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  • 1990-1994  (58)
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  • 1
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Formaldehyde is produced industrially from methanol by partial oxidation of oxidative dehydrogenation. In these processes, water is formed as a by-product. Anhydrous formaldehyde is required for many syntheses and, therefore, its production is of potential interest. In the present study, catalysts based on alkali compounds were found to be active in the dehydrogenation of methanol if absence of oxygen. Sodium carbonate doped with indium shows a selective of up to 75% for methanol conversion not exceeding 60%.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Copper and potassium containing Fe/Mn oxide catalysts for Fischer-Tropsch synthesis were investigated by X-ray microprobe technique, scanning electron microscopy, low-temperature argon sorption and carbon monoxide and carbon dioxide chemisorption at -80°C. The specific surface areas of the catalysts depend on the preparation method, e.g. addition of K or Cu by coprecipitation leads to an increase while impregnation results in a decrease in surface area. The resulting samples are inhomogeneous, as shown by all method. Mn and especially K accumulated on the surface of the catalysts. Addition of Cu and K considerably altered the selectivity and activity of the Fe/Mn oxide catalyst. High potassium contents produced high olefin to paraffin ratios but these catalysts became rapidly deactivated. Copper and a very small addition of potassium led to a very low olefin to paraffin ratio but showed a high and constant activity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new model of suspended bed of droplets for describing the vaour or gas the vapour or gas velocity at the flooding point in packed of columns for rectification and absorption under vacuum and normal pressure is presented metallic, ceramic and plastic packings with diameters of 8-90 mm as well on sheet metal and gauze packings, in a wide range of liquid and vapour loads. Approximately 650 literature measurements and own data were evaluated. The mean relative error in determining the gas velocity at flooding point is less than ±5%. On the basis of the double layer model, a new equation was derived for the hold-up at flooding point, which is needed for the calculation of the flooding gas velocity. An example of calculations for sample applications is also included.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 229-237 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new laboratory plant for batch cooling crystallization is described, which allows to maintain the supersaturation at a constant level during an experimental run. A method for continuous supersaturation measurements has been developed, using a density meter and a hydrocyclone. Experimental results obtained from a seeded solution in constant supersaturation cooling mode and at constant cooling rate are compared. In the case of a constant cooling rate, the supersaturation passes through a sharp maximum, whereby effective nucleation is enhanced. As a consequence, a smaller median crystal size is obtained than for cooling at constant supersaturation. Equation for controlled cooling at a constant supersaturation require an accurate description of the effective rate of nucleation. Therefore, the mechanical stress, to which the crystals are subjected, must be included as the main source of new nuclei. This is shown by the influence of stirrer on batch time.
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 241-251 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Pyrolysis of 2,3-dimethyl butane (DMB) was carried out in a quartz flow reactor in the temperature range from 740 to 1032 K at normal pressure. The input concentration of DMB was 3.3 × 10-3 mol/1 using argon as diluent. Reaction time ranged between 3.1 and 3.9 s. The following products were analyzed by two-column gas chromatography: hydrogen, methane, ethene, propane, propene, butenes, butadiene, 2-methyl-2-butene, isoprene, benzene and toluene. Compared to thermal decomposition of n-hexane under similar experimental conditions, the main difference concerned the formation of ethylene, ethane and branched alkanes. A reaction model, based on elementary reactions, was developed to predict the experimental results and to verify our data basis of elementary reactions under different conditions. The model gives a quantitative description of the complex chemistry of the process. In addition, an algorithm is presented for model reduction.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 264-272 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes general, asymptotic and speculative relationships which can be deduced directly from the time-averaged form of the basic, partial-differential model for the conservation of mass and momentum in fully developed turbulent flow of constant-property fluids through round and parallel-plate channels. Such relationship are shown to provide insight as well as useful forms for correlation. Several analogies for flow in round tubes and between parallel plates which have generally been overlooked are reexamined and extended. A generally overlooked anomaly which occurs for flow in concentric, circular annuli, for flow between plates of non-identical roughness, and for the combination of forced and wall-Ind.uced flow between parallel plates is also is noted. The data needed to test the above analogies and to quantify the deviations, if any identified, as well as those needed to generalize the anomalous behavior.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 298-303 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adsorption isotherms for n-hexane and methanol in mordenite and ZSM5 in the temperature range from 323 K to 473 K were found to be of type 1. The adsorbate-adsorbent interaction (C1) and adsorbate-adsorbate interaction (C2) wee computed according to Bradley and Wilkins model, whereas the Rees and Williams model predicts the adsorption characteristics. Finally, the thermodynamic parameters such as ΔGo, ΔSo, ΔHo, K, K+ have been evaluated for the sorption of n-hexane in mordenite and ZSM5.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Incineration processes are critical for the environment. SO2 and NOX removal with processes is nowadays commonplace. Up to now, heavy metal were recovered via precipitation. The alternative use of liquid ion exchange techniques offers an easy re-use of the heavy metals, which are obtained as concentrates. A separation process is described, starting from laboratory experiments and ending with pilot plant field tests. A cost comparison for extraction, permeation and precipitation gives the scope of the necessary expenses for such environmentally controlled processes.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In industrial processes, the reduction of nitrogen oxides by ammonia on activated carbons is carried out at temperatures between 90 and 190 °C. Adsorption of NO and NH3 on the catalyst was investigated separately. Reactions models for NO-reduction by carbon and ammonia were derived from experiments carried out in an integral reactor. In each case, the formation of an adsorbed (NO2)-complex is an important step. The kinetics of both reactions was described by modified Langmuir-Hinshelwood equations.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 289-297 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new stage-to-stage method has been developed for the calculation of NXx absorption columns. Each stage of the absorption column is simulated as a combination of a bubble column reactor (absorption) and an adiabatic plug for reactor (oxidation). The bubble column reactor is modelled as two single stirred tank reactors, one as a gas-phase and one as a liquid-phase reactor, both coupled by mass and heat transfer. In this hydrodynamic model, a dynamic approach is adopted, in which the gas-phase transport of N2O4 is the limiting step for the absorption. A gas-phasepseudo-enhancement for factor for N2O4 is therefore introduced. The balance equations for a single phase of the bubble column are solved with a Newton-Raphson algorithm. The entire column calculation is divided into a gas and a liquid side. On both sides, the stage-to-stage method is applied in such way that the overall calculation is performed as a loop process. The direction of the loop calculation follows that of the flow: gas-side upwards and liquid-side downwards.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 376-383 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical and experimental study of the electrohydrodimerization process to produce adiponitrile is used to determine an appropriate reaction model. From numerical simulations of five proposed reaction schemes and subsequent comparison with experimental data, the most favoured route is via an anion, intermediate of acrylonitrile. This route, a five step reaction involving electrochemical and chemical reaction in a diffusion/reaction layer, gives good predictions of product distributions over a wide range of current densities and acrylonitrile concentrations of product distributions over a wide range of current densities and acrylonitrile concentrations.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 397-402 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper presents a method of transforming the non-liner regression problem in the kinetic study of complex heterogeneous catalytic reactions into a linear regression problem. Application of this method reduced the number of parameters to be estimated by n-1, where n is the number of independent reactions. In addition, a stepwise model discrimination strategy in introduced to reduce the number of equation sets ad equations in the set undergoing parameter estimation. These two new approaches are very advantageous in reducing the computation effort, especially when the number of independent reactions is large. The linear regression method and the stepwise model discrimination strategy are successfully applied in the kinetic study of the methanol synthesis system in which the formation rates of methanol, methane, ethanol and ethane are considered.
    Additional Material: 4 Tab.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 41-49 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution presents the mechanical data of high performance carbon fibres currently available on the market, based on experimental studies on stabilization and pyrolysis of PAN (SAF) from Courtaulds. The effects of stabilization and carbonization temperatures on the properties as well as on the ultra- and crystalline structures of the fibres are shown in more detail.
