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  • Articles  (4,472)
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  • Wiley-Blackwell  (3,744)
  • Cambridge University Press  (728)
  • 1960-1964  (3,384)
  • 1950-1954  (1,088)
  • Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics  (4,472)
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  • 101
    Publication Date: 1964-05-01
    Description: It is shown in general how a two-dimensional flow can be justified as a physical approximation, notwithstanding the logarithmic singularity in pressure that occurs at infinity when the cavity expands or contracts at a varying rate. The argument presented, which affords a more natural interpretation than alternatives previously suggested, refers to the approximate equivalence-to a determinable degree of accuracy-between the hypothetical plane flow and the inner region of some real three-dimensional flow with small spanwise variations. The main ideas are illustrated by the example of a long ellipsoidal body which changes in volume while also undergoing shape perturbations. © 1964, Cambridge University Press. All rights reserved.
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  • 102
    Publication Date: 1964-05-01
    Description: A steady-state technique of heat-transfer measurement has been developed based on the method of Seban, Emery & Levy (1959) whereby energy is dissipated by the Joule effect in a thin metal sheet on the surface of a model. For the present application, use was made of very thin but mechanically resistant films of metal of very nearly constant thickness, obtained by a simple mirror-silvering technique. The present investigation was prompted by the desire to make very local measurements of heat transfer for application in regions where large variations in convective heat flux and therefore in temperature could be expected. Comparison between theory and experiment has been made in the simple case of a flat plate with constant heat flux for which a rigorous computation could be made based on the theory of Chapman & Rubesin (1949). The model was so conceived that the heat losses were small enough to be neglected. Therefore no corrections, which are often inaccurate, were needed for the experimental results, contrary to what is generally done when using other techniques for heat-transfer measurements. The excellent agreement between theory and experiment gives complete confidence in the method. The theoretical analysis showed that the measurements are simply related to the results that could be obtained in the case of an isothermal surface, because of the constant ratio that exists between the corresponding heat-transfer coefficients. © 1964, Cambridge University Press. All rights reserved.
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  • 103
    Publication Date: 1964-04-01
    Description: It is suggested that the use of prolate spheroidal co-ordinates in certain problems involving slender bodies may lead to results which not only are more likely to be uniformly valid for blunt bodies, but in many cases require less complicated analysis than results obtained by standard methods which use cylindrical co-ordinates. The method is developed for a simple problem in potential theory and is then applied also to a problem in Stokes flow, yielding a procedure for obtaining the Stokes drag on a slender body of arbitrary shape. For comparison purposes, consideration is also given to the use of both cylindrical and di-polar co-ordinates, and as a by-product of the comparison of results on cylindrical and spheroidal systems some new simple formulae involving Legendre polynomials are obtained heuristically, and then rigorously proved. © 1964, Cambridge University Press. All rights reserved.
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  • 104
    Publication Date: 1964-05-01
    Description: A weak expansion wave propagating in a relaxing gas is discussed with particular reference to the ‘near-equilibrium’ and ‘near-frozen’ regions. The concept of bulk viscosity is used in conjunction with Burger's equation in the near-equilibrium region. The asymptotic equilibrium simple wave is modified by diffusive regions in the neighbourhood of the first and last rays. It is shown that in the case of a weak expansion wave, Chu's asymptotic solution of the acoustic equation describes the wave-form for a finite time interval before convection effects become noticeable. In the near-frozen region a characteristic perturbation method is used to describe the flow near the wave-front. © 1964, Cambridge University Press. All rights reserved.
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  • 105
    Publication Date: 1964-05-01
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  • 106
    Publication Date: 1964-04-01
    Description: The object of this work was to investigate experimentally the structure of the early shear layer of high-speed jets and its relation to the mechanism of noise generation. Of special interest was the question of the existence of periodic fluctuations in the velocity field. The experimental investigation is divided in three parts. Optical observation of the jet flow by means of the shadowgraph technique. Measurement of mean Mach number and temperature profiles. Survey by means of hot-wire of the component of the fluctuating velocity field in the mean flow direction. The shadowgraphs show very interesting features of the breakdown process of free shear layers, but fail to show any propagation of strong acoustic disturbances in the near pressure-field. Mean profile measurements show that the flow field in the range 1 ⩽ x/d ⩽ 4 develops in a conical fashion, i.e. the mean profiles in Mach number and temperature can be expressed in terms of a single conical variable η = (2r–d)/2x. The fluctuating velocity field is described in terms of the intensity of turbulence, its spectral distribution, and two-point space-time correlation functions. Similarity laws are given for the power spectra and the space-time correlation functions. On the cylinder r = d, the convection speed of the turbulent field is different for the different eddy sizes, varying from the local mean speed for small eddies to U exit for the large eddies. Measurements of the angular correlation function are reported which show no correlation of the fluctuations across the jet diameter. © 1964, Cambridge University Press. All rights reserved.
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  • 107
    Publication Date: 1964-04-01
    Description: An investigation is carried out to determine the conditions marking the onset of convective motion in a horizontal fluid layer in which a negative temperature gradient occurs somewhere within the layer. In such cases, fluid of greater density is situated above fluid of lesser density. Consideration is given to a variety of thermal and hydrodynamic boundary conditions at the surfaces which bound the fluid layer. The thermal conditions include fixed temperature and fixed heat flux at the lower bounding surface, and a general convective-radiative exchange at the upper surface which includes fixed temperature and fixed heat flux as special cases. The hydrodynamic boundary conditions include both rigid and free upper surfaces with a rigid lower bounding surface. It is found that the Rayleigh number marking the onset of motion is greatest for the boundary condition of fixed temperature and decreases monotonically as the condition of fixed heat flux is approached. Non-linear temperature distributions in the fluid layer may result from internal heat generation. With increasing departures from the linear temperature profile, it is found that the fluid layer becomes more prone to instability, that is, the critical Rayleigh number decreases. © 1964, Cambridge University Press. All rights reserved.
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  • 108
    Publication Date: 1964-04-01
    Description: An exact solution is given for the flow in a convergent or divergent channel of a class of anisotropic fluids in which the fluid has a preferred direction. © 1964, Cambridge University Press. All rights reserved.
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  • 109
    Publication Date: 1964-04-01
    Description: When I was first asked to give a general lecture to the 5th British Theoretical Mechanics Colloquium (held at Liverpool University, 2–5 April 1963), I put up the title ‘Shock Waves’, thinking that I might run over a wide field of present-day research, pointing out some of the unanswered problems. In the intervening months, however, I came across the new book by Dr Bradley (1962) of Liverpool University, The Physics and Chemistry of Shock Waves, and as recently as last November there appeared a summarizing article by Pain bt Rogers (1962) of London University in Reports on Progress in Physics. The first of these deals in great detail with the modern physical and chemical aspects of the subject—with real gas effects and experimental techniques-and the second summarizes the general classical properties and gives an extended account of recent work, for example, on real gas effects and on magnetohydrodynamics. I also bore in mind that magnetogasdynamics received a majestic treatment at the 4th Colloquium from Dr Shercliff. In the end, then, I decided to confine my remarks to one particular problem, namely the reflexion and diffraction of shock waves, and to concentrate mainly on developments during the past ten years. This paper is the text of the lecture. © 1964, Cambridge University Press. All rights reserved.
