The crystalline morphology of a relatively high molecular weight isotactic polypropylene (i-PP) (M w = 18000 g/mol) with well-defined regio- and stereoirregularities is studied by means of atomic force microscopy (AFM), wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), and light microscopy. This i-PP crystallizes under certain crystallization conditions nearly exclusively in the γ-modification. The growth of the γ-phase is often influenced by the initial growth of the α-phase, but also the neat γ-phase is observable. The formation of the γ-phase can be related to stereo- and regioirregularities in the polymer chain caused by the polymerization mechanism using metallocene catalysts. WAXS measurements show that at large supercoolings the formation of α-phase i-PP is preferred, whereas at low supercoolings this sample crystallizes nearly exclusively in the γ-modification. Light microscopy and AFM reveal for the γ-phase i-PP morphologies different from the well-known spherulites formed by the α- or β-modification. However, it can be shown that the morphology development of γ-phase i-PP can be widely influenced by very small amounts of α-phase i-PP. A lamella thickness of about 4 nm and a long period of 12 nm of γ-phase i-PP isothermally crystallized at 100 °C are obtained from SAXS measurements. At very low supercoolings, supermolecular structures of the neat γ-modification are formed in competition with mixed (α and γ) morphologies. In thin films the neat γ-modification shows network structures, which are formed by triangular entities. Etched bulk samples reveal columns with a rectangular cross-section which are densely packed. On the molecular scale, the surface topography of the flat-on extended chain lamellae with periodic distances of rows of methyl groups of 3.6 Å is measured. This value is in excellent agreement with the distance of the methyl group rows on the crystallographic (010) plane according to the nonparallel chain packing model by Brückner and Meille.

Defined aggregates of polymers such as polymeric micelles are of great importance in the development of pharmaceutical formulations. The amount of drug that can be formulated by a drug delivery system is an important issue, and most drug delivery systems suffer from their relatively low drug-loading capacity. However, as the loading capacities increase, i.e., promoted by good drug–polymer interactions, the drug may affect the morphology and stability of the micellar system. We investigated this effect in a prominent system with very high capacity for hydrophobic drugs and found extraordinary stability as well as a profound morphology change upon incorporation of paclitaxel into micelles of amphiphilic ABA poly(2-oxazoline) triblock copolymers. The hydrophilic blocks A comprised poly(2-methyl-2-oxazoline), while the middle blocks B were either just barely hydrophobic poly(2-n-butyl-2-oxazoline) or highly hydrophobic poly(2-n-nonyl-2-oxazoline). The aggregation behavior of both polymers and their formulations with varying paclitaxel contents were investigated by means of dynamic light scattering, atomic force microscopy, (cryogenic) transmission electron microscopy, and small-angle neutron scattering. While without drug, wormlike micelles were present, after incorporation of small amounts of drugs only spherical morphologies remained. Furthermore, the much more hydrophobic poly(2-n-nonyl-2-oxazoline)-containing triblock copolymer exhibited only half the capacity for paclitaxel than the poly(2-n-butyl-2-oxazoline)-containing copolymer along with a lower stability. In the latter, contents of paclitaxel of 8 wt % or higher resulted in a raspberry-like micellar core.

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The melt miscibility of atactic poly(propylene) (a‐PP) with isotactic (i‐PP) and syndiotactic poly(propylene) (s‐PP), respectively, is investigated by diffusion experiments of i‐PP/a‐PP/i‐PP or s‐PP/a‐PP/s‐PP sandwich specimens using polarized light microscopy. It is shown that the system a‐PP/i‐PP is miscible in the melt, whereas for the system a‐PP/s‐PP no evidence for melt mixing is found. Pressure‐volume‐temperature (PVT) measurements of the three poly(propylene)s are carried out in order to determine the characteristic parameters of the Flory‐Orwoll‐Vrij equation‐of‐state theory. Theoretical predictions using the solubility parameter concept are in agreement with the observed miscibility behavior of the blends. Differences in the cohesive energy densities of a‐PP and i‐PP on the one side, and s‐PP on the other side, are found to be responsible for the phase behavior of the mixtures of poly(propylene)s with different stereoregularity. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1135–1144, 1997

SYNOPSISBlends of poly(styrene)-bloch-poly(ethene-co-but-l-ene)-bloch-poly(styrene) (SEBS) with isotactic polypropylene (PP) and syndiotactic PP, respectively, were investigated. The morphology was observed by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The cryofracture surfaces studied by SEM did not show any particles that were pulled out, so that a good compatibility between SEBS and different PPs could be assumed. The multiphase character of the blends could be well detected by TEM of RuO, stained samples. TEM micrographs of two-layer specimens revealed that SEBS tends to diffuse into the PP phase under formation of micelles. The block copolymer shows a reorientation phenomenon of large domains at the interface before the diffusion into the PP phase occurs. The interfacial strength as a function of annealing time was measured by a peel test of two-layer specimens. Mechanical properties are studied and related to the blend morphology.