The effect of composition on the properties of nylon 612 copolymers

The series of nylon 612 copolymers was synthesized from caprolactam (C) and laurolactam (L) at 145°C. The 50/50 C/L molar ratio copolymer was found to have the minimum melting temperature (T_m ) for the series. The glass transition temperatures (T_g 's) of the copolymers were affected by the crystallinity of the copolymers. The T_g was at a minimum for the 50/50 copolymer for crystalline samples. However, for amorphous samples there was a decrease in T_g with increasing L content. Percent crystallinity was determined by differential scanning calorimetry and X-ray techniques. It was found that the degree of crystallinity was at a minimum for copolymers of 70/30 to 40/60 C/L ratios. Coefficients of linear thermal expansion (CLTE) were obtained for the copolymers at 10°C intervals from 20 to 70°C for dry and from 20 to 50°C for samples conditioned at 50% relative humidity and 50°C. The dry samples gave lower initial values, but had a greater temperature dependence than the conditioned samples. As expected, the CLTE was found to be lowest for samples exhibiting the highest crystallinity. The tensile strengths and moduli decreased rapidly with increasing L up to the 70/30 C/L ratio after which they remained relatively constant. Elongations reached maximums between 70/30 and 40/60 C/L ratios. An inverse relationship was found between crystallinity and impact strength.     

Novel fluorine containing polyfluorenes with efficient blue electroluminescence

The synthesis, structural characterization, photo and electroluminescence, thermal and electrochemical properties of a new fluorinated fluorene-containing copolymer are described. The copolymer is formed by alternating mers of [2,3,5,6 tetrafluoro-1,4 phenylene] and [9,9′-dihexyl-2,7 fluorene] and emits blue light with low turn on voltages. The EL performance of the fluorinated copolymer was superior to those of the non-fluorinated analog copolymer and of the corresponding poly(9,9′dihexyl-2,7 polyfluorene) homopolymer.     

Comparative analysis of methods for determining the metabolic rate in order to provide a balance between man and the environment

The incorrect determination of metabolic rate can be linked to discrepancies between the model of the PMV (Predicted Mean Vote) and real thermal sensation collected in field studies. Aiming to improve the correlation of the PMV model and the real thermal sensation, this work established new values for the metabolic rate: one way being called “calculated” using Newton's Method and the other called "measured" using a metabolic analyzer. Welder's activities were evaluated, through the measurements of environmental and personal variables. New values of metabolic rate were determined for this activity. The values found for the calculated form and the measured one were, respectively, 178.63 and 145.46 W/m², different from the range provided by the table of ISO 8996 (2004) for this activity (75–125 W/m²). In order to verify which of the values of the metabolic rate was closer to the real thermal sensation of PMV, a linear regression was made between the PMV and the real thermal sensation in three ways: S × PMV_tabulated (R² = 0.1749), S × PMV_calculated (R ² = 0.7481) and S × PMV_measured (R² = 0.7854). It was found that the values measured by the instrument gave a higher coefficient of determination which was chosen for the correction of the table. The correction of the table provides a value of M_predicted, that is a value of metabolic rate that corrects the values provided by the tables of ISO 8996 (2004), by means of a correction coefficient. For the welder's activities in a metal-mechanics industry, tabulated values can be multiplied by the correction coefficient 1.4648 in order to minimize inaccuracies. The PMV_predicted, obtained through the M_predicted, when related to the actual thermal sensation, provides a coefficient of determination of 0.7511, thereby improving the model of the PMV.     

Effect of marangoni stresses on the deformation and coalescence in compatibilized immiscible polymer blends

The effect of physical compatibilization on the deformation and coalescence of droplets in immiscible polymer blends is discussed. Evidence is provided for the existence of concentration gradients in block copolymers along the interface during deformation. This causes complex changes in droplet shapes during deformation and relaxation. These concentration gradients also result in Marangoni stresses, which stabilize the droplets against deformation and breakup. Coalescence experiments have been performed, varying both the compatibilizer concentration and the shear rate. Existing coalescence models have been evaluated. An empirical extension of Chesters' partially mobile interface model is presented, that treats the effects of Marangoni stresses on the coalescence process as a higher effective viscosity ratio.     

Controlling the phase stability of polymer blends through the introduction of impenetrable interfaces

In this work, the effect of the introduction of modified solid surfaces into polymer blends on the phase‐separation process was investigated. Glass fibers with surfaces having different chemistries were introduced into polystyrene–poly(methyl methacrylate) blends. The glass fibers used either had fully hydrated surfaces or had surfaces covered with a random copolymer, poly(styrene‐co‐methyl methacrylate). The copolymer was synthesized by free‐radical polymerization of styrene and methyl methacrylate in the presence of previously vinyl silane‐treated glass fibers. The copolymerization and grafting procedures were investigated by FTIR and thermal analysis. Blends containing the fibers were studied using FTIR microscopy and optical microscopy. FTIR microscopy results showed that the composition of the phases in the blends was shifted by using fibers with different surface chemistries. Fibers with grafted copolymers were capable of narrowing the immiscibility region in the phase diagram, while fully hydrated fibers were able to expand the gap. It was proposed that interfacial interactions regulated by a hydrophilic–hydrophobic type of forces were responsible for guiding the described phase‐separation process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1619–1627, 2003     

Methanol Selective Oxidation to Formaldehyde over Iron-Molybdate Catalysts

This review deals with the important industrial reaction of formaldehyde manufacture by methanol oxidation over iron molybdate catalysts. Detailed reference is made to the used catalyst, preparation techniques (coprecipitation, sol-gel like, mechanical mixing, etc.) including unsupported and supported catalysts, promoters and characterization methods. The controversial active phase assignment (stoichiometric versus Mo rich iron molybdate) is discussed. The proposed reaction mechanisms and kinetic laws for the main and side reactions are examined. The catalyst deactivation processes are reviewed and the role of Mo excess on these processes is underlined. Finally conclusions and perspectives are presented.     