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  • 110
    Publication Date: 1964-05-01
    Description: The classical laminar boundary layer on a parabolic cylinder is calculated using the Blasius series, with modifications to improve convergence, and supplemented by an asymptotic expansion valid far downstream from the nose. The flow due to displacement thickness is thereby found with sufficient accuracy to permit evaluation of its second-order effect upon the boundary layer near the stagnation point. The skin friction and heat transfer are found to be reduced there by both displacement and curvature. © 1964, Cambridge University Press. All rights reserved.
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  • 111
    Publication Date: 1964-04-01
    Description: A solution of the Navier-Stokes equations is obtained for the flow resulting from the steady rotation of a semi-infinite right circular (solid) cylinder about its vertical axis. Incompressible viscous fluid is assumed to fill the space outside the cylinder on one side of a horizontal solid plane. In the proposed method of solution the pertinent physical quantities are expressed as series in positive powers of the Reynolds number Re with space-dependent coefficients. It is shown that the coefficients of (Re)M can be obtained by solving linear partial differential equations which depend on the coefficients of (Re)i, where i 〈 M. A truncated solution, which holds for small Re, is obtained by solving for the first two coefficients. These results indicate that at the flat end of the cylinder the pressure distribution is nearly constant, yet along the adjacent bounding plane it rises with the radial direction. © 1964, Cambridge University Press. All rights reserved.
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  • 112
    Publication Date: 1964-04-01
    Description: The flow of an electrically conducting fluid up a hot vertical plate in the presence of a strong magnetic field normal to the plate is considered. A solution is developed based on the idea of matching ‘outer’ and ‘inner’ solutions in the moving layer of fluid. An approximate Pohlhausen method of solution is also given which yields results in fairly good agreement with the exact analysis. © 1964, Cambridge University Press. All rights reserved.
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  • 113
    Publication Date: 1964-04-01
    Description: In the theory of thermal convective instability between two horizontal planes there are many solutions that are periodic in the horizontal co-ordinates, while in experiment convection is observed to take place in cellular patterns. It is often assumed, or decided after insufficient argument, that the periodic solutions of the mathematical model ‘explain’ or correspond to these patterns, but a completely satisfactory discussion of this correspondence has not been given. Indeed, with certain mathematical solutions ambiguities arise as to what cell centres and cellular boundaries are. A detailed discussion has recently become especially necessary because attempts are being made to predict which particular cellular pattern will occur in given experimental conditions.In this paper the topic is studied afresh and the question is asked: what features, in the mathematical model, correspond to what an experimentalist observes in cellular convective motion? In answer a definition of a cell is formulated which relates certain surfaces in the flow field of the mathematical model to steady vertical cellular boundaries that are observed in experiment, and which shows where the cell centres lie. In particular the classical hexagonal cellular pattern, of the mathematical model, is shown to be the prototype pattern of what is experimentally observed. On the other hand the square and so called ‘rectangular’ cases of linearized theory are shown not to correspond truly to square and rectangular cells at all. The new formulation is especially relevant to theoretical work on the prediction of cell shape and direction of flow in cells, since precise knowledge of the shapes of the cellular boundaries and locations of cell centres is essential if predictions are to be compared with observation.
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  • 114
    Publication Date: 1964-04-01
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  • 115
    Publication Date: 1964-03-01
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  • 116
    Publication Date: 1964-04-01
    Description: A linearized theory is developed for the oscillations of a slender body which is floating on the free surface of an ideal fluid, in the presence of incident plane progressive waves. Green's theorem is used to represent the velocity potential and the first-order slender-body potential is developed from asymptotic approximation. The general theory is valid for arbitrary slender bodies in oblique waves, and detailed results are presented for a body of revolution. © 1964, Cambridge University Press. All rights reserved.
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  • 117
    Publication Date: 1964-04-01
    Description: The problem of flow of an inviscid, incompressible fluid inside a circular pipe, with a sphere on the axis of the pipe, has been studied by Lamb (1936) (irrotational flow), Long (1953) and Fraenkel (1956) (swirling flow). Because of the difficulty of satisfying all the boundary conditions in the problem, only approximate solutions, valid for spheres of small diameter (compared with that of the pipe) have been obtained. In this paper, it is found that by introducing a vortex sheet over a segment of the diameter of the sphere, flow patterns can be obtained by an inverse method for the case of large spheres. Four different types of flow are considered: (1) irrotational flow, (2) swirling flow with constant axial and angular velocities far upstream, without lee waves, (3) swirling flow with constant axial and angular velocities far upstream, with lee waves, and (4) rotational flow with a paraboloidal velocity distribution far upstream. © 1964, Cambridge University Press. All rights reserved.
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  • 118
    Publication Date: 1964-04-01
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  • 119
    Publication Date: 1964-03-01
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  • 120
    Publication Date: 1964-03-01
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  • 121
    Publication Date: 1964-03-01
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  • 122
    Publication Date: 1964-03-01
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  • 123
    Publication Date: 1964-03-01
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  • 124
    Publication Date: 1964-03-01
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  • 125
    Publication Date: 1964-03-01
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  • 126
    Publication Date: 1964-03-01
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  • 127
  • 128
    Publication Date: 1964-02-01
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  • 129
    Publication Date: 1964-03-01
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  • 130
    Publication Date: 1964-03-01
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  • 131
    Publication Date: 1964-03-01
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  • 132
    Publication Date: 1964-02-01
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  • 133
    Publication Date: 1964-02-01
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  • 134
    Publication Date: 1964-02-01
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  • 135
    Publication Date: 1964-02-01
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  • 136
    Publication Date: 1964-03-01
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  • 137
    Publication Date: 1964-02-01
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  • 138
    Publication Date: 1964-02-01
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  • 139
    Publication Date: 1964-02-01
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  • 140
    Publication Date: 1964-01-01
    Description: An investigation is made of the disturbances produced in a closed, gas-filled tube by the oscillations of a piston at one end, when the piston oscillates at near resonant frequencies. Within a well-defined frequency band around each resonant frequency, shock waves appear in the solution; outside this interval the oscillations are continuous, but not purely sinusoidal.The solution includes the effects of compressive viscosity, and of shear viscosity in the boundary layer at the walls of the tube. For typical laboratory conditions the effect of compressive viscosity is found to be quite small (giving a shock thickness of the order of 10−4in.). The boundary layer effect can be more significant, though the most important modification required of the usual acoustic theory is found to arise from the non-linear terms.
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  • 141
    Publication Date: 1964-01-01
    Description: The theoretical treatments given by earlier authors are classified, reviewed and where necessary extended; then the predictions of twenty of these theories are evaluated and compared with all available experimental data, the root-meansquare error being computed for each theory. The theory of van Driest-II gives the lowest root-mean-square error (11.0%).A new calculation procedure is developed from the postulate that a unique relation exists betweencfFcandRFRwherecfis the drag coefficient,Ris the Reynolds number, andFcandFRare functions of Mach number and temperature ratio alone. The experimental data are found to be too scanty for bothFcandFRto be deduced empirically, soFcis calculated by means of mixing-length theory andFRis found semi-empirically. Tables and charts of values ofFcandFRare presented for a wide range ofMGandTS/TG. When compared with all experimental data, the predictions of the new procedure give a root-mean-square error of 9.9%.
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  • 142
    Publication Date: 1964-02-01
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  • 143
    Publication Date: 1964-02-01
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  • 144
    Publication Date: 1964-02-01
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  • 145
    Publication Date: 1964-02-01
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  • 146
    Publication Date: 1964-01-01
    Description: Consideration is given to the flow of an idealized elastico-viscous liquid contained in the narrow channel between two concentric cylinders, the motion being due to the relative rotation of the cylinders. It is shown that the presence of elasticity in the liquid lowers the value of the critical Taylor number at which instability occurs. The secondary motion arising at the onset of instability has the usual cellular pattern, the cell length being decreased by the presence of elasticity in the liquid.
