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  • 1970-1974  (7,953)
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  • 1
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    Bulletin of mathematical biology 32 (1970), S. 1-24 
    ISSN: 1522-9602
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract The usual method of tracer analysis for calculating the flow across a biological membrance is based on the assumption that the compartments on either side are well-stirred. Thus, the validity of the rate of flow determination is questionable for cases where the distribution of tracer is not homogeneous. In this study, a mathematical model is developed for the purpose of estimating the effect of slow mixing on the calculation of the flow rate. The model is applied to the measurement of the rate of flow of aqueous humor through the living eye by use of a fluorescent dye as a tracer. A transit time of several minutes for the passage of fluorescein through the posterior chamber and an extended period of nonuniform distribution of fluorescein in the anterior chamber was observed. The effect of slow mixing on the calculated flow rate is compared to rates derived from equations based on the assumption of rapid mixing. Aqueous flow rates determined by the two methods were found to agree to within ≈20%.
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  • 2
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    Bulletin of mathematical biology 32 (1970), S. 25-43 
    ISSN: 1522-9602
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    Notes: Abstract This paper presents a three-parameter model of the mechanism of dispersion of an indicator in the cardio-pulmonary system, based on the postulates that this dispersion can be described by the one-dimensional diffusion equation and that dispersion continues past the sampling site. The model is tested using indicator dilution curves obtained from dogs, and the coefficient of diffusion is thus measured. It is found that this coefficient increases in magnitude non-linearly with increasing blood speed.
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    Bulletin of mathematical biology 32 (1970), S. 45-58 
    ISSN: 1522-9602
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    Notes: Abstract Based on the ellipsoid model of the left ventricle and the helicoidal course of the left ventricular myocardial fibers, a theory has been developed for calculating the length of the individual myocardial fibers. Numerical solutions of the final equation show that when the left ventricle is distended, the increase in length of the myocardial fibers is not uniform throughout the thickness of the myocardial wall. It was shown that with increasing dimensions of the left ventricle, the distension of the myocardial fibers becomes smaller as one advances from the endocardium to the middle layer of fibers, whereas it increases as one advances from the middle layer to the epicardial layer. The mechanism by which this effect is brought about as well as its physiological implications are discussed.
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    Bulletin of mathematical biology 32 (1970), S. 59-63 
    ISSN: 1522-9602
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    Topics: Biology , Mathematics
    Notes: Abstract In an open circuit gas washout determination the output of test substance is shown to be of the form ∑ i=0 ∞ A i λ i k on thekth expiration whereA i 〉0,i=1,2,... and 1 〉 λ1 ≥ λ2...≥ 0 provided the transition from inspiration to expiration has certain symmetry properties with the transition from expiration to inspiration. In general, no direct physical interpretation such as volume for theA t ’s or fraction of retained gas on expiration for the λ i is justified.
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  • 5
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    Bulletin of mathematical biology 32 (1970), S. 71-78 
    ISSN: 1522-9602
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    Topics: Biology , Mathematics
    Notes: Abstract Previous studies by this author of the mathematical biology of automobile driving have emphasized only the biological aspects, except for such mechanical factors as the size of the car. Otherwise, the ideal case of an inertialess car was considered. In this paper the first step is made toward introducing the effects of the mass of the car and the side-slip of the tires when the direction of driving is even slightly altered and combining these with the previously studied biological aspects. Some tentative comparisons with available data are made.
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    Bulletin of mathematical biology 32 (1970), S. 65-69 
    ISSN: 1522-9602
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    Topics: Biology , Mathematics
    Notes: Abstract According to the occupation theory of drug receptor interaction, the response is a functionf of the number of receptors occupied by drug molecules. Considerable controversy exists regarding assumptions about this function. Without knowledge of the nature of the function, it is not possible to determine directly the rate constants, and hence the affinity constant, in the reaction between the receptor and an agonist drug. Instead, indirect determinations involving the use of antagonists have been employed, limiting the determination of affinity to those agents for which specific antagonists exist. The present paper discusses a method for the direct determination of affinity of an agonist drug. It is a “relaxation method,” i.e., the equilibrium is perturbed and the kinetics of the restoration process are studied. Assuming only thatf is non-decreasing and approximately linear over a limited domain of concentrations, it is shown that the change in response obeys first order kinetics, permitting a determination of the rate constants from the time course of the restoration process.
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  • 7
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    Bulletin of mathematical biology 32 (1970), S. 79-81 
    ISSN: 1522-9602
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    Notes: Abstract The basic postulate la, which governs the development of organismic sets, introduced previously (Bulletin of Mathematical Biophysics,31, 159–198, 1969), is generalized so as to contain also the rates of changes of the number and variety of differentQ-relations which determine an organismic set. It is thus brought closer to the Lagrangian principle in physics. It is pointed out that the postulate also provides a criterion of stability of an organismic set.
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    Bulletin of mathematical biology 32 (1970), S. 155-172 
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    Notes: Abstract A method is presented in this paper for the in-vivo estimation of the nonlinear pressure-volume relationship of the human aorta. The method is based on nonlinear elastic reservoir theory and utilizes clinical data that can be obtained with a high degree of accuracy, namely stroke volume, end diastolic ventricular volume and aortic pressure trace data. The computational procedure is described and then carried out for six cardiac patients. A method for the estimation of instantaneous left ventricular volume during the ejection period based on the considered nonlinear elastic reservoir theory is also presented. The method is applied for the six cardiac patients cited and the results compared with those obtained for the same subjects by a method of estimation based on linear elastic reservoir theory described in a previous paper by the author (1969).
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    Bulletin of mathematical biology 32 (1970), S. 249-262 
    ISSN: 1522-9602
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    Topics: Biology , Mathematics
    Notes: Abstract Deakin (1967b) suggested that flow of blood might obey a law of minimal energy dissipation. The present paper presents a simpler derivation of Deakin’s equations pointing out several previously unrecognized features. It is shown that these equations are unlikely to be applicable. In particular, the solution obtained by Deakin and Jones (1968) does not yield a true minimum for energy dissipation. The solution for which energy dissipation is actually minimized is shown to possess features which render it unlikely to apply to a real flow.
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    Bulletin of mathematical biology 32 (1970), S. 237-247 
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    Notes: Abstract The Kedem-Katchalsky equation for the flow of a non-electrolyte through a homogeneous membrane is shown to be a first order expansion of an exact integral of the Spiegler-Bearman-Kirkwood frictional equations under the assumption that the partial frictional coefficients, ζ ij , are concentration independent. The equations are solved in terms of volume flow; there are no water-to-volume flow correction terms for the permeability, ω, or the reflection coefficient, σ. The precision of the expansion depends upon the magnitude of the water flow. The frictional coefficientsf sm andf sw are given as functions of the experimentally determined parameters ω and σ; the frictions, are shown to be independent ofL p .
