High-temperature Sintering Process Research Articles

Ultrafast Sintered Composite Cathode Incorporating a Negative Thermal Expansion Material for High-Performance Protonic Ceramic Fuel Cells.

Protonic ceramic fuel cells (PCFCs) offer a promising, clean, and efficient energy conversion solution. However, thermal mismatch between cathodes and electrolytes remains a critical obstacle, leading to interfacial damage such as cracking and delamination. Incorporating negative thermal expansion (NTE) materials into the cathode can mitigate this issue. The challenge lies in integrating NTE materials without compromising electrochemical performance or causing unwanted reactions during sintering. This study introduces a novel BaFe0.9Zr0.1O3-δ (BFZ)-NdMnO3-δ composite cathode fabricated using an ultrafast high-temperature sintering (UHS) process. This approach mitigates thermal expansion while boosting the cathode's catalytic activity compared to a single-phase BFZ cathode. The resulting fuel cell achieves a high peak power density of ∼550 mW cm-2 at 600 °C and demonstrates excellent stability during a 100 h test at 550 °C. These findings highlight the potential of UHS for developing high-performance, thermally compatible cathode materials that advance the field of PCFCs.

Synergistically Engineering Grains and Grain Boundaries toward Li Dendrite-Free Li7La3Zr2O12.

Cation-doped cubic Li7La3Zr2O12 is regarded as a promising solid electrolyte for safe and energy-dense solid-state lithium batteries. However, it suffers from the formation of Li2CO3 and high electronic conductivity, which give rise to an unconformable Li/Li7La3Zr2O12 interface and lithium dendrites. Herein, composite AlF3-Li6.4La3Zr1.4Ta0.6O12 solid electrolytes were created based on thermal AlF3 decomposition and F/O displacement reactions under a high-temperature sintering process. When the AlF3 is thermally decomposed, it leaves Al2O3/AlF3 meliorating the grain boundaries and F- ions partially displacing O2- ions in the grains. Due to the higher electronegativity of F- in the grains and the grain-boundary modification, these AlF3-Li6.4La3Zr1.4Ta0.6O12 deliver optimized electronic conduction and chemical stability against the formation of Li2CO3. The Li/AlF3-Li6.4La3Zr1.4Ta0.6O12/Li cell exhibits a low interfacial resistance of ∼16 Ω cm2 and an ultrastable long-term cycling behavior for 800 h under a current density of 200 μA/cm2, leading to Li//LiCoO2 solid-state batteries with good rate performance and cycling stability.

Fabrication of Y2O3-doped MgO refractory raw materials based on magnesium hydroxide from salt-lake brine

High-purity magnesia refractories were fabricated by brine magnesium hydroxide from the salt-lake brine (Qinghai Salt Lake) and Y2O3 as an additive at 1780 °C. It avoided the substantial CO2 emissions and ultra high temperature sintering process (＞1900 °C) when compared with the conventional magnesite-calcination technical approach. The results confirmed that Y2O3 was dispersed on the MgO grains boundaries in the fabricated MgO aggregates, resulting in a decrease in apparent porosity and enhancing the grains' boundaries. With 3 wt% addition of Y2O3, the apparent porosity and bulk density of the sample reached to 15.9 % and 3.10 g/cm3 from 37.9 % to 2.30 g/cm3 of blank control group, respectively. Compared to the blank control without Y2O3-adding, the sample with 5 wt% Y2O3 exhibited a 54.17 % increase in the resistance to molten slag. SEM results indicated that the incorporation of Y2O3 in samples increased the porosity of small pores and enhanced grains boundaries, thereby suppressing slag's penetration. Furthermore, the Y2O3-adding was employed to disperse the MgO grains boundaries and existed as separate phases for grains boundaries enhancement. The slag attack of the fabricated MgO–Y2O3 refractory raw materials were controlled by an inter-crystalline corrosion process.