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  • 147
    Publication Date: 1964-01-01
    Description: A general treatment is given of the first-order effects of wall proximity on the increased resistance to translational motions of a rigid particle of arbitrary shape settling in the Stokes régime. The analysis generalizes a previous treatment (Brenner 1962) to the case where the principal axes of resistance of the particle may have any orientation relative to the principal axes of the bounding walls. It is shown that, to the first order in the ratio of particle-to-boundary dimensions, the increased resistance of the particle can be represented by a symmetric, second-rank tensor (dyadic) whose value is independent of particle shape and orientation.
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  • 148
    Publication Date: 1964-01-01
    Description: In Part 1 of this paper a free-streamline wake model was introduced to treat the fully and partially developed wake flow or cavity flow past an oblique flat plate. This theory is generalized here to investigate the cavity flow past an obstacle of arbitrary profile at an arbitrary cavitation number. Consideration is first given to the cavity flow past a polygonal obstacle whose wetted sides may be concave towards the flow and may also possess some gentle convex corners. The general case of curved walls is then obtained by a limiting process. The analysis in this general case leads to a set of two functional equations for which several methods of solution are developed and discussed.As a few typical examples the analysis is carried out in detail for the specific cases of wedges, two-step wedges, flapped hydrofoils, and inclined circular are plates. For these cases the present theory is found to be in good agreement with the experimental results available.
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  • 149
    Publication Date: 1964-01-01
    Description: Viscous flow perpendicular to a line (or ‘grating’) of evenly spaced identical cylinders is considered in the case when the spacing between the cylinders is much smaller than their cross-sectional dimensions. Lubrication theory is used to find the pressure drop across the grating and hence the force on each cylinder. A square array (or ‘lattice’) of closely packed cylinders is similarly treated.
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  • 150
    Publication Date: 1964-01-01
    Description: The properties of a turbulent flow are often described in terms of velocity correlations in space, in time, and in space-time. In this paper the interpretation of velocity correlation measurements which are made in a region of highintensity turbulence is considered in some detail. Under these conditions it is shown that some account must be taken of the effects of both mean and fluctuating shear stresses which are continuously modifying the turbulent structure. For an almost frozen pattern, for example, in the turbulence behind a grid, the turbulent convection velocity is amost equal to the mean flow velocity, while the space correlation and auto-correlation of the velocity fluctuations are simply related through this velocity. In contrast to this, when the intensity is high, the convection velocity may differ considerably from the mean velocity, while it is shown that different turbulent spectral components appear to travel at different speeds. This means that the turbulent spectrum and the turbulent space scales are no longer simply related. For example, the high-frequency spectral components may be ascribed to both the high-velocity eddies and the small wave-number components acting together.Experimental results are presented which indicate the conditions under which the assumption of a frozen pattern leads to uncertainties in the subsequent interpretation of the measurements. The measurements also show that the observed difference between the mean and the convection velocity may be qualitatively explained in terms of the skewness of the velocity signals.
    Print ISSN: 0022-1120
    Electronic ISSN: 1469-7645
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 151
    Publication Date: 1964-01-01
    Print ISSN: 0022-1120
    Electronic ISSN: 1469-7645
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 152
    Publication Date: 1964-01-01
    Description: In this paper some approximate results are presented for the problem of the stability of plane Poiseuille flow of a dusty gas, following a formulation given recently by Saffman (1962). It is assumed that the mass concentration of the dust, f, is small, and results are obtained by making a perturbation of the curve of neutral stability for a clean gas, using the approximate solutions given by Stuart (1954). The perturbation equation is expressed in terms of integrals by introducing the adjoint wave function, the calculation of which is described. The integral coefficients were evaluated by numerical integration using a Mercury computer, and the results are illustrated for f = 0.05 by a set of perturbed neutral stability curves at different values of the time relaxation parameter SR varying from 0 to 500. These results, whilst not of great numerical accuracy, are sufficient to show qualitatively how the curve of neutral stability is modified by the presence of the dust.
    Print ISSN: 0022-1120
    Electronic ISSN: 1469-7645
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 153
    Publication Date: 1964-01-01
    Description: Some simple similarity solutions are presented for the flow of a viscous fluid near a sharp corner between two planes on which a variety of boundary conditions may be imposed. The general flow near a corner between plane boundaries at rest is then considered, and it is shown that when either or both of the boundaries is a rigid wall and when the angle between the planes is less than a certain critical angle, any flow sufficiently near the corner must consist of a sequence of eddies of decreasing size and rapidly decreasing intensity. The ratios of dimensions and intensities of successive eddies are determined for the full range of angles for which the eddies exist. The limiting case of zero angle corresponds to the flow at some distance from a two-dimensional disturbance in a fluid between parallel boundaries. The general flow near a corner between two plane free surfaces is also determined; eddies do not appear in this case. The asymptotic flow at a large distance from a corner due to an arbitrary disturbance near the corner is mathematically similar to the above, and has comparable properties. When the fluid is electrically conducting, similarity solutions may be obtained when the only applied magnetic field is that due to a line current along the intersection of the two planes; it is shown that the effect of such a current is to widen the range of corner angles for which eddies must appear.
    Print ISSN: 0022-1120
    Electronic ISSN: 1469-7645
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 154
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    Journal of Applied Polymer Science 8 (1964), S. 1919-1919 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 155
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    Journal of Applied Polymer Science 8 (1964), S. 1903-1918 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The rate of crosslinking of concentrated gelatin solutions in water has been measured by means of a gelation timer. Some effects of temperature, pH, crosslinking agent, and gelatin concentration have been measured. The crosslinking agents have varied from fast-acting chrome alum, glutaraldehyde, and a carbodiimide to slow-acting mucobromic acid and dialdehyde starches. Detailed crosslinking mechanisms are discussed for dimethylol urea, mucobromic acid, and several dialdehyde crosslinking agents. Some effects of urea and other additives on the dimethylol urea crosslinking rate are described.
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  • 156
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    Journal of Applied Polymer Science 8 (1964), S. 1921-1939 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new method of curing phenolic novolac resins by means of cyclic formals under the catalytic influence of strong acids is given. It was proved that the formals react with the novolac molecules to form a highly crosslinked resite structure. As a practical consequence of this novel curing process it is possible to use the new resins at low or contact pressures in molding operations. The physical properties of the end products in general resemble those of the standard phenolic casting resins.
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  • 157
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    Journal of Applied Polymer Science 8 (1964), S. 1941-1947 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The analysis of a stationary, rotationally symmetric liquid jet which leads to an expression for the average normal stress at the exit of a capillary tube is reexamined with particular attention to the effect of surface tension. The limiting case of a nearly cylindrical jet is compared with the analysis presented by Gavis and Middleman.
