Bibliothek

Notizen: This investigation considers a hypothetical three-phase ordered composite to permit the design of a new material both stiffer and tougher than the matrix phase alone. The required elastic solution is greatly simplified and was based on a single layered inclusion in an otherwise infinite matrix under uniaxial tension. The solution presented is exact and generalized to accommodate any number of concentric layers of different thickness and composition.

Notizen: Attempts to use low-cycle fatigue techniques derived from the work of Coffin and Manson to predict the fatigue performance of six diverse structural plastics are discussed. Through an analysis of dynamic property and thermal behavior studies of polymer samples in reversed-tension fatigue, an improved model for the polymer fatigue process has been proposed. Laboratory test data are presented illustrating the relationship between the various models.

Notizen: It is postulated that property gradients exist at the interface forming an “interphase” between the insert and the matrix. Such gradients might be caused by partial solubility and diffusivity of the two phases comprising a composite. For simplicity, the “interphase” is replaced by a shell exhibiting averaged properties (Eshell = 1/2 Einsert + 1/2 Ematrix, etc.). An exact linear elastic solution was employed to evaluate stress fields throughout all regions. The possible effect of the “interphase” and its thickness on several physical properties of the composite are evaluated in terms of the particular stress fields.

Notizen: An investigation of the dynamic mechanical properties of several molten polymers was performed using the Maxwell Orthogonal Rheometer. Relaxation spectra derived from experimental data for the terminal region of viscoelastic response indicate that as molecular weight distribution broadens, terminal relaxation phenomena associated with molecular disentanglement and translation extend over a corresponding wider frequency range. The same data indicate that a true maximum relaxation time beyond which no elastic response is observed exists for the materials studied. Moreover, the maximum relaxation time corresponds to the reciprocal of the frequency where the dynamic viscosity deviates from its zero-shear value. Thus an estimate of the time necessary for complete elastic recovery in polymer melts is readily obtained experimentally.

Notizen: Tensile creep measurements were carried out on a commercial ABS polymer over a temperature range from 40 to 100°C at stress levels from 0.6 to 1.8 × 108 dynes/cm2. Experiments were conducted in a prototype of an apparatus designed to be compatible with digital acquisition systems. Analysis of the data indicated that application of the time-temperature super-position principle was of limited value due to the use of test temperatures near and below the effective glass transition temperature of the acrylonitrile-styrene component of the polymer. A strong stress dependence of the compliance was observed, even at relatively short times after loading. This was analyzed in terms of a model in which the height of the potential energy barrier to motion of the molecular flow unit is lowered by the application of stress. Analysis of the temperature dependence of the compliance at low stress levels indicated that the effective Tg of the acrylonitrile-styrene phase is about 85°C. The temperature dependence of the magnitude of the activation energy is considered as is the stress dependence of the glass transition temperature. Implications of short-time response in creep with regard to response under impact loading are pointed out. Practical application of results to the prediction of dimensional stability of molded parts is discussed as well as the limitations involved in extrapolation of experimental data to long times and high stress levels.

Notizen: Fine structures of several plastic/rubber two -phase polymer systems were studied by means of direct observations of ultrathin sections under the electron microscope using osmium tetroxide staining and a hardening procedure developed recently by Kato. Samples used are several types of both ABS polymers and high -impact polystyrenes, and several PVC/rubber blends and the results were discussed in relation to their dynamic viscoelastic properties. It is suggested that these studies may fruitfully be extended to clarify the structure -to property relationships by use of this method.

Notizen: The purpose of this paper is to describe a new deformation calorimeter, which is based on differential thermometry and uses a flowing gas stream as a heat transfer medium which allows it to operate under near-isothermal conditions. Also presented are some preliminary test measurements with a crosslinked polyurethane elastomer and crystalline polybutene-1.

Notizen: Antiplasticizers are considered to be diluents which when added to polymers result in mechanical property behavior opposite to that of plasticization. The addition of antiplasticizers to certain polymers such as Bisphenol A polycarbonate, polysulfone, and polyvinyl chloride results in the elimination of the secondary loss transitions of these polymers. As a drop in modulus accompanies these transitions, their elimination results in higher tensile strength and tensile modulus. As secondary transitions are commonly associated with ductility and impact strength, their elimination also results in the observed embrittlement characteristics. The addition of anti-plasticizers to polymers also restricts the diffusion of penetrants resulting from the decrease of molecular flexibility in the polymer matrix.

Notizen: A useful concept in polymer science is the degree of crystallinity - the fraction of the polymer that exists in a relatively ordered state. Methods of determination of the degree of crystallinity using density, infrared, thermal, N.M.R. and X-ray measurements are examined in light of modern notions of the structure of semi-crystalline polymers.

Notizen: The changes occurring when polythene melts are subjected to shear, have been investigated using a rotating bob fitted into a ram extruder. In addition to chain scission, low density polythene exhibits reversible changes in mechanical and viscoelastic properties. The magnitude of the changes is controlled by total shear strain, and is related to molecular weight and long chain branching. The mechanism appears to be one of reversible disentanglement operating mainly on the large highly branched molecules. The work is relevant to various extrusion processes and to other long-branched polymers.

Notizen: This investigation deals with the fatigue behavior of a group of thermoplastics fortified with discontinuous glass fibers dispersed by an injection molding process. The thermoplastics included nylon, polystyrene and polyethylene reinforced with short (1/8 in.) and long (1/2 in.) glass fibers.Several aspects of the fatigue behavior are included in the study. First, classical S-N curves were generated under fluctuating tension with R = 0.05 to show the loss of strength due to cyclic load application. Next, the extent of progressive fatigue damage was established by measuring the residual strength after cyclic loading. Finally, hypotheses pertaining to the fatigue mechanisms operative in all four materials were made based on microscopic examinations of sections removed from fatiguedamaged specimens.

Notizen: Twelve polymers and copolymers reinforced with random short glass fibers are used for the study of the strength -composition relationship. Six of these reinforced systems are new and have not been reported elsewhere. The effect of fiber volume fraction on tensile and flexural strengths is related to the Kelly and Tyson equation. For each composition the strengthening factor, F, is calculated and discussed with respect to the structure of the polymer. One factor pertaining to the actual performance of fiber glass, fiber efficiency, K, has been extrapolated for the fiber glass used for this study. The effects of fibers on toughness and the Izod notched impact strength are discussed. It is the impact strength ratio and not the toughness which is used to describe the net result of reinforcement.The deviations between the wet and the dry strengths are used to illustrate the effect of the fiber -matrix interfacial bond. A new parameter, Δθ, is introduced to describe the effect of structure on the fiber -matrix interface. The effect of water at the fiber -matrix interface is further demonstrated through the determination of dielectric constant and dissipation factor of the composite before and after water immersion. The rule of mixtures was found to apply to dry electrical properties of composites.

