Latest ArticlesPhosphorus (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.
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.
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.
Durability is a fundamental property of concrete, and research on concrete durability differs markedly among service environments. The deterioration mechanisms of concrete materials encompass a complex interplay of physicochemical processes, including carbonation, freeze-thaw damage, wet-dry cycling, sulfate erosion and chloride ion erosion. Considering the coupled erosion mechanism of chloride ingress and freeze-thaw cycling that persistently affect concrete structures in frigid coastal regions of northern China, the non-steady-state transport characteristics and spatiotemporal distribution patterns of chloride ions within concrete media are critical parameters for durability assessment in civil engineering applications. The development of predictive models for chloride ion transport in concrete matrices has therefore attracted increasing research attention. Conventional chloride ion transport models often ignore the dynamic effects of low-temperature environments on the micro-pore structure of concrete, resulting in insufficient model prediction accuracy. In this study, the microscopic mechanism of pore structure and chloride ion transport in concrete in low-temperature environments was studied, and a chloride ion diffusion model with higher engineering applicability was constructed.
The chloride ion transport model suitable for low-temperature environments was established in three steps. The first step was to determine the evolution mechanism of concrete pore structure. Under the combined effects of cryogenic conditions and saline solution infiltration, crystals tended to form within the concrete matrix. These crystals filled concrete capillary pores, densified the matrix, and helped improve concrete impermeability. Crystalline particles could create stress differences around pores, promoting pore expansion and crack formation, thereby reducing the durability of concrete. The second step was to construct a pore structure change model. The pore structure change model included two parts: a time-varying model of temperature field was constructed based on trigonometric functions. and a dynamic evolution equation of porosity considering the coupling effect of temperature fluctuation on crystal filling and microcrack propagation was established to achieve the quantitative characterization of multiphysics response of pore structure. The third step was to construct a chloride ion transport model considering age attenuation, multi-ion coupling, damage to the critical pore size and most probable pore size. The Bruggeman model is combined with the dynamic porosity model to modify the chloride diffusion coefficient. Based on the mathematical and physical nature of Fick's second diffusion law, a chloride ion transport model with time-varying parameters was constructed.
The microstructure evolution of pores had a significant influence on the transport characteristics and spatial distribution of chloride ions during chloride-ion erosion of structures at low temperature. Compared with the traditional diffusion model, the results showed that the chloride ion penetration depth and concentration predicted by the new model established in this study were more consistent with the exposure test data. The evolution of pore structure of concrete under low temperature could be divided into two characteristic stages: crystallization filling stage and micro-crack propagation stage. In the chloride ion transport mechanism, the enhancement effect of microcrack propagation on the effective chloride ion diffusion coefficient was significantly higher than that of crystal filling at low temperature. This phenomenon revealed the key controlling effect of crack network connectivity on ion migration channels.
This study constructs a modified model that accounts for the influence of concrete pore changes on chloride ion diffusion under time-varying temperature in northern coastal areas. Comparison with exposure test data verifies the applicability of the model, which is then used to study the transport behavior of chloride ions under the influence of temperature, tortuosity and initial porosity of concrete through finite element analysis. The main conclusions are as follows: Temperature has an important influence on chloride ion transport. Regulated by the crystallization-cracking mechanism, the temperature decreases from 273.15 K to 253.15 K, and the chloride ion concentration in concrete decreases first and then increases. This effect is more significant with time, and the effect of crystallization-cracking mechanism on chloride ion transport is most obvious at the depth of 9 mm. As a dynamic driving factor, the time-varying temperature has a stronger accelerating effect on chloride ion transport than the constant temperature condition. Under temperature cycling, chloride ions achieve faster and deeper migration through the crack network generated by freeze-thaw damage, and its peak concentration can reach 2.46 times that under constant temperature conditions. As an initial structural characteristic of concrete, the average particle size of aggregate is closely related to the tortuosity of concrete pore network and chloride ion diffusion capacity. The chloride ion transport process in concrete with different aggregate sizes is simulated under time-varying temperature conditions. A larger aggregate size, corresponds to lower tortuosity of the internal concrete pores, and the chloride ion diffusion coefficient of the concrete with an average aggregate size of 20 mm is 1.38 times that of the concrete with an average aggregate size of 16 mm. Affected by differences in the initial pore structure, under the cumulative effect of long-term chloride ion erosion, the difference of chloride ion concentration in concrete with different aggregate sizes gradually increases as the erosion duration increases. The initial porosity of concrete is closely related to the chloride ion transport behavior. The higher the initial porosity, the higher the chloride ion concentration, and as the erosion time increases, the acceleration effect of large porosity on chloride ion transport becomes more significant; in practical engineering applications, when the initial porosity of concrete increases from 0.10 to 0.15, the corrosion time of steel bars at a depth of 20 mm in the structure is shortened by 12.42 years.
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.
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.
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.
