Structure and viscosity of phase‐separated BaO–SiO2 glasses

Barium silicate glasses with 0‐40 mol% BaO were synthesized either by aerodynamical levitation and laser heating (at low barium content) or by conventional melting and quenching process. Characterization by means of Raman scattering spectroscopy and scanning transmission electron microscopy reveals a structural transition between glasses with low BaO content (<10 mol%) showing an atomic network resembling the one of amorphous silica, and glasses with a BaO content larger than 10 mol%, which exhibit the typical signature of a binary silicate glass with Q₂ and Q₃ units. Viscosity curves show a marked increase of the viscosity as the BaO content decreases below 20 mol%. Barium is found to easily diffuse and promote phase separation while silicon remains homogeneously distributed. A dramatic increase in the viscosity is observed as phase separation proceeds, resulting in the formation of Ba‐rich nodules in a percolating SiO₂‐rich matrix at low barium content, or in Ba‐poor nodules in a BaO‐rich matrix at large barium content.     

The filler effect: The influence of filler content and type on the hydration rate of tricalcium silicate

The partial replacement of ordinary portland cement (OPC) by fine mineral fillers accelerates the rate of hydration reactions. This acceleration, known as the filler effect, has been attributed to enhanced heterogeneous nucleation of C‐S‐H on the extra surface provided by fillers. This study isolates the cause of the filler effect by examining how the composition and replacement levels of two filler agents influence the hydration of tricalcium silicate (T1‐Ca₃SiO₅; C₃S), a polymorph of the major phase in ordinary portland cement (OPC). For a unit increase in surface area of the filler, C₃S reaction rates increase far less than expected. This is because the agglomeration of fine filler particles can render up to 65% of their surface area unavailable for C‐S‐H nucleation. By analysis of mixtures with equal surface areas, it is hypothesized that limestone is a superior filler as compared to quartz due to the sorption of its aqueous CO₃^2? ions by the C‐S‐H—which in turn releases OH^? species to increase the driving force for C‐S‐H growth. This hypothesis is supported by kinetic data of C₃S hydration occurring in the presence of CO₃^2? and SO₄^2? ions provisioned by readily soluble salts. Contrary to prior investigations, these results suggest that differences in heterogeneous nucleation of the C‐S‐H on filler particle surfaces, caused due to differences in their interfacial properties, have little if any effect on C₃S hydration kinetics.     

An improved basis for characterizing the suitability of fly ash as a cement replacement agent

Fly ash is a critical material for partial replacement of ordinary portland cement (OPC) in the binder fraction of a concrete mixture. However, significant compositional variability currently limits fly ash use. For example, the performance of OPC‐fly ash blends cannot be estimated a priori using current characterization standards (eg, ASTM C618). In this study, fly ashes spanning a wide compositional range are characterized in terms of glassy and crystalline phases using a combination of X‐ray fluorescence (XRF), X‐ray diffraction (XRD), and scanning electron microscopy with X‐ray energy‐dispersive spectroscopy (SEM‐EDS) techniques. The compositional data are distilled to a unitless parameter, the network ratio (N_r), which represents the network behavior of atoms that form alkali/alkaline earth‐aluminosilicate glasses that make up fly ashes. N_r is correlated with known composition‐dependent features, including the glass transition temperature and amorphous XRD peak (“hump”) position. Analysis of heat release data and compressive strengths are used to evaluate the impact of fly ash compositions on reaction kinetics and on the engineering properties of cement‐fly ash blends. It is shown that fly ashes hosting glasses with a high network ratio (ie, having a less stable glass structure) are more reactive than others.     

X-ray imaging of a high-temperature furnace applied to glass melting

The dynamics of soda-lime-silica glass grain melting is investigated experimentally using a nonintrusive technique. A cylindrical alumina crucible is filled with glass cullet and placed into a furnace illuminated by an X-ray source. This glass granular bed is gradually heated up to 1100°C, leading to its melting and the generation of a size-distributed population of bubbles rising in the molten glass. An image processing algorithm of X-ray images of the cullet bed during melting allows the characterization of bubbles size distribution in the crucible as well as their velocity. The introduction of tin dioxide μ-particles in the glass matrix before melting enhances the texture of the images and makes possible the determination of the bubble-induced molten glass velocity field by an optical flow technique. The bubble size distribution can be fitted by a log-normal law, suggesting that it is closely related to the initial size distribution in the cullet bed. The liquid motion induced by the bubbles in Stokes' regime is strongly affected by the flow confinement and the determination of bubble rising velocity along its trajectory unveils the existence of local tiny temperature fluctuations in the crucible. Overall, the measuring techniques developed in this work seem to be very promising for the improvement of models and optimization of industrial glass furnaces.     

