Boiling of binary mixtures—study of individual bubbles

Experiments are reported in which individual bubbles of vapour are grown at a plane wall in initially stagnant isothermal liquid. Such tests had already been done and satisfactorily analysed and understood for pure liquids, but here the liquids are binary mixtures of hexane and octane of varying composition.The chief result is that ciné observations of the general behaviour of such bubbles (rate of growth, change of shape, time and size at departure) presents no new problems; it is identical to behaviour in pure liquids, provided one change of parameter is made. That change is to substitute the correct temperature for the evaporating binary interface in place of the saturation temperature for the pure liquid. That interface temperature was determined by reference to recent analytic solutions for evaporation of semi-infinite binary liquid by diffusion of heat and mass.Detailed rapid thermometric observations were also made, of the temperatures at the wall below the bubble and inside the bubble. They showed some aspects which differ markedly from pure liquids (though not such as to affect general behaviour). Those aspects were explained by detailed analysis of diffusion of heat and mass in a thin layer of liquid (microlayer) left beneath the growing bubble.Implications for boiling heat transfer are also considered and it is shown that this analysis of individual bubbles does not, of itself, explain the known reduction in heat transfer coefficient between pure and binary liquids. Several existing methods of explaining that reduction are examined and shown to have a common basis close to that determined by our analysis of single bubbles. But on extending from that basis in a simple way, to predict boiling heat transfer rates, they fail, except where an additional pressure-dependent multiplier is introduced, on purely empirical grounds.     

Soil wettability as determined from using low-field nuclear magnetic resonance

The molarity of ethanol droplet and water drop penetration time methods are commonly used to determine soil wettability because these tests are quick and easy to perform. However, these tests do not provide reproducible results on the same sample. Low-field nuclear magnetic resonance (NMR) is shown as an alternative tool to determine soil wettability. Addition of small amounts of water in dry wettable porous media produces predominant amplitude peaks at transverse relaxation times (T2) of 100 ms or less while addition of water in dry water-repellent porous media with the same pore structure produce predominant amplitude peaks at T2 values near 1000 ms. The geometric mean of T2 (T(2gm)) from water-repellent samples immediately after the addition of water is greater than 1000 ms, which is close to that of bulk water, while T(2gm) from wettable samples immediately after the addition of water is significantly less than 1000 ms. Measurements over time show that water-repellent samples eventually reach the same equilibrium end point as its corresponding wettable sample when continually exposed to water. This paper will show that NMR can be used to formulate a screening criterion for quickly determining wettability. The advantage of using NMR is that the results are reproducible provided the sample is prepared and analyzed in a systematic manner.     

Mechanical properties of discontinuous fiber reinforced thermoplastics. II. Random-in-plane fiber orientation

The mechanical properties are presented for a series of discontinuous fiber-reinforced thermoplastic composites made with random-in-plane fiber orientation. The matrix and fiber materials were chosen to provide a wide range of strength, modulus, ductility and adhesive properties. In many cases strong, rigid, yet tough composites were fabricated. Strength levels of over 20,000 psi and modulus values over 1,000,000 psi were reached in several systems reinforced with short Kevlar-49 and graphite fibers. A strong dependence of composite strength and modulus on fiber strength and modulus was noted indicating good transfer of load from matrix to reinforcement. Fiber efficiency factors for modulus and strength were calculated for the experimental composite systems and averaged 0.19 and 0.11 respectively. Data were analyzed using basic composite theory. Properties of the experimental composites could not be predicted from constituent properties.     

Surface properties and platelet adhesion characteristics of acrylic acid and allylamine plasma-treated polyethylene

Acidic oxygen-containing and basic nitrogen-containing functional groups were incorporated onto thin films formed by plasma polymerization of acrylic acid and allylamine in a lowpressure glow discharge. ESCA, ATR–FTIR spectroscopy, and static contact-angle measurements confirmed the presence of these functional groups. Surface hydrophilicity of the acrylic acid plasma polymer decreased with time due to the diffusion of hydrophilic oxygencontaining functional groups away from the surface of the plasma-treated polyethylene. In contrast, the hydrophilicity of the allylamine plasma polymer increased with time because of the extensive post-plasma-treatment oxidation with atmospheric oxygen. In assessing the blood compatibility of these two types of plasma polymer surfaces by platelet adhesion and spreading, the acidic acrylic acid plasma polymers showed an improvement in thromboresistance, but the basic allylamine plasma polymers were more thrombogenic than was the untreated low-density polyethylene base material. © 1993 John Wiley & Sons, Inc.     

Mechanical and thermal properties of UV-curable polyurethane and polyurea acrylates

Soft-segment molecular weight, soft-segment crystallization, hard-segment-type, and reactive diluent level were examined in urea and urethane acrylates. Increasing soft-segment molecular weight led to a decreased tensile modulus, increased strength, and increased elongation at break. Soft-segment crystallization increased the modulus below the melting temperature, but decreased the modulus above the melting temperature because crystallization interfered with cross-linking. Materials with hard segments that allowed for greater phase separation showed a higher modulus, higher ultimate stress, and higher ultimate elongation. Materials with reactive diluents 2-hydroxyethyl methacrylate (HEMA) and N-vinyl pyrrolidinone (NVP) showed qualitatively different behavior. HEMA caused the modulus and strength to increase with little effect on elongation up to concentrations of 50 wt %; at higher concentrations, the elongation decreased. NVP also increased the modulus and strength; however, at 40 wt % NVP, ultimate elongation increased in a well-phaseseparated system and decreased in a poorly phase-separated system. In tensile tests, samples with 40% NVP also showed substantial sample necking and drawing. © 1993 John Wiley & Sons, Inc.     