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    Bulletin of mathematical biology 32 (1970), S. 459-473 
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    Notes: Abstract As was done by Sinclair and Ross (1969(, we consider a cellular population that consists initially (at time zero) ofN 0 newborn cells, all with the same volumev o. It is assumed that the occurrence of cell division is determined only by a cell’s age, and not by its volume. The frequency function of interdivision times, τ, is denoted byf(τ). If cell death is negligible, the expected number of cells,N(t), will increase according to the laws of a simple age-dependent branching process. The expression forN(t) is obtained as a sum over all generations; thevth term of this sum, in turn, is a multiple convolution integral, reflecting the life history ofvth generation cells (i.e., the lengths of thev successive interdivision periods plus the age of the cell at timet). Assuming that cell volume is a given function of cell age, e.g., linear or exponential, and that cellular volume is exactly halved at each division, it is possible to calculate the volume of a cell with a given life history, and thus the average cellular volume of the whole population as a function of time. If at time zero the volumes differ from cell to cell, the final equation must be modified by averaging over initial volumes. In the case of linear volume increase with age, a very simple asymptotic expression is found for the average cellular volume ast→∞. The case of exponential volume increase with age also leads to a simple asymptotic formula, but the resulting volume distribution is unstable. The mean cellular volume at birth and the second moment of the volume distribution can be calculated in a similar manner.
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    Bulletin of mathematical biology 32 (1970), S. 499-520 
    ISSN: 1522-9602
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    Topics: Biology , Mathematics
    Notes: Abstract The dynamic response of human musculo-skeletal framework is treated by (i) idealization of the musculo-skeletal framework as hybrid structural networks possessing feedback characteristics and then (ii) employing linegraph-flowgraph procedures for the feedback characterization of the hybrid structural networks. Topological procedures are used in which a “tree” of a network furnishes the skeleton upon which the “linkage” (muscle representing) members provide interaction. Feedback characterization (representing the sensitivity of the skeletal members to the tensile forces) is defined, between the internal “linkage” and “tree” members, by means of the flowgraph. Mikusinski operational calculus is used to facilitate representation of inertia effects by dynamic feedback characterization, with inclusion of initial conditions.
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    Bulletin of mathematical biology 32 (1970), S. 539-561 
    ISSN: 1522-9602
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    Notes: Abstract The representation of biological systems in terms of organismic supercategories, introduced in previous papers (Bull. Math. Biophysics,30, 625–636;31, 59–70) is further discussed. To state more clearly this representation some new definitions are introduced. Also, some necessary changes in axiomatics are made. The conclusion is reached that any organismic supercategory has at least one superpushout, and this expresses the fact that biological systems are multistable. This way a connection between some results of Rashevsky’s theory of organismic sets and our results becomes obvious.
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    Bulletin of mathematical biology 32 (1970), S. 521-537 
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    Notes: Abstract The full implications of a statistical model for growth of a microbial cell population using cell mass as the index of physiological state have been examined by solving the partial differential integral equations resulting from the model. Calculations reveal that a lag phase is predicted during the initial stages of batch growth although no specific cellular mechanism for the phenomenon of lag had been incorporated into the model. The model predicts several situations of batch and continuous growth in which the population density and biomass concentration show opposing trends due to significant variation in the cell mass distribution with time.
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    Bulletin of mathematical biology 32 (1970), S. 83-148 
    ISSN: 1522-9602
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    Notes: Abstract Information treatment, especially in a natural medium, may be done by a random system: given an input, possible solutions are randomly selected and successively tested until the right one is found and then emitted. This paper is a mathematical study of this type of system and its use as a model of some natural (biological) systems. The theoretical development is illustrated by several examples of possible applications to biological cases. We study, under different assumptions, the distribution of the number of trials needed to treat the input, the distribution of the time for this treatment, and the distribution of the average amount of information treated in a trial or in a unit of time. We consider the case of error, and study some optimal conditions of operation and the occurrence of memory influencing the treatment of an input according to previously processed inputs.
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    Bulletin of mathematical biology 32 (1970), S. 151-153 
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    Bulletin of mathematical biology 32 (1970), S. 173-178 
    ISSN: 1522-9602
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    Notes: Abstract The role of some inertial properties of the car, studied previously only for the case when the stimulus for the corrective turn is the perception of the angle between the direction of the car and the direction of a straight lane (Bull. Math. Biophysics,32, 71–78, 1970), is generalized to include such stimuli as the nearness to the edge of the lane and the anticipatory effect for a corrective turn, as well as the combination of all three stimuli. Conditions for stability of driving are deduced and discussed. They now depend on both biological parameters and such parameters as the position of the center of gravity of the car, its mass, and the side slip of the tires.
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    Bulletin of mathematical biology 32 (1970), S. 179-195 
    ISSN: 1522-9602
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    Topics: Biology , Mathematics
    Description / Table of Contents: Résumé Pour le biologiste, la notion dedistance entre deux ou plusieurs éléments d’un ensemble est très utile car elle sert à mesurer laproximité, laparenté, laressemblance qui existe entre ces éléments ou parties selon le caractère auquel on s’intéresse (position géographique, situation chronologique, aptitudes, phénotypes, composition chimique etc...).
    Notes: Abstract Adistance between two mobiles performing a random walk in one dimension is defined. At a given time this distance is directly related to theprobability of encounter for the mobiles. This definition is used when the motion of the mobiles is a Wiener-Levy process, first in the case of an unrestricted random walk, then if a reflecting or absorbing barrier is introduced.
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    Bulletin of mathematical biology 32 (1970), S. 197-213 
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    Notes: Abstract The qualitative effects of anisotropy and nonhomogeneity are considered in the evaluation of left ventricular stresses in the intact heart. Maximum stresses and their location are significantly dependent on the nonhomogeneity factors and to a lesser degree on anisotropy of the ventricular wall material. If the circumferential elastic modulus is assumed to vary in a parabolic manner through the wall thickness, maximum stresses occur within the endocardial layers, a result in qualitative agreement with experimental studies.
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    Bulletin of mathematical biology 32 (1970), S. 215-218 
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    Notes: Abstract Under the assumption that there is complete mixing in the dead space a series of equations are given which give the values for a washout test of the functional component of the pulmonary bellows (without a dead space) in terms of the washout values of the bellows with a dead space.
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    Bulletin of mathematical biology 32 (1970), S. 219-235 
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    Notes: Abstract Expressions are derived for the overall oxygen consumption and the O2 penetration depth into a tissue section in terms of the basic parameters, of the system under steady-state conditions. The approach differs from many previous analyses in so far as the oxygen molecules are regarded as reaching their sites of chemical assimilation by diffusion through extracellular fluid followed by bulk diffusion into irregular cells of significantly lower permeability. This “two-phase” model would seem to be compatible with the major experimental features of steady-state respiration, and gives a ratio of cellular to extracellular diffusion coefficients of the same low order as that found for inert gases under transient conditions. The greater oxygen penetration predicted by this model is discussed in relation to the survival of ischemic tissue and is shown to be consistent with data for myocardial infarction.
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    Bulletin of mathematical biology 32 (1970), S. 263-278 
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    Notes: Abstract Two models for a kidney-ureter system are considered: one model of one vessel in which a traced substance, undergoing exchange between the vessel and an external compartment, is emptying into the ureter; the second model of two approximately parallel, identical vessels in which a traced substance, undergoing exchange between each vessel and an external compartment, is emptying into the ureter. A single impulsive input of label into a vessel is assumed. For mathematical simplicity, the major conditions imposed on each system are: (1) rapid mixing transverse to a vessel axis and no mixing longitudinal to a vessel axis within the plasma; (2) small variation of the specific activity within the plasma in the longitudinal direction to a vessel axis; (3) constant flow rate of urine into the ureter and (4) constant exchange coefficients, tubule flow velocity and traced substance concentrations within individual compartments.
