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  • Industrial Chemistry  (386)
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  • 1985-1989  (56)
  • 1970-1974  (830)
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  • 1
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A pilot wet scrubber was examined experimentally. It is constructed like a plate column. Its plates are designed to set the gas into a whirling motion with tangential velocities of up to 25 m/s and to ensure a uniform distribution of the liquid throughout the gas flow. Particles suspended in the waste gas are collected by gas-atomized droplets to yield cut diameters between one and two microns. Energy consumption is lower than in the case of other scrubbers. The scrubbing mechanisms are analyzed by examining the measured pressure drops. Finally, methods of determining the collection efficiency are discussed and an empirical approach to its calculation is presented.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 139-148 
    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 suitability of any item of equipment for a given thermal separation process cannot always be judged solely in the light of efficient and loading range data. In vacuum rectification, involving a large number of theoretical stages, the vapour pressure drop per transfer unit exerts a considerable effect on the energy consumption and thus largely governs the choice of column fittings. Furthermore, the pressure drop per transfer unit determines the temperature at the bottom of a rectification column and, hence, the suitability of the equipment for the separation of heat-sensitive products. It is also an important criterion for compressor requirements in absorption processes. Another factor of considerable importance in separating heat-sensitive mixtures by distillation is the time during which the product, particularly the liquid phase, is exposed to a given temperature in the column. Therefore, a standardized liquid residence time has been adopted to evaluate the systems in their entirely. This residence time depends on the hydrodynamic conditions in the column and is thus closely related to pressure drop and efficiency. Further important factors, which may decide the selection of column internals, are the specific volume and mass of the column. Based on theoretical considerations, a flow model is derived for describing the main loading range of countercurrent packed columns; the relationships between the above mentioned parameters are presented.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 156-162 
    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 report is presented on the influence of liquid flow rate, NaOH concentration, column length and presence of 5 × 10-3 wt-% of the surfactant SLS on the rate of absorption of pure SO2 by aqueous NaOH solution in a sphere-and-cylinder column. The presence of sodium lauryl sulphate (SLS) prevented axial turbulence which increased mass transfer in longer columns and was almost independent of the flow rate. The enhancement factor due to the reaction between SO2 and NaOH with respect to the process of physical absorption was analyzed for the systems with excess OH- in the outflow. The results obtained in the presence of a surfactant are satisfactorily explained by film theory with a single reaction plane model. Those obtained in the absence of surfactant are best described by a two-plane model using renewal theory.
    Additional Material: 9 Ill.
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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: Experimental investigation of stirring processes require the measurement of temperature changes and concentration profiles in all the zones of the mixing volume. The conversion of simultaneous chemical reactions during the mixing process depends on the local temperature and concentration. The time-dependent temperature and concentration fields can be recorded for the entire mixing volume with the use of optical tomography and correlated with time. This technique offers the possibility of continuous measurement of temperature and concentration changes during the mixing process throughout the measurement volume. In the described investigations, optical tomography is used to examine the transport and equalization processes during mixing in stirred vessels.
    Additional Material: 14 Ill.
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  • 5
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical modelling of heat transfer to particle beds comprises two sequential steps: transfer from the heating surface to contacting particles followed by transfer to the interior of the bed. Two different limiting case can be formulated for the second step: unmixed and homogeneously mixed bed. In the case, heat is transferred gradually via a repeated sequence of heat transfer in the gap between adjacent particles and conduction in the particulate material. In the second case, heat is transferred to the interior of the bed by mixing of particles which have previously attained the temperature of the heating surface. On the other hand, the mixing motion maintains a homogeneous lower temperature throughout the bed. Theory predicts a significant and easily measurable difference in the behaviour of heat transfer coefficients for the two regimes at long contact times t: unmixed beds ∝ \documentclass{article}\pagestyle{empty}\begin{document}$$ \sqrt t $$\end{document} and homogeneously mixed beds ∝ 1/t. For short times t, both regimes show the same behaviour, namely of t.From a theoretical standpoint, it makes sense to differentiate further between the behaviour patterns of unmixed beds: at long times t, instantaneous heat transfer coefficients are independent of heat transfer form the heating surface to adjacent particles. Comparison with experimental result from literature shows that the derived models, which are consistent, are suitable for describing the heat transfer from submerged surfaces to unmixed and mixed beds of particles.
    Additional Material: 24 Ill.
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  • 6
    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 aim of the present paper is the discussion of the relevance of power dissipation as a criterion for the understanding and prediction of transfer and mixing efficiencies in contactors and chemical reactors. After reviewing the approach of Le Goff to the energetic efficiency of exchangers, based on the deviations from Chilton-Colburn analogy, the following processes are studied: mass transfer between a flowing fluid and a reactive solid surface, transfer to a fixed object in a stirred vessel, macro- and micromixing of miscible fluids, and mass transfer in fluid-fluid contractors (especially gas-liquid reactors). It is concluded from the various examples that a direct relationship between the dissipated power and intensity of transfer or mixing can be established only under the two following conditions: local values must be considered at the point where the actual transfer and mixing occur, and not average values over the whole device, and power dissipation must be coupled to transfer or mixing and appear physically as the driving force of the process.
    Additional Material: 10 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 402-407 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Increasing demand for regenerable processes with SO2 recovery is to be expected. Advantages and limitations of the earlier developed citrate and adipate absorption/ steam stripping process are compared with those of the Wellman-Lord (sulphite) process. On the basis of comprehensive laboratory studies, a new process is proposed which supplements the citrate and adipate process. In this new process, the absorbent is a concentrated sodium phosphate buffer and the loaded buffer is regenerated by evaporation. The main buffer component is Na2HPO4, but NaH2PO4 is added in order to obtain a more complete stripping of SO2 during regeneration. The new process promises excellent absorption properties for SO2 with extremely low oxidation losses, regeneration with few incrustation problems and appreciable energy savings.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988) 
    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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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 11-17 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Design and operation of a circulating fluidized bed requires the knowledge of fluid mechanics. According to heat and mass transfer as well as chemical reactions, the effect of the set superficial gas velocity on the axial pressure profile is of particular interest. The axial pressure profile was measured for a variety of solids, as a function of the superficial gas velocity, in a cylindrical circulating fluidized bed with an inner diameter of 0.19 m and an overall height of 11.5 m. Depending on the solids content and superficial gas velocity, two or one sections can be observed in the plant where the pressure gradient is constant. A pressure profile with one pressure gradient exists only at high gas velocities, so long as the acceleration pressure drop immediately above the gas distributor is negligible. Comparison of measured pressure drops in circulating fluidized beds with those measured in vertical pneumatic conveying led to a state diagram for vertical gas-solid flows. The operation behaviour of different types of circulating fluidized bed plants can be explained with the aid of this diagram.
    Additional Material: 9 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 17-25 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Crossflow microfiltration (CMF) is a pressure driven membrane process for the separation of suspended microparticles, bacteria and emulsion droplets. The fluid to be filtered flows in parallel to the membrane surface and restricts the formation of a filter cake. This contribution explains the basic process characteristics and the combination of the crossflow technique with other membrane cleaning methods (periodic backflushing, chemical cleaning). Special attention is paid to the influence of different process parameters on the flux through the membrane. The principle of plant design and different operation modes are described. Engineering aspects such as hydrodynamics, energy requirement and selection of construction materials are discussed in some detail.
    Additional Material: 10 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 25-31 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: While two- and multiphase flows find more and more application in chemical engineering practice, and the demand for theoretical information about mass and heat transfer processes in such systems is increasing, such data or at least experimental results which could be generalized are still lacking. The following pages are concerned with mass transfer in laminar suspension tube flows normal to the main direction of flow due to the individual motions of small, inert spherical particles. On the basis of a large number of experimental data, an interpretation is attempted of the role of nearly neutrally-buoyant particles in mass transfer enhancement, and a model for a semi-empirical description is suggested. The experimental arrangement uses the mass transfer of carbon dioxide in laminar flow of salt water during the process of gas permeation through a permeable membrane tube wall.
    Additional Material: 10 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 1-10 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Interfacial areas and gas hold-ups were determined at pressures of up to 1.7 MPa in a glass vessel, 88 mm in diameter and of standard geometry. Superficial gas velocities between 0.25 and 2.0 cm/s were used and the stirring speed varied between 4 and 30 rps. The interfacial areas were determined by the chemical method, using the model reaction between CO2 and aqueous diethanolamine (DEA). Hold-ups were determined by observation of differences in height. In contrast to literature indications, the gas hold-up was found to be independent of reactor pressure. This is also true for the interfacial area.
