Measurements and thermodynamic modeling of the solubility of squalene in supercritical carbon dioxide

The solubility of squalene in supercritical carbon dioxide (SC-CO₂) was measured and it was analyzed together with the values obtained by Catchpole and von Kamp (1997). The results showed that the experimental values obtained in this work agreed with the order of magnitude of those reported in the literature and correlated well with the Chrastil equation. The thermodynamic modeling using the Peng–Robinson equation of state only correlated well with the experimental values obtained when the critical properties and acentric factor reported by Ruivo et al. (2004) were used. The values predicted for the solubility of squalene in SC-CO₂ using modeling employing the GC-EOS, were only of the same order of magnitude as the experimental values for pressures below 200 bar, and its performance was influenced by the value of the critical hard sphere diameter.     

A transient 2D-finite-element approach for the simulation of mixed lubrication effects of reciprocating hydraulic rod seals

This paper presents a method for the computation of soft elasto-hydrodynamic lubrication (EHL) based on the strong coupling of a non-linear finite-element model with the transient Reynolds equation for thin fluid films. This approach allows the usage of arbitrary non-linear elastic or inelastic material models for the finite deformations. The transient Reynolds equation is simultaneously solved within a finite-element computation. In order to account for the effect of surface roughness in the sealing contact, flow factors are incorporated into the transient Reynolds equation. The method is currently restricted to planar or axisymmetric geometries.     

Ultra-low-energy ion-beam-synthesis of Ge nanocrystals in thin ALD Al2O3 layers for memory applications

Structural and electrical properties of ALD-grown 5 and 7 nm-thick Al₂O₃ layers before and after implantation of Ge ions (1 keV, 0.5–1 × 10¹⁶ cm^?2) and thermal annealing at temperatures in the 700–1050 °C range are reported. Transmission Electron Microscopy reveals the development of a 1 nm-thick SiO₂-rich layer at the Al₂O₃/Si substrate interface as well as the formation of Ge nanocrystals with a mean diameter of ～5 nm inside the implanted Al₂O₃ layers after annealing at 800 °C for 20 min. Electrical measurements performed on metal–insulator–semiconductor capacitors using Ge-implanted and annealed Al₂O₃ layers reveal charge storage at low-electric fields mainly due to location of the Ge nanocrystals at a tunnelling distance from the substrate and their spatial dispersion inside the Al₂O₃ layers.     

<Superscript>63</Superscript>Cu and <Superscript>115</Superscript>In NMR study of CuInS<Subscript>2</Subscript> semiconductor

Two CuInS₂ semiconductor samples synthesized from chemical elements with the equiatomic cation ratio (N _Cu/N _In = 1) and either an excess or stoichiometric sulfur content have been investigated by ⁶³Cu and ¹¹⁵In nuclear magnetic resonance. The spectra were recorded on a Bruker Avance-400 spectrometer at a temperature of 290 K and frequencies of 106.14 MHz (⁶³Cu) and 87.67 MHz (¹¹⁵In). Numerical simulation made it possible to determine the quadrupole coupling constants: 0.34 MHz (⁶³Cu) and 1.1 MHz (¹¹⁵In). For the samples synthesized with excess sulfur (above stoichiometry), distortions are revealed in both the ⁶³Cu and ¹¹⁵In spectra.     

PY181 Pigment Microspheres of Nanoplates Synthesized via Polymer‐Induced Liquid Precursors

Organic pigments are important crystalline substances, and their properties and applications rely on size and shape control. Pigment Yellow 181 (PY181) is an industrial azo pigment that is light and weatherfast and suitable for high temperature processing. One disadvantage is its needle‐like shape in the default β‐phase, which makes the pigment difficult to process in industry, e.g., in polymer melts, where a spherical structure would be ideal. Here, we show for the first time, that polymer‐induced liquid precursor structures can be formed even in association to a chemical reaction. Furthermore, it is demonstrated that biomineralization principles can be exploited for the generation of advanced functional materials, such as pigments with novel complex morphology and different properties. Stable PY181 microspheres of nanoplates in the β‐phase were obtained in mixed solvents of water and isopropanol by direct azo coupling under the directing influence of a designed copolymer additive aminobenzoylaminobenzamide‐acetoacetyl‐poly(ethylene imine)‐block‐poly(ethylene glycol) (ABABA‐acetoacetyl‐PEI‐b‐PEG).     