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    Bulletin of mathematical biology 32 (1970), S. 279-291 
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    Notes: Abstract We use the concept of a layered wall, where each separate layer is to be homogeneous, isotropic, and incompressible, to derive stress-strain relations for the middle layer muscle ring at the transverse midsection of the left ventricle; a convenient method of formulation is that based on the elastic potential function. The hoop or circumferential stress in all three layers is found using dimensional and mechanical parameters derived earlier. The various parameters are expressed as Fourier series so that their behavior over a complete ventricular cycle is known analytically. The cases of simple elongation and what we termcurvilinear simple elongation are considered for the middle layer muscle ring strain, and the resulting stress-strain relations are derived. The results are compared with an incompressible rubber-like material known as a Mooney material.
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    Bulletin of mathematical biology 32 (1970), S. 303-314 
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    Notes: Abstract The Peaceman-Rachford finite difference method is applied to cylindrically symmetric, transient heat conduction problems in biological media. Inhomogeneous media and internal sources which vary in both space and time are permitted. Boundary conditions are satisfied without sacrificing high local resolution by means of an exponentially stretched grid. Computation time on a Philco 2000/210 computer is approximately 5 msec per grid point per time step.
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    Bulletin of mathematical biology 32 (1970), S. 601-601 
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    Bulletin of mathematical biology 32 (1970), S. 599-600 
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    Bulletin of mathematical biology 32 (1970), S. 581-598 
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    Notes: Abstract The energy cost of the left ventricle is quantitatively analyzed on the basis of the following assumptions: (1) The left ventricle is assumed to be an isotropic, homogeneous elastic, thick, spherical shell. (2) The ventricular wall is made up of a finite number of thin concentric shells. (3) The energetics of the left ventricle is in accordance with the second law of thermodynamics. An expression for the work done during ventricular contraction is derived according to the definition of physical work. The energy liberation during isovolumic contraction is formulated parallel to the concepts of heat production in skeletal muscle during isometric contraction. This expression gives the total work done per stroke in terms of mean systolic pressure, end diastolic volume, stroke volume and wall thickness during diastolic phase.
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    Bulletin of mathematical biology 32 (1970), S. i 
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    Monatshefte für Mathematik 74 (1970), S. 1-5 
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    Monatshefte für Mathematik 74 (1970), S. 6-14 
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    Monatshefte für Mathematik 74 (1970), S. 21-29 
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    Monatshefte für Mathematik 74 (1970), S. 30-40 
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    Monatshefte für Mathematik 74 (1970), S. 15-20 
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    Monatshefte für Mathematik 74 (1970), S. 41-49 
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    Monatshefte für Mathematik 74 (1970), S. 50-55 
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    Monatshefte für Mathematik 74 (1970), S. 56-62 
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    Monatshefte für Mathematik 74 (1970), S. 63-69 
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    Monatshefte für Mathematik 74 (1970), S. 70-87 
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    Monatshefte für Mathematik 74 (1970), S. 97-107 
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    Monatshefte für Mathematik 74 (1970), S. 88-96 
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    Monatshefte für Mathematik 74 (1970), S. 108-118 
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    Monatshefte für Mathematik 74 (1970), S. 119-137 
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    Monatshefte für Mathematik 74 (1970), S. 145-149 
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    Monatshefte für Mathematik 74 (1970), S. 138-144 
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    Monatshefte für Mathematik 74 (1970), S. 150-153 
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    Monatshefte für Mathematik 74 (1970), S. 154-165 
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    Monatshefte für Mathematik 74 (1970), S. 172-178 
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    Monatshefte für Mathematik 74 (1970), S. 166-171 
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    Monatshefte für Mathematik 74 (1970), S. 179-182 
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    Monatshefte für Mathematik 74 (1970), S. 183-192 
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    Monatshefte für Mathematik 74 (1970), S. 223-238 
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    Monatshefte für Mathematik 74 (1970), S. 193-210 
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    Monatshefte für Mathematik 74 (1970), S. 239-243 
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    Monatshefte für Mathematik 74 (1970), S. 211-222 
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    Monatshefte für Mathematik 74 (1970), S. 258-272 
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    Monatshefte für Mathematik 74 (1970), S. 244-257 
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    Monatshefte für Mathematik 74 (1970), S. 273-276 
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    Monatshefte für Mathematik 74 (1970), S. 277-288 
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    Monatshefte für Mathematik 74 (1970), S. 289-301 
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    Monatshefte für Mathematik 74 (1970), S. 302-307 
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    Monatshefte für Mathematik 74 (1970), S. 323-329 
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    Monatshefte für Mathematik 74 (1970), S. 308-322 
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    Monatshefte für Mathematik 74 (1970), S. 330-335 
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    Monatshefte für Mathematik 74 (1970), S. 336-347 
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    Monatshefte für Mathematik 74 (1970), S. 348-350 
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    Monatshefte für Mathematik 74 (1970), S. 351-370 
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    Monatshefte für Mathematik 74 (1970), S. 371-384 
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    Monatshefte für Mathematik 74 (1970), S. 385-388 
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    Monatshefte für Mathematik 74 (1970), S. 389-397 
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    Monatshefte für Mathematik 74 (1970), S. 398-398 
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    Monatshefte für Mathematik 74 (1970), S. 399-409 
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    Monatshefte für Mathematik 74 (1970), S. 410-420 
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    Monatshefte für Mathematik 74 (1970), S. 437-444 
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    Monatshefte für Mathematik 74 (1970), S. 421-436 
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    Monatshefte für Mathematik 74 (1970), S. 445-461 
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    Monatshefte für Mathematik 74 (1970), S. 477-480 
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    Monatshefte für Mathematik 74 (1970), S. 462-476 
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    Colloid & polymer science 236 (1970), S. 38-42 
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    Description / Table of Contents: Zusammenfassung Zwecks Durchführung der Experimente wurden mikroheterogene Mischungen von isotaktischem Polypropylen mit Polyäthylen und von Polyvinylchlorid mit Polyäthylen vorbereitet, die höchstens 60 Vol.-% von dispergierter Phase (iPP oder PVC) bei 160°C für verschiedene Diffusionszeiten enthielten. Hierdurch konnte mit genügender Präzision mit dem Tetraeder-Gittermodell gearbeitet werden. Der Volumenbruch bei maximaler Dilatation (Φ m ) wurde aus der Abhängigkeit des Exzessvolumens vom Volumenbruch der dispergierten Phase auf Grund von additiven und tatsächlichen Dichten berechnet. Unter Voraussetzung desFickschen Gesetzes für die Diffusion war es möglich, die Dicke der Zwischenphasenschicht auszurechnen. Man stellt fest, daß die Diffusion für beide Polymerpaare nach 15 min praktisch zum Stillstand kommt. Diese Erscheinung, die durch die kinetische Behinderung bei der Durchdringung von Polymersegmenten verschiedener Art erklärt werden könnte, ergibt Abweichungen vomFickschen Verlauf.
