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  • 1990-1994  (59)
  • 1965-1969  (3,368)
  • Physics  (1,850)
  • Industrial Chemistry  (1,577)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Pharmacy world & science 15 (1993), S. 105-115 
    ISSN: 1573-739X
    Keywords: Calcium phosphates ; Drug compounding ; Excipients ; Particle size ; Physics ; Powders ; Tablets
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ten commercially available calcium phosphates used for direct tableting were evaluated. The particle size distributions, powder properties, Sorption isotherms and pH values of aqueous slurries were compared. All samples showed good or at least sufficient flowability. Scanning electron micrographs illustrated the different kinds of manufacturing and gave hints on their expectable behaviour under compaction pressure. The sorption isotherms of identical chemical substances, which had been manufactured by different methods, differed strongly. This can be related to their specific surface areas. Most of the hydroxylapatites have large surface areas and can absorb up to more than 15% water at 93% relative humidity. Dibasic calcium phosphate dihydrate was non-hygroscopic and absorbed less than 1% water. With the exception of monobasic calcium phosphate monohydrate all calcium phosphates behaved quite neutral in water. Monobasic calcium phosphate monohydrate can be regarded as a solid acid. Although the calcium phosphates are usually stable substances, the role of crystal water in the case of dibasic calcium phosphate dihydrate and monobasic calcium phosphate monohydrate is problematic due to possible interactions with active ingredients.
    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: 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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  • 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: 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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  • 4
    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.
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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    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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  • 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: 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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  • 10
    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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  • 11
    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.
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  • 12
    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.
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  • 13
    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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  • 14
    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.
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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: 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.
    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: 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.
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  • 17
    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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  • 18
    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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  • 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: 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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  • 20
    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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  • 21
    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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  • 22
    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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  • 23
    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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  • 24
    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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  • 25
    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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  • 26
    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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  • 27
    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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  • 28
    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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  • 29
    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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  • 30
    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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  • 31
    Electronic Resource
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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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  • 32
    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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  • 33
    Electronic Resource
    Electronic Resource
    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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  • 34
    Electronic Resource
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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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  • 35
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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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  • 36
    Electronic Resource
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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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  • 37
    Electronic Resource
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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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  • 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: 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.
    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: 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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  • 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: 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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  • 41
    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.
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  • 42
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    Weinheim : Wiley-Blackwell
    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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  • 43
    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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  • 44
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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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  • 45
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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.
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  • 46
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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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  • 47
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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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  • 48
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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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  • 49
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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.
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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: 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.
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  • 51
    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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  • 52
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    Weinheim : Wiley-Blackwell
    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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  • 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: 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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  • 54
    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.
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  • 55
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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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  • 56
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    Weinheim : Wiley-Blackwell
    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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  • 57
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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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  • 58
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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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  • 59
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    Weinheim : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 171-182 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To clarify the deformation mechanism in polyblends of polypropylene with ethylene-propylene rubber having different compositions, simultaneous measurements of the infrared dichroism with stress and strain under a constant rate of strain of 1.64%/min have been carried out. The orientation function of the crystallographic c axis of polypropylene in the blends has been obtained as a function of strain ranging from 0 to 20% and of polypropylene content ranging from 0.3 to 1.0. These results have been compared with the temperature dependences of the dynamic Young's modulus and of the loss modulus, as well as of stress-strain curves for the same blends. The modulus data analyzed by Kerner's equation reveal the occurrence of phase inversion at polypropylene contents higher than about 0.5, and this is supported by the infrared dichroism data. The strong effect of quenching on crystalline structure and mechanical properties of pure polypropylene has also been elucidated.
    Additional Material: 12 Ill.
