Water vapor volatilization and oxidation induced surface cracking of environmental barrier coating systems: A numerical approach

A numerical model is developed for surface crack propagation in brittle ceramic coatings, aiming at the intrinsic failure of rare-earth silicate environmental barrier coating systems (EBCs) under combustion conditions in advanced gas turbines. The main features of progressive degradation of EBCs in such conditions are captured, including selective silica vaporization in the top coat due to exposure to water vapor, diffusion path-dependent bond coat oxidation, as well as crack propagation during cyclic thermal loading. In light of these features, user-defined subroutines are implemented in finite element analysis, where surface crack growth is simulated by node separation. Numerical results are validated by existing experimental data, in terms of monosilicate layer thickening, thermal oxide growth, and fracture behaviors. The experimentally observed quasi-linear oxidation in the early stage is also elucidated. Furthermore, it is suggested that surface crack undergoes rapid propagation in the late stage of extended thermal cycling in water vapor and leads to catastrophic failure, driven by both thermal mismatch and oxide growth stresses. The latter is identified as the dominant mechanism of penetration. Based on detailed analyses of failure mechanisms, the optimization strategy of EBCs composition is proposed, balancing the trade-off between mechanical compliance and erosion resistance.     

Methanol Synthesis with Steel Mill Gases: Performance Investigations in an On-Site Technical Center

An on-site laboratory with direct access to cleaned and conditioned steel mill gases was recently put into operation. The long-term performance and stability of Clariant's MegaMax®800 methanol synthesis catalyst utilizing steel mill gases is currently being investigated. First test results revealed that in order to investigate deactivation mechanisms arising from particular properties of the cleaned steel mill gases, the overlaying effect of thermal deactivation of the catalyst has to be minimized.     

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.     

Sputtered Fe1·5CoNi0.5 coating: An improved protective coating for SOFC interconnect applications

In an attempt to optimize the properties of FeCoNi coating for planar solid oxide fuel cell (SOFC) interconnect application, the coating composition is modified by increasing the ratio of Fe/Ni. An Fe_1·5CoNi_0.5 (Fe:Co:Ni = 1.5:1:0.5, atomic ratio) metallic coating is fabricated on SUS 430 stainless steel by magnetron sputtering, followed by oxidation in air at 800°C. The Fe_1·5CoNi_0.5 coating is thermally converted to (Fe,Co,Ni)₃O₄ and (Fe,Co,Mn,Ni)₃O₄ without (Ni,Co)O particles. After oxidation for 1680 h, no further migration of Cr is detected in the thermally converted coating region. A low oxidation rate of 5.9 × 10^?14 g² cm^?4 s^?1 and area specific resistance of 12.64 mΩ·cm² is obtained for Fe_1·5CoNi_0.5 coated steels.     

Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Performance enhancement of methanol reforming reactor through finned surfaces and diffused entry for on-board hydrogen generation

Hydrogen-rich combustion in engines helps in reducing pollutants significantly. But hydrogen usage on a moving vehicle is not getting large-scale user acceptance mainly due to its poor energy storage density resulting in shorter driving ranges. This storage issue led to the hunt for mediums that can efficiently produce on-board hydrogen. Methanol proves to be an efficient alcohol fuel for producing hydrogen through steam reforming reaction. The heat energy required for such endothermic reaction is obtained through exhaust engine waste energy and this process is collectively known as thermochemical recuperation. However, the conventional reactor used for this process faces a lot of problems in terms of efficiency and methanol conversion. In this study, an attempt has been made to improve the design of the reactor for on-board hydrogen generation using engine exhaust heat for addressing the challenges related to performance and hydrogen yield. For enhancing the heat transfer, a finned surface (straight & wavy) was introduced in the reactor which resulted in an increment in methanol conversion significantly. It was found that wavy fin improved the methanol conversion up to 96.8% at an exhaust inlet temperature of 673 K. Also, a diffusing inlet section was introduced to increase the residence time of reactant gases while passing through the catalyst zone. Under given inlet conditions, the methanol conversion for 6° diffuse inlet reactor goes up to 87.9% as compared to 75.4% for the conventional reactor.     