Study on the properties of anorthite-based porous sound-absorbing materials prepared by steel slag and fly ash

The efficient utilization of solid wastes, such as fly ash and steel slag, has attracted significant attention across the globe. In this paper, these two kinds of waste materials are used to prepare porous sound-absorbing materials, so as to achieve efficient resource utilization and environmental protection, and promote green manufacturing and circular economy. In this study, steel slag and high-alumina fly ash were used as the primary raw materials to prepare green bodies via organic foam impregnation. Subsequently, a high-temperature sintering process was implemented to get the porous sound absorption material product from the green bodies. The effects of several factors, including the ratio of steel slag and fly ash, sintering temperature, and pore structure, on the sound absorption and mechanical properties of the product were investigated. Based on the anorthite region in the CaO–Al2O3–SiO2 ternary phase diagram region, the composition ratio of the material was designed. The composition and microstructure of the material were characterized by X-ray diffraction and scanning electron microscopy. From the results, with the increase of the ratio of fly ash and steel slag, the composition of low melting point substances in the system decreases, and the amount of liquid phase decreases, which weakens the pore blocking phenomenon inside the material, resulting in the increase of pore size and noise reduction coefficient of the material. Besides, higher sintering temperature tends to correlate to greater density and higher compressive and flexural strengths but lower porosity, and the sound absorption coefficient demonstrated a peak with respect to sintering temperature. Furthermore, when the reduction of polyurethane sponge body pore size was taken into account, the product's sound absorption coefficient also showed a peak. The optimal parameters for our porous materials are as follows: fly ash:steel slag = 48 : 25, polyurethane sponge pore size = 40 ppi, sintering temperature = 1160 °C at 1-h duration (bulk density = 573.98 kg/m3), compressive strength = 1 MPa, porosity = 79.35 %, and noise reduction coefficient = 0.47.

Polarization loss in rutile TiO2 doped with acceptor ions for microwave absorption

With an increase in electromagnetic (EM) pollution, inducing polarization loss using lattice defects has become one of the main strategies for the design and optimization of a new generation of microwave absorbers. In this study, point defects in TiO2 absorbers are designed and controlled using a sol–gel method. The influences of the electronegativity difference and the ionic valence states of the dopant ions on the microwave absorption (MA) performance of rutile TiO2 composites are investigated. The results show that the defects such as oxygen vacancy (VO∙∙) and Ti3+ can be adjusted continuously at a high-temperature sintering process. Cu2+, which has a larger electronegativity than Ti4+ (Cu2+χ = 1.90 > Ti4+χ = 1.54) promotes the localization of electrons. Furthermore, compared with Ag+, which has a similar electronegativity (Ag+χ = 1.93 ≈ Cu2+χ = 1.90), polyvalent copper ions (Cu2++e→Cu+) enhance the electron-hopping process. The formed electron-pinning defect dipole clusters (TiTi′, VO∙∙, CuTi″, CuTi″′, Ti3+→VO∙∙←Ti3+, Ti3+→VO∙∙←Cu2++e, Cu2++e→Cu+, Ti4++e→Ti3+) produce a stronger polarization relaxation process, which regulates the MA performance of TiO2 absorbers. Therefore, this study provides an essential reference for refining the EM wave attenuation performance of simple oxide absorbers.

Surface Chemistry Modulation of BaGd0.8La0.2Co2O6-δ As Active Air Electrode for Solid Oxide Cells.

Modulation of the surface chemistry of air electrodes makes it possible to significantly improve the electrocatalytic performance of solid oxide cells (SOCs). Here, the surface chemistry of BaGd0.8La0.2Co2O6-δ (BGLC) double perovskite is modulated by treatment in an acidic citric acid solution. The treatment leads to corrosion on the surface of BGLC particles, and the effect is dependent on the acidity of the solution. As the acidity of solution is low, Ba cations are selectively dissolved out of the BGLC surface, while as the acidity increases, the corrosion becomes more homogeneous. The Ba surface deficiency remarkably increases the concentration of surface oxygen vacancies and electrocatalytic activity of BGLC. To avoid the loss of Ba-deficient surface during the conventional high temperature sintering process, a sintering-free fabrication route is utilized to directly assemble the Ba-deficient BGLC powder into an air electrode. A single cell with the surface Ba-deficient BGLC electrode shows a peak power density of 1.04 W cm-2 at 750 °C and an electrolysis current density of 1.48 A cm-2 at 1.3 V, much greater than 0.64 W cm-2 and 1.02 A cm-2 of the cell with the pristine BGLC, respectively. This work provides a simple and effective surface chemistry modulation strategy for the development of an efficient air electrode for SOCs.

