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  • Chemical Engineering  (52)
  • Biochemistry and Biotechnology  (46)
  • 1990-1994  (98)
  • 1935-1939
  • 1
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 1452-1457 
    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 high-temperature radical scavenger, 2,2-diphenyl-l-picryl hydrazyl (DPPH), has been used to study the reaction mechanisms of polyacrylonitrile (PAN) on thermal treatment. The effect of DPPH on the cyclization reaction of PAN in both air and nitrogen, investigated by differential scanning calorimetry (DSC), helped to verify the proposed reaction mechanisms, i.e., the free radical and the ionic ones. For PAN homopolymer, the peak temperature of the reaction exotherm shifted to higher temperatures and the heat of reaction was decreased with increasing DPPH concentration. For PAN copolymer with methylacrylate and itaconic acid, however, the effects of DPPH on DSC thermograms were insignificant. The effects of IPPH suggest that the reaction of the nitrile groups proceeds by free radicals for the homopolymer while by ions for the copolymer. The activation energies for the thermal reactions of PAN in both air and nitrogen were also estimated by the dynamic DSC method, and they proved to be highly dependent on reaction mechanism, environment of thermal treatment, and DPPH concentration.
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 1445-1451 
    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 temperature dependence of the nucleation effect of three sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) was studied by means of isothermal crystallization kinetic analysis. Isothermal crystallization thermograms obtained by differential scanning calorimetry (DSC) were analyzed based on the Avrami equation. The Avrami analysis for the nucleated iPP was carried out with DSC data collected to 35% relative crystallinity, and the rate constants were corrected assuming the heterogeneous nucleation and three dimensional growth of iPP spherulites. A semi-empirical equation for the radial growth rate of iPP spherulites was given as a function of temperature and was used to determine the number of effective nuclei at different temperatures. The number of effective nuclei in the nucleated samples was estimated to be 3 × 102 ∽ 105 times larger than that in the neat iPP. The logarithmic numbers of the effective nuclei decreased linearly with decreasing degree of supercooling in the range of crystallization temperatures tested. The temperature dependence of the effect of the nucleating agents on iPP crystallization was given quantitatively in terms of the deactivation factor defined as a fraction of the particles that are active at a particular temperature but inert at the temperature one degree higher. The nucleation activity and its temperature dependence are considered to be cooperative effects of many factors, including the dispersion and the physical or chemical nature of the agent as well as the interaction between the agent and the polymer. It is suggested that the temperature dependence of the effect of a nucleating agent should be treated as a characteristic of a given polymer/ nucleating agent mixture.
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 867-872 
    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: Systematic changes of drying conditions of poly(acrylic acid) were tested to study their effect on the glass transition of the material. The materials were synthesized in two different mediums of water and benzene, respectively. The glass transition temperatures of the samples were determined by thermal analysis using DSC. The samples were also characterized by IR spectra. The glass transition of poly(acrylic acid) was found to be significantly dependent on the drying conditions and also dependent on the medium in which poly(acrylic acid) was prepared. The anhydride formation in poly(acrylic acid) was increased as the drying temperature was raised, resulting in the increase of the glass transition temperature. The “bound” water involved in the preparation of poly(acrylic acid) in water medium could affect significantly the glass transition of the sample. A significant discrepancy in the previously reported values of the glass transition temperature of poly(acrylic acid) seems to be due to the differences in the drying conditions of the materials.
    Additional Material: 10 Ill.
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  • 4
    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: Nucleation effects of two sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). A nonisothermal crystallization kinetic equation was employed to analyze the crystallization characteristics of iPP with or without the nucleating agents from DSC crystallization thermograms. The equilibrium melting temperature of iPP necessary for the kinetic study was obtained by the extrapolation method to be 209°C. The nonisothermal crystallization kinetic analysis for the unnucleated iPP at different cooling rates was possible by assuming the spherulite growth initiated simultaneously by heterogeneous and homogeneous nucleation. On the other hand, the crystallization kinetics of the nucleated iPP could be described by the heterogeneous nucleation and growth process alone. The addition of the nucleating agents up to their saturation concentrations in iPP increased the crystallization peak temperature by 17°C, and the number of effective nuclei by three orders of magnitude. A high concentration of the nucleating agents caused agglomeration of the agents to lower the number of effective nuclei.
    Additional Material: 10 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 110-115 
    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: A new crystallization kinetic equation has been derived considering the decrease in growth rate. The average linear growth rate of spherulite was assumed to be proportional to the m-th order of the uncrystallized fraction of the crystallizing material. A modified Avrami equation, 1 - Vc = exp[-Kf(t)n], was used where f(t) is the integral of the growth function, (1 - Vc)m. The validity of the equation was tested by analyzing the isothermal crystallization kinetic data of poly(ethylene terephthalate) from the melt using differential scanning calorimetry.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 625-631 
    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 curing and vitrification effect during the reaction of ATBN modified epoxy resin was studied through the dynamic differential scanning calorimetry method and a new reaction kinetic equation containing generalized WLF equation was developed to describe the reaction rate at both glassy and rubbery state. An autocatalytic mechanism was found to describe adequately the cure kinetics of the rubber modified epoxy resin and the overall order of reaction was assumed to be 2. The kinetic parameters were determined from the DSC data through the Marquardt's multivariable nonlinear regression method and Runge-Kutta integration technique. The presence of rubber indicated minor effect on the cure kinetics of epoxy resin. The Arrhenius type viscosity function was employed to establish a relationship between viscosity data measured by RMS and chemical conversion calculated from the reaction kinetic equation.