Notizen: The effects of shear stress on the crystallization kinetics and morphology of linear polyethylene and polybutene-1 were studied with the aid of a specially designed apparatus. With this equipment, it was possible to heat a thin polymer sample between glass slides to a melt temperature, quench the sample to a crystallization temperature, and then deform the sample in shear by applying a constant load to one of the glass slides. During the deformation, the crystallization process was observed and photographed under a polarizing microscope. Also, the displacement of the glass slide was simultaneously recorded which made possible a determination of the shear strain as a function of time.The results demonstrate that two phenomena may occur in the initially supercooled polymer samples in response to the applied shear stress. In one case, the sample deformed until it fractured, generally exhibiting no evidene of crystallization; in the other, the sample deformed until an inflection point was reached after which the sample became rigid. This latter phenomenon was attributed to crystallization.At low shear stresses, the inflection point was associated with the growth of spherulites which simply became large enough to bridge the glass slides and prevent further deformation of the sample. This generally occurred prior to the completion of the radial growth of the lamellae.At high shear stresses, however, no evidence of crystallization was seen in the microscope until the inflection point was reached. At this point, birefringence was observed in the sample. The resulting structure generally could not be resolved in the microscope, thereby indicating very profuse nucleation.The results obtained clearly demonstrate that the application of a sufficiently high shear stress to an initially supercooled melt has a substantial effect on the rates of crystallization of both polyethylene and polybutene-1. This was shown most dramatically at temperatures close to the melting point, e.g., both polyethylene at 130°C and polybutene-1 at 113°C, which require over 104 sec to crystallize under quiescent conditions, crystallized at approximately 0.05 seconds.The application of a shear stress to a polymer melt is envisaged as resulting in molecular orientation. In accord with the theories of Flory, and Krigbaum and Roe, the associated decrease in entropy of the melt may be considered to increase the supercooling. Under high stresses at which large increases in supercooling result, crystallization occurs more rapidy at the high temperatures and with polymers of lower molecular weight. At low shear stresses, the influence of temperature and molecular weight on the crystallization kinetics is essentially the same as that obseved under quiescent conditions.Observations through the microscope have shown that the application of a shear stress to a polymer melt leads to large increases in the number of crystalline structures formed and to the formation of oriented morphologies. This latter phenomenon arises due to nucleation lines formed by impurities and spherulites in the deforming melt. The impurities and spherulites apparently cause a disturbance which is thought to result in a local increase in stress of the melt and, hence, a local increase in supercooling. Lamellae then nucleate on these lines and grow out radially.

Notizen: Detailed crazing behavior in several plastic/rubber twophase polymer systems was studied by means of direct observation of ultrathin sections under the electron microscope by employing osmium tetroxide staining and hardening procedure. Samples used are ABS polymer, high -impact polystyrene and several PVC/rubber blends. All of the systems investigated showed evidence of stress -crazing when under flexural stress. Relationships between the dispersed rubber particles and the crazing behaviors were studied, and the role of rubber particles in the toughening mechanism of plastics was discussed based on these observations.

Notizen: The effects of temperature and penetrant activity on the sorption kinetics and equilibria of a series of alkanes in glassy, biaxially oriented polystyrene were studied. Normal isomers of pentane, hexane, and heptane cause crazing of polystyrene film samples at high penetrant activities (〉 0.85). Crazing kinetics are identical to the kinetics of Case II transport. Transport of these normal hydrocarbons in glassy polystyrene in the temperature range 25 to 50°C is markedly non-Fickian; limiting Case II transport is observed at activities in exces of 0.6. Sorption appears to be controlled by highly activated relaxation processes including primary bond breakage at these high penetrant activities. Fickian diffusion behavior is approached, however, as penetrant activity is reduced. Sorption of the branched isomers of these compounds does not result in polymer microfailure. The sorption kinetics of the branched isomers, although time dependent, appear to be controlled primarily by thermally activated diffusion rather than large scale polymer relaxations which control Case II transport.

Notizen: Some of the thermodynamic and physical properties of crystals of linear polyethylene, formed from dilute solution are discussed. These properties include density, enthalpy of fusion, infrared absorption spectrum, selective oxidation and dynamic mechanical measurements. Despite the fact that electron microscopic examination reveals an apparent geometric regularity to these crystals, all these physical measurements yield a consistent interpretation in that they require about 15-20% of the chain units to be in a non-random conformation, and to form a disordered amorphous overlayer.Detailed studies of the experimentally observed relations between the crystallite thickness, crystallization temperature, and dissolution temperature (melting temperature in a dilute solution) are also presented. A thermodynamic analysis of the dissolution temperature-size relations, based on independently determined equilibrium solubility temperatures, indicates that the interfacial free-energy characteristic of the mature crystallites is significantly different from that involved in nucleation. The interfacial structures of the nucleus and the crystallites must, therefore, also be different. Size control by a nucleation process can be demonstrated from very general theoretical considerations. However, the detailed molecular structure characteristic of the nucleus cannot be specified solely from the fact that this process is size controlling.

Notizen: Work at Stanford Research Institute on the deterioration of polymers is based on the assumption that aging in the light is the most serious problem and that it has at least three components that must be separated if we are to understand the overall process. We have started by measuring the production of free radicals on the polymer when pairs of t-butoxy radicals are generated from thermal decomposition of di-t-butylperoxy oxalate (DBPO) in bulk atactic polypropylene at temperatures approximating service conditions, 35-50°C. Our preliminary experiments have brought out experimental difficulties and have raised more theoretical questions than they have answered. Nevertheless, they show that the efficiency of production of polymer radicals is low and sensitive to the mobilities of the polymer chains. They also suggest that two kinetically different oxidation processes, with different dependencies on rates of initiation and with different susceptibilities to inhibitors, are proceeding simultaneously. The implications of these findings for results of some previous work and for design of improved accelerated tests is considered.

Notizen: Starting with specific constitutive equations, methods of evaluating material properties from experimental data are outlined and then illustrated for some polymeric materials; these equations have been derived from thermodynamic principles, and are very similar to the Boltzmann superposition integral form of linear theory. The experimental basis for two equations under uniaxial loading and the influence of environmental factors on the properties are first examined. It is then shown that creep and recovery data can be conveiently used to evaluate properties in one equation, while two-step relaxation data serve the same purpose for the second equation. Methods of reducing data to accomplish this characterization and to determine the accuracy of the theory are illustrated using existing data on nitrocellulose film, fiber-reinforced phenolic resin, and polyisobutylene. Finally, a set of three-dimensional constitutive equations is proposed which is consistent with nonlinear behavior of some metals and plastics, and which enables all properties to be evaluated from uniaxial creep and recovery data.

Notizen: Equations have been derived to convert Brabender flow curves to Instron flow curves for practical application purposes. The technique involved is simple and has been described and discussed in detail. Nine pairs of Brabender and Instron flow curves of three different high polymers, each at three operating temperatures, have been found to fit each other quite well. The converted Brabender flow curves overlap a part of the Instron curves and extend the shear range toward the Newtonian flow region. An important consequence of this work is that the Brabender Plastograph can now be regarded as a formal viscometer while still functioning as a miniature of the Banbury mixers used in industry. More work is being done to take advantage of this consequence.

Notizen: Constant stress creep and recovery experiments were performed in the nonlinear range under combined tension and torsion on a tubular specimen of polycarbonate. Nonlinear viscoelasticity theory was employed to describe the test results. It was found that the first three orders of stress terms and a power function of time adequately described the experimental results. The modified superposition principle satisfactorily predicted the recovery following creep. Recovery was almost complete in several days following two hours of creep.

Notizen: The physical optics of iridescent multilayered plastic films are analyzed theoretically relating the layer thickness, layer arrangement, and refractive index difference between layers to the reflection spectra for light at normal incidence. Very vivid iridescent and metallic-appearing films may be made by proper control of layer distribution.

Notizen: Salts of polyacrylic acid can be fabricated in heated molds using mixed powders of polyacrylic acid and metal oxides. Because of the strong intermolecular forces in these polyelectrolyte salts, they have elastic moduli several times greater than the moduli of conventional plastics. They also have very low coefficients of expansion and high compression strengths. Composites containing metallic and inorganic fillers have also been made and their mechanical properties measured.

Notizen: The dynamic thermal stability of rigid PVC resin compositions as determined from Brabender torque rheometer tests has a linear relationship of stability time and torque from which a practical measure of processability at a fixed torque can be derived. The stability time at 1500 m-g torque, t1500, has been used to characterize differences between PVC homopolymer and copolymer resins in tin, calcium-zinc, lead, and bariumcadmium stabilizer systems. In every case, the vinyl chloride-propylene copolymers are unique in giving substantial process-ability advantages.The logarithm of stability time at a fixed torque, t1500, is a linear function of intrinsic viscosity, [η], for PVC homopolymers, giving a single line function corresponding to the expression log t1500 = A + B [η]. The constants, A and B, vary with each of the four stabilizer systems, and are related to the effectiveness of the particular formulations used.The ratio of t1500 for copolymers to the basic t1500 value for PVC homopolymers at the same intrinsic viscosity (molecular weight) is a practical measure of relative processability, trel, which is characteristic of PVC resin types and independent of stabilizer systems.

