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  • 1990-1994  (6,439)
  • Chemical Engineering  (3,294)
  • Engineering General  (3,144)
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  • 101
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 794-798 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The polymeric foams investigated with regard to their mechanical properties were the rigid foams polystyrene, polyurethane, and phenolic, and the semirigid foam polyethylene. Preloading of the rigid foams was found to decrease the modulus by an amount that increased as the extent of preloading increased, and to decrease both the modulus and collapse stress in the case of the semirigid ones. The shape of the stress-strain curves of the foams was also significantly changed by the preloading, and a reduction in cushioning properties in static compression was observed.
    Additional Material: 12 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 821-826 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: When diffusion coefficients are measured with the cup method, the exposed area is often less than the area of the sample. Because of this masking effect the measured diffusion coefficient is overestimated. The present article presents simple formulas based on two-dimensional analytical solutions to correct for this in cylindrical cup samples. Different cases of anisotropical diffusion are dealt with. The error in the analytical solutions is determined by numerical computer simulations.
    Additional Material: 6 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 815-820 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A comparative study of warpage, global shrinkage, and residual quench stresses developed in rotational molding is made for a series of thermoplastics including various polythylenes, polypropylene, polyamide-6, polycarbonate, and polystyrene. The influence of rate of quench on uniaxial stress strain and impact behavior of rotomolded parts was also studied. Generally, warpage, global shrinkage, and residual stresses increase with increasing quench rate for all the polymers. Further, the levels of warpage and global shrinkage increases with extent of crystallization, i.e., products from glassy polymers exhibit little warpage and those from highly crystalline polymers are highly warped. Increasing rate of quench tends to increase elongation to break and impact strength.
    Additional Material: 10 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 799-803 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Measurements of melt strength and breaking stretching ratio of several blends of thermoplastic polymers with liquid crystalline polymers are presented. The melt strength behavior depends not only on the viscosity of the blends but also on the temperature dependence of the viscosity. In particular, even if the viscosities of the blends are, at the extrusion temperature, lower than that of the thermoplastic matrices, the melt strength can be larger than that of the pure thermoplastics if its viscosity-temperature curve exceeds that of the matrices far from the solidification temperature. This behavior allows one to spin or film blow these blends despite the low viscosity.
    Additional Material: 9 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 804-814 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model of the high pressure polymerization of ethylene in tubular reactors was tested with experimental data obtained from an industrial size tubular reactor. Series of experiments involving changes in operating conditions were carried out, and process data and polyethylene samples were collected. The collected samples were characterized for their molecular weight distributions and various rheological material functions involving shear and extensional flows. The findings of the model were compared against the generated process data and the molecular weight distributions of the samples. The determined rheological behavior exhibited strong dependence on the primary characteristics of the resins. Overall, this study should introduce a better understanding of the interactions between high pressure reaction conditions and the primary properties of polyethylene, including moments of molecular weight distribution and extent of branching on one hand and the interrelationships between primary properties and the rheological behavior of the high pressure polyethylene product on the other hand.
    Additional Material: 11 Ill.
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  • 106
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 827-834 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The Galerkin finite element method has been applied to study the three-dimensional flow field of power-law fluids inside an extrusion die. Two inlet designs, i.e., center-fed and end-fed, have been considered. The effects of inertial force as represented by the Reynolds number Re, inlet geometry, and the power-law index n on lateral flow uniformity and vortex formation in the entrance region have been examined. A flow visualization technique has been carried out to experimentally verify the theoretical prediction of the three-dimensional flow field inside a die. It has been found that increasing Re or decreasing n will deteriorate flow uniformity. Depending on the direction of the inlet jet stream, the inertial force may create a flow peak in the central region of a center-fed die, or the maximum flow rate will appear close to the end of the die for an end-fed die. For highly shear-thinning fluids, lower flow rates are always observed close to the end of the dies. It is concluded that creating a plug flow in the inlet tube of the extrusion die is advantageous for both center-fed and end-fed designs.
    Additional Material: 13 Ill.
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  • 107
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 835-846 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A two-phase model is presented for simulating the post-filling stage of injection molding of amorphous and semicrystalline materials. A finite-element scheme with quadratic shape function for the pressure is proposed. The melt is considered in terms of Hele-Shaw flow for a non-Newtonian fluid using a modified-Cross model with either an Arrhenius-type or WLF-type functional form to describe the viscosity under nonisothermal conditions; the compressible behavior of the polymer is assumed to obey either a double-domain Tait or single-domain Spencer Gilmore equation of state. The interfacial energy balance equation including the latent-heat effect for semicrystalline materials is coupled with the transient energy equation for the solid and melt phases in order to predict the solidified layer and temperature profile. Two well-characterized materials, namely a commercial-grade PP and PS, were used in the present work. Good agreement is obtained between the present simulation and experimental pressure traces from this study and from previous investigation in the literature. The effects of compressibility, viscosity model, and thermal properties upon the predicted pressure field are also considered.
    Additional Material: 10 Ill.
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  • 108
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 109
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 865-880 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A novel agglomeration technique, based on flow induced phase inversion (FIPI) is described and applied to the batch preparation of polyethylene-bound abrasive calcite agglomerates. Water soluble polymers are used to agglomerate the needle-like crystals of tetraacetylethylene diamine and also sodium chloride crystals. In a typical isothermal FIPI agglomeration process primary particles are dispersed in the molten binder, which is subsequently inverted by the addition of sufficient amount of primary particles, which also defines the critical filler concentration at phase inversion, Cc. Agglomerate particle size is primarily a function of Cp - Cc where Cp is the mean concentration of filler. Cc decreases with increasing binder molecular weight and primary particle surface area. Agglomerate size distribution is affected by processing, mainly by the mixing time after phase inversion. For the non-isothermal FIPI agglomeration process, phase inversion is induced locally, by the addition of fine particles in the molten binder. Phase inversion is then propagated by cooling the dispersion during mixing. Agglomerate characteristics such as particle size, particle size distribution, binder concentration distribution in each agglomerate size range, agglomerate topology, binder morphology in the agglomerates, agglomerate strength, and agglomerate dissolution rate in water were evaluated. These agglomerate characteristics are related to the binder and filler properties as well as to the processing conditions.
    Additional Material: 23 Ill.
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  • 110
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 881-887 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents the development of a nonlinear mathematical model and a microcomputer controlled servo-pump system for the study of the dynamics of a servo-pump controlled injection molding machine (IMM). The model is formulated by the Reynolds transport theorem which is applied to describe the polymer flow dynamics in the nozzle. The comparison between the simulation results and experimental investigations indicated that the nonlinear dynamic model is a reasonable representation of a servo-pump controlled IMM. The output flow rate and working pressure of a servo-pump controlled IMM can be reasonably represented by the nonlinear model when the acrylonitrile-butadiene-styrene (ABS) is injected.
    Additional Material: 11 Ill.
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  • 111
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 857-864 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two-dimensional indenters (flat plate and cylinder) were used to compress rectangular and trapezoidal foam energy absorbers as a function of polymer, foam density, and thickness. An increased deformation volume formed when the indenter contact area was less than the foam absorber area, resulting in both increased energy absorption and stress transmitted to the indenter (i.e., “load spreading”). The deformation volume was trapezoidal, not prismatic, and was characterized by the indenter geometry, dimensions, and foam thickness. Conservative energy absorber design can be achieved by using “energy absorption diagrams” that account for the indenter (i.e., product) and absorber geometry and degree of load spreading.
    Additional Material: 14 Ill.
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  • 112
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 888-893 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The large amplitude oscillatory shear test has been used to discriminate subtle differences in nonlinear viscoelasticity between two high density polyethyene blow molding resins with different processability. Structural network theory was used to explain the subtle differences in terms of entanglement kinetics with remarkable accuracy. The resin with better shape retention characteristics in programmed parison blow molding was found to have a higher kinetic rate constant for molecular re-entanglement.
    Additional Material: 6 Ill.
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  • 113
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1250-1253 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents a general method for estimation of diffusion coefficient and other relevant parameters for the analysis of vapor diffusion in polymers. Sorption curves generated by the constants estimated using the parameter estimation method presented here are in closer agreement with experimental curves than curves generated by other conventional methods.
    Additional Material: 3 Ill.
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  • 114
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1254-1259 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Crystallinities of films of copolymers of chlorotrifluoroethylene with 0 to 4% vinylidene fluoride, different molecular weights and thermal histories were calculated from differential scanning calorimetry (DSC), X-ray diffraction (XRD), and density measurements. The crystallinities for these films range between 16 to 58%, 11 to 71%, and 13 to 77% as determined by DSC, XRD, and density, respectively. Although the numerical value of the DSC, XRD, and density crystallinities obtained by each of the techniques are different, they correlate well with each other. The primary source of error in DSC is the uncertainty in drawing the baseline for separating the heat of fusion and heat of crystallization. In XRD, the ambiguities in the separation of the amorphous and crystalline peaks reduce the precision of the results. Calculation of crystallinity from density values requires that the distribution of the VF2 between the amorphous and crystalline regions be known. In addition, the density technique is not sensitive to variations in the crystalline and amorphous densities.
