Demulsification of oil-in-water emulsion under freezing conditions: Effect of crystal structure modifier

The demulsification of oil-in-water (O/W) emulsions under freezing conditions is connected to fat crystallization in the oil droplet. Therefore, demulsification can be prevented by the use of oil with a low melting point, and also by lowering the O/W ratio. However, an oil with a low melting point, such as sunflower, is rather expensive, and the O/W ratio has a significant effect on the texture of emulsions. We searched for an oil that is suitable for the production of a freeze-stable emulsion and found that soybean oil has unique characteristics. Normally, emulsions are more unstable at lower temperatures; soybean oil emulsion is unstable at −10°C and stable at −20°C. This unique characteristic results from the following two reasons. First, the solid fat content of soybean oil is almost the same at −10 and −20°C. Second, small crystals form a larger network over a period of time, and the higher temperature promotes faster restructuring. This structure formation was microscopically observed with the use of a thermostated stage. Structure formation was suppressed with the addition of a crystal structure modifier, polyglycerol fatty acid full ester, which also suppressed coalescence.     

Poly(L‐lactide). X. Enhanced surface hydrophilicity and chain‐scission mechanisms of poly(L‐lactide) film in enzymatic,alkaline, and phosphate‐buffered solutions

Attempts were carried out to enhance the surface hydrophilicity of poly(L ‐lactide), that is, poly(L ‐lactic acid) (PLLA) film, utilizing enzymatic, alkaline, and autocatalytic hydrolyses in a proteinase K/Tris–HCL buffered solution system (37°C), in a 0.01N NaOH solution (37°C), and in a phosphate‐buffered solution (100°C), respectively. Moreover, its chain‐scission mechanisms in these different media were studied. The advancing contact‐angle (θ_a) value of the amorphous‐made PLLA film decreased monotonically with the hydrolysis time from 100° to 75° and 80° without a significant molecular weight decrease, when enzymatic and alkaline hydrolyses were continued for 60 min and 8 h, respectively. In contrast, a negligible change in the θ_a value was observed for the PLLA films even after the autocatalytic hydrolysis was continured for 16 h, when their bulk M_n decreased from 1.2 × 10⁵ to 2.2 × 10⁴ g mol^?1 or the number of hydrophilic terminal groups per unit weight increased from 1.7 × 10^?5 to 9.1 × 10^?5 mol g^?1. These findings, together with the result of gravimetry, revealed that the enzymatic and alkaline hydrolyses are powerful enough to enhance the practical surface hydrophilicity of the PLLA films because of their surface‐erosion mechanisms and that its practical surface hydrophilicity is controllable by varying the hydrolysis time. Moreover, autocatalytic hydrolysis is inappropriate to enhance the surface hydrophilicity, because of its bulk‐erosion mechanism. Alkaline hydrolysis is the best to enhance the hydrophilicity of the PLLA films without hydrolysis of the film cores, while the enzymatic hydrolysis is appropriate and inappropriate to enhance the surface hydrophilicity of bulky and thin PLLA materials, respectively, because a significant weight loss occurs before saturation of θ_a value. The changes in the weight loss and θ_a values during hydrolysis showed that exo chain scission as well as endo chain scission occurs in the presence of proteinase K, while in the alkaline and phosphate‐buffered solutions, hydrolysis proceeds via endo chain scission. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1628–1633, 2003     

Oily Grime Formed on Hard Surfaces of Kitchen Appliances: Chemical Composition and Oxidation Mechanism

The cooking of oil-containing food products at high temperatures results in an insoluble, unsightly, greasy layer of grime on appliance surfaces in residential and commercial kitchens. Over time, adsorbed grime becomes difficult to remove using normal dishwashing detergents. A number of studies have focused on the deterioration and oxidation of oils and the harmful effects that volatile compounds associated with such processes have on human health. Little attention, however, has been paid to kitchen grime. The present study examined grime obtained from the surfaces of appliances such as sirocco fans, filters, and range hoods in residential kitchens in Tokyo. The grime was characterized by X-ray fluorescence spectroscopy (XRF), Fourier-transform infrared spectroscopy (FT-IR), size exclusion chromatography (SEC), thermal hydrolysis methylation–gas chromatography–mass spectroscopy (THM–GCMS), and nuclear magnetic resonance (NMR) techniques. The chemical composition and structure of the grime differed from those of the edible oils. The grime consisted mainly of polymerized and oxidized triacylglycerols. Bridging between unsaturated acyl groups of triglycerols occurred through thermal oxidation and aging in air, yielding their dimers, trimers, and highly polymerized products while also transforming unsaturated acyl groups into saturated ones. Cross-linking reactions involving dibasic acids also caused polymerization. Those polymerized products strongly adhered to the hard surfaces of the appliances. Small amounts of cellulose fibers from air or towel may also play a role in mechanically stabilizing the dirt structure.

An IR study on ion-specific and solvent-specific swelling of poly(N-vinyl-2-pyrrolidone) gel

Swelling degrees of poly(N-vinyl-2-pyrrolidone) (PVP) gel were measured in aqueous salt solutions and in water/organic solvent mixtures to find marked ion- and solvent-specificities. In order to investigate any correlation of those specificities with hydration or solvation of PVP, IR spectra band of the CO group was monitored by means of ATR method both for PVP gel and the relevant solution systems. Dependence of the peak frequency on the swelling ratio suggested that hydration of PVP carbonyl group in deswollen gel systems is different from that in the corresponding solution systems. In the solution systems, PVP carbonyl band showed a high-wavenumber shift for deswollen systems, which can be well correlated with changes in water proton charge through ionic hydration and with Gutmann's acceptor number of organic solvents. In the deswollen gel systems, the CO band showed a low-wavenumber shift, suggesting a strong hydration or doubly hydrated state. This unexpected behavior was interpreted by assuming an intermolecular hydrogen bond of two carbonyl groups intermediated by water molecules.     