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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 183-200 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equipment and methods have been developed which allow photomicrographic determination of the stress-strain properties of the individual craze. Serial cyclic tensile tests on polycarbonate crazes are described. Under stress the typical dry polycarbonate craze thickens solely by straining; no adjacent polymer of normal density is converted to craze material. The craze exhibits a yield stress followed by a recoverable flow to roughly 40-50% strain at 6000-8000 psi. On return to zero stress the craze exhibits creep recovery at a decelerating rate. The yield stress and loss factor of each cycle decrease with increasing initial strain and cycles initiating at 50% strain or more show completely Hookean behavior. Creep recovery results in recovery of yield stress and loss factor also. Craze tensile behavior is suggested to be essentially an extension of the craze formation process. Decrease in elastic modulus and yield stress with increasing strain are rationalized in terms of strain-produced decrease in density and resultant increase in stress concentration factor on the microscopic polymer elements of the craze. Polymer surface tension and the large internal specific surface area of the craze are suggested to be important factors in the large creep recovery rates of the craze.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 241-248 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of determining distributions of the degree of polymerization by means of probability theory is derived. This method, based on Kolmogorov's forward differential equation, is illustrated by application to two familiar kinetic schemes and is used to derive the distribution of degree of polymerization for free-radical polymerization with diffusion-controlled termination.
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 271-278 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of birefringence of a polymer film upon its photographic light-scattering pattern is considered for the case of a single, anisotropic, two-dimensional spherulite imbedded in a birefringent matrix. It is shown that for the case of a polarizer and analyzer crossed at +45° and -45° to the analyzer, the scattering pattern is modified in a manner agreeing with experimental observation.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 285-295 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotic-pressure, viscosity, and light-scattering measurements have been carried out on dilute solutions of poly-N-vinylcarbazole fractions (4 〈 10-4M 〈 230) in toluene, dioxane, and benzene. The theta temperature for poly-N-vinylcarbazole in toluene solutions has been found to be 37 ± 1°C. The intrinsic viscosity of poly-N-vinylcarbazole in toluene at 37°C is represented by [η]θ = 76.2 × 10-3M̄n0.50. Values of the characteristic ratios (〈L2〉0/M)1/2 and σ = (〈L2〉0/〈L2〉0f)1/2 have been obtained as 633 × 10-11 and 2.85, respectively. It appears that the large σ value is due to the steric repulsion between large side groups.
    Additional Material: 7 Ill.
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  • 65
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical relaxation data as a function of temperature (ca. 1 Hz) have been obtained for several samples of isotactic polypropylene crystallized from the melt, which exhibit both α and β forms as well as varying degrees of lamella orientation. The samples ranged in morphology from an unoriented sample showing only the α form to one highly oriented having approximately 90 per cent the β form. Results for the logarithmic decrement Δ and loss modulus G″ are that the low temperature (ca. -75°C) and glass temperature (ca. 0°C) relaxations show little or no sensitivity to orientation in the α form, but that the intensity of the two processes is different in the α form than in the β form for samples of nearly equal overall per cent crystallinity. In both Δ and G″, the low-temperature peak decreased and the glass temperature peak increased in intensity as the fraction of β form crystallinity present increased. Data for the high-temperature relaxation (ca. 80°C) indicate a dependence upon orientation and/or crystal form in addition to a dependence upon per cent crystallinity.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 411-422 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscometric behavior of linear polycaprolactam has been studied in the absence of the electroviscous effect in aqueous solvents containing 85% and 64.5% formic acid and in trifluoroethanol, as a function of temperature and also under unperturbed conditions. Results are discussed in terms of the existing theories; in particular, the negative temperature coefficient of the intrinsic viscosity arises only from the variation of the expansion coefficient, the molecule in the unperturbed state being a normal random coil. The absence of aggregation and draining effects in the above solvents has been varified.
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 463-473 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers of poly(N-acyl and N-aroyl aziridines) were studied by x-ray diffraction. All the crystalline polymers studied have a triclinic unit cell with two monomer units per unit cell. The a and c (fiber direction) parameters (4.9 and 6.5 A, respectively) are essentially the same for all the cells. The b parameter for the N-acyl polymers, however, increases steadily by a factor of 2 A per methylene group added to the lateral chains. The densities calculated for the unit cells are in agreement with the experimental values obtained. The most probable structure is one in which the molecules assume a planar configuration with the main chain not fully extended. The lateral groups are tilted from the c axis by an angle of 54° in a parallel configuration and alternate on each side of the main chain. This permits these lateral groups to assume packing similar to that of polyethylene. A brief description of the techniques used in this interpretation is included.
