Quiescent Melt Research Articles

Crystallization kinetics of oriented polymers

AbstractThe increase in the rate of polymer crystallization brought about by mechanical deformation above the polymer glass‐transition temperature is examined. For flexible macromolecules, this deformation results in alignment and extension of polymer chains. By hypothesizing that the instantaneous growth rate at a given constant temperature depends uniquely on the polymer chain orientation in the surrounding melt, an explicit expression is obtained for the growth rate of a spherulite in terms of experimentally measurable quantities. Isothermal meltspinning experiments were conducted with poly(ethylene terephthalate) (PET) using a laboratory setup. Very large values of the total crystallinity and significantly enhanced values of the crystallization rate were generated by operating at different temperatures that straddle the temperature of maximum crystallization rate for the quiescent melt. Measured rates of crystallization do, indeed, correlate with the instantaneous amorphous orientation. Furthermore, a masterplot, independent of temperature, is obtained by normalizing the crystallization rate under spinning conditions with that under quiescent conditions. This is the first time that such data have become available, and, given the processing history, such a master plot should be of use in predicting the crystallinity levels in actual nonisothermal industrial experiments.

Scattering Studies of Cyrstallization in Highly Oriented Polymers

The solidification of low molecular weight materials from their melts (in the absence of temperature fields) generally leads to a product with no preferred orientation, independent of the extent or rate of deformation of the melt. The solidification of polymers from a highly deformed melt or solution nearly always leads to a product with preferred molecular orientation. Further, the rate of solidification can be significantly increased by melt deformation. The change in rate, relative to that in a quiescent melt or solution, can be several orders of magnitude [1]. These differences, relative to small-molecule systems, arise from the degree to which orientation and local strain can be maintained in the melt. Due to the long-range connectivity within a polymer molecule, it is possible to impart large extensions to these molecules in the molten state, and significant time is often required for the molecules to relax back to their undistorted, coiled state. If crystallization or glass formation occurs before the chain can relax, an extended molecular configuration can be retained. Thus in the solidification of oriented polymers there exists a competition between the “freezing” of the molecular orientation and the relaxation (re-coiling) of the molecules.

The structure of propylene-ethylene sequential copolymers

Polypropylene is frequently modified by incorporating ethylene during polymerization or by blending with ethylene polymers or copolymers. Such ethylene-containing systems exhibit a very characteristic texture of small particles (globules) superposed on the spherulitic crystallinity of the polypropylene. The nature and occurrence of these particles have been investigated. The conclusion reached is that they contain ethylene polymers, both crystalline and amorphous, and that they can exist in a quiescent melt.

Crystal nucleation in sheared polymer melts

AbstractA semiquantitative procedure has been developed for analyzing crystal nucleation in undercooled polymer melts that are undergoing flow. This analysis was applied to the specific ease of molten high density polyethylene experiencing low levels of shearing flow. A custom‐made concentric cylinder viscometer, which could be operated by the Rheometrics mechanical spectrometer instrument, was used to make simultaneous measurements of transmitted torque and optical anisotropy in isothermal melts, The result of the analytical procedure developed here was molecular Size‐dependence of chain distensions caused by prevailing shear. This distribution function was verified by testing against experimentally obtained values of birefringence. Total entropy reduction resulting from this distorted state was then calculated, and the corresponding increase in free energy was found to be at least enough to account for comparable crystal nucleation rates in flowing melts at higher temperatures and in quiescent melts at lower temperatures.

Crystallization of polyethylene oxide under shear

AbstractA concentric cyclinder dilatometer was designed and built to study the influence of shear on the crystallization kinetics of polymers. This instrument allows crystallization to be followed at both constant temperature and shear rate. Several samples of polyethylene oxide (Carbowax 4000, Carbowax 20‐M, and WSR‐205) were used. A low molecular weight fraction of the Carbowax 20‐M, as well as the unfractionated material, was crystallized under shear. The WSR‐205 was studied only in a mixture with Carbowax 4000. It was shown that the kinetics of crystallization of uncrosslinked melts of polyethylene oxide are altered by shear. The induction times for the appearance of crystallinity are shorter in the sheared systems than in the quiescent melts. The Avrami exponents are also higher for crystallization in sheared melts than in quiescent systems and increase with decreasing supercooling. The high values of the Avrami exponent are attributed to the disruption of crystalline aggregates into particles larger than the critical sized nucleus. These particles will persist in the melt and continue to grow spontaneously. A continuous infusion of growing particles into the melt occurs.At constant temperature and shear rate, the induction time of the crystallization curve is influenced by polymer molecular weight. In moderate to high molecular weight samples, the effect of shear becomes saturated at very low shear rates. Decreasing the molecular weight separates the crystallization curves. The curves from the higher shear rates appear at the shorter induction times. However, decreasing the molecular weight below that at the critical entanglement molecular weight allows the nucleation rate, strongly dependent upon the supercooling, to influence the relative positions of the sheared crystallization curves.

Morphology of injection‐molded polypropylene

AbstractA surface zone composed of at least three distinct layers has been detected in injection‐molded polypropylene. The morphology of these layers as determined by optical and scanning electron microscopy forms a continuous picture from the “as‐molded” surface to the core. With the exception of the first layer which is always featureless, the observed morphology is mostly spherulitic. Starting in the second layer, the spherulites decrease steadily in size until they reach a minimum somewhere near the middle of the third layer. After passing this point, they increase in size—rather rapidly—as the boundary between layer 3 and the core is approached. In samples prepared at the shorter fill times, the spherulites continue to decrease in size until they are replaced by the mixed matted straw–flat plate texture. The overall morphological features of this surface zone are explained by using an extension of a model for the crystallization of a quiescent polymer melt. In this model, growth originates from heterogeneous nuclei whose density varies throughout the sample as a function of both a temperature gradient and the induction time. Interpretation of anomalies in the fine structure of the individual layers indicates that shear is influencing the crystalline morphology also.