Conventional lithium-ion batteries have been widely used in consumer electronics, electric vehicles, and energy storage systems. However, safety concerns such as the flammability of liquid electrolytes and the melting of separators at high temperatures have become increasingly prominent, limiting their further development in high-energy-density energy storage applications. In contrast, all-solid-state batteries (ASSBs), which use non-flammable solid electrolytes and high-temperature-resistant solid electrolyte membranes, offer advantages such as high safety and high energy density, making them a promising direction for next-generation battery technology.
Solid-state electrolytes (SSEs) are broadly classified as polymer, oxide, sulfide, and halide. Among them, halide SSEs have attracted particular interest owing to their combination of high oxidative stability with excellent processability and high Li+conductivity, making them ideal for high-energy-density ASSBs. When integrated into composite cathodes, they markedly improve electrochemical and thermal stability, rendering halides a leading choice of solid electrolyte for cathode composites. However, in halide-based composite cathodes, interface failure remains a significant challenge. The volume changes in the active material during cycling cause loss of interfacial contact, leading to rising impedance. Additionally, halide SSEs tend to oxidize at high potentials, generating insulating byproducts that hinder lithium-ion transport. The misalignment of energy bands at the interface also forms space charge layers, suppressing ion migration, which degrades battery performance.
In this review, recent research on the interfaces of halide-based composite cathodes is summarized, highlighting the progress in this field. The failure mechanisms at the cathode interface in halide-based ASSBs are discussed in detail, and strategies for achieving stable interfaces through materials design, interface engineering, and structural optimization are elaborated. On one hand, electrolyte optimization, including cation doping, anion substitution, high-entropy strategies, and surface coatings, can enhance intrinsic oxidative resistance. On the other hand, surface modification of the cathode, such as LiNbO3 coating or in-situ formation of LiF-rich electrolyte interface layers, can effectively block direct contact between the active material and electrolyte, thus suppressing interfacial side reactions. Moreover, the synergistic optimization of structural design and processing techniques (such as controlling component ratios, designing single-crystal cathodes, and employing dry pressing and solvent lamination) can further improve the ion/electron transport network and interfacial compactness of composite cathodes, significantly reducing interface impedance and extending cycling life. Through this systematic analysis, this review aims to provide a theoretical foundation and research direction for the optimization and industrialization of halide-based ASSBs materials, offering scientific guidance for the development of next-generation high-energy-density ASSBs systems.
Halide SSEs are regarded as ideal candidates for high-energy-density ASSBs owing to their high ionic conductivity, superior electrochemical stability, and good processability. Nevertheless, cathode interfacial instability remains a principal bottleneck in practical applications. Although notable advances have been achieved in materials optimization, interfacial engineering, and structural design, several scientific and engineering challenges remain unresolved.
1) Intrinsic materials stability. Under high-voltage operation, the chemical and electrochemical stability of halide SSEs are still limited. Anion substitution, cation doping, and high-entropy strategies can partially expand these windows, yet their action mechanisms and the governing rules for interfacial electronic-structure modulation are not fully elucidated. Future studies should integrate experiment and theory to establish quantitative links among chemical composition, electronic structure, and stability, considering density of states, space-charge layers, and band alignment at interfaces, to derive design principles for interfacial stabilization.
2) Construction and evolution of interfacial structures. Current efforts focus on electrolyte modification or cathode surface treatments, forming passivating layers from electrolyte decomposition or applying protective coatings to block direct contact between active materials and the electrolyte. Building on this, priority should be given to controllable synthesis that delivers nanoscale, uniform interfacial contact while avoiding byproducts and voids-key to enhancing electrochemical stability. Gradient architectures, core-shell designs, and in situ-formed interphases are promising, but their cycling evolution and mechanical matching require deeper investigation. In parallel, combining single-crystal cathodes with highly stable halide SSEs may offer a new balance between energy density and interfacial stability.
3) Processing and manufacturability. Halide-based ASSBs still face challenges in scalable fabrication and environmental sensitivity. Many halide electrolytes are extremely sensitive to moisture and polar solvents, limiting the direct use of conventional wet processes. Priority should be placed on developing coating, dry pressing, and lamination routes in low-polarity or non-solvent environments, and on mapping how processing parameters (pressure, temperature, atmosphere) affect interfacial structure and performance to unify electrochemical metrics with manufacturability.
In summary, halide SSEs present a compelling suite of advantages for ASSBs, yet cathode interfacial stability remains the key constraint on performance and deployment. Research on halide cathode interfaces is transitioning from mechanistic elucidation to controllable construction and engineering implementation. Future efforts should pursue coordinated advances in materials optimization, structural design, and process development to enable safe, high-energy-density storage. Through the integration of multiple strategies, halide ASSBs hold promise for achieving high energy density, long cycle stability, and industrial viability-advancing ASSBs technology and underpinning safer, more efficient energy-storage systems.
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.
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.