In situ characterisation for studying nucleation and growth of nanostructured materials and thin films during liquid-based synthesis

Knowledge about the nucleation, growth, and formation mechanisms during materials synthesis using sol-gel and solution-based methods is important to design a material with desired properties. We used aqueous chemical synthesis as an environmentally friendly and highly flexible route to tailored and reproducible synthesis of oxide nanomaterials and thin films. For studies of hydrothermal synthesis an in situ cell using synchrotron X-ray diffraction was used to investigate the formation mechanisms of SrxBa1-xNb2O6 piezoelectrics. Aqueous chemical solution deposition of phase pure oriented piezoelectric thin films demands strong control of processing parameters. An in situ cell for synchrotron X-ray diffraction studies of the annealing and crystallisation steps during aqueous chemical solution deposition was used to understand the nucleation and crystallisation of Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT). We discuss how the knowledge about nucleation and growth obtained by in situ characterisation can be used to design the optimal procedure for fabrication of oxide materials with desired properties

Electrical conductivity and thermopower of (1-x) BiFeO3 - xBi(0.5)K(0.5)TiO(3) (x=0.1, 0.2) ceramics near the ferroelectric to paraelectric phase transition

Ferroelectric BiFeO3 has attractive properties such as high strain and polarization, but a wide range of applications of bulk BiFeO3 are hindered due to high leakage currents and a high coercive electric field. Here, we report on the thermal behaviour of the electrical conductivity and thermopower of BiFeO3 substituted with 10 and 20 mol% Bi0.5K0.5TiO3. A change from p-type to n-type conductivity in these semi-conducting materials was demonstrated by the change in the sign of the Seebeck coefficient and the change in the slope of the isothermal conductivity versus partial pressure of O. A minimum in the isothermal conductivity was observed at ~10−2 bar O2 partial pressure for both solid solutions. The strong dependence of the conductivity on the partial pressure of O2 was rationalized by a point defect model describing qualitatively the conductivity involving oxidation/reduction of Fe3+, the dominating oxidation state of Fe in stoichiometric BiFeO3. The ferroelectric to paraelectric phase transition of 80 and 90 mol% BiFeO3 was observed at 648 ± 15 and 723 ± 15 °C respectively by differential thermal analysis and confirmed by dielectric spectroscopy and high temperature powder X-ray diffraction.Author preprin

The Formation and Disintegration of Rafts from Different Aluminas and Fines

Raft formation is a frequently encountered problem during alumina feeding in the Hall-Héroult-process and will delay alumina from being dissolved into the melt. The mechanisms for the formation and disintegration of rafts are however not thoroughly understood yet. The current study investigates the dissolution behavior and raft structure from three different types of secondary alumina in a lab cell, with a particular attention to effect of fines, and involves both sampling of rafts and video recordings of the feeding. The mass loss rate was calculated to vary between −1.57 and −0.42 g min−1 for regular bulk alumina, and −1.15 and −0.06 g min−1 for fines. Rafts created from bulk alumina were flat with a distinct bulge or crater placed in the center of it, while rafts created from fines had a pellet-shaped structure and traces of undissolved alumina in the middle. The observed structure is due to the initial spreading of powder, confirmed by video recordings.publishedVersio

A continuous multiphase model for liquid metal batteries

Liquid metal batteries (LMBs) are a promising alternative for large-scale stationary energy storage for renewable applications. Using high-abundance electrode materials such as Sodium and Zinc is highly desirable due to their low cost and excellent cell potential. LMBs undergo multiple complex mass transport dynamics and as a result, their operation limits and other critical parameters are not fully understood yet. In this work, a multiphase numerical model was developed to resolve electrode and electrolyte components in 1D and simulate the discharge process of a Na-Zn battery including the interfacial displacement of the molten metal electrodes. The variation in electrolyte composition was predicted throughout the process, including the species distribution and its effect on the cell conductivity and capacity. Volume change and species redistribution were found to be important in predicting the maximum theoretical capacity of the cell when neglecting convective phenomena

Influence of Atmosphere and Temperature on Polycyclic Aromatic Hydrocarbon Emissions from Green Anode Paste Baking

