Sizes and interfacial free energies of crystallites formed from fractionated linear polyethylene

Replicas of fracture surfaces of fractions of linear polyethylene, which were crystallized at elevated temperatures for extended time periods, were examined by electron microscopy. Striated. lamella-type crystallites were observed for all molecular weights over the range 3.2 × 10³?5.7 × 10⁵. In agreement with Anderson's previous report, for molecular weights of 12,000 or less, the crystallite thicknesses were comparable to the extended chain length. As the molecular weight increased above this level, however, the crystallite sizes increased only slightly and hence at high molecular weights were very much smaller than the extended chain length. From the measured melting temperatures, crystallite interfacial free energies were calculated from the theory for the melting of finite size crystals comprised of chains of finite length. The crystallite interfacial free energy was found to increase with molecular weight. Based on these results, a crystallization process is outlined which allows for the formation of either extended chain crystallites, or crystallites whose size is much smaller than the extended chain length without any change in nucleation mechanism or arbitrary adjustment in growth mechanism with molecular weight.     

Temperature dependence of the growth rate of spherulites

The spherulitic growth data that exist in the literature for a wide diversity of polymers have been analyzed according to various possible nucleation mechanisms. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the allowable nucleation processes which enables the data to be represented by a single straight line which encompasses all the polymers. The only quantities specific to a given polymer are the equilibrium melting temperature and the activation energy for transport. The magnitude of the latter quantity is shown to be dependent on the glass temperature of the polymer.     

Influence of structural and morphological factors on the mechanical properties of the polyethylenes

Force-length relations at ambient temperature have been determined for a set of polyethylenes which represent a wide range in molecular weight and molecular constitution. Taking advantage of previous work from this laboratory, samples have been prepared in such a manner that the important independent structural variables can be identified and isolated and their influence on the different aspects of the deformation process assessed. Partial melting-recrystallization processes appear to play an important role. For the linear polymers there is a direct influence of molecular weight. The influence of molecular weight manifests itself in the structure of the interlamellar zone which has a major influence on the initial modulus as well as the ultimate properties. Copolymers and branched copolymers display quite different behavior. The most striking difference is the invariance of the ultimate properties with molecular weight, branching, and level of crystallinity. From the set of experimental results that are presented the molecular factors involved in the deformation process can be sorted out. It becomes quite evident that all of the basic structural regions, characteristic of semicrystalline polymers, contribute to the observations. Focus solely on the changes in the crystallite, in analogy to the deformation of small-molecule crystalline systems, is inadequate in the case of crystalline polymers.     

Numerical analysis of lamellar thickness distributions

A comparison of crystallite thickness distributions, as obtained from thin section electron microscopy, small-angle x-ray scattering, and low-frequency Raman acoustical model (LAM), is discussed in detail. It is shown with the aid of a large number of examples that a reliable numerical estimate of crystal thicknesses and long spacings is a complex problem. The values that are obtained by the different experimental techniques depend not only on the crystallite morphology, such as curvature and lateral extension, but very specifically, and crucially, on the nature of the thickness distribution. A series of widely different types of size distributions have been developed by controlling the molecular weight and crystallization temperature. Studies of these distributions, by the aforementioned experimental techniques, have revealed the reasons when and why agreement or disagreement is obtained in the determination of the crystallite thickness distribution.     

A quantitative electron microscopic study of the crystalline structure of ethylene copolymers

Quantitative thin-section electron microscope studies were made on compositional fractions of ethylene copolymers crystallized under several extreme conditions. The co-units chosen were such that the chains contained either ethyl, hexyl, or acetate side groups. Certain general features are independent of the chemical nature of the co-unit. It was found that up to about 2 mol % co-unit content lamellae are observed in all copolymers which were slowly cooled from the melt. The lateral dimensions of lamellae are not as large as in corresponding homopolymers and the lamellae are segmented. As the branch content increases the lamellae become shorter and eventually degrade into small crystallites. Within this broad outline of behavior, differences between the copolymer types are discerned and discussed. By comparison with the Raman LAM it is shown that quantitative values for the crystallite size distribution are obtained by the electron microscopy method used. Furthermore, when the specimen consisted of well-ordered lamellar stacks the degree of crystallinity obtained from the electron micrographs was in quantitative agreement with the enthalpy of fusion.     

Search for hadronic decays of a light Higgs boson in the radiative decay Υ→γA0

We search for hadronic decays of a light Higgs boson (A(0)) produced in radiative decays of an Υ(2S) or Υ(3S) meson, Υ→γA(0). The data have been recorded by the BABAR experiment at the Υ(3S) and Υ(2S) center-of-mass energies and include (121.3±1.2)×10(6) Υ(3S) and (98.3±0.9)×10(6) Υ(2S) mesons. No significant signal is observed. We set 90% confidence level upper limits on the product branching fractions B(Υ(nS)→γA(0))B(A(0)→hadrons) (n=2 or 3) that range from 1×10(-6) for an A(0) mass of 0.3 GeV/c(2) to 8×10(-5) at 7 GeV/c(2).