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  • 158
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    Journal of Applied Polymer Science 8 (1964), S. 1889-1901 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The relationship between biaxial stress-rupture behavior and polymer morphology has been investigated for a series of compression-molded disks of linear polyethylene. Rupture data were obtained over a range of temperatures on polymers of several melt indices that had been solidified at two rates. Two failure mechanisms were observed: one at high stress levels, which was ductile; the other at low stress levels, which was brittle. The stress level at which the mechanism changed from ductile to brittle decreased as the measurement temperature increased, as the melt index of the polymer increased, and as the rate or solidification decreased. It was shown that initial pressurization of the disks causes the formation of microscopic surface fissures along spherulite boundaries as well as within individual spherulites. The extensive growth of these fissures at high stress levels sufficiently raises the stress on the sound portions of the polymer to cause large-scale macroscopic drawing of the spherulites. At low stress levels the initially formed fissures grow by a localized drawing process at their ends. A macroscopic crack forms by a chance coalescence of a number of individually growing fissures. This process is more rapid in disks of polymer that form large spherulites when cooled slowly from the melt. The spherulite size in disks of polymer of low melt index is much smaller under the same conditions of cooling and is less sensitive to the cooling rate than in disks of polymer of high melt index. Annealing of rapidly cooled disks whose microstructure contains relatively small spherulites reduces the stress at which the failure mechanism changes without appreciably altering the spherulite size. Oxidation of the polymer also reduces the transition stress.
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  • 159
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Many derivatives of phenyl salicylate turn yellow when they are exposed, in solution, to ultraviolet light. This limits their usefulness as ultraviolet stabilizers for plastics. Evidence is presented to support the postulation that the yellowing is due to the formation, by a photochemical ortho rearrangement, of a derivative of 2,2′-dihydroxybenzo-phenone. Aromatic salicylates, such as 2,6-dialkylphenyl salicylate, in which the ortho rearrangement is blocked, are found to be nonyellowing stabilizers, although less effective than the better yellowing varieties, such as p-octylphenyl salicylate. Loss of stabilizer by volatilization, either in compounding or during subsequent exposure, is shown to be an important factor in limiting the effective performance of the stabilizer.
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  • 160
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    Journal of Applied Polymer Science 8 (1964), S. 1985-1989 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new method for hydroxyl analysis is described in which excess toluene diisocyanate is reacted with a hydroxy compound, preferably in the presence of a catalyst, and the unreacted isocyanate is determined with dibutylamine reagent. The method is particularly applicable to polyethers intended for urethane foam preparation. It is rapid, is accurate, and has the added advantage of including such impurities as would be expected to consume isocyanate during a foam preparation.
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  • 161
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Determinations of the degree of chemical crosslinking and crosslinking efficiency values E (i.e., the number of sulfur atoms combined in the network per chemical crosslink present) have been used in conjunction with the chemical probes triphenylphosphine and sodium di-n-butyl phosphite to establish the structural features of sulfur links in vulcanizate networks derived from a variety of accelerated natural rubber-sulfur systems, from a cis-1,4-polyisoprene-TMTD-zinc oxide system, and from natural rubber and ethylene-propylene rubber crosslinked with a dicumyl peroxide-sulfur system. The triphenylphosphine converts polysulfide links into monosulfide and, to a lesser extent, disulfide links. The values of E′, i.e., the number of sulfur atoms combined in the network per chemical crosslink present after triphenylphosphine treatment are, therefore, a measure of the extent of main-chain modification in the network by cyclic monosulfide groups and/or pendant groups of the type: —Sx—Accel. (where x ≥ 1 and Accel. is an accelerator fragment). Sodium di-n-butyl phosphite cleaves di- and polysulfide crosslinks but leaves monosulfide and carbon-carbon crosslinks intact, and thus determination of the degree of chemical crosslinking before and after treatment with this reagent yields estimates of these two different classes of crosslinks. The combined results indicate that the efficiency of utilizing sulfur for crosslinking and, therefore, the structural complexity of the derived networks are very sensitive to the nature of the vulcanizing system (type and relative concentrations of crosslinking agent, accelerator, and activator) and vulcanizing conditions (time and temperature of cure). In general, the proportion of crosslinks which are di- and/or polysulfidic decreases with increasing cure time, and for the accelerated sulfur systems the structural complexity of the network increases with cure time, especially at higher vulcanizing temperatures and with low concentrations of fatty acid activator.
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  • 162
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    Journal of Applied Polymer Science 8 (1964), S. 2049-2065 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Small particles (ca. 700 A.) in an SB-R latex can be agglomerated (aggregation and coalescence) to the large size and heterogeneous distribution required for fluid high solids latex. This agglomeration is promoted by high molecular weight materials such as polyvinyl methyl ether (PVM). The mechanism of this agglomeration has been investigated. The effects of controlled variations in the amounts of PVM, electrolyte, soap and latex solids content were determined using statistically designed experiments. The agglomeration was found to differ from Smoluchowski kinetics in that it could best be described by the relationship: (1/n) = (1/n0) + at - bt2 where n = particle number, t = time and a and b are constants. The agglomeration rates were about 1011 to 1012 times slower than the theoretical Smoluchowski rapid coagulation rate. Increases in PVM, soap, and latex solids increased the agglomeration rate. The agglomerations were self-limiting and reached equilibria the level of which increased with increases in PVM and decreased with increases in soap. Regression equations relating the effects of the controlled variables on the agglomeration rate and the equilibria states are derived and presented graphically. The particle size distribution of the final latex was significantly correlated, with that expected from theoretical collision theory.
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  • 163
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    Journal of Applied Polymer Science 8 (1964), S. 2029-2048 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A. new theory for the acid-base properties of fibers is presented, resembling those for polyelectrolytes, and based on the normal titration of the charged groups of the fibers and the energy needed to remove the protons from the fiber to the solution, against the electrostatic, osmotic, and affinity differences. The acid titration equation for a poly-ampholyte fiber is: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm pH} = {\rm p}K_0 ^\prime - \log [{{\left( {1 - \alpha } \right)} \mathord{\left/ {\vphantom {{\left( {1 - \alpha } \right)} \alpha }} \right. \kern-\nulldelimiterspace} \alpha }] - \left( {{{0.4343} \mathord{\left/ {\vphantom {{0.4343} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)[\chi F + \tau \bar V_{\rm H} + \Delta \mu _{\rm H}^{\rm o} ] $\end{document} where pK0′ is the intrinsic dissociation constant of the titration groups in the fiber, α is the degree of dissociation, χ is the electrostatic potential of the fiber, τ the osmotic pressure, V̄H the partial molar volume of the hydrogen ion, and ΔμHo the difference of standard chemical potential in the fiber and the solution. In all cases examined, the osmotic term proved to be negligible. The electrostatic potential was calculated as suming it to be uniform over the fiber. For wool, pK0′ is independent of salt concentration but varies linearly with degree of dissociation, indicating that two pK's are operating, pKq = 3.585 for paired groups and pKp = 4.855 for nonpaired groups at 0°C., present in equal proportions. Titrations of wool with sulfuric acid and a wide range of strong monobasic acids also obey the theory, and values of the anion affinities in general agreement with those given by Gilbert and Rideal are found. The acid titration of native ox-hide collagen gave a constant value of pK0′ = 4.0. For nylon, the value of pK0′ is, to a first approximation, independent of degree of dissociation and salt concentration, in agreement with the theory.
