Dielectric properties of polyarylate (PAr) around the glass transition

Dielectric characterization of the α-relaxation in polyarylate (PAr) has been carried out by means of a dielectric spectroscopy technique in a frequency range of 10–30 kHz. Complementary thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry d.s.c.) measurements have also been performed. The results are interpreted in terms of the standard Cole-Cole plot and Havriliak-Negami distribution for the dielectric relaxation times. Information about the temperature and frequency dependence of a.c. conductivity is also obtained from the experimental curves. However, the behaviour of the main dielectric relaxation time is deduced from the experimental data in a wide range of temperature around the glass transition. This behaviour results in close agreement with the theoretical predictions of a free-volume approach for the dielectric α-relaxation recently proposed by the authors.     

Assessment of the environmental quality of two urbanized lotic systems using multiple indicators

Urbanization impacts ecosystems through loss and fragmentation of habitat, loss of diversity, increase in runoff, and contaminant discharges, and the invasion of exotic species. Potrero de los Funes Village (San Luis, Argentina) is experiencing not only a population increase during summer months due to tourism but also an accelerated growth of its permanent population. In order to evaluate the potential effects of urbanization, the environmental quality of Potrero de los Funes River and Las Chacras Stream was assessed, using physical–chemical and biological indicators. Macroinvertebrates, through the application of the Biotic Index for San Luis Sierras (BISLS), anuran amphibian richness and relative abundance, and riparian vegetation were used as bioindicators. While the Simplified Index of Water Quality (SIWQ) was used to characterize the physical–chemical quality of water at each site. SIWQ and BISLS scores were significantly different between sites (F_7,28 = 9.88, p < .001 and F_7,28 = 24.18, p < .001, respectively). SIWQ was significantly correlated with BISLS (Spearman correlation coefficient = 0.8, p < .001). Four anuran species were registered along Potrero River, with no significant differences in the intensity of vocalizations between sites. No species were detected in Las Chacras Stream. Average total plant species richness, exotic plants richness, and vegetation cover were higher at the most impaired system, Las Chacras Stream. The principal component analysis showed that the first two principal components (PCs) explained 76.3% of the total variance. PC1, with strong loadings of SIWQ, BISLS, and amphibian richness, was principally driven by chemical water quality and biological conditions. PC2 was mainly determined by plant richness. The chemical and biological water quality of Potrero and Las Chacras is somewhat impaired, being the upper Las Chacras Stream the most compromised area. This study provides information that will certainly be used to manage future impacts of urbanization on aquatic resources.     

Estimating discharge in gravel‐bed river using non‐contact ground‐penetrating and surface‐velocity radars

Discharge measurement is a critical task for gravel‐bed channels. Under high‐flow conditions, the elevation of the riverbed changes significantly by intensive torrential flow. The stage–discharge relations commonly used for stream discharge estimation may no longer be adequate. The contact‐type velocity measuring is also subject to measurement errors and/or instrument failures by the high‐flow velocities, driftwood, stumps, and debris. This study developed a new real‐time method to estimate river discharge in gravel‐bed channels. A systematic measuring technology combining ground‐penetrating radar and surface‐velocity radar was employed. The rating curves representing the relations of water surface velocity to the channel cross‐sectional mean velocity and flow area were established. Stream discharge was then deduced from the resulting mean velocity and flow area. The proposed method was examined in a steep gravel‐bed reach of the Cho‐Shui River in central Taiwan. The estimated stream discharge during three flood events were compared to the prediction by using the stage–discharge relation and the index‐velocity method. The proposed method of this study is capable of computing reasonable values of discharge for an entire flood hydrograph, whereas the other two methods tend to produce large extrapolation errors. Moreover, when the computed discharge is used in 2D flood flow simulation, the proposed method demonstrates better performance than the commonly used stage–discharge and index‐velocity methods.     

