National-scale implementation of mandatory freshwater farm plans: a mechanism to deliver water quality improvement in productive catchments in New Zealand?

Nutrient Cycling in Agroecosystems - Reducing agriculturally derived diffuse contaminant losses (via non-point sources) from land to water has proven difficult for decades. Owing to the diversity...     

Development and characterisation of a Y2Ti2O7-based glass-ceramic as a potential oxidation protective coating for titanium suboxide (TiOx)

A silica-based glass-ceramic, with Y₂Ti₂O₇ as the major crystalline phase, is designed, characterised and tested as an oxidation-protective coating for a titanium suboxide (TiO_x) thermoelectric material at temperatures of up to 600 °C. The optimised sinter-crystallisation treatment temperatures are found to be 1300 °C and 855 °C for a duration of 30 min, and this treatment leads to a glass-ceramic with cubic Y₂Ti₂O₇ and CaAl₂Si₂O₈ as crystalline phases. An increase of ~270 °C in the dilatometric softening temperature is observed after devitrification of the parent glass, thus further extending its working temperature range.Excellent adhesion of the glass-ceramic coating to the thermoelectric material is maintained after exposure to a temperature of 600 °C for 120 h under oxidising conditions, thus confirming the effectiveness of the T1 glass-ceramic in protecting the TiO_x material.     

Lipidomic Analysis of Plasma from Healthy Men and Women Shows Phospholipid Class and Molecular Species Differences between Sexes

The phospholipid composition of lipoproteins is determined by the specificity of hepatic phospholipid biosynthesis. Plasma phospholipid 20:4n-6 and 22:6n-3 concentrations are higher in women than in men. We used this sex difference in a lipidomics analysis of the impact of endocrine factors on the phospholipid class and molecular species composition of fasting plasma from young men and women. Diester species predominated in all lipid classes measured. 20/54 Phosphatidylcholine (PtdCho) species were alkyl ester, 15/48 phosphatidylethanolamine (PtdEtn) species were alkyl ester, and 12/48 PtdEtn species were alkenyl ester. There were no significant differences between sexes in the proportions of alkyl PtdCho species. The proportion of alkyl ester PtdEtn species was greater in women than men, while the proportion of alkenyl ester PtdEtn species was greater in men than women. None of the phosphatidylinositol (PtdIns) or phosphatidylserine (PtdSer) molecular species contained ether-linked fatty acids. The proportion of PtdCho16:0_22:6, and the proportions of PtdEtn O-16:0_20:4 and PtdEtn O-18:2_20:4 were greater in women than men. There were no sex differences in PtdIns and PtdSer molecular species compositions. These findings show that plasma phospholipids can be modified by sex. Such differences in lipoprotein phospholipid composition could contribute to sexual dimorphism in patterns of health and disease.     

Direct writing of textured ceramics using anisotropic nozzles

Direct writing is a unique means to align anisotropic particles for the fabrication of textured ceramics by templated grain growth (TGG). We show that alignment of tabular barium titanate (BT) template particles (20–40 μm width and 0.5–2 μm thickness) in a PIN-PMN-PT matrix powder (d₅₀ = 280 nm) is significantly improved during direct writing using anisotropic nozzles at high printing rates. The particle orientation distribution in as-printed filaments, and the texture orientation distribution in sintered ceramic filaments are shown to directly correlate with COMSOL Multiphysics-predicted torque distributions for direct writing with aspect ratio 2, 3 and 5 oval nozzles. Electromechanical strain properties of the textured piezoelectric ceramics significantly improved relative to random ceramics when printed with anisotropic nozzles. Simulations of aspect ratio 20 nozzles and nozzles with interior baffles demonstrate significantly increased torque and near elimination of constant shear stress cores (i.e. plug flow).     

Wire electrical discharge machinable SiC with GNPs and GO as the electrically conducting filler

SiC based composites filled with graphene nano-platelets (GNPs) or graphene oxide (GO) prepared by rapid hot-pressing exhibit sufficient electrical conductivity for their machinability by wire electro-discharge machining (WEDM). Composites microstructure anisotropy caused by graphene alignment as a consequence of rapid hot pressing was confirmed by measuring of electrical conductivity and thermal diffusivity. Electrical conductivity increased significantly with increased weight fraction of graphene in both measured directions. Highest value of 2031 S/m was obtained for composites with 15 wt. % of GNPs in parallel direction and only 1246 S/m in perpendicular direction to aligned GNPs. Thermal diffusivity is 63.3 mm²/s in parallel and only 23.3 mm²/s in perpendicular direction. The increase of the electrical conductivity has resulted in successful WEDM. The MRR was almost doubled when the filler concentration increased from 5 wt. % GNPs/GO to 15 wt. % GNPs. At the same time, the surface roughness decreased.     