Kinetic modeling of catalytic conversion of methylcyclohexane over USY zeolites: Adsorption and reaction phenomena

Catalytic conversion of cycloparaffins is a complex process involving competing reaction steps. To understand this process, FCC experiments using methylcyclohexane (MCH) on USY zeolite catalysts were carried out in the mini‐fluidized CREC riser simulator. Runs were developed under relevant FCC process conditions in terms of partial pressures of MCH, temperatures (450–550°C), contact times (3–7 s), catalyst‐oil mass ratios (5), and using fluidized catalysts. MCH overall conversions ranged between 4 to 16 wt %, with slightly higher conversions obtained using the larger zeolite crystallites. Moreover, it was found that MCH undergoes ring opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. A heterogeneous kinetic model for MCH conversion including thermal effects, adsorption and intrinsic catalytic reaction phenomena was established. Adsorption and kinetic parameters were determined, including the heat of adsorption (?40 kJ/mol), as well as thermal and primary catalytic intrinsic activation energies, which were in the range of 43–69 kJ/mol, and 50–74 kJ/mol, respectively. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Physical and microstructural aspects of sulfate attack on ordinary and limestone blended Portland cements

The consequences of external sulfate attack were investigated by traditional test methods, i.e. length and mass change, as well as by a newly developed, surface sensitive ultrasonic method, using Leaky Rayleigh waves (1 MHz). The macroscopic changes are discussed and compared with thermodynamic calculations and microstructural findings (SEM/EDS). The results show that the main impact of limestone additions on resistance to sulfate degradation are physical — i.e. addition of a few percent in Portland cement reduces the porosity and increases the resistance of Portland cement systems to sulfate; but higher addition of 25% increase porosity and lower resistance to sulfate. The kinetics of degradation were dramatically affected by the solution concentration (4 or 44 g Na₂SO₄/l) and the higher concentration also resulted in the formation of gypsum, which did not occur at the low concentration. However the pattern of cracking was similar in both cases and it appears that gypsum precipitates opportunistically in pre-formed cracks so it is not considered as making a significant contribution to the degradation. At 8 °C limited formation of thaumasite occurred in the surface region of the samples made from cement with limestone additions. This thaumasite formation led to loss of cohesion of the paste and loss of material from the surface of the samples. However thaumasite formation was always preceded by expansion and cracking of the samples due to ettringite formation and given the very slow kinetics of thaumasite formation it was probably facilitated by the opening up of the structure due to ettringite induced cracking.The expansion of the samples showed a steady stage, followed by a rapidly accelerating stage, with destruction of the samples. The onset of the rapidly accelerating stage occurred when the thickness of the cracked surface layer reached about 1–1.5 mm–10–15% of the total specimen thickness (10 mm).     

Analysis of flow in rotating packed beds via CFD simulations—Dry pressure drop and gas flow maldistribution

Three-dimensional unsteady-state turbulent rotating single-phase flows were simulated in rotating packed beds (RPB) and were validated using overall dry pressure drop measurements for three RPB designs [Liu, H.-S., Lin, C.-C., Wu, S.-C., Hsu, H.-W., 1996. Characteristics of a rotating packed bed. Industrial and Engineering Chemistry Research 35, 3590-3596; Sandilya, P., Rao, D.P., Sharma, A., Biswas, G., 2001b. Gas-phase mass transfer in a centrifugal contactor. Industrial and Engineering Chemistry Research 40, 384-392; Zheng, C., Guo, K., Feng, Y.D., Yung, C., 2000. Pressure drop of centripetal gas flow through rotating bed. Industrial and Engineering Chemistry Research 39, 829-834]. Analysis of the radial and tangential velocities highlighted the impact of gas feed entrance effects on the peripheral gas maldistribution in the rotating packing module. Recommendations were formulated for an optimum design with the aim to reduce gas flow maldistribution in RPBs. Breakdown of the overall pressure drop in its modular components for the housing, the rotating packing module, the free inner rotational zone, and the gas disengagement showed that the dissipation in the rotating packing could be a minor contributor to the overall pressure drop which may be undesirable in terms of RPB mass transfer and reaction efficiencies. Analysis of the simulated pressure drops allowed development of CFD-based Ergun-type semi-empirical relationships in which the gas-slip and radial acceleration effects, the laminar and inertial drag effects, and the centrifugal effect were aggregated additively to recompose the pressure drops in the rotating packing module.     

Lead emissions from road transport in Europe: A revision of current estimates using various estimation methodologies

Large-scale use of leaded gasoline was an important source of the neurotoxin lead in the European environment. After a sequence of regulations on the allowed gasoline lead content and, eventually, a ban on the use of lead additives in gasoline, road transport was no longer considered a source of atmospheric lead. Currently a discrepancy exists between measured atmospheric lead concentrations and model-predicted concentrations, suggesting that lead emissions to the atmosphere may be underestimated. Recently it was suggested that lead emission from unleaded gasoline combustion is still an important source and may (partly) fill the gap between modelled and observed atmospheric lead concentrations. In this paper we assess the plausibility of the latter suggestion by following various emission estimation methodologies. The uncertainty of lead emissions from road transport is further reduced by chemical analysis of fuel samples. The result of our assessment is that lead from road transport fuel combustion is not the missing lead source needed to fill the gap between modelled and observed lead concentrations. Road transport is still a source of lead through brake wear and a small contribution from exhaust emissions but this contributes no more than 5–8% of the EU25 total emission.