Effect of cell sintering temperature on the performance of non-noble metal loaded cerium oxide SOEC anodes

Abstract Introducing methane oxidation reaction into the anode of the high-temperature solid oxide electrolysis cell (SOEC) can reduce the power consumption for water electrolysis. Compared to the traditional conditions of methane oxidation, the methane oxidation catalyst sintered at the SOEC anode, which is closely related to the cell sintering process. This study uses non-noble metals as active sites for methane oxidation, zirconia, and samarium oxides doped ceria as catalyst support and oxygen ion conductors. The effects of anode sintering temperature on the electrochemical performance of SOEC assisted by methane oxidation were investigated. The results indicate that the high-temperature sintering process promotes the performance of the SOEC anode with Ni as the active site, while high temperature harms the performance of the Co-loaded anode. The sintering temperature exhibits a poor effect on the Fe-loaded anode. The Ni exhibits good enhancement of methane oxidation on reducing the electrolysis voltage of SOEC, while Co only exhibits methane oxidation assistance at low-temperature sintering. Differently, Fe has almost no obvious methane oxidation assistance for SOEC, which mainly represents good oxygen evolution performance.

Breakthrough in atmospheric plasma spraying of high-density composite electrolytes: Deposition behavior and performance of plasma-sprayed GDC-LSGM on porous metal-supported solid oxide fuel cells

The potential application of plasma spraying in the preparation of ceramic electrolyte for porous metal-supported solid oxide fuel cells (SOFCs) is highlighted by its ability to eliminate the need for a high-temperature sintering process. However, the challenge of achieving highly dense electrolytes through plasma spraying remains to be addressed. In this study, a novel electrolyte for porous metal-supported SOFCs (PMS-SOFCs) is developed. This involved the preparation of a highly dense structure of gadolinium-doped ceria (GDC)-lanthanum strontium gallium magnesium oxide (LSGM) composite coating using plasma spraying under atmospheric conditions. The composite electrolyte is prepared using atmospheric plasma spraying (APS). The addition of the low-melting-point LSGM phase enhanced the microstructural densification of the GDC-based composite coating and diminished electron loss in a reducing atmosphere, thereby improving the cell's open-circuit voltage. At 36 kW plasma arc power, the single cell with composite electrolyte exhibited a maximum power density of 371 mw/cm2 at 750 °C and achieved the highest open-circuit voltage (1.03 V) at 600 °C. Moreover, the open-circuit voltage remained stable over a 100-h test. These findings suggest that using APS to deposit a composite electrolyte with added low-melting-point secondary phases presents a promising approach for achieving relatively high OCV in PMS-SOFCs based on cerium oxide electrolytes.

Gradient fluorination engineering through interdiffusion reaction for high-voltage LiCoO2

The advancement of high charging cut-off voltage stands as a crucial avenue to enhance the energy density of LiCoO2 (LCO). However, LCO faces severe interface and bulk phase issues at high voltage (≥ 4.6 V), resulting in poor cycling stability. In this study, we reconstruct the surface structure of LCO based on the interdiffusion reaction between LCO and MgF2 in a high-temperature sintering process. Specifically, this interdiffusion reaction yields an ultra-thin LiF coating layer, artificially reinforcing the chemical structure of the cathode-electrolyte interphase (CEI) during cycling. This LiF-rich CEI not only effectively protects the surface structure of LCO, but also facilitates the lithium-ion diffusion. Furthermore, the diffusion of F and Mg into the LCO lattice significantly strengthens the structure, which inhibits unfavorable phase transitions from the O3 phase to the H1–3 phase at high voltage. Consequently, such modified LCO with concurrently enhanced interface and bulk structure exhibits outstanding long-term cycling performance within 3.0–4.6 V at 1 C, achieving a capacity retention of 84.9 % after 1000 cycles. Meanwhile, it also demonstrates excellent high-temperature performance, with a capacity retention of 85.0 % after 200 cycles under 45 °C.