Notizen: The melt flow behavior of straight emulsion-polymerized PVC in a capillary extrusion rheometer has been found to depend upon both the molecular weight and the particle size of the sample. Observations of flow-rate, post-extrusion swell, and extrudate appearance, as functions of extrusion temperature and pressure, suggest that both molecular deformation and particle slippage are involved in the flow mechanism. The relative importance of these two modes of flow varies with extrusion conditions and with the PVC molecular weight and particle size. Particle slippage is favored by large particle size, high molecular weight, and low temperature and by a shear stress above a critical yield value. Apparent melt viscosity, swelling, and roughness are minimized under conditions corresponding to the maximum contribution of particle slippage. In the proper range of temperature and shear rate, straight emulsion PVC yields smooth, low-swell extrudates of excellent physical properties.

Notizen: Re-examination of our work on internal plasticization of polyvinyl chloride leads us to suggest a number of guidelines in the synthesis of internally plasticized PVC with optimum combination of strength and low temperature properties: (1) use of comonomers of solubility parameter around 8.5 or 10.5, (2) use of a high molecular weight (long chain) comonomers in a low molar ratio, and (3) their non-uniform incorporation in the PVC chain.

Notizen: A number of polymers have been “cold” extruded (i.e. at temperatures well below their normal melting temperatures) by the application of relatively high pressures. In all cases extrudates of relatively large cross-sectional area have been produced, and non-circular cross-sections have also been extruded. The extruded products has been evaluated and the results discussed. In general it has been found that whilst extrusion gives an oriented product, the increase in tensile modulus is much less than for a comparably drawn fibre. This phenomenon has been discussed in terms of the changes in crystalline structure produced by extrusion.

Notizen: Polymer pellets are frequently melted on a melting grid. The melting capacity of the gird depends on the force with which the bed of pellets is pressed against the grid bars and on the difference between the temperature of the grid bars and the melt temperature. In this investigation, this dependence has been examined, theortically as well as experimentally, for the case where the pellets melt on the top of the grid. Agreement with the theory was found.

Notizen: This study was undertaken in order to understand the effect of low molecular weight additives on the visco-elastic properties of polymers and, in particular, Diamond Shamrock Corporation's PVC-40 resin. The viscous response has been reported in Part I of this series (11). This report describes the elastic properties of these mixtures.A new theoretical analysis of elastic response has been formulated. The direct calculation of stored elastic energy from capillary rheometer measurements is now possible.The conclusion drawn from both the viscous and elastic response study is that a change in viscosity is not a necessary nor sufficient condition for improved processability. Increased flow is obtained by lowering the viscous losses, but the melt fracture phenomena may be unchanged. In order to completely characterize the compound, both viscous and elastic response must be measured.

Notizen: A previously proposed but further modified theoretical model for melting in plasticating extruders, in the form of a computer program, which predicts the amount of unmelted polymer at any point in the extruder, was used to simulate the effect of geometrical and operating variables on the melting performance of the extruder. The results indicate in increasing screw length required to complete melting with increasing throughput and a decreasing length of melting with increasing frequency of screw rotation. They further indicate the existence of an optimum barrel temperature for a maximum rate of melting, an optimum number of threads for a maximum melting rate, and a significant decrease in the rate of melting with increasing flight clearance. The effect of other geometrical variables and of operating conditions on the rate of melting and power consumption are also discussed.

Notizen: The validity of the Busen-Roscoe reciprocity law in flash exposed dichromate sensitized polyvinyl alcohol (PVA) films was investigated. It was found that the flashlamp operating conditions were an important parameter in an exposure system, since a spectral distribution shift of the lamp output could be obtained by changing the pulse duration from 0.3 to 2.0 msec. The apparent reciprocity failure obtained by varying the pulse duration while maintaining the energy stored in the capacitor bank fixed was consistent with the spectral distribution shift in the lamp output. When this shift was accounted for there was only a negligible reciprocity failure found over the range of these flash exposures; however, comparison with a steady mercury are lamp showed that the flash exposure cross-linked the PVA about 200 times more efficiently.

Notizen: An investigation of the viscous flow properties of mixtures of low molecular weight materials, such as lubricants and plasticizer, with PVC has been carried out. In all examples studied the PVC exhibited a discontinuity in flow with increasing temperature. This was interpreted as a phase change in the melt. A diffusion fractionation of the low molecular weight species was used to rationalize the shear rate dependent viscous behavior of these melts.

Notizen: The effect of the room-temperature first-order transition on the plastic yield behavior of polytetrafluoroethylene (PTFE) has been investigated. Stress-strain curves were measured at different strain rates and temperatures. Tensile creep under constant dead load was also measured as a function of temperature and stress level. The effect of degree of crystallinity was investigated by using both a rapidly quenched and slow-cooled polymer. Observations were extended to large deformations, so that the phenomenon primarily observed was plastic yield rather than linear viscoelastic behavior.The curve of yield stress vs. temperature in the temperature range from -50 to +68°C was found to be almost identical with the curve of elastic modulus vs. temperature; the yield stress shows a marked local decrease at the first-order transition. The yield elongation was almost constant (at about 5%) over this same range, which is in accord with the above result. The more highly crystalline polymer is always more rigid than the less crystalline polymer at small deformations, but above 19°C its stress-strain curve shows a “cross-over” in stress level with the curve of the less crystalline polymer as extension increases. That is, above 19°C the less crystalline polymer shows a more rapid rate of “strain hardening”, even though the strain-hardening effect is pronounced in both polymers. Attempts to apply time-temperature superposition to creep data at different temperatures were partially successful; the lateral shifts required corresponded to an activation energy of approximately 80 kcal.The experimental observations suggest a model of the solid-state structure of PTFE which could be described as an “elastic-plastic network”, in which crystalline domains are connected by elastic amorphous regions, and in which the crystalline domains can flow plastically at sufficiently high stress or temperature.

Notizen: Rheo-optical techniques for the study of crystalline polymers, developed primarily in the United States and Japan, include dynamic birefringence, X-ray diffraction, dichroism, light scattering, and fluorescence. These permit the characterization of the rates of orientation of crystals, amorphous regions, and crystalline superstructures. The application of these methods has permitted the formulation of a model for the deformation of crystalline polymers.

Notizen: The fatigue failure of thermoplastics and glass-reinforced thermoplastics is a function of cyclic stress or deflection level, test frequency, viscoelastic polymer parameters and matrix-to-fiber stress transfer. This paper reports an investigation of the modes of high frequency fatigue failure in glass-reinforced and unreinforced thermoplastics. In particular the effects and control of dissipative heating of a working specimen and the role of efficient matrix-to-fiber stress transfer are considered. A test procedure with which the severity of dissipative heating can be continuously followed and controlled during an accelerated fatigue test is described.

Notizen: Empirical test data on low-density polyethylenes exposed to the elements for very long times are compared with results on samples of the same materials subjected to artificial “weathering” in a modified carbon arc machine.The test results conform to the expression \documentclass{article}\pagestyle{empty}\begin{document}$$ t_a = B + t_n^k $$\end{document} where ta is hours of accelerated weathering, tn years of natural exposure, and the constants B and k have values of 150 and 2.4, respectively, for the materials and test conditions involved.Earlier results are confirmed in that optimum weather resistance is found to depend on good dispersion of a fine-particle black. Protection improves with concentration up to the limit of about 5% by weight imposed by degenerative effects on mechanical properties from higher loadings of the fine channel blacks. Dependence of weatherability on molecular weight (melt index) is noted.