    Additional Material: 3 Ill.
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  • 115
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1269-1274 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Effects of hydrostatic extrusion on the thermal properties of polycarbonate (PC) and of high-impact polystyrene (HIPS) were studied using differential scanning calorimeter (DSC) measurements. A glass transition temperature (Tg) and a peak temperature were determined from the DSC curves for both PC and HIPS extrudates. The Tg values of the PC extrudates, with a percentage reduction in area, R, from 40 to 50%, change appreciably from the value for the as-received PC. The results of the hydrostatic extrusion of the PC billets suggest that a two stage deformation process of molecular chains may be involved. Shear-banding is observed for HIPS extrudates with R = 30 to 60%; this fact indicates that a sub-glass transition (β-transition) occurs at temperatures below Tg. It is suggested that the molecular chains of the HIPS extrudate with R = 70% are oriented in the direction of hydrostatic extrusion. The deformation mechanism of molecular chains caused by the hydrostatic extrusion is discussed.
    Additional Material: 11 Ill.
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  • 116
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1297-1303 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The acrylated diglycidyl ether of bisphenol-S was prepared by reacting diglycidyl ether of bisphenol-S (DGEBS) with acrylic acid using dimethyl benzylamine as a catalyst. The acrylated epoxy resin thus obtained was characterized by IR, 13C-NMR, and DSC. The curing reaction of the acrylated epoxy resin with dicumyl peroxide was investigated by differential scanning calorimetry at three different heating rates. The overall curing kinetics were found to be approximately second order, independent of the scan rate. The TGA was used to investigate the thermal decomposition of acrylated epoxy resin and to determine the kinetic parameters such as activation energy, preexponential factor, and reaction order. Such information can be used for quick estimation of polymer lifetimes.
    Additional Material: 9 Ill.
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  • 117
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1260-1268 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Blends of linear low density polyethylene (LLDPE) and polypropylene (PP) show diverse mechanical property behavior in the published literature. The main objectives of this work were: to investigate the effect of viscosity of the component phases on the mechanical properties of such blends and to use the results to obtain a method for compatibilizing diaper manufacturing waste. The significant result of the study was that although LLDPE/PP blends are often termed “incompatible,” when viscosity of the components was more closely matched to each other, increases of as much as 50% in tensile strength and modulus were observed over the “rule of mixtures” line. Also, scanning electron microscopy then showed a more diffuse interface between the component phases. Three dimensional views of plots of viscosity ratio of the blend components as a function of temperature and shear rate were used to demonstrate the closer matching of viscosities for the blend components of the higher performing blends. In processing diaper manufacturing waste, addition of a high molecular weight PP in a manufacturing scale single screw extruder, to provide a closer match of viscosities of the blend components, significantly improved mechanical properties.
    Additional Material: 15 Ill.
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  • 118
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1287-1296 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study investigates the influence of aggregates, glass fibers and a coupling agent on the compressive and flexural (three-point and four-point bending) behavior of a polyester mortar. Particle size of fine aggregates (quartz and limestone) varied from 0.1 to 5 mm (0.004 to 0.2 inch) and the glass fiber content was varied up to 6% by weight of mortar. A silane was introduced into the polyester mortar by pretreating the aggregates and the glass fibers. The mechanical properties of mortar were studied at room temperature. The test results indicate that the selection of aggregate type, size and distribution is very important. Silane treated aggregate systems showed more than 66% increase in compressive strength and 35% increase in flexural strength when compared to the untreated systems. Addition of glass fibers enhances the strength and toughness of the polyester mortar, and silane treatment of glass fibers helps to further enhance these properties. Flexural (three-point bending)-to-compressive strength ratio varied from 0.28 to 0.35 for unreinforced system and from 0.26 to 0.54 for the reinforced system. The mortar with only 14% polyester and 86% aggregates (by weight) and a coupling agent had a compressive strength of 103 MPa (15,000 psi) which is 94% of the polyester polymer strength. A stress-strain relationship is proposed to represent the complete stress-strain response under compression and flexural loading. Also, a method is proposed to quantify the failure patterns.
    Additional Material: 21 Ill.
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  • 119
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 120
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1314-1318 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The idea of separating the free energy of mixing into two contributions (corresponding to the “physical” or “nonspecific” and to the “specific” interactions, respectively) proposed by Painter and Coleman has been extended to ternary polymer/polymer/polymer blends. In this paper experimental phase diagrams of three ternary blends have been reproduced by estimating both contributions for the interaction energy density (Bij) which characterizes each polymer pair. In contrast to the Painter-Coleman Miscibility Guide rules, we have found that, in some cases, “specific” contributions positive and unfavorable to the mixing, due to the self-association of one of the components, can describe more adequately the experimental trends.
    Additional Material: 3 Ill.
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  • 121
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 122
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1354-1361 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Pipes of an unstabilized medium-density polyethylene have been pressure tested with internal stagnant water and moderately circulating air as the external medium at temperatures ranging from 70 to 105°C and changes in molecular structure and crystallinity have been studied. The stage III (fracture induced by thermal oxidation) life of the unstabilized polyethylene pipes was less than 12% of the life of the corresponding stabilized polyethylene pipes. Infrared spectroscopy and size exclusion chromatography showed an earlier and more extensive increase in the quantities of oxidation end-products and a more pronounced decrease in molar mass of the outer-wall-material than of the inner-wall-material of the pipe. Mass crystallinity, measured by differential scanning calorimetry, increased on an average by a quantity corresponding to 45 methylene groups per chain scission event. The life of the unstabilized pipe was divided into an induction period during which no detectable thermal oxidation occurred and a subsequent polymer degradation period. The induction period exhibited an Arrhenius-temperature-dependence with an activation energy of 75 kJ mol-1.
    Additional Material: 12 Ill.
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  • 123
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1033-1046 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A simulation technique for nonisothermal flow analysis of non-Newtonian fluid in a nonintermeshing counter-rotating twin screw extruder was developed by modifying the flow analysis network (FAN) method. The local shear viscosity in the flow field was calculated by an iteration method combing the three types of mean shear rate functions. The modified Cross model and an Arrhenius-type function for temperature dependence were also introduced. Streamlines in the flow field are represented by computing the movements of fluid particles based on the flux fields. The computed residence time from the streamlines led us to solve the energy equation by replacing the coordinate system. The profiles of pressure, shear rate, shear viscosity, temperature, and residence time were simulated. The influence of operating and geometrical parameters on the screw characteristics are discussed. Further, residence time distribution (RTD), strain distribution function (SDF), and interfacial area growth are predicted from the computation of streamlines to analyze the mixing capabilities of the extruder.
    Additional Material: 23 Ill.
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  • 124
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1305-1313 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Comb-shaped graft polymers were synthesized and complexed with a LiCF3SO3 salt to form a new class of polymer electrolytes. The polymers based on an acrylonitrile-butadiene copolymer (NBR) have pendant, short-chain poly(ethylene oxide) (PEO) grafted onto a butadiene unit. The characteristics of these polymer electrolytes were investigated in terms of number of pendant EO groups and grafting degree in the graft copolymer. The maximum conductivity was observed at the optimum side PEO chain length, and the PEO chain length for the maximum conductivity decreased with an increase in the grafting degree. And a solid 7Li NMR relaxation technique was used to study the local environments and dynamics of the ions in the polymer electrolytes. The maximum conductivity value obtained from our study was three orders of magnitude higher than that of classical PEO-based electrolytes at ambient temperature. These improved low temperature conducting polymers with higher relative mechanical strength are expected to be suitable for practical applications, such as in rechargeable lithium batteries or electrochromic devices.
    Additional Material: 9 Ill.
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  • 125
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1336-1345 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Injection molded samples of binary blends of Vectra (LCP) and the three amorphous polymers polyethersulfone (PES), polycarbonate (PC), and aromatic poly(ester carbonate) (APEC) have been subjected to morphological and rheological characterization, and coefficients of linear thermal expansion and Young's moduli have been determined. The Young's modulus of the PES/LCP blends exhibited a near lower-bound behavior that could be predicted by the one-adjustable-parameter equations of Halpin-Tsai (ζ = 0.18) and Takayanaga (b = 0.23), whereas the coefficients of linear thermal expansion followed the Takayanaga equation with a value of b = 0.50. The chain orientation of the LCP component was essentially constant in all PES/LCP blends with a Herman's orientation parameter of 0.39 ± 0.03. Transesterification reactions led to randomization of the constituents of the PC/LCP and APEC/LCP blends. The effect was more pronounced in the PC/LCP blends. The introduction of the LCP into the PC/LCP blends led to no reduction in melt viscosity and no self-reinforcement. APEC/LCP exhibited self-reinforcement in blends with a content greater than 27 vol% LCP, and especially the blend with 67 vol% LCP. The self-reinforcement was caused by the presence of an oriented LCP phase, confirmed by X-ray diffraction, and by improved interfacial bonding, presumably resulting from the transesterification reactions occurring at the phase boundaries.