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  • 164
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    Journal of Applied Polymer Science 8 (1964), S. 2067-2093 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Undrawn nylon was found to be susceptible within a few days to degradation in wet or humid conditions at temperatures between 50 and 90°C. Model N-substituted amides, although not affected by these conditions, were attacked by hydrogen peroxide solutions. The degradation proceeded principally by rupture of the bond between the nitrogen of the amide and the carbon of its α-methylene group, consequent upon oxidation at this carbon. Unsubstituted primary amide, carboxyl, and aldehyde endgroups were formed, together with ammonia by hydrolysis of the oxidized amide. The bond between the α and β carbons of an N-methylene chain also suffered breakage, giving formic acid and carbon dioxide. The former could also arise by rupture of any initially produced N-formyl or N-formoyl amides. The appearance of lactic acid from butylacetamide showed that oxidation could proceed along the N-alkyl chain. Fragments of suitable size broken from the main chain of nylon became water-soluble and relatively stable to further attack by air or oxygen. These pieces essentially retained the nylon structure, but possessed two carboxylic ends and an average molecular weight of less than 600. A maximum oxygen uptake of about 30 moles per mole of original amide was calculated, corresponding to complete conversion into these soluble fragments. Significant degradation did not occur for many months at 60°C. in dry conditions or in solutions of 8-hydroxyquinoline, a process which has been patented. The latter was considered to function by chelating heavy metals into an inactive form and inhibiting peroxide formation.
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  • 165
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    Journal of Applied Polymer Science 8 (1964), S. 2095-2115 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dynamic mechanical loss measurements were made on fibers at large tensile strains which caused nonlinear viscoelastic behavior. Measurements on fibers from polyethylene, polypropylene, nylon 66, nylon 4 and an experimental polymer led to seven energy loss peaks for each sample in the temperature range of 120-350°K. The peaks were evenly spaced in temperature at intervals of 30-35°K. rather than at unequal temperature intervals of approximately 100-150°K. normally observed under conditions of linear viscoelastic behavior. In every case, the array of evenly spaced peaks occurred only at temperatures below the glass transition temperature. The temperatures at the energy loss peaks were virtually independent of crystallinity and molecular orientation and were interpreted in terms of polymer molecular structure. The data could be explained only by a single mechanism, common to all polymers, which could operate in a quantized manner, e. g., diffusional motion of molecular chain segments. To account for the constant temperature spacing between peaks of a given sample, it was necessary to assume that the rate controlling step in the energy loss process is the return of a displaced segment to equilibrium. Calculations from the experimental data indicated that peaks at higher temperatures stem from displaced molecular segments which experience high potential energy barriers and which have to be excited to higher skeletal vibrational energies to overcome the barrier. Precedence for this interpretation is provided by Tanaka and Ishida, who have associated molecular vibrations with the well-known β loss peaks in polymers.
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  • 166
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    Journal of Applied Polymer Science 8 (1964), S. 2461-2461 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 167
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    Journal of Applied Polymer Science 8 (1964), S. 3-24 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The tensile properties of two cast and two extruded solid rocket propellants were studied at 25°C. and 50% R.H. over a range of failure times from 0.005 to 2500 sec. The effects of temperature were also investigated at the highest rate and at 0.1 in./in./min. over a range of -60 to 80°C. The results indicate that both temperature and rate of loading greatly affect the tensile properties of double-base propellants.
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  • 168
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Compounds other than peroxides may be used to enhance the self-extinguishing action of organic bromine compounds on polystyrene. The addition of certain chloramides or nitrosoamines converts some bromide-containing polystyrene compositions from flammable to instantly self-extinguishing. Two effective chloramides were N,N-dichlorotoluene sulfonamide or N,N′-dichloro-N,N′-diphenyl urea but they were of limited value because of hydrolysis by atmospheric moisture. The more effective nitrosoamines were N-nitroso-N-methylaniline, N-nitrosocarbazole and N-nitroso-diphenylamine. An undesirable characteristic of the three compounds is their inhibition of polymerization of styrene. The interaction of a nitrosoamine and an aliphatic bromine compound is apparent from the evolution of nitrogen, nitric oxide, and nitrous oxide. If the minimum temperature for gas evolution falls in the range of about 145-180°C. in a prescribed simple test, the nitrosoamine and bromine compound may be used for rendering polystyrene self-extinguishing.
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  • 169
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The preparation of radiation-induced graft polymers of cotton cellulose, while retaining the fibrous nature and high molecular weight of the cellulose, depended primarily on the radiochemical yields of cellulose reactions and of graft polymerization reactions. Yields of the initial major molecular changes in cellulosic polymer indicated that, in the case of scission of the molecule and carboxyl group formation, chain reactions were not initiated by radiation; however, in the case of carbonyl group formation chain reactions were initiated but quickly terminated. Generally, experimental procedures, used in graft polymerization reactions, were: (1) simultaneous irradiation reactions, that is, application of monomers or solutions of monomers to cellulose or chemically modified celluloses, then irradiation; and (2) post-irradiation reactions, that is, irradiation of cellulose or chemically modified celluloses, then after removal from the field of radiation, contacting the irradiated cellulose with monomer. Some of the most important factors influencing the radiochemical yields of graft polymerization reactions of styrene and acrylonitrile onto cellulose were: concentration of monomer in treating solution; solvent; ratio of monomer solution to cellulose; prior chemical modification of cellulose; and absence of oxygen, particularly in post-irradiation reactions. Experimental data were presented, and the direct and indirect effects of Co60 γ-radiation on these reactions were discussed.
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  • 170
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    Journal of Applied Polymer Science 8 (1964), S. 723-734 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The aerobic and anaerobic stress relaxation of unaccelerated natural rubber-sulfur vulcanizate networks has been examined before and after treatment with triphenylphosphine, a reagent which converts polysulfidic crosslinks into di- and monosulfide crosslinks. This treatment reduces the rate of anaerobic stress relaxation and makes the network more susceptible to protection by zinc dibutyldithiocarbamate against aerobic stress relaxation. Aerobic stress relaxation of the network after treatment with triphenylphosphine remains nonautocatalytic, indicating that it still contains the precursor of an antioxidant, and crosslinking continues to occur during aging, showing that the presence of polysulfide groups is not a sole prerequisite for such network formation.
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  • 171
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    Journal of Applied Polymer Science 8 (1964), S. 707-721 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Tensile fatigue failure of a gum vulcanizate of noncrystallizing SBR can be accounted for by the growth of small flaws initially present in the rubber. Fatigue of crystallizing natural rubber was shown in Part I to be attributable to the same cause. Cut growth results are interpreted in terms of the tearing energy theory of Rivlin and Thomas. SBR exhibits cut growth under both static and dynamic conditions; in each case the rate is approximately proportional to the fourth power of the tearing energy. Variation of the dynamic cut growth rate with frequency can be explained by the summation of a timedependent static component of growth and a cyclic component not dissimilar to that occurring in natural rubber. Fatigue failure, under both static and dynamic conditions, is predicted from the cut growth results. These predictions are found to account quantitatively for experimentally observed fatigue lives when a suitable value is assumed for the initial flaw size. Fatigue lives at different temperatures correlate well with cut growth results obtained by Greensmith and Thomas over the same temperature range. The results are compared to those obtained previously for natural rubber, and possible reasons for the differences in fatigue behavior of crystallizing and noncrystallizing rubbers are discussed.
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  • 172
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    Journal of Applied Polymer Science 8 (1964), S. 747-754 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermal dehydrochlorination of PVC has been examined on some samples prepared by fractionation of a commercial PVC, and some other samples obtained by polymerization at different temperatures. The results disagree with the concept of a continuous dehydrochlorination from one side to the other of the chain, that necessitates initiating structural anomalies in the macromolecule itself.
