Novel polymer blends based on poly(ether-urethane) ionomer and ion-containing styrene copolymer

The structure-property relationships of thermoplastic polymer blends based on poly(ether-urethane) ionomer (PEUI) and ion-containing styrene-acrylic acid copolymer (S-co-AA(K)) have been investigated by using DMTA, DSC and TGA, as well as tensile tests. Convergence of the glass transition temperature (T_g) values of the PEUI and the S-co-AA(K) components in the blends studied, as compared to the individual polymers, was found and explained by improving compatibility of the components due to increasing effective density of physical networks formed by ion-dipole and ion-ion interactions of ionic groups of the components. Character of E'=f(T) and E'=f(T) dependencies confirms the increase of the effective density of physical networks in the compositions studied compared to individual PEUI and S-co-AA(K). Improvement of end-use properties, i.e. thermal stability and tensile properties has been found for the PEUI/S-co-AA(K) compositions with lower content of S-co-AA(K) (i.e. <10 mass%) and explained by formation of additional network of intermolecular ionic bonds between the functional groups of PEUI and S-co-AA(K).     

Synthesis and characterization of polycyanurate/montmorillonite nanocomposites

The advantages of cyanate esters (CEs) versus competitor systems such as epoxies and polyimides, as well as the great reinforcing potential of organoclays properly dispersed into a polymeric matrix, have been examined in a series of polycyanurate (PCN)/montmorillonite (MMT) nanocomposites prepared under appropriate polymerization conditions. The curing schedule applied resulted in gradual propagation of polymerization. Through this procedure, the intragallery curing rate becomes comparable to the extragallery one, allowing intercalation before gelation. Systems with clay loadings from 1 to 3% per weight were synthesized, and their morphology and mechanical properties were studied by means of scanning electron microscopy (SEM), atomic force microscopy (AFM), wide angle X‐ray scattering (WAXS), dynamic mechanical analysis (DMA), and tensile tests. Microscopy investigations revealed better dispersion for the 3 wt % system compared to smaller concentrations, in which aggregation and, in some cases, agglomeration were the conspicuous features. Roughness and area analyses revealed more homogeneous dispersion for this nanocomposite. Topology and 3D‐phase images further suggested considerable reduction of the average particle diameters. WAXS analysis showed that the interlayer spacing of nanocomposites was increased compared to pristine MMT, indicating the formation of intercalated structures. On the other hand, tensile strength and elongation at break values displayed abrupt diminution with MMT addition, while Young's modulus exhibited a slight but systematic increment with MMT content. The decreasing glass transition tendency observed for small clay loadings was reversed in the case of 3 wt %, while secondary transitions were practically unaffected by the presence of MMT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1036–1049, 2008     

Structural changes in glassy polymers studied by thermal analysis and dynamic mechanical tests

Structural changes which take place in many amorphous polymers, when they are annealed at temperatures near the glass transition temperature, have important theoretical, physical, and mechanical consequences. In this paper the possible existence of some local ordering in highlycrosslinked epoxy resins is studied. Three kinds of tests—TMA, DSC, and dynamic experiments—are used for a type of epoxy resin, cured with six different amounts of curing agent. In order to study the effect of the thermal history on the behavior of the polymer at its transition region, as well as the morphology of the materials tested, three different thermal treatments have been followed. Interesting results were derived concerning the influence of these parameters to these parameters to the mechanical characterization of the polymer.     

Stress–softening effect of SBR/nanocomposites by a phenomenological Gent–Zener viscoelastic model

An experimental study of a tensile loading–unloading procedure, as well as multi-cyclic response in a strain-controlled program of a Styrene-Butadiene (SBR) elastomer reinforced with four different weight fractions of carbon nanotubes (CNTs) has been performed. The Mullins effect features, namely hysteresis, damage and residual strain, exhibited by the SBR/nanocomposites were analyzed by a modified Gent–Zener rheological model, and a damage function. Especially for the multi-cyclic stress–strain curves, phenomenological equation of the model parameters evolution with strain were also introduced. The same loading procedure was applied in pre-stressed materials, revealing a different stress–strain response due to strain prehistory. The model has been proven to accurately capture the loading–unloading behavior, the residual strain, hysteresis loops as well as the multi-cyclic behavior of the SBR/CNT nanocomposites.     

Development and validation of a new analytical method for the determination of 1,4-dichlorobenzene in honey by gas chromatography-isotope dilution mass spectrometry after steam-distillation

A simple, fast, sensitive and robust analytical method using gas chromatography (GC)-isotope dilution mass spectrometry (MS) was developed and validated for the identification and quantification of 1,4-dichlorobenzene (p-DCB) residues in honey samples. The proposed methodology is based on steam-distillation using a Clevenger-type apparatus followed by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring (SIM) mode employing the isotopically labeled analogue d₄-1,4-dichlorobenzene (d₄-p-DCB) as internal standard (IS). Validation of the method was performed in two different GC-MS systems, using quadrupole MS (QMS) and ion-trap MS (ITMS) detectors, with no statistically significant differences between two. Recoveries were better than 91% with percent relative standard deviations lower than 12%. The instrumental limits of detection were 1 μg kg⁻¹ in the GC-ITMS system and 0.6 μg kg⁻¹ in the GC-QMS system. The expanded uncertainty was estimated as 17% at the currently accepted “action level” of 10 μg kg⁻¹. The method was applied to the analysis of 310 honey samples in an extensive national monitoring study. A quality control (QC) system applied during the assays has demonstrated a good performance and long-term stability over a period of more than 8 months of continuous operation.     

