Enhancement of Dropwise Condensation Heat Transfer through a Sprayable Superhydrophobic Coating.

Improving the shedding rate of condensed droplets has many applications in industries and daily problems, including increasing heat transfer and self-cleaning properties. One way to achieve this goal is by enhancement of the wetting properties of surfaces. In this research, the hierarchical superhydrophobic coating over aluminum has been applied using a relatively cost-effective method, spraying, which is also applicable to any metal surface used as a condenser. According to the results obtained from the experimental tests, the fabricated surface is highly superhydrophobic, with a contact angle of 158° and contact angle hysteresis of less than 5°. The results show that the presented surface increases the heat transfer coefficient by 20.6% at the subcooling temperature of 25.5 °C when the surface temperature and relative humidity are 70 °C and 98%, respectively. In addition, this coated surface showed great potential at lower surface temperatures by increasing the water condensation rate as much as 50.5% at the subcooling temperature of 12 °C, when the surface temperature and relative humidity are 11.25 °C and 70%, respectively. Therefore, it is found that for the fabricated superhydrophobic paint in the present study, the effectiveness of the dropwise condensation mode profoundly depends on surface temperatures besides subcooling temperatures. In other words, a surface with lower temperatures shows better performance for the same subcooling temperatures. In addition, various types of durability tests are carried out. The results reveal that this coating has good durability against high surface temperatures, submerged conditions for 30 days, imposing hot steam for 150 h, corrosion, and organic solvents. Hence, it is suitable for industrial applications.

Coupled Ionic-Electronic Equivalent Circuit to Describe Asymmetric Rise and Decay of Photovoltage Profile in Perovskite Solar Cells.

In this research, we employed transient photo-voltage rise and decay measurements to investigate the origin of slow unsymmetrical rise and decay profiles in single and triple cation perovskite solar cells. Drastic changes in photo-voltage decay profile were observed upon insertion of Br-, Cs+ and FA+ ions into perovskite structures. In order to explain our observations, the activation energy for ionic defects was measured and an equivalent circuit model was proposed containing both electrical and ionic components. The electrical branch consists of a diode, the bulk capacitance and resistances for charge transport and recombination. In parallel we introduced an ionic branch describing the ionic response by a resistance for ionic charge transport and a capacitance describing ion accumulation at the interface to the charge transport layer. To reproduce the asymmetry of photo-voltage rise and decay, a diode with a parallel resistor is introduced leading to a belayed backflow of the accumulated ions. The results revealed that the activation energy of ionic defects became larger upon insertion of either halides or cations. There is larger amount of ionic defects in the case of MAPbI3 while the de-accumulation process of ions happens in much larger time scale in triple cation perovskite. The presence of ions at the interfaces results in band bending generating a potential barrier restraining electrons and holes from recombination; so the loss of built-in potential is delayed until de-accumulation of ionic double layer happens. Our model proposes that the loss of built-in potential depends on electrostatic potential drop, suggesting coupled electronic-ionic phenomenon in perovskite solar cells.

Computational investigation of gas detection and selectivity on TiS3 nanoflakes supported by experimental evidence.

Titanium trisulfide (TiS3), a transition metal chalcogenide, bears the potential to replace silicon, when taking the form of nanoflakes, due to its favorable band gap and optical response. In this paper, we investigate the response of TiS3 nanoflakes to gas detection through a careful quantum computational approach and a few succinct measurements. The computations are benchmarked and compared with a relevant experiment at each step, where their results/conclusions are discussed. The most stable surface of TiS3 particles is determined as (001), in agreement with the literature. The adsorption of 5 gas molecules is characterized through formulating and estimating their adsorption intensity values, rather than using singled-out values of binding energies. This formulation, which is rooted in a statistical view of the gas adsorption process, distinguishes H2 and CH4 molecules from H2O and O2 explicitly and unambiguously through comparing their adsorption profiles. The difference in the adsorption intensities thus predicts and elucidates the difference in the sensing behaviour of TiS3 particles. This work suggests that the computationally obtained profile for the adsorption spectrum of gas molecules serves as a tool/criterion to predict the selectivity of their detection by TiS3.