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  • 126
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    Polymer Engineering and Science 34 (1994), S. 59-68 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Four immiscible blend systems, styrene-maleic anhydride/styrene-acrylonitrile (SMA/SAN). styrene-maleic anhydride/acrylonitrile-butadiene-styrene (SMA/ABS), poly(vinylidene fluoride)/SAN (PVF2/SAN), and PVF2/ABS, were investigated. The effect of adding up to about 10 wt% of a third polymer that is miscible with each blend component, poly(methylmethacrylate) (PMMA), was determined. In every case, the addition of PMMA led to the improvement of properties such as tensile strength, tensile elongation, and notched impact strength. Furthermore, the addition of PMMA resulted in finer, more uniform dispersions of the primary blend components. The experimental results are interpreted in terms of interfacial activity of the common phase component, PMMA.
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  • 127
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    Polymer Engineering and Science 34 (1994), S. 81-85 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Differential scanning calorimetry (DSC) was used to investigate the solid-state cure process of poly(phenylene sulfide)(PPS) resin. Virgin PPS resin in an open sample pan was cured in DSC cell. Either air or oxygen was used as a curing atmosphere. Cure temperatures were in the range of 200 and 250 °C, which are below the melting point of PPS resin. Cure temperature as well as atmospheric condition influenced the cure behavior of PPS in the solid state. Both the rate and the amount of cure increased with increasing cure temperature. On the other hand, the time to reach the maximum cure rate was independent of cure temperature. Changing the atmosphere from air to oxygen increased both the cure rate and the amount of cure. The size effect of PPS particles on the cure reaction was also discussed.
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  • 128
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    Polymer Engineering and Science 34 (1994), S. 109-115 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Slow crack growth was measured in the perpendicular and parallel directions relative to the extrusion direction of the pipe. For five pipes from different manufacturers, the anisotropy factor, the lifetime to fracture in the perpendicular direction divided by lifetime in the parallel direction, varied from 1.2 to 4.7 for complete fracture and 1.4 to 4.0 for crack initiation. The degree of molecular orientation was determined by measuring the shrinkage that occured when a pipe specimen was heated near its melting point. The amount of shrinkage correlated with the anisotropy factor for slow crack growth. The shape change after shrinkage was related to the flow pattern of the resin during extrusion and the cooling rate after extrusion.
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  • 129
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    Polymer Engineering and Science 34 (1994), S. 135-140 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), of poly(ether sulfone) (PES), polysulfone (PSF), and polyethermide (PEI), were measured over the frequency range 1 to 130 Hz. The data were analyzed with a modified stress-optical rule: The Young's modulus was decomposed into two complex functions, EG*(ω) and ER*(ω); the modified stress-optical coefficient, CR and CG, associated with the rubber (R) and glass (G) components, respectively, were determined. The results for six polymers, including polystyrene, poly(α-methyl styrene), and bisphenol A polycarbonate were compared with each other. One of the coefficients, CR, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, CG, was in the range of 20 to 40 Brewsters, and did not strongly depend on the details of polymer structure. The component function, EG*(ω), which was located in the glassy region and originated from the high glassy modulus, was almost the same in shape when plotted against ω with double logarithmic scales. The R component, ER*(ω), located at the long time end of the glass-to-rubber transition zone, was slightly sensitive to the molecular structure of polymers.
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  • 130
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    Polymer Engineering and Science 34 (1994), S. 159-165 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: While there is abundant evidence that the molecular weight distribution (MWD) of a linear polymer has an influence on the shape of the viscosity function, the ability to convert the viscosity function to an MWD has been questioned. Using strictly numerical techniques, we have shown that the viscosity function can be transformed to the MWD, but always with some distortion. However, distinct bimodality can be qualitatively preserved through both the MWD-viscosity and viscocity-MWD transforms.
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  • 131
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    AIChE Journal 40 (1994), S. 676-691 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A semiempirical thermodynamic method is developed to establish a framework for calculating vapor-liquid and liquid-liquid equilibria in ternary systems containing water, an organic solvent, and a salt. Careful attention is given to precise definition of standard states. Short-range ion-solvent forces are taken into account primarily by a chemical-equilibrium method based on stepwise ion solvation; however, physical contributions also contribute. Water-cosolvent nonideality is described by an extended equation of the van Laar form. Long-range electrostatic forces between ions are taken into account by an extended Debye-Hückel equation with corrections for transferring from a McMillan-Mayer to a Lewis-Randall framework.The new method is illustrated with results for several systems including saturated aqueous mixtures of LiBr or LiCl with methanol where the salt concentration exceeds 20 molal. The method developed here is of particular interest for process calculations in extractive crystallization, a low-energy operation for producing salt from aqueous solution.
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  • 132
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    AIChE Journal 40 (1994), S. 178-181 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 133
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    AIChE Journal 40 (1994), S. 192-192 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 134
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    AIChE Journal 40 (1994), S. 215-228 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Many experimental studies on the cross-sectional distribution of particles in vertical risers have revealed marked segregation of particles. These flows are inherently unsteady with large fluctuations in suspension density. In this article, we have analyzed the time-smoothed equations for the motion of dense suspensions to demonstrate the role of these fluctuations on the occurrence of segregation. It is shown that the particles will congregate in regions where the kinetic energy of fluctuations associated with the particles is small. In the context of transport of small particles such as FCC, a simplified model based on the mixture velocity can be constructed. A speculative K-∊ model based on this velocity is analyzed to illustrate the extent of segregation of particles afforded by unsteady fluctuations.
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  • 135
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    AIChE Journal 40 (1994), S. 269-282 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new comprehensive real-time identification/control methodology based on the concept of nonlinear autoregressive exogenous input (NARX) models and adaptive, nonlinear, model-predictive control (ANMPC) is applied to a pH neutralization process. The existing NARX model theory has been extended by incorporating measured disturbances. NARX models have shown superior predictive characteristics in comparison to linear models. The proposed real-time methodology uses a pointer vector being created during an initial identification and model structure selection procedure. Using this pointer vector, which allocates the chosen elements from the pool of all possible linear and nonlinear combinations, one needs no explicit information about the model structure for the closed-loop control. The nonlinear programming problem encountered in ANMPC is solved by a gradient-based modified Marquardt and finite difference methods. The design procedure and explicit algorithms are discussed for the multiinput/multioutput case. A pH wastewater neutralization process used illustrates and verifies the procedure by computer simulations and a real-time laboratory-scale experiments.
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  • 136
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    AIChE Journal 40 (1994), S. 321-333 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model has been developed to predict the coupled hydrodynamics and high-molecular-weight protein transport in mammalian-cell hollow-fiber bioreactors (HFBRs). The analysis applies to reactors with isotropic ultrafiltration membranes under startup conditions when the extracapillary space (ECS) is essentially unobstructed by cells. The model confirms the experimental finding that secondary ECS flows, engendered by the primary flow in the fiber lumens, can cause significant downstream polarization of ECS proteins at typical mammalian-cell HFBR operating conditions. It also reveals that the osmotic activity of the proteins, by curtailing transmembrane fluid fluxes, can influence strongly the outcome of the polarization process. In fact, at order-of-magnitude higher protein concentrations and/or lower recycle flow rates, the secondary flow velocities can be reduced by as much as six orders-of-magnitude throughout the ECS, thereby virtually eliminating the polarization problem. This result has important implications for improved reactor startup procedures.
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  • 137
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    AIChE Journal 40 (1994), S. 349-360 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mixing effects in protein precipitation processes are very poorly understood. They impact apparent protein solubility, protein structure in precipitates, particle size, morphology and recoverable activity. In this work, a model is proposed to describe the impact of mixing on protein solubility in precipitation processes. A series of semibatch-mode precipitation experiments were performed using bovine liver catalase and ammonium sulfate to test model predictions. The process variables studied include initial protein supersaturation, agitation rate, and rate of addition of salt solution to the initial protein solution. The mixing model parameters were estimated independently with the aid of a series-parallel dye reaction. The results showed good agreement between model and experiment. The initial protein supersaturation was the most important variable at the 1-L scale. The influence of mixing on recoverable activity was also examined. Scale-up guidelines are suggested based on model simulations and experimental results.
