Real-Time Capturing of Microscale Events Controlling the Sintering of Lead-Free Piezoelectric Potassium-Sodium Niobate.

Sintering is a very important process in materials science and technological applications. Despite breakthroughs in achieving optimized piezoelectric properties, fundamentals of K0.5 Na0.5 NbO3 (KNN) sintering are not yet fully understood, facing densification versus grain growth competition. At present, microscale events during KNN sintering under reducing atmospheres are real-time monitored using a High Temperature-Environmental Scanning Electron Microscope. A two contacting KNN particles model satisfying the Kingery and Berg's bulk diffusion model is reported. Dynamic events like individual grain growth and grain elimination process are explored through a postanalysis of recorded image series. The diffusion coefficient for oxygen vacancies of 10-8 cm2 s-1 and average boundary mobility of 10-9 cm4 J-1 s-1 are reported for the KNN ceramics. Moreover, the local pore shrinkage is consistent with the Kingery and François's concept of pore stability except that pore curvatures are not all concave, convex or flat due to anisotropic grain-boundary energies. The global grain growth kinetics are described using parabolic and/or cubic laws. The effect of atmospheres and microstructure evolution on the intrinsic and extrinsic contributions to the dielectric response using Rayleigh's law is also explored. These results bring a new breath for KNN sintering studies in order to adapt the sintering process.

Modified zeolite-supported biofilm in service of pesticide biodegradation.

The development of biofilms on modified natural zeolites was investigated with purpose to obtain biocomposites with biodegradation activity towards pesticides MCPA (2-methyl-4-chlorophenoxyacetic acid) and glyphosate (N-(phosphonomethyl)glycine) for potential application in bioaugmentation of polluted agricultural soils. Microbial communities were selected from agricultural pesticide-contaminated soil/water samples and enriched on the basis of their ability to biodegrade the pesticides. In order to enhance affinity of microbial communities to the support material, the natural mineral zeolite was modified by nontoxic environmentally friendly cations (Li+, Na+, K+, NH4+, H+, Mg2+, Ca2+, Fe3+) by methods preserving its structure and characterised using powder XRD, surface area measurement and chemical composition analysis. Kinetics of pesticide degradation by the biocomposites was studied in liquid media. Results showed that according to zeolite modifications, the microbial activity and biodiversity changed. The best biodegradation rate of MCPA and glyphosate reached 0.12-0.13 mg/h with half-life of 16-18 h, which is considerably quicker than observed in natural environment. However, in some cases, biodegradation activity towards pesticides was lost which was connected to unfavourable zeolite modification and accumulation of toxic metabolites. High-throughput sequencing on the 16S rRNA genes of the biofilm communities highlighted the selection of bacteria genera known to metabolise MCPA (Aminobacter, Cupriavidus, Novosphingobium, Pseudomonas, Rhodococcus, Sphingobium and Sphingopyxis) and glyphosate (Pseudomonas). Altogether, results suggested that zeolites do not only have a passive role of biofilm support but also have protective and nutrient-supportive functions that consequently increase biodiversity of the pesticide degraders growing in the biofilm and influence the pesticide biodegradation rate.

Reducing the thermal conductivity of La2Mo2O9 with a trivalent praseodymium substitution for its potential use as a thermal barrier coating.

(La1-xPrx)2Mo2O9 powders were synthesized by solid state reaction for x = 0.00, 0.10, 0.25, 0.50, 0.75 and 1.00. Dense pellets were obtained by conventional sintering in air. Their thermal stability and thermal conductivity were measured from 100 to 700 °C and their cell parameters refined from X-ray powder diffraction pattern by the Rietveld method. A 50 mol% isovalent substitution of lanthanum in La2Mo2O9 by praseodymium stabilizes the high temperature ß phase while reducing the thermal conductivity of the parent compound by 11-18%. For a praseodymium content x higher than 0.75, the thermal conductivity increases and a phase transition similar to that of La2Mo2O9 is observed except that the room temperature phase appears to be this time triclinic in symmetry.

