Most ReadPolymer-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.
Solid oxide cells (SOCs) are core technologies for sustainable energy transition, operating reversibly as solid oxide fuel cells (SOFCs) to convert chemical energy from fuels like hydrogen and methane into electricity, and as solid oxide electrolysis cells (SOECs) to store renewable energy via the valorization of carbon dioxide and water. Their performance depends on a multi-layer structure comprising anode, cathode, electrolyte, and interconnect. The conventional SOCs rely on high-temperature operation mainly due to the insufficient ionic conductivity of thick electrolyte layers at low temperatures, leading to excessive cell impedance. Reducing operating temperature is critical for cutting costs, via enabling the use of low-cost metal interconnects, and mitigating performance degradation, but this requires the fabrication of thin, dense electrolyte films to compensate for reduced conductivity and protective coatings for Cr-containing interconnects to prevent cathode poisoning. This review represents key thin-film fabrication technologies for SOCs (focusing on electrolytes and protective coatings), compares their strengths, limitations, and scalability, and outlines future research directions.
Thin-film technologies for SOCs are categorized into vapor deposition (i.e., chemical vapor deposition, CVD, and physical vapor deposition, PVD) and liquid precursor coating (i.e., sol-solution processes and colloid-slurry processes) based on phase transition pathways and energy input methods. Vapor deposition technologies mainly include chemical vapor deposition (CVD) and physical vapor deposition (PVD). CVD-based technologies form films through the reaction or decomposition of gaseous precursors, featuring good compositional uniformity and low-temperature film formation. Their derivative technologies realize the preparation of electrolyte films at medium and low temperatures, some of these technologies can prepare dense electrolytes but suffer from low growth efficiency, while others combining spray and flame synthesis can significantly optimize the electrode-electrolyte interface performance and reduce cell polarization impedance. Atomic Layer Deposition (ALD) achieves atomic-level thickness control through pulsed precursor supply, and when used for electrode modification or interlayer preparation, it can effectively enhance the performance of low-temperature batteries and improve stability. PVD-based technologies form films through physical processes in vacuum or low-pressure environments, and can prepare low-defect electrolyte films or interconnect protective coatings on low-temperature substrates, effectively solving the problem of chromium volatilization, some technologies can accurately deposit multi-component stoichiometric films, and the prepared batteries show excellent long-term stability. Plasma spraying technology can realize direct film formation without sintering, and the density of electrolytes can be significantly improved after optimization, but it is necessary to solve the defect problems during film formation.
Liquid precursor coating technologies are divided into sol-solution coating processes and colloid-slurry forming processes, both of which have the characteristics of low equipment cost and simple operation. Sol-solution processes include spin coating, dip coating, spray pyrolysis, and electrostatic spray deposition. Dense electrolyte films can be prepared through multiple coatings and subsequent treatments, and the thickness of functional layers can be accurately controlled to effectively optimize the interface conduction performance of batteries. Among them, electrostatic spray deposition combines high-voltage electric field and pyrolysis, enabling film formation at lower temperatures and improving electrode polarization characteristics. Colloid-slurry processes, mainly screen printing and tape casting, are the mainstream technologies for large-scale production. Screen printing forms films via scraping slurry, and the preparation temperature of functional layers can be effectively reduced and the battery performance can be improved through process optimization. Tape casting technology and various derivative technologies can produce wide ceramic tapes, which realize the mass production of high-performance batteries and construct gradient porous structures to further optimize mass transfer and interface bonding inside batteries.
A comprehensive comparison of these technologies reveals clear trade-offs. Low-cost, scalable options such as screen printing, tape casting, spin coating, and dip coating are preferred for industrialization due to simple equipment and low material costs, but they require optimization of slurry formulations and sintering processes to minimize defects like cracks and pores. High-performance, high-cost technologies (i.e., ALD, PLD, and low-pressure plasma spraying) deliver superior film density and composition control, but they are constrained by slow deposition rates, high equipment investment, or complex parameter tuning, limiting their use to specialized applications like ultra-thin electrolytes. Emerging technologies such as 3D printing and laser-assisted manufacturing show a promising potential for fabricating complex structures and simplifying co-sintering, but they lack the technical maturity for large-scale SOC production.