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  • 138
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    AIChE Journal 40 (1994), S. 369-372 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 139
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    AIChE Journal 40 (1994), S. 380-381 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 140
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    AIChE Journal 40 (1994), S. 395-406 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A substantial effort has been made by numerous investigators to describe droplet breakage and coalescence in turbulent dispersions. An attempt is made here to improve these models based on existing frameworks and recent advances described in the literature. Two-step mechanisms are considered for both the breakage and coalescence models. The drop breakage function is structured as the product of the drop-eddy collision frequency and breakage efficiency which reflect the energetics of turbulent liquid-liquid dispersions. The coalescence function retains the former structure of the product of drop-drop collision frequency and coalescence efficiency. The coalescence efficiency model has been modified to account for the effects of film drainage for drops with partially mobile interfaces. These models overcome several inconsistencies observed in previous efforts and are applicable for dense dispersions (about φ[0.10-0.30]). For the daughter drops produced by breakage, a probability density is proposed based on the energy requirements for the formation of daughter drops.
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  • 141
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    AIChE Journal 40 (1994), S. 419-423 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Three-dimensional Stokes flow through a thin screen which has a regular array of holes with two orthogonal axes of symmetry has been studied. The governing equation is simplified by the Roscoe potential and solved by an efficient eigenfunction expansion and collocation method. The resistance is found for circular and square holes in square arrays, and circular and hexagonal holes in triangular arrays.
    Additional Material: 7 Ill.
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  • 142
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    AIChE Journal 40 (1994), S. 424-432 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mixing effects are evaluated for double jet semibatch and continuous stirred precipitators by a model which gives the variation of the primary nucleation flux from the mixing conditions. The predicted trends are compared with results of various authors, including those from a new study of calcium oxalate semibatch double-jet precipitation. Satisfactory qualitative agreement is found for the different chemical systems as a function of feed rate, stirring speed and feed locations for calcium oxalate precipitation. Two types of precipitation systems are demonstrated, depending on the ratio added/tank volume, the initial supersaturations and the intrinsic stiffness factor of a given precipitation. The difference between the two types depends on the increase or reduction of the primary nucleation flux by imperfect mixing with respect to the reference primary nucleation flux obtained with perfect mixing.
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  • 143
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    AIChE Journal 40 (1994), S. 445-462 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A molecular weight distribution (MWD) estimator for batch methyl methacrylate solution polymerization is implemented experimentally for on-line control and estimation of the MWD. The estimator is based on an extended Kalman filter and provides current estimates of the entire MWD, reaction temperature, monomer conversion, and initiator conversion. It uses a detailed polymerization model, on-line monomer conversion measurements, temperature measurements, and periodic, time-delayed measurements of the MWD from an on-line size-exclusion chromatograph. The estimator is shown to perform well with several on-line MWD estimation experiments. Real-time feedback control of the molecular weight is presented by utilizing the on-line MWD information. Temperature, monomer-addition, and simultaneous temperature and monomer-addition control are investigated experimentally to achieve a specific constant weight-average molecular weight. The on-line feedback control is effective in rejecting realistic disturbances which deteriorate molecular weight control.
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  • 144
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    AIChE Journal 40 (1994), S. 473-495 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This work concerns the synthesis of discrete-time feedforward/feedback control systems for general nonlinear processes with stable zero dynamics. Depending on the process under consideration, the derived feedforward/feedback controllers can completely eliminate the effect of measurable disturbances and produce a prespecified linear response with respect to a reference input, or provide integral-square error optimal response to step changes in the disturbances and a prespecified linear response with respect to a reference input. In either case, the developed feedforward/feedback controllers allow for the asymptotic rejection of unmeasurable disturbances. These controllers are derived within the globally linearizing control frame-work, first under full state information and then in the absence of state measurements. The internal stability of the closed-loop system is addressed. The derived controllers are interpreted from a model-predictive point of view, and their connections with the feedforward internal model control and the model algorithmic control are established. The theoretical results are illustrated through a continuous stirred-tank reactor example.
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  • 145
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    AIChE Journal 40 (1994), S. 506-520 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most olefin polymerization processes produce a wide range of resin grades to suit market demand. Determining the transition policy between these grades is an important consideration that can affect process economics and safety. In this article, we compare several grade transition strategies and the relative performance of solution, slurry, bulk and gas-phase processes for the production of polypropylene, linear low-density polyethylene, high-density polyethylene and ethylene-propylene rubber. It is shown that the most important parameters that determine the grade transition performance of a process are reactor design, residence time, runtime per grade and residence time distribution of the polymer, gas and/or solution phases. Slow hydrogen dynamics severely retard grade changes involving increases in product molecular weight. The simulation results are obtained by using the dynamic simulation package “POLYRED” developed at the University of Wisconsin-Madison.
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  • 146
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    AIChE Journal 40 (1994), S. 521-535 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The oxidative coupling of methane was carried out in the absence of catalyst in a continuous flow setup at total pressures up to 1,000 kPa, temperatures from 950 to 1,230 K, and inlet molar ratios of CH4/O2 down to 2.5. At constant temperature and residence time, the conversions of methane and oxygen increase drastically with increasing pressure. At oxygen conversions higher than 80%, product selectivities are comparable at different pressures. The space-time yield of the C2 products reaches a level comparable to that required for industrial operations from 400 kPa on. A radical-reaction network consisting of 38 elementary reactions allows to describe the experimental data. To describe adequately the effect of total pressure, the pressure fall-off behavior of the rate coefficients for the unimolecular reactions in the network has to be taken into account explicitly.General features of the reaction mechanism do not depend on the total pressure. Methyl and hydrogen peroxy radicals are the most abundant radicals. The total pressure increase results in a drastic increase of the concentrations of the chain carriers, particularly the hydrogen peroxy radical. Higher pressure favor the oxidative route from ethane to ethylene compared to the pyrolytic route. Increasing the total pressure leads to an increase of the primary and a decrease of the consecutive CO formation relative to the coupling. The balance between these nonselective routes determines the effect of the total pressure on the integral selectivity to C2 products at different conversions. The major contribution to the integral CO selectivity comes from the oxidation of methyl radicals.
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    AIChE Journal 40 (1994), S. 543-555 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Phase behavior data and FTIR spectra along with solubilities and solvatochromic shifts of ionic indicator dyes are reported for binary, ternary and quaternary systems composed of pentaethylene glycol n-octyl ether (C8E5), CO2, water, and n-pentanol as a function of temperature, pressure and composition. With the addition of n-pentanol as a cosurfactant, the water to surfactant ratio, W0, reaches values as high as 12. As water is added further, a surfactant-rich phase precipitates due to micellemicelle interactions. Ionic dyes are soluble at levels of 0.03 mM, far in excess of the negligible solubility in pure CO2.
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  • 148
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    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 149
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    AIChE Journal 40 (1994), S. 577-585 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Diffusivities of oxygen, nitrogen and their mixtures in carbon molecular sieve are measured under conditions used for kinetic separation of air by adsorption (elevated pressures). In binary diffusion, codiffusion enhances fluxes for both components, whereas counterdiffusion has the opposite effects; for both cases, the effects are significantly more pronounced for the fast diffusing component. The multicomponent diffusion theory developed earlier in this laboratory for surface diffusion is reformulated for diffusion in molecular sieves. Multicomponent diffusivities can be predicted from the following pure-component information: concentration-dependent diffusivities and diffusional activation energies. Predicted binary diffusion results agree fairly with the experimental data for oxygen and nitrogen in carbon molecular sieve.
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  • 150
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    AIChE Journal 40 (1994), S. 594-605 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Optimum experimental conditions and column design parameters are calculated for most economical separation of binary mixtures by preparative liquid chromatography. The solvent consumption and capital costs are regarded as the two major cost contributions. Calculations were performed by using the numerical solution of the equilibrium-dispersive model of chromatography and a nonlinear simplex algorithm. Solvent consumption depends only on the column efficiency, the retention factor, and the loading factor. The production rate depends on the particle size, the column length, the mobile-phase flow velocity, the retention and the loading factors, and can be optimized with or without recovery yield constraints. A hybrid objective function was constructed to find the tradeoffs between the production rate and the solvent consumption.
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  • 151
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    AIChE Journal 40 (1994), S. 613-620 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An advanced process is developed for the separation of H2S from natural gas through an electrochemical membrane. H2S is removed from natural gas by reduction to the sulfide ion and H2 at the cathode. The sulfide ion migrates to the anode through a molten salt electrolyte suspended in an inert ceramic matrix. Once at the anode it is oxidized to elemental sulfur and swept away for condensation in an inert gas stream. The natural gas is enriched with H2. Order-of-magnitude reductions in H2S concentration have been repeatedly recorded on a single pass through the cell. This process allows removal of H2S, while producing H2 and elemental sulfur directly. No absorbents are used, and there is no need for subsequent treatment of a concetrated H2S stream as with conventional gas sweetening technology. This makes the process economically attractive, since it is much less equipment-intensive than conventional technology.