    Additional Material: 22 Ill.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The residence time distribution in liquid phase was measured in a cocurrent upflow packed bed reactor for the system methanol-hydrogen at low Reynolds numbers and at elevated pressure. The plug flow with axial dispersion model was used to describe mixing in the system. The imperfect pulse method was used to measure the system response to a tracer pulse input. The parameters were calculated using the weighted moments method. The influence of the weighting factor was investigated. The experimental and theoretical outputs, as calculated by convolution, agreed very well. Different types of correlations were used for the Bodenstein number and liquid hold-up. From these correlations, the optimal one was selected for each parameter. A comparison was made between the ordinary moments and the weighted moments methods which led to the conclusion that the latter method is superior with respect to the accuracy of the estimated parameters and therefore strongly recommended.
    Additional Material: 11 Ill.
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  • 15
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the first part of this paper, a mathematical model is presented for a liquid fluidized bed bioreactor using immobilized enzymes with reversible Michaelis-Menten kinetics. The model is based on the axial dispersion model for the bulk liquid phase. Inter- and intraparticle mass transfer as well as enzyme catalyzed reaction inside the porous beads are considered. The overall efficiency of the biocatalysts is calculated by a numerical routine. For the calculation of the concentration profile inside the reactor, a semi-analytical solution is derived which takes into account the height dependence of the effectiveness factor.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 16
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Even though the influence of solids concentration in the feed on the separation efficiency of hydrocyclones has long been recognized, a systematic research on the change in pressure drop across the hydrocyclone and the latter's separation characteristics has thus far been lacking. If all other operating parameters are kept constant, an increase in feed concentration generally leads to a coarser cut size, reduced sharpness of separation and a rise in pressure drop. Apart from the particles hindering one another's radial motion, the limited capacity of the apex valve and the changes in the flow field within the hydrocyclone cause additional particles to be entrained by the overflow. The flow ratio thus becomes an additional parameter in determining the cyclone efficiency. A theoretical model, which takes these effects into account, has been developed and successfully tested against experimental data.
    Additional Material: 12 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 63-71 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bench scale experiments and computer simulations of transient crystal size distributions obtained in a 1.4 m3 sucrose crystallizer, which prove the existence of nuclei stock, are presented. This stock represents a large number of non-growing nuclei, which can be activated at increased supersaturations. The nuclei stock attenuates the dynamic behaviour of crystallization process.
    Additional Material: 8 Ill.
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  • 18
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Supersaturation is the driving force for crystallization from solution. For design and operation of crystallization processes, it is necessary to apply a set of criteria for the determination of appropriate or even optimum supersaturation. In this paper we present and discuss the results of our experimental and theoretical investigations on supersaturation during crystallization from solution. While the determination of the metastable zone width of the solution is frequently applied as a fast check on solution behaviour, we demonstrate that the determination of the induction period of the supersaturated solution is a useful aid in ascertaining the maximum allowable supersaturation. Theoretical considerations and experiments confirm that the induction period dependssoley on growth kinetics if secondary nucleation is the predominant mechanism. In order to avoid uncontrollable spontaneous value of between 70 and 130 μm during crystallization. Since growth kinetics turns out to be the only important system property for the determination of maximum possible supersaturation, we conclude the paper with some arguments concerning a closed representation of growth kinetics.
    Additional Material: 15 Ill.
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  • 19
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An airlift-loop reactor with a fluidized bed was used for the microbiological removal of a complex mixture of aromatic substances originating from coal tar process waters. A specially adapted mixed microbial culture derived from several soil and sludge samples was immobilized on fluidized sand particles and retained in a reactor at high biomas concentrations of 3 to 16 g dry matter per liter, depending on the COD-load. In a two-stage pilot plant, those aromatic substances which passed through the first stage either unaltered or only partially oxidized were effectively eliminated by the immobilized biomass in the second stage. Whereas most of the waste water components such as phenols and quinoline were already degraded by a conventional activated sludge system in the first stage, the majority of nitrogen-containing aromatic bases could be sufficiently eliminated with specially adapted micro-organisms in the second stage. Although the COD-feed load was increased to 12 and 15 kg m-3 d-1 in the first and second stages, respectively, it was removed to the extent of 87% on the average with an overall residence time varying between 11.5 and 29 h.
    Additional Material: 9 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 86-96 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The first part of this paper presents a relationship for the minimum velocity of rotating installations for foam breaking. The derivation is based on equilibrium of inertia and surface forces. Inertia forces occur during the acceleration of foam bubbles and act mainly at the plateau borders. High and definite acceleration can be obtained with a deformer composed of a rotor and a stator. The surface force is due to the dynamic surface tension because surface-active solutions react to a rapid change in surface area by altering their surface tension. The theoretical relationship is compared with experimental results of minimum velocities needed to break foams produced from aqueous solutions of detergents. The equation presented here explains why measured minimum velocities often range between 10 and 20 m/s. The second part of the paper deals with condensation of continuously generated foam in a closed system. In the process of condensation, foam is not completely separated into liquid and gas phase but turns into foam with small bubbles and high density. The collapse of this condensed foam must be considered for the control of persistent foams in a closed system. The collapse of foams made of aqueous solutions of different surface-active agents has been investigated. Different highly surface-active agents show small variations in times of coalescence. A relationship for the lifetime is given, which is based on laminar flow along plateau borders. Recommendations are made with respect to the geometry of the foam breaker, scale-up and operating variables such as rotational speed of the foam breaker and gas flow rate.
    Additional Material: 15 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 349-356 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Owing to imperfect mixing, the theoretical prediction of CSD for an MSMPR crystallizer deviates from the experimental results. In the present work, different modelling approaches were adopted to account for incomplete mixing in DTB and FC crystallizers. For DTB crystallizers, compartmental model, based on an earlier work of Nyvlt et al. has been proposed. For FC crystallizers, a mixed model comprising perfectly mixed and plug flow regimes has been put forward. This is based on the tracer response studies reported by de Jong. Predicted results were compared with experimental data of Bennett and van Buren for continuous urea crystallizers.
    Additional Material: 2 Ill.
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  • 22
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Compared to chemical reactors, there are additional requirements to be considered when selecting and designing a bioreactor. The cultivated organisms and most of the desired products are to a greater or lesser extent sensitive to temperature, pH and Shear stress. Furthermore, sterilization often plays an important role in maintaining a monoseptic process. Many design procedures for chemical reactors can be applied but requirements which are relevant to the biological system are sometimes decisive. Consequently, it is useful to first consider the essential features of the organisms with respect to the selection and design of bioreactors. Attention must be paid to the fermentation medium because its flow behaviour can range from slightly viscous and Newtonian to highly viscous, non-Newtonian. Many papers deal with low viscosity fermentation broths [1-5]. However, little is known about the design of bioreactors for highly viscous non-Newtonian liquids. Fundamentals for the design of bioreactors are presented. It has been attempted to apply theoretical equations suitable for both, low viscosity Newtonian and high viscosity non-Newtonian fermentation broths. Apart from the calculation procedure for the OTR-values, the difference between global and local values within bioreactor is demonstrated by means of velocity and shear stress profiles. Special requirements for bioreactors such as prevention of excessive foaming, shear sensitivity of micro-organisms and cell-lines and effective sterilization are also discussed.
    Additional Material: 15 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 392-397 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A Monte Carlo simulation scheme is proposed for transient crystal size distribution in a continuous crystallizer. The suggested scheme can taken into account dispersion effects of growth rate, shape factor and birth size on crystal size distribution. This method is simple and more versatile than solution of the number balance equation or the finite-state Markov chain model. The proposed algorithm of the process has a very simple structure and can be easily implemented on a personal computer. The present contribution is extension of an earlier work of Sen Gupta and Dutta.
    Additional Material: 3 Ill.
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  • 24
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The presented contribution reports on comprehensive hydrodynamic investigations in two pulsed sieve-plate extraction columns (PSE) on a pilot scale. The experiments were conducted with three different sieve plate geometries employing test systems recommended by EFCE, under varying pulsation conditions and throughputs. The results of the investigation add to the existing knowledge of relationships between hydrodynamic parameters, drop size, hold-up, flooding throughput and mixing and operating parameters. They also provide useful information for scale up, selection of sieve-plate geometry, most favorable operating range, and constructive design of equipment. On the basis of measurements, analytical methods are recommended for prediction of PSE hydrodynamics.
