Spray coating technology has demonstrated great potential in the slow release fertilizers industry. The better understanding of the key spray parameters benefits both the environment and low cost coating processes. The use of starch based materials to coat the slow release fertilizers is a new development. However, the hydraulic spray jet breakup of the non-Newtonian starchy solutions is a complex phenomenon and very little known. The aim of this research was to study the axial and radial distributions of the Sauter Mean Diameter (SMD) and velocity vectors in pulsing spray patterns of native and modified tapioca starch solutions. To meet the objective, high speed imaging and Phase Doppler Anemometry (PDA) techniques were employed to characterize the four compositions of the starch-urea-borax complex namely S0, S1, S2 and S3. The unheated solutions exhibited very high viscosities ranging from 2035 to 3030 cP. No jet breakup was seen at any stage of the nozzle operation at an injection pressure of 1-5 bar. However, at 80 °C temperature and 5 bar pressure, the viscosity was reduced to 455 to 638 cP and dense spray patterns emerged from the nozzle obscuring the PDA signals. The axial size distribution revealed a significant decrease in SMD along the spray centreline. The smallest axial SMD (51 to 79 μm) was noticed in S0 spray followed by S1, S2 and S3. Unlikely, the radial SMD in S0 spray did not vary significantly at any stage of the spray injection. This trend was attributed to the continuous growth of the surface wave instabilities on the native starch sheet. However, SMD obtained with S1, S2 and S3 varied appreciably along the radial direction. The mean velocity vector profiles followed the non-Gaussian distribution. The constant vector distributions were seen in the near nozzle regions, where the spray was in the phase of development. In far regions, the velocity vectors were poly-dispersed and a series of ups and downs were seen in the respective radial distributions.
First-principles calculations of anatase structured TiO2 and ZrO2 as well as of TiO2-B were carried up to 20 GPa in order to develop an understanding of the unusual compression and pressure-dependent phase transitions reported for nanocrystalline (nc) pure and Zr-doped anatase and nc TiO2-B. The computations, carried out using two global hybrid density functional-Hartree-Fock formulations and all-electron basis sets, reveal sharp lattice hardening along the crystallographic a direction and concurrent lattice softening along c for anatase TiO2 at 10-12 GPa, and smooth anisotropic compression for ZrO2 anatase. Significant structural changes beginning at ∼10 GPa are also predicted for TiO2-B, most dramatically shown by the pressure-dependent change in the monoclinic angle β. These structural changes, resulting from intrinsic crystal structure destabilization under extended pressure metastability, have been suggested as being responsible for the unusual mechanical behaviors reported for pure and Zr-doped nanocrystalline and microcrystalline anatase TiO2 and nc TiO2-B.
Molecular dynamics simulation and biophysical analysis were employed to reveal the characteristics and the influence of ionic liquids (ILs) on the structural properties of DNA. Both computational and experimental evidence indicate that DNA retains its native B-conformation in ILs. Simulation data show that the hydration shells around the DNA phosphate group were the main criteria for DNA stabilization in this ionic media. Stronger hydration shells reduce the binding ability of ILs' cations to the DNA phosphate group, thus destabilizing the DNA. The simulation results also indicated that the DNA structure maintains its duplex conformation when solvated by ILs at different temperatures up to 373.15 K. The result further suggests that the thermal stability of DNA at high temperatures is related to the solvent thermodynamics, especially entropy and enthalpy of water. All the molecular simulation results were consistent with the experimental findings. The understanding of the properties of IL-DNA could be used as a basis for future development of specific ILs for nucleic acid technology.
A mechanism regarding the redox reaction in lanthanum cerium oxide (LaxCeyOz) post-deposition annealed in reducing and oxidizing atmosphere was schematized and discussed in association with the presence of lanthanum as a substitutional cation. Analyses have been performed using X-ray diffraction, energy-filtered transmission electron microscopy, scanning transmission electron microscope-energy dispersive spectroscopy line scan, and capacitance-voltage measurements. The results showed the presence of an oxygen vacancy when La(3+) was in its substitution site, while annihilation of oxygen vacancy was accompanied by a displacement of La(3+) from the substitutional site to the interstitial site via a kick-out mechanism prior to its disappearance from the CeO2.
A poly(vinyledene difluoride)-lithium bis(oxalato)borate solid polymer electrolyte prepared by a solvent casting method has been irradiated with different doses of gamma-rays. Differential scanning calorimetry reveals that the polymer electrolyte irradiated with 35 kGy of γ-rays is the most amorphous sample. This is also supported by the results obtained from X-ray diffraction. The Fourier transform infrared spectrum of each irradiated sample has been deconvoluted in the wavenumber region between 1830 and 1758 cm(-1) in order to predict the percentage of free and contact ions in the samples. The sample exposed to 35 kGy of γ-rays contains the highest percentage of free ions and the lowest amount of contact ions. This sample also exhibits the highest room temperature conductivity of 3.05 × 10(-4) S cm(-1), which is 15% higher relative to the virgin sample. The number density of free ions is observed to have more control on the conductivity variation with the γ-radiation dose compared to ionic mobility. This study confirms that γ-irradiation can be a potential way to obtain highly conductive and mechanically stable polymer electrolytes.
