3-D molecular assembly of function in titania-based composite material systems

Various examples of composite titania-based nanostructured materials exhibiting cooperative functionalities between different active components are presented. The fabrication of these integrated composite materials is based on one-pot supramolecular templating techniques combined with acidic sol-gel chemistry. The defined 3-D nanoscale organization and integration of various functional components results in advanced optoelectronic and photonic applications such as visible light sensitization of mesoporous titania photocatalysts with cadmium sulfide nanocrystals acting as sensitizing integral part of the mesopore wall structure, narrow bandwidth emission from rare earth ion activated nanocrystalline mesoporous titania films, and mirrorless lasing in dye-doped hybrid organic/inorganic mesostructured titania waveguides.     

Emotionally charged earcons reveal affective congruency effects

In the present study, the affective impact of earcons on stimulus classification is investigated. We show, using a picture-categorization task, that the affective connotation of earcons in major and minor mode (representing positive and negative valence, respectively) can be congruent or incongruent with response valence. Twenty participants classified pictures of animals and instruments in 256 trials, using positive and negative Yes or No responses. Together with the pictures, either a chord in major mode or minor mode was played. The affective valence of the chords either did or did not match the valence of responses. Response-time latencies show congruency effects of the matching and non matching sound and response valences, indicating that it is important to carefully investigate human-computer interfaces for potential affective congruency effects, as these can either facilitate or inhibit user performance.     

Density modeling of polyurethane box foam

A model based on about a dozen fundamental differential equations is used to evaluate and simulate the urethane reactions and physical processes of urethane box foaming. This work focuses on quantitative modeling of foam density for foams using water and physical blowing agents. The final densities of foams range from 30 to 90% of the density as projected with full utilization of the blowing agent. The primary sources of inefficient use of blowing agent are loss of the physical blowing during open‐air mixing and degassing—basically, physical blowing agents with boiling points between 25 and 80°C will evaporate and experience cell rupture in box foams. This loss of blowing agent would not apply to in‐line mixers used for commercial production and should be taken into account with scaling up box or cup foams commercial processes. POLYM. ENG. SCI., 54:1503–1511, 2014. © 2013 Society of Plastics Engineers     

Optimal experimental conditions for hydrogen production using low voltage electrooxidation of organic wastewater feedstock

The dependence of electrooxidation on experimental conditions of organic molecules was investigated to optimize the production of hydrogen from potential wastewater sources using low voltage sources (∼1 V dc). Electrooxidation on platinum, gold, and stainless steel anodes with hydrogen production on the cathode was investigated using several different organic reductants, including: methanol, ethanol, glycerol, isopropanol, propanal, glycerol, glucose, sucrose, citric acid, and propionic acid. The electrolyte pH was varied from 2 to 12 in a 1 M Na₂SO₄ supporting solution. At 1 V, glycerol, citric acid, ethanol and methanol were found to yield the highest currents at low pH values (pH 2 and 7) on platinum electrode, glucose on gold electrode at pH 12 in 1 M Na₂SO₄ solution produced the highest total current density at 1 V with measured Faradaic efficiency for 1 M glucose of 70%. The hydrogen energy production efficiency was 86%. Practical limitations of glucose oxidation at optimum experimental conditions are discussed.     

A broadband Fourier transform microwave spectrometer based on chirped pulse excitation

Designs for a broadband chirped pulse Fourier transform microwave (CP-FTMW) spectrometer are presented. The spectrometer is capable of measuring the 7-18 GHz region of a rotational spectrum in a single data acquisition. One design uses a 4.2 Gsampless arbitrary waveform generator (AWG) to produce a 1 mus duration chirped pulse with a linear frequency sweep of 1.375 GHz. This pulse is sent through a microwave circuit to multiply the bandwidth of the pulse by a factor of 8 and upconvert it to the 7.5-18.5 GHz range. The chirped pulse is amplified by a traveling wave tube amplifier and broadcast inside the spectrometer by using a double ridge standard gain horn antenna. The broadband molecular free induction decay (FID) is received by a second horn antenna, downconverted, and digitized by a 40 Gsampless (12 GHz hardware bandwidth) digital oscilloscope. The second design uses a simplified pulse generation and FID detection scheme, employing current state-of-the-art high-speed digital electronics. In this spectrometer, a chirped pulse with 12 GHz of bandwidth is directly generated by using a 20 Gsampless AWG and upconverted in a single step with an ultrabroadband mixer. The amplified molecular emission is directly detected by using a 50 Gsampless digital oscilloscope with 18 GHz bandwidth. In both designs, fast Fourier transform of the FID produces the frequency domain rotational spectrum in the 7-18 GHz range. The performance of the CP-FTMW spectrometer is compared to a Balle-Flygare-type cavity-FTMW spectrometer. The CP-FTMW spectrometer produces an equal sensitivity spectrum with a factor of 40 reduction in measurement time and a reduction in sample consumption by a factor of 20. The CP-FTMW spectrometer also displays good intensity accuracy for both sample number density and rotational transition moment. Strategies to reduce the CP-FTMW measurement time by another factor of 90 while simultaneously reducing the sample consumption by a factor of 30 are demonstrated.     

