Latest ArticlesThe proton surface uptake and transport properties in air electrode materials can be complex due to the proton could be effective for protonic ceramic fuel/electrolysis cells. This review summaries the proton surface uptake, transport and the coupled properties in mixed conductors. The proton in mixed conductor with hole, oxygen vacancy and proton conductivity can be determined by thermogravimetric investigations, where the water vapor can occur due to acid-base reaction (hydration) or redox reaction (hydrogen uptake), depending on the oxygen partial pressure, i.e., on the material's defect concentrations. In addition, the reaction in hydrogenation reaction can be also determined by electrical conductivity relaxation method due the consumption of hole in proton uptake process, where the proton surface exchange kinetics can be calculated.
Proton conducting perovskites with significant hole and oxygen vacancy conductivity can make it working as cathode materials that suits for fuel cells using proton conducting electrolytes. Based on the existing studies, the proton transport process in mixed conductor is a complicate process where the three majority carriers, i.e., proton, oxygen ion and electron mixed together. And the effective diffusion coefficient of ions (i.e., oxygen ion and proton) can change, and these observed over-shooting relaxation profiles can be explained in terms of defect chemical model and transport equations for materials with three mobile carriers. For the complex transport kinetics, diffusion equations can be derived by the hypothesis of ideally dilute situation.
The two-fold diffusion process can be determined in the water uptake process. The hydration reaction firstly occurs at the consume of oxygen vacancy. However, in the diffusion step where the incorporated proton/oxygen ion diffuse from outer layer to the inner bulk, the highly mobile protons are charge compensated by holes under electric neutrality law. That is because of the much higher diffusion rate of proton rather than oxygen ion, so hole is formed locally instead of waiting for the slowly moved oxygen vacancy. The non-monotonic process can be monitored by an electrical relaxation method, and the optical absorption spectroscopic method can allow for an in-situ detection of such re-dox involved reactions as a function of space and time at high temperatures.
A cathode with mixed hole, oxygen vacancy, and proton conductivity extends the reactive zone for the oxygen reduction to water beyond the triple phase boundary, making the whole cathode surface an active electrocatalyst. The defect chemistry (i.e., concentrations and mobilities of point defects) of such materials with three charge carriers is complex, and some of the desired properties for a PCFC cathode material are in mutual conflict (i.e., proton uptake, electronic conductivity, catalytic activity, and long-term chemical stability). And the promising protonic cathode material needs a high catalytic activity for the oxygen reduction reaction to water to improve its performance. Nevertheless, the reactions both require the dissociation of the strong oxygen-oxygen bond.
The mechanism for this reaction is not exactly identical to that in oxide-ion-conducting cells (where the resulting oxide ions are incorporated into the cathode material, while on PCFC cathode, they are desorbed in the form of steam). The dependence of proton uptake on cation composition in cathode perovskites in order to extract the parameters that are most important for a high proton concentration. Regarding the optimization of PCFC cathode materials, refraining from striving for very high electronic conductivities is anticorrelated with proton uptake. It is prospected that the role plays due to oversized dopants in barium ferrate for enhancing the hydration properties. The beneficial effect on protonation is attributed to a higher degree of disorder in the local structure of doped samples, which translates in B-O-B bonds buckling. The B-O-B buckling reduces the Fe-O bond covalency (i.e., less Fe 3d-O 2p orbital overlap), thus decreasing the hole transfer from iron to oxygen. This leaves more negative charge density on the oxide ions, which increases their basicity and propensity for protonation.
In addition, although the existing thermogravimetric and electrical conductivity relaxation methods still have certain limitations in measuring proton concentration in mixed ionic conductors. The in-situ characterization techniques (such as in-situ transmission electron microscopy, in-situ spectroscopy, neutron diffraction, etc.) can be used to analyze the process of proton absorption and transport in mixed ionic conductors. Also, combining multi-scale simulations with experiments can further analyze numerical values such as the binding energy of proton absorption and the activation energy of diffusion. For instance, in-situ transmission electron microscopy is used to directly observe water entering Ba0.5Sr0.5Co0.8Fe0.2O3-δ via introducing a small amount of water vapor into the TEM chamber. Electron energy loss spectroscopy is also used to determine the formation of oxygen bubbles on the material surface, while the protons ultimately remain within the material. This result provides the most direct evidence for studying the reactions of water and protons in mixed ionic conductors.
Tremendous advances in high-speed communications technologies have enabled modern services, including live 4K video streaming, real-time remote surgery, artificial intelligence (AI), the Internet of Things (IoT), virtual reality (VR), cloud storage, and social media. The further development of these digital platforms will inevitably require increased data transmission rate, which significantly exceed the current capabilities of existing high-speed communications systems. To meet the ever-growing data traffic, it is necessary to develop and implement new advanced solutions. Multi-wavelength transmission technology is considered one of the most promising approaches, which can potentially increase a bandwidth of transmission data over optical fiber systems by utilizing an extended range of wavelengths (from O- to U-band), where the optical loss of conventional single-mode fiber is below 0.2-0.3 dB/km. However, the success of this approach depends on the development of new amplification technologies, as traditional optical amplifiers based on fibers doped with rare earth ions, especially Er3+ ions, are inherently incapable of providing effective amplification beyond the C+L telecom bands. This has spurred research into promising amplification media, which began more than 20 years ago.
