Cobalt molybdenum oxide catalysts for selective oxidation of cyclohexane

Oxidation of cyclohexane has been carried out using molecular oxygen over cobalt molybdenum oxide (CoMoO₄) catalysts in solvent free conditions. The catalysts were prepared using citrate method with three different molar ratios of Co:Mo, 1:1, 1:2, and 2:1 along with individual oxides for comparative studies. While all the catalysts showed significant activity and selectivity, CoMoO₄ with 1:1 ratio showed the best performance compared to the others with a conversion of 7.38%, with selectivity to cyclohexanol and cyclohexanone (KA oil) of 94.3%, in 1 h. The performance of the catalyst, has been studied as a function of oxygen pressure, reaction temperature, and catalyst loading. It was observed that the catalyst deactivates during the course of the reaction. The reasons for deactivation and methods for restoring the activity have been studied. A kinetic model is presented that captures the complex kinetics and matches well with the experimental data. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4384–4402, 2016     

Effect of combining ethylene/methyl acrylate/glycidyl methacrylate terpolymer and an organoclay on the toughening of poly(lactic acid)

Blends of poly(lactic acid) (PLA) and ethylene/methyl acrylate/glycidyl methacrylate terpolymer (EMA‐GMA) with and without the addition of an organoclay were prepared by melt mixing in a twin screw extruder. Mechanical, morphological, structural, and rheological properties of the systems have been investigated as function of its compositions. The impact strength (IS) of PLA increased with the addition of EMA‐GMA. Furthermore, the addition of 2.5 wt% of organoclay to the PLA/EMA‐GMA blend promoted improvements in the mechanical properties, such as IS, tensile strength, and strain‐at‐break. Further addition of organoclay, 5 wt%, led to a formation of a double percolated network, where the clay particles form bridges across EMA‐GMA droplets and glue them together, however, without coalescence. In addition, morphological and wide‐angle X‐ray scattering analyses evidenced that the clay presents a partially exfoliated structure and that remains inside the EMA‐GMA droplets, probably as a consequence of the approach used to produce the systems. POLYM. ENG. SCI., 54:1922–1930, 2014. © 2013 Society of Plastics Engineers     

Synthesis and characterization of 15% efficient CIGSSe solar cells from nanoparticle inks

We report a total‐area power conversion efficiency of 15% for a copper indium gallium disulfoselenide (CIGSSe) solar cell fabricated from a copper indium gallium disulfide (CIGS) nanoparticle ink based process. Careful optimization of the fabrication process has resulted in a significant improvement in efficiency compared to our previously reported efficiency of 12%. This efficiency ranks among the highest reported in the literature for solution processed CIGSSe. Despite having an absorber thickness of approximately 700–800 nm, which is less than half the thickness of high efficiency devices grown by both coevaporation and solution processes in the literature, our devices show good short‐circuit current (32.1 mA/cm²). Surprisingly, the sintered film shows lateral composition fluctuations, which have not been reported for other high efficiency devices and may be responsible for the lower open circuit voltage (636 mV) observed here. This suggests an avenue for further improvement through optimization of the nanoparticle selenization process to better control composition in the sintered film. Copyright © 2015 John Wiley & Sons, Ltd.     

Resolving Deep Sub-Wavelength Scattering of Nanoscale Sidewalls Using Parametric Microscopy

The quantitative optical measurement of deep sub-wavelength features with sub-nanometer sensitivity addresses the measurement challenge in the semiconductor fabrication process. Optical scatterings from the sidewalls of patterned devices reveal abundant structural and material information. We demonstrated a parametric indirect microscopic imaging (PIMI) technique that enables recovery of the profile of wavelength-scale objects with deep sub-wavelength resolution, based on measuring and filtering the variations of far-field scattering intensities when the illumination was modulated. The finite-difference time-domain (FDTD) numerical simulation was performed, and the experimental results were compared with atomic force microscopic (AFM) images to verify the resolution improvement achieved with PIMI. This work may provide a new approach to exploring the detailed structure and material properties of sidewalls and edges in semiconductor-patterned devices with enhanced contrast and resolution, compared with using the conventional optical microscopy, while retaining its advantage of a wide field of view and relatively low cost.     

Dynamic analysis and split range control for maximization of operating range of continuous microbial fuel cell

Human development is inherently connected with availability of water and energy. Energy production requires water, whereas water treatment needs energy. On the other hand, microbial fuel cell has capability to produce energy and water simultaneously from waste water or organic matter. In this paper, first principle-based model of variable volume microbial fuel cell is simulated. Hydraulic retention time is selected as the manipulated variable using the study of steady state and dynamic responses. Classical PI and model predictive control strategies are developed for controlling the produced power from the cell, and its performance is tested for servo problem. Settling time for positive and negative set points is found to be 126 and 889 h in case of classical PI and 120 and 750 h in case of linear MPC, respectively along with large increase (three times order of magnitude) in working volume for negative set point. These control challenges are overcome by using split range controller with variable and constant volume microbial fuel cells. The settling time for negative set point is found to be 49 and 21 h for classical PI and linear MPC schemes, respectively, which is significantly lower than using only variable volume microbial fuel cell. Also, there is no increase in the working volume of the constant volume microbial fuel cell. Hence, operating range of the microbial fuel cell is enhanced using split range controller.     