    Additional Material: 12 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 243-248 
    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 propane/argon mixture in the presence of trace quantities (0.1% and 0.9%) of ethane was investigated at reflected shock wave temperatures between 1200 and 2000K. Traces of ethane accelerated propane decomposition at high temperature. However, increase in the quantity of ethane added to propane/argon mixture did not result in the same increase of its accelerating influence. Ethylene, methane and acetylene were the main hydrocarbon reaction products, with small quantities of propylene and ethane detected only at lower temperatures. Below 1500K, addition of ethane slightly enhanced the yields of ethylene and methane at the expense of propylene and ethane respectively. The selectivity for acetylene increased with increasing temperature and with the decline of those for the other products. For none of the products, did the presence of ethane alter the relationship between product formation rates and temperature. The influence of ethane addition on propane pyrolysis at high temperatures was explained in terms of increased radical concentrations, especially hydrogen atoms and vinyl radicals, formed at high conversions. These accounted for the rapid acceleration of propane decomposition and the high yield of acetylene at high temperatures.
    Additional Material: 6 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 312-320 
    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 methods of measuring the mass transfer in centrifugal extractors and of determining it during the individual life stages of a fluid element of the dispersed liquid, i.e. drop formation, motion, coalescence and stay in the stationary layer of the dispersed phase. The experimental mass transfer coefficients of the dispersed and continuous phases are compared with well-known theoretical models developed for extraction columns in gravitational field. Due to the fast motion and coalescence of the fluid particles at high centrifugal field intensities, mass transfer in centrifugal extractors takes place during short contact times. Nevertheless, this contribution shows that mass transfer in a centrifugal field can be calculated with selected theoretical models of the gravitational field. The investigations on mass transfer are completed by a classification of the strongly deformed fluid particles in centrifugal field into regimes of circulating and oscillating drops. In addition, data on the performance of centrifugal extractors, undergoing several exchange steps, are given.
    Additional Material: 13 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 392-402 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of heterogeneously catalyzed methacrylic acid synthesis from isobutyric acid has been investigated. Initial catalyst screening pointed to 10-molybdo-2-vanado-phosphoric acid and its Cs-salts as the most promising catalysts. A model describing the reaction behaviour of all the different hetropoly-compounds used in this work was developed. A relationship was found between model parameters and composition of different catalysts. First insight was gained into the catalyst deactivation phenomena. Deactivation appears to be caused mainly by loss of molybdenum with simultaneous collapse of the Keggin structure.
    Additional Material: 18 Ill.
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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: Transient diffusion of inert gases into Zeolon 900 H, a zeolite of the mordenite type, was studied by the chromatographic method. Experiments were performed with argon and helium either as tracer or as carrier gas. The diffusion of argon was also studied in a carrier gas containing methanol at a low temperature (75°C, no reaction) and at higher temperatures (up to 130°C) when some dehydration of methanol to dimethyl ether takes place. The adsorption isotherm of argon is linear. In the absence of methanol, its penetration into microcrystals of zeolite is equally well represented either by an effective diffusion coefficient D′μ = 7.4 × 10-8exp(-2873/T)m2s-1 or by a mass transfer coefficient at the crystallite surface keμ = 1.9 × 10-4 exp(-1324/T) ms-1. A small amount of methanol in the carrier gas considerably slows down the transfer of argon (by a factor of 40 for D′μ and 550 for keμ) showing the “blocking” effect of adsorbed methanol. In addition, transient adsorption can no longer be accounted for by a single transfer time. The size distribution of microcrystals, determined from Scanning Electron Microscope photographs leads to a Transfer Time Distribution which account well for experimental breakthrough curves without any parameter fitting. This interpretation is supported by experiments under reaction conditions where transport of argon within crystallites increases faster with temperature than in the absence of reaction due to the transformation of methanol into dimethyl ether, which is less adsorbed and thus provides lesser hindrance to argon diffusion.
    Additional Material: 8 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: Fischer-Tropsch catalysts (Fe/V oxides with ZnO and K2CO3 as promoters) were exposed to CHCl3, thereby producing surface and bulk chlorides. The effect of this exposure on activity and selectivity was studied in a continuous recycle reactor at a total pressure of 10 bar (CO/H2 in most experiments: ca 1:1) in a temperature range between 200 and 343°C. CHCl3 was introduced in amounts of up to 1 × 10-2 mol chlorine per g catalyst. The catalyst samples were characterized by internal surface area, pore-size distribution and adsorption capacities for CO, H2 and C2H4. Prior to synthesis, the catalysts were reduced by H2. Catalyst exposure to CHCl3 resulted in a decrease of activity and considerable changes in product distribution. Hydrogenation and isomerization of 1-olefins were partly suppressed; the chain length of the products was slightly increased. Deactivation of the catalysts due to chlorine addition was partly reversible during operation, while olefin formation was not significantly altered with time-on-stream. The effect of chlorine on activity and selectivity is explained by dissociation of CO as the chain initiating step and CO insertion into a carbon/metal bond as a possible chain propagation step. Since adsorption capacity for H2 decreases on the addition of chlorine, this may also contribute to lower activity and change in selectivity, compared to the unexposed catalyst.
    Additional Material: 7 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 50-56 
    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 performance characteristic of a packed bed reactor has been analyzed by considering diffusional resistance of the biofilm. Model equations were solved by the method of orthogonal collocation for various classical enzyme inhibition kinetics, including partially non-competitive, partially competitive, partially uncompetitive, partially mixed and fully mixed. For all considered modes of inhibition, an increase in the inlet substrate concentration decreases the steady state conversion in the reactor. However, an increase in the Peclet number has been found to improve the conversion. The effects of various other process variables of physical importance were also investigated parametrically.
    Additional Material: 15 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 63-72 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Asymptotes are known to be useful, but their potential in interpreting and correlating chemical and physical behaviour is seldom exploited fully. The derivation and selection of asymptotes for particular as well as limiting cases is described. The evaluation of the range of validity and applicability, if any, of asymptotes is also considered. Asymptotes are shown to be uniquely useful in the identification of groupings of variables which minimize parameteric variations, as upper and lower bounds, as trial functions in the method of weighted residuals, and most especially as components of correlating equations.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 57-62 
    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 single variable pole-placement self-tuning controller (PPSTC) is used to simulate examples typical of chemical processes; i.e., open-loop stable, unstable, and unstable non-minimum phase systems with unknown varying process dead time. The PPSTC is shown to be effective in each case. Set-point tracking and rejection of randomly occurring deterministic disturbances for all three types of processes are achieved. Simultaneous estimation of process parameters and process time delay is realized by using a recursive extended least squares method.
    Additional Material: 10 Ill.
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  • 21
    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 important parameter influencing the crystal size distribution in mass crystallization from solution is the mechanical stress exerted on crystals in the crystallizer. This contribution presents the study of the influence of mechanical stress and attrition of the system potassium nitrate-water in an FC-crystallizer and in various draft-tube crystallizers, fitted with different types of impellers. The intensity of stress is a newly defined variable which is used to describe the level of stress in crystallizers. The reduction of crystal size by attrition is described by the linear attrition rate. The influence of impeller design and crystal hold-up on crystal size distribution and scale-up rules is discussed.
    Additional Material: 16 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 80-88 
    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 mean crystal size of coarse crystalline products is determined by secondary nucleation and crystal growth. Secondary unclei are mainly produced by contacts of crystals with parts of the crystallizer or with other crystals. As a consequence, attrition effects are very important. In this paper, a model is proposed in order to calculate the attrition rate of crystals, depending on the physical properties of the crystalline product, the geometry of the crystallizer and on the operating conditions such as the stirrer speed or the suspension density. The effective rate of secondary nucleation can be expressed in terms of the attrition rate by introducing effective values for number and size of attrition particles. Finally, a scale-up criterion based on this model is derived. This criterion allows to predict effective rates of secondary nucleation and mean crystal sizes if data obtained in a laboratory crystallizer are available.
    Additional Material: 11 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 95-104 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Settling characteristics of four different suspensions were measured by batch settling tests (glass spheres in glycerol-water mixtures and CaCO3) and by continuous settling test in a bench-scale vertical flow tank (activated sludge and kaolin in water), including the measurement of solids concentrations inside the tank. The characteristics could be described by different correlation functions which now include all the information about the settling behaviour of ideal suspensions. Continuous settling experiments in a bench-scale vertical flow tank were carried out with the same four material systems. These results correspond with sufficient accuracy to those from the theory of limiting flux if the settling characteristics determined earlier are considered.