    Additional Material: 12 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 30 (1990), S. 341-349 
    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: Binary blends of ethylene vinyl alcohol copolymers, containing 62 (EVOH-62) and 71 (EVOH-71) mole percent vinyl alcohols, with nylons (nylon-6, nylon-6/12, and nylon-12) have been prepared from melt mixing in a twin screw compounding machine. Morphological, thermal, rheological, and mechanical properties were determined. EVOH-62/nylon-6 and EVOH-71/nylon-6 blends showed homogeneous phase morphologies in the nylon-6-rich region, and fine phase separations (c.a. 2 × 10-7 m) in the EVOH-rich region. Melting point depression, positive deviations in viscosity and flexural modulus, and negative deviation in impact strength from the simple additive rule were generally observed. And the results were possibly interpreted in terms of compatibility and increased nylon/EVOH interactions over the nylon/nylon interactions. On the contrary, clean phase separations in large domains were observed from EVOH-71/nylon-6/12 and EVOH-71 /nylon-12 blends. Fibrillation was also obtained from EVOH rich blends. Probably due to the incompatible nature of these blends, yield at low rate of shear and a mechanical property drop were also observed.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 39 (1992), S. 336-342 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gluconic acid and sorbitol were simultaneously produced from glucose and Jerusalem artichoke using a glucose-fructose oxidoreductase of Zymomonas mobilis and inulinase. Inulinase was immobilized on chitin by cross-linking with glutaraldehyde. Cells of Z. mobilis permeabilized with toluene were coimmobilized with chitin-immobilized inulinase in alginate beads. The optimum amounts of both chitin-immobilized inulinase and permeabilized cells for coimmobilization were determined, and operational conditions were optimized. In a continuous stirred tank reactor operation, the maximum productivities for gluconic acid and sorbitol were about 19.2 and 21.3 g/L/h, respectively, at the dilution rate of 0.23 h-1 and the substrate concentration of 20%, but operational stability was low because of the abrasion of the beads. As an approach to increase the operational stability, a recycle packed-bed reactor (RPBR) was employed. In RPBR operation, the maximum productivities for gluconic acid and sorbitol were found to be 23.4 and 26.0 g/L/h, respectively, at the dilution rate of 0.35 h-1 and the substrate concentration of 20% when the recirculation rate was fixed at 900 mL/h. Coimmobilized enzymes were stable for 250 h in a recycle packed-bed reactor without any loss of activity, while half-life in a continuous stirred tank reactor (CSTR) was observed to be about 150 h.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 41 (1993), S. 88-94 
    ISSN: 0006-3592
    Keywords: cyclodextrins ; cyclodextrin glycosyltransferase (CGTase) ; product inhibition ; ultrafiltration membrane bioreactor ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cyclodextrin glycosyltransferase (CGTase) was found to be severely inhibited by cyclodextrins. In order to increase the conversion yield by reducing product inhibition and reuse the CGTase in the production of cyclodextrins from milled corn starch, an ultrafiltration membrane bioreactor system was employed. In a batch operation with ultrafiltration, the conversion yield was increased 57% compared with that without ultrafiltration. Operating conditions for the continuous production of cyclodextrins in the membrane bioreactor were optimized by taking into consideration the filtration rate and the conversion yield as follows: initial starch concentration, 7% (w/v); starch feeding rate, 240 mg/h; CGTase loading, 350 units/initial gram starch. When cyclodextrins were continuously produced in the membrane bioreactor under optimized conditions, 340 units of CGTase was require to produce 1 g of cyclodextrins for 48 h, while in the case of conventional batch operation, 1 g of cyclodextrins was produced for 24 h by 1410 units of CGTase. © 1993 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 40 (1992), S. 583-592 
    ISSN: 0006-3592
    Keywords: H2S removel ; photosynthetic bacteria ; growth kinetics ; fed-batch reactor ; light attenuation effect ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Hydrogen sulfide dissolved in water can be converted to elementary sulfur or sulfate by the photosynthetic bacterium Chlorobium thiosulfatophilum. Substrate inhibition occurred at sulfide concentrations above 5.7 mM. Light inhibition was found at average light intensities of 40,000 lux in a sulfide concentration of 5 mM, where no substrate inhibition occurred. Light intensity, the most important growth parameter, was attenuated through both scattering by sulfur particles and absorption by the cells. Average cell and sulfur particle sizes were 1.1 and 9.4 μm, respectively. Cells contributed 10 times as much to the turbidity as sulfur particles of the same weight concentration. The light attenuation factor was mathematically modeled, considering both the absorption and scattering effects based on the Beer-Lambert law and the Rayleigh theory, which were introduced to the cell growth model. Optimal operational conditions relating feed rate vs. light intensity were obtained to suppress the accumulation of sulfate and sulfide and save light energy for 2- and 4-L fed-batch reactors. Light intensity should be greater for the same performance (H2S removal rate/unit cell concentration) in larger reactors due to the scaleup effect on light transmission. Knowledge of appropriate growth kinetics in photosynthetic fed-batch reactors was essential to increase feed rate and light intensity and therefore cell growth. A mathematical model was developed that describes the cell growth by considering the light attenuation factor due to scattering and absorption and the crowding effect of the cells. This model was in good agreement with the experimental results. © 1992 John Wiley & Sons, Inc.
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