Microstructure and mechanical properties of high-pressure sintered B6O-SiC nanocomposites

Boron suboxide (B6O) is recognized as a superhard material with a low mass density, high resistance to chemical wear, and excellent wear resistance. Despite its desirable properties, the limited fracture toughness of B6O restricts its application in industrial contexts. This study presents the structural and mechanical characterization of B6O-SiC nanocomposites, which were synthesized via a high-pressure high-temperature sintering process of B6O powders and SiC whiskers. The sintering process induced fragmentation of SiC whiskers, resulting in the homogenous distribution of SiC fragments within the B6O matrix. An increase in SiC content was observed to decrease the composite's hardness, while initially reducing then enhancing its toughness. The nanocomposites containing 20 wt% and 30 wt% SiC whiskers exhibited significant improvements in fracture toughness, averaging 6.5 MPa m1/2 and 7.0 MPa m1/2, respectively—approximately threefold the toughness of polycrystalline B6O—while sustaining high hardness values of 36.3 GPa and 35.6 GPa on average. Microstructural analyses revealed that the composites’ superior mechanical performance is due to the presence of strong grain boundaries, as well as a high density of nanotwins and stacking faults. The findings demonstrate a viable method for producing B6O-based nanocomposites with enhanced hardness and toughness, potentially expanding their industrial applicability.

Unraveling the conundrum of electronic leakage in protonic ceramic cells: Operation-specific insights and rational design strategies

Electronic conduction through proton-conducting electrolytes significantly impairs the efficiency of protonic ceramic cells (PCCs). In this study, we explore the electron and ion mixed transport properties of four common protonic ceramics, BaZr0.8Y0.2O3-δ (BZY82), BaZr0.7Ce0.2Y0.1O3-δ (BZCY721), BaZr04Ce0.4Y0.1Yb0.1O3-δ (BZCYYb4411), and BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb1711). It marks the first instance of investigating these properties under operation-specific scenarios: fuel side of electrolysis cell, air side of electrolysis cell, fuel side of fuel cell, and air side of the fuel cell. BZCYYb1711 exhibits the highest ionic conductivity, but two to three times higher electronic leakage when exposed to oxygen-containing environments than the others. BZY82 exhibits approximately two times higher electronic leakage in a hydrogen-containing environment. BZCY721 demonstrates excellent ion transport numbers (∼0.95) across these four operating conditions. BZCYYb4411 behaves quite similarly to BZCY721. The most challenging operating environment for all candidates is the air side of fuel cell mode. This mode leads to a high initial electronic leakage, followed by a significant increase with polarization. The probable cause for this behavior is a H2-free, polarization-induced reduction that leads to the formation of VO•. The electron small polaron associated with VO• is released by the electrical field due to the Poole-Frenkel effect. ZnO and NiO sintering aids are found to be detrimental to the ionic conductivity of the electrolytes. In particular, NiO substantially lowers the ion transport number. The correlation of the operation-specific electronic leakage to full cells is discussed. It is suggested that a rational PCC design should synergistically couple BZCYYb1711 at fuel side with BZCY4411 at air side to deliver a well-balanced performance and faradaic efficiency simultaneously, and the high temperature sintering process with a NiO fuel electrode should be shortened or replaced by ultra-fast sintering techniques or using a fuel electrode scaffold-infiltration fabrication strategy.