    Additional Material: 15 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 113-119 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Thermal deactivation can be described either by deactivation kinetics or by the isokinetic effect. The latter expression is used synonymously with the “compensation effect” and the “Theta-Rule”. An examination of the original literature shows that only the compensation effect is applicable to thermal deactivation but not the Theta-Rule. The introduction of the preparation temperature as a parameter of the compensation effect results in a “modified Theta-Rule”, which describes the experimental data and is proposed for the non-separable kinetics. The consequence of the observed deviations from the validity range of the Theta-Rule is that the activation energy cannot be used as a universal activity criterion.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 89-94 
    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 number of topped crude oil residues were subjected to mild thermal cracking in the temperature range between 613 and 673K at N2 pressure of one atmosphere. It was found that the thermal stability of the six topped crude oils decreased in the order Brent 〈 Piper 〈 Auk 〈 Saudi Arabian 〈 Romashkinskaya 〈 Tia Juana Pesado. This was measured in terms of light end production (C1-C5 hydrocarbons). The asphaltene, sulphur and metal (nickel and vanadium) contents were also determined. The production of light ends, exemplified by methane, was found to be related to the metal asphaltene content of the crude oils, but the sulphur content exerted a moderating influence upon the extent of cracking. Hence, metal asphaltenes, probably as metal porphyrins, catalyse cracking but the presence of sulphur reduces that catalytic activity and can inhibit cracking. If cracking of long chain hydrocarbons is to be minimized, metal asphaltenes should be removed (preferably) or reduced in concentration or poisoned, in order to decrease their catalytic activity.
    Additional Material: 5 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 120-126 
    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 kinetics of non-catalytic as well as catalytic oxidation of Isobutyraldehyde has been investigated. Reaction rate equations for the formation of the main product isobutyric acid and of the side products acetone, CO and CO2 were derived. Kinetic parameters, namely the order of reaction, preexponential factor and activation energy were estimated by non-linear regression. The influence of selectivity and activity of the different type of catalysts employed was investigated quantitatively.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 228-236 
    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 interpretation of the term “compensation” obscures a logical contradiction, the catalytic paradox, which is caused by inconsistent validity ranges of the Arrhenius parameters, the pre-exponential factor and the activation energy. For this reason, a theory which contains the Arrhenius parameters cannot be established for the entire system (whole temperature range) on the basis of classical logic. Only the subsystems can be consistent and complete. One subsystem is the range of the topocatalytic concept which is relevant for thermal deactivation, thermal bistability and for all reactions with surface dependence of activity. The other is the range of the energetic concept which is preferred in fundamental research. In order to complete the subsystems, new consistent symbols are introduced. The change of particle size caused by thermal deactivation can result in four possible particle size effects, two of which have been discussed in the literature.
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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: Thermal radiation of gas/solid mixtures in high-temperature heat exchangers is of considerable importance for the design of heat exchange surfaces. Therefore, an experimental plant was constructed to measure solid particle emissivities, since there is a lack of relevant data in the existing literature. A theoretical equation was derived to describe the solid particle emissivity as a function of layer thickness, specific solid surface area, solid loading and absorption and scatter coefficients. Measurements were carried out for fluidized bed ash and quartz sand. The emissivities of these particle fractions increase with increasing layer thickness, slid loading, specific solid surface area and temperature. The description of these data by the derived model equation is very satisfactory. No dependence on wavelength was observed. The ash components do exert some influence which, for the present, cannot be described exactly.
    Additional Material: 14 Ill.
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  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 213-227 
    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 report is presented on the performance of modern dumped and structured packings for application in the field of thermal separation processes. The evaluation of the results is based on extensive experimental investigations of rectification, absorption, and desorption systems. The following are indicated: the efficiency in terms of the number of theoretical stages per unit height or in terms of the height of transfer unit or volumetric mass transfer coefficient, the pressure drop per unit height as well as per theoretical stage or per gas phase transfer unit, and the liquid hold-up, whereby either the gas capacity factor or the liquid load was adopted as influencing parameter, and finally the maximum gas capacity factor as a function of the flow parameter. The results are presented in diagrams and tables.
    Additional Material: 25 Ill.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 249-251 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is shown that the volumetric mass transfer coefficients, presented recently by Schmitz et al. [1] for viscous solutions of carboxymethyl cellulose (CMC) in aqueous sodium sulphite, are considerably underestimated as a result of unjustified neglect of the oxygen back pressure during oxygen absorption. Schmitz et. al. [1] found a decrease in the exponent n in the relationship between the oxygen mass transfer coefficient, kla, and the power dissipated per unit volume of the liquid phase, e (kla ∝ en), and ascribed it to viscosity effects. However, no such decrease is observed, provided that the actual oxygen back pressure is taken into account.
    Additional Material: 2 Ill.
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  • 31
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: NOx emissions from different commercial gas burners for metal heat treatment applications were measured for a research project of the Gaswärme-Institut. The burners, rated at up to 50 kW, were installed for the tests in a laboratory combustion chamber operated at temperatures of up to 1400°C. The air for combustion was preheated to maximum temperature of 600°C. Following the tests, the potentials of different NOx control techniques were investigated. Methods explored included staged combustion air injection, staged fuel injection and fuel gas injection into the flue for NOx reduction. The results showed that it is feasible to reduce the NOx content of flue gases by as much as 90%.
    Additional Material: 16 Ill.
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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: In the description of mixing processes influenced by viscosity in pseudoplastic (power-law) fluids, a definition of representative viscosity is normally used which takes into account the variable flow behaviour of the stirred material as a result of different shear stresses. In this context, the Metzner and Otto concept, which postulates that a representative shear rate is proportional to stirring speed, has become widely know, although the power calculation is inaccurate, particularly in the transient regime between the laminar and turbulent flow. A new model of fluid dynamics in the mixing vessel is presented, based on the increase of the mean flow velocity standardized with the stirrer's tip velocity in the transition regime. It provides a physical explanation for the above deviations. A suitable definition of representative viscosity substantially improves the accuracy of calculations of the stirring power in power-law fluids.
    Additional Material: 9 Ill.
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  • 33
    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 increasing demand for products from mammalian cells has prompted the authors to develop a new type of bioreactor. Its significant features include the supply of oxygen, homogeneous distribution of microcarrier suspensions and process control. Media with high protein contents, required for mammalian cell cultures tend to generate foam. This causes the flotation of solid particles. The reactor was equipped with a system of porous hydrophobic Accurel hollow fibre membranes in order to prevent the formation of bubbles. The membrane is coiled in the form of a basket, or fixed on several carriers. If the liquid pressure is higher than that of the gas phase inside the membrane, a bubble - free oxygen supply to the culture broth can be achieved. The problem of axial mixing of microcarier suspensions was solved by the use of a spiral agitator, attached underneath the aeration system at the bottom of the reactor. The combined aeration and mixing system, which is driven by an eccentric motor, undergoes a tumbling motion. Sufficiently homogeneous suspensions are produced in this system at low membrane velocities, i.e. in presence of low shear forces.
    Additional Material: 14 Ill.
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  • 34
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 195-199 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aqueous ethylenediamine-ethanol-anthraquinone (EDA-EtOH-AQ) pulping of Southern Yellow Pine was studied for lignin removal and pulp yield. Temperature, time and ethylenediamine concentration in the solvent solution were studied and equations for lignin content and lignin-free yield were developed. Lignin content is decreased by an increase of temperature, time or EDA concentration. Lignin-free yield of pulp decreased with an increase in temperature or time, but increased with increasing EDA concentration. Overall, the solvent is selective, that is, large quantities of lignin are removed while the retention of cellulose remains high.
    Additional Material: 2 Ill.
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  • 35
    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 investigation was undertaken in order to examine the factors affecting mechanical damage to micro-organisms in stirred bioreactors. Growth of the mould Rhizopus nigricans was studied in stirred bioreactors at different geometrical and operating parameters. Since experimental results cannot be described by conventional key parameters, a new concept has been suggested. It is based on the analogy to processes of mechanical disintegration. It is shown that the same key parameter, i.e. the ratio of power input to flow rate, can be used for a satisfactory correlation of experimental data on mechanical damage to micro-organisms, which is an important step in the recovery of intracellular products in biotechnology.
    Additional Material: 19 Ill.
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  • 36
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 199-205 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is shown how a consistent scale-up rule for the power consumption in agitated non-Newtonian liquids can be obtained. The new approach is based on the concept of including the real liquid in a set of liquids with similar rheological properties and of using, in a small scale laboratory system, a suitable member of that set instead of the original liquid. Considerations of similarity lead to simple unique selection rules for the actual test liquid and for the stirrer speed in the laboratory experiment as well as to a prediction of the power requirement in the real system. The theory is tested experimentally by means of different aqueous polyacrylamide solutions. The results are compared with predictions, according to Metzner and Otto as well as Rieger and Novák.