Crystallization of poly(3‐hydroxybutyrate) by exfoliated graphite nanoplatelets

Poly(3‐hydroxybutyrate) (PHB) has been shown to be efficiently nucleated by exfoliated graphite nanoplatelets (xGnP). The nucleating effect of xGnP was investigated using differential scanning calorimetry, optical microscopy and atomic force microscopy. Nonisothermal crystallization of PHB from the melt required lower activation energies for PHB containing 1 wt % and 3 wt % xGnP (?214 and ?102 kJ/mol respectively) than for pure PHB (?60 kJ/mol). A kinetic study of the PHB/xGnP crystallization employing a modified form of the Avrami equation revealed that the presence of xGnP increased the PHB crystallization temperature, as well as the crystallization rates, and generated smaller and more numerous spherulites. Optical microscopy and atomic force microscopy confirmed the incorporation of xGnP into the lamellar structure of the PHB spherulites and provided insight into the influence of xGnP on spherulite size and lamellae thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Study of the composition effect of glass ceramic and silver on poly(vinyl butyral) thermal degradation with thermogravimetric analysis

The thermal degradation of poly(vinyl butyral) (PVB)/glass ceramic, PVB/Ag, and PVB/glass ceramic/Ag composites was investigated with thermogravimetric analysis in nitrogen and air. Thermogravimetric data revealed that the compositions of both inorganic materials in air could greatly influence the thermal degradation of PVB. The degradation reactions of PVB/ceramic and PVB/Ag composites began earlier and accelerated rapidly at lower temperatures. The overall degradation period was obviously shortened for the thermal degradation of PVB/Ag in air, whereas a longer time was required for the PVB/ceramic composite than for PVB. Moreover, dual effects of ceramic and Ag on the thermal degradation of PVB were observed for PVB/ceramic/Ag composites. In addition, the catalytic effects of ceramic and Ag on the degradation reaction of PVB in air were verified with a kinetic analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2142–2149, 2004     

Behaviour of the Antitumor Agent Vanadocene Dichloride in Physiological and Therapeutic Media, Blood Plasma and Human Blood - An EPR Study

By means of EPR spectroscopy the behaviour of the vanadocene dichloride (I), Cp(2)VCl(2) (Cp=eta(5)-C(5)H(5)), in various deoxygenated and non-deoxygenated physiological media and therapeutic solution as well as in blood plasma and stabilized human blood was studied. On the basis of measured values of isotropic spectroscopic splitting factor g(iso) and isotropic hyperfine coupling constant A(iso), the vanadocene species, [Cp(2)V(H(2)O)Cl](+) (II; g(iso)= 1.985, |A(iso)| = 7.68 mT), [Cp(2)V(H(2)O)(2)](2+) (III; g(iso)= 1.983, |A(iso)| = 7.92 mT), [Cp(2)V(OH(2) (IV; g(iso)= 1.991, |A(iso)| = 6.285 mT), [Cp(2)VCl(DMSO)](+) (V; g(iso)= 1.985, |A(iso)| = 7.69 mT), the vanadyl species [VO(DMSO)(5)](2+) (VI; g(iso)= 1.964, |A(iso)| = 10.78mT) and [VO(H(2)O)(5)](2+) (VII; g(iso)= 1.955, |A(iso)| = 11.56 mT) have been identified. From the measurements it follows that I does not react in its first coordination sphere with any component of a system used other than water and DMSO, resp. As to water-containing media, its behaviour is fully consistent with that of I in pure aqueous media. It was found the only vanadocene species present after application of the therapeutic solution of I into human blood to be IV not interacting in its first coordination sphere with any blood component.     