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    AIChE Journal 40 (1994), S. 627-646 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Åström-Hägglund autotuner is extended to multivariable systems. The proposed multivariable automatic tuning performs the identification-design procedure in a sequential manner. Its advantages are discussed, as well as the process characteristics resulted from sequential design. One important feature is that the sequential design often leads to underdamped process characteristics. Given these characteristics, potential problems in the Ziegler-Nichols tuning are discussed and a modification is made. The sequential identification and the modified Ziegler-Nichols controller design method form the basic structure for the multivariable autotuner. The properties of convergence, the implications of tuning sequence, and the indications of undesirable pairing for the autotuner are explored. Consequently, a multivariable autotuning procedure is proposed. Two nonlinear distillation examples and a 3 × 3 linear system are used to illustrate the effectiveness of the autotuner. Simulation results show that good performance can be obtained with minimal engineering effort and the autotuner works well for very difficult processes in a very simple way.
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  • 153
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    AIChE Journal 40 (1994), S. 670-675 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Vented extruder devolatilization (DV) of PS melt containing 6,000 ppm styrene was studied by scanning electron microscopy (SEM) and video photography. Vacuum DV of a polymer is accompanied by foaming, which starts instantaneously upon supersaturation of the stretched melt and is enhanced at higher speeds of the vented extruder screw. As the volatiles are removed from the melt, foaming gradually ceases, starting with the pushing flight of the screw. The experimental installation design allowed us to quench the polymer melt in the DV zone at various stages of the process. Samples taken from four areas of the channel width were investigated by SEM. Bubble nucleation in the melt appears to take place mainly in the border area adjoining the gas phase. In the shear field caused by screw rotation, large bubbles become noticeably elongated. Their surface, as well as the free surface of the melt, is covered with blisters, 1-100 μm in size. Microblisters are often concentrated in areas subjected to stretching. Calculations of cooling due to volatile evaporation and of heating due to viscous dissipation near a growing bubble shows that the process of foam-enhanced DV of a PS/styrene system can be regarded isothermal if the initial volatile concentration does not exceed approximately 1%.
    Additional Material: 7 Ill.
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  • 154
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    AIChE Journal 40 (1994), S. 1067-1081 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Protein denaturation, common in hydrophobic adsorption systems, causes misinterpretation of adsorption mechanisms, interferes with analysis in analytical chromatography, and complicates the design of large-scale adsorption processes. A detailed adsorption model isolates the effects due to denaturation from those due to mass transfer and intrinsic adsorption kinetics. The model is verified using protein gradient elution data. Simulations establish that typical symptoms of denaturation in frontal and elution chromatogrrams include sensitivity to changes in feed composition, column length, particle size, and operating conditions (feed size, flow rate, and column history). When a denatured species adsorbs irreversibly, the elution chromatogram shows decreasing peak area with increasing incubation time and apparent adsorption hysteresis over repeated cycles. In gradient elution, the peak elution order, resolution, and relative peak height depend highly on modulator properties and operating conditions. Interfering species limit solid-phase induced denaturation by competing for binding sites. Strategies for detecting and minimizing denaturation are proposed.
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  • 155
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    AIChE Journal 40 (1994), S. 1418-1421 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 156
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    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 157
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    AIChE Journal 40 (1994), S. 1087-1088 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 158
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    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 159
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    AIChE Journal 40 (1994), S. 1117-1117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 160
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    AIChE Journal 40 (1994), S. 1105-1117 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pressure drops, gas holdup, and mass-transfer coefficients were measured in two concentric-tube airlift reactors of 30 and 300 L (nominal volume). The aspect ratio and the ratio of riser to downcomer cross section were the same for both reactors, but the geometry of the gas separation section was different. The influence of the bottom and top clearances was studied using water and carboxymethyl cellulose solutions and covering a range of effective viscosity from 10-3 to 25 × 10-3 Pa·s. The pressure drop results expressed as a Euler number were satisfactorily correlated with Fr, Ga, and a bubble disengagement group M. Correlations are presented also for the gas holdup in the riser, downcomer, and gas separator. The last-mentioned coincides with the correlation for the total holdup in the reactor. The gas-liquid mass-transfer coefficients for all the liquids and geometric variables in both reactors were successfully correlated as Sherwood numbers.
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  • 161
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    AIChE Journal 40 (1994), S. 1156-1166 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A Semibatch gas-liquid reactor model based on a lumped kinetic schem for the liquid-phase oxidation of p-xylene to p-toluic acid catalyzed by cobalt naphtenate is developed. The model accounts for the complex nature of the involved reaction network, as well as for the interphase and intraphase mass transport processes of both reactants and products. The model reliability is tested by comparison with suitable experimental data obtained in a semibatch oxidation reactor, where the role of the composition of both the gaseous and the liquid feed has been investigated. It is shown that the model describes the reactor behavior in any of the regimes which may prevail depending upon the operating conditions and the depletion of liquid reactants in time.
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  • 162
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    AIChE Journal 40 (1994), S. 1466-1478 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: As recently recognized, distillation columns, operating with reflux and boilup as independent inputs, may have multiple steady-state solutions, even in the ideal binary case. Two fundamentally different sources may cause the multiplicity, and in both cases some operating points are found to be unstable. This article provides evidence for the instability and discusses the effect of operating conditions on stability. Increasing the internal flow rates increases the probability of instability; when flows other than reflux and boilup are used as independent inputs, an operating point may become unstable if the level control is not sufficiently tight. In this case, a limit cycle, usually stable, appears as the steady state goes unstable.
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  • 163
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    AIChE Journal 40 (1994), S. 1223-1237 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Heavy metals like Cu2+, Cr6+, and Hg2+ were removed successfully from wastewater and concentrated in a strip aqueous solution for recycle using the hollowfiber-contained liquid membrane (HFCLM) technique. Using cotransport, Cr6+ and Hg2+ present as anions in the feed solution were transferred individually through a liquid membrane containing tri-n-octylamine in xylene and concentrated in an alkaline solution on the strip side. The removal efficiency of each heavy metal was studied as a function of the aqueous feed flow rate in an HFCLM permeator. Copper present as cation Cu2+ was removed and concentrated by countertransport using LIX84 in n-heptane as the liquid membrane. The efficiency of copper removal was studied as a function of feed copper concentration, feed flow rate, strip flow rate, and area ratio between the feed fiber set and strip fiber set. The strip side flow rate did not affect the Cu2+ transfer rate. A theoretical model presented predicts the copper transport rate from the feed solution to the strip solution in an HFCLM permeator with a variable feed to strip-side membrane area. Both feed aqueous boundary layer and interfacial complexation reaction on the feed side dominate the observed Cu2+ removal process through LIX 84 in n-heptane for feed concentration levels used 90-500 mg/L. It was verified by providing two times larger liquid-liquid interfacial area in the feed aqueous side or in the strip aqueous side. The model can be used to design the membrane area required on the feed and strip fiber sides to remove essentially all of the copper from a given wastewater stream.
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  • 164
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    AIChE Journal 40 (1994), S. 1629-1638 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The physical absorption of CO2 and propene into toluene/water emulsions is studied in a stirred cell and laminar film absorber. Experimentally observed masstransfer rates are compared to an absorption model, based on Higbie's penetration theory describing physical gas absorption into an emulsion. For all absorption experiments in a stirred cell absorber (toluene fractions and stirring rates), experimentally observed mass-transfer rates are considerably higher than the rates predicted by the absorption model. Moreover, the absorption rate decreases with increasing stirring rate, whereas no influence of the stirring rate is predicted by the absorption model. In contradiction to the absorption experiments in a stirred cell absorber, the observed mass-transfer rates in the laminar film absorber agree with the model simulations. Probable existence of a very thin toluene layer is observed on top of the emulsion for the stirred cell experiments, likely due to minor phase separation. Since in the laminar film absorber gas-liquid interface and the gravity force are parallel, this phenomenon does not probably occur significantly for absorption experiments in this absorber. The observed mass-transfer phenomena can be explained, at least qualitatively, from the occurrence of a thin toluene layer.
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  • 165
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    AIChE Journal 40 (1994), S. 1650-1664 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A strategy for the automatic synthesis of plant operating procedures, through the integration of artificial intelligence and mathematical modeling tools is discussed. This “predicative/numerical” modeling paradigm integrates qualitative and quantitative aspects of the problem in a same framework. It uses a “process-centered” qualitative modeling approach together with MILP optimization techniques to automatically generate operating strategies. The operation procedures network (OP-Net), formulated in terms of processes from a generic library, describes abstract (hardware-independent) processing paths leading to the desired operational goals. In this approach, the model assumptions, conservation expressions and data are described at the same level of abstraction, using the same formal representation. This permits the direct, automatic generation and modification of operation procedures in situations involving changes in basic assumptions and initial scenarios. Thus, flexibility, an essential feature of batch processing, is safeguarded.
