Internal friction investigation of phase transformation in nearly stoichiometric LaMnO3+δ

Rhombohedral LaMnO3+δ powders, prepared by two different soft chemistry routes (co-precipitation and hydrothermal synthesis), are sintered at 1400 °C for 2 h in air. Measurements of internal friction Q−1(T) and shear modulus G(T), at low frequencies from −180 to 700 °C under vacuum, evidence three structural transitions of nearly stoichiometric orthorhombic LaMnO3+δ. The first one, at 250 or 290 °C, depending on the processing followed, is associated to either a Jahn–Teller structural transition or a phase transformation from orthorhombic to pseudo-cubic. The second one at 610 or 630 °C is related to a phase transformation from pseudo-cubic or orthorhombic to rhombohedral. Below the Neel temperature, around −170 °C, a relaxation peak could be associated, for samples prepared according to both processing routes, to the motion of Weiss domains

Synthesis of CoAl2O4 by double decomposition reaction between LiAlO2 and molten KCoCl3

Submicronic CoAl2O4 powders were prepared by double decomposition reaction between solid LiAlO2 and molten KCoCl3 at 500 ◦C for 24 h. The reaction mechanism involves the dissolution of LiAlO2 shifted by the precipitation of CoAl2O4 until complete transformation and the reaction leads to powders with a very homogeneous chemical composition. The powders obtained were mainly characterized by XRD, FTIR, ICP, X.EDS, electron microscopy and diffraction and diffuse reflexion. The blue pigments obtained exhibit a high thermic stability allowing their use for the colouring of ceramic tiles

Variabilités spatiales et temporelles de la qualité physico-chimique et des invertébrés pélagiques des eaux de la retenue hydroélectrique de Petit Saut (Guyane française).