    Notes: Summary For the experiments there have been prepared such microheterogeneous mixtures of isotactic polypropylene with polyethylene and of polyvinylchloride with polyethylene which contained maximum 60 volume per cent of dispersed phase component (iPP; PVC respectively) at 160°C for various diffusion times, whereat with sufficient exactness the tetrahedric lattice model could be applied. From the dependence of the mixture excess volume on dispersed phase volume fraction, calculated from additive and real densities, the volume fraction at the maximum dilatation (Φ m ) was determined. At supposing theFickian course of the mutual diffusion, it was possible to calculate the thickness of the interphase layer. It was stated that for both polymer pairs the diffusion after 15 min had been practically stopped. This phenomenon, which could be explained by the kinetic hindrances during the interpenetration of the different nature polymer segments, is resulting in the deviation from theFickian course of diffusion.
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    Colloid & polymer science 236 (1970), S. 1-19 
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    Description / Table of Contents: Summary TheF/A isotherms of differently substituted siloxanes spread on water were recorded using a continuously operating, automatically recording film balance. The substituents have a partly considerable influence on the spreading behaviour. Depending on the characteristics of theF/A isotherms, three groups of siloxanes can be distinguished. A first group of siloxanes behaves in analogy with the polydimethyl and methyl-H-siloxanes earlier investigated and yieldsF/A isotherms with at least two more or less pronounced transformation pointsA 2 andB between which the only appreciable pressure increase occurs. This group includes several methyl organosiloxanes. A second group is characterized by isotherms with only one transformation point (A 2) which, when exceeded on compression, results in a steady, heavy pressure increase. This phenomenon is shown by siloxanes with very hydrophilic substituents. A third group, finally, yields smooth curves free of transformation points; they hardly reach any appreciable pressures on short-term contact with the water and do not approach, with respect toF/A values, the profile of the theoretical curve for films analogous to gases until on prolonged contact. This group includes siloxanes with higher aliphatic substituents as well as with aromatic ones. The discussion of the spatial requirements in the transformation points allows an interpretation of the molecular orientations of group I, which are passed when the film is compressed or expands. In the same way as with dimethyl and methyl-H-siloxanes the molecules, within a wide range of the space offered, are caterpillar-like stretched, “hydrated” by hydrogenbridge bonds, supported by the water surface. PointB, which is reached on compression under increasing pressure, always represents a densely packed, condensed film. When this point has been exceeded, the molecular chains are lifted from the water. The siloxanes of the second group, too, rest flatly on the water with their siloxane chains and, when compressed, contract to yield very dense packings. As a result of their hydrophilic substituents, however, the chains are “hydrated” to such an extent that any lifting of “anhydrous” chains from the surface is no longer possible. The siloxanes of the third group, finally, do not indicate that the molecular chains orient themselves on water The forces of adhesion to the water surface are low, which is a result partly of the increasingly paraffinic character of the siloxanes substituted with higher alkyl groups and partly of the basicity of the siloxane oxygen being reduced by electronegative substituents. Consequently, the siloxanes only spread very slowly. It is remarkable that those siloxanes which have proved useful as interface-active silicones in technology belong to groups I and II, which are commonly characterized by rapidly forming monomolecular films with defined states of order on the water surface.
    Notes: Zusammenfassung Mit Hilfe einer kontinuierlich arbeitenden, selbstregistrierenden Filmwaage wurden dieF/A-Isothermen verschiedenartig substituierter, auf Wasser gespreiteter Siloxane aufgenommen. Die Substituenten haben einen z. T. erheblichen Einfluß auf das Spreitungsverhalten. Je nach der Charakteristik derF/A-Isothermen lassen sich drei Gruppen unterscheiden. Eine erste Gruppe von Siloxanen verhält sich analog den früher untersuchten Polydimethyl- und Methyl-H-siloxanen und gibtF/A-Isothermen mit wenigstens zwei mehr oder weniger ausgeprägten TransformationspunktenA 2 undB, zwischen denen auch der einzige größere Druckanstieg liegt. Dieser Gruppe gehören mehrere Methylorganosiloxane an. Eine zweite Gruppe ist gekennzeichnet durch Isothermen mit nur einem Transformationspunkt (A 2), dessen Überschreitung bei Kompression zu einem stetigen starken Druckanstieg führt. Dieses Bild zeigen Siloxane mit stark hydrophilen Substituenten. Eine dritte Gruppe schließlich gibt glatt verlaufende, von Transformationspunkten freie Kurven, die bei kurzen Kontaktzeiten mit dem Wasser kaum nennenswerte Drucke erreichen und sich erst bei längerer Kontaktzeit im Verlauf derF/A-Werte der theoretischen Kurve für gasanaloge Filme annähern. Hierher gehören u. a. Siloxane mit höheren aliphatischen sowie mit aromatischen Substituenten. Die Diskussion des Flächenbedarfes in der Transformationsounkten ermöglicht eine Ausdeutung der Molekülorientierungen der Gruppe I, die bei Kompression bzw. Expansion des Filmes durchschritten werden. Wie bei Dimethyl- und Methyl-H-siloxanen sind in weitem Bereich des Flächenangebotes die Moleküle raupenförmig gestreckt, durch Wasserstoff brückenbindungen “Hydratisiert”, der Wasseroberfläche aufgelagert. Der bei Kompression unter Druckanstieg erreichteB-Punkt stellt stets einen dicht gepackten, kondensierten Film dar. Nach seiner Überschreitung werden die Molekülketten vom Wasser abgehoben. Auch die Siloxane der zweiten Gruppe legen sich flach mit den Siloxanketten auf das Wasser auf und werden bei Kompression zu dichtesten Packungen zusammengeschoben, sind aber zufolge ihrer hydrophilen Substituenten so stark “hydratisiert”, daß eine Abhebung “wasserfreier” Ketten von der Oberfläche nicht gelingt. Bei den Siloxanen der dritten Gruppe schließlich fehlen Anzeichen dafür, daß die Molekülketten sich auf Wasser strecken. Die Adhäsionskräfte zur Wasseroberfläche sind schwach, bedingt teils durch den zunehmend paraffinischen Charakter der mit höheren Alkylgruppen substituierten Siloxane, teils durch die Minderung der Basizität des Siloxansauerstoffs durch elektronegative Substituenten. Die Siloxane spreiten demzufolge auch nur langsam. Es ist bemerkenswert, daß diejenigen Siloxane, die sich in der Technik als grenzflächenaktive Silicone bewährt haben, den Gruppen I und II angehören, deren gemeinsames Kennzeichen schnelle Ausbildung monomolekularer Filme mit definierten Ordnungszuständen auf der Wasseroberfläche ist.