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  • 166
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    AIChE Journal 40 (1994), S. 1312-1327 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The open-loop optimal control strategy to regulate the crystal-size distribution of batch cooling crystallizers handles input, output, and final-time constraints, and is applicable to crystallization with size-dependent growth rate, growth dispersion, and fines dissolution. The objective function can be formulated to consider solid-liquid separation in subsequent processing steps.A model-based control algorithm requires a model that accurately predicts system behavior. Uncertainty bounds on model parameter estimates are not reported in most crystallization model identification studies. This obscures the fact that resulting models are often based on experiments that do not provide sufficient information and are therefore unreliable. A method for assessing parameter uncertainty and its use in experimental design are presented. Measurements of solute concentration in the continuous phase and the transmittance of light through a slurry sample allow reliable parameter estimation. Uncertainty in the parameter estimates is decreased by data from experiments that achieve a wide range of supersaturation. The sensitivity of the control policy to parameter uncertainty, which connects the model identification and control problems, is assessed. The model identification and control strategies were experimentally verified on a bench-scale KNO3-H2O system. Compared to natural cooling, increases in the weight mean size of up to 48% were achieved through implementation of optimal cooling policies.
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  • 167
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    AIChE Journal 40 (1994), S. 888-898 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design of efficient continuous sterilization equipment for flowing solid-liquid food mixtures requires that temperature and velocity distributions within the fluid are known. In electrical (ohmic) heating, electric current is passed through a two-sterilize it. This allows rapid sterilization of solid-liquid mixtures which minimizes quality loss. A computational process model simulates the effect of realistic physical property changes. The effect of variations in physical properties can have a significant effect on the temperature of the product and thus on its sterility. Realistic designs will have to cope with temperature differences between phases. Experimental data for velocities in a food flow have been incorporated into an enthalpy balance model for heat transfer in solid-liquid mixtures. The effect of inlet temperature on the length of hold tube required to give the necessary process sterility calculated shows the variation in output conditions that might results in real systems.
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  • 168
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    AIChE Journal 40 (1994), S. 1769-1781 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The baffled cavity flow - the first representative of a class of chaotic flows produced by time-dependent changes of geometries - is introduced and extensions to spatially-periodic systems proposed. Both experimental and computational results are reported. The goal of the study is to put into evidence some of the steps and considerations when designing a new mixing flow; a related objective is to demonstrate the use of an efficient and accurate numerical technique (BIEM) suitable for mixing studies in time-dependent geometries. Several parameters that affect the degree of mixing are studied: the mixing protocol - how the baffles are alternated and how many baffles are used in the flow during each piecewise motion; baffle sizes and shapes; geometrical and flow parameters, such as the wall displacement per period; and details of the baffle's motions.
    Additional Material: 17 Ill.
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  • 169
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    AIChE Journal 40 (1994), S. 1814-1824 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A class of models is derived for studying the effects of chemical kinetics on residue curve maps for reactive distillation. Activity-based rate and phase equilibrium expressions provide an accurate and thermodynamically consistent description of composition changes in nonideal, reacting vapor-liquid mixtures. For certain strategies of operation, which dictate the rate of product removal, the model equations are nonautonomous, leading to unusual dynamic behavior. However, for a certain special product removal policy, the effects of kinetics can be described by a single parameter, the Damköhler number, which measures the rate of reaction relative to product removal. For small values of the Damköhler number, the nonreactive simple distillation residue curve map is recovered and the singular points are the pure components and azeotropes in the nonreactive mixture. A bifurcation analysis shows the deformation and, in some cases, the disappearance of these singular points as the Damköhler number is increased until the equilibrium reactive residue curve map is recovered at large values. This bifurcation analysis reveals the limitations of the equilibrium analysis. A model problem for the reactive distillation of methyl tertbutyl ether from isobutene and methanol is solved.
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  • 170
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    AIChE Journal 40 (1994), S. 1865-1875 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recurrent neural networks are used to demonstrate the dynamic data rectification of process measurements containing Gaussin noise. The performance of these networks is compared to the traditional extended Kalman filtering approach and to published results for model-based nonlinear programming techniques for data reconciliation. The recurrent network architecture is shown to provide comparable, if not superior, results when compared to traditional methods. The networks used were trained using conventional nonlinear programming techniques in a batch fashion.
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  • 171
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    AIChE Journal 40 (1994), S. 1892-1900 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The phase and chemical equilibria of flue-gas/water systems containing sour gases such as HCl, HF, SO2, SO3, NOx and volatile heavy metal compounds such as Hg, HgCl2, and SeO2 are calculated from thermodynamic standard data using the Gibbs free energy minimization method. The Pitzer/Debye/Hückel equation is used for the activity coefficients of the ions in the aqueous solution. The inhibition of certain oxidation reactions is considered by a proper formulation of the atom matrix. The comparison of the calculated equilibrium values to experimental data from a coalfired power plant show that concentrations of most pollutants at the outlet of the absorbers are close to the equilibrium values of one single theoretical stage. The extension of the Gibbs free energy minimization to multistage countercurrent absorbers gives the concentration profiles of various components.
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  • 172
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    AIChE Journal 40 (1994), S. 1055-1066 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The conversion of radiant light energy into chemical affinity by microorganisms in photobioreactors is examined. The kinetics of entropy production in the system is theoretically established from entropy and energy balances for the material and photonic phases in the reactor. A negative chemical affinity term compensated for by a radiant energy term at a higher level of energy characterizes photosynthetic organisms. The local volumetric rate of radiant light energy absorbed, which appears in the dissipation function as an irreversible term, is calculated for monodimensional approximations providing analytical solutions and for general tridimensional equations requiring the solution of a new numerical algorithm. Solutions for the bluegreen alga Spirulina platensis cultivated in photoreactors with different geometries and light energy inputs are compared. Thermodynambic efficiency of the photosynthesis is calculated. The highest value of 15% found for low radiant energy absorption rates corresponds to a maximum quantum yield in the reactor.
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  • 173
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    AIChE Journal 40 (1994), S. 1929-1939 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The breakup of droplets in an inhomogeneous flow is the key to emulsification. Frequently, the local flow experienced by the drops is a (quasi-) simple shear flow. The breakup of droplets in a steady, simple shear flow in the absence of emulsifiers has been studied extensively. In the presence of emulsifiers, the droplet interface may acquire viscoelastic properties, which are important in the prevention of coalescence, but their influence on droplet breakup has not been established solidly. This article reports on a phenomenological approach, which links the droplet breakup dynamics to the interfacial viscoelasticity, identifying the latter with the elasticity modulus of a deforming planar interface. Over a viscosity ratio range of three decades, the results have been found to agree with the model, which uses only independently known quantities derived from equilibrium interfacial tension properties.
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  • 174
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    AIChE Journal 40 (1994), S. 1950-1960 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid-phase mass-transfer coefficients are determined for the absorption of sulfur dioxide by water drops larger than 1.1 mm in dia. A local model based on the large eddy interfacial model proposed by Fortescue and Pearson (1967) is obtained by the characteristic interfacial scaling. In particular, the agitation process of the liquid phase in the interfacial region is characterized by the interfacial liquid friction velocity. Experiments of sulfur dioxide absorption and desorption from large individually free-falling water drops are also carried out in a 5-m rain shaft under various environmental conditions. These experimental results agree well with those from the local model characterizing the interfacial process in water drops greater than 1.1 mm in dia.
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  • 175
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    AIChE Journal 40 (1994), S. 1982-1982 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 176
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    AIChE Journal 40 (1994), S. 1976-1982 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A 200-s PSA cycle involving both pressure equalization and product backfill steps has been experimentally studied on a four-bed system, where LINDE 5 A zeolites were used as the adsorbent to separate oxygen from air. This cycle is operated under a pressure ratio of 4.3. During the experiment, the pressure history and flow rates, as well as the concentration of the product stream have been continuously monitored. This is the first time detailed experimental data on a four-bed system are presented. Under favorable conditions, this system produces better than 90% oxygen at a recovery of 17%. For the low-pressure ratio, such a recovery could not have been achieved without the pressure equalization step and the reduced purge operation. Recovery and throughput, however, are not as high as one would expect from a linear local equilibrium model. The self-broadening effect of the purge wave has been identified as the major cause of underperformance.