Le bassin versant du fleuve Sinnamary est situé en Guyane française, au nord du continent sud américain, en zone néo-tropicale. Il s'étend entre 4 et 5°de latitude Nord et entre 52°50' et 53°30' de longitude Ouest. En 1994, la mise en eau du barrage hydroélectrique construit sur le site de Petit Saut occasionne l'ennoiement de 365 km2 de forêt primaire. Le remplissage s'effectue en 18 mois, et la demande en oxygène dissous nécessaire à la dégradation de la matière organique est telle qu'en quelques jours la masse d'eau se stratifie en un épilimnion oxygéné et un hypolimnion anoxique. Représentant quelques centimètres en 1994, l'épilimnion s'épaissit progressivement jusqu'en 1998. Depuis, cette progression s'est nettement ralentie et l'épilimnion oscille autour d'une valeur moyenne de 5 à 6 mètres. Il abrite la plus grande partie du zooplancton pélagique. L'hypolimnion est anoxique et riche en éléments réduits. Le zooplancton s'est rapidement installé avec des rotifères, des cladocères et des copépodes. Des ostracodes et des Chaoboridae y sont désormais associés. La retenue présente une zonation longitudinale, de la tête de la retenue vers la queue, aussi bien en termes de densités que de composition des peuplements. De même, il existe une zonation transversale, notamment marquée par un gradient croissant de la conductivité de l'axe vers les berges. Ces ressources endogènes ainsi que des apports complémentaires (végétaux, invertébrés terrestres, détritus…) sont utilisées par la faune ichtyque qui a su s'adapter au changement du milieu. Le temps de rétention des eaux qui fluctue saisonnièrement en fonction des pluies semble être le facteur prépondérant de variabilité pour la qualité physico-chimique des eaux et les communautés biologiques.The Sinnamary River is located in a neotropical zone, in French Guiana, in the northern part of South America. Its flood basin extends between 4° and 5° N latitude and 52°50' and 53°30' W longitude. The river is found in an equatorial climate, and is influenced by its proximity to the ocean. The temperature varies little, with an average of 25°C for the least hot month (January) and 27°C for the hottest month (October). The humidity is always high and averages more than 90%. The Sinnamary River bed is broad (> 50 m), and runs from south to north for approximately 240 km with a very weak slope (0.0003%). Petit Saut, the site of the hydroelectric dam, is located approximately 60 km from the mouth of the river, with a flood basin area of 5927 km2 and an average flow rate 260 m3 /s.The construction of the hydroelectric dam at Petit Saut in 1994 resulted in the flooding of 365 km2 of primary forest in a neotropical zone (the average depth of the reservoir is 11 m). The dam reservoir was filled over a period of 18 months and the amount of dissolved oxygen necessary for the organic matter to decompose was such that, in a matter of days, the body of water became stratified into an oxygenated epilimnion and an anoxic hypolimnion. Only centimeters thick in 1994, by 1998 the epilimnion had progressively expanded. Since that time it has varied between an average thickness of 5 to 6 m and is home to various biological communities. The hypolimnion is anoxic and rich in reduced compounds (nitrogen and phosphorus minerals, dissolved organic matter, particles, metals and gas). The products of the degradation of the flooded organic matter, which still prevail at the bottom, are gradually relayed towards surface by phenomena of dilution, hydrolysis and oxidation.The river fauna disappeared from the reservoir and was replaced after a few weeks by various pelagic fauna. The zooplanktonic communities, primarily confined to the epilimnion, were quickly settled with rotifera, cladocera and copepoda. Initially dominated by detritivores (Bosminidae) and Cyclopidae from February to May 1994, the settlements diversified with phytophagous zooplankton (Calanidae and Daphniidae) when the phytoplankton developed. This procession was quickly accompanied by Sididae, which has dominated the cladocera since mid-1996 and by ostracoda, which were particularly abundant from 1995 to 1997. Carnivores such as Chaoboridae larvae were also present in Petit Saut reservoir. In contrast to the other zooplankton species, Chaoboridae larvae occupy the entire water column. As a result of great quantities of organic matter available at the time the reservoir was filled, the biomasses were initially large and have gradually decreased with decreasing nutrient concentrations.The reservoir was not homogeneous in terms of zooplankton density, with a longitudinal zonation from the dam towards the upstream tail. In the tail, fauna were identical to those of the river. In the lake zone, phytophagous Calanidae dominated. In the intermediate zone, known as the zone of transition, the zooplankton biomass normalized to the volume of oxygenated water was less important than in the lake zone. Cyclopidae, well represented at the time of the reservoir colonization, dominated the communities in the transition zone. This distribution of zooplankton was likely connected with the dissolved oxygen concentrations, as well as with the quantities of phytoplankton and bacterio-chlorophyll. Similarly, there was a transverse zonation, marked by an increase in conductivity towards the reservoir banks. The density of the communities varied seasonally. The highest biomasses were measured along the central axis at the time of high waters and close to the banks at the time of low waters.The time of water retention, which fluctuates according to the rainy season, seemed to be the factor dominating the physicochemical water quality variability and the biological communities. The rainy season is characterized by the dilution of various elements (e.g., conductivity is reduced). Conversely, during the dry season, the elements concentrate again in the water mass. Nevertheless, the peaks of pelagic invertebrate density were observed during times of high waters, when the hydraulic conditions favour the exchanges between the hypolimnion (anoxic and rich in nutritive elements) and the epilimnion (oxygenated and very low in nutrients).These endogenous resources, as well as complementary contributions (vegetation, invertebrate, terrestrial, refuse), are used by the fish fauna, which adapted to the change in their environment. Predation contributes to the seasonal evolution of the zooplankton. Predation pressure was more important in the dry season than in the rainy season

A novel nanoindentation protocol to characterize surface free energy of superhydrophobic nanopatterned materials

Abstract Surface Free Energy (SFE) has become a relevant design parameter to produce materials and devices with controlled wettability. The non-destructive measurement of SFE in nanopatterned super-hydrophobic hard surfaces is a challenge in both research and industry since in most cases time-consuming contact angle measurements are not feasible. In this work, we present a novel nanoindentation based method for the measurement of pull-off adhesive forces by carefully controlling environmental and instrumentation issues. The method is found to measure SFE over five orders of magnitude, covering hydrophilic to super-hydrophobic surfaces, and has been validated with contact angle measurements. Its limitations and shortcomings are critically discussed, with a specific focus on the experimental issues that could affect the reliability and reproducibility of the results. Finally, the potential applications of the newly developed methodology include fast non-destructive mapping of SFE over heterogeneous surfaces with spatially controlled wettability. Graphic abstrac

