Morphology of α‐transcrystalline isotactic polypropylene under tensile stress studied with synchrotron microbeam X‐ray diffraction

The morphology of transcrystalline isotactic polypropylene under tensile stress was studied with wide‐angle synchrotron X‐ray diffraction. The strain was apparently generated predominantly within the amorphous phase because no change in the crystal structure or in the orientation of the lamellae was detected. The results are interpreted in terms of anchoring of the transcrystalline layer to the fiber surface, and the possible consequences of these morphological features on the mechanical properties of the aramid–polypropylene composite as a whole are discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2016–2021, 2001     

Investigation of the microstructure of polypropylene prepared with ansa and fluxional metallocene catalysts with an extended Coleman–Fox model

Temperature (T) effects on the microstructure of polypropylene made with metallocene catalysts have been investigated with the theoretical framework originally developed by Coleman and Fox and extended to the stereospecific polymerization of propylene with two‐state ansa and fluxional metallocene catalysts. T effects on the polymer microstructure are mainly due to factors other than changes in the intrinsic stereoselectivity of the two states. The model has been applied to the stereosequence distributions of polypropylene prepared with the C₁‐symmetric Me₂Si(Ind)(Flu)ZrCl₂ complex, activated with methyl aluminoxane, over a range of T and monomer concentration ([M]) values. The use of these two variables, in combination with the Coleman–Fox model (or a kinetic model), allows more reliable estimates of fundamental parameters, especially when the microstructure is a weak function of one of these variables at a constant value of T (e.g., [M]). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1797–1810, 2005     

Prediction and phase segregation in thin‐film of conjugated polymer blends

Blending conjugated polymers is an efficient method to improve the properties of the films. The phase diagram of poly(9,9‐dihexylfluorene) (PF) and poly(2‐methoxy‐5‐(2′‐ethyl‐hexyloxyl)‐p‐phenylene vinylene) (MEHPPV) was predicted by a modified Flory–Huggins theory based on the topological method (graph theory) for the structure‐property correlations. It shows that the two polymers have a strong trend to separate. Atomic/friction force microscopy (AFM/FFM) measurements show there exist microphase separations in film prepared at room temperature. After annealing at 160 °C, serious phase segregations took place in both the lateral and vertical direction. The photoluminescence of the thin films was also measured by a fluorophotometer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1382–1391, 2005     

Synthesis, structure and bioactivity of pHEMA/SiO2 hybrids derived through in situ sol–gel process

A novel procedure to synthesize poly(2-Hydroxyethylmethacrylate)-silica blend hybrids is presented. Methacrylate monomers bearing an alkoxysilyl unit, prepared by Michael addition of 2-Hydroxyethylmethacrylate (HEMA) to 3-Aminopropyltriethoxysilane (APTS), were employed. By ¹³C NMR and mass analysis it was possible to establish the formation of coupling hybrid species. A hybrid material, with final concentration of 30% w/w of silica gel to the mass of polymer, was obtained through basic catalysed sol–gel process of tetraethoxysilane (TEOS) and the alkoxysilyl unit of the hybrid monomer, followed by in situ free-radical polymerization. Optical transparency and higher glass transition temperature than pHEMA suggest an increase in either density or strong interphase interactions. Moreover, pHEMA/SiO₂ gel blend hybrid exhibits better thermal stability than the as-prepared polymer. Morphology and structure were studied through scanning electron microscopy (SEM), transmission electron spectroscopy (TEM), and dynamic light scattering (DLS). The structure of the hybrid consisted of nanosilica, 10 nm in mean diameter, uniformly dispersed in the pHEMA phase with strong interactions between the phases. Nevertheless, the swelling ratio of the hybrid was comparable to pHEMA. Using FT-IR spectroscopy, SEM and energy dispersive system (EDS), XRD analysis in vitro bioactivity of the hybrid, due to the inorganic phase, was ascertained therefore, the obtained hybrid can be used to make bioactive scaffold for bone engineering.     

Microporous membranes obtained from polypropylene blends with superior permeability properties

A blend of two polypropylene resins, different in molecular structure, one with linear chains and the other with long chain branches, was investigated to develop microporous membranes through melt extrusion (cast film process) followed by film stretching. The branched component significantly affected the row‐nucleated lamellar crystalline structure in the precursor films. The arrangement and orientation of the crystalline and amorphous phases were examined by wide angle X‐ray diffraction and Fourier transform infrared spectroscopy methods. It was found that blending of a small amount of a long chain branched polypropylene improved the orientation of the both crystalline and amorphous phases in the precursor films. Annealing, followed by cold and hot stretching were consequently employed to generate and enlarge pores in the films as a result of lamellae separation. SEM micrographs of the surface of the membranes obtained from the blend revealed elongated thin fibrils and a large number of lamellae. The lamellae thickness for the blend was much shorter in comparison to that of the linear PP precursor film. The permeability of the samples to water vapor and N₂ was significantly enhanced (more than twice) for the blend system. The porosity of the blend membrane showed a significant improvement with a value of 53% compared to 41% for the linear PP membrane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 148–157, 2008     

Toughening of highly crosslinked epoxy resins by reactive blending with bisphenol A polycarbonate. II. Yield and fracture behavior

The yield and fracture behavior of highly crosslinked epoxy resin modified by a reactive blending process carried out in the presence of bisphenol A polycarbonate has been studied. It was found that the fracture toughness of this blend system increases markedly with increasing PC content in the blend. Scanning electron microscopy of the fractured surfaces indicated a crack blunting mechanism as the main source of energy dissipation in the various investigated blend compositions. No evidence of phase separation of the minor component during the curing and postcuring steps was observed. The yield data were correlated with the fracture toughness data to evaluate the extent of crack-tip blunting. © 1994 John Wiley & Sons, Inc.     