Organic residue analysis of Neolithic pottery from North Greece

Organic residues associated with Neolithic pottery from two Late Neolithic sites, Paliambela and Makriyalos (Northern Greece), were analyzed by gas chromatography-mass spectrometry. The study aimed at identifying the origin of the tar used for waterproofing and gluing broken pots. Reference tars were prepared in laboratory conditions by pyrolysis of the bark from three tree species, namely from Betula pendula (silver birch), Ostrya carpinifolia (hop hornbeam) and Carpinus orientalis (Eastern hornbeam). The results suggest that mostly birch bark tar was used as glue for fixing broken pieces of the pots as well as for waterproofing close-shaped vessels. None of the archaeological tars derived from the two hornbeams. The analysis shows certain variability in the composition of birch bark tar, which is related to the production technique and to the re-use of tar. Of particular interest is the presence of characteristic diterpenoid biomarkers in several samples, which indicates that pine pitch was used for gluing and pine resin for waterproofing vessels for liquids. Correspondence: Sophia Mitkidou, Department of Science, School of Technological Applications, Technological Institute of Kavala, Greece     

Rapid and High-Throughput Detection and Quantitation of Radiation Biomarkers in Human and Nonhuman Primates by Differential Mobility Spectrometry-Mass Spectrometry

Radiation exposure is an important public health issue due to a range of accidental and intentional threats. Prompt and effective large-scale screening and appropriate use of medical countermeasures (MCM) to mitigate radiation injury requires rapid methods for determining the radiation dose. In a number of studies, metabolomics has identified small-molecule biomarkers responding to the radiation dose. Differential mobility spectrometry-mass spectrometry (DMS-MS) has been used for similar compounds for high-throughput small-molecule detection and quantitation. In this study, we show that DMS-MS can detect and quantify two radiation biomarkers, trimethyl-L-lysine (TML) and hypoxanthine. Hypoxanthine is a human and nonhuman primate (NHP) radiation biomarker and metabolic intermediate, whereas TML is a radiation biomarker in humans but not in NHP, which is involved in carnitine synthesis. They have been analyzed by DMS-MS from urine samples after a simple strong cation exchange-solid phase extraction (SCX-SPE). The dramatic suppression of background and chemical noise provided by DMS-MS results in an approximately 10-fold reduction in time, including sample pretreatment time, compared with liquid chromatography-mass spectrometry (LC-MS). DMS-MS quantitation accuracy has been verified by validation testing for each biomarker. Human samples are not yet available, but for hypoxanthine, selected NHP urine samples (pre- and 7-d-post 10 Gy exposure) were analyzed, resulting in a mean change in concentration essentially identical to that obtained by LC-MS (fold-change 2.76 versus 2.59). These results confirm the potential of DMS-MS for field or clinical first-level rapid screening for radiation exposure.

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Hydrogen production over a commercial Pd/Al2O3 catalyst for fuel cell utilization

In order to produce a hydrogen stream for fuel cell utilization, the study of the ethanol steam reforming process over an alumina supported palladium commercial catalyst was carried out. The effect of the reaction temperature, the H₂O/C₂H₆O molar ratios and the contact time on catalytic activity and stability was studied. It was found that even at very low temperature values complete ethanol conversion was possible. Hydrogen selectivities up to 98% were obtained at temperature values close to 625 °C. It was also observed that for different reactant molar ratios carbon monoxide concentration exhibits a minimum at a temperature value close to 450 °C. Furthermore, carbon formation was found to be negligible even for H₂O/C₂H₆O molar ratios equal to the stoichiometric one. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002     

A Numerical Method for 2-D Bed Morphology Calculations

A fully coupled two-dimensional sub-critical and/or supercritical, free-surface flow numerical model is developed to calculate bed variations in alluvial channels. Vertically averaged free-surface flow equations in conjunction with sediment transport equation are numerically solved using an explicit finite-volume scheme in integral form. The capabilities of the proposed method are first demonstrated by analyzing supercritical flow in an expansion channel. Thereafter, one and two-dimensional applications referring to aggradation and scouring are reported. For each of these test cases, computed results compare satisfactorily with measurements as well as with other numerical solutions. The method is stable, reliable and accurate, although time consuming, handling a variety of sediment transport equations with rapid changes of sediment transport at the boundaries.     

Characterization by gas chromatography-mass spectrometry of diterpenoid resinous materials in Roman-age amphorae from northern Greece

A combined gas chromatography-mass spectrometry approach has been used for the characterization of two lumps of resin and 17 adsorbed residues on Roman-age vessels, mainly amphorae, from northern Greece. The data show that a diterpenic resin from plants of the Pinacae family is the main component of the tarry material associated with the analyzed archaeological samples. The identification and mass spectrometric fragmentation of several characteristic diterpenoid biomarkers is discussed. The abundance of secondary products identified in the archaeological samples suggests that the oxidative degradation of abietic acid and dehydroabietic acid to aromatic products was the main pathway. Of particular interest is the presence of characteristic saturated abietane hydrocarbons in one sample, which indicate that a reductive process also occurred on a small scale. The overall similarity in the composition of the residues suggests the common use of pine tar as a waterproofing and sealing agent at different sites in northern Greece during the Roman period.