Bismuth (Bi)-doped fibers (BDFs) are a unique active medium suitable for optical amplifiers and lasers operating in a spectral range of 1.15-1.78 μm. The progress achieved in the development of BDFs and optical devices based on them gives hope that multi-band technologies capable of operating over the entire available spectral range can be successfully implemented in the near future. This is confirmed by the presence of commercially available devices developed by a number of telecom companies, as well as the start of implementation of bismuth-doped fiber amplifiers (BDFAs) for O-, E-, and S-band data transmission over optical communication systems. However, the progress achieved in the development of BDFA and BDF lasers was due not only to the solution of applied problems, but also to a deeper understanding of the fundamental principles of formation of bismuth active centers (BACs) and their physical nature. This review presents the main achievements in terms of optical characteristics of Bi-doped materials (crystals, ceramics, bulk glasses and optical fibers) and devices developed using these materials. This highlights that the structure and chemical composition of the glass matrix strongly influence the resulting optical properties of these media. Some fabrication strategies such as the modulation of topological order, coordination engineering, smart confined doping, and direct cluster control, and novel approaches for performance analysis (for example, "hidden potential") of BDFs are emphasized and discussed. The peculiar properties of bismuth active centers (BACs), in particular, optical anisotropy and "dark precursors", characterizing their structure and possible process leading to their formation are considered. Also, this review evaluates novel designs of BDFs, especially, heterogeneous glass-core fibers, which can be used for solution of the practical problems. For instance, such designs can be useful for developing a broadband flattop optical amplifier with adopted characteristics. In addition to bismuth-doped materials, this review includes the mainstream results in BDFAs for advanced optical technologies, summarizing the obtained results over two decades. Despite the significant progress the prospects for commercial production of BDFs remain uncertain that primarily due to difficulties in the reproducibility of Bi-doped fiber parameters and the high level of unsaturable loss in highly Bi-concentrated fibers. Addressing these challenges is essential to advancing commercialization and ensuring rapid deployment of this technology.
Bismuth-doped fibers (BDFs) have already proven themselves as active materials that can be used to develop optical devices with unique characteristics in previously inaccessible spectral ranges. Optical amplifiers based on these active fibers exhibit high gain and low noise across all telecommunication spectral bands (from O- to U-band), while BDF-based lasers offer the benefits of high efficiency and wide wavelength tunability. However, existing research still faces significant challenges in achieving a reliable technology for reproducing the parameters of BDFs, as well as in fabricating optical fibers with increased Bi concentrations and low unsaturable losses. Developing a high-gain, ultra-wideband amplifier that can be effectively integrated into existing communication systems remains a challenge. Future research should focus on balancing cost, energy efficiency, and device performance, which can be partially addressed by optimizing the BDF design and the device itself. All of this is necessary to meet the growing demand for high-speed data transmission over fiber-optic communication systems, which is crucial in the context of rapidly evolving artificial intelligence technologies. In this regard, the ability to utilize all available telecommunications bands appears very promising. We believe that progress in this area will undoubtedly lead to the development of optical communication systems with significantly increased bandwidth, where bismuth-doped optical amplifiers are key components. Moreover, thanks to ongoing advances in optical materials and process technology, bismuth-doped fiber technology can pave the way for efficient, reliable, and scalable solutions for next-generation fiber-optic systems.
Phosphorus (P) is an essential nutrient for aquatic ecosystems. However, excessive phosphorus discharge into surface water is one of the primary causes of eutrophication, thus triggering algal blooms, degrading water quality, and threatening aquatic life as well as human health. It is widely recognized that even low concentrations of phosphorus can significantly accelerate eutrophication processes, making efficient phosphorus removal a critical issue in water pollution control. Among the existing treatment technologies, adsorption has attracted increasing attention due to its operational simplicity, high efficiency for low-concentration phosphorus, and limited risk of secondary pollution.
Coal fly ash is one of the most abundant industrial solid wastes that are generated in large quantities in coal-fired power plants. Although its comprehensive utilization rate is increased, a considerable fraction of fly ash is still disposed of by landfilling or stockpiling, posing long-term environmental risks. Fly ash is a promising precursor for the preparation of ceramic materials due to its high contents of SiO2 and Al2O3. Moreover, the presence of Ca, Mg, and other alkaline components endows fly-ash-derived materials with a potential chemical affinity toward phosphate species. Transforming fly ash into functional ceramsite for water treatment therefore represents a typical "waste-to-resource" strategy.
Previous studies explored fly-ash-based ceramsite or related materials for phosphorus removal. However, most of them focused primarily on adsorption performance evaluation, while systematic optimization of preparation parameters and in-depth clarification of phosphorus removal mechanisms remained insufficient. Such limitations hinder the rational design and engineering application of these materials. In this work, fly ash was used as a main raw material, supplemented with municipal sludge, furnace slag, and cement to prepare porous ceramsite for phosphorus removal. The adsorption behavior, comprehensive physicochemical characterization, preparation conditions, and removal mechanism were systematically investigated.
Fly-ash-based ceramsite was prepared by a disc granulation method. Fly ash was mixed with municipal sludge as a pore-forming component, furnace slag as a functional additive, and cement as a binder. After granulation with deionized water, green pellets with a controlled particle size were obtained and subjected to preheating and high-temperature sintering. To optimize the preparation process, a Taguchi L25 (56) orthogonal experimental design was employed, considering six factors, i.e., fly ash-to-sludge ratio, preheating temperature, preheating time, sintering temperature, sintering time, and heating rate. Phosphate removal efficiency was selected as an evaluation index to determine the optimal preparation parameters.