    Additional Material: 15 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 304-312 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some properties of carboxylic acids are reviewed, with emphasis on recent experimental data, Qualified, consistent latent heat of vaporization data were developed for the series and a two-population viewpoint is suggested. The equation of state formulated by Grenzheuser [1] is also recommended as a practical tool, and its further development is urged.
    Additional Material: 16 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 328-332 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The linear algebraic character of the formal representation of chemical species and their reactions is compared with the procedure of searching for dimensionless numbers in a set of physical quantities. A straightforward algorithm is presented to find a finite set of solutions to the relevant system of “balance equations”, the so-called minimal (or simple) solutions. At the third stage of the hierarchy thus established, “mechanisms” among reactions as well as “representations” among dimensionless group can also be defined.
    Additional Material: 2 Ill.
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  • 27
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A heterogeneous fluid dynamic model has been developed to describe the complex flow structure of two-phase in bubble columns. The equation of continuity and momentum balances form the basis of the model. Coupling of the two phases occurs via an interaction force, deduced by a force balance around a single rising bubble. Multiphase flow mixing processes are taken into consideration by introducing turbulent viscosities of the two phases involved. The Simulation program was extended to reactive system, taking into account the mass balances of a second order gas-liquid chemical reaction as well as the different absorption/reaction regimes. The gas phase concentration profiles show pronounced axial and radial dependences, while the liquid phase can be regarded as a CSTR with respect to the liquid component. With reference to the gaseous component, which is being absorbed in the liquid phase, the degree of back mixing does not show CSTR behaviour as the influence of different absorption conditions in different axial and radial reactor positions is superposed on that of turbulent motion of the liquid carrier of the dissolved gaseous component.
    Additional Material: 13 Ill.
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  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    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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  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 119-125 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dynamic mathematical model has been developed which is suitable for thermally coupled distillation processes. An algorithm known as the equation-decoupled method was used for simulation. EPISODE software and LU decomposition method were adopted to solve the ordinary differential and algebraic equations of the model, respectively. The initial conditions, viz. a solution for the steady state of the process in dynamics simulation were obtained by means of modified Naphtali-Sandholm algorithm. Research on the dynamic behaviour of thermally coupled distillation processes was carried out on two examples. It was found, via the dynamic simulation, that a disturbance in the distribution of vapour coupled stream has a large effect on the composition of vapour side withdrawal and, similarly, for liquid coupled stream, on that of liquid side withdrawal when the fraction of side withdrawal is fixed, and a smaller effect when the quantity of side withdrawal is fixed.
    Additional Material: 6 Ill.
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  • 30
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 196-202 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A Random Crystal Growth (RCG)model is proposed to predict CSD in a continuous MSMPR crystallizer when the crystals exhibit growth rate dispersion. RCG model links two well-known models of growth rate dispersion, namely the Random Fluctuation (RF) and Constant Crystal Growth (CCG) Models. Monte Carlo simulation has been employed to solve the model equations. Predicted results are compared with experimental CSD data on sucrose reported by Bennett.
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  • 31
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The well-known formulae for efficiency and mean temperature difference of a heat exchanger as functions of its numbers of transfer units, or dimensionless lengths, can be written in a more compact form by introducing the auxiliary function ϕ(x) = x/(1 - e-x). The resulting new formulae show a number of advantages: They are shorter, easier to memorize, and in many cases the limiting values can be seen more directly. They may therefore contribute to easier and faster heat exchanger design, and to reduced probability of errors in the relevant calculations.
    Additional Material: 3 Ill.
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  • 32
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 258-264 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Deasphaltization of heavy crude oils and distillation residues may reduce the metal content of these oils to such an extend that the upgrading of deasphaltized oil in a catalytic process becomes economically feasible. Experimental results of deasphaltization of Boscan crude from Venezuela, using subcritical and supercritical carbon dioxide as deasphaltizing agent, are presented. Deasphaltization and demetalling with CO2 in the supercritical state is more effective. Under favorable conditions, the deasphaltized oil contains practically no asphaltenes and the metal content is reduced by 690 wt-%. The influence of n-heptane or n-pentane addition to the crude, which lowers viscosity and promotes flocculation, is also discussed. Furthermore, a multistage deasphaltization process is more efficient than a single stage process.
    Additional Material: 14 Ill.
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  • 33
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 277-288 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The present paper is a case study of an application of sensitivity analysis in chemical kinetics. Emphasis is laid upon chemical interpretation of sensitivity information and on identification of the most important model important model parameters. The kinetic model for reforming of C6 hydrocarbons proposed by Mobil [14] is extended to the analysis of the behavior of n-hexane conversion in an adiabatic reactor. The importance of six initial conditions (feed composition and initial temperature) is analyzed by the computation of normalized first order sensitivity gradients (y1o/y) (δyi/δy1o). The relative importance of 21 model parameters αj is estimated by the computation of normalized sensitivity gradients of the type (αj/yi) (δyi/δαj). The influence of the decisive model parameters ΔH6o and ΔH3o (activation enthalpies of benzene hydrogenation and methyl cyclopentane isomerization, respectively) as well as operating parameters is presented. The problem of uncertainly in the value of ΔH6o and its influence on the model solution is also sown. Finally, some advantages of the application of normalized gradients of the explanation of process behavior are discussed.
    Additional Material: 11 Ill.
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  • 34
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 319-322 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model based on experimental results is set up for a typical model reaction of hydrocarbon reforming, namely the dehydroisomerization of methyl cyclopentane. Computer simulations shows that the existing theory about the reaction path of hydrocracking reactions involving bifunctional catalysts may be only partly valid.
    Additional Material: 6 Ill.
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  • 35
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 322-327 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Deposition of particles from gas flows on ribbons in normally expected on the front side. Collision efficiencies of ribbons are presented for this case, obtained by means of single particle trajectory computation, which is based on numerically determined flow fields in the Reynolds number range between 2 and 50 and on the potential flow model. Further, it is shown, that deposition of particles on the rear side can be caused by eddylike motion of the fluid in the wake of the ribbon. For this to occur, two conditions must be fulfilled: the free shear layer between the wake and the outer flow must be turbulent to cause lateral transfer of particles into the wake and the Stokes number may not exceed 0.5.
    Additional Material: 6 Ill.
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  • 36
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 371-375 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A solution of 0.1 M 1,2-dichloroethane in 1 M H2SO4 was anodically converted to CO2, Cl2 and HCIO4 as the main products at smooth platinum. The current efficiency for CO2 exceeds 60% at low current densities, while HClO4 is obtained with about 20% current efficiency. Chlorinated products such as 1,2′,2-trichloroethane are formed in negligible amounts. Platinum plays a distinctive role as anode material and shows a reaction limited anodic prewave. Our experimental findings lead to a mechanism, whereby DCE is initially hydroxylated to form chloroacetaldehyde chlorohydrin which releases HCl and becomes rapidly further oxidized to monochloroacetic acid. The cleavage of the C—C bond proceeds via its anodic decarboxylation. Possible practical applications in the field of anodic water purification and in the direct electrosynthesis of vinyl chloride are discussed.
    Additional Material: 6 Ill.
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  • 37
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The collection of reactive and therefore extremely adhesive and cohesive fine particles (〈 1 μm) by means of bag filters with pulse-jet cleaning may present problems. The electron-beam dry scrubbing (EBDS) process, used to remove SO2 and Nox in a power plant of the Badenwerk AG, Karlsruhe, serves as an example. To solve the occurring problems and achieve a satisfactory filter performance, extensive know-how of process engineering is necessary. This contribution deal with the following aspects: construction of the cleaning system, selection of filter medium, precoating, and dosage of an auxiliary dust during filtration.