In summary, SOCs thin film preparation technologies can form a diversified system, but some common challenges remain. Although vapor-phase technologies have excellent performance, they generally face high equipment costs and great difficulty in scaling up. Liquid-phase technologies are prone to film cracks or pores due to drying and sintering stress. Future research should focus on three core directions, i.e., 1) promoting intermediate and low-temperature operation, further expanding the low-temperature application range of batteries through interface regulation and film formation process optimization; 2) pursuing high performance, developing three-dimensional structured films to expand reaction interfaces and improve mass transfer and catalytic efficiency; and 3) accelerating commercialization, optimizing low-cost preparation processes combined with intelligent manufacturing technologies, and breaking through the key technical bottlenecks of new film formation technologies. Thin film preparation technology will continue to be a core breakthrough to solve the high-temperature dependence and performance attenuation of SOCs, promoting their transition from laboratory research to commercial application.
With the continuous improvement of aero-engine thrust-to-weight ratio and turbine inlet temperature, the performance limitations of conventional superalloys become increasingly prominent. SiCf/SiC ceramic matrix composites (CMCs) can be core candidate materials for hot-section components due to their excellent high-temperature mechanical properties and low density. As a key technology to realize the engineering application of CMCs, compatible abradable/environmental barrier coatings (A/EBCs) that can simultaneously achieve gas path sealing, high-temperature protection and abradable performance become a research focus in the field of advanced aero-engine sealing technology. This review represents the research progress of such coatings from three dimensions, i.e., material design, microstructural regulation, and performance evaluation, while analyzing key technical challenges and development trends. In terms of material system design, conventional yttria-stabilized zirconia (YSZ) abradable coatings suffer from thermal expansion mismatch with SiCf/SiC CMCs, which are prone to failure, while conventional solid lubricants undergo oxidative degradation at > 1200 ℃. It is urgent to develop new matrix materials with a high thermal stability, a water vapor-oxygen corrosion resistance and a thermal expansion compatibility. Multi-layer structure is the main design to realize functional synergy, and the interface matching and thermal expansion adaptability between layers are a key to the service durability. The introduction of negative thermal expansion materials provides an idea to solve the mismatch problem. In addition, the construction of material system matching for multi-layer coatings and the compatibility analysis of interlayer interfaces/multiphase interfaces also become important aspects in the design of abradable/environmental barrier coating systems.
In the aspect of microstructural regulation, improving porosity is a main way to obtain excellent abradability, but there is a prominent contradiction among abradability, erosion resistance, corrosion resistance and thermal stability. Excessive or uneven porosity, as well as high-temperature sintering and closure, will lead to the performance degradation and early failure. The core challenge is to realize the precise regulation of multi-scale pore structure and the multi-performance synergy balance. In terms of performance evaluation, the existing test devices have high cost and poor universality, and it is difficult to simulate the real multi-field coupling service environment. The lack of perfect preparation and evaluation standards restricts the engineering and standardized development of CMC-compatible coatings. Finally, the development trends of A/EBCs are prospected, providing a reference for the research and development of high-temperature sealing technology and coating system for advanced aero-engines.
In summary, with the increasing service temperature of aero-engines, the abradable/environmental barrier coatings (A/EBCs) that match SiCf/SiC ceramic matrix composites (CMCs) become a key research direction. This review represents the research progress of A/EBCs in material design, microstructural regulation and performance evaluation, and points out that the current challenges mainly include thermal expansion mismatch between conventional coating materials and CMC substrate, poor high-temperature stability of lubricants, difficult balance between multi-scale pore structure and multi-performance, and lack of standardized evaluation systems and test standards suitable for multi-field coupling service environment. In the future, the research and development of A/EBCs should focus on the multi-objective synergistic design of material composition, multi-scale microstructure and performance evaluation system. It is necessary to strengthen the analysis of failure mechanism under multi-physical field coupling environment, develop new high-temperature stable matrix and lubricant materials, realize the precise regulation of multi-scale pore and interface structure, and establish a standardized preparation and performance evaluation system. Through the breakthrough of the above key technologies, the comprehensive performance and service durability of A/EBCs will be effectively improved, so as to promote the leapfrog development of high-temperature sealing technology and provide an important support for the performance improvement of next-generation aero-engines.