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  • 173
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    Journal of Applied Polymer Science 8 (1964), S. 735-745 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An apparatus is described for measuring the flow rate of cellulose xanthate solutions at known pressure gradients across spinning jets. It is shown that the jet hole behaves more like a capillary than an orifice in its effect on flow and that similar relationships exist for flow through spinning jet holes and a narrow pipe characterized by an equation of the form Q = Apb, where b has a value of approximately 1.5 for the high rates of shear strain found in spinning jets and 1.4 for the lower rates found in the pipe. A fundamental approach shows a similar discontinuity when comparing the relation between apparent viscosity coefficient and rate of shear strain, between low and high rates of shear. Experimental results are given for the effect of certain chemical factors in viscose solutions and the effect of spinning jet hole size, on the flow rate/pressure gradient curve.
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  • 174
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    Journal of Applied Polymer Science 8 (1964), S. 141-149 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Burst tests on thin wall circular cylinders of aluminum, brass and magnesium alloys, mild steel and polymethylmethacrylate plastic are described in which stress and strain are measured at impact velocities of 14-31 ft./sec. The apparatus consists of an hydraulic cylinder and piston assembly attached to the inside of the specimen, with a falling weight producing a pressure pulse. Measurement problems inherent in the technique are analyzed: e.g., local instability leading to blister formation. An increasing amount of uniform deformation occurs in the specimen as strain rate is increased.
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  • 175
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Techniques for studying brittle fracture over a strain rate range of 10-7-101 in./in./sec. and at temperatures from 75 to 1800°F are discussed. Techniques for achieving a uniaxial tensile stress in prismatic bars via a reflected stress wave method at strain rates up to 103 in./in./sec. at room and elevated temperatures are presented. Results of the aforementioned effects in flexure, and experimental verification of the stress-time-position history for the stress wave loading technique are presented along with applicable theoretical explanations. Applications of the above techniques to a broader spectrum of brittle and semi-brittle materials are described.
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  • 176
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    Journal of Applied Polymer Science 8 (1964), S. 119-140 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The standardization of notched Izod impact test data to normalized values of foot pounds per inch of notch is based on the assumption of a 1:1 increase in breaking strength with increasing notch width. This assumed relation is not supported by experimental tests on commercial thermoplastics. As notch width was increased from 1/8 to 1/4 to 3/8 to 1/2 in., nine of ten thermoplastics tested showed a decrease in normalized impact strength. Each material appears to show a characteristic loss in breaking strengths as the notch width increases. A technique developed for calibration of pendulum impact testers has been used to examine the variation of impact breaking strength in relation to the total kinetic energy of the hammer. Experimental tests show practically no change in impact strengths up to values that take 2/3 of the available hammer energy. Experimental work on the comparison of the impulse transferred by the hammer during breaking with impulse curves photographed by the Autographic Impact test show very good agreement for catastrophic breaks and fair agreement for plastic type breaks. The reduction in recorded impulse is attributed to the degrading of the sample during the plastic portion of the breaking cycle. The peak force of thermoplastics as measured by the Autographic Impact test increases as the temperature decreases from 100°C. or above to 0°C. Over the same temperature range flexural tests on small cantilever samples of these thermoplastics show the same thermal dependence for the flexural yield or permanent distortion stress. Plots of the impact peak forces and flexural yield stress at corresponding temperatures give a linear correlation. Each thermoplastic material exhibits a unique relation for this correlation between impact yielding and flexural yielding. This correlation between the impact and flexural tests over the range of temperatures is the first known experimental indication of a direct relation between impact properties and standard physical tests.
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  • 177
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    Journal of Applied Polymer Science 8 (1964), S. 1497-1497 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 178
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    Journal of Applied Polymer Science 8 (1964), S. 1667-1676 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Kinetic data for vulcanization of rubber with sulfur, accelerated with 2-mercaptobenzothiazole (MBT) are presented. The decrease in concentration of sulfur and MBT during vulcanization under various conditions of temperatures have been determined with a precise amperometric method developed by the authors. The order of reaction for disapperance of sulfur was found to be unity. The energy of activation and frequency factor were 28.8 kcal./mole and 4.0 × 1013, respectively. The kinetics of disapperance of MBT was also first-order, and the rate of reaction, energy of activation, as well as frequency factor were much lower than those for the disapperance of sulfur. The consumption of sulfur proceeded as long as any free sulfur was present in the sample, indicating that the consumption of MBT is closely tied up with the disapperance of sulfur. It was found that about 133 atoms of sulfur were consumed for the disappearance of one molecule of MBT. The mechanism of ring opening involving an attack by the accelerator radical as proposed by Gordon is supported by the present investigation.
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  • 179
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    Journal of Applied Polymer Science 8 (1964), S. 1677-1689 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The tensile properties of bisphenol A polycarbonate films were measured as a function of temperature from +25 to -180°C. The tensile properties at a given temperature were determined from the measured true stress-true strain behavior of the polycarbonate films by means of a photographic strain recording technique. The temperature dependence of the following tensile properties is presented: the yield stress, the fracture stress, the strain to yield, the cold-drawing strain, the fracture strain, and the strain-hardening rate.
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  • 180
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    Journal of Applied Polymer Science 8 (1964), S. 971-983 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: When well oriented and crystallized high density polyethylene film was redrawn, slip deformation and twin deformation, the mode of which depends upon the redrawing angle to the original drawn structure, could be observed. When the redrawing angle is very small, single slips, the direction of which is [001] to the original drawn structure, and homogeneous deformation bands attached to them are usually observed. The [001] directions of slipped and unslipped regions are slightly at an angle to each other. As the redrawing angle approaches a right angle, kink bands can be observed. From these results we may conclude that the structure of this drawn polyethylene film is very similar to that of a single crystal or metal.
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  • 181
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    Notes: The faint emission of light by various classes and types of polymers when heated in the presence of oxygen, oxyluminescence, was studied by means of a photomultiplier tube and sensitive microammeter. Among the polymers with a carbon-carbon backbone, the polymers having the greater number of tertiary carbon atoms generally showed greater intensities of luminosity. Polystyrene was a notable exception to this generalization. The shape of the luminosity versus time curves varied with the type of polymer. It was also found that the emission of light did not stop instantly when the oxygen atmosphere was replaced by an inert gas, but rather followed an exponential type of decay. The rate of decay appeared to be different with different types of polymers. The intensities of luminescence and the times required to reach maximum or steady state luminescence were compared with oxygen uptake data for various polymers. In general there was a qualitative, but not necessarily quantitative correlation between the luminous intensities and polymer stabilities in the presence of oxygen.
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  • 182
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    Journal of Applied Polymer Science 8 (1964), S. 1691-1698 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Acetic and formic acids and acetone are products of the oxidation of propylene and ethylene polymers and copolymers. The two- and three-carbon products can be accounted for as the result of intramolecular attack by radicals, leading to β-oxidation. A high proportion of scissions in polypropylene involves multiple intramolecular attack.
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  • 183
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    Journal of Applied Polymer Science 8 (1964), S. 1763-1776 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The insolubilization of polyvinyl alcohol by potassium dichromate on exposure to light has been investigated. Ultraviolet spectrometry shows that secondary hydroxyl groups are oxidized to ketone groups but insolubilization is attributed to crosslinking of polymer chains by co-ordination of alcohol groups to “nascent” chromic ions formed by reduction of the dichromate. Exposure to air saturated with water vapor eliminates the carbonyl absorption maxima from the ultraviolet spectrum of polyvinyl alcohol film but the spectrum can be restored by heating: this phenomenon is independent of the crosslinking reaction.