The Influence of Water Activity on the Hydration Rate of Tricalcium Silicate

Tricalcium silicate does not undergo hydration at relative humidities (RH's) below 80%. But, the rate at which its hydration rate decreases as a function of the RH has not yet been elucidated. By invoking correspondence between RH and water activity (a_H, unitless), both of which are related to the chemical potential of water, the reaction evolutions of triclinic tricalcium silicate (i.e., T1‐Ca₃SiO₅ or C₃S) are tracked in water + isopropanol (IPA) mixtures, prepared across a wide range of water activities. Emphasis is placed on quantifying the: (a) rate of hydration as a function of a_H, and (b) the critical (initial, a_H0c or the achieved) water activity at which hydration effectively ceases, i.e., does not progress; here identified to be ≈ 0.70. The hydration of tricalcium silicate is arrested even when the system remains near saturated with a liquid phase, such that small, if any, capillary stresses develop. This suggests that changes in chemical potential induced via a vapor‐phase or liquid‐phase route both induce similar suppressions of C₃S hydration. A phase boundary nucleation and growth (pBNG) model is fit to measured hydration rates from the onset of the acceleration period until well beyond the rate maximum when the water activity is altered. The simulations suggest that for a fixed hydrate nucleation density, any water activity reductions consistently suppress the growth of hydration products. Thermodynamic considerations of how water activity changes may influence reactions/hydrate evolutions are discussed. The outcomes improve our understanding of the chemical factors that influence the rate of Ca₃SiO₅ hydration.     

Cladosporin Derivatives Obtained by Biotransformation Provide Guidance for the Focused Derivatization of this Antimalarial Lead Compound

Cladosporin, a natural product known for decades, has recently been discovered to display potent and selective antiplasmodial activity by inhibition of lysyl-tRNA synthetase. It was subjected to a panel of oxidative biotransformations with one fungal and two actinomycetes strains, as well as a triple mutant bacterial CYP102A1, yielding eight, mostly hydroxylated, derivatives. These new compounds covered a wide chemical space and contained two pairs of epimers in the tetrahydropyran ring. Although less potent than the parent compound, all analogues showed activity in a cell-based synthetase assay, thus demonstrating uptake and on-target activity in living cells with varying degrees of selectivity for the enzyme lysyl-tRNA synthetase from Plasmodium falciparum and highlighting sites suitable for synthesis of future cladosporin analogues. Compounds with adjacent hydroxy functions showed different MS/MS fragmentation that can be explained in terms of an, in some cases, regioselective loss of water followed by a retro-Diels–Alder reaction.     

High Density Infill in Cracks and Protrusions from the Articular Calcified Cartilage in Osteoarthritis in Standardbred Horse Carpal Bones

We studied changes in articular calcified cartilage (ACC) and subchondral bone (SCB) in the third carpal bones (C3) of Standardbred racehorses with naturally-occurring repetitive loading-induced osteoarthritis (OA). Two osteochondral cores were harvested from dorsal sites from each of 15 post-mortem C3 and classified as control or as showing early or advanced OA changes from visual inspection. We re-examined X-ray micro-computed tomography (µCT) image sets for the presence of high-density mineral infill (HDMI) in ACC cracks and possible high-density mineralized protrusions (HDMP) from the ACC mineralizing (tidemark) front (MF) into hyaline articular cartilage (HAC). We hypothesized and we show that 20-µm µCT resolution in 10-mm diameter samples is sufficient to detect HDMI and HDMP: these are lost upon tissue decalcification for routine paraffin wax histology owing to their predominant mineral content. The findings show that µCT is sufficient to discover HDMI and HDMP, which were seen in 2/10 controls, 6/9 early OA and 8/10 advanced OA cases. This is the first report of HDMI and HDMP in the equine carpus and in the Standardbred breed and the first to rely solely on µCT. HDMP are a candidate cause for mechanical tissue destruction in OA.     

