Phase-transition induced optimization of electrostrain,electrocaloric refrigeration and energy storage of LiNbO3 doped BNT-BT ceramics

((Bi_0.5Na_0.5TiO₃)_0.88-(BaTiO₃)_0.12)_(1-x)-(LiNbO₃)_x (x = 0.0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, and 0.07; abbreviated as LiNbO₃-doped BNT-BT) ceramics possessing many excellent performances (large electrostrain, negative electrocaloric effect and energy storage density with high efficiency) was fabricated by the conventional solid-state reaction method. A large electrostrain (maximum ~ 0.34% at 100 kV/cm and room temperature) with high thermal stability over a broad temperature range (~80 K) is obtained at x = 0.03. A large energy storage density (maximum W_energy ~ 0.665 J/cm³ at 100 kV/cm and room temperature) with a high efficiency (η ~ 49.3%) is achieved at x = 0.06. Moreover, a large negative electrocaloric (EC) effect (maximum ΔT ~ 1.71 K with ΔS ~ - 0.22 J/(K kg) at 70 kV/cm)) is also obtained at x = 0.04. Phase transition (from ferroelectric to antiferroelectric and then to relaxor) induced by increasing the doping amount of LiNbO₃ plays a very key role on the optimization of these performances. These findings and breakthroughs make the LiNbO₃-doped BNT-BT ceramics very promising candidates as multifunctional materials.     

Experimental evaluation of MPC-based anti-surge and process control for electric driven centrifugal gas compressors

The present work concerns model predictive control (MPC) of centrifugal gas compressors and describes the development of an MPC application for the tasks of anti-surge and process control. More specifically, the MPC formulation focuses on the question of how the transient manipulation of driver torque can be used to improve the performance of anti-surge and process control. For the purpose of testing and validating the proposed control algorithm, an experimental compressor test rig is presented, which is designed to mimic a typical centrifugal compressor application in the oil and gas industry. Modeling and parameter identification of the experimental setup is followed by the realization of the MPC solution on an embedded system to comply with the stringent real-time requirements for anti-surge control. Testing is performed with experiments using suction and discharge side disturbances, which are created by rapid valve closures. For comparison the same tests are repeated with conventional control approaches. The test results indicate improvements in maintaining the distance to surge by up to 11%, while at the same time reducing the process control settling time by up to 50%.     

Microstructural characterization and high cycle fatigue behavior of investment cast A357 aluminum alloy

In order to observe the influence of strontium (Sr) modification and hot isostatic pressing (HIP) on an aluminum–silicon cast alloy A357 (AlSi7Mg0.6), the microstructure and the high cycle fatigue behavior of three batches of materials produced by investment casting (IC) were studied. The parts were produced by an advanced IC proprietary process. The main process innovation is to increase the solidification and cooling rate by immersing the mold in cool liquid. Its advantage is to produce finer microstructures. Microstructural characterization showed a dendrite arm spacing (DAS) refinement of 40% when compared with the same part produced by conventional investment casting. Fatigue tests were conducted on hourglass specimens heat treated to T6, under a stress ratio of R = 0.1 and a frequency of 25 Hz. One batch of material was unmodified but two batches were modified with 0.007% and 0.013% Sr addition, from which one batch was submitted to HIP after casting. Results reported in S–N diagrams show that the addition of Sr and the HIP process improve the 10⁶ cycles fatigue strength by 9% and 34% respectively. Scanning electron microscopy (SEM) observation of the fracture surfaces showed a variety of crack initiation mechanisms. In the unmodified alloy, decohesion between the coarse Si particles and the aluminum matrix was mostly observed. On the other hand, in the modified but non HIP-ed alloy, cracks initiated from pores. When the same alloy was subjected to HIP, a competition between crystallographic crack initiations (at persistent slip bands) and decohesion/failure of intermetallic phases was observed. When compared to fatigue strength reported for components produced by permanent mold casting, the studied material are more resistant to fatigue even in the unmodified and non HIP-ed states.     