Inhibition of cholesterol synthesis by cyclopropylamine derivatives of squalene in human hepatoblastoma cells in culture

Two squalene derivatives, trisnorsqualene cyclopropylamine and trisnorsqualeneN-methylcyclopropylamine, were synthesized and tested for inhibition of lanosterol and squalene epoxide formation from squalene in rat hepatic microsomes, and for the inhibition of cholesterol syntheses in human cultured hepatoblastoma (HepG2) cells. Trisnorsqualene cyclopropylamine inhibited [³H]-squalene conversion to [³H]squalene epoxide in microsomes (IC₅₀=5.0 μM), indicating that this derivative inhibited squalene mono-oxygenase. Trisnorsqualenen-methylcyclopropylamine inhibited [³H]squalene conversion to [³H]lanosterol (IC₅₀=12.0 μM) and caused [³H]-squalene epoxide to accumulate in microsomes, indicating that this derivative inhibited 2,3-oxidosqualene cyclase. Cholesterol biosynthesis from [¹⁴C]acetate in HepG2 cells was inhibited by both derivatives (IC₅₀=1.0 μM for trisnorsqualene cyclopropylamine; IC₅₀=0.5 μM for trisnorsqualeneN-methylcyclopropylamine). Cells incubated with trisnorsqualene cyclopropylamine accumulated [¹⁴C]squalene, while cells incubated with trisnorsqualeneN-methylcyclopropylamine accumulated [¹⁴C]squalene epoxide and [¹⁴C]squalene diepoxide. The concentration range of inhibitor which caused these intermediates to accumulate coincided with that which inhibited cholesterol synthesis. The results indicate that cyclopropylamine derivatives of squalene are effective inhibitors of cholesterol synthesis, and that substitutions at the nitrogen affect enzyme selectivity and thus the mechanism of action of the compounds.     

Lipase G-Catalyzed synthesis of monoglycerides in organic solvent and analysis by HPLC

Monoglycerides were synthesized with Lipase G fromPenicillium sp. as biocatalyst. This enzyme successfully catalyzed the esterification of glycerol with oleic acid (18:1 n-9) or eicosapentaenoic acid, EPA (20:5 n-3) in hexane. Esterification at 40°C for 24 hr resulted in 86.3 mol% and 64.3 mol% incorporation of 18:1 n-9 and 20:5 n-3, respectively. Lipase GC fromGeotrichum candidum was not effective in esterifying the fatty acids under the present experimental conditions. Lipase G was able to incorporate 98.5 mol% and 98.1 mol% of 18:1 n-9 onto glycerol in 24 hr or less at 25°C and 37°C, respectively, in the absence of molecular sieve 4A. The product formed was analyzed by high performance liquid chromatography (HPLC) with a combined evaporative light scattering mass detector (ELSD) and ultraviolet detection at 206 nm. The result of this study demonstrates that Lipase G is capable of incorporating long-chain fatty acids of potential health benefit onto glycerol.     

Poly(glycerol–sebacate) bioelastomers—kinetics of step‐growth reactions using Fourier Transform (FT)‐Raman spectroscopy

Kinetic studies of the esterification of glycerol (G) and sebacic acid (SA) at three molar ratios (0.6, 0.8, 1.0) and at three temperatures (120, 130, 140°C) to form poly(glycerol–sebacate) were performed and assessed using FT‐Raman spectroscopy. The quantitative changes in the concentrations of carboxylic acid and ester groups within the forming bioelastomer were measured and the chemical rate constants (k) determined from the kinetic scheme were first‐order, with respect to sebacic acid concentration. Increasing the reaction temperature by 20°C is noted to increase the chemical rate constant (k) by a factor of up to 4.5 and the total extent of conversion at early times for the molar ratios investigated. The activation energy (E_a) and the pre‐exponential factor (A₀) for these three stoichiometric ratios were calculated, which varied in accordance with the average functionality of the system. Under isothermal conditions, the chemical rate constant remained unchanged with an increase in the extent of the reaction (α) until a spontaneous transition resulted in the shift in the mechanism from kinetics to diffusion controlled. The Young's moduli of the PGS polymers were found to depend primarily on the average functionality of the system and the curing period. This investigation confirms the reaction mechanism for PGS polymer synthesis and shows the flexibility afforded to PGS properties and reaction times through varying the stoichiometric ratios of glycerol to sebacic acid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

THE KINETICS OF ZINC,COBALT AND NICKEL EXTRACTION IN THE D2EHPA-HEPTANE-HC104 SYSTEM USING THE ROTATING DIFFUSION CELL TECHNIQUE

The kinetics of the extraction of zinc, cobalt and nickel from perchlorate solutions using di 2-ethyl-hexyl phosphoric acid (D2EHPA) dissolved in heptane were studied using the Rotating Diffusion Cell technique. The extraction of each metal was investigated individually over a wide range of metal concentration, extractant concentration, pH and temperature conditions.

The data were analysed in terms of a mass transfer with chemical reaction (MTWCR) mechanism. Hughes and Rod'/s generalized MTWCR model was used to fit the cobalt data using kinetic and equilibrium parameters. The zinc and nickel data were quantitatively described within the framework of the MTWCR model. The zinc extraction rate was so fast that mass transfer alone was rate controlling. The nickel extraction experiments were so slow that the metal-ligand complex formation was incomplete in the aqueous film. Some reaction was determined to be occurring in the aqueous bulk solution as well.