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  • 184
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    Journal of Applied Polymer Science 8 (1964), S. 1751-1762 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An instrumented tensile impact test which allows a load time curve to be obtained coincident with the energy to rupture values has been applied to the examination of a series of linear polyethylene homopolymers and copolymers of varying molecular weight and thermal history. The effect of test specimen geometry was also investigated. A morphological examination of these resins indicated a strong dependence of spherulite size on molecular weight, and to a much lesser degree on molding conditions; it appeared to be independent of comonomer. The overall crystallinity, as determined by both x-ray and density methods, and crystallite perfection was increased by a slower crystallization rate, but was independent of molecular weight. The tensile impact strength (energy to rupture) was found to increase with molecular weight, and decrease on the introduction of comonomer. But the effect of thermal history gave rise to results which bore no clear-cut relation to molecular and morphological parameters. The value of the instrumented tensile impact test is shown by the fact that these apparent anomalies can now be resolved by separating the elastic and plastic portions of the deformation. An increased level and perfection of crystallinity results in higher load bearing properties accompanied by a reduction in duration of impact. It is primarily the duration, rather than the peak load, which is affected by molecular weight. The main effect produced by changing from a type L (long) tensile impact specimen to a type S (short) was to reduce considerably the duration of the plastic region while simultaneously raising the maximum elastic load; this is thought to be associated with a more localized deformation and therefore a higher rate of strain.
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    Journal of Applied Polymer Science 8 (1964), S. 1787-1799 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: We have prepared some nitroalkyl acrylates and methacrylates by a method involving alcoholysis, and investigated their polymerizability. 2-Nitrobutyl acrylate (NBA) was extensively studied. The especially purified NBA monomer has good polymerizability without inhibiting radical polymerization and gives a thermally stable polymer. From copolymerization experiments with styrene, methyl methacrylate, and acrylonitrile, the Q and e values of NBA were estimated to be 0.47 and 0.85, respectively. The copolymerization behavior of NBA with some polyglycol dimethacrylates and unsaturated polyesters are comparable to those of n-butyl acrylate. This monomer has little tendency to polymerize with organometallic initiators, but some polymers obtained are found to be crystalline. The polar and steric effects of the nitro group situated on the ester side chain are discussed.
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  • 186
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    Journal of Applied Polymer Science 8 (1964), S. 1801-1812 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: High resolution electron microscopy of sodium lignin sulfonates revealed a granular microstructure of spherical particles of diameters ranging from 30 to 90 A. The weight average particle weight, Pw was computed from the dimensions measured on the electron micrographs and the density of lignin. For a fraction of intermediate molecular weight, the particle diameter derived from Pw was 64 A., in fair agreement with a value of 49 A. computed from the sedimentation equilibrium molecular weight. A high molecular weight fraction contained, in addition to the granular moiety, larger structures which appeared to be aggregates of the granules. The particle weight distribution for the high molecular weight fraction was similar to the distribution of sedimentation constants previously found for alkali lignins. The spherical shapes for both the granules and the aggregates was in accord with the compact spherical configuration previously proposed for lignin sulfonates in aqueous solution.
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  • 187
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    Journal of Applied Polymer Science 8 (1964), S. 1813-1824 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The water sorption by adult and embryonic native and insoluble collagen was investigated, along with that of calfskin gelatin. Greater sorption was obtainable with the collagen fractions than with gelatin, but the technique could not distinguish the fractions themselves. The suggestion is made that the greater sorption by collagen over gelatin and differences in apparent wettability between the adult and embryonic insoluble collagen might be explained by the formation of helical grooves with aging. Density measurements of the collagen fractions indicate that collagen becomes more crystalline with aging. This also applied to the insoluble collagen. These results are consistent with the view that differences in collagen solubility are due to differences in molecular ordering. The density of the insoluble collagens and gelatin passes through a maximum at 3-4% sorbed water. The phenomenon is explained on the basis of water bridges comprised of a single water molecule double hydrogen bonded to closely aligned chains. A discussion is presented in this connection. A calculation based on the density yields a molecular volume of 4.32 × 10-19 cm.3 For tropocollagen. This is in agreement with the molecular dimensions and consistent with the idea that collagen is formed from an aggregation of the monomer.
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  • 188
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    Journal of Applied Polymer Science 8 (1964), S. 1077-1087 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of mastication on stress relaxation of raw rubber was studied in the range of 20-120°C. The stress relaxation time became shorter with increasing mastication, and the modulus also decreased. The modulus decreased with increasing temperature of measurement. Moreover, it is found that mastication caused the solution viscosity of rubber to decrease, and on heating an intermolecular reaction and cleavage of molecules by oxidation appeared to occur at the same time.
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  • 189
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    Journal of Applied Polymer Science 8 (1964), S. 1089-1096 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The labile hydrogen of the carbamate group is primarily responsible for color development in the thermal degradation of polyurethane. Replacement of this hydrogen by an alkyl group prevents back-dissociation. Accordingly, a number of N-substituted polyurethanes were prepared, including the methyl, benzyl, benzoyl, acetyl, and the (N-phenylamido) derivatives. Comparative studies at 150-155°C. showed that the N-methyl and N-benzyl polymers possess outstanding stability under the condition of our testing.
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  • 190
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    Journal of Applied Polymer Science 8 (1964), S. 1129-1146 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A continuum theory of nonlinear viscoelastic behavior has been developed which is applicable to the quantitative description of the rheological properties of high polymeric materials. Particular classes of deformations have been investigated. Special emphasis has been placed upon nonlinear effects in viscoelastic fluids such as normal stresses and variable viscosity. Two new classes of flows are defined: sufficiently smooth flow and isoelastic flow.
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    Journal of Applied Polymer Science 8 (1964), S. 1097-1111 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The approximate solutions of the three-dimensional, fundamental equation for the molecular orientation of a spun fiber are obtained, a rigid ellipsoid model for the molecular segments or the paracrystalline structure being assumed. A rate of strain G (sec.-1) of a molten fiber and a rotational diffusion constant D (sec.-1) of the segment are approximated as a function of time t (sec.) as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {G = G_0 + G_1 t + G_2 t^2 + \ldots } \\++ {D = D_0 + T_1 t + \ldots } \\ \end{array} $$\end{document} Under the conditions, 1〉〉G0t〉〉G1G2〉〉G2t3〉〉 … and 1〉〉D0t〉〉D1t2〉〉… a coefficient of the molecular orientation f of spun fiber is found to be: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\begin{array}{*{20}c} {f = \frac{2}{5}\int_0^t {Gdt} } \hfill & { - \frac{6}{5}G_0 \left( {\left. {D_0 - \frac{1}{{21}}G_0 } \right)} \right.t^2 } \hfill \\ {} \hfill & { - \frac{2}{5}\left( {\left. {\frac{2}{{21}}G_0 3 + \frac{4}{7}G_0 2D_0 - 6G_0 D_0 2 - \frac{1}{7}G_0 G_1 + 2G_0 D_1 + G_1 D_0 } \right)} \right.t^3 + \ldots } \hfill \\ \end{array}} $$\end{document} The applicability of these approximate, theoretical results is extremely limited in the neighborhood of the spinneret under practical melt spinning conditions. However, the theory should be useful in the case where the polymer temperature is near its melting temperature and the extension rate of spinning fiber is small.
