Good dielectric performance and broadband dielectric polarization in Ag,Nb co-doped TiO2

Due to the demand of miniaturization and integration for ceramic capacitors in electronic components market, TiO₂-based ceramics with colossal permittivity has become a research hotspot in recent years. In this work, we report that Ag⁺/Nb⁵⁺ co-doped (Ag_1/4Nb_3/4)_xTi_1−xO₂ (ANTOx) ceramics with colossal permittivity over a wide frequency and temperature range were successfully prepared by a traditional solid–state method. Notably, compositions of ANTO0.005 and ANTO0.01 respectively exhibit both low dielectric loss (0.040 and 0.050 at 1 kHz), high dielectric permittivity (9.2 × 10³ and 1.6 × 10⁴ at 1 kHz), and good thermal stability, which satisfy the requirements for the temperature range of application of X9R and X8R ceramic capacitors, respectively. The origin of the dielectric behavior was attributed to five dielectric relaxation phenomena, i.e., localized carriers' hopping, electron–pinned defect–dipoles, interfacial polarization, and oxygen vacancies ionization and diffusion, as suggested by dielectric temperature spectra and valence state analysis via XPS; wherein, electron-pinned defect–dipoles and internal barrier layer capacitance are believed to be the main causes for the giant dielectric permittivity in ANTOx ceramics.     

Effect of micro-cracks on the in-plane electronic conductivity of proton exchange membrane fuel cell catalyst layers based on lattice Boltzmann method

Micro-cracks commonly occur on the catalyst layers (CLs) during the manufacturing of catalyst coated membranes (CCMs). However, the crack shape parameters effect on CLs in-plane (IP) electronic conductivity λ_s is not clear. In this work, the relationship between crack parameters and the λ_s is obtained based on the two-dimensional (2D) multiple-relaxation time (MRT) lattice Boltzmann method (LBM). The LBM numerical model is validated by the normalized λ_s experiment applied on three different home-made cracked CLs, and the parameter study focus on crack width, length, quantity and phase angle are carried out. The results show that the decrease of λ_s has different sensitivity |k| to the parameters above. The crack width has little effect on λ_s decrease, and the |k_w| is 0.038. However, crack arm length and quantity show more significant impact, which |k_l| and |k_N| are 0.753 and 0.725, respectively. The CLs with different crack propagation directions show significant anisotropy on λ_s, and a 53.53% decrease in λ_s is observed between 0° and 90° crack phase angle change. To manufacture a high electronic conductivity CL, crack initiation and migration mitigation are highly encouraged.     

SLM printing of cermet powders: Inhomogeneity from atomic scale to microstructure

It is very challenging for 3D printing based on the selective laser melting (SLM) technology to obtain cermet bulk materials with high density and homogeneous microstructures. In this work, the SLM process of the cermet powders was studied by both simulations and experiments using the WC-Co cemented carbides as an example. The results indicated that the evolution of the ceramic and metallic phases in the cermet particle during the heating, melting and solidification processes were all significantly inhomogeneous from atomic scale to mesoscale microstructures. As a consequence, the microstructural defects were caused intrinsically in the printed bulk material. The formation and growth of the bonding necks between the particles were mainly completed at the later stage of laser heating and the early stage of solidification. Both simulations and experiments demonstrated that thin amorphous layers formed at the ceramics/metal interfaces. This work disclosed the mechanisms for the evolution from the atomic scale to microstructure during the SLM printing of cermet powders, and discovered the origin of the defects in the printed cermet bulk materials.     

Prediction of Chameleonic Efficiency

Chameleonic properties, i. e., the capacity of a molecule to hide polarity in non-polar environments and expose it in water, help achieving sufficient permeability and solubility for drug molecules with high MW. We present models of experimental measures of polarity for a set of 24 FDA approved drugs (MW 405-1113) and one PROTAC (MW 1034). Conformational ensembles in aqueous and non-polar environments were generated using molecular dynamics. A linear regression model that predicts chromatographic apparent polarity (EPSA) with a mean unsigned error of 10 Ų was derived based on separate terms for donor, acceptor, and total molecular SASA. A good correlation (R²=0.92) with an experimental measure of hydrogen bond donor potential, Δlog P_oct-tol, was found for the mean hydrogen bond donor SASA of the conformational ensemble scaled with Abraham's A hydrogen bond acidity. Two quantitative measures of chameleonic behaviour, the chameleonic efficiency indices, are introduced. We envision that the methods presented herein will be useful to triage designed molecules and prioritize those with the best chance of achieving acceptable permeability and solubility.     

Study on ice-melting performance of gradient gas diffusion layer in proton exchange membrane fuel cell

In this study, a three-dimensional model was established using the lattice Boltzmann method (LBM) to study the internal ice melting process of the gas diffusion layer (GDL) of the proton exchange membrane fuel cell (PEMFC). The single-point second-order curved boundary condition was adopted. The effects of GDL carbon fiber number, growth slope of the number of carbon fibers and carbon fiber diameter on ice melting were studied. The results were revealed that the temperature in the middle and lower part of the gradient distribution GDL is significantly higher than that of the no-gradient GDL. With the increase of the growth slope of the number of carbon fiber, the temperature and melting rate gradually increase, and the position of the solid-liquid interface gradually decreases. The decrease in the number of carbon fibers has a similar effect as the increase in the growth slope of the number of carbon fibers. In addition, as the diameter of the carbon fiber increases, the position of the solid-liquid interface gradually decreases first and then increases.     