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  • 68
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from characterization of melt-polymerized nylon 66 by various solution property measurements are reported and employed in analysis of typical molecular weight and compositional distributions for these systems. Critical attention is paid to application of standard procedures including light scattering, viscosity, membrane osmometry and other colligative property measurements in arriving at satisfactory specification of polymer molecular weight averages. Particular consideration is given to polymers extending appreciably beyond the lower and higher limits in molecular weight normally encountered. The conclusions drawn are: (1) in the range of number-average molecular weights less than about 25 000, nylon 66 as ordinarily prepared by melt condensation consists principally of linear species approximating the “most probable” distribution; (2) small amounts of cyclic oligomers are present in all samples: (3) increase in the extent of the melt polycondensation to progressively higher stages is accompanied by secondary reactions and the formation of branched components terminating ultimately in crosslinked, insoluble gels. Intrinsic viscosity-molecular weight relationships in seven solvents, applicable to nylon polymers meeting the requirements of (1) above, are derived.
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 57-76 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For an infinitely repeated regular polymer chain structure the only vibrations which are optically active are those in which the phase of the motion is the same in each unit (the factor-group modes). Frequencies for which the phase difference is nonzero are optically inactive but can become activated by the presence of defects in the chain. Such defects would normally be chemical impurities or conformational irregularities in the chain. A simple theory is developed which shows that for a dilute system of defects the major characteristics determining possible activation of the nonfactor-group modes are: (1) the strength of the coupling between the defect vibration and the vibrations of the neighboring chain, and (2) whether or not the natural frequency of the defect vibration lies inside a lattice band of the regular chain. An analysis of the low- and high-frequency regions of the spectrum of low-density polyethylene, based on the above considerations, indicates that several features of the spectrum can be associated with defect-induced absorption. A similar explanation can account for certain intensity changes in the C—Cl stretching region of syndiotactic poly(vinyl chloroide) when this polymer is submitted to mechanical treatment.
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  • 70
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general description is given for relations among the optical quantities obtained from fluorescence polarization measurements on bulk polymer stained by fluorescent groups: the moments of distribution of orientations of the fluorescent groups, and those of the structural units of the polymer (chain segments) on which the groups are adsorbed. Two assumptions as to the biaxial symmetry of the bulk polymer and the cylindrical symmetry of the optical anisotropy of the fluorescent element, both for the absorption and emission processes, reduce the intensities of the polarized fluorescence to a 3 × 3 matrix L which is asymmetric (Lij ≠ Lji), as has frequently been observed in experiments. The components of the L matrix are related to those of the J matrix which is so defined as to describe the fourth moments of the distribution of orientations of the structural units on the basis of a random distribution of the rotational angle of the unit about the segment axis. It is found that the use of the method of fluorescence polarization combined with absorption dichroism and/or emission gives the values of the optical anisotropy ratios of the fluorescent unit, and that the effects of the thermal agitation of the structural unit can be separated from the moments of the orientation distribution for the simplest case.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-748 
    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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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 753-762 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Eight epoxy-diamine networks have been formed, diamines with 2 to 12 methylene groups being used as curing agents. Dynamic mechanical tests revealed four transition regions in the dynamic loss modulus/temperature relationship. Two possible explanations for the relaxation of the glycidyl portion of the structure are proposed. One of the relaxations could be due to the breakdown of hydrogen bonds through the hydroxyl and ether groups. The second could be ascribed to the relaxation of the unbonded glycidyl groups or a second relaxation of the glycidyl groups after the breakdown of the hydrogen bonds.
