Isotactic polypropylene/polyisobutylene blends: morphology-structure-mechanical properties relationships

Morphological observations by optical and scanning electron microscopy, wide (WAXS) and small (SAXS) angle X-ray scattering, differential scanning calorimetry (DSC) and mechanical tests have been performed on sheet specimens of isotactic polypropylene (iPP)/polyisobutylene (PIB) blends obtained under different crystallization conditions. Two kinds of morphologies have been observed, particularly at high crystallization temperatureT _c, on thin sections of the same sheets: a spherulitic one in the centre and a row-like structure on the edges. The size of the spherulites, as well as the thickness of the row-like regions, decreases with diminishingT _c, and seemsto be independent of the amount of rubber. The adhesion among the spherulites and between the spherulites and the row-like regions seems to become poorer with higherT _c. The rubber particles seem to be evenly dispersed into the iPP matrix for samples quenched at low temperatures, whereas for samples isothermally crystallized (at highT _c) their concentration seems to be slightly higher at the border of the spherulites than in the centre. The overall crystallinity measured by DSC and by WAXS is an increasing function ofT _c and decreases with increasing amount of PIB. The index of iPP phase, quite low indeed (max 3%), drops with loweringT _c and with enhancing PIB percentage. The long spacingL for a given quenching temperatureT _q is independent of PIB content, whereas for isothermally crystallized samples at low undercooling varies differently according toT _c. The lamellar thicknessL _c is always a decreasing function of rubber content. Stress-strain analysis shows a more and more brittle behaviour both with increasingT _c (beyondT _c=122° C all the specimens are very brittle irrespective of PIB amount) and PIB amount in accordance with the morphological observations. Some tentative hypotheses have been made to explain the observed behaviour.     

Carbon dioxide as refrigerant for tap water heat pumps: A comparison with the traditional solution

Increased concern about the environmental impact of the refrigeration technology is leading toward design solutions aimed at improving the energy efficiency of the related applications, using eco-friendly refrigerants, i.e. ozone-friendly and with the least possible global warming potential (GWP). In this respect, carbon dioxide (ASHRAE R744) is seen today as one of the most promising refrigerants and is raising great interest in industrial and scientific fields. In the present work, the plant options are investigated, which are related to the design of air/water heat pumps for tap water using CO₂. A comparison is made, in terms of energy efficiency, between a system working with CO₂ and a similar one working with HFC R134a; such a comparison is carried out by means of a simulation model of a refrigerating machine/heat pump, characterized by a detailed representation of the heat exchangers, based on their subdivision into elementary volumes. Results show that carbon dioxide is an interesting substitute for synthetic fluids, if the design of the system is focused to take advantage of its properties.     

Phenol chlorination and photochlorination in the presence of chloride ions in homogeneous aqueous solution

Phenol chlorination was studied in the presence of dissolved Fe(III) and chloride under irradiation and of hydrogen peroxide and chloride in dark acidic solutions. In the former case phenol photochlorination is most likely due to the formation of Cl2*- as a consequence of Fe(III) irradiation in the presence of chloride. The most efficient pathway is the photolysis of FeOH2+ producing hydroxyl, which oxidizes chloride to Cl*. The latter finally yields Cl2*- upon further reaction with chloride. The importance of the pathway involving FeOH2+ is higher at higher pH and moderately low chloride concentration. At pH 2.0 and [Cl-] > 0.03 M chlorophenol generation rate decreases with increasing [Cl-], due to the formation of the much less photoactive species FeCl2+/FeCl2+. The photolysis of FeCl2+/ FeCl2+ yielding Cl* is likely to play an important role at pH 0.5 and high chloride, but under such conditions chlorophenol formation rates are about an order of magnitude lower than at pH 2.0. Due to pH and kinetic constraints, under most environmental conditions the photochemistry of FeCl2+/FeCl2+ can be expected to play a minor role toward chlorination when compared with the one of FeOH2+, which leads to hydroxyl-mediated chloride oxidation. Hydrogen peroxide and chloride react in dark acidic solutions to yield HClO, involved in electrophilic chlorination processes. Chlorophenol formation rates under such conditions are directly proportional to [H+]. The described chlorination and photochlorination processes can take place in acidic aerosols of marine origin, naturally rich in chloride and Fe(III). Antarctic aerosol is also rich of hydrogen peroxide and often strongly acidic due to the presence of sulfuric acid of biogenic origin.     

