Three-dimensional analysis of the spatial distribution of iron oxide particles in a decorative coating by electron microscopic imaging

The three-dimensional (3D) spatial structure of an iron oxide containing alkyd paint specimen has been investigated by serial block-face scanning electron microscopy (SBFSEM). The resultant images of the 3D structure clearly present the spatial distribution of the iron oxide pigment particles in the coating film and reveal the extent of aggregation of the particles in the matrix material. More than one-half of the iron oxide particles (in volume) had aggregated to form clusters of considerable sizes that follow a Gaussian spacing distribution in the measured coating film. Over 80% of the clusters have dimensions between 1.5 μm and 3.5 μm; also, pores are evident at the centres of clusters whose sizes are larger than 2 μm. The work demonstrated here reveals a new approach to fully characterize the 3D spatial structure of coatings and to explore their correlations with the performance of the materials.     

Towards the improvement of thermal efficiency in lignite‐fired power generation: Concerning the utilization of Polish lignite deposits in state‐of‐the‐art IGCC technology

Integrated coal Gasification Combined Cycle (IGCC) is the most advanced technology for coal‐fired power generation. The two‐stage entrained flow gasification process allows for the use of a wide range of coal, as long as the gasification temperature is above the ash melting point of a used fuel. In this gasification technology, lignite, which often has a low ash melting point, can be preferably utilized. However, ash fluidity is also another importance, because the behaviour of molten slag can diminish a stable ash discharge from a gasifier. As the eligibility of coal ash properties is a considerable factor, water physically and chemically kept in lignite (30 – 60% in mass) attributes to deteriorating gasification efficiency, because it causes significant heat loss and increasing oxygen consumption. Developing a thermal evaporative lignite drying method will be a necessary attempt to apply lignite to the coal gasification process. For those preceded objectives, coal and ash properties and drying characteristics of several grades of Polish lignite, extracted from Belchatow and Turow deposits, have been experimentally investigated in a preliminary study evaluating the applicability and consideration for its utilization in state‐of‐the‐art clean coal technology, IGCC. This paper particularly discusses the eligibility of Polish lignite from the perspective of the fusibility and fluidity of ash melts and the fundamental drying kinetics of lignite in superheated steam in the light of water removal. The viscosity of ash melts is measured at high temperature up to 1700 °C. In the drying tests, the significant influence of structural issues, because of the provenance and origin of lignite on the drying characteristics, was found by applying the method of sensitivity analysis of physical propensity. This paper concludes that the investigated Polish lignite has characteristics favourable for utilization in IGCC technology, once the precautions related to its high moisture have been carefully addressed. Copyright © 2016 John Wiley & Sons, Ltd.     

Enhanced catalytic activity of nanoshell carbon co-doped with boron and nitrogen in the oxygen reduction reaction

The use of carbon cathode catalysts in polymer electrolyte fuel cells instead of the current platinum catalysts is attracting increasing attention. We claim that two factors are important for enhancing the activity of carbon cathode catalysts in the oxygen reduction reaction (ORR): the formation of a nanoshell structure and co-doping with boron and nitrogen. Herein, we investigate the preparation and characterization of active ORR carbon catalysts that combine the above factors. Boron and nitrogen (BN)-doped nanoshell-containing carbon (BN-NSCC) was prepared by carbonizing a mixture of poly(furfuryl alcohol), cobalt phthalocyanine, melamine, and a trifluoroborane–methanol complex at 1000 °C. Transmission electron microscopy and X-ray photoelectron spectroscopy revealed the formation of nanoshell structures with distorted graphitic layers and the introduction of boron and nitrogen atoms, respectively. The ORR activity was evaluated in oxygen-saturated 0.5 mol dm^?3 H₂SO₄ using Koutecky–Levich analysis. The BN-NSCC showed an eight to ten times higher ORR activity than undoped NSCC, with an increased number of electrons participating in the reaction. Tafel analysis revealed a change in the rate-determining step caused by BN-doping. Thus, the combination of a nanoshell structure and co-doping with boron and nitrogen was found to improve the ORR activity of carbon catalysts.     

Grain Boundary Segregation Behavior of Boron in Low-Alloy Steel

The boron concentration profiles around prior austenite grain boundaries in Fe-0.05C-0.5Mo-0.001B (mass pct) are examined using aberration-corrected STEM-EELS. In order to obtain the precise distribution of boron around the boundaries, tilt series measurements with thin specimens (<30 nm) are performed and the EEL spectra are analyzed by principal component analysis (PCA) and multivariate curve resolution (MCR). The boron concentration profile changes with the cooling rate from the solid solution temperature. The concentration at grain boundaries is maximized at a medium rate (30 °C/s), where the concentration reaches 8 at. pct, and it decreases at a larger (250 °C/s) or smaller (5 °C/s) rate. On the other hand, the boron distribution becomes wider as the cooling rate becomes smaller. The current results suggest that the boron segregation in the alloy is formed by the “non-equilibrium segregation mechanism.”     

