Thermo-mechano-chemical deconstruction of cellulose for cellulose nanocrystal production by reactive processing.

The commercial production of cellulose nanocrystals (CNCs) requires high concentration of sulfuric or other acids such as hydrochloric, phosphoric, and nitric acids. However, these acids and the involved process are corrosive, toxic, energy-intensive, and not environmentally safe. In this work, a batch mixer reactive process that entails high shear was implemented using 1-butyl-3-methylimidazolium chloride (BmimCl) media and molten oxalic acid dihydrate (OA) to produce CNCs from cellulose. Through this, a maximum CNC yield (59 wt%) was obtained with a mixture composition of 1:0.7:0.075 (Cellulose:BmimCl:OA, w/w/w) and a processing time of 2.5 min. Further investigation revealed that the particle size, degree of crystallinity, and thermal stability of the produced CNCs were found to be competitive with those of a commercial CNC product. This study asserts the potential industrial application of an efficient ionic liquid and molten organic acid treatment for CNC production via reactive processing in a batch mixer.

Green mechano-chemical processing of lignocellulosic biomass for lignin recovery.

Lignin extraction from biomass is heavily dependent on chemical processes that are harmful to the environment and the quality of the recovered lignin. Ionic liquid solvents are some of the latest solutions in green processing; however, their implementation for lignin recovery is limited by their high cost, typically high loadings requirements, and long processing times. To overcome these issues, in this study, high loadings of mixed hardwood flour (MHF) were processed with 1-butyl-3-methylimidazolium chloride (BmimCl) in a batch mixer. The rheological behaviour of the biomass and ionic liquid mixture was studied. The mixture had a high complex viscosity (approx. 107 Pa s) at low shear rates and displayed pronounced shear thinning behavior at 50 wt% MHF loading. A 22 factorial design was also implemented to study the effects of MHF solid loading amount and residence time on lignin extraction yield. A maximum yield of 36.6% was obtained at the maximum solid loading amount and residence time (50 wt% and 45 min, respectively). The extracted lignin samples were also characterized in comparison with commercial Kraft lignin and lignosulfonate. The novelty of this study is the successful lignin extraction at high solid loadings and shorter residence times compared to previous biomass pre-treatments with ionic liquids that employs low solid loading and long processing times.

Lignin derived nano-biocarbon and its deposition on polyurethane foam for wastewater dye adsorption.

Historically, lignin has been produced as a waste by-product in industrial processes. In this study, lignosulfonate nanoparticles were fabricated and freeze-dried for use as a precursor material for carbonization. The use of the carbonized lignins for the adsorption of textile effluent as a value-added application is demonstrated. Characterization of the as received lignin (LN) and the developed nano-based freeze-dried lignin (NFLN) were performed prior to and after carbonization at 600, 750, 900 and 1050 °C. Using probe sonication, lignosulfonates were broken down into nanoparticles with lower weight-average molecular weight as verified by dynamic and static light scattering techniques. The difference between the LN and the NFLN was determined to be primarily morphological as the sonication and freeze-drying process imparted a platelet-like shape to the NFLN biocarbons and an increased surface area, while the remaining functionality was similar. The adsorption behaviour of methylene blue (MB), a synthetic cationic dye, was investigated using adsorption isotherm and kinetic models, with the NFLN exhibiting a maximum adsorption capacity of 109.77 mg/g. Overall, electrostatic attraction and hydrogen bonding contribute significantly to the MB adsorption. Further preliminary work was also performed demonstrating the coating of polyurethane foam for the adsorption of MB. These renewable biocarbons show promising properties for use as additive in adsorbent, coating, pigment or as a filler in polymer composite applications.

Degradation Behavior of Polypropylene during Reprocessing and Its Biocomposites: Thermal and Oxidative Degradation Kinetics.

Non-isothermal thermogravimetric analysis (TGA) was employed to investigate the degradation of polypropylene (PP) during simulated product manufacturing in a secondary process and wood-plastic composites. Multiple batch mixing cycles were carried out to mimic the actual recycling. Kissinger-Akahira-Sunose (KAS), Ozawa-Flynn-Wall (OFW), Friedman, Kissinger and Augis models were employed to calculate the apparent activation energy (Ea). Experimental investigation using TGA indicated that the thermograms of PP recyclates shifted to lower temperatures, revealing the presence of an accelerated degradation process induced by the formation of radicals during chain scission. Reprocessing for five cycles led to roughly a 35% reduction in ultimate mixing torque, and a more than 400% increase in the melt flow rate of PP. Ea increased with the extent of degradation (α), and the dependency intensified with the reprocessing cycles. In biocomposites, despite the detectable degradation steps of wood and PP in thermal degradation, a partial coincidence of degradation was observed under air. Deconvolution was employed to separate the overlapped cellulose and PP peaks. Under nitrogen, OFW estimations for the deconvoluted PP exposed an upward shift of Ea at the whole range of α due to the high thermal absorbance of the wood chars. Under air, the Ea of deconvoluted PP showed an irregular rise in the initial steps, which could be related to the high volume of evolved volatiles from the wood reducing the oxygen diffusion.

High yield production and purification of few layer graphene by gum arabic assisted physical sonication.

Exploiting the emulsification properties of low cost, environmentally safe Gum Arabic we demonstrate a high yield process to produce a few layer graphene with a low defect ratio, maintaining the pristine graphite structure. In addition, we demonstrate the need for and efficacy of an acid hydrolysis treatment to remove the polymer residues to produce 100% pure graphene. The scalable process gives yield of up to 5 wt% graphene based on 10 g starting graphite. The graphene product is compared with reduced graphene oxide produced through Hummer's method using UV-visible spectroscopy, SEM, TEM, and Raman spectroscopy. The two graphene materials show significant difference in these characterizations. Further, the film fabricated from this graphene exhibits 20 times higher electrical conductivity than that of the reduced graphene oxide. Sonication processing of graphite with environmentally approved biopolymers such as Gum Arabic opens up a scalable avenue for production of cheap graphene.

Controllable delivery of small-molecule compounds to targeted cells utilizing carbon nanotubes.

Carbon nanotubes (CNTs) have emerged as a new alternative and efficient tool for transporting molecules with biotechnological and biomedical applications, because of their remarkable physicochemical properties. Encapsulation of functional molecules into the hollow chambers of CNTs can not only stabilize encapsulated molecules but also generate new nanodevices. In this work, we have demonstrated that CNTs can function as controllable carriers to transport small-molecule compounds (SMCs) loaded inside their hollow tunnels onto targeted cells. Using indole as model compound, CNTs can protect indole molecules during transportation. Labeling indole-loaded CNTs (indole@CNTs) with EphB4-binding peptides generates cell-homing indole@CNTs (CIDs). CIDs can selectively target EphB4-expressing cells and release indole onto cell surfaces by near-infrared (NIR) irradiation. Released indole molecules exhibit significant cell-killing effects without causing local overheating. This establishes CNTs as excellent near-infrared controllable delivery vehicles for SMCs as selective cell-killing agents.