Towards more sustainable material formulations: a comparative assessment of PA11-SGW flexural performance versus oil-based composites

The replacement of commodity polyolefin, reinforced with glass fiber (GF), by greener alternatives has been a topic of research in recent years. Cellulose fibers have shown, under certain conditions, enough tensile capacities to replace GF, achieving competitive mechanical properties. However, if the objective is the production of environmentally friendlier composites, it is necessary to replace oil-derived polymer matrices by bio-based or biodegradable ones, depending on the application. Polyamide 11 (PA11) is a totally bio-based polyamide that can be reinforced with cellulosic fibers. Composites based on this polymer have demonstrated enough tensile strength, as well as stiffness, to replace GF-reinforced polypropylene (PP). However, flexural properties are of high interest for engineering applications. Due to the specific character of short-fiber-reinforced composites, significant differences are expected between the tensile and flexural properties. These differences encourage the study of the flexural properties of a material prior to the design or development of a new product. Despite the importance of the flexural strength, there are few works devoted to its study in the case of PA11-based composites. In this work, an in-depth study of the flexural strength of PA11 composites, reinforced with Stoneground wood (SGW) from softwood, is presented. Additionally, the results are compared with those of PP-based composites. The results showed that the SGW fibers had lower strengthening capacity reinforcing PA11 than PP. Moreover, the flexural strength of PA11-SGW composites was similar to that of PP-GF compositesPostprint (published version

Comparison between two different pretreatment technologies of rice straw fibers prior to fiberboard manufacturing: Twin-screw extrusion and digestion plus defibration

The present work compares two different pretreatment technologies, i.e. twin-screw extrusion, and steaming digestion plus defibration, for producing a thermo-mechanical pulp from rice straw for fiberboard manufacturing. Five liquid/solid ratios from 0.43 to 1.02 were tested for twin-screw extrusion pretreatment, while liquid/solid ratios from 4 to 6 were used for digestion pretreatment. Energy consumption, and characteristics of the extrudates (twin-screw extrusion) and pulps (digestion) (including fiber morphology, chemical composition, thermal properties, apparent and tapped densities, as well as color) were the analyzed parameters for the resulting lignocellulosic fibers. The results showed that liquid/solid ratio had influence on energy consumption of the equipment for both defibrating methods For the twin-screw extrusion method, a lower liquid/solid ratio required more energy while for the digestion plus defibration the effect was the opposite. The corresponding total specific energy consumption ranged from 0.668 kW h/kg to 0.946 kW h/kg dry matter for twin-screw extrusion, and from 6.176 kW h/kg to 8.52 kW h/kg dry matter for digestion plus defibration. Thus, the pulping method consumed about nine times more energy than that of the twin-screw extrusion. In addition, for twin-screw extrusion, the liquid/solid ratio did not have a substantial effect on fiber characteristics with similar chemical compositions and thermal properties. For twin-screw extrusion, the energy consumption was 37% reduced when the liquid/solid ratio was increased from 0.43 to 1.02. Instead, for digestion plus defibration, the energy increase was 38% when the liquid/solid ratio increased from 4 to 6

Valorization of Hemp Core Residues: Impact of NaOH Treatment on the Flexural Strength of PP Composites and Intrinsic Flexural Strength of Hemp Core Fibers

Hemp core is a lignocellulosic residue in the production chain of hemp strands. Huge amounts of hemp core are gathered annually in Europe (43,000 tons) with no major application end. Such lignocellulosic wastes have potential as filling or reinforcing material to replace synthetic fibers and wood fibers in polymer composites. In this study, hemp core biomass was treated under different NaOH concentrations and then defibrated by means of Sprout Waldron equipment to obtain single fibers. Polypropylene matrix was reinforced up to 50 wt.% and the resulting hemp core fibers and the flexural properties were investigated. The results show that the flexural strength of composites increased with the intensity of NaOH treatment. The effect of NaOH was attributed to the removal of extractives and lignin in the fiber cell wall leading to improved interfacial adhesion characteristics. Besides, a methodology was established for the estimation of the intrinsic flexural strength of hemp core fibers. The intrinsic flexural strength of hemp core fibers was calculated to be 940 MPa for fibers treated at 10 wt.% of NaOH. In addition, a relationship between the lignin content and the intrinsic strength of the fibers was established