Notizen: Existing theory of polymer flow has been applied to a definition of shift factors which reduce the widely different melt viscosity/shear rate diagrams of plasticized PVC compounds to well-defined master curves. The master curves are temperature dependent and also define the flow properties of the unplasticized polymer on which a group of plasticized compounds is based. For given plasticizers, the value of the shift factor was found to depend on melt temperature and plasticizer volume fraction. Explicit relationships have been generated for three plasticizer systems; for these, melt viscosity/shear rate data can be precalculated over several decades of shear, and in the temperature range of 150-200°C. Absolute values of the shift factors depend on the type of plasticizer, and a correlation with polymer/diluent interaction parameters has been attempted. Initial results, valid only at high plasticizer volumes and near the reduced melt temperature of a polymer/plasticizer mixture, support the existence of such a correlation.

Notizen: This discussion will illustrate some of the factors which go into the design of experiments required to solve problems in the field of plastics. Two quite diverse problems were considered. In the first case a series of experiments was described which provided a very general technique for predicting polyethylene flow behavior as a function of shear rate over a wide range of temperatures from a minimum of new data. In this case the experimentation concerned only the viscous aspect of flow and was not limited by the availability of special samples. In the second case it was desired to learn what the effect of a specific molecular structural variable was on the general melt rheological properties of polyethylene. This required the polymerization of special samples followed by detailed characterization by both solution property and melt rheological techniques.

Notizen: Derivative stress-strain curves at constant strain rate for polyacrylonitrile copolymer fibers have been obtained by simple modification of conventional tensile testing apparatus. These derivative curves, considerably more complex and eventful than stress-strain curves, have been interpreted as direct records of changes undergone by the apparent Young's modulus during experiments which extend from infinitesimal strain to failure. Analysis of the data shows that these changes in the apparent Young's modulus cannot be accounted for to any significant extent by viscoelastic time effects and must therefore be consequences of the deformation process itself. In the light of this analysis, it is concluded that polyacrylonitrile fibers “soften” considerably in the strain range 0.5-3% and that they exhibit moderate “hardening” in the strain range which extends from ca 3% to the breaking strain (10%).

Notizen: Some properties of multilayered films are summarized in relation to the properties of the component materials. Polymers may be selected for co-extrusion into layered films to obtain various combinations of properties, such as barrier, stiffness, heat sealability, optics, and toughness. Properly chosen combinations of high and low modulus materials exhibit mutual interlayer reinforcement. Permeabilities of multilayer films can be calculated from layer geometry and individual component properties.

Notizen: Spherulitic films of polybutene-1 have been stressed under biaxial tension. Direct microscopic observations indicate that the deformation is localized at the spherulite centers and at the intersections of boundaries in agreement with previous results obtained with linear polyethylene. The results demonstrate an increasing tendency for brittle failure with decreasing molecular weight. Effects of surfactants and solvents are also presented.

Notizen: Each statocyst in Apylsia californica contains 13 neurons. The statocyst nerve, which connects each statocyst to the cerebral ganglion, contains only the 13 axons of the statocyst neurons. The size of the statocyst, the number of neurons in the statocyst, and the average axonal diameter does not change even though the statocyst nerve lengthens greatly as the animal enlarges. A description of the statoconia and the supporting cells in this organ has been given. This prepazation may be useful for microelectrode studies designed to test whether the gap and cytoplasmic specializations that are used to identify active synapses, are necessary for all types of chemical synaptic transmission.

Notizen: The venom system of Nasonia vitripennis is well-developed and composed of an unbranched acid gland and associated reservoir. Fine-structural, histochemical and electrophoretic studies indicate that the venom is produced by two protein-secreting epithelia. The bulk of the venom is synthesised in the columnar cells of the acid gland and discharged via “vesicular organelles” and the efferent ductular system into the lumen of the reservoir. The acid gland also contains squamous chitogenous cells, situated either around the central lumen or interposed between the bases of the columnar cells. Once within the reservoir, the venom is probably activated by enzymatic secretions from the reservoir secretory cells. Each of these cells has a “vesicular organelle” but, in contrast to the columnar cells of the acid gland, the cytoplasm contains a preponderance of free ribosomes, and protein segregation apparently occurs outside the Golgi complexes.The venom is expelled through the efferent discharge duct by muscular contractions, which open the duct lumen and bring it into contact with the funnel of the ovipositor. Excessive distortion of the duct is prevented by a massive ventral ligament.

Notizen: The developmental cytology of the apical tissue of the testis of Tenebrio molitor and Zophobas rugipes was studied with light and electron microscopy. In the early larvae of both species the tisue was found to be a thickened protrusion of nongerminal cells appearing at the apical end of each testis follicle following gonadal differentiation. The cells persist through pupal and adult stages in both species, becoming more prominent at these stages in Z. rugipes, despite tracheal invasion in both species. In older adults the apical tissue regresses and ultimately distintegrates.Ultrastructurally the apical cells are distinguished from adjacent germinal cells by their (1) small, rounded or oval nuclei, (2) highly convoluted plasma membrane, (3) electron-opaque cytoplasm, (4) profuse concentrically-stacked, granular endoplasmic reticulum, (5) large aggregates of glycogen-like granules, (6) numerous small, tubular mitochondria, (7) well-developed Golgi centers and (8) striking arrays of microtubules. These cells have many cytological features in common with the androgenic gland cells of crustaceans, but not with the steroidogenic cells of vertebrates. Evidence for the formation of protein granules is also lacking. As yet, experimental procedures have not indicated an endocrine function for these cells in tenebrionids. However, their cytology is consistent with secretory activity of some kind.

Notizen: The rectum of Periplaneta americana L. is lined with cuticle and has six radially arranged cushion-shaped thickenings, the rectal pads, composed of columnar cells. Narrow strips of simple rectal cells lie between the pads. Tall junctional cells form a thin but continuous collar around the pads where they join the rectal cells. The epithelium is surrounded by a layer composed of circular and longitudinal muscles and connective tissue. This layer of muscle and connective tissue is innervated and tracheated, and is separated from the pad surface by a subepithelial sinus. Fluid flowing through the sinus enters the haemolymph through openings in the muscle layer whre large tracheae penetrate. These openings can be sealed by muscle contractions that appress the muscle around the openings against the pad surface. The tracheae pass on into the pads, following basement membrne-lined indentations of the pad surface. Within the pad tracheolar cells send fine branches between the cells. Near the apical and basal surfaces the lateral membranes of pad cells are bridged by septate desmosomes that form a continuous band around the cells. Between apical and basal septate desmosomes is an interconnected labyrinthine system of intercellular spaces. There are three kinds of space, dilations and apical sinuses, both of variable size, and narrow communicating channels about 200 Å wide. The membranes of the latter have mitochondria closely associated with them. Continuity between the system of spaces and the subepithelial sinus is established by the basement membrane-lined invaginations of the basal surface where tracheae penetrate between pad cells. Apical surfaces of the pad cells are highly infolded and are also associated with mitochondria. However, unlike the lateral membranes facing the narrow channels, the apical membranes have a cytoplasmic coating of particles. Both associations of mitochondria with membranes constitute discrete structural entities that are found in many transporting epithelia, and we have termed them “plasmalemma-mitochondrial complexes.” As the rectal pads are organized into systems of spaces that ultimately open in the direction of fluid movement, existing models of solute-coupled water transport can be applied. However, the rectal pads are structurally more complex than fluid-transporting tissues of vertebrates. This complexity may be related to the ability of the rectum to withdraw water from ion-free solutions in the lumen. We present a structural model involving solute recycling to explain the physiological characteristics of rectal reabsorption.

Notizen: The ultrastructure of mouse tracheal epithelium was examined. The three cell types, basal cells, ciliated cells and goblet cells, described for other mammalian trachea were found to be present although goblet cells occurred only rarely. A cell type, termed the nonciliated cell, not described in other mammalian trachea was frequently found in mouse tracheal epithelium. These cells contained abundant smooth and rough endoplasmic reticulum, free ribosomes, a large Golgi complex, and many mitochondria. There were many vesciles containing an electron dense material near the luminal surface of these cells; these cells were positive for PAS. These features suggested a secretory function for the cells. This, along with the scarcity of goblet cells, suggested that the nonciliated cells of mouse tracheal epithelium fulfill the function of the goblet cells found in other mammalian trachea.

