María J. Galante

The degree of crystallinity of monoclinic isotactic poly(propylene)

The degree of crystallinity of a set of monoclinic (alpha) isotactic poly(propylenes), prepared by a metallocene-type catalyst, were determined at room temperature. Three different methods were used: density, enthalpy of fusion, and wide-angle X-ray scattering, and the results compared. The relation between the heat of fusion and the specific volume of these poly(propylenes) was found to be nonlinear, thus precluding any linear extrapolation to obtain the heat of fusion of the pure crystal (ΔHu). The value of ΔHu obtained from depression of the melting temperature by diluents is used. Based on the unit cell density of monoclinic crystals formed from a low defected fraction, the density obtained crystallinity levels were found to be between 0.l5–0.25 higher than those calculated from the heat of fusion. This relatively large difference holds for the isothermally crystallized and quenched isotactic poly(propylenes), and reflects the contribution of the interphase to the density determined crystallinity, which does not contribute to the heat of fusion. Paralleling results found in other systems, the crystallinity levels obtained from wide-angle X-ray scattering agree with those obtained from density, indicating a significant contribution of the partially ordered phase to the total diffraction. Emphasis is given on the need to account for the large differences in the crystallinities of poly(propylene) measured by different techniques when evaluating the dependence of properties on this quantity.

The crystallization of blends of different types of polyethylene: The role of crystallization conditions

Abstract Cocrystallization in blends of linear and branched polyethylenes has been studied under both isothermal and slow-cooling crystallization conditions. Before the more common, polydisperse-type polyethylenes were studied and the results analysed, model systems were investigated in detail. The components used in the model binary blends were molecular weight fractions of linear polyethylene, hydrogenated poly(butadiene) as a model for the ethylene-1-alkene copolymers, and a three-arm star hydrogenated poly(butadiene) as a model for the long chain branched polyethylenes. It was found that a key factor in governing the extent of cocrystallization in these blends is the closeness of crystallization rates of each of the components. The extent of the cocrystallization thus diminishes with increasing concentration of the linear component in the blend. It is found that copolymer composition and molecular structure also have a strong influence on cocrystallization. The amount of cocrystallization is favoured at the lowest isothermal crystallization temperatures and is maximized under quenching conditions. The general features that influence cocrystallization, which have evolved from this study, are discussed.

Crystallization kinetics of metallocene type polypropylenes

The crystallization kinetics from the melt of metallocene type isotactic poly(propylenes) having the same chain defect concentration and molecular weights ranging from 68480 to 288430 have been studied by differential scanning calorimetry. The crystallization rates and the variation of the rates with crystallization temperature follow a pattern that is basically independent of molecular weight. This result contrasts with the molecular weight dependence on the crystallization rate observed in linear polyethylene, random ethylene copolymers as well as other semicrystalline systems.Most significant is the fact that the metallocene poly(propylenes) show apparently significantly higher σeσu products than do the Ziegler type fractions of matched molecular weight and defect concentration. This difference can be interpreted as the metallocene type crystallites having higher effect on surface interfacial free energies than the Ziegler type, or can result from the two different chain types having different sequence propagation probabilities.

Light responsive thin films of micelles of PS-b-PVP complexed with diazophenol chromophore

We have incorporated push-pull azobenzene units into diblock-copolymer micelles by supramolecular assembly. Specifically, we encapsulated a phenol-functionalized chromophore, DO13, within PS-b-P4VP micelles in toluene by means of H-bond interactions developed between DO13 molecules and pyridine groups of P4VP block. The solutions were spin-coated onto glass substrates resulting in multi- or mono-layered thin films of micelles with P4VP(DO13) core and PS corona. We show that the use of DO13 as a building block of micellar aggregates allowed us to manipulate the developed nanostructures. Spherical to cylindrical micellar transition was found when we increased the degree of chromophore complexation. Also, it was found that the polymer concentration in the solution plays an important role in determining the micellar nanostructures. The chain extension and change in composition of the P4VP core in the presence of the chromophore may be responsible for the structural changes observed in the micelles. The optical properties of the thin films have been investigated focusing on the effect of the micellar morphology over the photoinduced birefringence. The optical anisotropy (Δn) increased with respect to the analogous homogeneous system P4VP(DO13), indicating that the protective micelle environment can enhance the optical properties of the embedded chromophores significantly. Furthermore, we show very interesting new results in which we have related changes in optical properties to the film morphology (spheres to cylinders). This can be exploited for producing optical devices having improved optoelectronic properties and stability.