Suitability of wheat straw semichemical pulp for the fabrication of lignocellulosic nanofibres and their application to papermaking slurries

The present work studies the feasibility of wheat soda pulp as a raw material for the fabrication of cellulose nanofibres and their application as an additive in papermaking. Wheat straws were cooked under alkaline conditions and the resulting pulp was used as a raw material for the production of lignocellulosic nanofibres (LCNF). Nanofibres were fabricated by intense mechanical beating followed by highpressure homogenization. The produced LCNF were characterized and applied to papermaking slurry based also on wheat straw soda pulp. Paper sheets made thereof were analysed for their physical and mechanical properties. The results indicated that paper strength was improved after addition of LCNF, whereas density increased and porosity was reduced. These improvements in properties (except the Tear Index) are significant because they were achieved using LCNF with lower fibrillation degree compared to previous works where chemically pre-treated LCNF were used as reinforcement

On the path to a new generation of cement-based composites through the use of lignocellulosic micro/nanofibers

Due to its high biocompatibility, bio-degradability, and low cost, cellulose finds application in disparate areas of research. Here we focus our attention on the potential applications of cellulose nanofiber in cement-basedmaterials for the building sector. We first describe the chemical/morphological composition of cellulose fibers, their process and treatment, the characterization of cement-based composites, and their flexural strengthPeer ReviewedPostprint (published version

Evaluation of thermal and thermomechanical behaviour of bio-based polyamide 11 based composites reinforced with lignocellulosic fibres

In this work, polyamide 11 (PA11) and stone ground wood fibres (SGW) were used, as an alternative to non-bio-based polymer matrices and reinforcements, to obtain short fibre reinforced composites. The impact of the reinforcement on the thermal degradation, thermal transitions and microstructure of PA11-based composites were studied. Natural fibres have lower degradation temperatures than PA11, thus, composites showed lower onset degradation temperatures than PA11, as well. The thermal transition and the semi-crystalline structure of the composites were similar to PA11. On the other hand, when SGW was submitted to an annealing treatment, the composites prepared with these fibres increased its crystallinity, with increasing fibre contents, compared to PA11. The differences between the glass transition temperatures of annealed and untreated composites decreased with the fibre contents. Thus, the fibres had a higher impact in the composites mechanical behaviour than on the mobility of the amorphous phase. The crystalline structure of PA11 and PA11-SGW composites, after annealing, was transformed to ’ more stable phase, without any negative impact on the properties of the fibresPostprint (published version

Study of the flexural modulus of lignocellulosic fibers reinforced bio-based polyamide11 green composites

The stiffness of a material has high impact when its industrial use is considered. Moreover, this property has interest in the case of short fiber reinforced materials due to its dependence on the orientation of the fibers against the loads. Due to nowadays-environmental concerns, greener alternatives to oil-based composites are under study and development showing some promising results. In this work, a polyamide 11 reinforced with lignocellulosic fiber composite is evaluated as such sustainable alternative. Previous works showed the suitability of PA11-based composites to replace glass fiber reinforced polypropylene. Nonetheless, there is a lack of information about the flexural modulus behavior of these composites. This is of interest because, under some conditions, flexural modulus is more representative of a material behavior than Young's modulus. The flexural moduli of these composites were analyzed under a three point bending test and the results were evaluated from macro and micromechanical points of view. The increment of the modulus with the fiber contents implied a good dispersion of the reinforcements. Nonetheless, the results were lower than those observed for the tensile modulus. This was unexpected due to the anisotropy of the bending test. The micromechanics analysis showed a lower performance of the fiber during the flexural test. These lower results were related with a non-optimal interface or with the non-adequate compression of the fibers. Additionally, the calculus of the void volume showed low void contentsPostprint (published version

Research on the strengthening advantages on using cellulose nanofibers as polyvinyl alcohol reinforcement