Interfacial microstructure and mechanical properties of Ti3SiC2 ceramic and TC11 alloy joint diffusion bonded with a Cu interlayer

Reliable joints of Ti₃SiC₂ ceramic and TC11 alloy were diffusion bonded with a 50 μm thick Cu interlayer. The typical interfacial structure of the diffusion boned joint, which was dependent on the interdiffusion and chemical reactions between Al, Si and Ti atoms from the base materials and Cu interlayer, was TC11/α-Ti + β-Ti + Ti₂Cu + TiCu/Ti₅Si₄ + TiSiCu/Cu(s, s)/Ti₃SiC₂. The influence of bonding temperature and time on the interfacial structure and mechanical properties of Ti₃SiC₂/Cu/TC11 joint was analyzed. With the increase of bonding temperature and time, the joint shear strength was gradually increased due to enhanced atomic diffusion. However, the thickness of Ti₅Si₄ and TiSiCu layers with high microhardness increased for a long holding time, resulting in the reduction of bonding strength. The maximum shear strength of 251 ± 6 MPa was obtained for the joint diffusion bonded at 850 °C for 60 min, and fracture primarily occurred at the diffusion layer adjacent to the Ti₃SiC₂ substrate. This work provided an economical and convenient solution for broadening the engineering application of Ti₃SiC₂ ceramic.     

Analysis of surface and interior degradation of gas diffusion layer with accelerated stress tests for polymer electrolyte membrane fuel cell

The effects of surface and interior degradation of the gas diffusion layer (GDL) on the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) have been investigated using three freeze-thaw accelerated stress tests (ASTs). Three ASTs (ex-situ, in-situ, and new methods) are designed from freezing ?30 °C to thawing 80 °C by immersing, supplying, and bubbling, respectively. The ex-situ method is designed for surface degradation of the GDL. Change of surface morphology from hydrophobic to hydrophilic by surface degradation of GDL causes low capillary pressure which decreased PEMFC performance. The in-situ method is designed for the interior degradation of the GDL. A decrease in the ratio of the porosity to tortuosity by interior degradation of the GDL deteriorates PEMFC performance. Moreover, the new method showed combined effects for both surface and interior degradation of the GDL. It was identified that the main factor that deteriorated the fuel cell performance was the increase in mass transport resistance by interior degradation of GDL. In conclusion, this study aims to investigate the causes of degraded GDL on the PEMFC performance into the surface and interior degradation and provide the design guideline of high-durability GDL for the PEMFC.     

Symmetric and asymmetric membranes based on La0.5Sr0.5Fe0.7Ga0.3O3-δ perovskite with high oxygen semipermeation flux performances and identification of the rate-determining step of oxygen transport

This work focuses on identifying the rate-determining step of oxygen transport through La_0.5Sr_0.5Fe_0.7Ga_0.3O_3-δ membranes with symmetric and asymmetric architectures. The best oxygen semipermeation fluxes are 3.4 10⁻³ mol. m^-2.s^-1 and 6.3 10⁻³ mol. m^-2.s^-1 at 900 °C for the symmetric membrane and asymmetric membrane with a modified surface. The asymmetric membrane with a modified surface leads to an increase of approximately 7 times the oxygen flux compared to that obtained with the La_0.5Sr_0.5Fe_0.7Ga_0.3O_3-δ dense membrane without surface modification. This work also shows that the oxygen flux is mainly governed by gaseous oxygen diffusion through the porous support of asymmetric La_0.5Sr_0.5Fe_0.7Ga_0.3O_3-δ membranes.     

Metal chlorides-promoted ammonia absorption of deep eutectic solvent

Ammonia is considered as a promising hydrogen or energy carrier. Ammonia absorption or adsorption is an important aspect for both ammonia removal, storage and separation applications. To these ends, a wide range of solid and liquid sorbents have been investigated. Among these, the deep eutectic solvent (DES) is emerging as a promising class of ammonia absorbers. Herein, we report a novel type of DES, i.e., metal-containing DESs for ammonia absorption. Specifically, the NH₃ absorption capacity is enhanced by ca. 18.1–36.9% when a small amount of metal chlorides, such as MgCl₂, MnCl₂ etc., are added into a DES composed of resorcinol (Res) and ethylene glycol (EG). To our knowledge, the MgCl₂/Res/EG (0.1:1:2) DES outperforms most of the reported DESs. The excellent NH₃ absorption performances of metal–containing DESs have been attributed to the synergy of Lewis acid–base and hydrogen bonding interactions. Additionally, good reversibility and high NH₃/CO₂ selectivity are achieved over the MgCl₂/Res/EG (0.1:1:2) DES, which enables it to be a potential NH₃ absorber for further investigations.