ALBERT

Notes: Moore and Mesler postulated microlayer evaporation beneath a bubble to explain the sudden temperature drops observed by them during nucleate boiling of water.A method was devised to estimate the microlayer thickness from the deposit formed by a series of bubbles during nucleate boiling of saturated calcium sulfate solution containing radioactive sulfur-35. The results support the microlayer evaporation hypothesis.

Notes: Differently shaped bubbles were observed growing during nucleate boiling of water at atomspheric pressure. The surface temperature beneath the bubbles was measured simultaneously with a fast response surface thermocouple. The evaporation from the base necessary to account for the observed cooling was calculated. A comparison of the ratio of vapor volume formed at the base to the total volume of the bubble shows a dependency on bubble shape. The ratio is smallest for spherical bubbles, largest for hemispherical and intermediate for oblate bubbles.

Notes: No Abstracts.

Notes: 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.

Notes: Fracture surfaces record the kinetics of failure at two levels in the structure of polymeric solids. The first is evidenced by the formation of geometric markings resulting from the interaction of the primary fracture front with secondary fractures developing radially just ahead of the primary fracture. These markings are often visible to the unaided eye and have minimal dimensions in the micron range. The second fracture phenomenon appears to involve the orientation of molecular chains or bundles. Such orientation manifests itself in the interference-color producing film found on the fracture surfaces of poly (methylmethacrylate) and polystyrene. It is also apparent in the free or adherent film found on the surfaces of large fractured crazes. Some evidence is presented for the existence in these films of chain bundles 30A or less in diameter. It would seem that similar mechanisms are operating in the production of “craze matter” and of fracture surface films.

Notes: 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.

Notes: Amoco AI amide imide polymer is an all aromatic polymer which is currently being used as a high temperature wire enamel. It also looks promising as a high temperature laminating material. It is available in a stable solid form and is readily formulated in its laminating solvents. B-Staged coated glass cloth with excellent shelf stability is easily prepared. AI laminates retain their initial flexural strength after four weeks at 500°F. They retain 50% of their initial flexural strength after one week at 572°F. Other modifications of this type of polymer are being investigated as laminating materials.

Notes: 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.