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  • 38
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Holographic interferometry is used for the determination of surface deformation of items of equipment. The material failure which caused the surface deformation can then be identified. Because a double-pulsed laser is used to plot the hologram, non-vibration stabilized holographic equipment is necessary. Thus, non-destructive testing of equipment components is also possible during plant operation. In this report, we present the experimental results of non-destructive testing of composite materials. We examined centrifugally cast pipes and filament wound pipes, which were made from glass fibre reinforced plastic and carbon fibre reinforced graphite. As a rule, the severity of failure is characterized by the apparent perturbation of its holographically stored fringe pattern. In this report, we present the experimental results which yield the relationship between the perturbation of interference fringes and the extent of the specific types of failure. Measurement results were compared with displacements calculated by the finite element method. By using the interferogram, and with the knowledge of tension stress beneath the surface, the size of the crack can be estimated. The size of the smallest detectable flaw was clearly smaller than the critical flaw size. Thus, holographic interferometry is suitable for detecting damage to cylindrical containers.
    Additional Material: 15 Ill.
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  • 39
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution reports on the breakthrough behaviour of binary gas mixtures with ideal and non-ideal multicomponent adsorption equilibria. Investigations were carried out on mixtures CO2/C2H4 and C2H4/C2H6, both adsorbed on molecular sieve 5A (ms5A). The adsorption equilibrium of the system CO2/C2H4/ms5A may exhibit azeotropic behaviour, which subsides with decreasing active pressure (= sum of partial pressures of adsorbable components) or on raising the temperature. In contrast, the system C2H4/C2H6/ms5A maintains its ideal behaviour also at higher active pressures or lower temperatures. Attempts to calculate the non-ideal adsorption equilibrium from measured single component isotherms have failed when known models were applied. The investigation of the effect of azeotropic equilibrium on the fixed bed adsorption led to intersecting breakthrough curves of the two components. This behaviour is due to a displacement of equilibrium caused by the change in the active pressure and partial pressures, and a superposed temperature effect. This can be shown by calculating the breakthrough curves with the equilibrium model.
    Additional Material: 9 Ill.
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  • 40
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the first part of this contribution, a mathematical model was presented for a liquid fluidized bed using immobilized enzymes, with reversible Michaelis-Menten kinetics. This part is focused on the experimental results. The reaction kinetics of native and immobilized enzymes was determined in continuous stirred tank reactors under comparable conditions. The influence of external mass transfer was investigated in a fixed bed reactor column. The extend of pore diffusional resistance was examined in a continuous stirred tank reactor and with a numerical simulation. Hydrodynamics was measured in different reactor columns (diameter dt = 0.052 - 0.225 m; length L: 1.0-2.0m) and with a static mixer. Further, the concentration profile was determined in a fluidized bed reactor with side stream analysis for different biocatalyst samples, fluid velocities and bed heights. The simulation of experimental results indicates that they are well described by the developed model. Furthermore, the model is well suited to predicting the influence of specific parameters on the effective kinetics of the biocatalyst and the expansion of the fluidized bed.
    Additional Material: 8 Ill.
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  • 41
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    Chemical Engineering & Technology - CET 13 (1990), S. 97-101 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Laboratory-scale measurements were performed on the absorption of NO2 gas into diluted nitric acid. The concentration of NO2 gas, which represents an NO2/N2O4 equilibrium, varied from 1000 to 20000 ppm, the carrier gas being nitrogen. The concentration of nitric acid ranged from 15 to 60 mass-%. The absorption experiments were carried out in a double stirred cell, with a defined gas/liquid interface as the mass transfer area. The liquid phase was conducted periodically and the gas phase continuously. Mass flow rates were determined. The well-known film model of absorption was used for analyzing the experimental results. Only the N2O4 species was considered to pass the gas/liquid interface. The measured data yielded values of HN2O4(k D1)1/2 as well as their variation with temperature and nitric acid concentration.
    Additional Material: 5 Ill.
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  • 42
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The BF-Uhde-Mitsui Process uses active coke for SO2- and NOx-removal from flue gases in the temperature range between 100 and 190 °C, Experimental methods of thermal regeneration were applied to the evaluation of the state of the adsorbent after use in flue gas cleaning and of the parameters for disrober design. A reaction model was derived from experiments carried out in differential and back-mix reactors. The parameters were evaluated by adaptation of the model to the adsorption spectra. The model was successfully applied to the regeneration of active coke in a fluidized bed reactor.
    Additional Material: 16 Ill.
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  • 43
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 113-118 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The hydrodynamic and mass transfer characteristics in countercurrent, cocurrent and liquid batch operations with various Newtonian liquids were studied experimentally using the same bubble column. Taking the effect of gas sparger geometries, operating variables and liquid properties into account, empirical correlations were obtained for the gas hold-up and the volumetric liquid-phase mass transfer coefficient.
    Additional Material: 8 Ill.
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  • 44
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 125-130 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Critical temperatures and pressures have been determined experimentally for the four lowest n-alcohols, 2-propanol, 2-butanol, and 2-methyl-1-propanol, and are given in the penultimate line of Table 3. The last line of Table 3 lists the weighted mean critical pressures, with the corresponding critical temperatures obtained from he vapour pressure equation. Comparison with the corresponding data from standard reference books reveals deviations from the experimental data in some [2, 4] and incorrect critical pressure for ethanol in all five reference books quoted in Table 3. In addition, vapour pressure data were obtained for the same alcohols in the temperature range approaching the critical point. The measurements are reproduced by the simplified Clausius-Clapeyron equation with the constants and standard deviation given in Table 2.
    Additional Material: 4 Ill.
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  • 45
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 131-135 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The sulphur dioxide to sulphur trioxide oxidation process in a fixed bed catalytic reactor is simulated in the case of cyclic change in the direction of the reaction mixture feed. It is shown that, for transient condition, the amount of catalyst in the reactor may be substantially reduced by its partial substitution with inert material of suitable form, dimensions and thermophysical properties, at the end of the layer. This makes the direct regenerative heat transfer process in these zones controllable, producing the same conversion and overall height of the layer. The results are significant for sulphuric acid production from gases poor in sulphur dioxide.
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  • 46
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 136-143 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For the dimensioning of condensers in film condensation, the heat transfer coefficient between film surface and cooled tube wall must be known. Generally, Nusselt equations are used which have been verified by experiments. When there is no significant gas flow, a large number of equations correlate the experimental. data very well. The description of heat transfer enhancement by a significant gas flow is not sufficiently covered by the available literature. For film wise condensation in a vertical tube, a calculation method is presented which reproduces this phenomenon characterized by the interfacial shear stress at the film surface. This method is based on the assumption that, in the proximity of gas flow, the condensation process also affects the interfacial shear stress. A comparison with known experimental local Nusselt numbers showed a good agreement with water as the fluid. For test fluid MWA, which was used by Blangetti, the measured values show only a moderate agreement with theoretical calculations. Possibly, this is related to entertainment which occurred during measurements at film Reynolds numbers of over 80.
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  • 47
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 150-156 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental set-up is presented for the measurement of steady-state reaction rates in the liquid phase methyl tertiary butyl ether (MTBE) synthesis from isobutene and methanol using ion exchange resin as catalyst. This apparatus was used for a separate investigation of the main side reaction, i.e., the formation of isobutene dimers (DIB), in the temperature range between 60 and 90°C. The reaction catalyzed by Amberlyst 15 (A15) showed no steady-state behaviour, but the catalytic activity declined at a rate dependent on the reaction conditions. Time constants for activity loss were determined in the range from 3.5 to 30 h. The deactivated A15 catalyst could be regenerated through MTBE synthesis experiment. Deactivation is assumed to be caused by blocking of the microparticle gel phase by higher isobutene oligomers. The DIB formation, using 1-butene as solvent, was of 2nd order with respect to isobutene and showed an apparent activation energy of about 40 kJ/mol.
    Additional Material: 8 Ill.
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  • 48
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 13 (1990), S. 161-171 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Knowledge of modelling and computer simulation is an essential prerequisite for type design and operation of packed bed systems. Unfortunately, the existing models are based on a number of weak assumptions of which plug flow can be considered as a common deficiency. Such a simplification would inevitably have a noticeable bearing on the accuracy of the final design and consequently calls for the development of a coherent mathematical description of the packed bed systems so that reliable design information can be explored. A two-dimensional heterogeneous transient model has been developed which allows for the radial variations of velocity and void age. The model equations have been solved using numerical approximation. The simulated results reveal significant differences between the present refined data and those established from existing plug flow models.