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  • 37
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 205-212 
    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 on the bubble column have been reported by Japanese researchers since around 1960. They include studies of bubble behaviour, bubble size distribution, transition from the homogeneous bubbly flow regime to the heterogeneous liquid circulation regime, liquid velocity distribution, longitudinal liquid mixing, hydrodynamic modelling, the gas holdup, and the volumetric coefficient of gas-liquid mass tranfer kLa. Studies covered various modified bubble columns, such as the airlift reactor with an external or internal loop, the packed bubble column, and others. Performance of three-phase bubble columns, which deal with suspensions or emulsions, and their use as bioreactors or chemical reactors were also studied.
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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: A control concept which includes an adaptive multivariable control algorithm and an observer model has been put into practice in the operation of a distillation column which separates water from a solvent. The model yields predictions of solvent concentration in the waste water which forms the top product. Early detection of disturbances permits an adjustment of the process in time. This has resulted in an exceptionally smooth operation of the column, with a drastic reduction in solvent concentration fluctuations, observed with conventional control technology. Since the only measurements required are pressure, temperature and the rate of flow, this control system is largely free from disturbances. In addition to considerably reducing the burden on operating personnel, use of this control system has lowered the costs of waste water treatment, solvent losses, analysis expenditure and energy consumption.
    Additional Material: 15 Ill.
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  • 39
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), 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: The alternative effects of reaction kinetics, mass, heat and momentum transport on mass conversion by chemical reactions are examined theoretically for a reacot tube with laminar flow. The reaction enthalpy is considered. A heterogeneous reaction between several gaseous components takes place at the inner surface of this reactor tube. Strongly exothermic reactions lead to self-acceleration of the reaction, unless reaction enthalpy is removed through the tube wall. Under certain conditions, there will be a sudden change from mass transfer controlled by the reaction to that controlled by diffusion. This phenomenon is known as ignition of the reaction. The effect of ignition and its sensitivity to reaction enthalpy, thermal conductivity and diffusivity of the fluid as well as activation energy of the first order heterogeneous wall reaction are investigated by a numerical solution of the transport equations. Axial conduction of heat and mass is neglected both in the fluid and in the tube wall. Non-stoichiometric wall reactions of first order, with temperature dependent reaction rates and equilibrium constants, are considered. The results are presented in graphical form, as plots of the local mass flux at the reacting wall as functions of the dimensionless tube length.
    Additional Material: 7 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: Precipitation is a rapid solidification. As a rule, it applies to substances which are sparingly soluble and is coupled with a chemical reaction or with a salting out process. The chemical engineer has to ensure that the product obtained has a constant and preferably coarse size distribution. This contribution compares the literature data on crystallization of soluble and sparingly soluble substances; it can be shown that, during precipitation processes, nuclei are formed, most probably by a primary mechanism. Analysis of the processes occurring during precipitation, such as chemical reaction, mixing and crystallization, leads to recommendations for the operation of precipitation processes.
    Additional Material: 18 Ill.
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  • 41
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 259-263 
    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 deterioration of mass transfer efficiency of an extraction column with increasing column diameter is the result of developing residence time distributions. These effects can be described by one-dimensional dispersion model. However, it must be verified whether the requirements for its application are fulfilled in the different types of agitated extraction columns. For the columns for which the dispersion model can be applied, a relationship will be derived between the necessary increase of column height with column diameter. This is based on the equations for calculation of the dispersion coefficient of the continuous phase. If the dispersion model cannot be applied to given a type of column, an investigation will be made on the possible modifications of operation or changes in construction, in order to permit a scale-up procedures as proposed here.
    Additional Material: 7 Ill.
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  • 42
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model of the dynamic behaviour of non-isothermal fixed-bed adsorbers has been developed which takes into account the various mass and heat transfer resistances. Comparison of experimental and simulated results confirms that the model can predict the adsorption and desorption breakthrough curves of an adiabatically operated column, using only equilibrium data and tortuosity factors obtained from single pellet experiments. A simplified model with a reduced number of parameters was derived by investigation of the dimensionless transfer parameters under industrial conditions. It becomes evident that the main transfer mechanisms are convective heat and mass transfer in the bulk flow and diffusion within the pores of the particle. Dimensionless effluent concentration is expresses in terms of dimensionless time, a transport parameter, a non-isothermal parameter, the adsorption equilibrium and the inlet and initial concentrations and temperatures in the simplified model. For a chosen system of adsorbate and adsorbent, design charts can be developed by computer simulation, to determine graphically the breakthrough time as a function of significant process parameters, i.e. the dimensionless transfer parameter and the feed concentration.
    Additional Material: 8 Ill.
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  • 43
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 298-305 
    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 bench scale flue gas desulphurization spray dry scrubbing unit was employed to study the effect of fly ash on the removal of SO2. The equipment consisted of a spray dryer with and ultrasonic nozzle for atomization and a pulse jet baghouse. The flue gas rate was 1500 lN/h (dry gas). Four fly ashes, originating from different countries were investigated. The alkalinity and reactivity of the fly ashes were determined in a pH-stat equipment. Pure fly ash removed SO2 in both the spray dryer and in the baghouse. An increase of humidity divided the fly ashes into two groups. The high calcium fly ash gave a considerably higher SO2 removal than the medium and low calcium fly ashes which showed similar SO2 removals. Fly ash did not enhance the removal of SO2 when added to a lime slurry because lime suppresses the dissolution of the alkali in the fly ashes. The pressure drop build-up in the fabric filter showed a strong dependence on material properties.
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  • 44
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 320-327 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Detailed knowledge of the physical phenomena involved in subcooled boiling is of great importance for the design of liquid-cooled heat generating systems with high heat fluxes. Experimental heat transfer data were obtained for forced convective boiling of dichloro-difluoroethane (R 12). The flow is circulated upwards through a concentric annular vertical channel. The inner and outer diameters of the annulus are 0.016 m and 0.03 m respectively. The reduced pressures studied were 0.24 ≤ p/pcrit ≤ 0.8, inlet subcooling varied from 10 to 75 K and mass fluxes from 500 to 3000 kg/m2s, which corresponds to Re numbers from 30000 to 300000. The experiments, described in this study, demonstrate that liquid fluorocarbons show certain unusual boiling characteristics in the subcooled flow, such as hysteresis of the boiling curve. These characteristics are attributed to the properties of the fluid, mainly the Pr number and the very low surface tension. The pronounced boiling curve hysteresis can be explained by the fact that large nucleation sites may have been flooded prior to incipient boiling. A dimensionless regression formula is presented which predicts the onset of subcooled boiling as a function of reduced pressure (p/pcrit), Boiling-(Bo), Reynolds-(Re), and a modified Jacob number (Ja), over the whole range of parameters studied, with a good accuracy, including water data from literature.
    Additional Material: 14 Ill.
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  • 45
    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 special type of jet loop reactor (JLR), designed for continuous operation and short residence times was investigated with regard to its mass transfer behaviour, described by the volumetric mass transfer coefficient kLa. The jet stream and superficial gas velocities are varied in two JLRs of different sizes, equipped with different nozzles. Fully desalinated water, 0.08 molar NaCI solution and solutions of different concentration of carboxymethyl cellulose (CMC) are used as the liquid phase. A steady-state physical method is employed to determine kLa: air oxygen is purged from the liquid phase by gaseous nitrogen. The measurements show that the reactor is characterized by high power density and high mass transfer performance. No limit of mass transfer capacity was observed in the chosen ranges of volumetric gas and liquid flow rates, i.e. at a given jet stream velocity, the relationship between kLa and the superficial gas velocity is nearly linear. The investigations show that the mass transfer contributed by the jet stream largely depends on liquid phase composition.
    Additional Material: 11 Ill.
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  • 46
    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 order to investigate the suspension behaviour of solid particles in bubble columns without and with draft tube, minimum gas velocities for generating and maintaining complete solid suspension were determined. Experiments were carried out in a bubble column with a diameter of 200 mm and a height of 2 500 mm. The bubble column could be equipped with a draft tube with a diameter of 120 mm and a length of 1 500 mm. The state of suspension was determined by measuring the hydrostatic pressure as a result of suspended solid particles with an inductive pressure gauge. Solid content εs, solid density ϱs, particle size dp, particle shape, particle size distribution, and solid wettability were varied. Furthermore measurements of integral gas holdup were carried out.
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  • 47
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 327-334 
    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 model is presented which consists of steady-state and transient codes for the description of reacting multiphase flow fields, including hydrodynamic fragmentation of liquid drops in relative flows. An application of this model for the description of large scale melt-coolant interactions (thermal detonations) is described. A simulation of two-phase chemical detonations, especially those with hydrodynamic disintegration of liquid fuel drops in the reaction zone, is possible, in principle, within the framework of the modeling.
    Additional Material: 7 Ill.