Proton exchange membrane from the blend of poly(vinylidene fluoride) and functional copolymer: Preparation,proton conductivity,methanol permeability,and stability

A polymer electrolyte membrane is considered as the heart of fuel cells. Here we report the preparation of proton exchange membranes (PEMs) of poly (vinylidene fluoride) (PVDF) blend poly (methyl methacrylate)-co-poly (sodium-4-styrene sulfonate) (PMMA-co-PSSNa) by solvent evaporation method. Three different types of PEMs have been prepared by using different ratios of PVDF and PMMA-co-PSSNa copolymer. We have investigated the effect of concentration of PVDF on water uptake, ion exchange capacity, mechanical, thermal, and oxidative stability, proton conductivity (K^m), and methanol permeability (P_M) of the blend membranes. These blend PEMs showed good physicochemical and electrochemical properties along with thermal and oxidative stability. The membrane prepared from PVDF (45% w/w) to PMMA-co-PSSNa (55% w/w) exhibited optimum P_M at room temperature (8.38 × 10^?7 cm²s^?1). This low fuel crossover and high relative selectivity can make our prepared blend membranes a potential candidate in polymer electrolyte membrane fuel cells (PEMFCs) or direct methanol fuel cells (DMFCs).     

Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Reasonable construction of proton conducting channel via biomimetic caterpillar-like alumina fiber to improve the properties of its composite proton exchange membrane

In this paper, we prepare a novel biomimetic caterpillar-like alumina fiber with the characteristic of continuous alumina backbone and fine needle whiskers spine. Then the high-performance caterpillar-like alumina fiber composite proton exchange membrane (CAPEM) is obtained by introducing the amino modified biomimetic caterpillar-like alumina fiber into sulfonated polysulfone (SPSF) matrix, which successfully reasonable construction of the proton conducting channels in both vertical and horizontal orientation. The properties of CAPEM, including proton conductivity, methanol permeability, etc. Are systematically studied. The results show that the proton conductivity of CAPEM increases with rising the temperature, which reaches the maximum of 0.263 S/cm at 80 °C and 100% RH, respectively. The excellent proton conductivity of CAPEM is attributed to the long-range continuous proton conducting channel formed by the horizontal continuous alumina skeleton in the in-plane direction and the vertical overlapped fine needle whiskers spine in the through-plane direction. In addition, the interfacial compatibility between amino modified caterpillar-like alumina fiber and SPSF matrix is enhanced through the reasonable construction of proton conducting channels, which effectively inhibits the methanol permeation of the composite membrane with 4.18 × 10^?7 cm² s^?1 and improves the comprehensive performance of the CAPEM.     

High H2 selectivity with low coke formation for methanol steam reforming over Cu/Y1.5Ce0.84Ru0.04O4 catalyst in a microchannel plate reactor

The synthesized novel metal oxides Y_xCe_yRu_zO₄ (x = 1.5, y = 0.84, z = 0.04) which was produced by the sol-gel method was used as a support for Cu active metal on the surface of a microchannel plate reactor in the methanol steam reforming (MSR) process. The prepared catalysts were characterized by X-ray powder diffraction (XRD), BET surface area analysis (S_BET), energy-dispersive X-ray analysis (EDX), field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), temperature-programmed desorption (NH₃-TPD), and temperature-programmed reduction (H₂-TPR). High methanol conversion (99.5%) and H₂ selectivity (98.7%) and low CO selectivity (1.4%) were achieved for Cu/Y_xCe_yRu_zO₄ coated microchannel reactor at 250 °C. FE-SEM images and TGA curve of the spent catalyst displayed no coke formation on the surface of the catalyst after 32 h on stream at 300 °C. The low reduction temperature of Cu, high BET surface area, and high pore volume of the catalyst are considered imperative factors that cause a better dispersion of copper on the Y_1.5Ce_0.84Ru_0.04O₄ support.