Processing and properties of transparent hydroxyapatite and β tricalcium phosphate obtained by HIP process

Stoichiometric β-tricalcium phosphate (β-TCP) and hydroxyapatite (HA) powders were synthesized by chemical precipitation of aqueous solutions of diammonium phosphate and calcium nitrate. After a calcination treatment and a milling step, the powders were shaped by slip casting. The sintering temperature effect on the relative density and the average grain size was investigated. By natural sintering at 1200 and 1120 °C, densities of 98% and 99% were obtained for HA and TCP, respectively. After determination of minimum temperatures to obtain only closed porosity and a pre-sintering at these temperatures, hot isostatic pressing (HIP) treatment was carried out. Transparent or translucent samples were obtained, indicating a relative density very close to the theoretical value (>99.9%). Mechanical properties (three-point bending strength, fracture toughness, Young's modulus and Vickers hardness) were measured on both materials with similar grain size (～ 1 μm). Bending strengths of 181 and 105 MPa were measured for TCP and HA, respectively.     

Spark Plasma Sintering of fine alpha-silicon nitride ceramics with LAS for spatial applications

Many space systems such as satellite mirrors and their supporting structures require to be made from very low-thermal expansion materials combining both high hydrostability and relatively high mechanical properties. In this study, we have applied the “composite concept” in order to explore the possibility of fabricating near zero thermal expansion silicon nitride based ceramics. Consequently, a negative thermal expansion material belonged to the lithium aluminosilicate family (LAS powder crystallized under de β-eucryptite structure) was introduced in an alpha-silicon nitride fine powder (5 and 20 vol% of LAS) and the resulting composite system was sintered by Spark Plasma Sintering (SPS) at 1400 and 1500 °C. In the case of 20 vol% LAS compositions, relatively well-densified ceramics (94.4% of the theoretical density) were produced without adding any further sintering additive. The addition of yttria and alumina oxides allowed enhancing the densification level up to 98.2% (20 vol% LAS compositions) or from 62.3% up to 96.7% of the theoretical density in 5 vol% LAS materials. Nevertheless, it was impossible to full consolidate silicon nitride/LAS composite ceramics at temperatures lower than the temperature at which β-eucryptite melts, even by using SPS technology. Moreover, because of the relatively low temperatures involved in SPS, the α to β-Si₃N₄ transformation was avoided, resulting in microstructures composed of fine equiaxed α-Si₃N₄ grains (<200 nm) and of a glassy phase. Even if the effect of having a very large negative thermal expansion material was lost during the sintering step (because of the β-eucryptite melting), ceramics containing only 20 vol% of LAS-based phase exhibited very interesting values as regards of mechanical properties (strength, hardness, toughness, and Young's modulus), thermal conductivity and thermal expansion coefficient. We discuss in this work why we are so interested in developing dense silicon nitride/LAS ceramics sintered without any further additive addition, even though β-eucryptite is melted during the process and the transformation to the β phase is avoided.     

Conductive-probe atomic force microscopy characterization of silicon nanowire

The electrical conduction properties of lateral and vertical silicon nanowires (SiNWs) were investigated using a conductive-probe atomic force microscopy (AFM). Horizontal SiNWs, which were synthesized by the in-plane solid-liquid-solid technique, are randomly deployed into an undoped hydrogenated amorphous silicon layer. Local current mapping shows that the wires have internal microstructures. The local current-voltage measurements on these horizontal wires reveal a power law behavior indicating several transport regimes based on space-charge limited conduction which can be assisted by traps in the high-bias regime (> 1 V). Vertical phosphorus-doped SiNWs were grown by chemical vapor deposition using a gold catalyst-driving vapor-liquid-solid process on higly n-type silicon substrates. The effect of phosphorus doping on the local contact resistance between the AFM tip and the SiNW was put in evidence, and the SiNWs resistivity was estimated.     

Nitrous oxide production kinetics during nitrate reduction in river sediments

A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R_m) ranged between 3.0 and 7.1 μg N g⁻¹ h⁻¹, and affinity constant (K_m) ranged from 7.4 to 30.7 mg N-NO₃⁻ L⁻¹. These values were higher in slurry incubations with an R_m of 37.9 μg N g⁻¹ h⁻¹ and a K_m of 104 mg N-NO₃⁻ L⁻¹. Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4 ng N g⁻¹ h⁻¹ for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates).     

The application of near-infrared (NIR) and Raman spectroscopy to detect adulteration of oil used in animal feed production

Basic vegetable blends (BVB’s) and soya oils, used in the animal feed industry, are sometimes adulterated with transformer and mineral oil as a means of illegally increasing profit. A set of BVB’s and soya oil samples adulterated with transformer oil and mineral oil were characterised using both NIRS and Raman spectroscopy. Applying chemometrics to the NIRS and Raman spectral data, very good calibration and prediction statistics were obtained for transformer and mineral oils. Using NIRS, R² values greater than 0.99 were obtained with corresponding values for root mean squared error of calibration and prediction (<0.57 and <0.55, respectively). Using Raman, R² values greater than 0.97 were obtained with the root mean squared error of calibration (<2.01) and prediction (<1.92) calculated. Furthermore, using a qualitative approach it was possible, using PCA, to discriminate between 100% soya and BVB. This study demonstrates that both NIRS and Raman technology can be successfully applied as rapid screening techniques for the detection of oil adulteration and fraud in the food and feed industry.