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  • 48
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adsorptive separation of oxygen from nitrogen and argon is carried out during the desorption steps of a pressure swing adsorption (PSA) process which uses carbon molecular sieves developed by Bergbau-Forschung GmbH. The adsorption isotherms of the three main components of air are very similar. On account of the pore size distribution of CMSN2, the diffusion coefficient of oxygen is more than eight times those of nitrogen and argon so that air separation occurs by adsorption kinetics. Experimental results for the individual steps and cyclic operation of the PSA process are presented and compared with the predictions of an isothermal plug-flow model. Adsorption rate is represented by a linear driving force equation. If the diffusion coefficients are adapted separately to every step, a good agreement is observed between the model calculations and experimental results.
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  • 49
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 359-365 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One of the most important tasks to eliminate dangers in chemical plants is the prevention of corrosion. This implies the provision of safe enclosures and reaction spaces for the substances to be processed. The present contribution deals with the procedure in the selection of materials for equipment exposed to corrosion and stresses the difficulties connected with the elimination of local corrosion. The relevance of prevention of crack forming corrosion processes is emphasized. Problems to be solved in order to obtain results from investigations, suitable for a safe application of a materials under practical conditions, are indicated.
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  • 50
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 352-358 
    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 adsorption solvent recovery process, known as Recursorb which involves desorption and cooling steps by a circulated inert gas, is analyzed in detail on the basis of equilibrium theory. Employing the method of characteristics, the model is solved for each step of the overall process. The estimations confirm that the process performance with respect to final gas purity, activated carbon useful capacity and operation times depends on condenser and heater temperatures. Simple expressions are derived for the calculation of adsorption, desorption and cooling times.
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  • 51
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 367-375 
    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 mathematical model for the description of the non-steady state process of decoking of a fixed bed catalytic reactor is presented. The relevant dimensionless groups are identified and their influence on the process discussed. Appropriate relationships are given for the estimation of the maximum temperature in the bed. Methods of monitoring the process and of controlling it in the case of unknown or variable coke contents are explained.
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  • 52
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The new model discrimination method is based on the correlation coefficient test of experimental data sets for different reactions, without requiring a prior parameter estimation. The new parameter estimation method reduces by n the number of dimensions to be tested, compared to the classical method where n is the number of independent reactions in the system. This has reduced the computation time for most complex reactions to a level, comparable to that needed for single reactions. The example used is the kinetic study of methanol synthesis in which the formation rates of methanol, methane, ethanol and ethane are considered. Two adequately accurate models were obtained from an extensive range of plausible models by using the new model discrimination and parameter estimation method with a relatively small computation effort.
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  • 53
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 11 (1988), S. 384-391 
    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 were carried out with the ternary mixture 2-propanol/water/glycerol. In a cylindrical vessel, the stirred and thermostated liquid was exposed to a preheated and either dry or humidified air stream. The mixture was evaporated either from a free surface or from the surface of a porous plate. On evaporating the mixture from a porous plate into a dry air stream, the less volatile component water escapes preferentially; in the case of evaporation from a free surface, water is retained in the mixture. In the former case, selectivity is liquid diffusion controlled, in the latter, the gas-side mass transfer and the thermodynamic equilibrium are the controlling mechanisms. On reducing the gas flow rate, the more volatile alcohol evaporates preferentially in both cases; the selectivity is controlled only by thermodynamic equilibrium. Humidification of the air stream with water vapour causes preferential evaporation of the alcohol at an increased rate. Furthermore, instabilities in the liquid boundary layer due to density gradients and surface tension effects may affect the selectivity of evaporation. Experimental results show that the selectivity of evaporation can be manipulated by choosing appropriate evaporation conditions. The theory, which applies the generalized Stefan-Maxwell equations to diffusion in the liquid, can describe these effects.
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  • 54
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    Chemical Engineering & Technology - CET 11 (1988), S. 425-431 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To our benefit, the modelling of fluid-solid catalyzed reaction-reactor systems has long been the keen concern of Hanns Paul Hofmann. In the light of his instruction we remark upon key aspects of modelling for the (a) fixed bed (b) fluid bed and (c) moving bed/transport line reactors. There emerges from such analyses a properly renewed awareness of the need for a more sophisticated respect for reliable physical-chemical data. As Hanns has taught us, our models are no btter than our data.
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  • 55
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two-phase flow in porous media depends on many factors, such as displacement vs steady two-phase flow, saturation, wettability conditions, wetting fluid vs non-wetting fluid is displacing, the capillary number, interfacial tension, viscosity ratio, pressure gradient, uniformly wetted vs mixed-wet pore surface, uniform vs distributed pore throats, small vs large pores, well-connected pores vs pores connected by small throats, etc. These parameters determine how the two fluids are distributed in the pores, e.g. whether they flow in seperate channels or side-by-side in the same channels, either with both fluids being continous or only one fluid being continous and the other discontinuous. In displacement, the capillary number and the viscosity ratio determine whether the displacement front is sharp, or if there is either capillary or viscous fingering.
    Additional Material: 19 Ill.
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  • 56
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gas-solid reactions cover a wide spectrum of industrial products. Over the years, many conceptual models have been developed to describe the progress of a gas-solid reaction starting outside the solid particle as well as that occurring throughout the particle. But the behaviour of a reaction, initiated inside the pellet, is less known. In this paper, a brief outline is given of this relatively rare but important mode of gas-solid reaction. The causes of this relatively less known behaviour and characteristic features of five typical systems displaying it are discussed.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 85-114 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the small-angle scattering power and the degree of crystallinity in melt-crystallized high-density polyethylene have been used to evaluate the “amorphous” density in situ by the relation, \documentclass{article}\pagestyle{empty}\begin{document}$ (2\pi/V)\int_0^\infty {S\tilde g} (S)dS = (\rho_{\rm c} - \rho_{\rm a})^2 \upsilon_{{\rm er}} (1 - \upsilon_{{\rm er}}) $\end{document} where V is the irradiated volume and ḡ(S) is the “slit-smeared” absolute intensity. The amorphous density is a function of sample history and is always higher than the extrapolated melt density. After slit-height correction, and within the experimental error, the ratio of the two observed long periods is 2:1 at all temperatures (25--126°C). The lamellar thickness and the average interlamellar spacing are obtained from the degree of crystallinity and the first corrected long period. At increasing temperatures between 25°C and 110°C, the lamellae become thinner while the interlamellar zone expands by almost half. Over this range the changes are reversible with temperature. Above 110°C, both the lamellae and the interlamellar region expand with temperature. The thickening is partially reversible upon recooling. Other results obtained include measurements of stacking disorder and of microstructural changes with crystallization temperature and with time at ambient temperature.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 143-160 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Work on two sheet organosilicon polymers, one derived from the mineral chrysotile and the other from the mineral apophyllite, is described. This work provides direct evidence that both these polymers are composed of sheets. In addition, it shows that in the chrysotile-derived polymer the sheets curl into scrolls, and that in the apophyllite-derived polymer the sheets are essentially flat.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 209-243 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shear creep and creep recovery behavior of narrow molecular weight distribution polystyrene samples of low molecular weight, 1.1 × 103, 3.4 × 103, and 1.57 × 104 are reported as a function of temperature, near and above the glass temperature. Time-temperature equivalence for the total creep compliance is found to be nonapplicable, and in fact the steady-state recoverable compliance, Je, is a strong function of temperature. The time-scale shift factors for the recoverable compliance are analyzed in the light of free volume theory. Viscosity data are presented for samples with molecular weights between 1.1 × 103 and 6.0 × 105. The temperature dependence of the characteristic time constant ηJe can be explained in terms of free volume concepts whereas that of viscosity η cannot. Effects of residual molecular weight heterogeneity are demonstrated.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 295-311 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical calculation of the Hv light-scattering patterns for deformed three-dimensional spherulites is presented. Affine deformation is assumed. The optic axis of the scattering element is allowed to lie at an arbitrary angle ß to the radius which is permitted to change in the course of the deformation in a manner that may depend upon the angular location in the spherulite. The consequences of twisting of the optic axis about the spherulite radius are also explored.