Cathodoluminescence Studies of Defects in Coated Boron Nitride

Optical emission properties of Boron Nitride (BN) substrates, BN with alumina (Al2O3) coating, and thermally-annealed alumina-coated boron nitride (an-BN/Al2O3) were investigated under electron irradiation using cathodoluminescence (CL) measurements. Tests were performed temperatures ranging from ~100 K to ~300 K, with monoenergetic beams from 5 keV to 30 keV, and electron flux densities from 1 nA.cm-2 to 500 nA.cm-2. These experiments were conducted to identify the effects of coating and thermal annealing on the nature and occupation of defect states in different samples with BN substrates. Previous studies have shown that these treatments can limit the charging of BN substrates. Consequently, thorough investigations of electron trapping and recombination processes as a function of low temperature, dose and charging/discharge were performed in order to explain the differences of electrical behaviour and compare the CL spectra of the three different samples studied. Broad features associated with the BN and sharper features resulting from the annealed alumina coating were observed. Changes in the intensity, energy, and width of the features with sample treatments were observed. Different incident beam parameters were used to associate these features with specific types of defect states. The effects of charging, temperature- and dose-dependent conductivity, and thermal annealing and aging of the samples on the CL spectra were investigated. These were used to study defect creation and occupation and to understand the predominant physical mechanisms and main structural and chemical differences between these ceramic configurations

Investigation of the thermal expansion and heat capacity of the CaCu3Ti4O12 ceramics

The thermal expansion of the CaCu3Ti4O12 ceramics has been measured over a wide temperature range 120–1200 K. The high quality of the samples under study has been confirmed by good agreement of the results of measurements of the heat capacity in the range 2–300 K and in the vicinity of the phase transition of magnetic nature at 25 K with the data for the single crystal. No anomalies in the thermal expansion that can be associated with the phase transition at 726–732 K assumed by other investigators have been found. The influence exerted on the thermal expansion by the heat treatment of the sample in a helium atmosphere and in air has been investigated

Investigation of the reactivity of AlCl3 and CoCl2 toward molten alkali-metal nitrates in order to synthesize CoAl2O4

Cobalt aluminate CoAl2O4 powder, constituted of nano-sized crystallites, is prepared, involving the reactivity of AlCl3 and CoCl2 with molten alkali-metal nitrates. The reaction at 450 °C for 2 h leads to a mixture of spinel oxide Co3O4 and amorphous γ-Al2O3. It is transformed into the spinel oxide CoAl2O4 by heating at 1000 °C. The powders are mainly characterized by XRD, FTIR, ICP, electron microscopy and diffraction, X-EDS and diffuse reflection. Their properties are compared to those of powders obtained by solid state reactions of a mechanical mixture of chlorides or oxides submitted to the same thermal treatment

Cation distribution in manganese cobaltite spinels Co3−xMnxO4 (0 ≤ x ≤ 1) determined by thermal analysis

Thermogravimetric analysis was used in order to study the reduction in air of submicronic powders of Co3−x Mn x O4 spinels, with 0 ≤ x ≤ 1. For x = 0 (i.e. Co3O4), cation reduction occurred in a single step. It involved the CoIII ions at the octahedral sites, which were reduced to Co2+ on producing CoO. For 0 < x ≤ 1, the reduction occurred in two stages at increasing temperature with increasing amounts of manganese. The first step corresponded to the reduction of octahedral CoIII ions and the second was attributed to the reduction of octahedral Mn4+ ions to Mn3+. From the individual weight losses and the electrical neutrality of the lattice, the CoIII and Mn4+ ion concentrations were calculated. The distribution of cobalt and manganese ions present on each crystallographic site of the spinel was determined. In contrast to most previous studies that took into account either CoIII and Mn3+ or Co2+, CoIII and Mn4+ only, our thermal analysis study showed that Co2+/CoIII and Mn3+/Mn4+ pairs occupy the octahedral sites. These results were used to explain the resistivity measurements carried out on dense ceramics prepared from our powders sintered at low temperature (700–750 °C) in a Spark Plasma Sintering apparatus

Crack Bridging Mechanism for Glass Strengthening by Organosilane Water-Based Coatings

We used an epoxysilane/aminosilane coating deposited from an aqueous solution to strengthen flat glass. We studied film formation, interfacial and mechanical properties of the film. The film is highly cross-linked with a 6 GPa Young's modulus and good adhesion. Our results suggest that crack face bridging accounts for most of the 75 % reinforcement in this system