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    Journal of Applied Polymer Science 8 (1964), S. 1113-1128 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A theory of tensile rupture in a noncrystallizing rubber, a particular instance of a more general theory of rupture in simple extension, is outlined. The theory assumes that failure takes place by growth of a crack from some imperfection in the material where the stress is high locally. The imperfections are considered as being equivalent, in terms of stress concentration effects, to small cracks initially present in the material, and the conditions for crack growth to occur are then treated on the basis of the tearing energy criterion of Part I. It is assumed, by analogy with tearing on a macroscopic scale, that the crack grows continuously with time at a rate, dc/dt, given by: dc/dt = ATn, where A and n are constants and T is the energy expended per unit increase in crack length, per unit thickness of specimen. The predicted relationships of the breaking time to the stored energy density and initial crack length for specimens tested by stretching at uniform rates and by holding at fixed extensions are first compared with the results of model experiments on test pieces containing small tears and cuts. Values of A and n derived from tear test data are used in the theoretical relationships, and it is shown that there is fair agreement with experiment. Results of tests on tensile test pieces containing no deliberately introduced tears or cuts are then shown to be consistent with a failure mechanism of the above type. It appears, however, that the tearing energies in tensile rupture are lower than those observed in tear tests, and reasons for this difference are discussed.
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    Journal of Applied Polymer Science 8 (1964), S. 1185-1204 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In the present investigation the kinetics of thermal polymerization of shellac has been studied. A linear relationship between the intrinsic viscosity [η] and the time of polymerization has been observed up to a certain extent of reaction followed by a sharp rise in value of [η] near the gel point. After gelation the intrinsic viscosity of the sol fraction again falls abruptly. Besides, an attempt has also been made to understand the nature of gelation from the weight fractions of gel formed after prolonged curing at different temperatures.
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  • 194
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    Journal of Applied Polymer Science 8 (1964), S. 1147-1168 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Syntheses are described where dimer fatty acid (C36), or anhydrides of trimellitic, or pyromellitic, or dodecenylsuccinic acids are substituted in part for components of a model polymer derived from 1 mole each phthalic anhydride and glycerol, and 0.4 mole of linoleic acid. These polymers are compared at several degrees of polyesterification with respect to endgroup analysis, melt and intrinsic viscosity, and fractionation and emulsification behavior in water-solvent mixtures. The data suggest that predictions of the gel point in terms of functionality concepts are of general value only for defining the reaction degrees where insoluble molecules can first appear. The experimental event of gelatification can be delayed to varying degrees by different types and concentrations of inert solvent. The extent of reaction where molecular complexity can give a gellable polymer in the absence of solvency retardation occurs near the theoretical gel point and can be located by inspection of functions relating either melt or intrinsic viscosity to molecular weight. Significant differences in polymer structure have a very small effect on this parameter, nor is there much evidence to show preferential reactivity of similar functional groups associated with different structures. Other data here cited demonstrate some practically useful facts regarding how composition and molecular weight affect solvency behavior; however, no general correlations were found which relate solubility behavior to quantities here miasured.
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    Journal of Applied Polymer Science 8 (1964), S. 1205-1211 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In the present communication the effect of p-toluenesulfonic acid catalyst on thermal polymerization of shellac has been investigated. The difference in activation energy for uncatalyzed and catalyzed reaction, has been computed to be 7.4 kcal. when c = 0.1%. The activation energy for uncatalyzed reaction, calculated on this basis comes to 12.5 keal.
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  • 196
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    Journal of Applied Polymer Science 8 (1964), S. 1169-1183 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermal antioxidant behavior of carbon black was studied in vulcanized cis-polybutadiene and related to the surface chemistry of the black. Continuous and intermittent stress-relaxation and oxygen absorption measurements were employed to determine the antioxidant ability of the carbon blacks. The blacks were characterized by the surface concentrations of oxygen-containing functional groups, using methods described in the literature. Antioxidant activity was found to be highest in carbons containing relatively large amounts of bound oxygen. These carbons are also acidic and decompose peroxides by the ionic mechanism. This was demonstrated with dicumyl peroxide. However, even though the acidity and ability to decompose dicumyl peroxide to phenol and acetone could be destroyed by methylation, this treatment did not seriously impair the antioxidant activity, so that the role of acidic groups appears to be minor. Evidence is presented which suggests strongly that the antioxidant behavior of carbon blacks is due to surface quinones, possibly hydrogen-bonded with adjacent hydroxyl groups. Measurements made on samples vulcanized in peroxide and sulfur curing systems indicate that the antioxidant behavior of carbon black is independent of the method of vulcanization in the absence of other antioxidants. A characteristic feature of the antioxidant action of carbon blacks is their tendency to repress the oxidative crosslinking reactions, the relative amount of compensation of chain scission by crosslinking being smaller than in gum vulcanizates.
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  • 197
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    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 1213-1220 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The OH → OD exchange reaction between deuterium oxide vapor and cellulose has been studied for thirteen different types of cellulose; the extent of exchange in a cellulose was determined by measuring the increase in the dry weight of the sample. With each cellulose the deuteration reaction was in two stages, a rapid stage followed by a slow stage; the material that exchanges during the rapid stage is the infrared-amorphous fraction of the cellulose, and therefore values for the amorphous fractions of the thirteen samples could be obtained. These amorphous fractions were found to be linearly related to the moisture regains of the samples. There is tentative evidence that the cellulose II samples absorb slightly more water into a unit amount of amorphous material than cellulose I samples.
    Additional Material: 2 Ill.
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  • 198
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 1275-1279 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Samples of PVC, obtained by bulk polymerization were tested. Molecular weight distribution by nephelometric titration, number of branching by viscosity measurement, and density of the powders and films using a density gradient column were assessed. Microphotographs of the powders were taken. It was found that the average number of branching in 1000 monomer units is approximately proportional to the contact surface of the liquid and solid phase.
    Additional Material: 3 Ill.
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  • 199
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 1221-1255 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Ease of processing suspension-polymerized polyvinyl chloride (PVC) is related to its ability to accept sufficient plasticizer, while remaining a dry, free-flowing powder. The successful incorporation of plasticizer, termed cold preblending or hot dryblending, depends upon basic physicochemical factors. Cold preblending corresponds to a purely geometrical filling of intraparticle pores and fissures, while hot dryblending depends additionally upon a time-dependent absorption. Quantitative laboratory tests for these two effects were developed and standardized. When applied to experimental and commercial lots of PVC and their fractions, the tests gave results which showed slight correlation with gross properties of the particles. However, intercorrelation between tests for cold preblending and hot dryblending was strong, indicating that the same factors may be responsible for both. The tests also provided good ratings of polymers for actual processing behavior. It is possible to control particle geometry via the process variables of suspension polymerization, and thence to regulate cold preblending behavior; the effects on hot dryblending are not as clear. Post-polymerization grinding markedly alters the PVC particle surfaces and can substantially improve hot dryblending capacity. Severe grinding is needed to change particle geometry enough for any large improvement of cold preblending.
    Additional Material: 14 Ill.
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  • 200
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 1281-1286 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The method of calculation of the intrinsic viscosity [η] from one viscosity measurement according to the Solomon and Ciutǎ's equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} [\eta ]c = \sqrt 2 \sqrt {\eta _{sp} - \ln \eta _r } \\ \\ \end{array} $$\end{document} has been analysed. The difference between [η] extrapolated from the measurement of viscosity at several concentrations and [η] calculated has been defined in dependence on the product [η]c and the value of Huggins' constant k'. It has been demonstrated that the proposed equation is often useful but not generally valid; the range of its applicability has been defined.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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