With the advancement of the era, the demand for ultraviolet photodetectors in environmental monitoring and communication security continues to grow, leading to increasingly stringent performance requirements. In this case, self-driven ultraviolet photodetectors emerge to meet the needs of energy conservation and device miniaturization. However, conventional self-driven ultraviolet photodetectors still face some challenges such as low efficiency in photo-generated carrier separation, poor photoresponse performance, and limited response speed. Ferroelectric thin films with a high remnant polarization can form a depolarization field that penetrates the entire bulk material, enabling an effective separation of internally generated photo-generated electrons and holes. This provides a promising solution to the aforementioned issues. Pb(ZrxTi1-x)O3(PZT) is a typical ABO3-type perovskite ferroelectric material. This material is widely used in ferroelectric memories, micro-electromechanical systems, and photodetectors due to its excellent ferroelectric, piezoelectric, and photoelectric properties. Extensive studies show that the composition significantly affects the crystal phase structure and ferroelectric properties of PZT thin films. However, its impact on the photoelectric performance requires a further systematic investigation. This work was to analyze the photoelectric characteristics of PZT thin films with different Zr/Ti ratios, in order to elucidate the influence of compositional modulation on the photoelectric effect.
Pb(ZrxTi1-x)O3 ferroelectric thin films with different Zr/Ti ratios were prepared by a sol-gel method. The selected precursors and solvents were high-purity lead acetate [Pb(CH3COO)2·3H2O], zirconium n-propoxide (C12H28O4Zr), and titanium isopropoxide (C12H28O4Ti) as sources for lead, zirconium, and titanium, respectively, glacial acetic acid as a chelating agent, and n-propanol as a stabilizer. Semitransparent gold electrodes were deposited on the surface of the thin films by a model VZZ-300 high-vacuum thermal evaporation system (VANNO Co., China) to fabricate self-driven ultraviolet photodetectors with an Au/PZT/FTO vertical structure. The crystal structure of the films was characterized by a model D8 Advance X-ray diffractometer (XRD, Bruker Co., USA). The surface roughness of the films was determined by an atomic force microscope (AFM, Bruker Dimension Edge Co., USA). The optical properties of the films were analyzed by a model UV-3600 Plus ultraviolet-visible-near-infrared spectrophotometer (UV-Vis-NIR, Shimadzu, Japan). The ferroelectric properties were measured by a model Precision LC II ferroelectric test system (Radiant Co., USA). The current-time (I-t) curves were obtained by a model Keithley 2400 source meter, with a 150 W ultraviolet-enhanced xenon lamp as a light source.
The XRD patterns indicate that the three prepared PZT thin films with different Zr/Ti ratios all exhibit a typical perovskite structure, and no diffraction peaks from impurity phases appear aside from those originating from the FTO substrate. As the Zr content increases, the surface morphology of the films transitions from elongated needle-like structures to island-like structures, and finally to wavy undulations. The lowest root mean square (RMS) roughness of 2.62 nm is obtained at a Zr/Ti ratio of 0.52:0.48. The remnant polarization first increases from 27.9 μC/cm2 (Zr/Ti=0.49/0.51) to a maximum of 33.2 μC/cm2 (Zr/Ti=0.52/0.48), and then decreases to 31.1 μC/cm2 (Zr/Ti=0.55/0.45) as the Zr content increases. A higher remnant polarization is beneficial to forming a stronger built-in electric field, thereby improving the separation efficiency of photogenerated carriers. The PZT films with different Zr/Ti ratios are all wide-bandgap semiconductors (>3.6 eV). As the Zr content increases, the bandgap widens from 3.60 eV to 3.68 eV, showing a blue-shift trend. When a negative poling voltage is applied, the depolarization field inside the PZT aligns with the built-in field induced by the interfacial Schottky barrier, synergistically enhancing the driving force for carrier separation and leading to a significant increase in photocurrent. For the sample with a Zr/Ti ratio of 0.52:0.48 at a poling voltage of -2 V, the responsivity and detectivity reach 3.2 mA/W and 0.33×1011 Jones, respectively. Even under a weak illumination of as low as 0.17929 mW/cm2, the device still generates a photocurrent of 1.02 nA, demonstrating the excellent detection sensitivity.