Notizen: Cytodifferentiation during spermiogenesis in Hydra littoralis was studied at the fine structural level. Concentration of nuclear material as well as specific orientation of granular and filamentous nuclear elements are apparent in two regions of the early spermatid: where the nuclear envelope is in contact with mitochondrial membranes at one pole of the cell and at an opposite region where the nucleus is closely apposed to the plasma membrane. Ultimately the mass of condensed nuclear material becomes concentrated at the mitochondrial pole of the cell. Additional electron-dense material is extruded from the nucleus into a large vacuole which is in continuity with the nuclear membrane as well as associated with Golgi lamellae and vesicles. Eventually all residual cytoplasm is sloughed, leaving the nucleus, mitochondria, and flagellum. These observations are suggestive of nucleocytoplasmic interactions during development, especially influences of mitochondria and plasma membranes on chromatin condensation.

Notizen: The development of the eye in embryos of Rana pipiens raised at two different temperatures was studied in detail from Shumway stage 16 through Shumway stage 25. One clutch of eggs from each of ten different female frogs was divided into two groups, one of which was raised at a temperature of 14°C and the other at 19°C. The 14° to 19° difference falls in the middle of the temperature range for normal development of Rana pipiens as established by Atlas ('35), Moore ('39), and Ryan ('41). Two hundred embryos, one embryo from each of the ten clutches, raised to each of ten stages at 14° or at 19°, were sectioned for microscopic study of the eye region. Descriptions of the morphology and histology of the developing eye are illustrated by photographs and provide a reference to which development of experimental embryos may be compared. A synoptic checklist is provided which specifies the changes occurring at each stage studied.

Notizen: The fine structure of the mid-gut epithelium and regenerative cells of larvae of a moth (Ephestia kühniella) is described. Particular attention is paid to the absorptive and goblet cells and their lateral junctions; these features are discussed in terms of the digestive and regulatory functions of the epithelium. One digestive pathway has been investigated with the aid of ingested ferritin; intake of this marker by endocytosis and the evident involvement of Golgi vesicles in the transformation of endocytic vesicles into multivesicular bodies, together with the fate of the latter, are discussed in terms of the digestive function of this part of the alimentary tract and of the lysosome concept.

Notizen: A fine structural study of the ventricular muscle of Venus mercenaria has revealed that it is an invertebrate smooth muscle. In the relaxed state induced by acetylcholine, both thick (350 Å) and thin (80 Å) myofilaments are observed. These are loosely distributed in bundles in the periphery of the mononucleated myocytes. The central core of the cell contains an ovoid nucleus, α-glycogen rosettes, round mitochondria and numerous smooth surfaced vesicles of the endoplasmic reticulum. After exposure to serotonin, all myofilaments are compacted in the peripheral cytoplasm and become oriented parallel to the longitudinal cellular axis. This produces contraction bands visible in phase contrast microscopy. Because these myofilaments attach to the cell membrane at sites of attachment plaques, contraction of the cell results in the serial evagination or blebbing of the cell surface. The above features are clearly demonstrable in this invertebrate smooth muscle and strongly suggest a sliding filament model as the contractile mechanism in this tissue. Moreover, the cell surface is thought to play an active and major role in that process.

Notizen: Three-dimensional, histological, and x-ray techniques provide a picture of body segment and limb morphogenesis. Cell multiplication begins in the proliferation region (“meristem”) during the molt from the preceding instar. By four days post-molt, the cells that will form the new segments are well under way in their anterior, lateral, and dorsal migration. It is suggested that after the anlagen for all the new segments are estabilshed, a mitotic wave commences in the most anterior anlagen and moves posteriorly during the remainder of the instar. When cell proliferation is complete, final differentiation of the segments takes place.The process of limb formation is one of cell proliferation and perhaps migration. Each limb develops in a membranous pocket during the instar following the one in which its respective body segment was formed.

Notizen: Bovine parotid glands exhibit outstanding structural differences when compared with those of non-ruminant mammals. The acini are tortuous, branched and lined with cells of different heights, imparting a scalloped appearance to acinar lumina. Numerous microvilli, ca. 1.5 μ in length, extend into the lumina and intercellular canaliculi. Intercellular canaliculi measure ca. 3 μ in diameter and interweave in close association with intercellular tissue spaces. Intercellular tissue spaces are separated from the extraacinar spaces across a basal lamina only, whereas junctional complexes guard canaliculi from direct continuity with tissue spaces and/or extraacinar spaces. Flattened cytoplasmic lamellae extend from adjacent acinar cells and loosely interdigitate with one another across the tissue spaces. Acinar cells contain more mitochondria and less granular endoplasmic reticulum than parotid glands of non-ruminant mammals. Two types of secretory material, in the form of inclusions which vary in size and electron density, are present in the acinar cells. Intercalated ducts connect acini with striated ducts which in turn, empty into collecting ducts located between gland lobules. In terms of frequency of “basal infoldings” and numbers of mitochondria, striated ducts of calf parotid glands are not as well developed as those of certain other salivary glands. Myoepithelial cells are most often present at junctions of acini and intercalated ducts where they may attach to both acinar and ductal epithelium. Nerve “terminals” were not observed on the epithelial side of basement membranes in relation to the secretory cells.

Notizen: The endoskeletal structure supporting the gill-books of Limulus polyphemus has been investigated by means of light and electron microscopy, chemical analysis and x-ray diffraction. This tissue is a cartilage which has significant correspondences with both vertebrate cartilage and plant tissues. Morphologically, the Limulus cartilage resembles certain cellular vertebrate cartilages with relatively scant matrix, and also certain plant parenchyme, collenchyme and sclerenchyme tissues. Of particular interest, was the observation that during cytoplasmic division, a phragmasome-like structure appears between the daughter cells of the dividing gill cartilage cells. This phragmasome-like structure appears to be a precursor of new matrix (cell-wall) formation between the young chondrocytes, in much the same fashion as its counterpart in plant tissues. Perichondrial cells and underlying chondrocytes contain lipid droplets, abundant glycogen and ribosomes, as do corresponding vertebrate cartilage cells. In some of the Limulus cells, glycogen and ribosomes appear to be admixed with lipid, forming aggregates in which all three materials are in intimate intraparticulate relationship. During molting, the number of ribosomes seen in chondrocytes increases. The tissue contains both hydroxyproline and hydroxylysine, and gives a weak x-ray diffraction pattern.

Notizen: A principal component analysis revealed that the two major components of mandibular shape variation among individuals within breeding groups of white-tailed deer in Canada and the United States involve contrasts between the mandible and the dentition and between the premolars and the molars. Size variation appeared to account for 34% of the total variation within the groups, and the two major shape variations accounted for 23% and 8% respectively.A canonical analysis was used to identify the major components of mandibular variation among the breeding groups and to provide measures of the proportion of the total variation accounted for by each component. Among male groups, size variation was associated with latitude, and the major shape variation was closely associated with longitude, so a bivariate plot of the first two canonical variates reflected the general geographic orientation of the populations.The mandibular size in a Tennessee population that descended from Wisconsin and Michigan ancestors appears to have not decreased appreciably in the more southerly habitat after introduction more than 20 years ago. Changes in range conditions in eastern Upper Michigan over the past 30 years have not influenced local mandibular morphology as reflected by the first two canonical variates. Regardless of general smallness of individuals, the mandibular morphology of the deer from the Cross Timbers area in Kansas appears to approximate more closely that of northern populations than that of the more southerly populations from Oklahoma and Texas.Sexual dimorphism on the first two canonical axes was observed.