Batch adsorption experiments were conducted using simulated phosphate solutions prepared from potassium dihydrogen phosphate. The effects of dosage, initial pH value, coexisting ions, and humic acid were systematically investigated to evaluate adsorption adaptability under different water chemistry conditions. Adsorption isotherms were analyzed using the Langmuir, the Freundlich, the Sips, and the Dubinin-Radushkevich models, while adsorption kinetics were interpreted using pseudo-first-order, pseudo-second-order models, i.e., Elovich, and intraparticle diffusion models.
The physicochemical properties and adsorption mechanisms of the ceramsite were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). In addition, the leaching risk of heavy metals was also assessed using standard toxicity characteristic leaching procedures to evaluate environmental safety.
The results of orthogonal experimental analysis reveal that sintering temperature is the most dominant factor affecting phosphate removal performance, following by sintering time and heating rate. The excessively high sintering temperature leads to pore collapse and crystallization of stable mineral phases, thereby reducing adsorption capacity. The optimal preparation conditions obtained are a fly ash-to-municipal sludge ratio of 7∶3, preheating at 600 ℃ for 5 min, sintering at 1050 ℃ for 5 min, and a heating rate of 5 ℃/min. Under the optimal conditions, the ceramsite achieves a phosphate removal efficiency of 90.77%, which is significantly higher than that of all orthogonal experimental groups.
The SEM images show that the optimized ceramsite has a rough surface with abundant interconnected pores, originating from the thermal decomposition of organic matter in municipal sludge and gas evolution during high-temperature reactions. The XRD patterns indicate that mullite and anorthite are the dominant crystalline phases, while Ca- and Mg-containing components are retained in reactive forms. The results of batch experiments demonstrate that phosphate removal efficiency increases with increasing dosage but decreases under strong alkaline conditions. The ceramsite maintains effective phosphorus removal in a wide range of pH values, with optimal performance under weakly acidic to neutral conditions.
The coexisting anions exhibit varying degrees of inhibition on phosphate removal, following a decreasing order CO32- >HCO3- > SO42- > NO3- > Cl-, whereas common monovalent cations show a negligible influence. In contrast, the presence of Ca2+ and Mg2+ significantly enhances phosphate removal due to additional precipitation reactions. Humic acid notably suppresses adsorption via competing for active sites and altering phosphate speciation.
Adsorption isotherm analysis shows that the Langmuir and Sips models both fit the experimental data, while the Sips model provides a better physical interpretation, indicating a heterogeneous surface adsorption. The kinetic analysis reveals that the pseudo-first-order model can describe the adsorption process, indicating that surface reactions are dominant the rate-controlling step. The XPS spectra confirm the formation of Ca- and Mg-phosphate species on the ceramsite surface after adsorption, showing that phosphate removal occurs based on a synergistic mechanism involving physical adsorption and chemical precipitation.
The results of leaching tests indicate that the concentrations of heavy metals released from the ceramsite are well below regulatory limits, having its environmental safety for water treatment applications.
A fly-ash-based ceramsite was prepared using municipal sludge and furnace slag as auxiliary components for efficient phosphate removal in water. The ceramsite exhibited a high removal efficiency, a broad pH value adaptability, and a stable performance under complex water chemistry conditions via systematic optimization of preparation parameters and comprehensive adsorption studies. The phosphate removal mechanism was dominated due to the synergistic effect of surface adsorption and Ca/Mg-induced chemical precipitation. Moreover, the ceramsite showed a negligible heavy-metal leaching risk, indicating a good environmental compatibility. This study could provide a feasible approach for the large-scale resource utilization of fly ash and offer a promising adsorbent for phosphorus control in aquatic environments.
The active-matrix light-emitting diodes (LEDs) array is a main development direction of the next-generation display technology, which requires high efficiency, wide color gamut, high contrast, high resolution, fast response, and cost-effectiveness. Perovskite CsPbX3 nanocrystals emerge as promising candidates, offering tunable emission wavelength, remarkable photoluminescence quantum yields, cost-competitiveness, and integration with diverse solution-based pixilation methods. Based on these unique properties from lead halide perovskite and nanomaterials, CsPbX3 nanocrystals demonstrate a formidable potential for active-matrix LEDs. However, the integration of perovskite LEDs with active-matrix remains a challenge. The efficiencies of both red and green perovskite LED have exceeded 28%, approaching the theoretical limit of light out-coupling efficiency for planar LED. The existing efficiency of sky-blue perovskite LED reaches 20%, while the efficiency of pure-blue perovskite LED is still lagging. Thus, improving the efficiency of pure-blue perovskite LED becomes imperative to realize full-color display. In addition, the slow electroluminescence response time caused by ion migration in perovskite under an electric field is also a critical issue, which is a limiting factor for the development of high-refresh-rate active-matrix display using perovskite LEDs.