Morphology—properties relationships in binary polyamide 6/rubber blends: Influence of the addition of a functionalized rubber

The modification of an amorphous random ethylene-propylene rubbery copolymer (EPM) has been accomplished by solution grafting of maleic anhydride molecules promoted by radical initiators, The resulting EPM-g-succinic anhydride (EPM-g-SA) and EPM have been used to obtain binary polyamide 6/EPM or polyamide 6/EPM-g-SA and ternary polyamide 6/EPM/EPM-g-SA blends by melt mixing. The formation of an EPM-g-PA6 graft copolymer during the blend preparation has been assumed. Different blend morphologies were observed by scanning electron microscopy (SEM) according to the nature and content of the rubber used. The tensile mechanical properties and the impact behavior of the prepared blends were investigated and correlated with the SEM analysis of the fracture surfaces. Binary and ternary blends containing 20 percent by weight of total rubber show a significant improvement of the impact properties at low temperature (?20°C) when the rubber is partly or entirely EPM-g-SA. In the case of PA6/EPM-g-SA (80/20) blend these results are related to the presence of rubbery domains of very small size strongly adherent to the PA6 matrix. In the case of 80/10/10 ternary blends, a much more complicated overall morphology is observed. Such morphology is characterized by the presence of large EPM domains, likely containing some EPM-g-PA6 graft molecules acting as an interfacial agent, and domains of EPM-g-PA6 of smaller size strongly adherent to the matrix as in the previous case.     

Probing the structure of polymer blends by vibrational spectroscopy: the case of poly(ethylene oxide) and poly(methyl methacrylate) blends

The blends of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) are prepared in the form of thin films from solution casting. The Fourier transform infrared spectra of the blends are recorded in the spectral range 400–4000 cm^?1. The spectra are analysed using various recent techniques of vibrational spectroscopy. It is concluded that upon blending PEO takes preferentially a planar zig-zag structure. Furthermore the intermolecular interactions between the molecules of PEO and PMMA in blends are very weak and their compatibility as blends is more ‘physical’ than ‘chemical’. Further, on the basis of the atomic charges transferred from model molecules it is seen that the blending is preferred with isotactic PMMA when compared to syndiotactic PMMA.     

Phase structure and morphological variations induced by straining in injection-moulded samples of PA6/EVA blends: influence of molecular structure of EVA copolymers

The influence of molecular structure and composition of ethylene-co-vinyl acetate (EVA) copolymers, differing in molecular mass and, for a given molecular mass, in vinyl acetate content (wt/wt), on morphological and structural changes undergone by injection-moulded samples of Nylon 6 (PA6)/EVA blends during uniaxial tensile straining at room temperature up to sample rupture and on properties of such materials was studied. Direct correlations between molecular structure and composition of EVA copolymers and the shape and size of domains of dispersed phase and ultimate properties of PA6/EVA materials have been drawn. For the dumb-bell-shaped specimens strained just beyond the yielding point, it was found that the original layered structure was strongly modified by straining. Three layers were, in fact, generated: a skin surface, where no domains of EVA dispersed phase were observed, an outer layer, where the EVA domains were elongated along the draw direction assuming mainly cylindrical shape, and a core where the EVA phase was segregated in ellipsoidal-shaped domains having their major axis oriented along the draw direction. For the samples strained to break it was found that the PA6/EVA fibres showed a single glass transition temperature, whose value is lower than that found for the fibre of plain PA6, but higher than that shown by PA6 phase in the unstrained samples; such a value, moreover, tends to be decreased on increasing the vinyl acetate content along the EVA chain, irrespective of copolymer molecular mass. The calorimetric measurements performed revealed, moreover, a noticeable increase of the observed melting temperature values of EVA phase in PA6/EVA fibres. In the PA6/EVA samples strained to break, only two different layers were seen: an outer skin, free of EVA domains, and a core where the EVA dispersed phase segregated in ellipsoidal-shaped domains. The values of stress at break, _B, and of the elongation at break, _B, exhibited by PA6/EVA fibres were found to be lower than those shown by the plain PA6. The trends of _B and _B values against the EVA vinyl acetate content showed, moreover, that _B and _B values decreased with increasing vinyl acetate content along the copolymer chain.     