Inversion Boundaries and Phonon Scattering in Ga:ZnO Thermoelectric Compounds.

We investigated the high-temperature thermoelectric properties of Ga:ZnO bulk compounds, synthesized using a simple and scalable solid-state process. The effects of a low gallium content (x ≤ 0.04 in Zn1-xGaxO1+x/2) on the structural features and electrical/thermal properties are reviewed. Transmission electron microscopy analyses showed that 2D, nonperiodic defects had formed from a doping content as low as x = 0.01 Ga. The structural description of these nanoscale interfaces is, for the first time, carefully investigated in such low-Ga-content samples by HAADF-STEM analyses combined with structural modeling. It was found that the formation of head-to-head inversion twin (h-IT) boundaries and tail-to tail inversion boundaries (t-IB) in the bulk compounds is responsible for strong phonon scattering, while maintaining relatively good electrical conductivity and thereby enhancing the thermoelectric properties. The absolute value of the Seebeck coefficient decreases abruptly from 475 µV/K for x = 0 down to 60 µV/K for x = 0.005 at 350 K. At the same time, the electrical resistivity drops from 1 ohm cm for x = 0 to 1.7 × 10-3 ohm cm for x = 0.005. For higher Ga additions (x > 0.01), the increase in electrical resistivity is likely linked to the formation of interface defects at a larger extent in the wurtzite structure. The thermal conductivity also drops sharply with the increase in the Ga content from ∼33 W/m K for x = 0 to ∼8 for x = 0.04 at 350 K. This study is progress toward the synthesis of other thermoelectric materials where nanoscale interfaces in bulk compounds provide tremendous opportunities for further enhancing both the phonon scattering and the overall figure of merit.

New protocol for the rapid quantification of exopolysaccharides in continuous culture systems of acidophilic bioleaching bacteria.

In this study, we investigate exopolysaccharide production by a bacterial consortium during the bioleaching of a cobaltiferrous pyrite. Whereas comparable studies have looked at exopolysaccharide production in batch systems, this study focuses on a continuous system comprising a series of four stirred bioreactors and reveals the difficulties in quantifying biomolecules in complex media such as bioleached samples. We also adapted the phenol/sulphuric acid method to take into account iron interference, thus establishing a new protocol for sugar quantification in bioleached samples characterised by low pH (1.4) and high iron concentration (2 g l(-1)). This allows sugar analysis without any prior sample preparation step; only a small amount of sample is needed (0.5 ml) and sample preparation is limited to a single filtration step. We found that free exopolysaccharides represented more than 80% of the total sugars in the bioreactors, probably because stirring creates abrasive conditions and detaches sugars bound to pyrite or bacteria and that they were produced mainly in the first two reactors where bioleaching activity was greatest. However, we could not establish any direct link between the measured exopolysaccharide concentration and bioleaching activity. Exopolysaccharides could have another role (protection against stress) in addition to that in bacterial attachment.

Leaching of lead metallurgical slag in citric solutions--implications for disposal and weathering in soil environments.

Metallurgical slags from primary lead smelting were submitted to a 30-day batch leaching procedure in 20 and 8 mM citric solutions in order to determine the kinetics of release of Pb, Cu, Zn and As. The experiment was coupled with the PHREEQC-2 speciation-solubility modelling and mineralogical study of newly formed products (SEM/EDS, XRD, TEM/EDS and Raman spectrometry). A strong scavenging of metals and metalloids from the 8 mM citric leachate was observed due to the formation of newly formed products. The secondary precipitate consisted of well-developed calcite (CaCO3) crystals and amorphous organo-mineral matrix composed of hydrous ferric oxides and amorphous SiO2. Metals (Pb, Zn, Cu) and arsenic released into the solution were subsequently bound onto the newly formed product (adsorption on oxides) or trapped within the calcite structure (Zn, Mn). Similar scavenging mechanism can be taken into account in real soil systems with lower concentration of citric acid. Then, the covering of slag dumps with a thick soil layer and subsequent re-vegetation might be a possible scenario for slag management on some metallurgical sites.