and length of several micrometers. Fourier transform electron microscopy studies described the removal of the noncellulosic components like lignin, hemicellulose, and pectin substances from the base materials in both the cases by employing acid hydrolysis method. Additionally, nanocomposites of CNC isolated from PPW along with polypropylene (PP) matrix were fabricated using melt blending method followed by injection molding. Maleic anhydride grafted PP (MAPP) acts as a compatibilizer for improving the dispersibility of hydrophilic CNC within the nonpolar PP matrix. The addition of CNC (3 wt%) along with MAPP at 5 wt% showed optimum tensile strength and modulus to the tune of 10.39 and 25.53%, respectively, when compared to their counterparts without MAPP. Dynamic mechanical analysis revealed an increased stiffness of PP in its nanocomposite system due to the addition of CNC. Scanning electron microscopy studies revealed uniform distribution of CNC within the nonpolar PP matrix in the presence of MAPP.     

The challenge of predicting spinnability: Investigating benefits of adding lignin to cellulose solutions in air-gap spinning

In this study, the underlying mechanism for improved spinnability when mixing lignin and cellulose in solution was investigated. Co-processing of lignin and cellulose has previously been identified as a potential route for production of inexpensive and bio-based carbon fibers. The molecular order of cellulose contributes to the strength of the fibers and the high carbon content of lignin improves the yield during conversion to carbon fibers. The current work presents an additional benefit of combining lignin and cellulose; solutions that contain both lignin and cellulose could be air-gap spun at substantially higher draw ratios than pure cellulose solutions, that is, lignin improved the spinnability. Fibers were spun from solutions containing different ratios of lignin, from 0 to 70 wt%, and the critical draw ratio was determined at various temperatures of solution. The observations were followed by characterization of the solutions with shear and elongational viscosity and surface tension, but none of these methods could explain the beneficial effect of lignin on the spinnability. However, by measuring the take-up force it was found that lignin seems to stabilize against diameter fluctuations during spinning, and plausible explanations are discussed.     

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.     

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.     

Rheological behavior of cellulose nanocrystal suspension: Influence of concentration and aspect ratio

The steady and dynamic rheological behaviors of two cellulose nanocrystal (CNC) suspensions were investigated over a wide range of concentrations. The viscosity, storage and loss modules increased with increasing CNC concentration, and both CNC suspensions showed three regions in a viscosity‐concentration graph. The two critical concentrations depended on the aspect ratio and corresponded to the overlap and gelation concentration. Because of the higher aspect ratio, switchgrass CNC suspension transitioned into a biphasic state and formed a hydrogel at lower concentrations than those of cotton CNC suspensions. Furthermore, the complex viscosities of both CNC suspensions were higher than their steady viscosities; therefore, neither CNC suspension followed the Cox–Merz rule, which may be attributed to the existence of a liquid crystal domain in each suspension. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40525.     

Melt compounded nanocomposites with semi‐interpenetrated network structure based on natural rubber,polyethylene, and carrot nanofibers

The present study deals with the processing and characterization of cellulose nanocomposites natural rubber (NR), low‐density polyethylene (LDPE) reinforced with carrot nanofibers (CNF) with the semi‐interpenetrated network (S‐IPN) structure. The nanocomposites were compounded using a co‐rotating twin‐screw extruder where a master‐batch of NR and CNF was fed to the LDPE melt, and the NR phase was crosslinked with dicumyl peroxide. The prepared S‐IPN nanocomposites exhibited a significant improvement in tensile modulus and yield strength with 5 wt % CNF content. These improvements are due to a better phase dispersion in the S‐IPN nanocomposites compared with the normal blend materials, as demonstrated by optical microscopy, electron microscopy and ultraviolet–visible spectroscopy. The S‐IPN nanocomposite also displayed an improved crystallinity and higher thermal resistance compared with NR, CNF, and the normal blend materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45961.     

Size controlling of monodisperse carboxymethyl cellulose microparticles via a microfluidic process

Monodisperse carboxymethyl cellulose containing phenolic groups (CMC‐Ph) microdroplets with a radius of 100–400 μm and a coefficient of variation below 3% were produced in a coflowing microfluidic device. The CMC‐Ph solution containing horseradish peroxidase was used as the disperse phase and liquid paraffin containing H₂O₂ and lecithin as the continuous phase. The size of microdroplets decreased with the decreasing diameter of the inner channel and concentration of the disperse phase. When using a 0.04% CMC‐Ph solution and the device with the inner diameter of 160 μm, the size of the microdroplets can be further controlled by the flow rates of both the continuous phase and disperse phase following exponential models. The volume of the microdroplet was not inversely proportional to the flow‐rate ratio of the continuous phase to the disperse phase. There was a weak dependence of the volume on the flow of the continuous phase. The monodisperse microparticles possessed potential application for sensor, drug delivery system, cell encapsulation, catalysis, and imaging. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40663.     

Influence of wood pulp quality on the structure of carboxymethyl cellulose

The quality of carboxymethyl cellulose (CMC) prepared from different wood-derived market pulps is examined. The pulps represent kraft and sulfite qualities with different levels of hemicellulose (1.5–22.8 wt %), intrinsic viscosity (391–780 mL g⁻¹), and content of extractives (0.04–0.13 wt %). The pulps are carboxymethylated in aqueous medium at three different levels of sodium hydroxide concentration, resulting in three levels of degree of substitution (DS), 0.3, 0.7–0.8, and 1.3–1.4 (according to nuclear magnetic resonance spectroscopy and high-performance liquid chromatography). CMC with DS 0.7–0.8 is found to be near the limit for water solubility and the resulting ranking for that solubility is shown to be correlated to DS. The DS is found to be impaired by a high content of impurities and high degree of Cellulose II in the pulp. The sulfite pulps yield CMC with the best solubility in water. A high level of extractives does not interfere with reactivity. Moreover, it is found that impurities, such as lignin and xylan, inhibit thickening behavior even at high DS, and that the ratio of substitution on Position 3 is a measure of the xylan content, which suggests that this position in xylan has extremely high reactivity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47862.     