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    Colloid & polymer science 236 (1970), S. 76-79 
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    Description / Table of Contents: Zusammenfassung Lange undSchwuger haben kürzlich gezeigt, daß in einer homologen Serie von Natrium Alkylsulfaten eine Änderung in denKrafft-Temperaturen sei zwischen Alkylketten, die eine geradzahlige oder ungeradzahlige Nummer von Kohlenstoffatomen enthalten. Sie fanden keine solche Änderung in der kritischen Mizellekonzentration und schlossen, daß der Mizellkern sich wie eine Flüssigkeit verhält. Es wurde hier gezeigt, daß in den freien Energien der Mizellformation solche Änderungen existieren. Diese Beobachtung in Verbindung mit anderen läßt vermuten, daß es im Inneren der Mizelle eine lange Ordnungsreihe gibt. Die Größe dieser Änderung ist jedoch viel kleiner als diejenige, die bei der Schmelzwärme der Fettsäuren oder Kohlenwasserstoffen beobachtet wurde. Die Existenz von irgendeinem “Festkörper-ähnlichen” Charakter in der Mizelle stimmt überein mit vorhergehenden Folgerungen, daß die Entropie von diesen Ketten im Inneren der Mizelle wahrscheinlich geringer ist als diejenige flüssiger Kohlenwasserstoffe. DerLaplace-Druck, der im Inneren der Mizelle entsteht und durch die Krümmung der Mizell-Zwischenschicht gekennzeichnet ist, wird zusätzlich als möglicher Faktor herangezogen.
    Notes: Summary Lange andSchwuger have recently shown that in a homologous series of sodium alkyl sulphates, there is an alternation in theKrafft temperatures between alkyl chains containing odd and even numbered carbon atoms. They found no such alternation in the critical micelle concentrations, and concluded that the micelle core is liquid-like. It is shown here that alternations do exist in the free energies of micelle formation. This observation, in conjunction with some others, suggests that there is some long-range order inside a micelle. The magnitude of the alternation, however, is much less than those observed in heats of fusion of fatty acids or hydrocarbons. The existence of some ‘solidlike’ character in the micelle agrees with previous deductions that the entropy of the chains inside a micelle is likely to be less than that of hydrocarbon
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    Colloid & polymer science 236 (1970), S. 79-83 
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    Notes: Summary In this paper is described a simulation technique applicable to the gel filtration of an ionic surfactant in the presence of an electrolyte. The applicability was tested by using sodium dodecyl sulfate as a surfactant and sodium chloride as an added salt. In qualitative aspects, the theoretical elution curves showed good agreements with the experimental ones. Disagreements found between both elution curves seemed to be ascribable to the adsorption of the surfactant on the gel surface which was neglected in the theory.
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    Colloid & polymer science 236 (1970), S. 97-98 
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    Colloid & polymer science 236 (1970), S. 118-125 
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    Notes: Zusammenfassung Im Rahmen von Untersuchungen zur Temperaturabhängigkeit der Löslichkeit von Polymeren in Systemen Polymer/Lösungsmittel/Fällungsmittel hatte sich gezeigt, daß bei Temperaturen unterhalb des θ-Punktes (des binären Systems Polymer/Lösungsmittel) in einem gewissen Bereich das Lösevermögen des reinen Lösungsmittels durch Zugabe geringer Mengen an Fällungsmittelverbessert werden kann. Derartige Systeme sind bereits mehrfach beschrieben worden, jedoch tritt der Effekt weit häufiger auf, als bisher angenommen wurde. Die theoretischen Vorstellungen darüber stellen aber keine befriedigende Erklärung dar. In dieser Arbeit wird eine Interpretation des Effektes unter Einbeziehung der Entropie über den Wert der freien Enthalpie gegeben.
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    Colloid & polymer science 236 (1970), S. 111-115 
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    Description / Table of Contents: Zusammenfassung Beim Strecken von Nylon-6-Fasern im Vakuum resultieren gut auflösbare Spektren, die dem Sekundärradikal (I)−CO−NH−ĊH−CH2−zuzuschreiben sind. Setzt man die gestreckten Fasern der Luft aus (Sauerstoff), so erhält man die entsprechenden Peroxydradikale $$(II) - CO - NH - CH\dot O_2 - CH_2 - $$ . Die Reaktion ist reversibel. Das Radikal (I) ist identisch mit dem, das man durch γ-Bestrahlung im Vakuum erhält und das bei Luftzutritt unverändert bleibt. Tatsächlich ergibt sich mit γ-Strahlung in Luft ebenfalls dieses Spektrum. Die Leichtigkeit, mit der Sauerstoff im ersten, aber nicht im 2. Fall mit den Radikalen reagiert, legt nahe, daß im 1. Fall die Radikale meist in den amorphen Teilen entstehen, während im 2. Fall die Radikale vorwiegend in den Kristallbereichen vorliegen. Beim Strecken der Probe werden die kürzesten Brückenmoleküle in den amorphen Bereichen, die die Kristallamellen verbinden, zerrissen. Die Strahlung jedoch schafft Radikale über die ganze Probe, so daß der Hauptanteil im Kristallinen sitzt.
    Notes: Summary Stretching of nylon-6 fibers in vacuum results in well-resolved spectrum which is attributed to the secondary radical (I)−CO−NH−ĊH−CH2−.Exposure of stretched fibers to air (oxygen) yield the corresponding peroxy radical $$(II) - CO - NH - CH\dot O_2 - CH_2 - $$ . This reaction is reversible. The radical I is identical with those obtained by γ-irradiating nylon-6 fibers (in vacuum) which remain unchanged on opening to air. In fact, γ-irradiation in air also resulted in the same spectrum. The ease with which oxygen reacts with the radicals in the former and not in the latter case, strongly suggests that in the former case, the radicals are trapped mainly in the amorphous region, whereas in the latter case such radicals are present predominantly in the crystalline region. In stretching the sample the shortest tie molecules located in the amorphous regions and connecting the crystal lamellae are ruptured. Radiation, however, creates radicals indiscriminately all over the sample so that the majority is located in crystalline regions.
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    Colloid & polymer science 236 (1970), S. 137-140 
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    Notes: Zusammenfassung Durch stufenweise Dinitrophenylierung von Caseinmicellen und quantitative elektrophoretische Auswertung des nicht umgesetzten Caseinanteils wurde die Komponentenzusammensetzung an der Oberfläche, in der Mittelschicht und im Kern der Micellen festgestellt. Danach ist die Oberfläche besonders reich an γ-Casein, während der Kern bevorzugt β-Casein enthält. Untersuchungen mit η-Caseinfraktionen zeigten, daß γ-Casein offenbar eine wichtige Schutzkolloidkomponente innerhalb des Gesamtcaseins ist.
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    Colloid & polymer science 236 (1970), S. 164-170 
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    Colloid & polymer science 236 (1970), S. 147-151 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Vorausgehende Untersuchungen haben gezeigt, daß nichtionische oberflächenaktive Substanzen wie n-Dodecylhexaoxyäthylen-glykol-monoäther beträchtliche Schutzwirkung Silberjodidsolen gegenüber Flokkung durch anorganische Kationen verleihen. In der vorliegenden Untersuchung wird die Wirkung der Hydrolyse flockender Kationen, Lanthan, Aluminium und Thorium, geprüft. Es wurde gefunden, daß durch die hydrolisierten Kationen die Schutzwirkung der nichtionischen oberflächenaktiven Substanz beträchtlich vermindert wird. Daraus ist zu schließen, daß die hydrolisierte Ionenart stärker als das nichtoberflächenaktive Agens adsorbiert wird und deshalb das letztere von der Oberfläche entfernt wird oder genügend große interpartikuläre Brücken, bildet, um Flockung zu verursachen.