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  • 177
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    AIChE Journal 40 (1994), S. 1993-2021 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The interest in emulsion polymerization is strong because it offers the possibility of producing products with special properties not easily produced by other types of polymerization processes. Because the main reaction medium is water, not an organic solvent, its importance is steadily increasing with efforts to design environmentally benign processes. The control of emulsion polymerization is a challenging problem due to major limitations encountered in its modeling and on-line monitoring. Although emulsion polymerization has been studied and used for several decades, progress has been slow. Industrial practice relies heavily on experience while several controversial issues are still being studied. The literature related to this issue is vast and sometimes contradictory, and most deals with experimental investigation of specific emulsion polymerization systems to improve the process understanding and develop a process model. However, universally accepted conclusions are scarce. This article reviews the major issues related to control of emulsion polymerization. The latest contributions in process understanding, mathematical modeling, sensor technology, and process control techniques for emulsion polymerization are discussed. Emphasis is on contributions, which are important in resolving the control of emulsion polymerization processes.
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  • 178
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    AIChE Journal 40 (1994), S. 1341-1348 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An automated distillation sequencing system (DSEQSYS) is presented, which consists of three components: a control program, a fuzzy heuristic synthesis program, and a process simulator. DSEQSYS, when applied to problems previously reported in the literature, overcomes some of the disadvantages of using heuristics or mathematical programming alone. DSEQSYS can address problems involving nonsharp separations, nonideal chemical behavior, and conflicting heuristics. A simple approach for converting the traditional separation heuristics into corresponding fuzzy heuristics is also demonstrated.
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  • 179
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    AIChE Journal 40 (1994), S. 1349-1360 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The search for potential solvents for liquid extraction and extractive distillation is carried out through a group contribution molecular design of solvents (MOLDES) approach. A set of submolecular groups (UNIFAC) is used for the synthesis of molecular structures with desired solvent properties. Submolecular group combination (linking) properties are characterized to ensure the chemical feasibility of the MOLDES generated molecular structures. The size of the combinatorial problem posed by the molecular synthesis procedure is reduced by group selection and by imposing physical and molecular constraints at different stages. Criteria are developed for solvent evaluation and the reliability of the VLE and the LLE UNIFAC parameter tables for solvent screening are compared with experimental data for the recovery of oxychemicals by liquid extraction from dilute aqueous solutions.
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  • 180
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    AIChE Journal 40 (1994), S. 120-130 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Spatiotemporal patterns existing in a one-dimensional fixed-bed reactor with oscillatory or excitable kinetics are analyzed to develop the methodology of motion identification and classification. The reactor model accounts for a local (solid-phase) oscillator and a global (gas-phase) convective interaction. The local oscillator incorporates a fast and diffusing surface temperature and a localized activity as its dynamic variables. Such kinetics admit a traveling pulse solution or homogeneous oscillations in a uniform medium. In a fixed-bed reactor, the local conditions in the bed (the phase plane character) vary along the system. The response of an excitable bed to local perturbations depends on its location (at inlet or outlet) and the nature of the initial steady state ( ignite or extinguished). The main spatiotemporal-sustained patterns in the bed are: almost homogeneous oscillations that appear as parallel bands in the time-space contour map; oscillatory fronts that emerge from the reactor exit, and aperiodic motion that appears as split-bands. Pattern selection is determined by the phase planes spanned by the reactor and the ratio of the two slowest time scales: front residence time and period of oscillations.
    Additional Material: 11 Ill.
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  • 181
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    AIChE Journal 40 (1994), S. 131-142 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Thermolysis of coal yields a complex mixture of many extract products whose molecular-weight distribution (MWD) varies with time for continuous-flow, semi-batch experiments. A laboratory flow reactor with a differential fixed bed of coal particles contacted by supercritical tert-butanol was used to provide dynamic MWD data by means of HPLC gel permeation chromatography of the extract. The experimental results, multipeaked, time-dependent MWDs of extract molecules, are interpreted by a novel mathematical model based on continuous-mixture kinetics for thermal cleavage of chemical bonds in the coal network. The parameters for the MWDs of extractable groups in the coal and the rate constants are determined from the experimental data. The effect of temperature on the kinetics of the extraction is explained in terms of one- and two-fragment reactions of the extractable groups in the coal. At lower temperatures (613 and 633 K) single-fragment reactions dominate, but at higher temperatures (653 and 673 K) more bonds in the coal are broken and the two-fragment reactions become significant. Also, the detailed MWDs are related to conventional lumped data for the thermolytic extraction process. The results yield information about the structure of coal, as well as the kinetics and mechanism of supercritical thermolytic reactions.
    Additional Material: 10 Ill.
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  • 182
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    AIChE Journal 40 (1994), S. 143-151 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A flue gas desulfurization process being developed for coal-fired power plants removes and concentrates sulfur oxides (SOx). The key element is an electrochemical cell using a sulfur oxide selective membrane. It achieves 90% sulfur oxide removal with near 100% electric current efficiency.Recent research has focused on improving the structure of the electrochemical membrane and its interface with the electrodes. The capillary forces of the membrane and porous electrodes establish an equilibrium. To maintain electrode surface area enhancement, it is necessary to retain the electrolyte in the membrane and allow only wetting of the electrode pores. Chemically-stable matrix materials for the membrane have been identified; several fabrication techniques were used to prepare the actual membrane structure. A new electrode material, (LiO)xNiO, possesses the proper chemical stability and electrical properties in the corrosive environment. These modifications have led to an order of magnitude increase in flux and operating lifetime.
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  • 183
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    AIChE Journal 40 (1994), S. 738-739 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 184
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    AIChE Journal 40 (1994) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 185
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 186
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    AIChE Journal 40 (1994), S. 726-737 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Environmental concerns have dictated the replacement of CFC-12 refrigerant with HFC-134a in automotive air-conditioning (A/C) systems. Since polyglycols are synthetic compounds compatible with HFC-134a and considered as lubricants for the A/C compressor, interations of HFC-134a with glycol-type compounds and thermodynamic properties of the solutions are important in designing an A/C system. In this work, the solubility of HFC-134a in four glycol-type compounds was measured at -5 to 80°C and 90 to 960 kPa. HFC-134a had the greatest solubility in tetraethylene glycol dimethyl ether. HFC-134a was less soluble in hexylene glycol and tetraethylene glycol and least soluble in triethylene glycol. Mixtures of HFC-134a with TRIG or TGDE showed phase separation. Solubility data were used to calculate the activity coefficient of HFC-134a in glycol solutions. An equation of the form, lnγr = (1 - xr)[A + Bxr], was found to correlate γr to the mole fraction of HFC-134a in the solution where A and B are constants which may depend on the temperature. Based on a model assuming a specific interaction between molecules and using the activity of HFC-134a, a higher degree of interaction is expected between HFC-134a and tetraethylene glycol dimethyl ether molecules than between the molecules of HFC-134a and other glycols. In general, glycols with free -OH groups may have less affinity for HFC-134a. Solubility is discussed in terms of its parameters and chemical structure of the glycols, as well as the effect of temperature on the solubility, the activity coefficient, and the thermodynamic properties of the HFC-134a/glycol solutions.
    Additional Material: 15 Ill.
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  • 187
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    AIChE Journal 40 (1994), S. 777-785 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The desorption profiles of various organics from soil and activated carbon using dense liquid and supercritical carbon dioxide were modeled. The model accounts for effective diffusion of the organics in the solid pores, axial dispersion in the fluid phase, and external mass transfer to the fluid phase from the particle surface. This model, involving partial differential equations, is solved using the orthogonal collocation on finite elements. The model is able to predict the experimental data quite well without any adjustable parameters. The importance of each parameter depended on the system, although adsorption equilibrium and the effective pore diffusion of the organic were the most significant parameters in all the systems investigated.
    Additional Material: 13 Ill.
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  • 188
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    AIChE Journal 40 (1994), S. 767-776 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid-liquid dispersions are commonly used for separations and reaction systems, because the added interfacial area due to dispersion aids in mass transfer and chemical reaction rates. Transient coalescence experiments have been performed for a wide range of dispersed-phase fractions and impeller speeds. A similarity transformation of the experimental drop-size distribution is possible for most of the experiments. The drop-size-dependent coalescence frequency is obtained from an inverse problem procedure previously developed. Over the range of drop sizes encountered in our experiments, the coalescence frequency increases with increases in the size of the coalescing drops, the dispersed-phase fraction, and the impeller speed. For a dispersephase system of neutrally buoyant droplets of benzene/carbon tetrachloride in water, the coalescence frequency is K(v, v′)= 3.72 (10-3)φ1.42N20.52(v1/2+v′1/2) as a function of dispersed-phase fraction, φ, impeller speed, N2, and volumes of the coalescing droplets, v and v′. The results are compared with previous models for the coalescence frequency. Models predicting an eventual decrease in coalescence rates with drop size are disqualified unless this decrease occurs beyond the sizes observed in our experiments.