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 783-794 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous theoretical calculations of elastic constants for cellulose based on force constants for bond stretching and bending of valence angles have yielded axial stiffness values admittedly too low. The present analysis accounts for a hitherto unexamined geometrical effect associated with deformation of interchain hydrogen bonds. To do this, most primary bond deformations are neglected so the resulting calculation gives an upper bound for the axial stiffness. By using two different sets of hydrogen bond force constants, values of 24.6 and 31.9 × 1011 dyne/cm2 were obtained for Young's modulus in the chain direction. These values are very much larger than earlier calculations and experimental determinations from cellulosic fibers, indicating both the importance of the effect considered here and the likelihood of an exact analysis yielding an acceptable result.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 845-853 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational energy contribution (ΔUconf) to the heat of solution in polymer-solvent systems is presented and discussed in connection with chain conformational properties. In particular, ΔUconf has been discussed in terms of various possible mechanisms of coil deformation.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 889-896 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that in a filled polymer the thermal stresses resulting from the difference in the thermal expansion coefficients of the filler and the polymer have significant effect on the apparent coefficient of thermal expansion of the composite. A model is constructed to aid the thermal stress analysis, and the results are found to agree well with the experimental data obtained from other sources. An expression for the apparent densities of filled polymers is also obtained but the agreement between the present prediction with an existing test result is found to be only qualitative.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 947-962 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients and solubilities of methane in polyisobutylene have been measured at four temperatures between 102 and 188°C. in the pressure range 23-341 atm. Diffusion coefficients extrapolated to atmospheric pressure range from 1.72 × 10-6 cm.2/sec. at 102°C. to 1.5 × 10-5 cm.2/sec. at 188°C. corresponding to an activation energy for diffusion of 8.7 ± 0.4 kcal./mole. Solubilities are small, about one molecule of methane for every forty carbon atoms in the polyisobutylene at 300 atm. partial pressure of methane. Solubilities vary little with temperature, but show an apparent minimum between 127 and 188°C. With improved methods of data analysis, diffusion coefficients and solubilities have been recalculated from previously reported studies on nitrogen in branched polyethylene and methane in branched polyethylene, linear polyethylene, and polystyrene. Recalculated diffusion coefficients are essentially the same as those reported previously, but the recalculated solubilities are decreased from 2 to 30%. The solubilities of all five systems show strong deviations from Henry's law, i.e., increases in partial pressure of methane and nitrogen with respect to solubility exceed linearity. The partial pressure (or fugacity) - solubility data may be interpreted in terms of a sorption model in which sorbed molecules are accommodated in widely dispersed, unoccupied volumes or sites in the polymer. An almost equivalent, solution model in which the first sorbed molecules to enter the polymer are accommodated to a large extent in existing volumes in the polymer, with successively sorbed molecules swelling the polymer to a greater extent (i.e., partial molal volume of sorbed molecules, V1, increasing with concentration) can also account for these data.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1021-1031 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The discrepancy between the values of the anisotropy of methylene groups determined from crystal refractive indices, stress-optical data, and gas and liquid light-scattering depolarization is explained on the basis of the effect of the internal field on the polarizability of the isolated molecule. The internal field may arise from intermolecular or intramolecular interactions which depend upon molecular conformation and state of aggregation. A simple continuum calculation based upon an extension of the calculation of the Lorenz-Lorentz field is shown capable of accounting for the discrepancy.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1059-1073 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 66 films exhibiting form I melting behavior show the γ mechanical relaxation at -140°C. Samples which have form II melting behavior do not show this relaxation. The γ relaxation disappears when material having form I behavior is converted to material having form II behavior by annealing or by cold drawing. The form I and form II types of melting behavior are also found in poly(ethylene terephthalate); the interconversions and thermal behavior of the forms are analogous to the nylon 66 case. In poly(ethylene terephthalate), the β relaxation at -40 to -60°C is present only when form I melting behavior is found. Conversion to form II melting behavior by annealing or drawing (80°C) again causes the relaxation to disappear. No β relaxation was found in amorphous polymer. The γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) can therefore be associated with the crystalline structure responsible for form I melting behavior. Form I melting behavior has been associated with foldedchain crystals based on previous work. It is therefore postulated that the γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) are associated with motions in the chain folds. This assignment is not inconsistent with the change in the γ dispersion of nylon 66 with the number of backbone CH2 units, since these will affect the fold structure.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1116-1118 
    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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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1151-1163 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength-limiting process in the fracture of semicrystalline fibers and highly oriented films is the rupture of tie molecules connecting the folded chain lamellae in the machine direction. This view is supported by the data on stress and temperature dependence of lifetime of fibers under load and on radical formation during the fracture experiment. The observed tensile strength, however, is about 10 times smaller and the number of fractured chains between 100 and 1000 times larger than expected on the basis of the known number of tie molecules in the fracture plane. This discrepancy is a consequence of the inhomogeneity of the micromorphology of fiber structure, which causes a much larger stress concentration on the most unfavorably located tie molecules than the average value one would expect in the case of perfectly uniform stress distribution on identical tie molecules. The fluctuation of amorphous layer thickness, of number and length of tie molecules, produces such a high stress concentration on some tie molecules throughout the sample that they rupture long before the average stress concentration is sufficient for chain fracture. By accumulation of damage caused by gradual chain rupture the weakening of the sample locally proceeds so far that at the maximum damage concentration, microcracks start to form, and the fiber breaks.