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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 331-343 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of polydimethylsiloxane polymers from solution on glass has been studied. The amount of polymer adsorbed depends markedly on the solvent because of specific solvent - surface interactions. The presence of silanol groups in the polymer, particularly as endgroups, markedly increases the amount of polymer adsorbed. Large differences are shown between the adsorption of the commercially available, and fully trimethylsilylated polydimethylsiloxanes of narrow molecular weight distribut on. Possible adsorption mechanisms are discussed.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 383-384 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 421-430 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is given for the analysis of long-chain branching in polymers by using combined GPC and intrinsic viscosity measurements. A computer program was written to evaluate branching indices by a tabular, iterative method. The method was applied to the evaluation of long-chain branching in low-density polyethylene.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 431-435 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of stereoregularity on the low-temperature relaxation processes were studied by dynamic mechanical measurements on isotactic and syndiotactic polyisobutyl methacrylates (iso-PiBMA and syn-PiBMA). The α, β, and γ relaxation processes were observed in both stereoregular forms. Both the α, and β loss peaks were at lower temperatures for iso-PiBMA than for syn-PiBMA. The γ loss peak was observed at about -155°C at 30 Hz for both forms, and the apparent activation energy of this process was same for both samples within experimental error (6.7 ± 0.5 kcal/mole). It was reduced from these results that the α and β processes are both considerably influenced by the isotactic configuration but the γ process is not.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 15-26 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gelation reaction of acetoguanamine with formaldehyde was investigated in the light of the gelation theory for tetrafunctional amino resins described in the previous paper. The gel time and extents of reaction of formaldehyde, amino groups, and imino groups varied with the molar ratio in the feed, but values of K (the ratio of the rate constant for condensation to that for addition) and k (the ratio of the rate constant for addition of the imino group to that of the amino group) were nearly constant. When the catalyst concentration was increased, the gel time, extents of reaction of each functional group, and the values of K and k varied; in particular K increased markedly. From the results of varying the molar ratio and concentration of acidic catalyst, it was found that the number of methylol groups per molecule of acetoguanamine at the gel point was influenced by the reaction conditions but the number of methylene linkages per molecular of acetoguanamine was nearly constant at about 0.6, regardless of reaction conditions. The number-average molecular weights up to the gel point varied with the reaction conditions, but at the gel point they were all nearly constant at about 385.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 543-555 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photocurrents developed in polyethylene in the wavelength range 360-180 nm have been measured. The action spectra show features which can be related to the corresponding features in the absorption spectrum, and in addition there is electron injection from the metal electrode at a wavelength determined by the electrode material. The time dependence of the response indicates that a long-lived space charge is formed in the material.
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 569-576 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Large photocurrents have been observed in films of some simple polymers (containing no π-orbitals), of which poly(vinyl fluoride) is a typical example. Not only are the currents large (up to 10-5 A/cm2) but also they are capable of being excited by light in the visible wavelength region where absorption by the polymer is too low to be detectable. The results indicate that the effects are electronic, rather than ionic, in nature.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 577-584 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It was previously shown that for a stationary random copolymer of A, B, and C, we have in general p(AB) + p(AC) = p(BA) + p(CA), etc., in place of p(AB) = p(BA) which is valid for a stationary binary copolymer. Here, p(AB) for example, is the probability that a randomly picked pair of consecutive comonomers in the polymer consists of an A followed by a B. For a stationary ternary copolymer produced by a first-order Markovian addition mechanism, we show that PABPBCPCA/PACPCBPBA = k, where k is a constant characteristic of a particular set of three monomers but independent of its composition. Here, PAB is the conditional probability of finding a monomer of B given that its immediate predecessor is an A. We further show that if the individual rate constants of the monomer additions involved take a special form such as used in the Alfrey-Price Q-e scheme, then we have k = 1 irrespective of the kinds of monomers, and in addition we have p(AB) = p(BA), p(AC) = p(CA), etc. Thus, although these latter results were previously proposed by Ham as an alternative basis to supplant the Q-e scheme, they may rather be regarded as mathematical consequences of special assumptions adopted for the form of the individual rate constants. For a stationary random copolymer of four components A, B, C, and D, we have p(AB) + p(AC) + p(AD) = p(BA) + p(CA) + p(DA), etc., in general. For a first-order Markovian four-component copolymer, we show that there are seven different combinations of the conditional probabilities that are constants (k1, k2,…, k1) independent of the monomer composition. Again, if we assume the same special form for the rate constants involved, we find that all the seven constants k1, k2, …, k7 reduce to unity and p(XY) = p(YX) for X,Y, = A, B, C, D.
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 717-729 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several copolymers as well as homopolymers of vinylidene chloride and vinyl chloride have been examined by Raman spectroscopy. Probabilities of concentrations of monomer sequences have been calculated from known reactivity ratios. Surface scattering intensities at some frequencies were found to be linearly proportional to specific microstructure concentrations. Normalization of scattering intensities was accomplished using the intensity of the CH2 asymmetric stretching mode at 2926 cm-1, which is common to all samples examined. Good correlation was found for the concentrations of comonomer sequences {B}, {BB}, {BBB}, {AA} and {AAAA} in which A denotes vinylidene chloride and B vinyl chloride.
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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 755-758 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mass flux entering the Fick's diffusion equation is considered as an arbitrary analytical function of concentration, concentration gradient, and of the gradient of concentration gradient. The restrictions imposed on the flux by the principle of material objectivity are stated and briefly discussed.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 759-762 
    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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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1287-1303 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelasticity and volume expansion of the raw polymerizate of ethylene-propylene copolymer with vinyl chloride grafts, and of the individual components has been studied. The raw polymerizate (composite) and the pure ethylene-propylene-vinyl chloride graft copolymer were found to consist of two phases. The pure graft copolymer has an ethylene-propylene matrix containing some fraction of poly(vinyl chloride) (PVC) grafts and a microphase with the remainder of the PVC grafts. The raw polymerizate consists of a PVC matrix plasticized with ethylene-propylene chains and a microphase of the ethylene-propylene copolymer. An attempt has been made to calculate the participation of components in microphases and the minimum dimension of the PVC microphase aggregates.
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1333-1339 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lattice-theory equations for the surface tension of polymer solutions based on the parallel-layer model have been extended to include more than two components. The surface tensions of tetrachloroethylene solutions of some blended polydimethylsiloxane fluids have been measured at room temperature. The results are in nearly quantitative agreement with the theoretical calculations.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1371-1378 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new relaxation process, explaining the change of elasticity in rubberlike polymers at critical stress (0.1-0.5 kgf/cm2) has been discovered. This process is characterized by the low value of activation energy (weak temperature dependence of relaxation times) and large sizes of kinetic units (strong dependence of relaxation time on stress). Critical stress depend on temperature and for rubberlike polymers turns to zero at 40°-60°C. Mechanism of the phenomena can be explained by the existence of the ordered molecular microregions, creating additional crosslinking points of nonchemical nature with free chains of the network, breaking up at critical stress. Observed phenomena is analogous to the process of forced rubber elasticity of those polymers in glassy state. Critical stress is analogous to the limit of forced rubber elasticity below glass transition temperature.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1449-1469 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-line NMR spectra have been obtained on an oriented sample of drawn nylon 66 fibers at temperatures between -196°C and 200°C and at alignment angles between the fiber axis and the magnetic field of 0°, 45°, and 90°. At -196°C, 20°C, and 180°C, the complete angle dependence of the NMR spectrum has been measured. The second moments of these spectra have been compared to theoretical second moments calculated for various models of chain segmental motion in an attempt to elucidate the mechanisms involved in the low-temperature segmental motion (γ process) and the high-temperature segmental motion (αc process). In agreement with earlier suggestions, the present results indicate that the γ process consists of segmental motion in noncrystalline regions. The overall decrease in second moment caused by the γ process is consistent with a model in which all noncrystalline segments rotate around axes nearly fixed in space. Furthermore, this decrease shows a pronounced dependence on the alignment angle. It is believed that this is due to tie molecules which become highly oriented along the fiber axis during drawing; their axes of rotation will therefore be nearly parallel to the fiber axis. The segments in noncrystalline entities such as chain folds and chain ends are less well oriented along the fiber axis and make an essentially isotropic contribution to the second moment decrease. The second moment at 180°C indicates the presence of considerable motion in the crystalline regions, and this motion is denoted the αc process. The second moment Sc of the crystalline regions is strongly dependent on the alignment angle, the predominant feature being a relatively high value of the second moment when the fiber axis is directed parallel to the magnetic field. This is in qualitative, but not quantitative, agreement with the motional model recently advanced by McMahon, which assumes full rotation of the chains around their axes. Excellent quantitative agreement with experiment has been obtained by superimposition of rotational oscillation around the chain axis of amplitude roughtly 50°, and torsion of the chains with neighboring CH2 groups oscillating around the C—C bond with a relative amplitude of about 40°. A model in which the chains perform rotational jumps of 60° between two equilibrium sites has also been considered (60° flip-flop motion). A distinction between this model and rotational oscillation has not been possible.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1525-1529 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 6 Ill.