To enhance the device performance of red, green and blue quantum dot LEDs, it is crucial to control the surface structure at the nanoscale of metal halide quantum dots. Previous extensive studies carried out on the atomic composition of the surface, the types and coordination modes of surface ligands, ligand density and developed various surface reconstruction strategies and ligand application paradigms to improve the quality of metal halide quantum dot crystals and the integrity of the surface lattice. This review systematically demonstrates recent research achievements, summaries the principles and ligand functions of different reconstruction strategies, and represents single-color demo of quantum dot LEDs integrated with active-matrix, providing a reference for the further development of full-color active-matrix displays based on metal halide quantum dots.
In this review, we summary various strategies for surface reconstruction of quantum dots, discuss the selection and design principles of surface and ligands for quantum dots applied in electroluminescence, and finally represent recent research progress in the integration of lead halide and its quantum dots with active-matrix displays. To further promote the realization of efficient full-color active drive LEDs, a key interim goal in the next step is to break through the pixelization technology for lead halide quantum dots, thereby achieving the integration of red, green, and blue colors onto the active-matrix TFT backplane simultaneously. Many scientific and technical issues need to be solved in this process. For instance, how to ensure that the morphology and photoelectric performance of the lead halide quantum dot film are not damaged during pixelization. The need for high resolution means that thousands of pixel points should be arranged very closely, having high requirements for the precise positioning of pixelization technology. In addition, avoiding color crosstalk caused by ion exchange between pixel points is also a technical problem that must be solved due to the easy ion exchange of halogen ions.
The hydration of binder is an exothermic reaction, which results in an obvious temperature increase in concrete in the early hydration period. The shrinkage of hardened concrete due to the temperature drop is a main cracking trigger of concrete. A kind of temperature rising inhibitor is developed to decrease the hydration heat of binder in early hydration age, which can reduce the cracking risk of concrete. Cyclodextrin is a main functional composition of the temperature rising inhibitor. C3A is an important clinker mineral influencing the early exothermal characteristics of Portland cement. In this paper, the effect of cyclodextrin on the hydration of tricalcium aluminate-gypsum (C3A-CaSO4·2H2O) was investigated. This work could favor understanding the action mechanism of the temperature rising inhibitor to reduce the cracking risk of concrete structures.
Pure C3A was calcined, the chemical pure gypsum and cyclodextrin was used. The hydration exothermal curves of C3A-CaSO4·2H2O pastes containing different dosages of cyclodextrin were measured. The hydration products of C3A-CaSO4·2H2O pastes containing different dosages of cyclodextrin in different ages were in-situ determined by quantitative X-ray diffraction (QXRD). The morphology of hydration products on the surface of C3A particles immersed in different solutions was characterized by scanning electron microscopy (SEM). The etching situation on the surface of C3A particles washed by different solutions was determined by three-dimensional white light interferometric surface profilometry.
The beginning time of second hydration of C3A moves up and its exothermic rate decreases, but its reacting time prolongs with the increase of cyclodextrin dosage. The heat output of C3A during its second hydration stage varies little. The consumption of C3A and CaSO4·2H2O increases continuously and the exhausting time of gypsum reduces with the increase of cyclodextrin dosage. The forming quantity of ettringate in the paste containing cyclodextrin is greater than that in controlling paste. The transformation of ettringate to AFm is suppressed after the exhaust of gypsum. Cyclodextrin can expedite the dissolution of C3A in CaSO4 solution to form more deeper etch pits on the surface of C3A particles, which speeds up the hydration of C3A. Needle-like ettringite changes to stick-like one, and the transformation of ettringite to AFm restrains when cyclodextrin exists in pastes.
Cyclodextrin could promote the initial hydration of C3A to move up the beginning of the second hydration of C3A. The consumption of C3A and CaSO4·2H2O increased continuously in the first hydration stage and the exhausting time of gypsum reduced with the increase of cyclodextrin dosage. Cyclodextrin reduced the reaction speed and prolonged reacting time of C3A during its second hydration stage, its heat output changed little. Cyclodextrin could enhance the dissolution of C3A in gypsum solution to form more deep etch pits on the surface of C3A particles, speeding up the hydration of C3A. Cyclodextrin could change needle-like ettringate to stick-like one and suppress the transformation of ettringate to AFm.
ZrB2-based multiphase ceramics are representative ultra-high temperature ceramics (UHTCs). Their service temperature significantly exceeds the sintering temperature, often requiring substantial amounts of SiC as a sintering aid to achieve the densification and enhance the oxidation resistance. The transition metal carbides (MCs) are superior sintering aids for UHTCs, effectively removing the oxygen-impurity and improving high-temperature strength. From some projects supported from the National Natural Science Foundation of China, our studies focus on the effect of MC on controlling the multiphase microstructure of UHTCs. The results obtained reveal the reactive-sintering mechanism engaging the high-viscous liquid-phase and explore the mutual-solution behavior in multiphase ceramics along with the structure-property relationship. The quantitative characterization for microstructures indicates the dominance of bora-carbide sintering-melts on reactive-sintering and densification, and on regulating the multi-level evolution of high-solution microstructures. MC additives are transformed into ZrC grain boundary phases via the sintering-melt, and its exchange-reaction with the primary phase governs the multiphase relationship. The melt as a transient liquid enables a bi-solubility of M to create prevalent core-rim structures. In the later stages of sintering, ZrC second-phase precipitates with a higher solubility of M.