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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 525-536 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic shear behavior of four highly amorphous polymers in the unstretched and stretched states (draw ratios 3:1 to 6:1) was investigated with a torsion pendulum at temperatures from 4.2°K to 180-300°K and frequencies from 0.4 to 3.2 cps. The polymers studied were polystyrene, poly(vinyl acetate), poly(vinyl propionate), and poly(isobutyl vinyl ether). Previously unreported loss maxima were found at 48°K (1.5 cps) and 149°K (1.3 cps) for poly(vinyl proplonate), at 10°K (1.0 cps) for poly(vinyl acetate) and at 9°K (1.6 cps) for poly(isobutyl vinyl ether). Uniaxial orientation increased the shear storage modulus G, measured with the torsion axis parallel to the stretch direction and caused changes in the loss peaks which depended on the polymer material studied.
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 551-561 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering studies were made on bulk-crystallized samples and annealed oriented films of TMPS. The temperature dependence of the small-angle scattering was determined over a range of annealing conditions. The effect of sample molecular weight on the small-angle peaks was also studied. The peak intensity, measured at room temperature after annealing, was strongly dependent on the annealing conditions. The position of the peak gradually moved to smaller angles (larger d spacings) as the annealing temperature was raised. Surface free energies were deduced from the melting point dependence of the crystallite size. This surface energy was found to increase with molecular weight in accord with values deduced for spherulite growth rate-temperature dependence.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 593-600 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is proposed to account for the regular twisting of radial ribbons in certain polymer spherulites. The model assumes that the ribbons have crystallographically regular fold surfaces and that growth of the ribbons is nucleation-controlled. The model leads directly to a possible mechanism of spherulitic growth in some polymers.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 659-666 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures; at larger undercoolings, however, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature in the range 109-113°C. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 675-685 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength and extensibility of an unfilled styrene-butadiene rubber vulcanizate were determined in constrained biaxial tension (essentially pure shear) by stretching thinwalled cylindrical specimens in the axial direction with an Instron tester while gas pressure was admitted to maintain constant the outside diameter of a specimen. The rupture stress, λ1b, and the extension ratio, λ1b, in the axial direction and the rupture stress, σ2b, in the circumferential direction were determined at extension rates from 0.0031 to 3.1 min-1 and temperatures from 25 to 90°C. Rupture data in simple tension were also obtained by testing ring specimens under similar test conditions. The time-temperature shift factor, aT, obtained by superposing rupture data at different temperatures, gives a constant activation energy of 35 kcal. Doubly logarithmic plots were prepared showing the dependence of σ1b/λ1b, σ2b, and λ1b from the biaxial tensile tests and of σb/λb and λb from the simple tensile tests on the temperature-reduced extension rate, \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. (The quantities σ1b/λ1b, σ2b, and σb/λb are rupture stresses based on the dimensions of undeformed specimens.) At equal values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}, the extension ratios λ1b and λb are sensibly identical. The ratios σ1b/σb and σ2b/σb, as well as λbσ2b/σb, were obtained from rupture data read from the composite curves at selected values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. Also, similar ratios were derived from stress data at equal extensions in biaxial and simple tension for 1.25 ≤ λ ≤ 3.0, the range comparable to that in which rupture data were obtained. A consideration of the ratios given by both the rupture and the stress data shows that the von Mises failure criterion is not applicable, although the departure is small except at the larger values of λb.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-747 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 750-750 
    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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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 775-782 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A statistical model for the stereospecific polymerization of vinly monomers on Ziegler-Natta catalytic systems is presented. The basic assumptions of the model are: (a) the catalytic centers are asymmetric, so that at a given catalytic center the monomer CH2=CHR is inserted into the chain with two different rates according to the two different configurations of the opening carbon atom having the R group; (b) the insertion of a monomeric unit in the growing chain is affected also by interactions with the previous monomeric unit. Isotactic, syndiotactic, atatic, or stereoblock polymers are obtained according to the relative values of the two energy parameters expressing these two effects.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 821-827 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures, whereas at larger undercooling, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature about 5°C below Tp. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
    Additional Material: 3 Ill.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 855-866 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heats of solution (ΔHexp) in solvents of increasing thermodynamic power have been measured for four polymers: polystyrene (PS), poly(vinyl acetate) (PVAc), polyisobutylene (PIB) and polydimethylsiloxane (PDMS). After subtraction from ΔHexp of an interaction term (calculated by the Hildebrand treatment based on solubility parameters) and the excess volume term, the quantity remaining is interpreted as the conformational energy contribution (ΔUconf) to the heat of solution. ΔUconf appears to correlate well with some basic conformational properties of the chain, such as the sign of the temperature coefficient of unperturbed dimensions derived from solution properties, and shows a monotonic behavior with α, the expansion coefficient of the polymer coil in the final solution. Numerical values of ΔUconf, at least for those cases in which polymer solubility parameters are known with some certainty, are much larger than those evaluated from rubber elasticity experiments (through the experimentally accessible value of the energy component of the force of retraction im simple elongation).
