New formulations for unsaturated polyester resins and their interactions with low-profile agents and glass fibres

Special anhydrides, such as hexahydrophthalic, methyl-hexahydrophthalic, nadic, methylnadic and methyl-tetrahydroxyphthalic, have been polycondensed with glycols such as propylene and di-propylene, to obtain new formulations for unsaturated polyesters. The properties of these resins, such as tensile behaviour and ultraviolet resistance, neat or mixed with anti-shrinkage additives have been examined and compared to standard polyester resins. Particular attention was paid to the study of the influence of low-profile agents on the resulting phase structures of cured systems. Moreover, the role played by the different phases on the fibre/matrix addition in composite materials reinforced with coated glass fibres was also investigated.     

Flood Forecasting and Decision Making in the new Millennium. Where are We?

This paper reviews the development of real time flood forecasting systems from the early 1970 approaches to the recent probabilistic ones. A preliminary discussion on the motivations for developing real time flood forecasting systems is introduced to explain their evolution in the last four to five decades. It will be shown how recent probabilistic flood forecasts are more robust and effective than the traditional deterministic ones. In particular, when combined with Bayesian decision approaches, probabilistic forecasts are the most appropriate tools for rational decision making in flood warning and flood management.Moreover, they allow taking into account the information from several models to be taken into account by combining into a unique predictive density the deterministic predictions of several hydrological or hydraulic models of a different nature, while in the multi-temporal forecasting extensions, they provide to answers questions such as: Which is the probability of overtopping a dyke in the next 24 h? When will this event be more likely to occur during the next 24 h?The work concludes with a discussion on the still unresolved problems, namely how decisions makers can fully take advantage of the probabilistic forecasts and how these forecasts must be communicated to them in order to meet this objective.     

Effect of the addition of EPM copolymers on the properties of high density polyethylene/isotactic polypropylene blends: II. Morphology and mechanical properties of extruded samples

The influence of the addition of two ethylene-propylene random copolymers (EPM) with different composition on the mechanical properties, thermal behavior and overall morphology of high density polyethylene (HDPE)/isotactic polypropylene (iPP) blends, was investigated on extruded samples. The experimental data showed that the morphology of binary HDPE/iPP blends is drastically modified by these additives and that the ultimate mechanical properties of these mixtures are greatly improved. A reasonable explanation of these results can be ascribed to the fact that these copolymers can act as “compatibilizing agents” in the amorphous regions of the two semicrystalline homopolymers. The extent of such effects is dependent on the chemical structure and/or on the molecular mass of the added copolymer as well as on the HDPE/iPP blend compositions.     

Absolute rate constants for radical-monomer reactions

Summary A method is described for determining the absolute rate constants for the first few propagation steps in radical polymerization. The procedure involves a product analysis of the oligomeric alkoxyamines formed when an initiator is decomposed in monomer containing a very low concentration of a nitroxide radical scavenger. The method is illustrated with analysis of data for methyl acrylate. The rate constants for the first two propagation steps for polymerization of this monomer,k _p(1) andk _p(2), are at least an order of magnitude greater thank _p(average). Values of the absolute rate constants for reactions of phenyl and primary alkyl radicals with methyl acrylate are also estimated.     

Influence of composition and molecular mass on the morphology,crystallization and melting behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends

Results are reported on the influence of composition and molecular mass of components on the isothermal growth rate of spherulites, on the overall kinetic rate constant, on the primary nucleation and on the thermal behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends. The growth rate of PEO spherulites as well as the observed equilibrium melting temperatures decrease, for a given T_c or ΔT, with the increase of PMMA content.Such observations are interpreted by assuming that the polymers are compatible in the undercooled melt, at least in the range of crystallization temperatures investigated. Thermodynamic quantities such as the surface free energy of folding σ_e and the Flory-Huggins parameter χ₁₂ have been obtained by studying the dependence of the radial growth rate G and of the overall kinetic rate constant K from temperature and composition and the dependence of the equilibrium melting temperature depression ΔT_m upon composition, respectively.     