    Additional Material: 11 Ill.
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  • 49
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Many experimental studies reveal that suspended solids considerably alter the coalescence behaviour and hydrodynamic functions of wo-phase flow. But no systematic efforts have yet been undertaken to separate the effects of different particle properties on local gas hold-up, bubble size and interfacial area gas/liquid. The aim of this paper is to present the local values of these parameters in three-phase fluidized beds of different solids, using miniaturized optical fiber and conductivity needle probes. It is shown that particle concentration, size and, in particular, density are decisive for the change in coalescence behaviour. Ranges of normal (ϱS 〉 ϱL) and inverse fluidization (ϱS 〈 ϱL) must be distinguished and the flow regime also exerts a strong influence on the interactions between the dispersed phases, the transition point itself being a function of particle properties can be observed, This effect is evaluated for different column diameters, between 0.1 and 0.3 m.
    Additional Material: 13 Ill.
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  • 50
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aerated emulsions are gaining significance in fermentation as well as in inorganic and organic chemistry. In these processes, liquid-liquid mass transfer can be the limiting step. Therefore, the effect of gassing rate on droplet size was investigated as a function of dispersed liquid phase concentration and power input in different vessels. At high power inputs, the droplet size decreased. With increasing dispersed phase concentration and gassing rate, the droplet size increased and its dependence on power input subsided.
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  • 51
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    Chemical Engineering & Technology - CET 13 (1990), S. 214-220 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental investigations of thermal bulk polymerization of styrene in pilot plants of different sizes have been performed. Each pilot plant is composed of a tubular recycle reactor, connected in series with a tubular reactor, both completely filled with Sulzer motionless mixers. Kinetic, reactor and viscosity models have been verified in a wide range of styrene conversions (up to 96%) temperatures (up to 210 °C) and polystyrene molar masses (up to 360 000). Scale-up studies were carried out which confirmed that multitubular reactors of special design can be applied for industrial polymerization process.
    Additional Material: 11 Ill.
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  • 52
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Warm concentrated industrial wastewaters are preferably treated in an anaerobic reactor for reasons of energy generation and low surplus sludge production. Problems to be solved in the practical application concern a low growth rate of the micro-organisms, their low settling rate, process instability and the need for after treatment of the noxious anaerobic effluent which often contains NH4+ and HS-. The use of biomass immobilized on small suspended carriers (〈 0.5 mm) has proven to be a suitable means to overcome most of these problems. Results are presented on pilot and full-scale pretreatment of industrial wastewater in an anaerobic 2-state fluidized bed reactor for CH4-production and laboratory and pilot scale post-treatment of the anaerobic effluent, which contains NH4+ and HS- in an aerobic air-lift suspension reactor for the production of NO3- and SO42-.
    Additional Material: 13 Ill.
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  • 53
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The production of dioxins/furans during waste incineration, and particularly the development of measures for minimizing the amount of generated pollutants, continue to command a considerable scientific as well public interest. Experiments are reported which were performed at the TAMARA municipal solid waste pilot incineration, erected on the premises of the karlsruhe Nuclear Research Centre. These experiments show that the solid waste mass flow rate and moisture content influence the dioxin/furan formation, Good removal efficiencies of dioxins/furans have been In wet cleaning. Hydrogen peroxide added to the crude gas is an interesting “killer” reagent for dioxins/furans.
    Additional Material: 8 Ill.
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  • 54
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    Chemical Engineering & Technology - CET 13 (1990), S. 251-258 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Regeneration of diesel particulate filters can be accomplished by complete combustion of a collected particulate. A reactor has been developed for study of the regeneration in the presence of catalysts, additives and ignition aids. This reactor allows an accurate measurement of soot ignition temperatures and a kinetic study of soot oxidation with an undisturbed soot layer and under a defined gas composition. Results of various investigations carried out with this reactor are presented.
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  • 55
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    Chemical Engineering & Technology - CET 13 (1990), S. 273-277 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The majority of the fluidized-bed reactor models are models are rooted in the tacit assumption that transport between the bubble, cloud, and emulsion phases occurs in series with chemical reaction. A more realistic model that anticipates simultaneous transport and reaction is presented in terms of a fluid-bed effectiveness factor which embraces the limits between chemical and mass transport control. Analysis of the predictive capacity of this model vis-a-vis the Kunii-Levenspiel model reveals signal differences in chemical conversion.
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  • 56
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    Chemical Engineering & Technology - CET 13 (1990), S. 384-392 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Simultaneous measurements of power consumption P and heat transfer coefficient α for a jacketed, baffled, agitated vessel of diameter D = 0.45 m, equipped with a conical turbine, were carried out. The following geometric parameters of the agitator were tested: diameter d, blade width b and number Z, and distance from the bottom of the vessel to the lower edge of the blade h. The results of these investigations were generalized mathematically. On the basis of optimization, the best geometric parameters with respect to heat transfer are proposed for the conical turbine agitator.
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  • 57
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    Chemical Engineering & Technology - CET 13 (1990), S. 422-425 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Markov process approach, as used in the modelling of particle residence time distribution in a flow system of interlinked compartments, has been compared with the deterministic model of a complex reaction system of the first order. In the latter model, interfacial reactions take place between flowing phases, corresponding to the compartments in the stochastic model. It has been demonstrated that the two approaches are equivalent. A direct method of calculating the higher moments of the residence time distribution has been verified.
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  • 58
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    Chemical Engineering & Technology - CET 13 (1990), S. 426-431 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A general model is proposed to predict the crystal size distribution from multistage MSMPR Crystallizers taking into account shape factor, birth size and growth rate dispersions. Two cases, namely nucleation in the first crystallizer and the same process in all crystallizers have been considered. The developed equations can be solved easily by the Monte Carlo technique. The model represents an extension of the earlier work of Sen Gupta and Dutta.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1-9 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been shown in this investigation that the permeation of propane and propylene through polyethylene membranes exhibit a generalized behavior in the vicinity of the condensation point of the penetrant. Correlations to evaluate the permeation flux are presented.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 43-50 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Natural rubber crosslinked by dicumyl peroxide in amounts up to 25 parts per hundred of rubber (phr) showed a maximum in tensile strength near 1 phr, followed by a steep decrease to a minimum near 5 phr. The ultimate elongation decreased from 870% at 0.5 phr. to about 10% above 10 phr. The modulus increased linearly with increase of crosslinking. The creep rate decreased from 5.6% per decade at 0.5 phr to zero at 5 phr and higher values. Crystallization, with a resultant abrupt increase in creep, was noted in specimens held in the stretched condition for more than one day. Between 5 and 25 phr this system (when crystallization is avoided) appears to function as an ideal elastic network and can be recommended for studies of rubber elasticity since no variation of modulus with time is observed.
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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 151-157 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of the segregation of subchains in an isolated molecule of an A-B block copolymer is closely related to that of the mutually excluded volume of two chemically differing macromolecules. Therefore, by resorting to the “segment cloud” model used by Flory and Krigbaum to calculate the excluded volume, it was possible to derive an expression for the number of contacts between the two blocks in the same molecule. From the results of the calculation it follows that only partial block segregation can be expected unless the condensation of one of the subcoils to a dense globule occurs, owing to the effect of a poor solvent quality.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 171-189 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentration dependence of the reduced viscosity of a number of polyelectrolytes was found to be adequately described by the equation \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm \eta }_{sp} /c = [{\rm \eta }]_\infty [1 + k/\sqrt c ] $\end{document} as long as the concentration is not too low. The parameter [η]∞ represents the intrinsic viscosity of the well-shielded polyion and corresponds to values of [η] determined in salt solutions and may possibly correspond to the theory of Harris and Rice on polyion expansion. Heuristic arguments based in part on the work of Katchalsky et al. lead to a definite expression for the parameter k in terms of molecular properties. This result shows that the above equation is valid only for strong polyelectrolytes with constant activity coefficients of counterion. The calculated values of k agree well with experiment except when specific intramolecular interactions (e.g., internal hydrogen bonding) occur. For highly charged polyions we find, surprisingly, that k depends only on the properties of the polymer backbone and not on electrical properties.