    Additional Material: 5 Ill.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1101-1109 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyvinylpyridine of molecular weight 0.77 × 106 was crosslinked by 2.5, 5, and 10% BrCH2C6H4CO(CH2)8COC6H4CH2Br and by 10% ClCH2C6H4CH2Cl; quaternization of the gel was completed with n-butyl bromide. Swelling ratios in aqueous solutions of lithium, sodium, and 4-isopropyl-N-n-butylpyridinium bromide and in methanolic lithium bromide were determined. Selectivity increased in the sequence Li+ 〈Na+ 〈PrN+-C5H5. The Flory parameter χ1, which measures interaction between solvent and polymer, decreased from 1.5 kT to nearly zero with increasing density of crosslinks in the aqueous solutions, and from 3 kT to 0.5 kT in the methanol solutions. The inverse proportionality of q2/3 (q = swelling ratio) to the crosslinking density was approximately verified for swelling of the resins in water, methanol, and dimethylformamide.
    Additional Material: 5 Ill.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1165-1186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The proton spin-lattice relaxation times (T1) of linear polyethylenes (PE) of varying morphology were measured as a function of temperature. The T1 of oriented bulkcrystallized and solution-crystallized material was isotropic, in disagreement with calculations based on a sample dipole pair model. Motion in the non-crystalline regions of the samples is shown to be responsible for the T1 minimum occurring around -20°C. The dependence of T1 at the minimum on the long period reinforces the model of an amorphous fraction composed of disordered lamellar surface layers. The temperature of the T1 minimum and the dependence of T1 on the long period imply that the mobility of these amorphous regions is reduced in cold-drawn and solution-crystallized samples. This mobility irreversibly increases with annealing. In highly relaxed samples the motion of a small portion of the disordered regions is almost liquidlike, as indicated by the presence of a second shorter T1.
    Additional Material: 12 Ill.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 963-981 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural and steric isomerism of propylene polymers has been estimated on the basis of solution properties as well as infrared and high-resolution nuclear magnetic resonance spectra. Three general types of polypropylenes were prepared: polymers prepared with the cationic catalytic system AlCl3-C2H5Cl, stereoblock polymers obtained by successive extraction from a commercial product and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polymer followed by hydrogenation with Adam's catalyst in dioxane at 40°C. The characterization of all samples was accomplished by equilibrium ultracentrifugation, vapor-pressure osmometry, viscometry, and gel-permeation chromatography. It is found that the molecular chain of cationically prepared polymer is somewhat branched owing to structural isomerism during polymerization. Isoamyl acetate is found to be a theta solvent for stereo-block as well as for atactic and syndiotactic polymers; the theta temperature is determined as the temperature at which the light-scattering second virial coefficient A2 vanishes. A close correlation is found between the theta temperature and stereoisomerism. The absorbances of the 1154 and 974 cm-1 bands in the infrared spectra decrease with decreasing molecular weight; in addition to the mere existence of alternating CH2 and CH(CH3) groups in the polymer chain, rather long sequences of this type are required for the appearance of these bands. Changes in the absorption band at 997 cm-1 show that chains consisting of over ten isotactically connected monomer units can assume a helical conformation. From the high-resolution NMR spectra of different polypropylenes, including isotactic polymers of low molecular weight, it is found that in estimating the microstructure, account must be taken of the effects of stereoisomerism within tetrads of monomer units on the apparent widths of the methylene proton resonances. If substantial concentrations of several of the possible types of tetrads are present (i.e., if the tactic sequence lengths are quite short), then it is difficult to determine the relative amounts of tactic dyads accurately from the 100 Mcps methylene proton resonances.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1033-1057 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of double melting, as manifested by two characteristic endotherms in the melting region on a differential thermal analysis (DTA) scan, has been studied in nylon 66 and polystyrene as a function of sample treatment by annealing or drawing. A variety of techniques were used in these studies including DTA, x-ray diffraction, electron microscopy, and mechanical testing. It is shown that the two endotherms are not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phase changes. It is proposed that one endotherm is caused by the melting of foldedchain crystals, while the other is due to the melting of less perfect bundle crystals. This view is well supported by the results, especially by the DTA measurements made at different heating rates. Published data on the thermal behavior of annealed and drawn poly(ethylene terephthalate) and on polyethylene crystallized at various pressures may also be explained on this basis if it is allowed that in polyethylene the chains may be more extended.