Pb(ZrxTi1-x)O3 ferroelectric thin films with different zirconium-to-titanium ratios (i.e., Zr/Ti=0.49:0.51, 0.52:0.48, 0.55:0.45) were fabricated by a sol-gel method, and self-driven ultraviolet photodetectors with an Au/PZT/FTO structure were constructed. The structural characterization revealed that all PZT thin films exhibited a pure perovskite phase with a good crystalline quality. The AFM analysis indicated that the film surfaces were smooth, dense, and displayed a uniform grain distribution. The ferroelectric property measurements further confirmed that all films with different Zr/Ti ratios showed characteristic ferroelectric hysteresis loops and possessed a high remnant polarization, having a maximum value of 33.2 μC/cm2 at Zr/Ti=0.52:0.48. The results of photoelectric tests demonstrated that the device based on this optimal composition exhibited stable and reproducible photocurrent responses. At a poling voltage of -2 V, its responsivity and detectivity were significantly enhanced. In summary, the rational adjustment of the Zr/Ti ratio could effectively optimize both the ferroelectric properties of PZT thin films and the photoelectric characteristics of the corresponding devices. This work could innovatively utilize the inherent bulk depolarization field of PZT ferroelectrics as a driving force to achieve an efficient separation of photogenerated electron-hole pairs. Moreover, it could provide a systematic optimization strategy from the perspectives of compositional design and polarization modulation, offering an effective material- and physics-based solution to overcome the key bottlenecks of low responsivity and detectivity in self-driven ultraviolet photodetectors.
Abstract The downstream glass industry in South Korea exhibits a distinctive structure compared with that of other non-Asian countries, as its semiconductor and display sectors are tightly integrated with the glass materials supply chain. In this review, the distinct features of glass-related industrial research and development in South Korea are addressed by taking two representative applications of glasses, i.e., glass core substrate for semiconductor packaging applications and ultra-thin glass for use as cover window of flexible display modules. In the case of glass core substrate and glass interposer, the inherent brittleness of glassy materials imposes constraints across the process flow, requiring precise control over laser irradiation, chemical etching, redistribution layer formation, and singulation. Ultra-thin glass needs to be durable during repeated deformations, so that its thickness is typically on the order of several tens of micrometers. At such thickness levels, resistance to mechanical deformations becomes a primary concern, and therefore processing steps from cutting, chamfering, and healing to chemical strengthening play a decisive role in determining mechanical reliability and optical clarity of ultra-thin glass. Flexible display devices with other form factors featuring multi-foldable, slidable or rollable capability would be realized along with advancement of processing technologies associated with ultra-thin glass.
With an emphasis on the application-oriented research activities directly or indirectly related to glass materials led by South Korean universities, four different topics are introduced in this review: 1) a thermodynamic database for glass-forming systems, 2) mold flux systems used in steel casting, 3) glasses doped with quantum dots and/or perovskite nano-crystals, and 4) chalcogenide glasses for thermal imaging. For each topic, recent advances are described in conjunction with their basic concepts and future perspectives. The CALPHAD (CALculation of PHAse Diagrams) thermodynamic database for glass-forming system and glassmaking process has been actively developed to assist glass research and the manufacturing process. In addition, a multi-component diffusion model for glass systems is being actively studied for various kinetic simulations. Recent research focuses on the expansion of the database to address key issues relevant to the decarbonization of the glassmaking process such as water solubility in glass, new redox agents, refractory wear in glass melting furnace, and electrode materials for an electric melting furnace. However, the limited availability of phase diagram and thermodynamic data pose challenging issues for the database development relevant to the decarbonization process.
In order to meet the demands for advanced glass lubricants for continuous casting of steel, investigations of structural understandings and their effects on non-Newtonian rheology, thermal properties, and glass forming ability are being actively pursued. In particular, application of mixed alkali effect and Mie scattering is believed to be an effective design principle to enhance lubrication without deteriorating heat transfer controlling ability. In consideration of the necessity of increasing scrap recycling to achieve carbon neutrality during steel manufacturing, further investigations should be done on rheological behavior of supercooled silicate glass lubricant melts in order to mitigate the cracking on continuously cast steels with a greater number of accumulated impurities.
