RESUMEN
As integral parts of fuel cells, polymer electrolyte membranes (PEM) facilitate the conversion of hydrogen's chemical energy into electricity and water. Unfortunately, commercial PEMs are associated with high costs, limited durability, variable electrochemical performance and are based on perfluorinated polymers that persist in the environment. Nanocellulose-based PEMs have emerged as alternative options given their renewability, thermal and mechanical stability, low-cost, and hydrophilicity. These PEMs take advantage of the anionic nature of most nanocelluloses, as well as their facile modification with conductive functional groups, for instance, to endow ionic and electron conductivity. Herein, we incorporated for the first time two nanocellulose types, TEMPO-oxidized and sulfonated, to produce a fully bio-based PEM and studied their contribution separately and when mixed in a PEM matrix. Sulfonated nanocellulose-based PEMs are shown to perform similarly to commercial and bio-based membranes, demonstrating good thermal-oxidative stability (up to 190 °C), mechanical robustness (Young's modulus as high as 1.15 GPa and storage moduli >13 GPa), and high moisture-uptake capacity (ca. 6330 % after 48 h). The introduced nanocellulose membranes are shown as promising materials for proton-exchange material applications, as required in fuel cells.
RESUMEN
Redox flow batteries (RFBs) are increasingly being considered for a wide range of energy storage applications, and such devices rely on proton exchange membranes (PEMs) to function. PEMs are high-cost, petroleum-derived polymers that often possess limited durability, variable electrochemical performance, and are linked to discharge of perfluorinated compounds. Alternative PEMs that utilize biobased materials, including lignin and sulfonated lignin (SL), low-cost byproducts of the wood pulping process, have struggled to balance electrochemical performance with dimensional stability. Herein, SL nanoparticles are demonstrated for use as a nature-derived, ion-conducting PEM material. SL nanoparticles (NanoSLs) can be synthesized for increased surface area, uniformity, and miscibility compared with macrosized lignin, improving proton conductivity. After addition of polyvinyl alcohol (PVOH) as a structural backbone, membranes with the highest NanoSL concentration demonstrated an ion exchange capacity of 1.26 meq g-1, above that of the commercial PEM Nafion 112 (0.98 meq g-1), along with a conductivity of 80.4 mS cm-1 in situ, above that of many biocomposite PEMs, and a coulombic efficiency (CE), energy efficiency (EE) and voltage efficiency (VE) of 91%, 68% and 78%, respectively at 20 mA cm-2. These nanocomposite PEMs demonstrate the potential for valorization of forest biomass waste streams for high value clean energy applications.
RESUMEN
The engineering thermoplastics industry has largely limited the use of natural fiber reinforcements due to their susceptibility to low-onset thermal degradation and water absorption. Therefore, in order to utilize these economically viable and environmentally friendly materials effectively through common composite fabrication methods such as hot pressing, safeguarding them from thermal degradation becomes essential. This work presents a viable industrially technique called sequential ball milling for processing unbleached softwood kraft pulp fibers (PF) with an engineering thermoplastics polyamide 6 (PA6) with high melting temperatures (>220 °C). An additional eco-friendly modification step that employs ball milling and cellulose nanocrystal (CNC) has been implemented in this study to enhance the mechanical properties of the composites. Special attention is given to fine-tuning key variables, such as milling duration and PF particle size, to produce optimal composites. Leveraging the ability of sequential ball milling to evenly distribute pulp fibers into PA6, a 160% increase in Young's modulus was achieved with the incorporation of 30 wt % PF. Importantly, the introduction of a 5 wt % CNC modifying agent elevated Young's modulus to 4.3 GPa, marking a 187% improvement over unmodified PA6. Diverse techniques, including rheological analyses, thermomechanical evaluations, morphological examinations, and assessments of moisture absorption, were utilized to validate the efficiency of the suggested processing approach and the modification phase.
RESUMEN
Bringing biobased nanomaterials into polymer manufacturing is essential to enhance polymers' properties and address the challenges posed by plastic waste. Using polymers such as polyamide 6 (PA6) in advanced industries, e.g., automotive sector, has been impeded as a direct consequence of their inability to meet the required mechanical properties. Herein, we utilize bio-based cellulose nanofibers (CNFs) to enhance the properties of PA6 by green processing, with no footprint on the environment. We address the issue of the dispersion of the nanofillers in polymeric matrices and demonstrate direct milling (cryo-milling and planetary ball milling) to facilitate a thorough integration of the components. Nanocomposites incorporating 1.0 wt% CNF, processed by pre-milling followed by compression molding, are shown to possess a storage modulus of 3.8 ± 0.2 GPa, Young's modulus of 2.9 ± 0.2 GPa, and ultimate tensile strength of 63 ± 3 MPa (all measured at room temperature). To show the superiority of direct milling in achieving these properties, other frequent approaches used to disperse CNF in polymers, such as solvent casting and hand mixing, are meticulously investigated and compared for the performance of their resulting specimens. The ball-milling method is demonstrated to provide PA6-CNF nanocomposites with excellent performance, better than solvent casting, with no associated environmental concerns.