Single chamber Solid Oxide Fuel Cells selective electrodes: A real chance with brownmillerite-based nanocomposites

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca₂FeAl_0.95Mg_0.05O₅) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA + FeO_x/CGO/CFA + FeO_x) and complete cells (CFA + FeO_x/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeO_x is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated.     

Reversible formation-melting of nano-crystals in supercooled oxyfluoride germanate liquids

The nanocrystals play a critical role in generating and affecting functionalities of glass materials. Therefore, scientists have made considerable efforts in clarifying microscopic mechanisms of nanocrystal formation in glass to obtain the desired type of nanocrystals. However, the phase transitions of nanocrystals during heating have not been well understood. Here we report on a discovery of the reversible melting-formation of nanocrystals in an oxyfluoride germanate glass during heating-cooling circles. Using a differential scanning calorimetry (DSC), we detected a striking endothermic event at 925 K during heating, after the glass underwent a DSC upscan to a temperature between 925–986 K and subsequent cooling. Based on Raman spectroscopy, X-ray diffraction and transmission electron microscopy, the endotherm is attributed to the melting of nano-crystal BaGeF₆ (˜20 nm). An exothermal response was observed at 890 K during the DSC downscan, implying the re-formation of BaGeF₆ nano-crystals. This suggests that the melting-formation of BaGeF₆ nano-crystals is a typical first-order transition.     

Additive manufacturing of bipolar plates for hydrogen production in proton exchange membrane water electrolysis cells

Water electrolysis is a process that can produce hydrogen in a clean way when renewable energy sources are used. This allows managing large renewable surpluses and transferring this energy to other sectors, such as industry or transport. Among the electrolytic technologies to produce hydrogen, proton exchange membrane (PEM) electrolysis is a promising alternative. One of the main components of PEM electrolysis cells are the bipolar plates, which are machined with a series of flow distribution channels, largely responsible for their performance and durability. In this work, AISI 316L stainless steel bipolar plates have been built by additive manufacturing (AM), using laser powder bed fusion (PBF-L) technology. These bipolar plates were subjected to ex-situ corrosion tests and assembled in an electrolysis cell to evaluate the polarization curve. Furthermore, the obtained results were compared with bipolar plates manufactured by conventional machining processes (MEC). The obtained experimental results are very similar for both manufacturing methods. This demonstrates the viability of the PBF-L technology to produce metal bipolar plates for PEM electrolyzers and opens the possibilities to design new and more complex flow distribution channels and to test these designs in initial phases before scaling them to larger surfaces.     

Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

Direct additive manufacturing of melt growth Al2O3-ZrO2 functionally graded ceramics by laser directed energy deposition

Functionally graded ceramics (FGC), which combine properties of different ceramics in one part, usually have better comprehensive function and structural efficiency. In this study, four different gradient transition Al₂O₃-ZrO₂ FGC samples were prepared by laser directed energy deposition (LDED) method. The results show that there is an obvious interface in direct transition sample. The transition section bears tensile stress caused by difference of thermophysical properties of materials, resulting in significant longitudinal cracks. Element transition in interface region shows a step sharp transition. The direct transition sample shows intergranular fracture and the bonding strength is very low. Gradient transition mode can effectively suppress cracks, and avoid the step transition of microstructure and elements. Elements, microhardness of 25, 20 wt% FGC samples realized a nearly linear smooth transition. The interface fracture of FGC samples changed to transgranular fracture, bonding strength was significantly improved, and the maximum flexural strength reached 160.19 MPa.     