Modeling of quantitative relationships between physicochemical properties of active pharmaceutical ingredients and tensile strength of tablets using a boosted tree

Objectives: The aim of this study was to explore the potential of boosted tree (BT) to develop a correlation model between active pharmaceutical ingredient (API) characteristics and a tensile strength (TS) of tablets as critical quality attributes.

Methods: First, we evaluated 81 kinds of API characteristics, such as particle size distribution, bulk density, tapped density, Hausner ratio, moisture content, elastic recovery, molecular weight, and partition coefficient. Next, we prepared tablets containing 50% API, 49% microcrystalline cellulose, and 1% magnesium stearate using direct compression at 6, 8, and 10?kN, and measured TS. Then, we applied BT to our dataset to develop a correlation model. Finally, the constructed BT model was validated using k-fold cross-validation.

Results: Results showed that the BT model achieved high-performance statistics, whereas multiple regression analysis resulted in poor estimations. Sensitivity analysis of the BT model revealed that diameter of powder particles at the 10th percentile of the cumulative percentage size distribution was the most crucial factor for TS. In addition, the influences of moisture content, partition coefficients, and modal diameter were appreciably meaningful factors.

Conclusions: This study demonstrates that BT model could provide comprehensive understanding of the latent structure underlying APIs and TS of tablets.     

Interface control for resolved CFD-DEM with capillary interactions

In this work, a resolved CFD–DEM coupling model for the simulation of gas-liquid-solid flows is developed: the interface capturing method based on the colour function is employed for fluids (i.e. a gas and liquid) whilst Discrete Element Method (DEM) is used for particles. The Volume Penalisation (VP) method is adopted to consider the hydrodynamic interactions between fluids and particles along with the Immersed Free Surface (IFS) method, which artificially extends the gas-liquid interface into the interior of the particle to account for the wettability. The unique point of the proposed model is that the thickness of the gas-liquid interface can be controlled by using both interface compression and diffuse interface techniques simultaneously. From the simulation results, it is presented that the accurate evaluation of the surface tension force as well as the capillary force can be achieved by appropriately controlling the interface thickness. Moreover, the major two methods in the literature to calculate the capillary force are compared in this work. The validity of the proposed model is presented for both static and dynamic cases. The behaviour of two colliding particles with a dynamic liquid bridge is then simulated to demonstrate the applicability of the proposed model to a complex three-phase system.     

Local structure and photocatalytic property of sol–gel synthesized ZnO doped with transition metal oxides

ZnO nanoparticles doped with up to 5 at% of Co and Mn were prepared using a co-precipitation method. The location of dopant ions and the effect of doping on the photocatalytic activity were investigated. The crystal structure of nanoparticles and local atomic arrangements around dopant ions were analyzed by X-ray absorption spectroscopy. The results showed that the Co ions substituted the Zn ions in the ZnO wurtzite phase structure and induced lattice shrinkage, while Mn ions were not completely incorporated in the crystal lattice. The photocatalytic activity under simulated sunlight was characterized by the decomposition of Rhodamine B dye molecules. It was revealed that Co-doping strongly reduced the photocatalytic activity but Mn-doping showed a weaker effect on the reduction of the photoactivity.     

Antitermitic activity of extracts from Chamaecyparis obtusa branch heartwood

The antitermitic activity of extracts from the branch heartwood of Chamaecyparis obtusa (hinoki) against Japanese termites (Reticulitermes speratus) was compared with that of the trunk. Samples of branch and trunk heartwood were extracted with n-hexane, ethyl acetate, and methanol successively. n-Hexane extracts of branch and trunk heartwood were strongly antitermitic, and branch heartwood contained greater quantities of active n-hexane extracts than trunk heartwood. Germacra-1-(10), 5-dien-4β-ol, t-cadinol, α-cadinol, hinokiresinol, and hinokinin were separated from the branch extracts and the termiticidal and antifeedant activity of these compounds was tested by no-choice and dual-choice test methods. The sesquiterpenoids, germacra-1-(10), 5-dien-4β-ol, t-cadinol and α-cadinol were strongly termiticidal. The norlignan hinokiresinol and lignan hinokinin had weak termiticidal, and strong antifeedant and repellent activity. High concentrations of germacra-1-(10), 5-dien-4β-ol and hinokiresinol were present in branch heartwood. These compounds protect hinoki branches from termites and other harmful organisms. Hinoki branch heartwood, which is usually unused, is a potential source of active antitermitic compounds.