Quantum dots and perovskite nanocrystals are still widely studied for next generation color converters or phosphoric materials for high picture quality displays including micro-LED display and anti-counterfeit applications, thus offering high chances for robust quantum dot or perovskite nanocrystal embedded glasses. However, several issues such as sub-micron sized glass powders with stable PL-QY, Pb-free perovskite nanocrystals, and glass materials for direct driving LED remain as challenging issues for their future applications.
The thermal imaging market is expected to steadily expand with a conspicuously steep inflection arising in the automobile industry caused by the regulations mandating employment of the autonomous emergence braking system. It is noteworthy that the cost of LWIR image sensors based on microbolometer arrays is decreasing rapidly to meet the demands of the automotive industry, and in this regard a group of well-qualified chalcogenide glasses will be promising as molded lenses for the high-resolution thermal cameras. Specifically, those chalcogenide glasses consisting of environmentally less harmful and relatively cheaper constituents would be preferred in the civilian sectors.
Across diverse application domains, glass materials are engineered to meet increasingly stringent criteria with regard to performance, reliability, and sustainability. It is worth mentioning that the most advanced display modules and semiconductor chips are currently manufactured mostly in East Asia. This geographic imbalance provides unique opportunities and challenges for both of the glass industry and academia. New applications such as ultra-thin glass for flexible display modules and glass core substrate for semiconductor packaging will present unprecedented functionalities and benefits to glass materials.
Continuous silicon carbide fiber reinforced silicon carbide ceramic matrix composites (referred to as SiCf/SiC composites) become the preferred high-temperature and lightweight thermal structure materials for high thrust-to-weight ratio aero engines due to their excellent high-temperature properties. However, their poor high-temperature oxidation and corrosion properties limit their long-life use. It is effective to improve the oxidation and corrosion properties of SiCf/SiC composite matrix through matrix modification, and the commonly used modified materials mainly include self-healing components, network intermediate oxides and rare-earth silicates.
The self-healing components form the liquid phase of B2O3 or borosilicate glass phase in the process of oxidative corrosion that has a certain fluidity and viscosity at a high temperature, which can fill the cracks and holes in the matrix. The volume expansion caused by oxidation makes the small defects heal when the oxidizing medium diffuses in the cracks as the oxidation phase, which can effectively block the diffusion of the oxidizing medium to the key areas that are easy to oxidize such as fibers and interfaces, thus enhancing the oxidation resistance of the material and extending its service life. The network intermediate oxide can absorb the "free oxygen" in the borosilicate glass melt and change its coordination from [MO6] to [MO4], reconstructing the silicate network damaged by water vapor erosion and maintain its integrity, and significantly improving the stability of the self-healing glass phase under high temperature water vapor conditions and the oxidation and corrosion properties of composites. Rare-earth silicate itself has excellent antioxidant corrosion properties, and the rare-earth elements migrate to the near surface of the matrix to form an antioxidant layer during the oxidative corrosion process, which inhibits the penetration of oxidative corrosion medium into the matrix and the reaction between borosilicate glass and water vapor, reduces the generation of gaseous substances, and slows down the oxidative corrosion of the matrix to a certain extent.
There are two main ways to introduce modified materials into the matrix, i.e., one refers to the direct introduction of antioxidant corrosive materials without changing their phases during use, such as directly introducing rare-earth silicates into the matrix, and another refers to the introduction of the precursor of the modified material or substances containing modified elements into the matrix, and the target modified material is obtained through chemical reactions during the oxidative corrosion process, usually in this way the introduction of self-healing components and oxidation corrosion phases into the matrix. In addition, the synthesis process of modified materials mostly adopts CVI, PIP, RMI, SI, etc., and their advantages and disadvantages of different modification processes are different. For instance, the preparation temperature of CVI process is low, but the densification cycle is long and the cost is high. The RMI process is simple, the cycle is short, and the composite material with a high density is prepared, but the melting temperature is high, which is easy to heat damage to the fiber and interface. Besides a single process, composite processes are mostly used to achieve complementary advantages, introducing modified materials into the matrix and realizing the densification of composite materials.