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1553-1577 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As is well known, the chemical potentials of polymer and solvent in solution and, hence, the Flory-Huggins interaction parameter χ can be determined from scattered light intensities from dilute and concentrated solutions of the polymer in the solvent concerned. Preferably, measurements should be performed at temperatures as low as possible, provided the temperature exceeds the cloudpoint for the concentration used. It is shown that the lower the temperature and, consequently the higher the scattered light intensity, the better is the accuracy of the parameters obtained. At each temperature the scattered light intensity shows a maximum at some concentration. Below the theta temperature the ratio of scattered light intensity and concentrations also shows a maximum at some concentration. The values and the concentrations of these maxima for various temperatures enable the maximum of the spinodal to be determined. The spinodal itself can be determined by an extrapolation procedure of the reciprocal scattered light intensities. Measurements have been performed with three narrow-distribution polystyrene samples in cyclohexane. On the basis of the results, χ, and its dependence on concentration, temperature, and molecular weight can be determined to high accuracy.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1641-1655 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of high-density polyethylene crystallized under simultaneous pressure and shear in an Instron capillary viscometer has been examined by scanning electron microscopy, electron microscopy, and selected-area electron diffraction. Two distinct fibrous morphologies were observed in these unusually transparent strands. The outer sheath was composed of fibers, 3000 Å in diameter, aligned parallel to the extrusion direction and apparently interconnected by a lamellar cross texture. A highly crystalline ribbon texture composed of fine fibers, 200-250 Å in diameter, dominated the inner core. Sharp-spot electron diffraction patterns obtained from these central ribbons indicated a high degree of c-axis orientation parallel to the fibers and an extended-chain crystal structure. The melting behavior of both irradiated and unirradiated strands examined by differential scanning calorimetry was consistent with the formation of two distinct crystalline morphological units.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1681-1691 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the nature of exchangeable cations on the tacticity of poly(methyl methacrylate) (PMMA) prepared from montmorillonite-MMA adsorption complexes was investigated. The strength of ion-dipole interactions was estimated either by the value of the electrostatic interaction potential or by the value of the carbonyl-stretching frequency shift. It was shown that Pi, the percentage of isotactic triads in the polymer, increases with increasing strength of the ion-dipole interactions, while the persistence ratio and the mean length of closed isotactic (or syndiotactic) sequences remain essentially unchanged regardless of the nature of the cation. It was shown that values of Pi may vary from 0.15 for weakly interacting ions to 0.5 for strongly interacting ones, reaching at the upper limit the value calculated from the model proposed in a previous paper, thus confirming its validity.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1693-1702 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential thermal analysis (DTA) of some commercial nylons has disclosed some anomalous phenomena with respect to the glass transition, generally considered to occur at 40-50°C. On the first heat cycle the transition occurs normally. On cooling, however, no corresponding transition occurs, and on an immediate rerun the transition has disappeared. If another DTA thermogram is made after a few hours, the transition begins to reappear, but at a temperature lower by a few degrees. After about five days rest, the transition is again normal in size and temperature. On annealing at 75°C, the 43°C transition is pushed up to about 92°C. On resting after annealing, transitions appear at both 40 and 92°C. These phenomena are explained in terms of the slow formation of a hydrogen-bonded network in the amorphous regions of the polymer. It is the disruption of this network that is normally considered to be the glass transition in nylons. The network is slow in re-forming because of problems involved in matching up potential hydrogen-bonding sites, which are, of course, distributed at intervals along the polymer chain. The temperature at which the network is disrupted is apparently dependent not so much on the ratio of bonding to nonbonding sites, as on the temperature at which it was formed.
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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1793-1805 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Detailed critical examinations of three aspects of nitric acid treatment of polyethylene are reported. (1) The endgroups introduced by the nitric acid are examined. It is concluded that in samples degraded to a single-crystal traverse stage, carboxyl features only as endgroup, and conversely each chain-end is terminated by such a group. Consequently, the carboxyl content can be used for quantitative characterization of the cut chain length. The function and position of the nitro group remains unexplained. (2) The morphological selectivity of the nitric acid-induced degradation is scrutinized. It is concluded that the crystal core is attacked and thinned by the acid; the slowing down of the reaction is principally due to accumulation of reaction products. Accordingly, the usual distinction between a vulnerable amorphous layer and a resistant crystal core is not justified on the basis of such degradation experiments. It follows that meaningful structural information is obtained only when the relevant crystal properties are studied as a function of chain cutting, assessed from the molecular weight distribution (GPC), as opposed to that of degradation time alone. (3) The role of sample consistency and reagent strength has been examined. It is demonstrated that for the reaction to be sufficiently uniform throughout the sample for the results to be meaningful, the reaction rate has to be slow compared to the rate at which the reagent diffuses into the specimen. To realize these conditions, finely dispersed samples and weak reagents were found to be favorable
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1871-1885 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several samples of a copolymer were examined by means of equilibrium centrifugation in a density gradient. The results for the samples without compositional distribution (homogeneous polymers) were used to determine the relation between the chemical composition and the distance from the center of rotation. For one of the homogeneous polymers a quantitative analysis of the schlieren curve was made in order to show the kind of accuracy that can be achieved. For the inhomogeneous polymer it was found that the schlieren curve could, in principle, be described quantitatively by the assumption that fluctuations in composition are independent of fluctuations in molecular weight, but on this basis the average square of the fluctuations in composition is more than four times smaller than the value derived from chromatographic data. A more satisfactory explanation of the experimental results is provided by assuming a linear correlation between average molecular weight and composition, but it is not claimed that this is necessarily the only model that explains the data.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1887-1905 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Time-dependent, apparent heat capacities of glucose, poly(vinyl chloride), polystyrene, selenium, poly(methyl methacrylate), and poly(2,6-dimethyl-1,4-phenylene ether) in the glass transition region were determined by differential thermal analysis. The thermal history was set by linear cooling at rates between 0.007 and 160°C/min. Linear heating for analysis was carried out at rates between 0.3 and 600°C/min. Average activation energies of 52, 81, 90, 54, 77, and 108 kcal/mole, respectively, were evaluated by using the hole theory of glasses previously developed. Within experimental limitations all data could be described quantitatively by the theoretical expressions using only one parameter, the number of frozen-in holes, to described the thermal history. Experimental and theoretical limitations are discussed.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1915-1918 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 85
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical development interrelating the orientation distribution functions of three kinds of orientation units for a polymer spherulite (i.e., a crystal lamella, a crystallite, and a given reciprocal lattice vector of the crystallite) is formulated on the basis of series expansions of the distribution functions in generalized spherical harmonies. Two types of uniaxial deformation models of a polyethylene spherulite, taking account of micronecking and untwisting of crystal lamellae, and of chain tilting and untwisting of crystal lamellae, respectively, both in addition to affine deformation of the lamellae are discussed. The models are tested by comparison of the theoretical orientation distribution functions of some reciprocal lattice vectors of the crystallite with the results of x-ray diffraction experiments.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 2033-2042 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-line NMR spectra of nylon 66 fibers have been obtained at different alignment angles between the fiber axis and the magnetic field, at varying water contents (H2O and D2O), and at different temperatures. At 28°C the spectrum of the dry fibers consists of a nearly structureless broad line. At water regains of 1.4% by weight (dry basis) and higher a sharp line appears which originates from highly mobile water molecules. The width of this line decreases with increasing water content, implying an increase of water mobility. Moreover, the width is a function of the alignment angle; this shows that the water is not reorienting isotropically owing to specific water-polymer interaction. The amount of mobile water is always smaller than the amount of water absorbed. At water contents close to saturation, a mobile polymer line appears with a width intermediate between the broad line (immobile polymer) and the sharp water line. This line, most clearly observed at an alignment angle of 0°, is due to a shift of the αa process to lower temperatures in the presence of water. A similar line is observed in the dry fibers at 120°C. It is shown that the αa process decreases the NMR second moment only slightly. The shift of the high temperature drop in second moment to lower temperatures in the presence of water is therefore interpreted as due to a shift of the αc process, and not of the αa process, to lower temperatures.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 2099-2103 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 2119-2130 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general theory of non-Gaussian elasticity is presented for real polymeric chains having fixed bond angles and restricted internal rotations. The theory contains the displacement-vector distribution given by Nagai, and the Flory-Wall-Hermans procedure is used for the calculation of network properties. Whereas the treatment is valid for all types of polymer chains, it is not totally satisfactory from a practical standpoint because of a slow series convergence if the chains are stiff. It is best utilized for flexible polymers under conditions of light crosslinking. Detailed network behavior is investigated only for polyethylene type chains having uncorrelated internal rotations. In this instance the fractional contribution fe/f of the internal energy of the total force f is found to be a function of elongation at high degress of stretching. It may decrease, or increase, depending upon the sign of fe/f at low elongations. Furthermore, the variation of fe/f with elongation is independent of the fixed bond angle of the chain backbone. Stress-strain behavior and energy-strain behavior are in opposition, i.e., when the non-Gaussian contribution to the stress is greatest, it is the least for the ratio fe/f, and vice versa. The presence of correlated internal rotations would not be expected to greatly alter these general conclusions.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 2247-2251 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 90
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two linear polyethylene fractions (Mη, 11,260 and 100,000) and mixtures of these fractions have been isothermally crystallized from the melt under pressures up to 3000 atm. Characterization of individually crystallized fractions with transmission electron microscopy indicates that pressure can be used to produce a crystallite whose thickness is a measure of the chain length within it. Although the high molecular weight fraction yields spherulites containing individually varying lamellae thicknesses, the maximum thickness of each lamella is a measure of the chain length within it. Both electron micrographs and differential thermal analysis results show that crystallization of homogeneous mixtures of the high and low molecular weight fractions under high pressure results in a distinct fractionation and segregation according to molecular weight.