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  • 63
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ten unfractionated poly(2,6-diphenyl-1,4-phenylene oxide) samples were examined by gel permeation chromatography (GPC) and intrinsic viscosity [η] at 50°C in benzene, by intrinsic viscosity at 25°C in chloroform, and by light scattering at 30°C in chloroform. The GPC column was calibrated with ten narrow-distribution polystyrenes and styrene monomer to yield a “universal” relation of log ([η]M) versus elution volume. GPC-average molecular weights, defined as M̄gpc = \documentclass{article}\pagestyle{empty}\begin{document}$\Sigma w_i [\eta ]_i M_i /\Sigma w_i [\eta ]_i$\end{document}, wi denoting the weight fraction of polymer of molecular weight Mi, were computed from the GPC and [η] data on the polyethers. The M̄GPC were then compared with the weight-average M̄w from light scattering. The intrinsic viscosity (dl/g) versus molecular weight relations for the unfractionated poly(2,6-diphenyl-1,4-phenylene oxides) determined over the molecular weight range 14,000 ≤ M̄w ≤ 1,145,000 are log [η] = -3.494 + 0.609 log M̄w (chloroform, 25°C) and log [η] = -3.705 + 0.638 log M̄w (benzene, 50°C). The M̄w(GPC)/M̄n(GPC) ratios for the polymers in the molecular weight range 14,000 ≤ M̄w ≤ 123,000 approximate 1.5 according to computer integrations of the GPC curves with the use of the “universal” calibration and the measured log [η] versus log M̄w relation. The higher molecular weight polymers (326,000 ≤ M̄w ≤ 1,145,000) show slightly broadened distributions.
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  • 64
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization and melting temperatures of an unfractionated poly(2,6-dimethyl 1,4-phenylene oxide) (PPO) sample, PM2, were determined at 0.25°C/min cooling and heating rates in five binary toluene - PM2 and fifteen ternary toluene - polystyrene - PM2 solutions. The total polymer weight fraction range studied was 0.12-0.40 and the PM2 weight fraction range was 0.026-0.40. The heat of fusion Hf of the PM2 was computed to be 10.1 cal/g from the melting point depressions. A toluene - PM2 pair interaction parameter χ13 = 0.890 - 223.5/T was found. Although a reliable polystyrene-PM2 interaction parameter could not be computed, the data are consistent with χ23 = 0. Setting χ23 = 0 we calculate the toluene - polystyrene interaction parameter to be χ12 = 0.495 - 15.46/T. This χ12 is in remarkable agreement with values reported in osmotic pressure studies.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 381-384 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 385-432 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anisotropic growth of β-form crystals of isotactic polypropylene in type III and type IV spherulites has made possible microanalysis of the unit cell structure, optical properties, and crystal arrangement within the spherulites. Micro x-ray studies of the type III and type IV spherulites show that interspherulitic β-form crystals have a hexagonal unit cell with dimensions; a = 19.08 Å and c = 6.49 Å. The intrinsic refractive indices of these β-form crystals are 1.506 along the a axis and 1.536 along the c axis. The organization of the crystals within the spherulites and the optical properties of the spherulites are also quantitatively evaluated. Both the type III and type IV spherulites have the a axis of the crystal radial while the crystals rotate randomly around the type III spherulite radii and periodically around the type IV spherulite radii. The radial refractive index for both the type III and type IV spherulites has the same value of 1.496. The tangential refractive index of the type III spherulite has a constant value of 1.509; it varies periodically between a minimum of 1.496 and a maximum of 1.519 in the type IV spherulite. Microtechniques such as micro x-ray diffraction, interference microscopy, birefringence, and optical microscopy were required for acquisition of the data.
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 541-548 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tack of cis-polybutadiene was measured by means of a Skewis tackmeter, and the results, which showed considerable variability, could be represented by a double exponential cumulative distribution function of Gumbel. It was concluded that there exists a linear relationship between the applied forces (contact and break) and the time that these forces are applied in the tack test. The mechanism of tack is considered in terms of two distinct processes: (a) the development of a bond and (b) the strength of the bond thus formed. The latter is rationalized by applying Eyring's absolute rate theory. A simple equation is derived which predicts an inverse linear relation between the breaking time and breaking force, which is in agreement with the experiment. The theory also suggests that the area of actual interpenetration of polymer interfaces depends largely on the contact pressure, whereas the depth of penetration appears to depend to a similar degree on both contact pressure and contact time.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 571-573 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 607-614 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A number of empirical equations are presented that are good approximations to computed probability density functions of the one, two and three-dimentional radii of gyration of linear random-flight chains. Equations are given that are in good agreement with the distributions over the range of the radii of most physical interest. Alternative equations are presented that give especially good fit for small values of the one and two-di-mensional radii.
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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 647-656 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to investigate the role of solid morphology on molecular relaxation in crystaline polymers, the effect of melting on the α relaxation in poly(hexamethylene sebacamide) (nylon 610) was measured dielectrically. It was found that the α loss peak was continuous into the melt with respect to location in the frequency-temperature domain and with respect to the shape of the peak. However, the strength of the process, as measured by the difference in the relaxed and unrelaxed dielectric constants, was discontinuous on melting, the process being much stronger in the melt. These observations are consistent with a two-phase model of discrete crystalline and amorphous regions. The relaxation takes place in the amorphous regions, and melting creates more of this material but does not greatly after its nature. The correlation of the amount of amorphous material as measured by dielectric relaxation with that infrared from density measurements is discussed for nylon610, polyoxymethylene, and poly(ethylene oxide).
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 715-720 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic behavior of different types of rubbery polymers (natural rubber, polybutadiene, silicone, and polyisoprene) networks at various degrees of vulcanization and swelling was examined in extension and compression. The data are represented by the Mooney-Rivlin equation. In compression, although C2 is zero, C1 decreases strongly with increasing swelling to a limiting value which, in some cases, may be correlated with the value of C1 found in extension and hence related to the theoretical modulus for highly swollen networks. A possible explanation is presented in terms of supramolecular order in the amorphous materials.