Structural studies on Ca3Al4MgO10 (C3A2M)—A ternary phase in the system CaO–Al2O3–MgO

In a sequence of temperature-dependent solid-state reactions in the system CaO–Al₂O₃–MgO the formation of the ternary phase Ca₃Al₄MgO₁₀ or C₃A₂M has been studied. Whereas the compound could not be prepared at 1200°C, a yield of 85 wt.-% of Ca₃Al₄MgO₁₀ was obtained at 1320°C (incongruent melting point: 1330°C). Powder diffraction data compare well with results of previous investigations from the 1960s. Single crystals of Ca₃Al₄MgO₁₀ could be retrieved from the sinter-pellets. Basic crystallographic data are as follows: orthorhombic symmetry, space group Pbcm, a = 5.14073(8), b = 16.7576(2), c = 10.70977(16) Å, V = 922.61(2) ų, Z = 4. Using synchrotron diffraction data it was possible to solve the crystal structure. Least-squares refinements resulted in a residual of R(|F|) = 0.021 for 1000 independent observed reflections with I > 2σ(I) and 97 parameters. The structure contains [TO₄]-tetrahedra (T=Al,Mg) forming a three-dimensional (3-D) framework whose topological characteristics have been determined. Al-Mg distributions on the different T-sites have been studied. The calcium cations are located in voids of the network. More than 50 years after its first observation our investigation clarifies the crystal structure of a compound belonging to a system that is of relevance for several fields of materials science.     

Applications of analytical electron microscopy to guide the design of boron carbide

Compositional analysis of boron carbide on nanometer length scales to examine or interpret atomic mechanisms, for example, solid-state amorphization or grain-boundary segregation, is challenging. This work reviews advancements in high-resolution microanalysis to characterize multiple generations of boron carbide. First, ζ-factor microanalysis will be introduced as a powerful (scanning) transmission electron microscopy ((S)TEM) analytical framework to accurately characterize boron carbide. Three case studies involving the application of ζ-factor microanalysis will then be presented: (1) accurate stoichiometry determination of B-doped boron carbide using ζ-factor microanalysis and electron energy loss spectroscopy, (2) normalized quantification of silicon grain-boundary segregation in Si-doped boron carbide, and (3) calibration of a scanning electron microscope X-ray energy-dispersive spectroscopy (XEDS) system to measure compositional homogeneity differences of B/Si-doped arc-melted boron carbides in the as-melted and annealed conditions. Overall, the improvement and application of advanced analytical tools have helped better understand processing–microstructure–property relationships and successfully manufacture high-performance ceramics.     

Conversion kinetics of container glass batch melting

Understanding the batch-to-glass conversion process is fundamental to optimizing the performance of glass-melting furnaces and ensuring that furnace modeling can correctly predict the observed outcome when batch materials or furnace conditions change. To investigate the kinetics of silica dissolution, gas evolution, and primary foam formation and collapse, we performed X-ray diffraction, thermal gravimetry, feed expansion tests, and evolved gas analysis of batch samples heated at several constant heating rates. We found that gas evolving reactions, foaming, and silica dissolution depend on the thermal history of the batch in a similar manner: the kinetic parameters of each process were linear functions of the square root of the heating rate. This kinetic similarity reflects the stronger-than-expected interdependence of these processes. On the basis of our results, we suggest that changes in furnace operating conditions, such as firing or boosting, influence the melting rate less than what one would expect without consideration of batch conversion kinetics.     

Ultrathin Dual‐Scale Nano‐ and Microporous Membranes for Vascular Transmigration Models

Selective cellular transmigration across the microvascular endothelium regulates innate and adaptive immune responses, stem cell localization, and cancer cell metastasis. Integration of traditional microporous membranes into microfluidic vascular models permits the rapid assay of transmigration events but suffers from poor reproduction of the cell permeable basement membrane. Current microporous membranes in these systems have large nonporous regions between micropores that inhibit cell communication and nutrient exchange on the basolateral surface reducing their physiological relevance. Here, the use of 100 nm thick continuously nanoporous silicon nitride membranes as a base substrate for lithographic fabrication of 3 µm pores is presented, resulting in a highly porous (≈30%), dual‐scale nano‐ and microporous membrane for use in an improved vascular transmigration model. Ultrathin membranes are patterned using a precision laser writer for cost‐effective, rapid micropore design iterations. The optically transparent dual‐scale membranes enable complete observation of leukocyte egress across a variety of pore densities. A maximal density of ≈14 micropores per cell is discovered beyond which cell–substrate interactions are compromised giving rise to endothelial cell losses under flow. Addition of a subluminal extracellular matrix rescues cell adhesion, allowing for the creation of shear‐primed endothelial barrier models on nearly 30% continuously porous substrates.