Significantly high electromagnetic shielding effectiveness in polypyrrole synthesized by eco-friendly and cost-effective technique

A facile and eco-friendly synthesis of polypyrrole from monomer pyrrole using nominal amount of ferric chloride hexahydrate (FeCl₃.6H₂O) oxidant in aqueous solution by chemically oxidative polymerization method has been reported. The use of aqueous solvent and ferric chloride hexahydrate salt in polypyrrole synthesis have an eco-friendly route favorable for the production of polypyrrole in large quantities. The synthesized polypyrrole samples exhibit good electrical conductivity (2 S/cm) and yield of 80% for reaction time of 8 hr at 5°C. Quality and properties of polypyrrole samples have been thoroughly investigated with varying reaction time and temperature while other synthesis parameters like molar ratio of oxidant to monomer, oxidant concentration, and solvent were kept constant. X-ray diffraction analysis of polypyrrole with a shorter reaction time shows the presence of iron oxide (Fe₂O₃) peaks. The complete reaction may not occur at shorter reaction times due to which residual ferric ions converted into Fe₂O₃. X-ray photoelectron spectroscopy measurement of polypyrrole also confirms the formation of Fe₂O₃. Appropriate selection of reaction time and temperature produced pure phase polypyrrole with high yield and good conductivity. Synthesized polypyrrole by our eco-friendly and cost-effective technique exhibits prominent electromagnetic shielding effectiveness value of 30 dB in the X-band (8–12 GHz).     

Ultrafiltered milk reduces bitterness in reduced-fat Cheddar cheese made with an exopolysaccharide-producing culture

The objectives were to reduce bitterness in reduced-fat Cheddar cheese made with an exopolysaccharide (EPS)-producing culture and study relationships among ultra-filtration (UF), residual chymosin activity (RCA), and cheese bitterness. In previous studies, EPS-producing cultures improved the textural, melting, and viscoelastic properties of reduced-fat Cheddar cheese. However, the EPS-positive cheese developed bitterness after 2 to 3 mo of ripening due to increased RCA. We hypothesized that the reduced amount of chymosin needed to coagulate UF milk might result in reduced RCA and bitterness in cheese. Reduced-fat Cheddar cheeses were manufactured with EPS-producing and nonproducing cultures using skim milk or UF milk (1.2×) adjusted to a casein:fat ratio of 1.35. The EPS-producing culture increased moisture and RCA in reduced-fat Cheddar cheese. Lower RCA was found in cheese made from UF milk compared with that in cheese made from control milk. Ultrafiltration at a low concentration rate (1.2×) produced EPS-positive, reduced-fat cheese with similar RCA to that in the EPS-negative cheese. Slower proteolysis was observed in UF cheeses compared with non-UF cheeses. Panelists reported that UF EPS-positive cheese was less bitter than EPS-positive cheese made from control milk. This study showed that UF at a low concentration factor (1.2×) could successfully reduce bitterness in cheese containing a high moisture level. Because this technology reduced the RCA level (per g of protein) to a level similar to that in the control cheeses, the contribution of chymosin to cheese proteolysis would be similar in both cheeses.     

Electrochromic performance of a poly(3,4-ethylenedioxythiophene)-Prussian blue device encompassing a free standing proton electrolyte film

Electrochromic devices incorporating an electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT) film and a free standing, transparent film of a proton conducting polymer electrolyte with high ambient temperature ionic conductivity of 10⁻² S cm⁻¹ have been fabricated with and without the ion storage electrodeposited Prussian blue (PB) counter electrode layer. While coloration efficiency increases as a function of applied potential in the sole PEDOT device with largest values of CE_(max,VIS) ∼ 120 cm² C⁻¹ and CE_(max,NIR) ∼ 133 cm² C⁻¹ attained at V_c = −1.9 V, the PEDOT:PB device shows a digression from this trend. Much higher coloration efficiencies in the visible (247 cm² C⁻¹ at 570 nm) and NIR (116 cm² C⁻¹ at 1100 nm) regions are achieved for the PEDOT:PB device at a relatively lower reducing voltage of −0.8 V. The PEDOT:PB device shows fast switching redox process (t_c = 2.6 s and t_b = 1.3 s for a 50% optical contrast at 632.8 nm) and a highly reversible charge density as the ratio of Q_inserted to Q_extracted was found to vary between 0.8 and 1.0. When switched between the clear and blue states for 2000 cycles, the insignificant drop in peak current density maxima observed for the PEDOT:PB device, i.e. the good cycling stability, the facile fabrication of device assembly, the ease of scaling up the electrolyte and electrochromic coatings, indicate that this method can be adapted as a simple and inexpensive alternative to conventional electrochromic windows with high cost components.