Browsing by Author "Navarro, Fernando"

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    Cellulose Nanocrystals: Size Characterization and Controlled Deposition by Inkjet Printing
    Navarro, Fernando (Virginia Tech, 2010-06-29)
    Inkjet printing has generated considerable interest as a technique for the patterning of functional materials in the liquid phase onto a substrate. Despite its high promise, the phenomena associated with inkjet printing remain incompletely understood. This research project investigates inkjet printing of cellulose nanocrystals (CNCs) as a possible method for the fabrication of cellulose micropatterns. CNCs were prepared from wood pulp by H₂SO₄ hydrolysis and characterized in terms of length, width, and thickness distributions by atomic force microscopy (AFM) and dynamic light scattering. Aqueous CNC suspensions were characterized in terms of shear viscosity with a rheometer. Glass substrates were cleaned with a detergent solution, aqua regia, or a solvent mixture, and characterized in terms of surface chemical composition, surface free energy, polarity, roughness, ζ-potential, and surface charge distribution in air by X-ray photoelectron spectroscopy, contact angle measurements, AFM, streaming potential, and scanning Kelvin probe microscopy (SKPM). Additionally, poly(ethylene glycol)-grafted glass substrates were prepared and characterized in terms of surface free energy, polarity, and roughness. Aqueous CNC suspensions were printed in different patterns onto the different glass substrates with a commercial, piezoelectric drop-on-demand inkjet printer. Inkjet deposited droplet residues and micropatterns were analyzed by AFM, scanning electron microscopy, and polarized-light microscopy. At low CNC concentrations (0.05 wt %), inkjet-deposited droplets formed ring-like residues due to the "coffee drop effect". The "coffee drop effect" could be suppressed by the use of higher CNC concentrations. The resulting dot-like droplet residues exhibited Maltese cross interference patterns between crossed polarizers, indicating a radial orientation of the birefringent, elongated CNCs in these residues. The observed Maltese cross interference patterns represent unprecedented indirect evidence for a center-to-edge radial flow in drying droplets. The degree of definition of the micropatterns depended strongly on the surface properties of the glass substrates. Well-defined micropatterns were obtained on aqua regia-cleaned substrates. In addition to the surface free energy and polarity, other factors seemed to play a role in the formation of the inkjet-printed micropatterns. If these factors can be identified and controlled, inkjet deposition of CNCs could become an attractive method for the fabrication of cellulose micropatterns.
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    Multi-axis alignment of Rod-like cellulose nanocrystals in drying droplets
    Pritchard, Cailean Q.; Navarro, Fernando; Roman, Maren; Bortner, Michael J. (Elsevier, 2021-12)
    Hypothesis: Radial capillary flow in evaporating droplets carry suspended nanoparticles to its periphery where they are deposited and form a coffee-ring. Rod-like nanoparticles seeking to minimize their capillary energy will align with their long-axis parallel to the contact line. Particles exhibiting electrostatic repulsion, such as cellulose nanocrystals (CNCs), establish a competition between capillary flow-induced impingement against a growing coffee-ring and entropic minimization leading to enhanced particle mobility. Therefore, balancing these effects by manipulating the local particle concentration in drying droplets should result in deposition with a controlled orientation of CNCs. Experiments: The dynamic local order in aqueous suspensions of CNCs in evaporating sessile droplets was investigated through time-resolved polarized light microscopy. The spatial distribution of alignment in deposited CNCs was explored as a function of nanoparticle concentration, droplet volume, initial degree of anisotropy, and substrate hydrophobicity. Computational analysis of the rotational Péclet number during evaporation was also investigated to evaluate any effects of shear-induced alignment. Findings: Multiple modes of orientation were identified suggesting local control over CNC orientation and subsequent properties can be attained via droplet-based patterning methods. Specifically, high local particle concentrations led to tangential alignment and lower local particle concentrations resulted in new evidence for radial alignment near the center of dried droplets.