Notizen: Structural and functional changes have been correlated during metamorphic degeneration of a single muscle fiber, the plantar retractor of G. mellonella, its axon, and their junctions to determine which features persist as long as muscle contractility. Changes commence simultaneously in muscle and nerve near cuticular attachments, and spread towards the center. Alterations associated with the muscle, including appearance of collapsed tracheoles and mitochondria with dense bodies, begin late in the last larval instar. Within 12 hours after pupal ecdysis some tracheolar withdrawal occurs, sarcoplasmic reticulum becomes reduced, and many mitochondria have dense bodies, dense membranes, or are enlarged. By 17-19 hours primary myofilaments and striations begin to disappear, microtubules and autophagic vacuole-like bodies appear, and phagocytes invade the muscle. It remains partially contractile upon electrically stimulating its nerve, the ventral nerve, until these changes spread throughout the fiber.Neuromuscular junction changes, including appearance of dense mitochondria and isolation bodies, begin late in the last larval instar. Junctions become fewer, and none remain in those muscle areas where tracheoles, sarcoplasmic reticulum, and primary myofilaments have disappeared.Preliminary studies on nerve discharge activity to the muscle suggest that nerve silence occurs at approximately the time when the muscle loses all contractility. In some axons isolation bodies appear and neurotubules are lost, other axons remain unchanged, and new ones develop later in the pupal state. Phagocytes invade the neural lamella and it disappears in the late pupa, but it reappears in the adult.The adult ventral nerve has over three times more axons and a thinner layer of glial cells than the larval nerve.

Notizen: Ampullary receptor organs of the South American weakly electric gymnotid fish Eigenmannia virescens consist of a pore at the surface of the skin, a canal through the epidermis, and the expanded basal end of the canal in the corium. The cavity of the organ contains a jelly that is filled with fine fibers. The canal wall consists of three to six layers of flattened cells that appear to be derived from the adjacent skin. Along the lumen of the organ the cells are joined by tight junctions. Usually there are four spherical receptor cells in the base of the organ. They are innervated by single neural terminals. These organs are compared to tuberous receptor organs found in the same species, and the functional significance of the fine structure observed in these cells is discussed.

Notizen: The viscometric behavior of linear polycaprolactam has been studied in the absence of the electroviscous effect in aqueous solvents containing 85% and 64.5% formic acid and in trifluoroethanol, as a function of temperature and also under unperturbed conditions. Results are discussed in terms of the existing theories; in particular, the negative temperature coefficient of the intrinsic viscosity arises only from the variation of the expansion coefficient, the molecule in the unperturbed state being a normal random coil. The absence of aggregation and draining effects in the above solvents has been varified.

Notizen: Polymers of poly(N-acyl and N-aroyl aziridines) were studied by x-ray diffraction. All the crystalline polymers studied have a triclinic unit cell with two monomer units per unit cell. The a and c (fiber direction) parameters (4.9 and 6.5 A, respectively) are essentially the same for all the cells. The b parameter for the N-acyl polymers, however, increases steadily by a factor of 2 A per methylene group added to the lateral chains. The densities calculated for the unit cells are in agreement with the experimental values obtained. The most probable structure is one in which the molecules assume a planar configuration with the main chain not fully extended. The lateral groups are tilted from the c axis by an angle of 54° in a parallel configuration and alternate on each side of the main chain. This permits these lateral groups to assume packing similar to that of polyethylene. A brief description of the techniques used in this interpretation is included.

Notizen: A theoretical discussion is presented on the mechanisms by which an isolated pulsating air bubble in a viscoelastic solid dissipates its energy. The analysis is limited to the situation where the amplitude of motion is assumed to be sufficiently small that the stress strain relations may be described by linear equations with convected differentiation replaced by ∂/∂t. The theoretical thermal, radiation, and viscous damping constants are calculated for resonant air bubbles in unvulcanized natural rubber; however, the results are typical of elastomers in general.

Notizen: The birefringence of several biaxially oriented polypropylene films swollen with a number of fluids has been measured and found to exhibit a minimum when plotted against the fluid refractive index, as predicted by the theory of Wiener. However, a discrepancy in the form birefringence behavior is observed when samples of different degrees of crystallinity but the same total birefringence are compared. These results are interpreted in terms of Bullough's theory and suggest that this discrepancy arises because of different morphologies. A refractometric technique was employed that makes possible the simultaneous determination of birefringence and the volume fraction of fluid.

Notizen: The orientation of crystallites grown isothermally in several drawn trans-polychloroprene networks is studied as a function of crystallization temperature tx, degree of crystallinity ω, and elongation ratio α. The orientation distribution is particularly simple for this polymer since the crystallographic c axis (chain axis) orients preferentially along the stretching direction, while a and b are randomly arranged about c. Hence the parameter cos2 χc adequately characterizes the distribution, where χc is the angle between the c axis and the fiber axis, and the average is taken over all crystallites. A treatment due to Krigbaum and Roe is utilized to obtain values of v (the number of statistical segments comprising the crystallization nucleus of critical size) through comparison of the average orientation of crystallites and amorphous statistical segments. The behavior observed falls into two categories. First, if the initial amorphous network is well oriented, 〈cos2 χc〉 is independent of crystallinity during both crystallization and melting, and v varies with tz (or the degree of supercooling) as predicted by nucleation theory. If different networks are to have the same crystallite orientation distribution, they must not only be crystallized at the same supercooling, but must also have the same distribution of amorphous segment orientations. Both the relative elongation and the network crosslink density affect the latter distribution. Next, we consider the second category. If the initial amorphous orientation is poor, 〈cos2 χc〉 decreases linearly during crystallization and increases along approximately the same path during melting. Further, 〈cos2 χc〉 for a given tz yields v values which are too large. These two behaviors can be explained if, in the former case, nucleation involves the best oriented statistical segments of all network chains, while in the latter there is a selection according to the chain displacement vector orientation. Thus, if the amorphous orientation is poor, both the orientation and thermodynamic stability of the crystallites decreases with further crystallization. If this decreased stability is reflected in shorter fold lengths, the reversible variation of long period spacing with temperature reported earlier for an oriented polychloroprene network can also be explained as a preferential melting process.

Notizen: The design of a differential thermal analysis apparatus for use at elevated pressure is described. Experiments on melting and crystallization of folded-chain crystals of polyethylene and poly(ethylene-butene-1) copolymer, and melting of extended-chain polyethylene crystals have been conducted at pressures up to 4200 bars. The precision in transition temperature measurement was ±1°C. The Clausius-Clapeyron equation predicts the melting point increase with pressure at atmospheric pressure to be 32.0°C/kb. The melting point depression due to copolymerization remained constant over the complete pressure range analyzed on the poly(ethylene-butene-1) used in this study. Crystallization of polyethylene is retarded at elevated pressures, and a 50% larger degree of supercooling is necessary at 5000 bars to give a crystallization rate equal to that observed at atmospheric pressure. The difference in melting point between folded-chain and extended-chain polyethylene increases from 8.4°C at 1 bar to 25.6°C at 3000 bars.

Notizen: The conformational energy contribution (ΔUconf) to the heat of solution in polymer-solvent systems is presented and discussed in connection with chain conformational properties. In particular, ΔUconf has been discussed in terms of various possible mechanisms of coil deformation.

Notizen: It is demonstrated that in a filled polymer the thermal stresses resulting from the difference in the thermal expansion coefficients of the filler and the polymer have significant effect on the apparent coefficient of thermal expansion of the composite. A model is constructed to aid the thermal stress analysis, and the results are found to agree well with the experimental data obtained from other sources. An expression for the apparent densities of filled polymers is also obtained but the agreement between the present prediction with an existing test result is found to be only qualitative.