Crystallization,morphology, structure and thermal behaviour of nylon-6/rubber blends

An experimental study was carried out in order to investigate the morphological, kinetic, structural and thermodynamic properties of nylon-6/rubber (namely ethylene-propylene copolymer (EPM) and ethylene-propylene copolymer functionalized by inserting along its backbone succinic anhydride groups (EPM-g-SA)) blends. The morphology and the overall kinetics of crystallization of the blends strongly depend on the type of copolymer added to nylon and on the blend composition. The EPM-g-SA acts as a nucleating agent for the Ny spherulites and at the same time causes a drastic depression of the overall kinetic rate constant. This decrease is related to the increase of the melt viscosity observed in Ny/EPM-g-SA blends. The crystalline lamella thickness of the Ny phase in the blends is lower than that of pure Ny crystallized at the same T_c suggesting that the presence in the melt of an elastomeric phase disturbs the growth of the Ny crystals. The rubber does not influence the thermal behaviour of the nylon. The results found lead to the conclusion that in the melt nylon-6 is incompatible with both EPM and EPM-g-SA copolymers.     

Effect of the addition of ethylene-propylene random copolymers on the properties of high-density polyethylene/isotactic polypropylene blends: Part 1—morphology and impact behavior of molded samples

Two random commercial ethylene-propylene copolymers (EPM) with different ethylene content have been added to binary isotactic polypropylene (iPP)/high density polyethylene (HDPE) blends by melt mixing in a Brabender-like apparatus. Impact Izod tests and a morphological analysis on the fractured surfaces of broken specimens have been performed and discussed, in order to improve the deficiency in toughness of the binary HDPE/iPP mixtures. The results show that the impact performance of both homopolymers and HDPE/iPP binary blends is strongly improved by the addition of the EPM copolymers. Such an effect is related to the fact that the overall morphology, as well as the mechanism and mode of fracture, are greatly modified by the presence of such additives. The extent is dependent on factors such as the nature of the matrix (HDPE or iPP), the composition, and the chemical structure and/or the molecular mass of the added copolymer.     

Thermoplastic elastomers from iPP/EPR blends: Crystallization and phase structure development

The phase morphology and structure of thermoplastic elastomers obtained from isotactic polypropylene (iPP) and ethylene—propylene random copolymer (EPR) blends by means of the dynamic curing of EPR rubbery component carried out during its melt mixing with iPP in a Banbury mixer at 180°C were investigated. Samples obtained by compression molding and by using isothermal crystallization conditions of the iPP phase were analyzed by means of differential scanning calorimetry, of optical, scanning, and transmission electron microscopy, and of wide-angle and small-angle X-ray diffraction. The influence of cooling below the melting point and of EPR molecular structure on the kinetic and thermodynamic parameters related to crystallization process of the iPP phase was also studied. It was found that the process of dynamic curing of the EPR component dramatically affects the development of the phase morphology and structure in the material. As a matter of fact, the blend containing the uncured EPR is characterized by the presence of iPP domains randomly distributed in the EPR rubbery matrix, whereas in the blend containing the cured EPR the iPP phase becomes the continuous phase crystallizing in a structure that resembles a cobweb tending to surround the EPR cured particles; moreover such an iPP cobweb appears to be contituted by row structures of stacked lamellae. It was found that the addition of EPR phase interferes dramatically with the crystallization process of the iPP, thus inducing drastic modification in its intrinsic morphology (size, neatness, regularity of spherulites, inner structure of spherulites, etc.). Such interference was found to be comparatively stronger when the iPP phase crystallizes in presence of cured EPR. The elastic behavior of the thermoplastic elastomer material was accounted for by applying the “leaf spring model” to the morphology and structure of the iPP phase crystallized in presence of cured EPR. © 1994 John Wiley & Sons, Inc.     

Influence of titanium dioxide on crystallization behavior of an ethylene–propylene copolymer

Crystallization of an ethylene–propylene copolymer (E/P) filled with diverse weight percentages of titanium dioxide (TiO₂) was performed under isothermal and nonisothermal conditions to investigate the influence of the inorganic substance on the nucleation and growth mechanisms of the matrix. The overall and radial crystallization rates of the composite materials were measured using, respectively, differential scanning calorimetry (DSC) and optical microscopy. The nucleation density of E/P spherulites as a function of composition was investigated by scanning electron microscopy (SEM), revealing a nucleating effect of TiO₂. A comparison between the spherulitic texture of specimens showed a higher fineness of the composites relative to the neat matrix, whereas no changes of surface nucleation density were appreciable among composites within the explored compositional range. The thermal behavior is discussed in the light of the enhanced thermal conductivity of polymer composites, which conciliates the crystallization kinetics of the matrix, analyzed using the Avrami equation, to optical and SEM observations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3409–3416, 2003