The multi-levelled control of multiphase microstructures by the reactive-melt is analogous to "dissolution-reprecipitation" process for liquid-phase sintering in the transformable microstructures of silicon-based ceramics, with silicate-melts and glassy phases at grain boundaries. In contrast to the monolithic ceramics of high-entropy MB2 and MC, the multi-levelled solid-solutions and the associated multiphase microstructures of MⅠB2-MⅡC UHTCs offer ample and novel routes for comprehensive control, better optimization and further enhancement in high-performance UHTCs. The coherent hetero-interfaces created from the multi-levelled solutions via solid-state phase-separations and their interconnected dislocation networks can further improve the high-temperature strength, and those phase-boundaries, grain-boundaries, and solute-segregates allow a precise control over the multiscale semi-coherent microstructures. The research on this synergistic evolution of intergranular phases and sintering-melts at high temperatures along with the multiphase transformation has a promising potential for future advancements in ceramic genomes and levelled structure-property relationship for multiphase UHTCs governed by solid-solutions as enthalpy-regulation.
Basic magnesium sulfate cement (BMSC) is a new type of magnesium-based cementitious material modified by the chemical additive such as citric acid or boric acid on the basis of magnesium oxychloride cement. BMSC has the abundant mineral resource for the raw material, low energy consumption of production, and high utilization rate of the solid waste. BMSC has the green and environmental advantages, such as the conservation of energy, material, land, and low-carbon emissions. The systematic research on the durability of BMSC is still needed if BMSC are applied to the special environment such as the ocean and saline soil area. The main progress of the durability of BMSC material in past ten years is summarized in this paper, which includes the water resistance, carbonization and resistance of seawater, salt brine, freeze-thaw of BMSC material. and the influencing factors, the evolution law of corrosion and mechanical properties of internal steel bars, the mechanical properties of BMSC components under the natural exposure condition for 869 days. The relative dynamic modulus of the elasticity and mass change, corrosion products, and the microstructural changes of BMSC in the harsh environment is studied. The analysis of mechanism is also conducted on the durability of BMSC. The durability performance of the BMSC material is related to the composition and microstructure of BMSC. It can be found that the stable and abundant formation of 5·1·7 phase, which is the main hydration product in BMSC, is the fundamental reason for the good durability and high mechanical properties of BMSC-based material. BMSC concrete is not prone to carbonation and the internal steel reinforcement is not easily corroded in the atmospheric environment. The main changes in the microstructure of the carbonized zone on the surface of BMSCs during the carbon dioxide curing are the transformation of some hydration product Mg (OH))2 into MgCO3. The long-term retention rate of the compressive strength of BMSC concrete is closely related to its initial strength before the immersion in the seawater. The polarization resistance Rp decreases with the prolonged exposure time in the environment of seawater immersion. BMSC concrete with the compressive strength of C40 or above, BMSC mixed with KLJ rust inhibitor or the steel bar coated with epoxy resin are recommended to be used in the environment of seawater immersion. The freeze-thaw life of BMSC concrete exceeds 40 times, far exceeding that of Portland cement concrete. Compared to PCC components, the BMSC beams and columns under the coupling effects of the acid rain and freeze-thaw have less degradation of mechanical performance, lower rate of the internal steel corrosion, and higher enhancement effect of cracking load. The effective additive, suitable activity of MgO, appropriate addition of polymers, 5·1·7 crystal seed, slag (or fly ash), and solution immersion of KH2PO4 or NH4H2PO4 can optimize the composition of hydration product of BMSC, increase the stability of the 5·1·7 phase of hydration product, effectively improve the microstructure of BMSC, and enhance the durability of BMSC-based material in the harsh environment. The prospect for the application of BMSC material is discussed. Due to the advantages of BMSC, such as resistance to carbonization, salt brine corrosion, low transmission, and reinforcement protectio, it can be found that the BMSC material can be used in the area with harsh environment such as the ocean, western saline soil, and Qinghai Tibet Plateau after KLJ rust inhibitor being added. The military engineering, pavement repair of cement concrete, crack repair in the brick and stone masonry of ancient building and prefabricated construction have good application prospects in the harsh environments such as the Qinghai Tibet Plateau and saline soil area. Finally, the problems of durability are discussed as follows: the mechanism of microstructure formation and evolution of BMSC-based material under the harsh environment, the corrosion resistance of BMSC concrete to sulfate, magnesium, and chloride salt under the wet dry and freeze-thaw cycles, mechanism of corrosion resistance of 5·1·7 phase and BMSC concrete, the dynamic evolution and mechanism of intrinsic degradation of the interfacial bonding performance between BMSC repair material and the old material under the harsh service condition, the structural damage, disasters, and life extension and toughening under the interaction response of permafrost and engineering in the high-altitude environment, the stress damage, degradation of structural performance, identification of field effects and long-term performance, and design for the expected lifespan of BMSC in the harsh environment such as the ocean and saline soil, the mechanism of transport and failure of BMSC concrete in the harsh environments, the reinforcement and long-term protection system of the surface of BMSC concrete, the model of the rapid life prediction for BMSC-based material. This paper can provides the theoretical basis for the application, durability evaluation, and engineering design of BMSC in the harsh environment.