Notizen: Diffusion coefficients and solubilities of methane in polyisobutylene have been measured at four temperatures between 102 and 188°C. in the pressure range 23-341 atm. Diffusion coefficients extrapolated to atmospheric pressure range from 1.72 × 10-6 cm.2/sec. at 102°C. to 1.5 × 10-5 cm.2/sec. at 188°C. corresponding to an activation energy for diffusion of 8.7 ± 0.4 kcal./mole. Solubilities are small, about one molecule of methane for every forty carbon atoms in the polyisobutylene at 300 atm. partial pressure of methane. Solubilities vary little with temperature, but show an apparent minimum between 127 and 188°C. With improved methods of data analysis, diffusion coefficients and solubilities have been recalculated from previously reported studies on nitrogen in branched polyethylene and methane in branched polyethylene, linear polyethylene, and polystyrene. Recalculated diffusion coefficients are essentially the same as those reported previously, but the recalculated solubilities are decreased from 2 to 30%. The solubilities of all five systems show strong deviations from Henry's law, i.e., increases in partial pressure of methane and nitrogen with respect to solubility exceed linearity. The partial pressure (or fugacity) - solubility data may be interpreted in terms of a sorption model in which sorbed molecules are accommodated in widely dispersed, unoccupied volumes or sites in the polymer. An almost equivalent, solution model in which the first sorbed molecules to enter the polymer are accommodated to a large extent in existing volumes in the polymer, with successively sorbed molecules swelling the polymer to a greater extent (i.e., partial molal volume of sorbed molecules, V1, increasing with concentration) can also account for these data.

Notizen: Stress-strain and rupture data were determined on an unfilled styrene-butadiene vulcanizate at temperatures from -45 to 35°C and at extension rates from 0.0096 to 9.6 min-1. The data were represented by four functions: (1) the well-known temperature function (shift factor) aT; (2) the constant strain rate modulus, F(t,T), reduced to temperature T0 and time t/aT, i.e., T0F(t/aT)/T; (3) the time-dependent maximum extensibility, λm(t/aT); and (4) a function Ω(χ) where χ = (λ - 1)λm0/λm, in which λ is the extension ratio and λm0 is the maximum extensibility under equilibrium conditions. The constant strain rate modulus characterizes the stress-time response to a constant extension rate at small strains, within the range of linear response; λm is a material parameter needed to represent the response at large λ; and Ω(χ) represents the stress-strain curve of the material in a reference state of unit modulus and λm = λm. The shift factor aT was found to be sensibly independent of extension. At all values of t/aT for which the maximum extensibility is time-independent, the relaxation rate was also found to be independent of λ. These observations indicate that the monomeric friction coefficient is strain-independent over the ranges of T and λ covered in the present study. It was found that λm0 = 8.6 and that the largest extension ratio at break, (λb)max, is 7.3. Thus, rupture always occurs before the network is fully extended.

Notizen: The ultimate properties of an unfilled styrene-butadiene rubber vulcanizate in equal biaxial tension were determined by inflating a circular membrane into a bubble. Tests were made at several extension rates (evaluated at the pole) from about 0.15 to 4 min-1 and at temperatures from -43 to 90°C. The stress in the vicinity of the pole when rupture occurred was evaluated from the pressure, the radius of curvature, and the extension ratio λ, the latter two quantities being obtained from photographic data. Below 70°C, the ultimate extension ratio λb is approximately 5.2 and is essentially independent of extension rate and temperature, in striking contrast to the behavior in simple and constrained biaxial tension (pure shear). Likewise, the rupture stress is manyfold greater than in either simple or constrained biaxial tension. From the extremum points of failure envelopes, the maximum extension ratio (λb)max in equal biaxial tension is 5.7 and in simple tension is 7.2. An examination of ruptured membranes showed that, except at 70 and 90°C, rupture began away from the pole in a region where the stress state is unequal biaxial tension. Hence, values of the ultimate properties in truly equal biaxial tension are no doubt somewhat greater than those obtained from the membrane tests. However, it is shown that (λb)max in truly equal biaxial tension must be lower than that in simple tension by at least 10%. A consideration of rupture data in simple, constrained biaxial, and equal biaxial tension leads to the conclusion that no simple failure criterion is applicable for interrelating data obtained under the several states of combined stress. The rupture patterns and factors that affect the site of rupture initiation and the mode of crack growth are also discussed.

Notizen: It is shown that, at the yield stress, glassy polymers exhibit viscous flow which is in agreement with the generalized theory of Eyring. The study of the yield stress over a wide range of temperatures and strain rates provides evidence on the secondary transitions found by other methods. From our measurements we conclude that every secondary transition corresponds to the liberation of one of the degrees of freedom of a segment of the main chain.

Notizen: Dynamic mechanical properties determined with a torsion pendulum were used to ascertain the glass transition temperature Tg of poly-ε-caprolactone. By measurements on compatible blends of poly-ε-caprolactone and poly(vinyl chloride), the Tg of amorphous poly-ε-caprolactone was shown to be 202°K at about 1 cps. This is 16°K lower than the Tg of annealed, crystalline polymer. The blend transition data were well fitted by both the Fox and the Gordon-Taylor expressions. The Fox expression was also used to describe the decrease from 233°K of the secondary low-temperature relaxation due to poly(vinyl chloride) by assuming the low temperature relaxation of poly-ε-caprolactone, 138°K, was responsible for the decrease in the blends. The 138°K relaxation due to poly-ε-caprolactone was decreased when more than 50% poly(vinyl chloride) was present.

Notizen: Poly(vinyl chloride) sheet was oriented by hot drawing. The yield behavior of the oriented sheet was then investigated under uniaxial tension at room temperature as a function of the angle between the tensile axis and the molecular alignment direction. The onset of yield was localized in deformation bands. The variation of yield stress with direction and the direction in which the deformation bands formed were found to be satisfactorily accounted for in terms of a yield criterion based on that of von Mises, provided that a term representing internal compressive stress in the molecular alignment direction was included. The internal stress was found to increase from zero with increasing draw ratio of the prior hot drawing. It is pointed out that other workers have found polymers to obey the yield criterion of Coulomb rather than that of von Mises.

Notizen: The Fickian diffusion coefficient of methylene chloride in a glassy epoxy polymer is calculated with the use of Crank's model of discontinuous change of D with concentration C. The diffusion constant is obtained as 1.93 × 10-6 cm2/sec. The swollen layer behind the advancing solvent front is essentially in the rubbery state of the same polymer. The case II swelling by benzene is discussed in terms of a convective transport arising from the partial stress (internal) tensor of the penetrant. The superposition of Fickian and case II diffusion found with mixtures of methylene chloride and benzene is also discussed briefly.

Notizen: “Regular” sequence copolymers having the structure {[—CH2—C(CH3)(C6H5)—]m(CH2—CH2)n}p with relatively small values of m and n were prepared by means of “living” polymerization techniques. The intrinsic viscosities of fractions of these copolymers were obtained in various solvents including a theta solvent. The molecular weights of these fractions were determined by the Archibald ultracentrifugal method. The results show that the intrinsic viscosity-molecular weight relations of the regular sequence copolymers are affected not only by the average composition of the copolymer, but also by the sequence length in the copolymer molecule. It is suggested that the effective conformation of a chain element in the copolymer is not always the same as that in the homopolymer.

Notizen: The effects of ultraviolet radiation on dilute aqueous solutions of poly(acrylic acid) and of other polyelectrolytes were studied by viscosity measurements in connection with the effects of ionizing radiation. It was found that ultraviolet light of wavelength below about 2300 Å brought about degradation of polymer chains mainly by indirect action via water, while light of wavelength above 2300 Å caused degradation by direct action in some polymers. It was deduced from the experiments that the protective effect of NaCl could be largely attributed to a decrease in the indirect action. It was also found that a low concentration of methanol was effective in preventing degradation by direct action, although methanol promoted degradation when present in high concentration. Since the promotive effect was not observed when light of wavelength below 3700 Å was eliminated by a filter, this effect was attributed to active products of the irradiation of methanol.

Notizen: Raman spectra have been obtained for a typical poly(vinyl chloride) (PVC) of low crystallinity and for a highly crystalline sample of syndiotactic PVC obtained by irradiation of a urea-canal complex. Raman measurements have been made on the three different ordered chain structures possible for ordinary PVC. Extended and folded conformations for the syndiotactic structure and a helical structure for the isotactic molecule obey different selection rules and have different dichroic properties in the infrared and Raman spectra. The observed Raman spectrum is consistent with the model of the extended syndiotactic conformation for crystalline PVC. With the new Raman data some additional assignments can be made in the vibrational spectra of PVC.