Re-evaluation of Radiation-Energy Transfer to an Extraction Solvent in a Minor-Actinide-Separation Process Based on Consideration of Radiation Permeability

ABSTRACT

Absorbed-dose estimation is essential for evaluation of the radiation tolerance of minor-actinide-separation processes. We propose a dose-evaluation method based on radiation permeability, with comparisons of heterogeneous structures seen in the solvent-extraction process, such as emulsions forming in the mixture of the organic and aqueous phases. A demonstration of radiation-energy-transfer simulation is performed with a focus on the minor-actinide-recovery process from high-level liquid waste with the aid of the Monte Carlo radiation-transport code PHITS. The simulation results indicate that the dose absorbed by the extraction solvent from alpha radiation depends upon the emulsion structure, and that from beta and gamma radiation depends upon the mixer-settler-apparatus size. Non-negligible contributions of well-permeable gamma rays were indicated in terms of the plant operation of the minor-actinide-separation process.     

The effects of air pollution and climatic factors on atmospheric corrosion of marble under field exposure

The atmospheric corrosion of marble was evaluated in terms of SO₂ concentration as air pollution and climatic factors such as rainfall, relative humidity, temperature and so on under the field exposure. Marble of calcite type (CaCO₃) was exposed to outdoor atmospheric environment with and without a rain shelter at four test sites in the southern part of Vietnam for 3-month, 1- and 2-year periods from July 2001 to September 2003. The thickness loss of marble was investigated gravimetrically. X-ray diffraction and X-ray fluorescent methods were applied to study corrosion products on marble. The corrosion product of marble was only gypsum (CaSO₄ · 2H₂O) and was washed out by rain under the unsheltered exposure condition. It was found that the most substantial factors influencing the corrosion of marble were rainfall, SO₂ concentration in the air and relative humidity. Based on the results obtained, we estimated the dose-response functions for the atmospheric corrosion of marble in the southern part of Vietnam.     

Very high temperature annealing effect on amorphous carbon films grown on refractory oxide substrates by pulsed laser deposition

We have carried out very high temperature heat treatment at 1400–2700 °C of about 10 nm-thick amorphous carbon thin films deposited on refractory substrates MgO, Al₂O₃, and yttria-stabilized zirconia (YSZ) using pulsed laser deposition techniques. After the annealing, a few nanometer scale sp² crystallization of the films and a large corrugation with a height of more than 1 μm were observed by Raman spectroscopy analysis and optical/atomic force microscopes, respectively. The corrugation is probably caused by the formation of gases at the film/substrate interface during the heat treatment.     

Methylcyclohexane dehydrogenation for hydrogen production via a bimodal catalytic membrane reactor

The dehydrogenation of methylcyclohexane (MCH) to toluene (TOL) for hydrogen production was theoretically and experimentally investigated in a bimodal catalytic membrane reactor (CMR), that combined Pt/Al₂O₃ catalysts with a hydrogen‐selective organosilica membrane prepared via sol‐gel processing using bis(triethoxysilyl) ethane (BTESE). Effects of operating conditions on the membrane reactor performance were systematically investigated, and the experimental results were in good agreement with those calculated by a simulation model with a fitted catalyst loading. With H₂ extraction from the reaction stream to the permeate stream, MCH conversion at 250°C was significantly increased beyond the equilibrium conversion of 0.44–0.86. Because of the high H₂ selectivity and permeance of BTESE‐derived membranes, a H₂ flow with purity higher than 99.8% was obtained in the permeate stream, and the H₂ recovery ratio reached 0.99 in a pressurized reactor. A system that combined the CMR with a fixed‐bed prereactor was proposed for MCH dehydrogenation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1628–1638, 2015     

Influence of a fiber-network microstructure of paper-structured catalyst on methanol reforming behavior

A novel microstructured catalyst that consists of Cu/ZnO catalyst powders and ceramic fibers was successfully prepared using pulp fibers as a tentative matrix by a papermaking technique. As-prepared material, called a paper-structured catalyst, possessed porous microstructure with layered ceramic fiber networks (average pore size ca. 20 μm, porosity ca. 50%). In the process of methanol autothermal reforming (ATR) to produce hydrogen, paper-structured catalysts demonstrated both high methanol conversion and low concentration of undesirable carbon monoxide as compared with catalyst powders and pellets. The catalytic performance of paper-structured catalysts depended on the use of pulp fibers, which were added in the paper-forming process and finally removed by thermal treatment before ATR performance tests. Confocal laser scanning microscopy and mercury intrusion analysis suggested that the tentative pulp fiber matrix played a significant role in regulating the fiber-network microstructure inside paper composites. Various metallic filters with different average pore sizes, used as supports for Cu/ZnO catalysts, were subjected to ATR performance tests for elucidating the pore effects. The tests indicated that the pore sizes of catalyst support had critical effects on the catalytic efficiency: the maximum hydrogen production was achieved by metallic filters with an average pore size of 20 μm. These results suggested that the paper-specific microstructures contributed to form a suitable catalytic reaction environment, possibly by promoting efficient diffusion of heat and reactants. The paper-structured catalyst with a regular pore microstructure is expected to be a promising catalytic material to provide both practical utility and high efficiency in the catalytic gas-reforming process.