The predominant orientation of LiMn2O4 synthesized through the different methods is attributed, using the crystal shape algorithm (a new tool advanced to study the crystal shapes of crystalline materials), to the (331) plane. Existing literature evidence however shows that the (400) plane is the thermodynamically most stable hkl direction of LiMn2O4. Observations from the crystal shape algorithm and literature evidence of the thermodynamic stabilities of the hkl planes of LiMn2O4 point to the operation of a kinetically controlled mechanism governing the LiMn2O4 synthesis reactions currently available in the literature. This finding can have important consequences on the electrochemical characteristics of the material such as its rate capability.
In this work, we introduce a method based on impedance spectroscopy and the equations developed to evaluate, with a good degree of accuracy, the number density, mobility and diffusion coefficient of mobile ions. Nyquist plots of electrolytes based on poly(acrylonitrile) or PAN and methyl cellulose (MC) incorporated with lithium bis(oxalato)borate have been established from impedance measurements. Equivalent circuits based on a resistor and "leaky capacitor(s)" have been determined and the relevant impedance equations derived. The values of the parameters required in the equation are obtained from the Nyquist plots and the parameters that cannot be obtained from the respective plots have been obtained by trial and error in order to fit the Nyquist plots. The transport parameters are calculated using the developed equations and the results have been compared with those obtained from the broadband dielectric response (BDR) method. Finally, Fourier transform infrared (FTIR) spectroscopy has been used to verify the results obtained from the two approaches at room and elevated temperatures.
Through atomistic molecular dynamic simulations using a GROMOS53a6 force field for the carbohydrate, we studied the lyotropic reverse hexagonal phase HII from a glycolipid, namely the Guerbet branched-chain β-d-glucoside, at 14% and 22% water concentrations. Our simulations showed that at low water concentration (14%) the sugar head group overlapped extensively and protruded into the water channel. In contrast, in the 22% concentration system a water column free from the sugar headgroup ('free' water) was formed as expected for the system close to the limit of maximum hydration. In both concentrations, we found anomalous water diffusion in the xy-plane, i.e. the two-dimensional space confined by the surface of the cylinder. On the other hand, along the z-axis, the water diffusion obeyed the Einstein relation for the 22% system, while for the 14% system it was slightly anomalous. For the 22% system, the diffusion along the z-axis of the 'free' water obeyed the Einstein relation, while that of the 'bound' water is slightly anomalous. The xy-plane displacement of the 'bound' water was higher than that for the 'free' water at times longer than 200 ps, as a consequence of the exchange of water molecules between the two regions. Based on our findings, we proposed an alternative explanation to the observed spatial heterogeneity in the HII phase from probe diffusion by Penaloza et al. (Phys. Chem. Chem. Phys., 2012, 14(15), 5247-5250). We found the extent of contact with water was different at different oxygen atoms within the sugar ring. Generally, a higher probability of hydrogen bonding but a shorter lifetime was found in 22% water compared to the case of 14% water. Finally, we examined the extension and compression of the alkyl chain of a columnar.
The possibility of achieving many electrons per absorbed photon of sufficient energy by quantum dots (QDs) drives the motivation to build high performance quantum dot solar cells (QDSCs). Although performance of dye-sensitized solar cells (DSCs), with similar device configuration as that of QDSCs, has significantly improved in the last two decades QDSCs are yet to demonstrate impressive device performances despite the remarkable features of QDs as light harvesters. We investigated the fundamental differences in the optical properties of QDs and dyes using DFT calculations to get insights on the inferior performance of QDSCs. The CdSe QDs and the ruthenium bipyridyl dicarboxylic acid dye (N3) were used as typical examples in this study. Based on a generalized equation of state correlating material properties and photoconversion efficiency, we calculated ground and excited state properties of these absorbers at the B3LYP/lanl2dz level of DFT and analyzed them on the basis of the device performance. Five missing links have been identified in the study which provides numerous insights into building high efficiency QDSCs. They are (i) fundamental differences in the emitting states of the QDs in the strong and weak confinement regimes were observed, which explained successfully the performance differences; (ii) the crucial role of bifunctional ligands that bind the QDs and the photo-electrode was identified; in most cases use of bifunctional ligands does not lead to a QD enabled widening of the absorption of the photo-electrode; (iii) wide QDs size distribution further hinders efficient electron injections; (iv) wide absorption cross-section of QDs favours photon harvesting; and (v) the role of redox potential of the electrolyte in the QD reduction process.
Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O-H covalent bonds within a single water molecule adsorbed on the MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on the MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the first-order electronic-phase transition temperature.
The electrochemical behaviour of ferrocene (Fc) is investigated in six different deep eutectic solvents (DESs) formed by means of hydrogen bonding between selected ammonium and phosphonium salts with glycerol and ethylene glycol. Combinations of cyclic voltammetry and chronoamperometry are employed to characterise the DESs. The reductive and oxidative potential limits are reported versus the Fc/Fc(+) couple. The diffusion coefficient, D, of ferrocene in all studied DESs is found to lie between 8.49 × 10(-10) and 4.22 × 10(-8) cm(2) s(-1) (these do not change significantly with concentration). The standard rate constant for heterogeneous electron transfer across the electrode/DES interface is determined to be between 1.68 × 10(-4) and 5.44 × 10(-4) cm s(-1) using cyclic voltammetry. These results are of the same order of magnitude as those reported for other ionic liquids in the literature.
Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation-anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation-anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application.
Novel self-activated yellow-emitting BaLuAlxZn4-xO7-(1-x)/2 photoluminescent materials were investigated by a combined experimental and theoretical analysis. The effects of Al/Zn composition modulation, calcination atmosphere and temperature on the crystal structure and photoluminescence properties have been studied via engineering oxygen vacancies. Accordingly, BaLuAl0.91Zn3.09O7 prepared in an air atmosphere was found to be the stable crystalline phase with optimal oxygen content and gave a broad yellow emission band with a maximum at 528 nm. The self-activated luminescence mechanism is ascribed to the O-vacancies based on the density functional theory (DFT) calculation. A theoretical model originating from the designed oxygen vacancies has been proposed in order to determine the influence of O-vacancies on the band structure and self-activated luminescence. Therefore, the appearance of a new local energy level in the band gap will cause the wide-band optical transitions in the studied BaLuAlxZn4-xO7-(1-x)/2 materials.
Extracted, formulated, and processed natural Aloe vera has been used as an active layer for memory applications. The functional memory device is realized by a bottom-up structure of ITO/Aloe vera/Al in which the Aloe vera is spin-coated after mixing with different concentrations of ethanol (0-80 wt%) and subsequently dried at different temperatures (50-120 °C). From the current density-voltage measurements, the device can exhibit a reproducible bipolar switching characteristic with pure Aloe vera dried at 50 °C. It is proposed that charges are transported across the Aloe vera layer via space-charge-limited conduction (SCLC), and clusters of interstitial space formed by the functional groups of acemannans and de-esterified pectins in the dried Aloe vera contribute to the memory effect. The formation of charge traps in the Aloe vera layer is dependent on the drying temperature. The drying temperature of a memory-switching Aloe vera layer can be extended to 120 °C with the addition of appropriate amounts of ethanol. The concept of using natural Aloe vera as an active material for memory applications has been demonstrated, and the read memory window, ON/OFF ratio, and retention time are approximately 5.0 V, 10(3), and >10(4) s, respectively.
Copper (Cu, 1-5 wt%) was loaded onto carbon nanotubes (CNTs) by a simple electrochemical method. The physicochemical properties of catalysts (Cu/CNTs) were characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen (N2) adsorption-desorption, Fourier transform infra-red spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electron spinning resonance (ESR). The results showed that the Cu was distributed well on the CNT surface by the interaction of Cu(2+) ions with -OH and -COOH groups on the CNT surface, which preferentially occurred at the defect sites along the CNT backbone. The Cu-O-C bonds formed were found to play an important role in enhancing the photoactivity of the catalysts. The highest number of Cu-O-C bonds possessed by 3 wt% Cu/CNTs demonstrated the best performance in the degradation of p-chloroaniline (96%) under UV light irradiation within 5 h of reaction at 27 °C and under neutral pH conditions. Kinetic studies showed that the degradation followed the pseudo-first order model and the surface reaction was the controlling step. It is believed that these results could contribute to the synthesis of various supported catalysts for various applications.
Ethanol-based nanofluids have attracted much attention due to the enhancement in heat transfer and their potential applications in nanofluid-type fuels and thermal storage. Most research has been conducted on ethanol-based nanofluids containing various nanoparticles in low mass fraction; however, to-date such studies based on high weight fraction of nanoparticles are limited due to the poor stability problem. In addition, very little existing work has considered the inevitable water content in ethanol for the change of thermal conductivity. In this paper, the highly stable and well-dispersed TiO2-ethanol nanofluids of high weight fraction of up to 3 wt% can be fabricated by stirred bead milling, which enables the studies of thermal conductivity of TiO2-ethanol nanofluids over a wide range of operating temperatures. Our results provide evidence that the enhanced thermal conductivity is mainly contributed by the percolation network of nanoparticles at low temperatures, while it is in combination with both Brownian motion and local percolation of nanoparticle clustering at high temperatures.