ATR-FTIR and density functional theory study of the structures, energetics, and vibrational spectra of phosphate adsorbed onto goethite.

Periodic plane-wave density functional theory (DFT) and molecular cluster hybrid molecular orbital-DFT (MO-DFT) calculations were performed on models of phosphate surface complexes on the (100), (010), (001), (101), and (210) surfaces of α-FeOOH (goethite). Binding energies of monodentate and bidentate HPO(4)(2-) surface complexes were compared to H(2)PO(4)(-) outer-sphere complexes. Both the average potential energies from DFT molecular dynamics (DFT-MD) simulations and energy minimizations were used to estimate adsorption energies for each configuration. Molecular clusters were extracted from the energy-minimized structures of the periodic systems and subjected to energy reminimization and frequency analysis with MO-DFT. The modeled P-O and P---Fe distances were consistent with EXAFS data for the arsenate oxyanion that is an analog of phosphate, and the interatomic distances predicted by the clusters were similar to those of the periodic models. Calculated vibrational frequencies from these clusters were then correlated with observed infrared bands. Configurations that resulted in favorable adsorption energies were also found to produce theoretical vibrational frequencies that correlated well with experiment. The relative stability of monodentate versus bidentate configurations was a function of the goethite surface under consideration. Overall, our results show that phosphate adsorption onto goethite occurs as a variety of surface complexes depending on the habit of the mineral (i.e., surfaces present) and solution pH. Previous IR spectroscopic studies may have been difficult to interpret because the observed spectra averaged the structural properties of three or more configurations on any given sample with multiple surfaces.

Differential pair distribution function study of the structure of arsenate adsorbed on nanocrystalline γ-alumina.

Structural information is important for understanding surface adsorption mechanisms of contaminants on metal (hydr)oxides. In this work, a novel technique was employed to study the interfacial structure of arsenate oxyanions adsorbed on γ-alumina nanoparticles, namely, differential pair distribution function (d-PDF) analysis of synchrotron X-ray total scattering. The d-PDF is the difference of properly normalized PDFs obtained for samples with and without arsenate adsorbed, otherwise identically prepared. The real space pattern contains information on atomic pair correlations between adsorbed arsenate and the atoms on γ-alumina surface (Al, O, etc.). PDF results on the arsenate adsorption sample on γ-alumina prepared at 1 mM As concentration and pH 5 revealed two peaks at 1.66 Å and 3.09 Å, corresponding to As-O and As-Al atomic pair correlations. This observation is consistent with those measured by extended X-ray absorption fine structure (EXAFS) spectroscopy, which suggests a first shell of As-O at 1.69 ± 0.01 Å with a coordination number of ~4 and a second shell of As-Al at ~3.13 ± 0.04 Å with a coordination number of ~2. These results are in agreement with a bidentate binuclear coordination environment to the octahedral Al of γ-alumina as predicted by density functional theory (DFT) calculation.

Development of a reactive force field for iron-oxyhydroxide systems.

We adopt a classical force field methodology, ReaxFF, which is able to reproduce chemical reactions, and train its parameters for the thermodynamics of iron oxides as well as energetics of a few iron redox reactions. Two parametrizations are developed, and their results are compared with quantum calculations or experimental measurements. In addition to training, two test cases are considered: the lattice parameters of a selected set of iron minerals, and the molecular dynamics simulation of a model for alpha-FeOOH (goethite)-water interaction. Reliability and limitations of the developed force fields in predicting structure and energetics are discussed.

An algorithm for mass matrix calculation of internally constrained molecular geometries.

Dynamic models for molecular systems require the determination of corresponding mass matrix. For constrained geometries, these computations are often not trivial but need special considerations. Here, assembling the mass matrix of internally constrained molecular structures is formulated as an optimization problem. Analytical expressions are derived for the solution of the different possible cases depending on the rank of the constraint matrix. Geometrical interpretations are further used to enhance the solution concept. As an application, we evaluate the mass matrix for a constrained molecule undergoing an electron-transfer reaction. The preexponential factor for this reaction is computed based on the harmonic model.