Ti-6Al-4V (TC4) titanium alloy is widely used in industrial and biomedical fields due to its excellent mechanical properties and biocompatibility. However, its inherently poor wear resistance significantly limits its further application. Plasma electrolytic oxidation (PEO) as a green and efficient method for in-situ fabrication of ceramic coatings with strong adhesion to the substrate, offering an excellent solution for surface protection of titanium alloys. However, conventional PEO coatings exhibit a porous outer layer composed mainly of high friction TiO2, resulting in insufficient wear and friction reduction performance. To overcome this limitation, incorporating MoS2 (a solid lubricant with a layered structure) can be introduced to the PEO coating to form a composite coating, which has been demonstrated as an effective approach to enhance its tribological properties. Although previous studies have confirmed the potential value of TiO2/MoS2 composite coatings in antifriction, most studies rely on high concentrations of MoS2 additives or prolonged treatment times, which often lead to particle agglomeration and high energy consumption. Even at lower concentrations, the friction coefficient remains high, and systematic studies on the influence of key process parameters, such as applied voltage are still lacking. Therefore, this study aims to systematically investigate the effects of different PEO voltages on the microstructure, chemical composition, and tribological properties of TiO2/MoS2 composite coatings under low MoS2 concentration and short processing time, so as to provide theoretical and practical guidance for the design and fabrication of high-performance wear resistant and antifriction coatings.
In this study, Ti-6Al-4V alloy was employed as the substrate. TiO2/MoS2 composite coatings were fabricated in a single-step process via PEO with incorporation of MoS2 nanoparticles. The applied voltage was varied at 400, 500 V, and 600 V. The influence of voltage on the coating surface morphology was characterized using scanning electron microscopy (SEM) and laser scanning confocal microscopy (LSCM). Localized chemical analysis of different regions on the coating surface was performed by energy dispersive spectroscopy (EDS) attached to the SEM. Phase composition was further determined by X-ray diffraction (XRD). Finally, the tribological properties of the coatings were evaluated using a ball-on-disk friction and wear tester.
The test results demonstrate that as the PEO applied voltage increases, the pore size, coating thickness, surface roughness, and deposited MoS2 content of the coatings all increase. Tribological tests on samples prepared at different voltages demonstrated that the coating produced at 500 V exhibited the lowest friction coefficient of approximately 0.2, representing a 69.2% reduction compared to the substrate, indicating excellent antifriction performance. In contrast, coatings prepared at 400 V and 600 V exbibited significantly higher friction coefficients of 0.75 and 0.82, respectively, and suffered from severe adhesive and abrasive wear. The primary reasons for this behavior are as follows: At the lower voltage (400 V), the coating thickness is thin and the MoS2 content is insufficient to provide effective lubrication. During the running-in stage, the coating lacks adequate capacity to accommodate wear debris, leading to inadequate debris removal. This results in pronounced abrasive wear, rapid penetration of the coating, and direct interaction between the substrate and the counterface, thereby increasing the friction coefficient. At the higher voltage of 600 V, although the coating thickness and MoS2 content increase substantially, the surface roughness rises significantly ((4.7 ± 0.3) μm). This leads to the generation of large, coarse debris during the initial running-in stage. Before the coating can effectively accommodate these debris particles, they cause rapid spallation of the coating, generating even more debris and accelerating wear. Under these conditions, the MoS2 particles embedded in the outer layer fail to provide any meaningful lubrication, and the coating is quickly worn through, resulting in a sharp increase in the friction coefficient. At the applied voltage of 500 V, the coating exhibits moderate thickness and surface roughness, maintaining adequate coating thickness and MoS2 content without excessive surface roughness. The friction and wear mechanism of the TiO2/MoS2 composite coating under this voltage can be elucidated as follows: The inherent porous outer layer of the PEO coating undergoes initial smoothing of surface asperities during friction, generating wear debris containing embedded MoS2 particles that fill surface depressions and inherent pores. With continued sliding, the MoS2 particles within the debris gradually spread across the contact interface. Owing to their unique two-dimensional layered structure, these particles undergo interlayer sliding under shear stress, forming a continuous surface film with excellent lubricating properties. Furthermore, the porous structure of the coating not only accommodates wear debris but also functions as a reservoir for MoS2 particles, enabling continuous replenishment of lubricant to areas where the surface lubricating film becomes locally depleted, thereby achieving remarkable self-lubricating performance.
At the optimized voltage of 500 V, the TiO2/MoS2 composite coating exhibits a moderate thickness ((28.0 ± 0.6) μm) and surface roughness ((3.0 ± 0.2) μm), along with a relatively high MoS2 content. This combination results in the lowest friction coefficient of 0.2, representing a 69.2% reduction compared to the uncoated Ti-6Al-4V substrate; During the friction process, MoS2 particles embedded in the TiO2/MoS2 composite coating are progressively exposed under shear stress and undergo interlayer sliding. This leads to the formation of a lubricating film on the wear track, which provides effective self-lubrication and significantly enhances the tribological performance of the Ti-6Al-4V alloy.
Polymer-derived ceramics are prepared via forming precursors through the polymerization of tiny molecules and cracking at high temperatures. Compared to conventional ceramics, their advantage lies in an ability to precisely control the microstructure and crystalline phase composition through the design of the molecular structure and elemental composition of the precursor and subsequent thermal treatment, thereby producing the optimal final properties. Among these, SiBCN ceramics stand out within the polymer-derived ceramics due to their flexible molecular structure designability. This enables the in-situ formation of multi-phase synergistic loss systems incorporating SiC, BN and graphitic carbon, coupled with a unique oxidation resistance mechanism, which excel particularly within polymer-derived ceramic systems. However, SiBCN ceramics primarily exist in an amorphous state at lower temperatures (i.e., < 1400 ℃), thus limiting their application in electromagnetic wave absorption. The paper was to introduce Ti nanopowder during the ceramicization process to catalyze the formation of nano-dielectric crystals such as SiC, TiC, and crystalline graphite. These crystals could enhance the dielectric imaginary part of SiBCN ceramics, thereby strengthening their electromagnetic wave attenuation capabilities.
