Synthesis, structure and catalytic properties of Fe-substituted barium hexaaluminates

A sol–gel method using Ba and Al isopropylates and iron nitrate has been used to synthesise barium hexaaluminate partially substituted with iron. After calcination under oxygen at 1200°C the -alumina structure was obtained. Formation of the mixed BaFe_xAl_12-xO₁₉ phase occurred for x=1–4. XRD measurements showed a good crystallinity of the structure and expansion of unit cell parameters due to the presence of larger Fe³⁺ ions substituting Al³⁺ ones in octahedral sites only. Mössbauer spectroscopy revealed that Fe³⁺ ions are present in four different octahedral sites slightly distorted. Catalytic activity in methane combustion showed that an optimum was obtained for solid containing 2 Fe ions per unit cell: the increase of the amount of introduced iron was counterbalanced by the decrease of specific surface area. Intrinsic activities have been calculated for the four solids in both the fresh and aged states. It is observed that increasing iron content increases relative activities in the same ratio as the populations of iron located in two sites as deduced from Mössbauer spectroscopy. It is then tentatively assumed that activity is attributed to octahedrally coordinated Fe³⁺ ions in some specific sites.     

Ice sheet survey over Antarctica using satellite altimetry: ERS-2, Envisat,SARAL/AltiKa,the key importance of continuous observations along the same repeat orbit

From September 2002 to October 2010, the Envisat radar altimeter surveyed Greenland and Antarctica ice sheets on a 35 day repeat orbit, providing a unique data set for ice sheet mass balance studies. Up to 85 repeat cycles are available and the whole Envisat data set may be along-track processed in order to provide height variability and trend with a good spatial resolution for the objectives of ice sheet survey.

Soon, a joint Centre National d’Etudes Spatiales/Indian Space Research Organisation mission, SARAL (Satellite with Argos and AltiKa), with the AltiKa payload on board, will be launched on exactly the same orbit (less than 1 km of the nomimal orbit in the across-track direction). This will allow an extension of previous European Remote Sensing (ERS) satellite, ERS-1 and ERS-2, and Envisat missions of the European Space Agency (ESA), in particular from the point of view of ice altimetry. However, AltiKa operates in the Ka band (36.8 GHz), a higher frequency than the classical Ku band (13.6 GHz), leading to important modifications and potential improvements in the interactions between radar wave and snow-pack.

In this paper, a synthesis is presented of all available information relevant to ice altimetry scientific purposes as derived from the Envisat mission: mean and temporal derivatives of the height ? but also of the backscatter and of the two waveform parameters ? snow-pack change corrections, across-track surface slope at 1 km scale, etc. The spatial and temporal variability of ice sheet surface elevation is investigated with the help of the high-resolution Envisat along-track observations. We show that at least 50 repeat cycles are needed to reach the required accuracy for the elevation trend. It is thus advocated as potentially highly beneficial for SARAL/AltiKa as a follow-on mission. Moreover, the novel characteristics of SARAL/AltiKa are promising in improving our understanding of snow penetration impact.     

Complete Oxidation of Methane at Low Temperature over Pt Catalysts Supported on High Surface Area SnO2

The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH₄ traces under lean conditions at low temperature was studied in the absence and in the presence of water (10 vol.%) or H₂S (100 vol.ppm). Their catalytic properties were compared to those of Pd/Al₂O₃ and Pt/Al₂O₃. In the absence of H₂S in the feed, Pt/SnO₂appears as a very promising catalyst for CH₄ oxidation, being even significantly more active under wet conditions than the best reference catalyst, Pd/Al₂O₃. Catalysts steamed-aged at 873 K were also studied in order to simulate long term ageing in real lean-burn NGV exhaust conditions. To this respect, Pt/SnO₂ is slightly less resistant than Pd/Al₂O₃. In the presence of H₂S, Pt/SnO₂catalysts are rapidly and almost completely poisoned, comparably to Pd/Al₂O₃and the catalytic activity is hardly restored upon oxidising treatment below 773 K. A synergetic effect between Pt and specific surface SnO₂sites active in CH₄oxidation is proposed to explain the superior catalytic behaviour of Pt/SnO₂.     

Effect of dynamic vulcanization on the microstructure and performance of polyethylene terephthalate/elastomer blends

Blends of polyethylene terephthalate (PET) and ethylene‐ethyl acrylate‐maleic anhydride terpolymer (E‐EA‐MAH) were dynamically crosslinked in a one‐step extrusion process. An amine‐terminated glycol reacting with MAH moieties was used as the crosslinking agent. The effect of blend composition and dynamic crosslinking on the microstructure and mechanical properties were investigated. Blend ratios ranging from 80:20 to 20:80 PET/E‐EA‐MAH were studied. The region of phase inversion was located for uncrosslinked and dynamically crosslinked blends. The rheological characterization was also carried out for these blends in comparison with the neat materials. After dynamic crosslinking, the phase inversion is shifted from the 30–40% range to the 70–80% range of elastomer content. This shift is induced by the increase of viscosity and elasticity of the network formed. Dynamically crosslinked blends show significant improvements in impact strength but also exhibit a decrease in elongation at break.     