Influence of water on phase transition and rheological behavior of cellulose/ionic liquid/water ternary systems

The influence of water content on liquid crystalline (LC) gel formation and the rheological behavior of a ternary microcrystalline cellulose (MCC)/1‐ehtyl‐3‐methylimidazolium acetate (EmimAc)/water system was investigated using polarized optical microscopy (POM) and rheometry. POM indicated that the distinct water content range for forming a fully anisotropic LC gel with 14 wt % MCC was 4–10 wt %. Adding water to the MCC/EmimAc system resulted in enhanced complex viscosity and storage and loss moduli, and ultimately LC gel formation. Comparison of creep compliance vs. time revealed that the system without water showed representative viscoelastic behavior, while the time dependence of creep compliance disappeared as the water content increased, suggesting elastic‐solid behavior. Additionally, hydrogen bonding between cellulose and EmimAc weakened as water content increased, whereas the intra‐ and intermolecular hydrogen bonds of cellulose became stronger because of strong self‐association. This strong bonding caused aggregation, chain entanglement, and self‐supporting LC gel network formation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44658.     

Waterborne polyurethane nanocomposites based on vegetable oil and microfibrillated cellulose

This work analyzes the differences in the final properties of two waterborne polyurethanes (WBPU) prepared with two macrodiols of different chemical structure, but similar molecular weight, as well as the variations caused by incorporating low percentages of microfibrillated cellulose nanocrystals. One of the polyurethanes was based on a synthetic but biodegradable precursor (polycaprolactone diol, PCL) and a second one based on a bio‐based macrodiol derived from castor oil (CO1). The bio‐based material presented higher mechanical properties at room temperature than the synthetic one, with the Young's modulus (MPa) ranging from 2.23 ± 0.09 to 84.88 ± 0.96 for the PCL and bio‐based WBPUs, respectively. Additionally, the PCL‐based WBPU showed to be more sensitive to the incorporation of cellulose than the bio‐based WBPU, and it also suffered changes during time due to delayed crystallization. The behavior of the two systems were compared and related to the different structure of the macrodiols that led to different interfacial interactions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44207.     

New biocomposite obtained using poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) and microfibrillated cellulose

This research evaluates the effects of filler content and silanization on thermal, morphological and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH)-based composites. Microfibrillated cellulose (MFC) was obtained by a mechanical treatment of high-pressure homogenization, starting from oat hull fiber, a byproduct of the agri-food sector. MFC reinforced PHBH composites were prepared by melt compounding. SEM and FT-IR analysis showed a good dispersion of the filler in the polymeric matrix, denoting the effectiveness of the surface silanization process. The thermal stability of PHBH composites remains substantially unchanged, and the glass transition temperature marginally increases with the increase of the filler content. Furthermore, silanized MFC shows slightly reinforcing mechanical effects on PHBH composites, such as the increase of 10% of the Young modulus with an increase of the maximum tensile stress as well. This finding has an economical interest since the results showed that MFC, deriving from a byproduct, can be successfully used as filler, decreasing the cost of the bio-based compound leaving substantially unaltered its mechanical and thermal properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48953.     

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.     

Synthesis of polyamide 6/11 copolymers and their use as matrix polymer in wood‐plastic composites

The goal of this study was to investigate the synthesis and the resulting thermal, rheological, and mechanical properties of polyamide 6/11 copolymers (PA 6/11) as a function of their composition and to further investigate their usability as matrix polymers for wood‐plastic composites (WPC). A significant composition dependency of the melting temperature was found due to the hindered crystallization of the PA 6/11 copolymers with increasing content of the minor component. In result, the lowest melting temperature of the copolymers was measured at 120 °C for 40 wt % of ?‐caprolactam (PA 6/11‐40/60) by DSC analysis. Due to its low melting point and feasible mechanical properties, a copolyamide with 70 wt % of ?‐caprolactam (PA 6/11‐70/30) was chosen as matrix material for the processing of WPC. Incorporation of 30 wt % of wood fibers into PA 6/11‐70/30 caused a significant increase in tensile modulus and a decrease in tensile strength and strain at break. However, the processed WPC still showed an exceptional ductility with a strain at break of 15 to 20%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44155.     

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.     

Melt processing of nanocomposites of cellulose nanocrystals with biobased thermoplastic polyurethane

Nanocomposites of thermoplastic polyurethane (TPU) with cellulose nanocrystals (CNC) without and with surface treatment are obtained by melt processing. Nanocomposites are obtained with nanofiller weight content near of the theoretical percolation threshold (3.9 wt%). Visual observation of CNC agglomerates is sufficient to prove the inefficiency of the mixing in systems with untreated CNC. The crystallization kinetics of the TPU changes with the addition of CNC and this is confirmed by differential scanning calorimetry analysis. Thermogravimetric analysis prove that the addition of CNC increases the thermal stability of the TPU. From the rheological analysis it is possible to verify the absence of percolation and an intermediate state of sol–gel transition in the nanocomposites. CNC/TPU nanocomposites with 5 wt% of treated CNC present better mechanical performance than de neat TPU and the other processed nanocomposites and display around 130% increase in Young's modulus while retaining significant values of toughness, tensile strength and elongation at break.