    Notes: Summary Previous studies have indicated that non-ionic surface active agents, such as n-dodecylhexaoxyethylene glycol monoether, confer considerable protection on silver iodide sols to flocculation by inorganic cations. In the present study the effects of hydrolysis of the flocculating cations, lanthanum, aluminium and thorium have been examined. It was found that with the hydrolysed cations the protective action of the non-ionic surface active agent was considerably diminished. It was deduced that the hydrolysed species are more strongly adsorbed than the nonionic surface active agent and either displace the latter from the surface or form species which are large enough to cause flocculation by interparticle bridging.
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    Colloid & polymer science 236 (1970), S. 175-176 
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    Colloid & polymer science 236 (1970), S. 99-111 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Es werden verschiedene, während der Kristallisation in einer gerührten Lösung von linearem Polyäthylen wahrgenommene Erscheinungen eingehend beschrieben. Es zeigt sich, daß eine einfache Strömung unter Scherung die Bildung von Primärkeimen bei gesteigerten Temperaturen in einer 5% igen Xylollösung von linearem Polyäthylen (Marlex) nicht zu beschleunigen vermag. Es wird festgestellt, daß die Bildung von Faserkristallen einsetzt, wenn die Rührgeschwindigkeit des Innenzylinders einesCouette-Gerätes einen der Entstehung derTaylorschen Wirbel entsprechenden Minimalwert übersteigt. Geschlossene Ringe von Faserkristallen, welche sich periodisch um den Rührer bilden, rotieren in Bahnen, welche durch die Mittelpunkte derTaylor-Wirbel gehen. Anscheinend ist eine turbulente Strömung das zweckmäßigste Mittel zum Hervorrufen einer Faserkristallisation; es wird hiermit in der 5% igen Xylollösung von Marlex eine maximale Kristallisationstemperatur von 112°C erreicht. Ferner wird ein Mechanismus zur Bildung von Primärkeimen vom garbenförmigen Typ vorgeschlagen auf Basis von Orientierung und Deformation von Aggregaten in den Geschwindigkeitsfeldern mit parallelen Gradienten zwischen den Wirbeln. Lösungen von Polyäthylen mit hohem Molekulargewicht (Mw=1,5×106) zeigen einen ausgeprägtenWeissenberg-Effekt, der dem Auftreten der ersten Fasern vorangeht. Normalspannungen erniedrigen den kritischen Wert der Rührgeschwindigkeit, bei der in einemCouette-Gerät eine Wirbelbildung auftritt. Dies dürfte eine Erklärung bieten für die beobachtete Faserkristallisation des hochmolekularen Polyäthylens bei Rührgeschwindigkeiten, welche im Falle derNewtonschen Flüssigkeiten zu einer demTaylorschen Kriterium entsprechenden Laminarströmung führen. Die Ablagerung des Fasernetzes auf dem Rührer ist auf Sekundärströmung zurückzuführen.
    Notes: Summary A detailed description of several phenomena observed during crystallization in a stirred solution of linear polyethylene is presented. It is found that simple shear flow is incapable of accelerating the formation of primary nuclei at elevated temperatures in 5% xylene solution of linear polyethylene (Marlex). The onset of fibrillar crystal formation is noted when the stirrer speed of the inner cylinder of aCouette instrument exceeds a minimum value which corresponds to the onset ofTaylor vortices. Closed loops of fibrillar crystals occurring periodically around the stirrer, revolve in orbits which coincide with the centers of theTaylor vortices. Turbulent flow seems to be most effective in inducing fibrillar crystallization and a maximum crystallization temperature of 112°C was achieved with the 5% xylene solution of Marlex. A mechanism is proposed for the formation of primary nuclei of bundlelike type which is based upon orientation and deformation of aggregates in regions of elongational flow between the vortices. Solutions of high molecular weight polyethylene (M w=1.5×106) exhibit a pronouncedWeissenberg effect prior to the appearance of the first fibers. Normal stresses lower the rate of stirring inCouette flow at which vortices occur. This may account for the observed fibrillar crystallization of the high molecular weight polyethylene at stirrer speeds which in case ofNewtonian fluids give rise to laminar flow according to theTaylor criterion. Settlement of the fibrous network on the stirrer results from secondary flow.
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    Colloid & polymer science 237 (1970), S. 297-302 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Die Adsorption von Äthylen-Vinylacetat-Copolymeren, die aus zwei unterschiedlichen Segmenten hinsichtlich der Adsorptionsenergie bestehen, aus der Lösung an Glaskugeln wurde untersucht. Die Adsorption hängt vom Molekulargewicht ab; und die Konstante α, erhalten durch Anwendung derUllmanschen Gleichung, nimmt mit der Zunahme des Molekulargewichts ab. Die Molekulargewichts-Abhängigkeit der Adsorption läßt vermuten, daß die Polymerketten, in der Grenzfläche adsorbiert, aus Sequenzen und Schleifen bestehen. Die Beziehungen zwischen maximaler Adsorption und mit adsorbierter Polymerketten besetzter Fläche aus verschiedener Lösung wird diskutiert und die Lösungsmittel-Abhängigkeit der maximalen Adsorption wurde aus dem Unterschied der Polymer-Löslichkeit erklärt.
    Notes: Summary The adsorption of ethylene-vinyl acetate copolymer which consists of two different adsorption energy segments from solution onto glass sphere was studied. The adsorption depends on molecular weight and the constant α obtained by application ofUllman's equation is decreased with the increase of molecular weight. The molecular weight dependence of adsorption suggests that the polymer chain adsorbed at solution-solid interface consist of sequences and loop chains. The relation between maximum adsorption and area occupied with adsorbed polymer chain from various solution was discussed, and the solvent dependence of maximum adsorption was explained in the difference of polymer solubility.
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    Colloid & polymer science 237 (1970), S. 311-316 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Oberflächenverhalten und Eigenschaften von Polyäthylen wurden hinsichtlich Adhäsion und chemischer Bindungsfestigkeit diskutiert. Der Bruch von Adhäsionsbindungen zwischen oxydativ aktiviertem Polyäthylen und Aluminium hat zwei Seiten: Einmal spielt die Konzentration an Fehlbaustellen in der Grenzfläche Aluminium/Polyäthylen, nämlich wenn letzteres schwach oxydiert, eine Rolle. Zum anderen ist die Struktur des gesamten Oberflächenbereichs des Polyäthylens bis zu einer gewissen Tiefe gestört, wenn letzteres stark oxydiert. Im ersten Fall wirkt die Einführung von Polyäthylengruppen durch die Oxydation bindungsfördernd. Und aus dem Anwachsen dieser Art Bindungsfestigkeit schließen wir, daß die Adsorption für die Erklärung des Adhäsionsmechanismus eine Rolle spielt und damit eine Adsorptionstheorie für die quantitative Fassung der Adhäsion im entsprechenden Rahmen angemessen ist.
    Notes: Summary The character of the surface and bulk properties of polyethylene have been considered with respect to adhesion and bond strength. Rupture of adhesion oxidatively activated polyethylene to aluminum has two faces. One of them is an apparent failure at the interface of aluminum-polyethylene which was moderately oxidized and another is the failure at the surface region of polyethylene which was strongly oxidized. In the former case the introduction of polar groups with oxidation is effective for the promotion of bond strength, and from the increasing behavior of bond strength we conclude that the adsorption theory on adhesion is appropriate for the elucidation of adhesion mechanism.
