Single-particle longitudinal motion and pairwise lateral motion was investigated while the particles were excited by an oscillating electric field directed normally to an electrode proximate to the particles. The electrode was polarized over a range of potential insufficient to drive electrochemical reactions, a range called the "ideally polarizable region". The particles' motion was qualitatively dependent on the choice of electrolyte despite the absence of electrochemical reactions. As when electrochemical reactions were not explicitly excluded, the phase angle θ between particle height and electric field correlated with the particles' separation or aggregation during excitation. A simple harmonic oscillator model of the particles' response, including colloidal and hydrodynamic forces and including the Basset force not previously cited in this context, showed how θ can increase from 0° at low frequencies, cross 90° at ∼100 Hz, and then increase to 180° as frequency was increased. The model captured the essence of experimental observations discussed here and in earlier works. This is the first a priori prediction of θ for this problem.
Associative polysaccharides, decorated by multiple but short, side-chain hydrophobic stickers (typically 6–20 carbon long) that associate in solution, are used as thickeners for an extensive range of aqueous-based formulations. Characterizing and elucidating the influence of stickers on the response to extensional flows that spontaneously arise in pinching necks formed during spraying, jetting, or coating fluids have remained longstanding experimental and analytical challenges due to relatively low viscosity and elasticity of industrially relevant systems. In this contribution, we contrast the shear rheology as well as extensional rheology and pinching dynamics of hydrophobically modified hydroxyethyl cellulose (hmHEC, M w = 300 kg/mol) as a sticky polymer with the bare chain of a higher molecular weight (hydroxyethyl cellulose (HEC), M w = 720 kg/mol) using the recently developed dripping-onto-substrate (DoS) rheometry protocols. We show that sticker associations enhance zero shear viscosity and relaxation time (elasticity), and both quantities display stronger concentration-dependent variation for sticky polymers. Striking differences are observed in neck shapes, radius evolution profiles, and extensional viscosity plotted as a function of strain as well as strain rate. We present a comprehensive analysis of changes in pinching dynamics, concentration-dependent variation in steady, terminal viscosity as well as filament lifespan as a function of the sticky polymer concentration and describe the influence of multiple stickers on the macromolecular strain, relaxation, and dynamics of associative polysaccharides.
Nanostructured TiO 2 thin films were prepared by pulsed laser deposition (PLD) on indium doped tin oxide (ITO) substrates. Results from X-ray photoelectron spectroscopy (XPS) show that Ti 2p core level peaks shift toward the lower binding energy with decrease in the buffer gas pressure (O 2 :Ar = 1:1). This suggests that oxygen vacancies are created under insufficient oxygen conditions. Anatase to rutile ratio is also found to be system pressure dependent. Under deposition pressure of 750 mTorr only anatase phase was observed even at 1073 K substrate temperature which is much higher that the bulk anatase to rutile phase transformation temperature. The deposited TiO 2 thin films were fabricated as photoanodes for photoelectrochemical (PEC) studies. PEC measurements on TiO 2 photoanodes show that the flatband potential (V fb ) increases by 0.088 eV on absolute vacuum energy scale (AVS) with decrease in the deposition pressure, from 750 to 250 mTorr at 873K. The highest incident photon to current conversion efficiency [IPCE(λ)] of 2.5 to 6 % was obtained from the thin films prepared at substrate temperature of 873K.Combining the results from XPS and PEC studies, we conclude that the deposition pressure affects the concentration of the oxygen vacancies which changes the electronic structure of the TiO 2 . With reference to photoelectrochemical catalytic performance, our results suggest that it is possible to adjust the Fermi energy level and structure of TiO 2 thin
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