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Composites of isotactic polypropylene with various contents of white clay or titanium dioxide TiO 2 were prepared by extrusion molding. The extruded composites were melt-pressed at two different temperatures, and, thereafter, either slowly cooled, or quenched to room temperatures. It is shown that the structure of all the samples, as revealed by wide-angle X-ray scattering and small-angle X-ray scattering (SAXS), depends on the processing conditions. The lack of SAXS maxima in the composites suggests that the presence of the microadditives hinders the stacking of iPP lamellae. Furthermore, the microindentation hardness H in the slowly cooled composites is influenced by the type and amount of the filler used. However, in the quenched samples H depends only on the amount of the filler used, and not on its type. In case of the quenched iPP/clay composites, the relationship between H and the Young's modulus E is found to be H/E ≈ 0.12, in good agreement with Struik's theoretical predictions of σ e ≈ E/30, in consonance with results previously obtained for a series of polyethylene samples with different morphology. © 2011 Wiley Periodicals, Inc., Contract grant sponsor: Spanish Ministry of Science and Innovation (MICINN); contract grant numbers: FIS2010- 18069, MAT2009-00789. Contract grant sponsors: Alexander von Humboldt Foundation, Germany, EC Research Infrastructure (FP6 Program) (Desy Project II-07-031 EC).

Recent developments concerning the meth- odology used to prepare composites of iPP and nanoclays are reported. Conventional (reactive melt mixing) and in situ preparations were performed, and the structural prop- erties exhibited by the composites are discussed. Results suggest that the nanoclay could exhibit partial and, maybe, total exfoliation within the composites. Adhe- sion between the polymeric matrix and the nanoclay layers is similar to that obtained after grafting. The ex- perimental procedure used and the analysis performed by means of the wide-angle X-ray scattering and differ- ential scanning calorimetry techniques permit to describe, at nanoscale level, the contribution of the nanoclay to the polymer composite system. The micro- hardness values of the iPP-clay composites depend on the clay content and on the preparation method, and linearly correlate, according to the additivity law, with the degree of crystallinity. V C 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 2654-2662, 2010

Reversibly crosslinked isotactic polypropylene (iPP) was prepared in the presence of dicumyl peroxide. The effects of the peroxide oxy-radicals in the melt were investigated in relation to the modification of the polymer. The dynamic rheology analysis of the crosslinking process was carried out by using a plastograph. The crosslinking reaction was evaluated by the Monsanto method. The resulting structure of the modified samples was studied by means of differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), microhardness, and mechanical properties. The degree of crystallinity of the modified iPP, derived from DSC and WAXS, remains almost unchanged, i.e., the crystalline structure is unaffected, though the lamellar thickness slightly decreases. The impact strength of the crosslinked iPP is greatly improved with reference to that of the unmodified material. A transition from brittle to ductile behavior appears in the modified iPP for all the crosslinking agents studied.

The evolution of the amorphous structure of starch was characterized during the drying process by real time X-ray wide-angle scattering. The X-ray diffractograms of injection-molded starch show two superposed, rather broad, scattering maxima indicative of noncrystalline structures. The location of the two peaks has been associated to disordered starch single helices. A third maximum that arises upon drying the material in vacuum is associated to the scattering emerging from regions containing double helices. A model for the starch network is proposed, assuming a primary and a secondary component. The wider, temperature stable component appearing first, is correlated to the entanglement network of the melt. The narrower network component, which is created later, at lower temperature (secondary network), is explained by the formation of double helix regions that densify the wider primary network. The secondary network is increased strongly by the drying process. X-ray experiments performed during the penetration of water, provoking a higher molecular mobility, reveal a better-packed helical structure that becomes the precursor of a double helix crystalline formation. When temperature increases, the secondary network is dissolved and water molecules arrange themselves in better-organized crystals as strongly bound crystal water.

Native starches with wide varying amylose content were processed by injection molding. The injection- molded materials were conditioned in water for 20 days and sealed in glass capillaries. Simultaneous wide- and small- angle X-ray scattering (WAXS and SAXS, respectively) were recorded during thermal heating using a synchrotron source. Crystallinity, SAXS invariant, Q, and long period, L, were measured as a function of heating temperature. The injection-molding process provokes a destruction of the crystal forms A (cereal starch) and B (tubercle starch) but favors a development of the crystal form Vh. After wet conditioning, WAXS of the injection-molded samples shows again the appearance of the crystal forms A or B, and crys- tallinity reaches values similar or larger than those of native starch. A constant heating rate (5°C/min) was particularly used for a comparison of potato and corn starch with a similar amylose content. While the crystallinity associated to forms A and B slowly decreases below 55°C and then rap- idly decreases until its disappearance at 85-90°C, the invari- ant shows a maximum around 40°C and rapidly decreases thereafter. The total nanostructure disappearance occurs at temperatures about 10°C higher for the case of potato starch. In addition, a recovery of the WAXS and SAXS maxima during the subsequent cooling process before reaching room temperature was observed only for potato starch. Analysis of WAXS and SAXS for the rest of the starch materials reveals clear differences in the structural parameters of the samples that cannot be easily explained solely on the basis of the amylose content. Thus, for Cerestar and Roquette, it is noteworthy that there was a continuous decrease of L until its total disappearance as well as the persistence of crystal- linity (form B), presumably stabilized by the presence of the Vh structure (12-15%). Real-time crystallization experiments on two amorphous injection molded samples, waxy maize (free amylose starch) and potato starch, are also discussed. It is shown that the absence of amylose delays the recrystalli- zation of amylopectine during the experiment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 301-309, 2004