It is effective to introduce self-healing components, network intermediate oxides and rare-earth silicates into the SiCf/SiC composite matrix to fill the pores and cracks of the material via generating self-healing components during the oxidative corrosion process, and forming a dense oxide layer on the surface of the material to resist further erosion by the oxidizing medium, thus improving the water and oxygen corrosion resistance of the composites. However, there are still some challenges. Firstly, the research on the oxidation corrosion mechanism of composite materials is still in-depth, and there is a lack of data on oxidation kinetics, oxidative corrosion rate and oxidative corrosion depth, and the basic research on the damage evolution mechanism of materials in different environments is still relatively weak. It is thus necessary to construct a complete and reliable performance database of SiCf/SiC composites modified with different substrates, clarify the oxidative corrosion damage mechanism, and provide design parameters and theoretical support for the practical application of composites. Secondly, the effective temperature range of a single modified substance to improve the oxidative corrosion performance of composites is limited. The temperature range of B group is below
1000 ℃, and the temperature range of Al group is 1000-1300 ℃. The synergistic effect of multiple modification strategies is explored via introducing multiple modified substances into the matrix of composites at the same time. It is expected to achieve the oxidation and corrosion properties of SiCf/SiC composites in a wide temperature range and achieve a long-life cycle protection. Finally, it is also worth to develop new preparation processes, such as nano-infiltration and transient eutectic (NITE), or use hybrid processes to achieve material densification and improve the performance of SiCf/SiC composite substrates while modifying them.
The 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.
Quartz ceramics (SiO2) possess unique properties such as low thermal expansion, excellent chemical stability, and outstanding dielectric performance, making them widely used in semiconductor manufacturing, optoelectronic devices, and high-frequency electronic components. Traditional sintering of quartz ceramics typically requires temperatures above 1000 ℃, which inevitably induces polymorphic transformations from α-quartz to β-quartz or cristobalite, hindering the preparation of single-phaseα-quartz ceramics. Recently, the cold sintering process (CSP) has emerged as a promising low-temperature densification route for ceramics, utilizing transient liquid phases to induce "dissolution-precipitation" or interfacial reaction mechanisms. However, for low-solubility ceramics such as quartz, CSP often fails to achieve full densification and crystallization due to insufficient dissolution kinetics and weak interfacial reactivity. The critical scientific problem addressed in this work is how to effectively trigger the amorphous-to-crystalline phase transition of low-solubility quartz at low temperature, thereby enabling the preparation of denseα-quartz ceramics.
This study systematically investigates the cooperative effects of transient solvent alkalinity, sintering temperature, and uniaxial pressure on the amorphous-to-α-quartz phase transition during CSP. A transient alkaline liquid phase is introduced to regulate interfacial reactions and crystallization kinetics, aiming to provide a theoretical basis and technical strategy for the low-temperature processing of low-solubility ceramics.
Amorphous mesoporous silica (SBA-15) powders were used as the starting material. The powders were homogeneously mixed with different transient solvent phases: deionized water (neutral), 5 mol·L-1 NH3·H2O (weak alkaline), and NaOH solutions of varying concentrations (0.5-10.0 mol·L-1, strong alkaline). Approximately 0.4 g of powder was thoroughly ground with the liquid phase in a mortar and then loaded into a 10 mm diameter steel die. Uniaxial pressures ranging from 200 MPa to 600 MPa were applied, while the sintering temperature was varied between 200 ℃ and 350 ℃. Heating was conducted at a rate of 15 ℃·min-1 and held for 40 min at the target temperature. After natural cooling, the sintered pellets were mechanically polished for further characterization.
The density of the cold-sintered ceramics was calculated by dimensional and weight measurements using a vernier caliper and electronic balance, and relative density was determined based on the theoretical density of quartz (2.2 g·cm-3). Phase composition and structural evolution were analyzed using X-ray diffraction (XRD, Cu Kα radiation, λ = 0.154 06 nm, 50 kV, 100 mA, scanning range 10 °-90 °, step size 0.01). Fourier-transform infrared spectroscopy (FTIR-ATR) was used to identify bonding characteristics and confirm phase transitions. Microstructural evolution and fracture features were observed by field-emission scanning electron microscopy (FE-SEM). The mechanical properties of the sintered ceramics were evaluated by Vickers hardness tests (3 kgf load, 10 s dwell), flexural strength using the modified small punch (MSP) method, and fracture toughness (KIC) calculated by the Anstis equation. Poisson's ratio and Young's modulus were determined by ultrasonic measurements.