Low temperature synthesis of plate-like Na0.5Bi0.5TiO3 via molten salt method

In this study, plate-like Na_0.5Bi_0.5TiO₃ (BNT) templates with perovskite structure were obtained by two-step molten salt synthesis (MSS) method at a low temperature. Firstly, Bi₄Ti₃O₁₂ precursors were synthesized at 1030 °C in NaCl–KCl molten salt. Secondly, plate-like Na_0.5Bi_0.5TiO₃ particles with perovskite structure were obtained from plate-like layer-structured ferroelectric ceramic of Bi₄Ti₃O₁₂ by topochemical microcrystal conversion method. Result showed that excessive Na₂CO₃ was beneficial to facilitate the low temperature synthesis. In the case of an excess of 30 mol% Na₂CO₃, plate-like BNT particles could be obtained by synthesis at temperatures ranging from 760 °C to 800 °C, which indicated a flexible processing route. Also, it has been observed that plate-like BNT particles show a high aspect ratio with 1 μm in thickness and 10–20 μm in length. These Na_0.5Bi_0.5TiO₃ plate-like particles can be good candidates for the preparation of lead-free BNT-based piezoelectric ceramics with oriented grain microstructure.     

Study on the influence of segmented fuel cell by grooving method and its application in oxygen starvation diagnosis

The oxygen starvation in fuel cells is an important reason for the deterioration of durability. The segmented fuel cell is a method to study the gas distribution inside the fuel cell. In order to study the influence of the grooving method on segmented fuel cell and its application in oxygen starvation diagnosis, a five-serpentine-channel three-dimensional two-phase simulation model is established by FLUENT. Through steady-state simulation, the effect of grooving method on fuel cell performance is studied. The overall performance (polarization curve) of the fuel cell drops slightly, but the current density distribution on the anode graphite plate changes greatly due to the grooves. The “current concentration” phenomenon is proposed based on the current density distribution. Through dynamic simulation, the oxygen starvation under current load mode and voltage load mode is simulated, and the “starvation coefficient” is defined as an oxygen starvation diagnostic index. In the current load mode, the “starvation coefficient” never exceed 15%, because when the oxygen starvation is severe, the simulation cannot converge or even cannot maintain, which corresponds to the voltage reversal in reality. However, in the voltage load mode, the “starvation coefficient” can reach up to 100%. The conclusions have important guiding significance for the judgment of the internal reaction uniformity of the segmented fuel cell by grooving method and provide a theoretical basis for judging whether a fuel cell is out of oxygen by segmented fuel cell.     

Degradation mechanisms of proton exchange membrane fuel cell under typical automotive operating conditions

The proton exchange membrane (PEM) fuel cell is an ideal automotive power source with great potential, owing to its high efficiency and zero emissions. However, the durability and life-span limit its large-scale application. Complex automotive operating conditions significantly accelerate fuel cell aging, and result in diverse degradation mechanisms that require comprehensive understanding. This review focuses on three harsh conditions of open-circuit/idling, dynamic load, and startup-shutdown. In-situ and ex-situ accelerated stress tests (ASTs) for the three conditions are summarized in terms of methodology, research objectives, and conditions of application. Reversible decay may arise during ASTs and lead to an over-estimation of the aging state, of which the causes and recovery procedures are emphasized. The degradation mechanisms are elaborated systematically according to parameter characteristics, microstructure, and aging reactions. First, increased gas permeation and a high cathode potential during open-circuit/idling combine to intensify generation of free radicals that cause membrane degradation. Pt degradation and migration are also accelerated, characterized by increased Pt particle growth and precipitation in the membrane. The debate regarding the effect of Pt precipitation on membrane degradation is resolved based on a literature review. Second, dynamic load brings about changes in the thermal/humidity state, altered reactant demand, and potential cycling, which lead to mechanical degradation, gas starvation, and Pt particle growth, respectively. To account for the accelerated particle growth, electrochemical Ostwald ripening and increased Pt dissolution are reviewed. Third, an air/hydrogen boundary appears in the anode under startup-shutdown condition and causes carbon corrosion in the local cathode via the reverse current mechanism. The cathode thereby suffers from severe and non-uniform structural damage and even structural collapse, accompanied by Pt agglomeration and detachment. Meanwhile, difficulties in mass transfer arise because of ionomer redistribution, decreased porosity, and carbon surface hydrophilization. In addition, cold start produces severe damage to component structures. This paper seeks to guide further investigation into improved fuel cell durability via mechanism analysis, condition optimization, control strategy development, structural design of the membrane electrode assembly, and component material development.     