Eco‐friendly durable press finishing of cellulose‐containing fabrics

To impart easy‐care properties to cellulose‐containing fabrics along with avoiding any harmful effects of formaldehyde on both the health and the environment, attempts have been made to use citric acid (CA) as an ester crosslinking agent along with different catalytic systems in the absence and presence of certain additives. Further, fixation conditions, type of crosslinking agent, as well as type of substrate have been studied. Results revealed that the enhancement in carboxyl content, performance properties, and the decrease in tear strength (TS) as well as in whiteness indices (WI) of the finished fabric samples were increased by increasing CA concentration up to 80 g/L and by raising thermofixation temperature from 140 up to 180°C for 90 s. Inclusion of triethanolamine hydrochloride (TEA. HCl), decreased the carboxyl content, TS, color strength K/S, as well as oily stain release rating (SRR) of the finished fabric samples along with an increase in bound nitrogen (%N), wrinkle recovery angle WRA, and an improvement in WI without affecting the durable press rating (DP). Within the range examined (0–30 g/L), increasing PEG‐600 concentration improved the wet resiliency, TS, as well as WI properties of the finished samples. Increasing DMDHEU ratio in the CA/DMDHEU crosslinking system gave rise to an increase in %N, WRA (dry and wet), DP, as well as in free CH₂O of finished fabrics, along with a slight improvement in WI values. On the other hand, the TS, carboxyl content, K/S, SRR values of the finished fabric samples were lower at a higher DMDHEU ratio. Increase in carboxyl content, %N, WRA (dry and wet), DP and SRR, as well as extent of post dyeing (K/S) of the treated fabric samples upon using different ester crosslinking agents followed the descending order: citric acid > pyromellitic dianhydride. The opposite holds true for the TS, and WI values. Among the esterifying catalysts used, and for a given set of finishing conditions, NaH₂PO₂ · H₂O proved to be the most effective one, and the following order of effectiveness may be drawn: NaH₂PO₂ · H₂O > K₂HPO₄ > Na₃–citrate > Na₂–tartrate. Inclusion of silicone softener in the finishing formulation brought about an improvement in softeness degree, WRA, %N, DP, TS as well as K/S values along with a decrease in carboxyl content, SRR, and WI values of the treated fabric samples, regardless of the used silicone softener.The performance properties of the finished fabric samples were determined by the type and nature of the substrate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2243–2253, 2002     

Synthesis,characterization, and thermal properties of phosphorus‐containing,wholly aromatic thermotropic copolyesters

A series of phosphorus‐containing, wholly aromatic thermotropic copolyesters from acetylated 2‐(6‐oxide‐6H‐dibenz〈c,e〉〈1,2〉oxa phosphorin‐6‐yl)‐1,4‐dihydroxy phenylene, p‐acetoxybenzoic acid, terephthalic acid, and isophthalic acid were prepared by melting polycondensation. The structure and basic properties of the polymers, such as the glass‐transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity, were investigated with Fourier transform infrared, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray diffraction, and hot‐stage polarizing optical microscopy. The copolyesters had relatively high T_g values ranging from 183 to 192°C. The T_m values obtained from DSC curves for samples P‐20 and P‐25 were 290 and 287°C, respectively (where the number in the sample name indicates the molar fraction of the phosphorus‐containing monomer in the reactants). The initial flow temperatures of other samples observed with hot‐stage polarizing microscopy were 271–290°C. The 5% degradation temperatures in nitrogen ranged from 431 to 462°C, and the char yields at 640°C were 41–52%. All the copolyesters, except P‐40, were thermotropic and nematic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1278–1284, 2002     

Poly(etherimide)/montmorillonite nanocomposites prepared by melt intercalation

A novel aromatic amine organo‐modifier synthesized in our previous work was used to treat montmorillonite (MMT) and the organo‐modified MMT was used to prepare poly(etherimide) (PEI)/MMT nanocomposites by a melt intercalation method. MMT treated by this amine exhibited large layer‐to‐layer spacing and a high ion‐exchange ratio (>95%). The nanocomposites were characterized with X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical analysis, a universal tester, thermogravimetric analysis, and by differential scanning calorimetry. The results of XRD and TEM showed that the nanocomposites formed exfoliated structures even when the MMT content was 10 wt %. When the MMT content was below 3 wt %, the PEI/MMT nanocomposites were strengthened and toughened at the same time. The nanocomposites also showed marked decreases in coefficient of thermal expansion and solvent uptake. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1857–1863, 2003     

Curing of mixtures of epoxy resins and 4‐methyl‐1,3‐dioxolan‐2‐one with several initiators

Diglycidyl ether of bisphenol A or 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate were mixed with different proportions of 4‐methyl‐1,3‐dioxolan‐2‐one and cured using lanthanide triflates as initiators. In order to compare the materials obtained, conventional initiators such as boron trifluoride complexes and N,N‐dimethylaminopyridine were also tested. The curing process was followed by differential scanning calorimetry (DSC) and Fourier transform IR in attenuated total reflectance mode. This technique proved that the carbonate accelerates the curing process because it helps to form the active initiating species, although it was not chemically incorporated into the network and remained entrapped in the material. The DSC kinetic study was also reported. © 2006 Wiley Periodicals Inc. J Appl Polym Sci 102: 2086–2093, 2006