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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 755-760 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 767-768 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 823-833 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of isotactic polystyrene, crystallized from the melt and from dilute solutions in trans-decalin, has been studied by differential scanning calorimetry and solubility measurements. The melting curves show 1, 2, or 3 melting endotherms. At large supercooling, crystallization from the melt produces a small melting endotherm just above the crystallization temperature Tc. This peak originates from secondary crystallization of melt trapped within the spherulites. The next melting endotherm is related to the normal primary crystallization process. Its peak temperature increases linearly with Tc, yielding an extrapolated value for the equilibrium melting temperature Tc° of 242 ± 1°C as found before. By self-seeding, crystallization from the melt could be performed at much higher temperature to obtain melting temperatures as high as 243°C, giving rise to doubt about the value of Tc° found by extrapolation. For normal values of Tc and heating rate, an extra endotherm appears on the melting curve. Its peak temperature is the same for both melt-crystallized and solution-crystallized samples, and independent of Tc, but rises with decreasing heating rate. From the effects of heating rate and partial scanning on the ratio of peak areas and of previous heat treatment on dissolution temperature, it is concluded that this peak arises from the second one by continuous melting and recrystallization during the scan.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 857-861 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It was shown previously that in sedimented mats of solution-grown nylon crystals the 001 wide-angle reflection due to the unit-cell period along the chain and the low-angle reflection due to the lamellar periodicity are both along the same azimuth (meridian) in the x-ray diffraction pattern.1 Presently in photographs which contain both the wide-angle and low-angle regions a series of new meridional reflections have been observed between the low-angle and 001 reflections and between 001 and 002 reflections. This finding implies that, with the large chemical repeat distances in question, diffraction effects at low and wide angles cannot be considered in isolation as is usual in most polymer crystal studies. In particular, the new reflections promise to provide a direct diffraction approach to the structure of the chain-folded lamellae.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 877-886 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several important aspects of the flow in polymer melts through capillaries remain unexplored. This paper examines experimentally one such effect associated with the radial shear-stress gradient in capillaries. During capillary melt flow of a polymer with a wide molecular weight distribution, migration of the large molecules away from the region of highest shear stress, i.e., at the capillary wall, has been predicted but only modestly investigated. This effect has the potential to produce a molecular weight spectrum over the cross section of extruded polymer. Studies of distribution in shear were conducted on a well-characterized wide-distribution polystyrene (M̄w = 234,000). An Instron Rheometer equipped with a long capillary (length/diameter ratio of 66.7) was used to perform the extrusion at temperatures of 160-250°C. A solvent coring procedure was used to dissolve away concentric layers of polymer from the extrudate for molecular weight analyses. The method has been shown to cut clean sections without selective extraction. Values of M̄w, M̄n and M̄w/M̄n were calculated from complete molecular weight distribution data obtained by calibrated gel permeation chromatography. For a wide range of shear rates and temperatures, no evidence for molecular fractionation was observed. Shear degradation of this polymer was found to be small. However, at high shear rates at 250°C, evidence indicating extensive shear-induced thermal degradation was found. No evidence for oxidative degradation at the extrudate surface was found at either low or high shear rates at this temperature.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 909-918 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A modified BET apparatus has been developed to measure the surface area of polymer samples in the range 0.2-3.0 m2. The sample holder is designed to permit easy entry for bulky samples, such as polymer shavings, which cannot be loaded through a capillary or exposed to the high temperature required to seal glass. Other apparatus modifications, which allow the accurate measurement of surface area, include the addition of a dibutyl phthalate differential manometer in conjunction with a pressure reservoir. Corrections for the dead volume, nonideality of nitrogen, and the thermal gradient in the sample holder are developed. Calibrations of the equipment with inorganic samples of known areas from 1.81 to 11.8 m2 gave highly accurate values of 1.74 to 11.6 m2. Results on high-density polyethylene shavings showed precision in determinations and very close agreement in the value of 49.7 for C in the BET equation with the published value, 47.7.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 957-959 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 975-981 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of cis-polybutadiene were cross-linked in the presence of decalin at values of φr (the volume fraction of rubber) ranging from 0.25 to 0.50. After the diluent had been removed, a study was made of the force-extension and thermoelastic behavior of the networks. Within experimental error, the ratio of the Mooney-Rivlin constants 2C2/2C1 was found to be zero for networks prepared at low φr (0.25 and 0.30) but started to increase towards the conventional value at higher φr. The quantity fe/f was found to be independent of the ratio 2C2/2C1 and of the extension ratio α; the average value of fe/f was found to be 0.11.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1013-1022 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon fibers of various draw ratios have been used as the adsorbents in the adsorption of low molecular weight acids and of polyacrylic acids from solution. Polymer adsorption is lower than on a precipitated nylon and decreases with fiber orientation; however, propionic acid and glutaric acids do not show this dependence on nylon structure. The structural alterations consequent on fiber drawing also reduce swelling in hydroxylated liquids. The greater accessibility of the precipitated nylon is shown by vapor sorption and extends to nonhydroxylated vapors; however, the differences in behavior between polyamide powder and fiber cannot be fully attributed to the former possessing a porous structure, in the sense normally employed in surface chemistry.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1023-1028 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption behavior on silica of some polystrenes of moderate molecular weight distribution, both singly and in mixtures, has been examined. The adsorption isotherms indicate that, in both a good solvent (trichloroethylene) and under theta conditions, the species of higher molecular weight is preferentially adsorbed at or near full surface coverage, but that the smaller adsorbate has an improved opportunity for adsorption at low surface coverage. The use of tritiated adsorbates substantiate the isotherm data in cyclohexane solution.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1047-1059 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Shear stress P21 and normal stress P11 -P22 functions of moderately concentrated aqueous solutions of sodium poly (acrylate) were measured under steady shear flow at various shear rates \documentclass{article}\pagestyle{empty}\begin{document}$\dot \gamma$\end{document} with a Weissenberg rheogoniometer. The compliance function Js = (P11 - P22)/2P212 is found to vary with shear rate. The double logarithmic plot of Js versus \documentclass{article}\pagestyle{empty}\begin{document}$\dot \gamma$\end{document} can be superposed with respect to molecular weight at constant concentrations of added neutral salt and polymer. These reduced plots differ markedly as the concentration of added salt is varied but converge to a single line at high shear rates.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1085-1095 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to study the crazing behavior in rubber-toughened glassy polymers, polystyrene samples containing two rubber balls of the same diameter with varying separations have been prepared. They were subjected to simple tension, and their crazing behavior was observed. When the two balls are close together, the craze-initiation stress is considerably lower than that of single-ball samples. With increase in the distance between the two balls the craze-initiation stress increases at first almost linearly and levels off when l/d reaches about 1.45, where l and d are the center-to-center distance and the diameter of the balls, respectively. When l is sufficiently small, the crazes are seen to develop extensively at the inner surfaces of the balls and finally bridge with each other. The crazes bridged between the balls expand largely in the plane perpendicular to the applied load.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 23-42 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Statistical radii of gyration, second virial coefficients, and intrinsic viscosities of sharp fractions (M̄w/M̄n ≈ 1.1) of polyisobutylene (PIB) covering a wide range of molecular weight (1.6 × 105 to 4.7 × 106) were determined in isoamyl isovalerate (IAIV) at a number of temperatures ranging from 20 to 60°C, in n-heptane at 25°C, and in cyclohexane at 25°C by light-scattering and viscosity measurements. It was found that IAIV at 22.1°C is a theta solvent for PIB. Analysis of the data by the methods described in preceding papers of this series indicated that, except for minor differences, the conclusions derived from similar studies with polychloroprene, polystyrene, and poly-p-methylstyrene hold equally for solutions of the typical linear polymer investigated here. In particular, no decisive evidence for the drainage effect was found.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 89-99 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of dissociation of a nonionic detergent, octylphenyl polyoxyethylene ether, was studied by a temperature-jump technique. A relaxation process which is concentration-dependent was observed. A linear relation between the reciprocal relaxation time and the detergent concentration above the critical micelle concentration was obtained, from which the rate constant of dissociation kn,n-1 of one molecule of detergent from the micelle has been determined. Values of kn,n-1 equal to 0.4 ± 0.05 and 73 ± 5 sec-1 at 24.8°C were obtained for detergents with 16 and 30 ethylene oxide units per molecule of surfactant, respectively, showing and increase of the rate constant of dissociation with the length of the hydrophilic-head chain.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 133-150 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on tensile strength and elongation at break for a series of Viton A-HV vulcanizates are discussed. The data were obtained at various extension rates at temperatures from -5 to 230°C (25 ≲ T  -  Tg ≲ 260°C) on seven vulcanizates having crosslink densities ve (estimated from C1 in the Mooney-Rivlin equation) from 0.46 × 10-5 to 24.4 × 10-5 mole/cm3. At an extension rate of 1 min-1, an increase in ve affects the tensile strength σb (based on the undeformed cross-sectional area) and the true tensile strength σbσb (based on the cross-sectional area of a deformed specimen) as follows: σb is essentially constant at a low temperature; it passes through a decided maximum at intermediate temperatures; and it increases to a plateau at elevated temperatures. In contrast, λbσb decreases markedly at all temperatures, an exception being the most lightly crosslinked vulcanizate(s). Application of time - temperature superposition to the ultimate-property data gave log aT; its temperature dependence is that typical of nonpolar rubbery polymers. Data on the vulcanizates were compared in corresponding temperature states by plotting log 273σb/T, log 273λbσb/T, and (λb  -  1)/(λb  -  1)max against logtb/(tb)max, where tb is the temperature-reduced time to break and (tb)max is the value at which the ultimate extension ratio λb attains its maximum, (λb)max. Except for the most lightly crosslink vulcanizate, the comparison shows that 273λbσb/T and (λb  -  1)/(λb  -  1)max are substantially independent of (or only weakly dependent on) crosslink density, that 273λb/T increases with ve, and that 273λb/T ∝ ve0.6 and λb ∝ ve-0.4 at a large value of tb/(tb)max.