Notizen: Polyvinylpyridine of molecular weight 0.77 × 106 was crosslinked by 2.5, 5, and 10% BrCH2C6H4CO(CH2)8COC6H4CH2Br and by 10% ClCH2C6H4CH2Cl; quaternization of the gel was completed with n-butyl bromide. Swelling ratios in aqueous solutions of lithium, sodium, and 4-isopropyl-N-n-butylpyridinium bromide and in methanolic lithium bromide were determined. Selectivity increased in the sequence Li+ 〈Na+ 〈PrN+-C5H5. The Flory parameter χ1, which measures interaction between solvent and polymer, decreased from 1.5 kT to nearly zero with increasing density of crosslinks in the aqueous solutions, and from 3 kT to 0.5 kT in the methanol solutions. The inverse proportionality of q2/3 (q = swelling ratio) to the crosslinking density was approximately verified for swelling of the resins in water, methanol, and dimethylformamide.

Notizen: Extensive studies of the kinetics of spherulitic crystallization have been made on fractionated samples of TMPS. An analysis of these results reveals that a two-dimensional growth rate mechanism is a more likely mode of growth than a three-dimensional one. This conclusion is substantiated by experimental evidence from optical microscopy and light scattering from within spherulites. The crystallite end surface energy is found to increase as the molecular weight is raised.

Notizen: Data existing in the literature for the spherulitic growth rate of molecular weight fractions of linear polyethylene, poly-(tetramethyl-p-silphenylene)siloxane, and trans-1,4-polyisoprene have been analyzed according to nucleation theory on taking into account the influence of chain length on the free energy of fusion. All three polymers display very similar behavior in that the interfacial free energy reaches an asymptotic value at high molecular weights, decreases as the molecular weight is lowered, and appears to also reach an asymptotic value at low molecular weights. Although the changes in the interfacial energy with molecular weight are quite distinct, the relative change is much less than has been previously reported when a molecular crystal analysis is used. The same general behavior observed points out the dominating influence of the chain-like character of the molecules in governing the growth rate.

Notizen: Batch polymerizations of vinyl acetate were conducted at 60°C and 72°C, and rate constants for branching were established from the variation of M̄n and M̄w with extent of conversion. The calculated branching densities (branch points per polymer molecule) are slightly higher at 72°C for all conversions. Selected samples were saponified and reacetylated to determine the amount of branching through the acetate group. Changes in M̄n, M̄w, and [η] indicate 63%, 75%, and 70%, respectively, of saponificable branches. These percentages are independent of branching density in the original polymer. Molecular weights extrapolated to zero conversion appear to be unchanged by saponification and reacetylation, showing that short chain branching through the acetate group is absent, or at least very infrequent.

Notizen: Dilatometric melting experiments were performed on an extended-chain crystalline polyethylene with a broad molecular weight distribution and on four samples crystallized from fractionated polyethylenes. The melting curves were compared with computer calculations based on the assumption of eutectic separation. For the fraction of lowest molecular weight, agreement between experiment and calculation was achieved. The melting behavior of all other samples indicated that only for molecular weights up to 10,000-12,000 did eutectic separation occur. The higher molecular weight portion of each sample crystallized in the form of mixed crystals. Of the experimental maximum melting-point lowering of these mixed crystals, 0.1-0.9°C is due to the lower molecular weight diluents. Another 2-3°C lowering in melting point is due to the fact that the phase diagram of polyethylene mixed crystals has a minimum.

Notizen: A comparison is made between the experimentally obtained molecular weight distributions of nitric acid-oxidized polyethylene with a wide range of initial morphologies and the predictions of a random attack model. Deviations from the theoretical expectations are explained.

Notizen: Rates of crystallization of polyethylene fractions have been studied at high undercoolings by differential calorimetry to demonstrate the utility of this technique for fast crystallization analysis. It has been shown that there is continuity in the crystallization kinetics from low to high undercoolings. On the other hand, the influence of molecular weight on the crystallization rates, as the undercooling increases, is very moderate, as would be expected.

Notizen: The yield-stress behavior of two glassy polymers is studied through the glass transition region over a wide range of strain rates. For temperatures below the glass transition temperature, the yield stress behavior could be described as a non-Newtonian flow in agreement with Eyring's theory, if one excepts a narrow range relating to the slowest strain rates. For temperatures above Tg, the yield-stress behavior is still nonlinear but fits the relations based on the concept of free volume.

Notizen: The distribution of molecular weights in realistic free-radical polymerizations with branching was analyzed theoretically. Series solutions were obtained for the fraction of molecules with r repeating units and the number of branch points contained in molecules with r repeating units. Branching by transfer processes was found to increase the proportion of both high and low molecular weight components in the system. The apportioning of branch points among r-mer molecules was shown to be somewhat narrower than a Poisson distribution. The major difference between the calculated distributions and previous model distributions for branched systems was the absence of discontinuities in the moments at all levels of branching.

Notizen: The problem of the structural theory of macromolecular networks is formulated and discussed in general terms. The conditions required for a system to become a homogeneous macromolecular network are defined and discussed. Networks are divided according to the nature of their junctions into three classes: energetic (with chemical or quasi-chemical crosslinks), topological (with entangled chains), and contact (with frictional interactions). The main features of these three classes are discussed. A distribution density function ψ describing the configurations of macromolecules in network systems is introduced. The phase space of variables is 4(N + 1)-dimensional and includes the coordinates of (N + 1) vectors hi joining the adjacent network junctions and (N + 1) contour lengths li of the network chains. The system of simultaneous equations required for the determination of the function ψ includes the equation of continuity, kinematic equations for the deformation velocity of the individual junctions, the force balance equation needed for the determination of sliding rates li, kinetic equations for the processes of junction breakage and reformation, and the equilibrium distribution of network junctions defining the initial conditions for the distribution function ψ.

Notizen: Extended-chain crystals of high molecular weight polymethylene, a polyethylene with a broad molecular weight distribution, and three fractions of polyethylene were grown from the melt under elevated pressure. Comparison of the crystal size distribution in the molecular chain direction (measured on fracture surfaces by electron microscopy) with the molecular weight distribution (measured by gel-permeation chromatography) gave the following results. Up to molecular weight 10,000 all samples showed eutectic separation into fully extended chain crystals of narrow molecular weight distribution. Above molecular weight 10,000 mixed crystals were formed. Under the chosen crystallization conditions larger chain extension was achieved with higher molecular weights. However, an increase in molecular weight by a factor of 1000 led only to a tenfold increase in chain extension. These facts are discussed in the light of a proposed mechanism of crystal growth.

Notizen: The Kuhn-Grün theory for the birefringence and dichroism of rubbery polymers is extended to the case of copolymers consisting of two or more statistical segments of differing lengths. It is shown that the previous equations are applicable provided that the anisotropy of polarizabilities and absorptions are replaced with suitable averages in which the segment anisotropies are weighted by the squares of their segment lengths. This indicates that the stress-optical coefficient will not generally vary linearly with composition. The orientation measured from the dichroism of bands arising from different segments will be different.

Notizen: There are eight retinula cells in the ommatidium of the compound eye of the toadbug (Gelastocoris oculatus), two of which are central in position. Along the axial sides of the six peripheral retinula cells expand six cytoplasmic processes from the apical crystalline cone cells. These processes, which contain longitudinally-oriented microtubules, are associated with all eight retinula cells by means of desmosomal junctions. In addition to providing structural support, the possibility is set forth that the interconnecting cone processes might also serve to functionally integrate the retinula cells of an ommatidium. The eight retinula cells possess microvillus surfaces, which are especially prominent in the six peripheral cells, where they extend into the lumen of the ommatidium. There is evidence of pinocytotic activity at the bases of microvilli. Multivesicular bodies are present in the cytoplasm of retinula cells, and the means by which these bodies might be elaborated are discussed.