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    Colloid & polymer science 237 (1970), S. 332-335 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung 1. Seidenfibroin (Bombyx mori) wird in Lithiumrhodanid gelöst und im pH-Stat mit Chymotrypsin abgebaut. Der wasserunlösliche Teil der Abbauprodukte (Cp) wird in Lithiumrhodanid-Lösung mit Papain weiter abgebaut. Der Einfluß von Lithiumrhodanid-Konzentration und Enzym-Substrat-Verhältnis auf den Abbaugrad wird untersucht. 2. Bei Lithiumrhodanid-Konzentrationen geringer als 1% wird Chymotrypsin nicht denaturiert; bei höheren Konzentrationen sinkt die enzymatische Aktivität sehr rasch. 3. Das beim chymotryptischen Abbau in Lithiumrhodanid in Lösung verbleibende Cp weist auf Grund seines Verhaltens bei der Ionenaustausch- und Gelchromatographie die gleiche Inhomogenität auf wie das beim Chymotrypsin-Abbau wäßriger Fibroinlösungen als Niederschlag ausfallende Cp. 4. Bei Lithiumrhodanid-Konzentrationen unter 10% ist kein merkbares Absinken der enzymatischen Aktivität des Papains festzustellen. 5. Die Dinitrophenylierung der Aminogruppe des N-terminalen Glycins sowie der Hydroxylgruppe des C-terminalen Tyrosins in Cp hat keinen Einfluß auf den Abbau mit Papain. 6. Die mittlere Kettenlänge der Peptidfragmente nach Papain-Abbau von Cp bzw. DNP-Cp beträgt 4 bis 5 Aminosäurereste.
    Notes: Summary 1. Bombyx mori silk fibroin is digested by chymotrypsin in lithiumthiocyanate solution in a pH-stat. One of the digestion products, the chymotryptic precipitate (Cp), is further digested by papain in lithium-thiocyanate solution. The influence of lithiumthiocyanate concentration and enzyme: substrate ratio on the rate of digestion are examined. 2. Chymotrypsin is not denatured by a lithiumthiocyanate concentration lower than 1%; at higher concentrations the enzymic activity decreases rapidly. 3. The Cp remaining in solution after digestion of fibroin in lithiumthiocyanate was found to be as inhomogeneous as the chymotryptic precipitate from a water solution of fibroin by ion-exchange and gel chromatography. 4. Concentrations lower than 10% of lithiumthiocyanate do not decrease the enzymic activity of papain markedly. 5. Dinitrophenylation of N-terminal glycine and the hydroxyl group of C-terminal tyrosine of Cp has no influence on the digestion by papain. 6. Peptide fragments from the digestion of Cp and DNP-Cp by papain have an average chain length of 4–5 amino acid residues.
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    Colloid & polymer science 237 (1970), S. 372-375 
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    Colloid & polymer science 237 (1970), S. 376-384 
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    Colloid & polymer science 238 (1970), S. 389-395 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Zwei Theorien der Polymerkristallisation werden kurz wiedergegeben und diskutiert auf der Grundlage einer Revision der allgemeinen Keimbildungstheorie, wie in einer vorhergehenden Veröffentlichung dargelegt. Da Kristallisationskeime, wie sie üblicherweise definiert werden, nicht existieren, ist die freie Energie zur Keimbildung, wie sie zur Berechnung der Keimbildungs-häufigkeit oder Kristallwachstumsgeschwindigkeit herangezogen wird, ein irreführender Begriff. Diese Größen sind in Abhängigkeit von Parametern zu beschreiben, die die Angliederung von Polymersegmenten an die wachsenden Kristalle bzw. deren Abtrennung von diesen beherrschen. Es wird jetzt angenommen, daß die Kristallisation von Polymeren durch Angliederung von Segmenten erfolgt, die aus einem einzigen oder einigen wenigen Monomereinheiten bestehen, statt durch einzelne Schritte von ganzen “Faltungslängen”. Kettenfaltung alsVorbedingung zur Kristallisation wird als höchst unwahrscheinlich verworfen; sie könnte alsErgebnis der Kristallisation auftreten. Kinetische Daten der Kristallisation von Polymeren allein geben keinen Schlüssel zur Frage, welche die richtige Theorie ist, da die hergeleiteten Parameter der freien Grenzflächenenergie im wesentlichen die freien Parameter der Theorie sind.
    Notes: Summary Two polymer crystallization theories are reviewed and discussed against the background of a revision of general nucleation theory, given in a preceding paper. Since crystallization nuclei, as usually defined, do not exist, the free energy of formation of a nucleus, such as it is applied for the calculation of nucleation frequency or rate of crystal growth, is a misleading concept. The latter quantities must be described as functions of parameters governing the attachment of polymer segments to, and their separation from, the growing crystal. The crystallization of polymers is supposed to proceed via attachment of segments of one or a few polymer repeating units rather than by steps of a whole “fold length” at once. Chain folding as aprerequisite for crystallization must be rejected as being highly improbable; it may be theresult of crystallization. One cannot decide from data on polymer-crystallization kinetics alone which theory is right or wrong, since it is the derived interfacial free-energy parameters that are actually the adjustable parameters of the theory.
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    Colloid & polymer science 238 (1970), S. 410-415 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Die dynamisch-mechanischen Eigenschaften von Filmen und Fasern aus Nylon 66 wurden als Funktion der Temperung und Verstreckung mit einem Virbon-Viskoelastometer untersucht. Die α′-Umwandlung wird wenig durch die Temperung beeinflußt, aber erhöhte Orientierung läßt siezu höheren Temperaturen verlagern. Messungen der Röntgenstreuung bei erhöhten Temperaturen führen zu dem Schluß, daß der Übergang triklin/hexagonal nicht wesentlich zu der α′-Umwandlung beiträgt. Proben aus verstrecktem Nylon-66-Film, parallel und senkrecht zur Streckrichtung geschnitten, zeigen, daß die Kurven des dynamischenE-Moduls gegen die Temperatur für beide Orientierungen sich in der Nachbarschaft der α′-Umwandlung überkreuzen. Diese Beobachtung wird hinsichtlich der Vermutung diskutiert, daß die α′-Umwandlung den Glasübergang in Nylon 66 darstellt.
    Notes: Summary The dynamic mechanical properties of nylon 66 films and fibers have been examined, as a function of annealing and drawing, with a Vibron viscoelastometer. It is found that the α′ transition is little affected by annealing treatments, but increase in orientation causes the transition to move to a higher temperature. Experiments, with X-ray diffraction of samples at elevated temperatures, lead to the conclusion that the triclinic to hexagonal phase change does not contribute significantly to the α′ transition. Samples cut parallel and perpendicular to the drawing direction of nylon 66 film, have been used to show that the curves of dynamic tensile modulus versus temperature, for the parallel and perpendicular directions, cross in the neighborhood of the α′ transition. This observation is discussed in relation to the suggestion that the α′ transition is the glass transition in nylon 66.