This experimental design allows for a systematic investigation of how transient solvent alkalinity, temperature, and pressure cooperatively affect densification and amorphous-to-crystalline transformation during CSP of quartz.
The phase composition of the sintered bodies was strongly influenced by the type and concentration of transient solvent. Without a liquid phase or with neutral water, the sintered samples remained largely amorphous and exhibited low relative density (~80%). Weak alkaline NH3·H2O increased compaction and relative density (~92%) but failed to trigger phase transformation. In contrast, strong alkaline NaOH solutions (≥3 mol·L-1) effectively promoted the dissolution of Si-OH surface species, forming soluble silicate intermediates. These intermediates subsequently underwent reprecipitation and recrystallization under external pressure and temperature, leading to complete transformation into α-quartz at 300 ℃ and 500 MPa. XRD and FTIR confirmed the disappearance of the amorphous broad peak and the emergence of α-quartz characteristic double peaks at 798 cm-1 and 778 cm-1, indicating a complete amorphous-to-α-quartz transition.
A clear alkalinity-dependent phase transition sequence was identified: amorphous → keatite (0.5 mol·L-1 NaOH) → keatite +stishovite (1 mol·L-1) → keatite + α-quartz (3 mol·L-1) → α-quartz (≥5 mol·L-1). Simultaneously, relative density increased from 71% (no solvent) to 95.7% (10 mol·L-1 NaOH). SEM revealed that strong alkalinity produced well-defined grain boundaries and uniform microstructures, while weak or neutral conditions resulted in porous, poorly bonded networks.
The phase transition was also sensitive to sintering temperature and pressure. At 200 ℃, no crystallization occurred even at 600 MPa. Crystallization initiated at 250 ℃ and 300 MPa, and complete α-quartz formation occurred at ≥300 ℃ and ≥400 MPa. Increasing pressure facilitated particle rearrangement, pore elimination, and enhanced atomic diffusion at the interface, accelerating phase transition. A comprehensive temperature-pressure-phase diagram was established, clearly delineating the non-crystalline, partially crystalline, and fully crystalline regions.
Mechanical properties were strongly correlated with microstructure and phase composition. The α-quartz ceramics cold-sintered with 5 mol·L-1 NaOH exhibited a Vickers hardness of 5.1 GPa, Young's modulus of 67.8 GPa, fracture toughness of 0.98 MPa·m1/2, and flexural strength of (58 ± 7) MPa. These values represent increases of 30%, 40%, and 110% in hardness, modulus, and toughness, respectively, compared to the amorphous samples. The enhanced mechanical properties are attributed to the formation of well-bonded crystalline interfaces that enable efficient stress transfer and crack deflection, unlike the disordered amorphous structure.
This work demonstrates a controllable strategy to induce amorphous-to-α-quartz transformation in low-solubility silica ceramics through the regulation of transient solvent alkalinity during cold sintering. By introducing strong alkaline NaOH solutions (≥3 mol·L-1), the activation energy for crystallization can be significantly reduced, enabling complete transformation at 300 ℃ under 500 MPa. The critical crystallization threshold was identified at 250 ℃ and 200 MPa, and a detailed temperature-pressure-phase diagram was established to illustrate the transition pathways. The resulting ceramics achieved a relative density above 95% and exhibited excellent mechanical performance, including a Vickers hardness of 5.1 GPa, Young's modulus of 67.8 GPa, fracture toughness of 0.98 MPa·m1/2, and flexural strength of (58 ± 7) MPa. These results clearly indicate that alkaline regulation during CSP not only enables precise control of phase structure but also produces dense, mechanically robust α-quartz ceramics at dramatically reduced sintering temperatures. This approach provides both fundamental insights and practical guidance for the low-energy fabrication of advanced low-solubility ceramic components.