For the synthesis of polymer precursor, tetrahydrofuran (THF)-methylvinyl dichlorosilane and borane dimethyl sulfide complex were mixed into a three-neck flask and conducted in argon for 24 h. Also, methyl dichlorosilane and hexamethyldisilazane were introduced, and the reaction was continued at the ambient temperature for 24 h. Subsequently, the mixture was then heated from room temperature to 170 ℃ for amide copolymerization reaction. After holding at this temperature for 3 h, vacuum distillation was performed, and filtrated for three cycles, thus producing a pale yellow polyborosilazane (PBSZ). For the synthesis of SiBCN ceramibs, polyborosilazane (PBSZ) was placed in a tube furnace and heated to 280 ℃ for 2 h to fully cure the precursor. The cured sample was subjected to ball grinding. The resultant ground powder was mixed with Ti nanopowder at different Ti mass contents (i.e, 0%, 5%, 10%, and 15%), and then was ground to produce different composite powders, . The composite powders were pressed into discs with the diameter of φ20 mm. The discs were heat-treated in a vertical tube furnace(i.e., firstly heating at 800 ℃ for 1 h, and thenheating at 1000 ℃ for 2 h) to allow enough molecular diffusion for TiC crystal formation, resulting in SiBCN ceramics.
The analysis of the four-component doped ceramics reveals that Ti nanoparticles doping positively affects both the phase composition and dielectric properties of SiBCN ceramics. The XRD patterns indicate that pure SiBCN ceramics remain amorphous after heat treatment at 1000 ℃, whereas the addition of Ti nano-particles promotes the formation of TiC crystals within the ceramics, thereby enhancing their crystalline properties. The SEM and TEM images demonstrate that varying the nano-Ti doping content alters the microstructure of SiBCN ceramics. Nano-Ti addition promotes the formation of a porous structure within the ceramics and facilitates the growth of crystals such as TiC and carbon nanotubes, enriching the phase composition of the ceramics. Varying Ti nanoparticles doping contents alters SiBCN's electromagnetic wave absorption and loss capabilities. Compared to pure SiBCN ceramics, Ti nanoparticles doping confers higher electromagnetic parameters and lower reflection loss, and 10% Ti nanoparticles-doped SiBCN exhibits the optimum electromagnetic wave absorption performance. The incorporation of Ti nanoparticles optimizes the ceramic structure, with synergistic interactions among various crystals and structural components, thus enhancing the overall performance.
This study demonstrated that doping Ti nano-particles into SiBCN ceramic could enhance the ceramic dielectric loss and impedance matching qualities. Ti nano-particles enhanced the low-temperature crystallization property of SiBCN. The crystallinity and microstructure of SiBCN ceramics could be adjusted by varying the nano-Ti doping content. The ceramics heat-treated at 1000 ℃ could develop porous architectures, TiC, and crystalline phases such as crystalline carbon. Ti nanoparticles improved the electromagnetic wave attenuation properties of SiBCN. The formation of TiC and carbon nanotubes, along with the heterogeneous interfaces formed with the amorphous matrix, could boost the electromagnetic wave attenuation performance of SiBCN ceramics. The crystallinity of SiBCN ceramics and the presence of abundant atomic defects resulted in a significant polarization loss, thereby enhancing the ceramic's electromagnetic wave absorption capability. At Ti nanoparticles content of 10%, the RLmin value of SiBCN ceramics at 6.24 GHz achieved -44.5 dB, with an EAB as high as 3.43 GHz, indicating that adding Ti nanoparticles could effectively enhance the electromagnetic wave absorption capacity of low-temperature heat-treated SiBCN ceramics.
To achieve the 2050 carbon neutrality vision, it is necessary to promote research and development of efficient and economically beneficial green hydrogen production technologies. In the process of global transition to a low-carbon energy system, hydrogen as a key zero carbon energy carrier continues to attract much attention. This review provides a comprehensive evaluation of high-temperature solid oxide electrolysis cell technology, focusing on analyzing some related challenges and potential pathways for large-scale application.
Compared to low-temperature alternatives such as alkaline and proton exchange membrane electrolysis, SOEC has unique advantages due to its high-temperature operation, It uses ceramic materials without precious alloys and can operate at 650-1000 ℃, and it can improve the electrochemical performance, resulting in an energy conversion efficiency of > 80%, These characteristics make SOEC a promising solution for low-cost production of green hydrogen gas, The existing domestic technology is still in demonstration stage with project scales typically ranging from tens to hundreds of kilowatts. Commercial deployment needs to overcome challenges of "three highs and one low". A key is to improve power density of battery stack, increase its service life, improve system integration, and reduce costs. To solve this problem, collaborative progress is needed in fields of material innovation, structural design, and system integration.