Noncatalytic alcoholysis kinetics of soybean oil

Reaction kinetics for the alcoholysis of soybean oil with methanol, ethanol, and isopropanol were evaluated in the absence of catalyst. Metal reactor surfaces catalyzed these reactions, so the reactions were conducted in glass capillary tubes at 120, 150, and 180°C. The reactivity of the alcohols increased with decreasing carbon number. Higher temperatures promoted faster reactions. Higher alcohol stoichiometries did not significantly increase reaction rates; this was attributed to the limited solubility of the alcohol in the soybean oil. At less than 20% conversion, the solubility of the alcohol in the oil phase continuously increased, resulting in increased reaction rates. At approximately 20% conversion, the reaction systems became homogeneous until a glycerine phase was formed at high conversions. In addition to their fundamental value, these data provided a basis on which catalytic reactions can be investigated between 100 and 200°C.     

Noncatalytic polymerization of ethylene glycol and epoxy molecules for rigid polyurethane foam applications

The study investigated an approach to incorporate modified epoxidized soy‐based vegetable oil polyol as a replacement for petroleum‐based polyether polyol and to substantially reduce the isocyanate loading in the rigid foam formulation. Noncatalytic polymerization of epoxidized bodied soybean oil and ethylene glycol (EG) was carried out in a closed batch reaction. Cleavage of the oxirane rings and hydroxyl group attachment at optimum conditions provided the desired polyol products. The polyols were characterized based on its hydroxyl numbers, acidity, viscosity, iodine number, and Gardner color index for quality purposes. Reactions of oxirane ring and EG were verified by spectroscopic FTIR. Crosslinking performance was evaluated by extractability analysis on the polyurethane (PU) elastomer wafers. Rigid foaming performed at 50 and 75% petroleum‐based polyether polyol replacements have shown excellent thermoinsulating and mechanical properties compared with epoxidized soybean oil (ESBO) alone or petroleum‐based polyether polyol alone. A reduction of up to 8% of the polymeric diphenylmethane diisocyanate was achieved using the synthesized ESBO‐EG‐based polyols. A higher average functionality polyol is key component to the reduction of isocyanate in PU synthesis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rigid polyurethane foams made from high viscosity soy‐polyols

This study investigated the physical properties of water‐blown rigid polyurethane (PU) foams made from VORANOL®490 (petroleum‐based polyether polyol) mixed with 0–50% high viscosity (13,000–31,000 cP at 22°C) soy‐polyols. The density of these foams decreased as the soy‐polyol percentage increased. The compressive strength decreased, decreased and then increased, or remained unchanged and then increased with increasing soy‐polyol percentage depending on the viscosity of the soy‐polyol. Foams made from high viscosity (21,000–31,000 cP) soy‐polyols exhibited similar or superior density‐compressive strength properties to the control foam made from 100% VORNAOL® 490. The thermal conductivity of foams containing soy‐polyols was slightly higher than the control foam. The maximal foaming temperatures of foams slightly decreased with increasing soy‐polyol percentage. Micrographs of foams showed that they had many cells in the shape of sphere or polyhedra. With increasing soy‐polyol percentage, the cell size decreased, and the cell number increased. Based on the analysis of isocyanate content and compressive strength of foams, it was concluded that rigid PU foams could be made by replacing 50% petroleum‐based polyol with a high viscosity soy‐polyol resulting in a 30% reduction in the isocyanate content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013