High-temperature vibration sensors are indispensable key components for the health detection of core equipment in fields such as aerospace and nuclear energy. The BiScO3-PbTiO3(BS-PT) system has attracted much attention due to its high Curie temperature (TC≈450 ℃) and excellent piezoelectricity (d33≈450 pC/N). However, the poor insulation properties of this material hinder its application in high-temperature vibration sensors because high electrical resistivity (ρ) and a long time constant (τ) are critical to prevent thermal runaway and ensure signal integrity. Manganese (Mn) doping is a commonly used modification method for piezoelectric ceramics. Previous studies on Mn-doped BS-PT were controversial regarding the valence state distribution and substitution positions of Mn ions, which could not be conducive to the design of high-temperature piezoelectric ceramics with the collaborative optimization of multiple electrical parameters. Therefore, this work was to clarify the defect chemical mechanism associated with manganese doping through refined structural characterization combined with electrical performance analysis, and to obtain the modified BS-PT piezoelectric ceramic components suitable for high-temperature vibration sensors.
0.365BiScO3-0.635PbTiO3-x% MnO2 (BSPT-x% MnO2, x=0.00, 0.01, 0.25, 0.50, 0.75, 1.00, 1.25, 1.50, 1.75, 2.00) ceramics were synthesized by a conventional solid-state reaction method. The powders were firstly calcined at 800 ℃ for 2 h and then sintered at 1050 ℃ for 2 h. The phase composition was analyzed by X-ray diffraction (XRD). The rietveld refinements were performed using a software named GSAS. The microstructure and elemental distribution were examined by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDS). The average grain size was estimated by a software named Nano Measurer. The Mn valence states were determined by X-ray photoelectron spectroscopy (XPS). For electrical measurements, poled samples (120 ℃, 5 kV/mm, 30 min) were used. The piezoelectric coefficient (d33) was measured by a model CAS ZJ-6A quasi-static meter. The electromechanical coupling coefficient (kp) was measured by a model Agilent 4294A impedance analyzer. The temperature-dependent dielectric properties were measured by a model Agilent E4980A LCR analyzer. The high-temperature DC resistivity (ρ) was measured by a model Keithley 6517B high-resistance electrometer. The in-situ d33 was measured by a model Julang TZFD-600 variable temperature quasi-static d33 measurement system.
The Mn doping mechanism and high-temperature performance of BS-PT ceramics are systematically clarified. The XPS results confirm the coexistence of Mn2+ and Mn3+. To quantitatively verify the substitution site, the rietveld refinement reveals a non-monotonic evolution of unit cell volume. Based on the EDS evidence of Sc segregation without Ti precipitation, Mn ions preferentially substitute for B-site Sc3+. The dominant aliovalent substitution introduces defect dipoles accompanied with strong local random electric fields, significantly enhancing a relaxor behavior, while triggering a "hardening" effect that reduces tanδ and εr. The decoupling of piezoelectric and dielectric properties is achieved in specific compositions due to the grain boundary effect compensating for the hardening effect, especially obtaining the optimal piezoelectric voltage constant (g33) at the component with x of 1.00. For high-temperature capabilities, the optimal composition (x=1.00) demonstrates a superior stability, with in-situ d33 variation remaining within 20% up to 400 ℃. The thermally stable defect dipoles effectively trap oxygen vacancies, leading to a high resistivity of 109 Ω·cm and an enhanced time constant of 0.072 s at 350 ℃. Consequently, the ceramic with x of 1.00 exhibits a high g33 of 0.012 V·m/N when evaluated at a unified service temperature of 350 ℃, which is 50% higher than that of the undoped counterpart. These results indicate that the modified ceramic achieves an optimal balance of sensitivity and insulation for high-temperature vibration sensors.
This work clarified the Mn doping mechanism in BS-PT ceramics. The results of correlative XPS, Rietveld refinement, and EDS analysis confirmed that Mn ions could preferentially substitute for B-site Sc3+. The dominant aliovalent substitution induced a hardening effect, while the recovery of d33 was dominated by grain size restoration. The optimal composition (x=1.00) exhibited a robust stability with d33 variation within 20% at 400 ℃. The thermally stable defect dipoles could obtain a high resistivity (109 Ω·cm) and time constant (0.072 s) at 350 ℃. Meanwhile, a superior piezoelectric voltage coefficient (g33) of 0.012 V·m/N was achieved at 350 ℃, which was 50% higher than that of the undoped counterpart, validating its potential for high-temperature sensors.