Thermal stability of <Emphasis Type="Italic">Abies alba</Emphasis> wood according to its radial position and forest management

Most of the defects affecting heat-treated wood quality are often attributed to heterogeneous heat transfers in industrial kilns. Even if interspecific variability of wood has been reported to affect thermal degradation of the material, little has been reported on the effects of intraspecific variability. The aim of this work was to study the effect of intraspecific variability of silver fir (Abies alba Mill.) wood on its thermal degradation. For this purpose, wood samples were sampled along the radius of cross-sections to estimate the effect of radial position on wood thermal degradation. Sampling was carried out on discs of four trees, two resulting from dynamic growth stand and two from standard growth stand. The study was performed at different scales: at wood compartments scale involving juvenile and mature heartwood, transition zone between heartwood and sapwood and sapwood as well as at intra-ring scale. Wood samples were ground to sawdust and subjected to thermogravimetric analysis and chemical analysis. Juvenile heartwood was shown to be more sensitive to thermal degradation than other compartments. The thermal behavior of sapwood was not particularly different from that of heartwood, and the presence of extractives did not influence significantly thermal degradation. Earlywood was more sensitive to thermal degradation than latewood explaining the higher susceptibility of fast growing heartwood containing larger rings with higher contents of earlywood.     

Efficiency improvement for geothermal power generation to meet summer peak demand

Geothermal power is an important part of New Zealand's renewable electricity supply due to its attractive cost and reliability. Modular type binary cycle plants have been imported and installed in various geothermal fields in New Zealand, with plans for further expansion. Power output of these plants deteriorates in the summer because plant efficiency depends directly on the geothermal resource and the ambient temperature. As these plants normally use air-cooled condensers, incorporating a water-augmented air-cooled system could improve the power output in summer thereby matching the peak air-conditioning demand. In this work, power generation for the Rotokawa plant was characterized using a similar plant performance and local weather. The improved performance was modelled for retrofit with a wet-cooling system. Maximum generation increase on the hottest day could be 6.8%. The average gain in power over the summer, November–February, was 1.5%, and the average gain for the whole year was 1%. With current binary unit generation capacity at the Rotokawa plant of 35 MW, investment in a water-augmented air-cooled system could provide 2 MW of peak generation on the hottest days. This investment in efficiency is found to compare favourably to other supply options such as solar PV, wind or gas.     

Soot formation from a distillation cut of a Fischer–Tropsch diesel fuel: A shock tube study

The kinetics of soot formation from Fischer–Tropsch (FT) fuels was studied in a heated shock tube under homogeneous conditions. Soot induction delay time and soot yield were measured between 10 and 17 atm using a distillation cut at 403 K of a Fischer–Tropsch fuel diesel. Two fuel concentrations were investigated in pyrolysis: 0.2% and 0.4% FT in Ar. Equivalence ratios (Φ) = 18 and 5 were also investigated for the highest fuel concentration. During this study, a second growth of the soot volume fraction profile was observed with the highest fuel concentration in pyrolysis and at Φ = 18. It was shown that this second growth appears only at temperatures higher than the temperature at which the soot yield is maximum. Under the conditions investigated, the soot induction delay time was found not to be very sensitive to the fuel concentration. A careful analysis of the soot volume fraction profiles showed that this finding was linked to the measurement method usually adopted. Nevertheless, this method was found adequate for a systematic comparison between different fuels or for an investigation of the oxygen concentration effects. The addition of oxygen to the mixture promotes soot formation in its early stages by decreasing the soot induction delay time. A shift of the soot yield curve toward lower temperatures was also observed. Moreover, oxygen addition reduces the amount of soot produced. This reduction is proportional to the O₂ concentration. Comparisons with literature data showed that a Fischer–Tropsch fuel primarily composed of n-paraffins can be correctly represented by an n-paraffin with a molecular size comparable to the average molecular size of the Fischer–Tropsch fuel. The maximum soot yield of the Fischer–Tropsch distillation cut studied was not significantly different from that of a diesel fuel surrogate previously studied (Mathieu et al., Combust. Flame 156 (2009) 1576–1586).