Collaborative design approach involving electrodes, electrolytes, and sealing components is crucial in development of materials and structures. For precise microstructure control and interface optimization, battery pack can operate stably at a high current density of 2 A/cm2, while controlling attenuation rate of < 1mV/h, and significantly extending actual service life.
Optimizing multi energy data collaboration system is equally crucial, and SOEC can leverage industrial waste heat and renewable energy resources to utilize medium to low temperature thermal energy (i.e., 200-300 ℃), thereby reducing external power consumption by approximately 30% and improving overall energy utilization efficiency, It is also necessary to build a regional supply chain that covers entire process from raw material and battery preparation to integrated assembly and system integration. The integration cost should be controlled within RMB 2500 kilowatt hours, and the design life should reach 50 000 h. A key is to lay a foundation for widespread application.
The widespread promotion of SOEC still faces several constraints, i.e., loss of electrode materials under high temperature and high humidity conditions, stability challenges caused due to power input fluctuations, and relatively high initial costs. Future research should focus on developing more durable electrode materials, establishing intelligent management systems that adapt to changes in renewable energy, and promoting standardization and cost control throughout entire industry chain to achieve technological popularization.
The combination of wind and solar energy with water electrolysis can build a more adaptable clean energy resource system, Integration helps alleviate grid stability issues related to intermittent renewable energy resources and significantly reduces electricity cost of hydrogen production. Hybrid wind and solar energy system can increase hydrogen production, while reducing costs. A key is that when SOEC is matched with fluctuating power sources, oxygen electrode/electrolyte interface will degrade under frequent thermal cycles, which is an important factor affecting long-term stability of system. In global, green hydrogen production driven by renewable resources is gradually known as a key approach of reducing greenhouse gas emissions. Electrolytic hydrogen can utilize local wind and solar energy to decompose water into hydrogen and oxygen, reducing production costs. Moreover, solar and wind energy are widely distributed and naturally compatible with electrolysis equipment. Excess electricity can be chemically stored as hydrogen, efficiently regulating spatial and temporal imbalance of energy supply and demand. Therefore, generated hydrogen and oxygen can be directly applied in transportation and industrial fields without conversion, making hydrogen both a primary energy source and a data carrier.
Compared with conventional methods, the SOEC technology has a better hydrogen production efficiency and a lower unit energy consumption, and its commercialization key lies in increasing lifespan of fuel cell stack from less than 104 h to 5 × 104 h, reducing cost of hydrogen to below $1.5/kg. The current costs of photovoltaics and wind power continue to decline. In combination with growing demand for green hydrogen in industries such as chemical metallurgy, the SOEC is expected to achieve large-scale applications in "electricity hydrogen ammonia/methanol" integrated system, distributed energy network, and sustainable financing model. Its core position lies in serving as a fundamental supporting technology for carbon neutrality goals.
In transition towards a decarbonized energy system globally, hydrogen plays a crucial role as a zero carbon energy carrier. In this context, solid oxide electrolysis cell (SOEC) technology with its advantages in high-temperature operation significantly reduces material costs and improves overall system energy efficiency, compared to low-temperature solutions such as alkaline and proton exchange membrane electrolysis. SOEC system adopts a non-precious metal ceramic structure. When operating at 650-1000 ℃, electrochemical kinetics acceleration mechanism achieves a conversion efficiency of > 80%, providing a feasible approach to reduce cost of green hydrogen leveling. The existing domestic demonstration projects are limited to a scale of tens to hundreds of kilowatts, and the commercial implementation needs to break through bottleneck of "three highs and one low", thus increasing power density of fuel cell stack, extending its service life, and optimizing system integration, while reducing assets and operation and maintenance costs. Solving these obstacles requires collaborative efforts in three major fields, and innovation in materials and structures must break through conventional design framework of electrodes, electrolytes, and sealing glass. With precise microstructure design and interface stress control, system can maintain a high current density of 2 A·cm-2, while controlling degradation rate at 1 mV per thousand hours, significantly extending lifespan of battery pack. Multi-energy coupling optimization is crucial, which requires integrating the SOEC with industrial waste heat and renewable resources, thus utilizing low-grade thermal energy (i.e., 200-300 ℃), efficiently offsetting internal heating demand, reducing external electricity consumption by approximately 30%, and comprehensively improving energy utilization efficiency. For those localized supply chains, establishing a complete domestic production capacity from precursor powder to single cell manufacturing, stacking and assembly to system integration is particularly crucial. The goal is to control stacking cost at RMB 2500 per kW and achieve an operating life of 5×104 h, laying a foundation for large-scale applications. At present, although the SOEC has significant energy efficiency advantages, its promotion and application still face multiple constraints, i.e., gradual decay of oxygen electrodes under high temperature and high vapor partial pressure, mechanical and electrochemical damage caused by power fluctuations, and daunting initial capital investment. Subsequent exploration should focus on preparing new electrode materials with a higher stability, establishing flexible thermoelectric synergistic regulation mechanisms to adapt to fluctuating renewable energy, and promoting standardization and cost reduction and efficiency improvement throughout entire industry chain. The cost of photovoltaic and wind power continues to decrease, coupled with increasing demand for green hydrogen in chemical and metallurgical fields. Solid oxide electrolysis cell technology is expected to be widely applied in "electricity hydrogen ammonia/methanol" integrated system, distributed energy system, and sustainable refining scenarios. This technology will undoubtedly become a key pillar technology supporting the dual carbon goals in China.