Improved Corrosion Resistance of Selective Laser Melted Ti–5Cu Alloy Using Atomized Ti–5Cu Powder

The different types of metal powder used for selective laser melting(SLM) process would cause distinct corrosion behavior due to the uniformity of the obtained microstructure.The SLM-produced Ti–5Cu alloy using atomized Ti–5Cu metal powder(SLMed Ti–5Cu) in this work reveals a relatively uniform microstructure with overwhelming acicular α/α′ phase and shows great advantages on corrosion resistance compared with the SLM-produced Ti–5Cu alloy using the mixture powder(SLMedM Ti–5Cu).The effect of the micro-galvanic cells decreases due to the undetectable Ti_2Cu phase in the microstructure of the SLMed Ti–5Cu.An apparent passivation behavior was observed for SLMed Ti–5Cu instead of severe pitting phenomenon for the SLMed-M Ti–5Cu.The charge transfer resistance of SLMed Ti–5Cu in this work is 10.09 ± 2.63 MΩ cm~2, which is significantly higher than that of SLMed-M Ti–5Cu(4.76 MΩ cm~2).The above result indicates the atomized Ti–5Cu powder plays an important role in the formation of the uniform microstructure of SLMed product, thereby enhancing its corrosion resistance in Hank's solution at 37 ℃.     

Numerical investigation of gelled crude oil particle melting in water for hydrogen production

This paper describes a numerical analysis of the melting process of gelled crude oil in water for hydrogen production. The melting characteristics of crude oil particles are analyzed, and the influence of flow velocity, particle radius, and hot water temperature on the melting process is discussed. The results indicate that the melting rate on the surface of the crude oil is different, the oil particles do not melt concentrically, and the monitoring points and rate of increase in temperature are not substantially affected by the phase change interval. The flow rate and particle radius are found to have a significant influence on the phase distribution of the oil droplets, but changes in water temperature have little effect. After validating a model of the melting process, we investigate the influence of oil particle size, water temperature, flow rate, and oil temperature. It is found that increases in water temperature and flow rate, or a decrease in oil particle size, tend to reduce the melting time.     

Selective Hydrogenation of Biomass-Derived Succinic Acid: Reaction Network and Kinetics

The conversion of bio-based succinic acid (SA) to the value-added chemicals 1,4-butanediol (BDO), γ-butyrolactone (GBL), and tetrahydrofuran (THF) can replace the corresponding petrochemical production routes to achieve a sustainable process. The reaction network for aqueous-phase catalytic hydrogenation of succinic acid over a supported Re-Pd catalyst was identified and the reaction kinetics was determined. With the developed kinetic model, the composition of the product mixture regarding the desired products (BDO, GBL, THF) can be described as a function of educt concentration, temperature, and pressure. The maximum BDO yield was achieved at high pressure and low temperature, while low pressure and high temperature favored GBL and THF production.     

Analysis of acoustic Doppler current profiler mean velocity measurements in shallow flows

Acoustic Doppler current profilers (ADCPs) are commonly used instruments for measurement of natural streamflow and flow in manmade channels. Velocities measured in a profile by the instrument are used to estimate the discharge in a channel. A Teledyne RD Instruments StreamPro ADCP was used to measure the mean velocity simultaneously with a laser Doppler anemometer (LDA) in a laboratory flume. An average of 3.9% under-prediction of the mean velocity measured by the ADCP occurred when compared to the measurements of the LDA. Moreover, this study shows that the sampling duration of the measurements significantly impacts the mean point velocities measured by up to 50%.     

Effects of graphite nano-flakes on thermal and microstructural properties of TiB2–SiC composites

In the last decades, the production of ultra-high temperature composites with improved thermo-mechanical properties has attracted much attention. This study focuses on the effect of graphite nano-flakes addition on the microstructure, densification, and thermal characteristics of TiB₂–25 vol% SiC composite. The samples were manufactured through spark plasma sintering process under the sintering conditions of 1800 °C/7 min/40 MPa. Scanning electron microscopy images demonstrated a homogenous dispersion of graphite flakes within the TiB₂–SiC composite causing a betterment in the densification process. The thermal diffusivity of the specimens was gained via the laser flash technique. The addition of graphite nano-flakes as a dopant in TiB₂–SiC did not change the thermal diffusivity. Consequently, the remarkable thermal conductivity of TiB₂–SiC remained intact. It seems that the finer grains and more interfaces obstruct the heat flow in TiB₂–SiC–graphite composites. Adding a small amount of graphite nano-flakes enhances the densification of the mentioned composite by preventing the grain growth.