Free volume,glass transition,and degree of branching in metallocene‐based propylene/α‐olefin copolymers: Positron lifetime,density, and differential scanning calorimetric studies

Positron annihilation lifetime spectroscopy (PALS), density, and differential scanning calorimetric (DSC) measurements were used to study systematically the variation of the glass‐transition temperature (T_g) and the size v and number density N_h of local free volumes in n‐alkyl‐branched polypropylenes. The samples were metallocene‐catalyzed propylene copolymers with different α‐olefins (from C₄ to C₁₆) and a different α‐olefin content (between 0 and 20 mol %). From the total specific volume and crystallinity the specific volume of the amorphous phase V_a was estimated and used to calculate the fractional free (hole) volume h and value of N_h. The variations of T_g, v, V_a, h, and N_h were related to the degree (number and length) of branching. T_g decreases and v increases linearly with the number and length of n‐alkyl branches. This behavior was attributed to an increased segmental mobility caused by branching. Both values, T_g and v, follow linear master curves as a function of the degree of branching (DB) if this is defined as the number of all side‐chain carbons with respect to a total of 1000 (main‐chain and side‐chain) carbons. Only propylene/1‐butene copolymers deviated from these relations. A linear relation between v and T_g was also found. The number density of holes was estimated to be N_h = 0.49(±0.07) nm^?3 and N_h′ = 0.58(±0.11) × 10²¹ g^?1, respectively. It shows a slight variation with the DB, which is also seen in the behavior of the specific volume V_a. This variation was explained by the appearance of sterical hindrances resulting from short‐chain branches that may prevent an efficient packing of the chains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 434–453, 2002; DOI 10.1002/polb.10108     

Miscible blends of zinc-neutralized sulfonated polystyrene and poly(2,6-dimethyl 1,4-phenylene oxide)

Zinc-neutralized sulfonated polystyrene ionomers (ZnSPS) and poly(2,6-dimethyl 1,4-phenylene oxide) homopolymer (PXE) form miscible blends up to at least 7.8 mol % sulfonation, as measured by thermal and mechanical criteria. The addition of an equal weight of PXE raises the glass transition temperature of ZnSPS by 40–50°C. However, this miscibility is not achieved by eradicating the microdomain structure present in ZnSPS, even though the PXE coils are considerably larger than the spacings between ionic aggregates. Small-angle x-ray scattering indicates that while the average interaggregate spacing is roughly the same in ZnSPS and its 50/50 blend with PXE at a given sulfonation level, the extent of phase separation is reduced upon PXE addition, indicating that more ionic groups are dispersed in the matrix. Factors influencing miscibility in the ZnSPS/PXE materials and related blends are discussed.     

Interaction at the Interface of Phosphorus-Containing Carbon Fibers and Diglycidil Ether of Bisphenol-A

Two-component blends of phosphorus-containing carbon fibers (PCF) and diglycidyl ether of bisphenol-A (DGEBA) are investigated. It is found that PCF are better wetted by the epoxy oligomer considered than unmodified carbon fibers. It is stated that the equilibrium work of adhesion of the epoxy oligomer to PCF increases considerably. Heating the two-component blends is accompanied by conversion of epoxy groups and formation of a gel-fraction nonextractable from the fiber surface. The investigation results indicate that chemical bonds are formed at the fiber-oligomer interface, which causes grafting of the DGEBA immediately to the surface of PCF without the use of intermediate compositions usually employed in such cases. It is shown that a transition layer is formed whose morphology differs from that of the fibers and polymer in the blend volume.     

Stress relaxation as a microstructural probe for immiscible polymer blends

Relaxation has been investigated in immiscible blends that consist of slightly viscoelastic components. Both the shear and normal stresses have been measured after cessation of steady shear flow as well as after transient shear histories. The latter can generate a fibrillar structure which can relax by either retraction or break-up via end-pinching or Rayleigh instabilities. Each of these three relaxation mechanisms is reflected in the shape of the stress curves, from which also the corresponding structural time scales can be deduced. The experimental results have been used to evaluate the Doi-Ohta and Lee-Park models for immiscible blends. The scaling relations by Doi-Ohta are confirmed by the experimental results, but none of the existing models can correctly predict the complex relaxation behaviour observed for a highly deformed droplet phase. In the present study an alternative approach has been proposed. The stress relaxation due to fibril break-up via Rayleigh instabilities has been predicted successfully by combining physical models for the structural changes with the basic approach of the Doi-Ohta model.