Thermodynamic analysis of different two-stage transcritical carbon dioxide cycles

The aim of this paper is the thermodynamic evaluation and optimisation of different two-stage transcritical carbon dioxide cycles. Five different cycles are studied: basic single-stage cycle, single-throttling with two-stage compression cycle, split cycle, phase separation cycle and single-stage cycle coupled with a gas cooling circuit. Each basic cycle is analysed for the effect of internal heat transfer between different streams of refrigerants. In the case of two-stage compression, intermediate cooling between the compressor stages is present. An analysis on the Plank cycle for intermediate pressure higher than critical one is performed. Each cycle is optimised with regards to energy performance, calculating the optimal values of both the upper and the intermediate pressures. In the case of split cycle, the ratio of the mass flow rate in the main stream to the one in the auxiliary stream is also optimised.     

Evaluation of the anti-rutting potential of polymer-modified binders by means of creep-recovery shear tests

In the experimental study reported in this paper a creep-recovery shear test method was used to evaluate the anti-rutting potential of different polymer-modified bituminous binders. The effects of several factors related to modification were investigated, such as polymer type (SBS, styrene–butadiene–styrene vs. ethylene–vinyl–acetate), composition (styrene content), structure (linear vs. radial SBS) and dosage (3–6 % by weight of the base bitumen). The effect of short-term aging was also considered by comparing binder response before and after treatment with the rolling thin-film oven test. Following previous work on the development of the test protocol, experimental results were analyzed by referring to shear modulus curves G(t) and to permanent compliance (J _P), obtained by dividing residual strain at the end of the unloading phase by the stress applied during creep loading. Results indicated the effectiveness of the proposed method in discriminating between the behavior of the different polymer-modified binders and in capturing the effects caused by the factors considered in the investigation. Reliable rankings of the binders were established and were explained by referring to the specific behavior of employed modifiers.     

Effect of Fermentation and Drying on Procyanidins, Antiradical Activity and Reducing Properties of Cocoa Beans

This work was aimed to determine the effect of fermentation and drying on the content and profile of procyanidins (from monomers P1 to polymers P10) as well as on the antiradical and scavenging properties of cocoa beans. To this purpose, three experiments were carried out: a traditional fermentation process followed by air drying and two pilot-scale fermentation processes by either natural microbiota or starter followed by sun drying. Procyanidins were evaluated by HPLC analysis, while the total polyphenol index (TPI), the antiradical activity as well as the reducing power were determined by means of the reaction with the Folin–Ciocalteu reagent, the decolorization assays of the ABTS radical (TEAC) and the Ferric Reducing Antioxidant Power (FRAP) methods, respectively. Both the traditional and pilot-scale processes resulted to affect the profile and content of the procyanidins fractions as well as the antiradical and reducing power functionality. Drying caused a severe reduction of compounds and thus resulted to be the critical step for the loss of procyanidins and monomers in particular. The indices of functionality generally showed a decreasing trend as a consequence of processing, and their evolution was similar to that observed in procyanidins content. To study the relationship between the individual procyanidins and the antioxidant activity expressed as TEAC, FRAP and TPI, the data set were processed by modified partial least squares regression. The obtained models presented a good predictive ability. Normalised regression coefficients showed that the relative contribution of each single class of compounds to total antioxidant activity resulted as follows: P1?>?P2?>?P3?>?P4?>?P6?>?P8?>?P5?>?P7?>?P9?>>?P10.