Offset printing inks based on rapeseed and sunflower oil. Part I: Synthesis and characterization of rapeseed oil-and sunflower oil-modified alkyd resins

Two sets of alkyd resins of variable oil lengths with the required properties for offset printing ink formulations, modified by sunflower and rapeseed oil, were synthetized according to the “monoglyceride” process. The influence of the acyl composition of the modifying vegetable oil and of the oil content on alkyds’ properties was determined by detailed chemical and rheological characterization. Molecular structure, size, and molecule size distribution appeared to be linked to these two factors. A comparative study with two usual linseed oil-modified alkyds led to determination of the more appropriate alkyds for applications in offset varnishes.     

Structure and functional complementation of engineered fragments from yeast phosphoglycerate kinase

Previous studies have shown that, although the isolated structuraldomains of yeast phosphoglycerate kinase recover a quasi-nativestructure in vitro as well as in vivo, they do not reassociatenor generate a functional enzyme. The aim of this work was firstto study the folding of complementary fragments different fromstructural domains and second to determine the requirementsfor their reassociation and functional complementation. Themethod used for producing rigorously defined fragments consistsof the introduction of a unique cysteinyl residue in the proteinfollowed by a specific cleavage by 5'5'-dithiobis(2-nitrobenzoate)/potassiumcyanide at this residue. Two pairs of complementary fragmentswere thus obtained, 1–96/97–415 and 1–248/249–415.The structure and stabilities of the different fragments werestudied. The short fragments, i.e. 1–96 and 249–415were found to contain some secondary structure, but to havea low stability. Each large fragment has a high structural contentand a stability close to that of the corresponding domain. Incontrast to that observed with the isolated domains, a weakbut significant complementation was observed for the two pairsof fragments; the pair of fragments 1–248/249–415recovered 8% of the activity of the native enzyme upon complementation.An independent refolding of the complementary fragments beforereassociation decreased the yield of complementation for thepair of fragments 1–96/97–415, but did not affectthe complementation for the other pair (1–248/249–415).From the present data and previous work on the isolated domains,it appears that the correct folding of the isolated fragmentsis not a prerequisite for their complementation.     

Low Breakdown Voltage Varistors by Grain Boundary Diffusion of Molten Bi2O3 in ZnO

Diffusion of molten Bi₂O₃ into the grain boundaries of sintered, alumina-doped (0.23 and 0.7 mol%) ZnO pellets resulted in varistors with breakdown voltages in the 3–5 V range and nonlinearity coefficients of 10–24. The varistors were fabricated by spreading a thin layer of Bi₂O₃ powder on the surface of ZnO pellets and heating the combination to various temperatures (860–1155°C) and different times. The highest nonlinearity coefficients (20–24) and lowest breakdown voltages (3–5 V) were recorded in samples annealed at 860°C for 35 min. Longer annealing times and/or higher temperatures resulted in progressively higher breakdown voltages. Eventually the devices became insulating, which was attributed to the formation of an insulating Bi₂O₃ layer between the grains. Separate wetting experiments have shown that the penetration of Bi₂O₃ into ZnO grain boundaries was a strong function of alumina doping —the penetration rate was decreased by a factor of 5–7 as the ZnO was doped with as little as 0.2 mol% alumina. It is this slowing down of the penetration of the ZnO grain boundaries that is believed to be critical in the development of the low breakdown voltages observed.     

Rate of adsorption to and desorption from a langmuir surface: The case of zero activation barrier to adsorption without dissociation

Many rate constants of elementary steps on single crystals have been measured. Their pre-exponential factors can now be compared to those calculated by transition state theory. Such a calculation is presented in this Letter with due attention to microscopic reversibility, standard states, and configurational entropy.     

Ethanolysis of rapeseed oil: Quantitation of ethyl esters,mono-, di-, and triglycerides and glycerol by high-performance size-exclusion chromatography

High-performance size-exclusion chromatography (HPSEC) was used to evaluate the influence of different variables affecting the transesterification of rapeseed oil (RSO) with anhydrous ethanol and sodium ethoxide as catalyst. The effect of temperature, ethanol/RSO molar ratio, catalyst concentration, and time can be interpreted by observing the variations of the reaction medium composition. HPSEC has made the quantitation of ethyl esters, mono-, di-, and triglycerides and glycerol possible. The best results for laboratory-scale reactions were obtained at 80°C with a 6:1 molar ratio of EtOH/RSO and 1% of NaOEt by weight of RSO.     

Cure kinetics of an epoxy/liquid aromatic diamine modified with poly(ether imide)

The cure kinetics and mechanisms of an epoxy oligomer based on diglycidyl ether of bisphenol A (DGEBA), polymerized with a liquid aromatic diamine based on diethyl toluene diamine (DETDA 80), and its blends with poly(ether imide) (PEI) at concentrations of 0–15 wt % were studied with differential scanning calorimetry under dynamic and isothermal conditions. The kinetic analyses were performed with a phenomenological approach. The reaction mechanism of the blends remained the same as that of the neat epoxy. However, the addition of PEI had a marked effect on the cure kinetics in the DGEBA/DETDA 80 system. The rate of reaction decreased with an increase in the thermoplastic content. Diffusion control was incorporated to describe the cure behavior of the blends in the latter stages. Greater diffusion control was observed as the PEI concentration increased and the cure temperature decreased. Polymer blends based on this epoxy/liquid aromatic diamine had not been previously studied from a kinetic viewpoint. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 660–672, 2005