The present work aims to combine the unique properties of cellulose nanofibers (CNF) with polyvinyl alcohol (PVA) to obtain high-performance nanocomposites. CNF were obtained by means of TEMPO-mediated ((2,2,6,6-Tetramethylpiperidin-1-yl)oxyl) oxidation, incorporated into the PVA matrix by means of compounding in a single-screw co-rotating internal mixer and then processed by means of injection molding. It was found that CNF were able to improve the tensile strength of PVA in 85% when 4.50 wt % of CNF were added. In addition, the incorporation of a 2.25 wt % of CNF enhanced the tensile strength to the same level that when 40 wt % of microsized fibers (stone groundwood pulp, SGW) were incorporated, which indicated that CNF possessed significantly higher intrinsic mechanical properties than microsized fibers. SGW was selected as reference for microsized fibers due to their extended use in wood plastic composites. Finally, a micromechanical analysis was performed, obtaining coupling factors near to 0.2, indicating good interphase between CNF and PVA. Overall, it was found that the use of CNF is clearly advantageous to the use of common cellulosic fibers if superior mechanical properties are desired, but there are still some limitations that are related to processing that restrict the reinforcement content at low contents.Peer ReviewedPostprint (published version

Dynamic light scattering plus scanning electron microscopy: usefulness and limitations of a simplified estimation of nanocellulose dimensions

Measurements of nanocellulose size usually demand very high-resolution techniques and tedious image processing, mainly in what pertains to the length of nanofibers. Aiming to ease the process, this work assesses a relatively simple method to estimate the dimensions of nanocellulose particles with an aspect ratio greater than 1. Nanocellulose suspensions, both as nanofibers and as nanocrystals, are subjected to dynamic light scattering (DLS) and to field-emission scanning electron microscopy (FE-SEM). The former provides the hydrodynamic diameter, as long as the scatter angle and the consistency are adequate. Assays with different angles and concentrations compel us to recommend forward scattering (12.8°) and concentrations around 0.05–0.10 wt %. Then, FE-SEM with magnifications of ×5000–×20,000 generally suffices to obtain an acceptable approximation for the actual diameter, at least for bundles. Finally, length can be estimated by a simple geometric relationship. Regardless of whether they are collected from FE-SEM or DLS, size distributions are generally skewed to lower diameters. Width distributions from FE-SEM, in particular, are well fitted to log-normal functions. Overall, while this method is not valid for the thinnest fibrils or for single, small nanocrystals, it can be useful in lieu of very high-resolution techniques.Peer ReviewedPostprint (published version

Polyelectrolyte complexes for assisting the application of lignocellulosic micro/nanofibers in papermaking

A novel procedure based on the addition of polyelectrolyte complexes (PECs) onto the pulp containing lignocellulosic micro/nanofibers (LCMNF) is presented. This procedure allows increasing paper strength avoiding an excessive loss in drainability. LCMNF were obtained from partially delignified kraft pine sawdust using a high-pressure homogenizer. Cationic complexes (CatPECs) were prepared by adding the anionic polyelectrolyte solution (polyacrylic acid) on the cationic polyelectrolyte solution (poly(allylamine hydrochloride)). According to turbidity and surface morphology changes, an interaction between CatPECs and LCMNF could be established. Different CatPEC dosages (from 0.3 to 1.0% on pulp) were added on a recycled unbleached softwood kraft pulp containing 3% of LCMNF. For a PEC dosage of 0.75% on pulp, an optimum balances between negatively and positively charged materials [near to zero value of the logarithm of the colloidal titration ratio (logCTR)] was found. Britt Dynamic Drainage Jar test showed a high retention of fines and LCMNF for all PEC dosages. A maximum in retention value was obtained for the addition of 0.75% of PECs on pulp, dosage that was suggested as optimum by the logCTR. In addition, the best drainability value (18°SR) was obtained for this PEC addition level. Papermaking properties were clearly improved for all dosage of PECs. Particularly for a dosage of 0.75% of PECs on pulp, tensile strength was noticeably increased (+48%) and both compressive resistance Concora Medium Test (CMT) and Short-span Compressive Test (SCT) were markedly increased (+64% and +39%, respectively). These results suggest that PECs are a possible alternative to assist the application of LCMNF in papermaking.Fil: Schnell, Carla Natali. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulósica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Tarrés, Quim. Universidad de Girona; EspañaFil: Galván, María Verónica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulósica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Mocchiutti, Paulina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulósica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Delgado Aguilar, Marc. Universidad de Girona; EspañaFil: Zanuttini, Miguel Angel Mario. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Instituto de Tecnología Celulósica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Mutjé, Pere. Universidad de Girona; Españ