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  • 189
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    AIChE Journal 40 (1994), S. 756-766 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The falling liquid film has become a popular means of transferring heat and mass from a vapor to a binary liquid, especially in gas-fired heat pump systems. Ideally, the required amount of heat and mass transfer can be accomplished by using a simple cylindrical tube; however, increasingly stringent size and weight requirements for the machine prohibit use of the simple cylindrical surface, and other more complex surfaces with higher absorption capacities have been sought. In this article, absorption of a single component and condensation of a binary mixture on an axially fluted tube is considered. The solution to the problem hinges on the energy equation, although the entire energy transfer process is mass-transfer-limited. Significant mass transfer is limited to a thin layer near the liquid-vapor interface. Solutions to the energy equation are obtained for both the conduction- and convection-dominated regimes. In the latter, significant heat transfer occurs within a thin layer near the liquid-vapor interface which contains the mass transfer layer; this “boundary layer” structure does not appear to have been recognized in previous work in this area. Using the present results, the capacity of a given tube may be predicted as a function of governing geometrical and physical parameters. The principal objective of this work is to develop the theoretical tools from which computations may be carried out during a design process. The theoretical results may be applied to mixtures typical of application in the absorption heat pump industry.
    Additional Material: 4 Ill.
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  • 190
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    AIChE Journal 40 (1994), S. 786-798 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new approach for developing fundamental equations of oxygen permeation through thin mixed-conducting oxide ceramic is presented considering both surface reactions on membrane-gas interfaces and the diffusion of charged species in the bulk oxide. The essence of this work is the coupling of surface reactions with the bulk diffusion using a novel approach which differs from the conventional Wagner. Theory applicable only to limited cases. With this approach, fundamental equations based on various permeation mechanisms can be derived for oxygen permeation through thin mixed-conducting oxide membranes, which is impossible using conventional approach. In general, the final results are a complex implicit equation correlating the oxygen permeation flux to the driving force, membrane thickness, and rate constants with physical significance in each step. Somewhat simpler theoretical oxygen permeation equations are obtained for some special cases (mixed-conducting membranes with a rate-limiting step, ionic-conducting membranes, ionic-conducting membranes with a reducing agent in permeate side). Theoretical results derived using this new approach agree excellently with the experimental oxygen permeation data. It is theoretically and experimentally shown that for ionic conductors, the surface permeation parameter measured by the dynamic permeation method is directly related to the oxygen isotope exchange rate constant measured under equilibrium conditions.
    Additional Material: 5 Ill.
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  • 191
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    AIChE Journal 40 (1994), S. 160-165 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Water vapor pressure for cornstarch and popcorn grits at a temperature of between 100 and 180° C was determined by measuring vapor pressures generated at various moisture contents in a heated, closed system. At a higher temperature, fugacity of water increased with increasing temperature probably because of melting or partial melting of starch. The apparent heat of sorption for cornstarch changed significantly with moisture content and temperature. Noncondensible gases were produced by heating popcorn grits to temperatures above 150°C. It is not accurate to estimate vapor pressure based on the heat of sorption or extrapolation of currently used empirical isotherm equations to a temperature above 100°C. Vapor pressure inside popcorn at the instant of popping are. roughly 758 to 827 kPa (110 to 120psia).
    Additional Material: 8 Ill.
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  • 192
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    AIChE Journal 40 (1994), S. 849-861 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A systematic methodology applicable to the optimal design of stable process systems is presented. It is based on the formulation of a parametric problem that provides bounds on the optimal stable solution and an iterative algorithmic approach that attains convergence of the bounds in a finite number of iterations. The bounds on the optimal stable solution are based on analytical expressions of bounds on the eigenvalues of the Jacobian matrix using the concept of the measure of the matrix. When extended to the synthesis problem of reactor networks, the approach is able to couple the optimization problem with stability issues even in cases where the number of reactors is large and the reaction mechanism is described by a general complex reaction scheme. Furthermore, since at the synthesis level the reactor network represents an exhaustive superposition of the existing structural and operational alternatives, the approach fully exploits these alternatives and coordinates a weighted optimal search that improves the objective and accommodates a stable reactor network. This approach is not restricted to the synthesis of reactor networks and can be applied to the design of total process flowsheets.
    Additional Material: 9 Ill.
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  • 193
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    AIChE Journal 40 (1994), S. 870-877 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Oxidative coupling of methane was conducted by using membrane reactors. The nonporous membrane film that consisted of PbO modified by alkaline or alkaline earth compound was supported on porous SiO2-Al2O3 tube. Higher hydrocarbons were successfully synthesized with high selectivity (about 90%). A kinetic analysis was conducted to clarify whether oxide ion transportation through PbO film participated in the oxidative coupling of methane. The evaluated value of the diffusion coefficient of oxide ion transport based on the methane oxidation agreed well with that of published data. The simulated gradient of the oxide ion concentration through the PbO membrane agreed well with that measured by electron probe X-ray microanalyzer. A transient response simulated by using kinetic parameters evaluated from steady-state analysis also agreed well with the experiment. These results prove the validity of the reaction model that consists of surface reactions of methane with oxide ion which is transferred from inside to outside of the membrane reactor. Alkali modifiers on the PbO membrane surface exhibited a promotional effect on the surface reaction of methane coupling. Another membrane reactor containing Bi2O3 showed higher activity than the PbO membrane.
    Additional Material: 17 Ill.
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  • 194
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    AIChE Journal 40 (1994), S. 908-910 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 195
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    AIChE Journal 40 (1994), S. 899-907 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Optimal control strategies for maximizing the production of induced foreign protein by recombinant bacteria were sought by the optimal control theory. Nutrient and inducer feeding rates were selected as key control variables. Since the problem is linear in the control variables, the optimal control is bang-bang or singular. Singular solutions are shown to exist. The optimal control theory showed that the specific growth rate with respect to nutrient concentration must be kept in its maximum phase and that there exist both a cell growth period and a protein production periods. The optimal control theory calculates exactly the growth and production periods. The glucose concentration is controlled along a singular are to give a maximum specific growth rate. The inducer level is controlled along a separate singular arc.
    Additional Material: 6 Ill.
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  • 196
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    AIChE Journal 40 (1994), S. 911-911 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 197
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    AIChE Journal 40 (1994), S. 935-943 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equilibrium and kinetic data for adsorption of trace CF2Cl2 (Freon-12) from various carrier gases on BPL activated carbon are reported. Coadsorption of the bulk carrier gas can severely reduce the equilibrium adsorption capacity and adsorptive mass-transfer coefficient of strongly adsorbed CF2Cl2. The difference in size between CF2Cl2 and the bulk carrier gas molecules plays a major role in establishing the binary or multicomponent equilibrium adsorption properties. The multisite (single and multicomponent) Langmuir model, which accounts for differences in adsorbate sizes, provides a reasonable framework for describing the size effects. The adsorptive mass transfer of CF2Cl2 under the experimental conditions investigated is dominated by surface diffusion into the pores of the activated carbon. The surface diffusivity is a strong function of the extent of coverage and strength of adsorption of the bulk components.
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  • 198
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    AIChE Journal 40 (1994), S. 956-956 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 199
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    AIChE Journal 40 (1994), S. 966-979 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behavior of processing systems exhibits both continuous and significant discrete aspects. Process simulation is therefore a combined discrete/continuous simulation problem. In addition, there is a critical need for a declarative process modeling environment to encompass the entire range of processing system operation, from purely continuous to batch. These issues are addressed by this article.A new formal mathematical description of the combined discrete/continuous simulation problem is introduced to enhance the understanding of the fundamental discrete changes required to model processing systems. The modeling task is decomposed into two distinct activities: modeling fundamental physical behavior, and modeling the external actions imposed on this physical system. Both require significant discrete components. Important contributions include a powerful representation for discontinuities in physical behavior, and the first detailed consideration of how complex sequences of control actions may be modeled in a general manner.
    Additional Material: 12 Ill.
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  • 200
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    AIChE Journal 40 (1994), S. 991-1004 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The spontaneous ignition of coal stockpiles is a serious economic and safety problem. This phenomenon is analyzed using the approach of modern reaction engineering, which is made challenging by the nonlinear interactions of chemical reaction, heat transfer, and buoyancy-driven flows within and around the stockpile. A model developed represents reaction and transport within a realistically-shaped stockpile and transport and flow in the surrounding air. A new methodology based on the Galerkin finite-element method (Salinger, 1993b) allows for efficient solution of flows in both porous and open domains. Bifurcation analysis is used to track steady-state model solutions of relevant parameters, such as the Damköhler number (dimensionless reaction rate), Rayleigh number (dimensionless driving force for buoyant flow), and dimensionless permeability of the stockpile. The solutions provide an understanding of the roles of various transport mechanisms on the ignition behavior and nonlinear coupling between these mechanisms. Results clearly demonstrate the need for incorporating realistic descriptions of flow and transport in the surrounding air into the model.
    Additional Material: 9 Ill.
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