Coal tar pitch, a well-known source of polycyclic aromatic hydrocarbons (PAHs), is used as a binder of petroleum coke in prebaked anodes used for electrolysis of aluminum. Anodes are baked up to 1100 °C over a 20-day period, where flue gas containing PAHs and volatile organic compounds (VOCs) are treated using techniques such as regenerative thermal oxidation, quenching, and washing. Conditions during baking facilitate incomplete combustion of PAHs, and due to the various structures and properties of PAHs, the effect of temperature up to 750 °C and various atmospheres during pyrolysis and combustion were tested. PAH emissions from green anode paste (GAP) dominate in the temperature interval of 251–500 °C, where PAH species of 4–6 rings make up the majority of the emission profile. During pyrolysis in argon atmosphere, a total of 1645 μg EPA-16 PAHs are emitted per gram of GAP. Adding 5 and 10% CO2 to the inert atmosphere does not seem to affect the PAH emission level significantly, at 1547 and 1666 μg/g, respectively. When adding oxygen, concentrations decreased to 569 μg/g and 417 μg/g for 5% and 10% O2, respectively, corresponding to a 65% and 75% decrease in emission.publishedVersio

A Study of Bubble Behavior and Anode Effect on the Graphite and Industrial Carbon Anode in a See-Through Furnace During Aluminium Electrolysis

Anode gas bubble behavior and anode effect on graphite and industrial carbon rod-shaped anode in a cryolite melt have been studied using a see-through furnace. The different carbon materials have different properties which can affect bubble behavior and electrochemical properties. Industrial carbon is more inhomogeneous with respect to structure, pore, aggregates and impurities in comparison to the graphite. More bubbles were nucleated on the industrial carbon than on the graphite for the same current density. The time related to the coalescence process for both anodes was found to be in interval 16 to 24 ms and independent of the current densities. Bubbles detached from the horizontal surface of the anode have similar average diameter value for both anodes for current densities 1.0 A cm−2, the average diameter is lower for the industrial carbon anode. The onset of the anode effect occurred faster on the graphite than on the industrial anode. The PFC-containing gas layer appeared to be thicker and more stable on the graphite anode than on the industrial carbon anode.publishedVersio

STEM-EDS of Inception Sites of Vented Trees in a HV XLPE Subsea Cable

High voltage XLPE cable cores have been subjected to wet ageing following the recommendations in CIGRE TB 722. The electrical ageing was performed at 500 Hz and 10 kV/mm. Vented water trees were detected initiating and growing from the semi-conductive screens. The inception sites of the trees were cut by cryo-microtomy and studied using scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM-EDS). Inorganic impurities were detected on both sides of the smooth XLPE-semiconductive screen interface close to the inception site. KEYWORDS High voltage XLPE cables, Vented water trees, STEM-EDS, Inception siteSTEM-EDS of Inception Sites of Vented Trees in a HV XLPE Subsea CablepublishedVersio

Design of multi-luminescent silica-based nanoparticles for the detection of liquid organic compounds

Tracer testing in reservoir formations is utilised to determine residual oil saturation as part of optimum hydrocarbon production. Here, we present a novel detection method of liquid organic compounds by monodisperse SiO2 nanoparticles (NPs) containing two luminophores, a EuIII:EDTA complex and a newly synthesised fluorophore based on the organic boron-dipyrromethene (BODIPY)-moiety. The particles exhibited stable EuIII PL emission intensity with a long lifetime in aqueous dispersion. The fluorescence of the BODIPY was also preserved in the aqueous environment. The ratiometric PL detection technique was demonstrated by using toluene and 1-octanol as model compounds of crude oil. The optimal synthesis conditions were found to give NPs with a diameter of ~100 nm, which is suitable for transport through porous oil reservoir structures. The cytotoxicity of the NPs was confirmed to be very low for human lung cell and fish cell lines. These findings demonstrate the potential of the NPs to replace the hazardous chemicals used to estimate the residual oil saturation. Moreover, the ratiometric PL detection technique is anticipated to be of benefit in other fields, such as biotechnology, medical diagnostics, and environmental monitoring, where a reliable and safe detection of a liquid organic phase is needed.Design of multi-luminescent silica-based nanoparticles for the detection of liquid organic compoundspublishedVersio