Light metal compound casting

‘Compound casting’simplifies joining processes by directly casting a metallic melt onto a solid metal substrate. A continuously metallurgic transition is very important for industrial applications, such as joint structures of spaceframe constructions in transport industry. In this project, ‘compound casting’ of light metals is investigated, aiming at weight-saving. The substrate used is a wrought aluminium alloy of type AA5xxx, containing magnesium as main alloying element. The melts are aluminium alloys, containing various alloying elements (Cu, Si, Zn), and magnesium. By replacing the natural oxygen layer with a zinc layer, the inherent wetting difficulties were avoided, and compounds with flawless interfaces were successfully produced (no contraction defects, cracks or oxides). Electron microscopy and EDX investigations as well as optical micrographs of the interfacial areas revealed their continu- ously metallic constitution. Diffusion of alloying elements leads to heat-treatable microstructures in the vicinity of the joining interfaces in Al-Al couples. This permits significant variability of mechanical properties. Without significantly cutting down on wettability, the formation of low-melting intermetallic phases (Al3Mg2 and Al12Mg17 IMPs) at the interface of Al-Mg couples was avoided by applying a protective coating to the substrate.     

Well-defined polymer precursors synthesized by RAFT polymerization of N,N-dimethylacrylamide/N-acryloxysuccinimide: random and block copolymers

N,N-dimethylacrylamide (DMA) and N-acryloxysuccinimide (NAS) were copolymerized by the reversible addition–fragmentation chain transfer (RAFT) polymerization technique, to obtain random and block copolymer precursors onto which different side-groups may be statistically grafted via the reactive NAS units. These reactive copolymers have interesting applications in various fields such as coatings and paints, water purification and biology. Random poly(DMA-co-NAS) copolymer chains were synthesized with a 75/25 molar ratio, high conversion, an excellent molecular weight (MW) control from 5000 to 130 000 g mol⁻¹, and low polydispersity index (M_w/M_n<1.1). Poly(DMA-b-NAS) block copolymers were synthesized by a two step method, in which a poly(DMA) homopolymer was prepared first and then used as macro-chain transfer agent to polymerize NAS. For example, a poly(DMA-b-NAS) sample was obtained with an average molecular weight of 44 300/7400 g mol⁻¹ corresponding to 447 DMA and 44 NAS units. Such block copolymers had not yet been synthesized by any controlled polymerization technique. They can be used to prepare polymers with exactly the same backbone and an increasing number of different side groups (e.g. hydrophobic, ionic or fluorescent).     

The role of the Tm3+ concentration on CaMoO4 properties processed by microwave hydrothermal under stirring condition

The compounds based on calcium molybdate (CaMoO₄) are the subject of extensive research due to their excellent optical properties and a broad range of potential technological applications. In this work, we report a systematic study of CaMoO₄:Tm³⁺ phosphors synthesized by coprecipitation and processed in a microwave-hydrothermal system at low temperature (100°C) and stirring. The effect of the Tm³⁺ doping content (0%–12%) is studied in full detail to understand their role in the CaMoO₄:Tm³⁺ morphological, structural, and luminescent properties. The X-ray diffraction, Raman, and Fourier Transform Infrared spectroscopic techniques revealed that all the prepared powders have a tetragonal crystal structure with a distinct density of cation vacancies and structural disorders. The band gap remains almost constant for doping levels lower than 8%, but it narrows strongly for powders doped with 12% Tm³⁺ ions. The designed phosphors have shown two emission bands in which intensity depends on the Tm³⁺ ions doping level. For doping levels lower than 2%, the photoluminescence profile displays a broad emission band peaking at 543 nm (green). For concentrations higher than 4%, the band centered at 543 nm decreases in intensity and the near-infrared emission band at around 800 nm, assigned to ³F₃, ³H₄ → ³H₆ transitions from Tm³⁺ ion, become more intense. The outcomes of this work reveal that appropriated Tm³⁺ ions doping levels can be applied to suppress the PL emission in the visible range and improve that in the near-infrared region in CaMoO₄-based materials.     

Importance of Reservoir Tributaries to Spawning of Migratory Fish in the Upper Paraná River

Regulation of rivers by dams transforms previously lotic reaches above the dam into lentic ones and limits or prevents longitudinal connectivity, which impairs access to suitable habitats for the reproduction of many migratory fish species. Frequently, unregulated tributaries can provide important habitat heterogeneity to a regulated river and may mitigate the influence of impoundments on the mainstem river. We evaluated the importance of tributaries to spawning of migratory fish species over three spawning seasons, by comparing several abiotic conditions and larval fish distributions in four rivers that are tributaries to an impounded reach of the Upper Paraná River, Brazil. Our study confirmed reproduction of at least 8 long‐distance migrators, likely nine, out of a total of 19 occurring in the Upper Paraná River. Total larval densities and percentage species composition differed among tributaries, but the differences were not consistent among spawning seasons and unexpectedly were not strongly related to annual differences in temperature and hydrology. We hypothesize that under present conditions, densities of larvae of migratory species may be better related to efficiency of fish passage facilities than to temperature and hydrology. Our study indicates that adult fish are finding suitable habitat for spawning in tributaries, fish eggs are developing into larvae, and larvae are finding suitable rearing space in lagoons adjacent to the tributaries. Our findings also suggest the need for establishment of protected areas in unregulated and lightly regulated tributaries to preserve essential spawning and nursery habitats. Copyright © 2014 John Wiley & Sons, Ltd.