The molecular dynamics of a synthetic branched chain glycolipid, 2-decyl-tetradecyl-β-d-maltoside (C14-10G2), in the dry assemblage of smectic and columnar liquid crystal phases has been studied by dielectric spectroscopy as a function of frequency and temperature during the cooling process. Strong relaxation modes were observed corresponding to the tilted smectic and columnar phases, respectively. At low frequency (∼900 Hz to 1 kHz) in the smectic phase, Process I* was observed due to the tilted sugar bilayer structure. The process continued in the columnar phase (Process I) with an abrupt dynamic change due to phase transition in the frequency range of ∼1.3 kHz to 22 kHz. An additional process (Process II) was observed in the columnar phase with a broader relaxation in the frequency range of ∼10 Hz to 1 kHz. A bias field dependence study was performed in the columnar phase and we found that the relaxation strength rapidly decreased with increased applied dc bias field. This relaxation originates from a collective motion of polar groups within the columns. The results of dielectric spectroscopy were supported by a molecular dynamics simulation study to identify the origin of the relaxation processes, which could be related to the chirality and hydrogen bonds of the sugar lipid.
Ionic liquids have been objects of extensive research for physical sorption of CO2 and a number of myths have been perpetuated in the literature, for lack of a critical analysis, concerning their potential for CO2 capture. This study carries a critical analysis of a number of widely accepted ideas and others not so well accepted that have been repeatedly expressed in the literature concerning the CO2 physical sorption in ionic liquids. Using the CO2 solubility in eicosane as benchmark, it will be shown that there is no evidence that ILs display a physical sorption of CO2 larger than n-alkanes when analyzed in adequate concentration units; the fluorination of the ions has no impact on the CO2 solubility and the oxygenation will marginally contribute to a decrease of the solubility. Ionic liquid-based deep eutectic systems are also shown to have a poor CO2 solubility. Although these widely used approaches to physically enhance the CO2 solubility in ILs do not seem to have any positive influence, this does not mean that other types of interaction cannot provide enhanced CO2 solubility as in the case of the anion [B(CN)4] confirmed here by a critical analysis of the published data. The mechanism of CO2 physical sorption in ionic liquids is discussed based on the results analyzed, supported by spectroscopic measurements and molecular simulations previously reported and further suggestions of possibilities for enhanced physical sorption based on fluorinated aromatic rings, other cyano based anions, mixtures with other ILs or solvents or the use of porous liquids are proposed.
We have presented a detailed analysis of the phase transition kinetics and binding energy states of solution processed methylammonium lead iodide (MAPbI3) thin films prepared at ambient conditions and annealed at different elevated temperatures. It is the processing temperature and environmental conditions that predominantly control the crystal structure and surface morphology of MAPbI3 thin films. The structural transformation from tetragonal to cubic occurs at 60 °C with a 30 minute annealing time while the 10 minute annealed films posses a tetragonal crystal structure. The transformed phase is greatly intact even at the higher annealing temperature of 150 °C and after a time of 2 hours. The charge transfer interaction between the Pb 4f and I 3d oxidation states is quantified using XPS.
In this study, nano- and microsized zinc oxide (ZnO) materials were doped with different manganese (Mn) contents (1-5 mol%) via a simple sol-gel method. The structural, morphological, optical and chemical environments of the materials were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), UV-visible spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS). XRD results revealed that all synthesised materials were pure and single phased with a hexagonal wurtzite structure of ZnO. However, at a low annealing temperature, a nanorod-like shape can be obtained for all Zn(1-x)MnxO materials. In addition, EDX spectra confirmed the presence of Mn in the ZnO lattice and the atomic percentage was nearly equal to the calculated stoichiometry. UV-vis spectroscopy further revealed that materials in nano size exhibited band gap widening with an increase of the Mn content in the ZnO lattice. In contrast, micron state materials exhibited band gap narrowing with increasing Mn content up to 3% and then begin to widen when Mn > 3%. This is because the band gaps of these materials are affected by the dimensions of the crystals and the Mn content in the materials. Furthermore, XPS results revealed the existence of multiple states of Mn in all synthesised materials. By combining the information obtained from UV-vis and the XPS valence band, shifting in the valence band maximum (VBM) and conduction band minimum (CBM) was observed. Based on XPS results, the calculation of density functional theory studies revealed that the presence of Mn2+, Mn3+, and Mn4+ ions in the materials influences the band gap changes. It was also revealed that the nanosized Zn0.99Mn0.01O exhibited a higher photocatalytic activity than the other samples for degrading methylene blue (MB) dyes, owing to its smallest crystallite size.