    Additional Material: 15 Ill.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1745-1754 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield-stress behavior of two glassy polymers is studied through the glass transition region over a wide range of strain rates. For temperatures below the glass transition temperature, the yield stress behavior could be described as a non-Newtonian flow in agreement with Eyring's theory, if one excepts a narrow range relating to the slowest strain rates. For temperatures above Tg, the yield-stress behavior is still nonlinear but fits the relations based on the concept of free volume.
    Additional Material: 5 Ill.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1811-1818 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A “dual sorption” model has been proposed by Michaels, Vieth, et al. to explain extensive equilibrium sorption data for several gases in some glassy polymers. To explain data on sorption kinetics, it was further postulated that one of the sorption modes immobilizes the gas molecules. Stated mathematically, this model leads to a modified form of Fick's second law. Both normal and desorption time lags for diffusion have been computed here for this model of diffusion in glassy polymers. The computed time lags are shown to be dependent on the boundary concentrations used in permeation. Experimental measurement of these time lags would be a sensitive and critical test to ascertain the validity of this theory.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1863-1882 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methyl methacrylate) tensile bars were prepared containing nearly spherical polytetrafluoroethylene particles in concentrations from one to a thousand particles per gauge length of the bars. Particle diameters varied from 0.0035 to 0.018 in. Exhaustive tensile tests were performed at sufficiently high strain rate to assure brittle fracture and the results analyzed statistically by the theory of extreme values as proposed by Epstein. The results suggested that the polytetrafluoroethylene particles themselves did not act as flaws, but that they intensified the stress field on natural flaws which acted as the origin of fracture. Assuming a Laplace distribution as the underlying distribution of tensile strength (not to be confused with observed distribution of tensile strengths) gave predicted fracture statistics in good agreement with experiment.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1937-1954 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The distribution of molecular weights in realistic free-radical polymerizations with branching was analyzed theoretically. Series solutions were obtained for the fraction of molecules with r repeating units and the number of branch points contained in molecules with r repeating units. Branching by transfer processes was found to increase the proportion of both high and low molecular weight components in the system. The apportioning of branch points among r-mer molecules was shown to be somewhat narrower than a Poisson distribution. The major difference between the calculated distributions and previous model distributions for branched systems was the absence of discontinuities in the moments at all levels of branching.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1983-1986 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2005-2018 
    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 structural theory of macromolecular networks is formulated and discussed in general terms. The conditions required for a system to become a homogeneous macromolecular network are defined and discussed. Networks are divided according to the nature of their junctions into three classes: energetic (with chemical or quasi-chemical crosslinks), topological (with entangled chains), and contact (with frictional interactions). The main features of these three classes are discussed. A distribution density function ψ describing the configurations of macromolecules in network systems is introduced. The phase space of variables is 4(N + 1)-dimensional and includes the coordinates of (N + 1) vectors hi joining the adjacent network junctions and (N + 1) contour lengths li of the network chains. The system of simultaneous equations required for the determination of the function ψ includes the equation of continuity, kinematic equations for the deformation velocity of the individual junctions, the force balance equation needed for the determination of sliding rates li, kinetic equations for the processes of junction breakage and reformation, and the equilibrium distribution of network junctions defining the initial conditions for the distribution function ψ.
    Additional Material: 7 Ill.
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