    Additional Material: 12 Ill.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 159-170 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decay in birefringence of glassy polycarbonate held at constant extension has been studied at 23°C, in the time-scale range 10-103 sec, up to about 6% strain. The results show that, under these conditions, the birefringence can be validly expressed as a linear hereditary integral of the strain history up to a relatively high strain level which is about 3.4% for an experimental time-scale of 100 sec. Comparison with previously obtained data on the stress relaxation behavior of the same polymer shows that, other factors remaining constant, mechanical relaxation is linear only up to about 1.1% strain. The earlier onset of mechanical nonlinearity is discussed and it is suggested that the mechanical relaxation spectrum is richer than the optical spectrum in relatively long relaxation times, corresponding to relatively slow molecular motions. It is further suggested that these slow molecular motions are accelerated first as the polymer is extended beyond the limit of linear viscoelastic behavior. The observed nonidentity between strain limits for linear mechanical and linear optical behavior is discussed in the light of current practices in photomechanical stress analysis.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1145-1152 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1167-1170 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1175-1177 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Tab.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1153-1165 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The anisotropy of the α and β relaxations in oriented poly(ethylene terephthalate) has been studied by dynamic mechanical and dielectric relaxation measurements. The α relaxation shows considerable mechanical anisotropy but gives rise to an isotropic dielectric process. The β relaxation, on the other hand, shows pronounced dielectric anisotropy but very little mechanical anisotropy. The implication of these results with regard to possible interpretations of the relaxations are discussed.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1171-1174 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1179-1182 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1183-1191 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an attempt to facilitate a better understanding of the role of noncrystallizable components on the crystallization kinetics, spherulitic growth rates as well as the morphology and melting behavior of isotactic polystyrene in blends with various molecular weight atactic polystyrenes (900 to 1,800,000) over a wide range of concentrations have been studied. The growth rates are uniformly depressed with increasing amounts of atactic diluent. In addition, they are dependent on the molecular weight of the added polystyrene, generally decreasing in the molecular weight ranges between 4800 and 19,800 and between 51,000 and 1,800,000. However, between these two ranges, anomalous growth rates showing a sudden increase are observed, which may be explained by an increase in the entrapment of the noncrystallizable diluent. An explanation based on morphological observations, which showed an increase in coarseness of the spherulites with increasing molecular weight of the added atactic polystyrene, is offered.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1193-1206 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle light scattering in Hv and Vv modes is calculated for elliptical disks with the use of an elliptical coordinate system. The method is general for all degrees of ellipticity, from a circular disk to rodlike extensions, and permits the definition of any desired dipole orientations. The solution is obtained by computer-assisted numeric integration. Two models are considered, an “elliptical” one an “affine deformation” one differing in the orientation of scattering dipoles. The calculated patterns show a significant dependence of the distribution of the scattered intensity on the size and the elliptical axial ratio in both models, permitting the determination of both the size and the degree of ellipticity of the disk from its patterns. In addition, the differences between the calculated results for the two models are sufficiently large to permit the selection of the experimentally appropriate model, at least within the range of moderate degree of ellipticity.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1221-1236 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallite sizes have been obtained from the breadth of equatorial x-ray reflections from polypropylene samples subjected to a draw ratio of 6 at 21°C and then annealed at 155°C, 140°C, and 120°C, respectively. For all samples it was found that the ratio of the dimension of the crystallite perpendicular to the {110} planes to that perpendicular to the (040) plane is a constant. The ratio of the lateral crystallite size to the meridional long period was also found to be constant, independent of annealing temperature. In contrast, the thickness of the crystallites in the direction parallel to the draw direction, as calculated from the meridonal long period and density data, was not proportional to the lateral crystallite size.
    Additional Material: 7 Ill.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1237-1254 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray scattering (WAXS) patterns of two polypropylene samples, a quenched sample drawn at 21°C and an annealed sample drawn at 100°C, were investigated in a range of values of draw ratio λ very closely spaced through the neck region. In both cases, a range of small λ where deformation occurred by spherulite deformation was followed by one of higher λ where microfibrils were formed. The contribution to the WAXS pattern of microfibrils could be clearly distinguished from that of deformed spherulites because of the better orientation parallel to the draw direction of the former as compared to the latter. Additionally, for a drawing temperature of 21°C, microfibrils crystallize in the “smectic” phase as compared to the monoclinic phase for the initial sample and deformed spherulites. At this temperature, plastic deformation proceeds through the spherulite deformation mechanism up to λ = 1.4 accompanied by an increase in chain orientation with increasing λ. For λ 〉 1.4 plastic deformation appears to occur exclusively through microfibril formation. For drawing at 100°C, spherulite deformation is accompanied by very little change in chain orientation up to λ = 2, where microfibril formation begins. For λ 〉 2 (Td = 100°C) plastic deformation is accompanied by both microfibril formation and some spherulite deformation as reflected by changes in both orientation and crystallite size. At this temperature the lateral crystallite size in the microfibrils is related to the long period according to the “equilibrium crystallite shape” previously found for annealed polypropylene.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1255-1272 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of annealing processes on the thermal behavior of organic glasses in the glass-transition interval has been investigated and analyzed quantitatively. In detailed annealing studies of atactic polystyrene and Aroclor 5460, the absorption of thermal energy superposed on the increase in the specific heat at the glass transition, observed with suitably chosen heating rates, was followed by the differential thermal method. It is concluded that the absorption of thermal energy observed under these conditions parallels the extent of molecular relaxation that has taken place during the annealing period. It is not necessary to postulate a first-order process to account for the energy absorption. Moreover, such a postulate leads to severe conceptual difficulties regarding the development of crystallinity in crystallizable materials. The areas and the shapes of the endotherms are considered in terms of the original physical properties of the quenched glasses and the anticipated equilibrium properties. Relationships between the extent of energy absorption and time-dependent processes such as volume relaxation are discussed.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1285-1296 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As part of a study of chemical and physical changes accompanying the formation of carbons by the pyrolysis of polymers, conventional electron microscopy, electron diffraction, and scanning electron microscopy techniques have been used to examine structural and morphological features of polyacrylonitrile (PAN) crystals, powder, and fibers, and of Saran and poly(vinylidene chloride) (PVDC) powder. Changes accompanying the heating of these polymers in air and in nitrogen have been investigated. PAN crystals grown from propylene carbonate were similar to those obtained by Klement and Geil. When heated in air at 220°C they retained their morphology, and electron diffraction gave the same reflections as PAN. On further heating to 400°C in nitrogen the morphology was retained, but the diffraction was lost. Crystals treated in nitrogen alone at 200°C showed morphology similar to that of the polymer. PAN powders and fibers retained discernable external features of their morphology on heating to 800°C. These results are discussed with reference to changes which take place when poly(vinylidene chloride) and Saran are heated in the range 150-180°C, which results in the loss of one hydrogen chloride per monomer unit, and are subsequently carbonized at 800°C. The development of pore structure and the adsorptive properties of Saran carbons are also discussed.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1207-1219 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilatometric, calorimetric, and dissolution studies have been made of two crystalline modifications of trans-1,4-polyisoprene in order to determine their equilibrium melting temperatures. This parameter is of fundamental importance in the formal treatment of polymorphism in crystalline polymers. A consistent set of thermodynamic parameters has been derived for both crystalline modifications. The equilibrium melting temperature of the polymorph, which was previously observed to melt from carefully crystallized bulk material at 64°C, was calculated to be at least 82.4°C. The other form, which melts from the bulk at 74°C, has an equilibrium melting temperature of 79.5 ± 0.5°C. The trans-1,4-polyisoprene, crystallized by stirring n-butyl acetate solutions at 49°C, was found by x-ray diffraction to be in the first form and melts at 81.2 ± 0.5°C when very slow heating rates are applied. This melting temperature is very close to the independently derived equilibrium melting temperature and lends support to the possibility that extended chain crystals are present in these solution crystallized crystals. Using the newly found melting temperatures of the two crystalline modifications it can be derived from the free energies of fusion that the first crystalline form is more stable at temperatures above approximately 66°C, whereas the other form is more stable below this temperature.
    Additional Material: 7 Ill.
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