The influence of molecular architecture on the mechanical properties of styrene/butadiene block copol- ymers was investigated by means of the microhardness technique. It was found that the microhardness of the sty- rene/butadiene block copolymers is dictated by the nature of microphase separated morphology. In contrast to poly- mer blends and random copolymers, in which the micro- hardness generally follows the additivity rule, the behavior of the investigated block copolymers was found to signifi- cantly deviate depending on their molecular architecture. The glass-transition temperature of the polystyrene phase (Tg-PS), which practically remained constant and that of the polybutadiene phase (Tg-PB), which varied with the change in the block copolymer architecture, apparently do not in- fluence the microhardness values of the block copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1670 -1677, 2003

The microstructure (crystallinity, long spacing) and the micromechanical properties (microhardness H) of two series of nylon 6 and nylon 66 monofilaments and their blends were investigated as a function of annealing temperature TA and uniaxial deformation in a wide composition range. In case of the homopolymers, the gradual rise of microhardness with TA is interpreted in the light of the increasing values of the crystallinity a and the hardness of the crystals Hc. The depression of the hardness values of the blends from the additive behavior of the hardness of individual compo- nents is discussed in the basis of the crystallinity depression of one component by the second one and viceversa. Finally, the influence of drawing and pressing the blends at 130°C which leads to a hardness increase is also explained in the light of an increase in the Hc value of nylon 66 due to orientation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 636 - 643, 2000

SUMMARY: A high molecular weight, linear aromatic poly(ether ketone ether ketone ketone) (PEKEKK) has been synthesized by electrophilic Friedel-Crafts acylation condensation of 1,4-diphenoxybenzophenone with terephthaloyl chloride. The syntheses were performed as precipitation polycondensations, and the polyketones were obtained in particle form. The viscosity (molecular weight), shape and size of these particles were found to be strongly dependent on the reaction conditions. For low monomer concentration, highly ordered needle-like particles were also obtained. The chemical structure of the polymers obtained was confirmed by 'H and 13C NMR spectroscopy, and para-substitution in aryl fragments of the main chain was identified. Analysis of the expanded 'H NMR spectra for the ring proton resonances reveals defect mefa- and ortho-structures. The amount and isomer ratio of these defect structures depend on the monomer concentration used.

The microhardness of a series of biodegradable polyesters was determined. The nanostructural features of these materials were studied by wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), and differential scanning calorimetry. Analysis of the SAXS and WAXS patterns allowed direct derivation of the degree of crystallinity and crystal thickness values, and correlations of the micromechanical properties are presented. The differences in the thermal and mechanical properties exhibited by the studied systems and the ones found in other aromatic polyesters are explained as due to the different chemical natures of the monomeric units.

A line profile analysis of the (hk0) reflections of sintered poly(p-phenylene) is presented. The wide angle X-ray diffraction maxima were analyzed to study the average size of the coherently diffracting domains as a function of annealing temperature TA. The results show that the lateral size of the coherently diffracting domains increase first slightly for TA 300°C. This is related to a rearrangement of rigid chains from disordered into the crystalline regions. The absence of SAXS supports the view of a nematic frozen-in liquid crystalline structure contributing to about 40% of the material. Eine Linienprofilanalyse der (hk0)-Reflexe von gesintertem Poly(p-phenylen) wird vorgestellt. Die Maxima der Weitwinkelrontgenbeugung wurden analysiert, um die mittlere Grose der koharent streuenden Bereiche in Abhangigkeit von der Temperatur TA zu untersuchen. Die Ergebnisse zeigen, das die Querabmessung der koharent streuenden Bereiche bis TA = 300°C zuerst leicht zunimmt und dann fur TA > 300°C stark anwachst. Dies hangt mit der Umordnung starrer Ketten aus den ungeordneten in kristalline Bereiche zusammen. Das Fehlen einer Rontgenkleinwinkelstreuung stutzt die Annahme einer eingefrorenen nematischen flussig-kristallinen Struktur, die etwa 40% des Materials umfast.