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  • 91
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is described and a computer program outlined whereby gel-permeation chromatographic analysis of fractions from gradient-elution fractionation of branched polyethylenes provides a complete molecular weight evaluation of each fraction and the parent resin. The procedure involves the use of the universal calibration concept of Benoit et al. in a way that eliminates the ambiguities present in attempts to apply it directly to whole polymers. The resultant molecular weight data for fractions, when related to their solution viscosity and low-shear melt viscosity and to their infrared analysis, provides a total structural evaluation of a branched polyethylene resin, including molecular weight molecular weight distribution and the distribution of both long-and short-chain branching. The potential of this method for providing a comprehensive structural evaluation of branched polyethylene is illustrated by examples of its application in the analysis of some commercial resins.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 2255-2258 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 27-42 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A three-dimensional polarized infrared technique was used to obtain information about molecular orientation in both uniaxially and biaxially drawn nylon 6 films. The 835 and 930 cm-1 bands were used to describe the orientation of the A (extended chain) conformation while absorptions at 1175 cm-1, and 1120 cm-1 and 1075 cm-1 were used to give some information about orientation of the B (twisted chain) conformation. On the basis of the 835 and 930 cm-1 bands, it was shown that the hydrogen-bonded sheets made up of chains in the A conformation are parallel to the film surface in the biaxially drawn film. Uniaxially drawn films obtained by drawing both at 100 and 150°C showed a high degree of chain alignment in the draw direction for the A conformation at draw ratios greater than 2.5. Some planar orientation was also observed in these uniaxially drawn films for both the A and B conformations at high draw ratios.
    Additional Material: 11 Ill.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 59-66 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystals of poly-trans-1,4-butadiene of uniform size have been grown from three solvents (n-heptane, methyl isobutyl ketone, and toluene) by using a minimum dissolution temeprature technique. The percentage of double bonds available for reaction in the crystals was determined by epoxidation in suspension; crystal thicknesses were measured by electron microscopy. These values were used to calculate the number of monomer units per fold. The number of available double bonds was found to increase with decreasing molecular weight, evidence for the presence of non-reentrant chains (cilia) at the crystal surfaces. The nature of the chain fold in poly-trans-1,4-butadiene crystals is discussed.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 161-173 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new device for measuring the electrostriction constant of polymer films is described. Observed values for various polymers except poly(vinylidene fluoride) and poly(methyl methacrylate) agree well with those calculated from the Clausius-Mosotti equation. Elongational piezoelectricity, the pyroelectric current, and the electrostriction constant are measured for undrawn and roll-drawn poly(vinylidene fluoride) films. The piezoelectricity and pyroelectric current are attributed to space charges antisymmetrically distributed along thickness direction of the film for two reasons: (1) the polarity coincides between these two phenomena for all specimens, and (2) the piezoelectricity and the electrostriction constant have the same anisotropy for drawn films. Similarity of signs between piezoelectricity and pyroelectric current is observed also in poly(vinyl chloride) films. The electrical behavior of poly(vinylidene fluoride) is interpreted in terms of the ferroelectric nature of the β-form crystal.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 181-186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A γ-phase to α-phase transformation in a specimen of isotactic polypropylene crystallized under conditions of high pressure was induced by drawing at 100°C. X-ray studies showed that the unoriented component remained in the γ-phase, and that the oriented component was found only in the α-phase. This evidence supports a previous suggestion that the phase transformation is martensitic in character. The consequences of such an assumption are discussed. The role of dislocations in polymeric systems is generally believed to be not too significant, but since martensitic reactions involve cooperative movements of atoms, an exception in this case is suggested. A possible mechanism for the phase transformation is suggested.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1603-1627 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition and relaxation phenomena in 26 structurally related polyquinoxalines and other aromatic polymers were studied over a temperature range from 70 to 770°K by means of calorimetric, dilatometric, dynamic mechanical, and dielectric techniques. Differential thermal analysis and x-ray data showed these polymers to be essentially amorphous. The lack of crystallinity is attributed to geometric isomerism, resulting in conformational as well as configurational disorder. Calorimetric measurements gave discontinuities in heat capacities ranging from 12 to 54 cal/°C per mole of repeat-unit structures and provided unambiguous assignments of glass transition temperatures of these polymers. Depending upon structure, Tg varied from 489 to 668°K. Thermal expansion curves of annealed bulk polymer samples between 70 and 770°K exhibited only one discontinuity over the entire temperature range, namely at Tg, thus indicating the absence of any motion leading to transitions in the solid state of these polymers. Viscoelastic properties were obtained by means of torsional braid analysis and a longitudinal vibrational apparatus. In a typical case, the dynamic mechanical relaxation spectrum contained three loss maxima. A peak of low amplitude occurring at 483°K was attributed to impurity effects, resulting from endgroups and species of low molecular weight. The second and only major relaxation process occurred at 579°K, in the glass transition interval. A third, weak loss peak of unknown origin was found in the liquid state at 683°K. On the other hand, the dielectric loss curves of various polymers exhibited only one broad and strong absorption maximum at temperatures 30 to 100°K higher (depending upon a particular polymer) than equivalent major mechanical loss peaks. These differences are interpreted from a mechanistic point of view. Major mechanical relaxations occurring in the glass transition interval of these polymers are proposed to result from translational motions.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1669-1679 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fluorescence quenching of the doubly charged quinine cation by Fe++, Ag+, and Br- was studied in the presence and absence of polyvinylsulfonate (PVS). The quenching by cationic species was greatly enhanced by PVS at low polyion concentrations; at higher concentrations of PVS, the fluorescence intensity increased owing to displacement of the quinine cations from the polyion domain. Quenching of quinine fluorescence by Br- was repressed by PVS. Interpretation of the data with the use of Fe++ as the quenching agent led to “effective concentrations” of counterions in the polyion domain similar to those calculated from the catalysis of the redox reaction of Co(NH3)5Cl++ with Fe++. This may indicate that the reagent ions are not rigidly bound to the polyion chain, since such binding would affect differently processes with high and low activation energies. The Stern-Volmer constant for self-quenching of the quinine fluorescence can also be obtained from fluorescence intensity data in PVS solution.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1703-1717 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelastic properties of a 4% solution of monodisperse polystyrene (molecular weight 394,000) in Aroclor 1260 were determined by the following techniques: creep recovery, stress relaxation upon cessation of steady flow, dynamic measurements, and normal stress difference and shear stress measurements in steady flow. All measurements were carried out with cone and plate geometry in a Weissenberg rheogoniometer. The modification of this instrument to perform creep and creep recovery experiments by use of an air-bearing suspension and an air-turbine drive is described. A broad range of shear rates and frequencies encompassing both linear and nonlinear behavior was employed. The elastic behavior is described in terms of the recoverable shear strain s or the steady-state compliance Je°. The first three techniques gave identical results for Je° in the range of linear viscoelasticity for which it is defined. The normal stress difference measurements confirmed Lodge's relation s = (P11 - P22)/2σ21. Reasons for previous experimental disagreement with this result are discussed.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1747-1761 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The contribution to the disorder scattering by imperfect spherulites resulting from fluctuations in the magnitude of the anisotropy is analyzed for two-dimensional spherulites. The fluctuations are described in terms of a parameter characterizing the meansquare amplitude of the fluctuation and a correlation function describing the distance over which the correlation occurs. Cases considered are those where the correlation depends on either the radial or the angular separation of the scattering volume elements. As with the case of disorder in orientation, one finds that disorder in anisotropy may result in a nonzero value of intensity at μ = 0° and 90°, a decrease in the higher-order variation of scattered intensity with θ, and an increase in the intensity of scattering at higher values of θ over that for a perfect spherulite. In addition, disorder in the angular direction leads to an increase in the scattered intensity at small values of θ as compared with the zero intensity of scattering from a perfect spherulite at θ = 0°.
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