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    Colloid & polymer science 237 (1970), S. 336-358 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Der Bericht befaßt sich zuerst mit der großen morphologischen Mannigfaltigkeit faseriger, bei erhöhter Temperatur aus gerührten Lösungen gefällter Polyäthylenkristalle. Bei 112°C aus gerührten Xylollösungen von linearem Polyäthylen herauskristallisierte Schaschlik-Strukturen zeigen eine lamellare Überwachsung mit einer Dicke von etwa 150 Å, woraus u. a. geschlossen wird, daß sich bei Kristallisations-temperaturen über 100°C nur Faserkerne bilden und daß die umringenden polymeren Moleküle sich bei niedrigeren Temperaturen “epitaxial” auf dem Substrat ablagern. Die Verschiedenheit in der Form der Überwachsung und die Inhomogenität der Proben lassen sich erklären durch eine unregelmäßige Ablagerung auf dem Rührer und durch Unterschiede in der Auswaschbarkeit der faserigen Kristalle, welche Unterschiede weitgehend auf das nicht einheitliche Strömungsbild längs der verschiedenen Rührerteile zurückzuführen sind. Ungewöhnliche lamellenartige Formen, interlamellare Verbindungen, Häutchen zwischen den Lamellen und die vonKeller undMachin festgestellte Verschleierung der Schaschlikgebilde lassen sich sehr gut durch denKeith-, Padden- undVadimsky-Mechanismus einer durch die Kristallisation verursachten Orientierung von Makromolekülen zwischen den Lamellen und durch die anschließende Bildung von “extended-chain” Kristallen erklären. Wie sich zeigt, gruppiert sich die lamellare Überwachsung um den Kern entsprechend einer logarithmischen Normalverteilung; der mittlere Durchmesser der lamellaren Kristalle nimmt zu mit der mittleren Größe der Zwischenabstände, wobei beide ungefähr gleich groß sind. Die faserigen Kristalle enden in allmählich spitz auslaufenden Gebilden mit Längen von etwa 5 bis 8 μ. Diese Faserenden stimmen gut überein mit dem für das Wachsen faseriger Kristalle in Strömungsgebieten vorgeschlagenen “unroll”-Modell, falls im Durchschnitt jedes Molekül eine Kettenfaltung einleitet und die Kettenenden willkürlich in das Kristallgitter aufgenommen werden. Lineares Polyäthylen mit einem Molekulargewicht unter 50×103 und Hochdruckpolyäthylen kristallisieren nicht in der faserigen Form, während —wie sich zeigt—Copolymere von Äthylen und geringen Propylen- und Butylenmengen in der Lage sind, faserige Kristalle zu bilden und isotaktisches Propylen schöne und überwachsene Fibrillen ergibt.
    Notes: Summary This paper primarily describes the large diversity in morphology of fibrillar polyethylene crystals precipitated from stirred solutions at elevated temperatures. Shish-kebabs crystallized at 112°C from stirred xylene solutions of linear polyethylene exhibit lamellar overgrowths having thicknesses of the order of 150 Å from which it was concluded i. a. that at crystallization temperatures above 100°C only backbones are formed and that the surrounding polymer molecules deposit epitaxially on the substrate at lower temperatures. The variation in the appearance of the overgrowth and the inhomogeneity of the samples can be traced back to irregular stacking and to differences in washability of the fibrillar crystals, these differences being largely due to the non-uniform flow pattern along the various stirrer parts. Unusual lamellar shapes, interconnections, sheets between lamellae, the “veil” on the Shish-kebab noted byKeller andMachin, may well be explained byKeith, Padden andVadimskys mechanism of crystallization-induced orientation of macromolecules between the lamellae and the consequent formation of extendedchain crystals. The lamellar overgrowth appears to be arranged along the backbone according to a logarithmic normal distribution, and the average diameter of the lamellar crystals increases with the average spacing, both being approximately equal in size. The fibrillar crystals end in smooth tapered tails having lengths varying between 5 and 8 μ. These observed fibre ends agree best with the “unroll” model proposed for fibrillar crystal growth in flow fields if on the average each molecule introduces one chain fold and the chain ends are randomly assimilated by the crystal lattice. Linear polyethylene below molecular weight of 50×103 and low density polyethylene did not crystallize in fibrillar habit. whereas copolymers of ethylene and slight amounts of propylene and butylene proved capable of forming fibrillar crystals and isotactic polypropylene yielded smooth and overgrown fibres.
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    Colloid & polymer science 238 (1970), S. 396-405 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Summary The 2g1-Kink is considered as an elastic dipole in the idealized PE-crystal, with 4 possible positions, that is 4 dipol-tensors. The calculated relaxation strength for the γ-process in PE — kinkstep (γII′) and kinkjump (γII) — agrees with the results obtained by considering a simple shear displacement (7) and with experiment, assuming h. The mean number h of 2g1-kinks in a bloc and the thermal expansion Δα due to these kink defects are discussed under the additional condition that 2g1-kinkconcentrationc is constant.
    Notes: Zusammenfassung Die 2g1-Kinke wird als Baufehler mit 4 möglichen Lagen im idealisierten PÄ-Kristall elastizitätstheoretisch durch je einen Kräftedipol beschrieben. Die Berechnung des Relaxationsbetrags für den γ-Prozeß in PÄ — Kinkschritt (γII′) und Kinksprung (γII) — ergibt mit h·c=0,0006 Übereinstimmung mit der in (7) verwendeten paraelastischen Abgleitvorstellung und mit dem Experiment. Mittlere 2g1-Kinkblockgrößeh und Defektanteil der thermischen Ausdehnung Δα werden unter der Nebenbedingung konstanter 2g1-Kinkkonzentrationc diskutiert.
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    Colloid & polymer science 238 (1970), S. 405-409 
    ISSN: 1435-1536
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Summary After sudden release of uniaxial pressure, inorganic oxide glasses exhibit a delayed variation of state, which has been investigated by measurement of the dielectric constant at about 1 Mc/sec. The results, differing as well for samples of various thickness, as for samples with “virgin” (fire-polished) surfaces and emery-ground surfaces respectively, are interpreted by the combination of a volume effect and a surface effect, the latter present only with ground samples. The volume effect causes an increase of the dielectric constant with increasing time after release of the pressure, whereas the surface effect gives a decrease in time. — Probably the surface effect is connected with the delayed adjustment of absorption-adsorption-equilibria of water in the uppermost layers of the glass network.
    Notes: Zusammenfassung Die relaxierten Zustandsänderungen des Netzwerks anorganischer Oxydgläser nach Drucksprung wurden durch Messungen derDK im MHz-Bereich verfolgt. Die zunächst scheinbar widersprüchlichen Erscheinungen an geschliffenen und ungeschliffenen Proben sowie Proben unterschiedlicher Dicke lassen sich widerspruchsfrei deuten unter der Annahme eines Volumen-und eines nur an den geschliffenen Flächen auftretenden Oberflächeneffekts. Der Volumeneffekt bedingt einen zeitlichen Anstieg derDK nach Drucksprung; er liegt bei den 0,1-mm-Proben im Meßbereich und ist bei den dickeren Proben mit ihren niedrigeren Konfigurationstemperaturen zu so langen Zeiten verschoben, daß er sich dem Nachweis entzieht. Der Oberflächeneffekt dagegen bedingt einen zeitlichen Abfall derDK und wird mit Erscheinungen in der Schleifschicht, vermutlich Adsorptions-Absorptions-Gleichgewichten von Wasser, in Verbindung gebracht.
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