Fabrication,structural and dielectric property of lead-free perovskite silver niobate ceramics

Dielectric capacitors with high recoverable energy density are in high demand for their application in electrical and electronic systems. Among lead-free dielectric materials, silver niobate (AgNbO₃) has attracted growing interest due to its superior energy storage density at room temperature. The field-induced phase transition from antiferroelectric (AFE) phase to ferroelectric (FE) phase contributes to its large energy density. In this work, pure perovskite silver niobate ceramics were fabricated in an oxygen atmosphere by the solid-state reaction technique. The Pbcm orthorhombic phase of AgNbO₃ was closely observed using the Rietveld refinement method to provide explanation for the origin of high spontaneous polarization within a unit cell. Local structural analysis via piezoelectric force microscopy revealed the existence of ferroelectric nano domains, which may contribute to the high energy storage efficiency (η = 99.9926%) in AgNbO₃ at low electric fields. The phase transitions of AgNbO₃ were also investigated via the dependence of the dielectric permittivity (ε′ and ε″) and loss angle tangent (tanδ) on temperatures, providing insights into the further modification of AgNbO₃.     

Failure of reinforced concrete and tuff stone masonry buildings as consequence of hydrogen pipeline explosions

Pipelines are the most efficient method of transporting large quantities of hydrogen, and the low volumetric energy density of gaseous hydrogen requires that the gas must be compressed to extremely high pressure to be used as a transport fuel. The failure of high pressure hydrogen gas pipelines and subsequent explosion may induce heavy damage to buildings. In this paper, such an issue is addressed for existing reinforced concrete framed buildings and tuff stone masonry buildings. Physical features such as the gas jet release process, flammable cloud size, blast generation and propagation, and explosion effects on structural components of buildings are considered and evaluated through the SLAB integral model, Multi-Energy Method and pressure‒impulse diagrams. Damage to both types of structural components was evaluated and the maximum distance of blast damage was derived in several environmental conditions, contributing to land-use planning and performance-based design/assessment of pipelines and buildings.     

Synergistic effects of binary oxygen carriers during chemical looping hydrogen production

The use of binary oxygen carrier allows for the materials of enhanced activity or stability during chemical looping process. However, the lack of mechanical understanding of the origin of the improvements hindered the rational design and control of the doping process in the oxygen carrier production. Here, we synthesized a series of M_0.6Fe_2.4O_y (M = Ni, Cu, Co, Mn) binary spinel materials and carried out various characterization techniques to study how the dopants influenced the material phase change, the oxygen transfer as well as the chemical looping performance. The results showed the chemical looping reactivity can be related to the oxygen transformation between lattice oxygen and oxygen vacancy, which was determined by the redox properties of both dopants and iron. The metal in tetrahedral site for Cu, Mn, Ni-doped sample were relatively stable, limiting oxygen transformation ability. In comparison, Co dopant promoted the reducibility of iron in tetrahedral site as well as metals in other sites, making almost all lattice oxygen rapidly transformed to oxygen vacancy during reduction. This was the main cause for the subsequent high hydrogen production rate (average ∼0.02 mmol. g⁻¹.s⁻¹) and yield (∼15.9 mmol.g⁻¹). Upon cycling, the phase separation of single oxides from Co_0.6Fe_2.4O_y and Mn_0.6Fe_2.4O_y spinels led to the decreased ability of oxygen transformation. However, the performance was extremely stable for Cu_0.6Fe_2.4O_y with reversible phase change between spinel and (Fe, Cu) wusitite by the Cu-Fe interaction. Based on the current results, this work points to a promising Cu-Co co-doping material with both good reactivity and stability.