Preparation and electrochemical properties of a ceramic solid electrolyte with high ionic conductivity, Li1.3Al0.3Ti1.7(PO4)3

The emergence of lithium-ion solid electrolytes greatly increases the safety risk of liquid electrolytes. Among the many solid electrolytes, aluminum-doped Li1.3Al0.3Ti1.7(PO4)3(LATP) has become a research hotspot due to its high ionic conductivity and good air stability. However, the traditional high-temperature sintering process has the problems of lithium volatilization and secondary phase formation. Therefore, it is very difficult to prepare high-quality LATP solid electrolytes. The X-ray diffraction pattern and analysis showed that the LATP samples prepared in this paper showed rhombohedral structure and could be indexed by the R3c space group, and a new method of excess lithium compensation sintering was proposed, in which lithium compensation (LiNO3) could well reduce the impact of lithium volatilization. It can be used as a sintering additive to promote the sintering densification of LATP. In this paper, the optimal sample for sintering at 900°C was determined by measuring the microstructure and electrochemical properties of the electrolyte, and lithium doping was studied. The LATP solid electrolyte with 10 wt% lithium doped has a conductivity of 7.2× 10−4 S/cm and a low activation energy (0.278 eV). Its mechanical properties (elastic modulus and hardness) are the best, which are 103.024 GPa and 8.053 GPa, respectively, and the value of its elastic modulus is much greater than that of lithium metal shear modulus of 4.25 GPa, which can effectively inhibit the growth of lithium dendrites. And the magnitude of the grain boundary conductivity and particle size of the lithium-doped sample correspond to the dielectric constant results.

Investigation of the Effect of High-Frequency Induction Sintering on Phase Structure and Microstructure of SiC Reinforced Aluminum Matrix Composites

In this study, SiC-reinforced aluminum matrix composites were powder metallurgically (PM) prepared and sintered using high-frequency induction system (HFIS). The samples with different ratios of SiC (wt.%10, 20 and 40) added to the aluminum matrix were sintered at 660, 800, and 1000 °C. In addition, Al/SiC composites were compared by sintering with the conventional sintering (CS) method under similar sintering conditions. The heating rate for the sintering process using HFIS was 500 °C/min, while the CS method used a heating rate of 10 °C/min. The effect of the temperature and SiC ratio on the density, hardness, phase structure, and microstructure of composites was investigated. The optimum sintering temperature was determined according to the SiC additive amount. When 10%, 20%, and 40% SiC by weight were added to the aluminum matrix in the sintering process with HFIS, the required sintering temperatures were determined as 660, 800, and 1000 °C, respectively. While new phases were not formed as a result of short-term HFIS sintering, a high-temperature Al4C3 phase was detected in CS sintering. HFIS sintered Al/SiC composite samples were obtained in Al and SiC phases with high density and hardness ranging from 43-118 HV. In the high-temperature sintering process with HFIS, the formation of Al4C3 was prevented and its physical and mechanical properties were improved.

Synthesis of rGO-reinforced MgAl2O4 spinel composites by solid-state powder route mechanism: A comparative analysis between non-reinforced and rGO-reinforced spinel composites

Reduced Graphene Oxide (rGO)-reinforced MgAl2O4 spinel composite was successfully synthesized by a solid-state powder route mechanism via high-energy planetary ball milling of corresponding metal oxide precursors followed by a high-temperature single-stage sintering process. The effect of rGO on the homogeneity, phase development, morphology, chemical composition, rate of formation of spinel, and cation anti-site formation of the composites was methodically investigated. For comparison, a stoichiometric non-reinforced MgAl2O4 spinel was also synthesized. The addition of 0.2 wt% and 0.4 wt% of rGO as reinforcement increased the homogeneity of the ball-milled composite powder, with Polydispersity Index (PDI) values of 0.19 and 0.15 respectively, as compared to 0.24 obtained in non-reinforced spinel composite. The X-ray diffraction pattern and IR spectrum of 1650 °C sintered composites confirmed the formation of highly crystalline phases with spinel structure. The microstructural analysis revealed that the addition of rGO led to a reduction in porosity and improved the process of sintering. Calorimetric studies showed that spinelization started to occur at 858 °C and 880 °C for 0.2 wt% and 0.4 wt% rGO-reinforced composites respectively, which was faster than non-reinforced composite. 27Al solid-sate nuclear magnetic resonance (SS-NMR) analysis depicted that ceramic composite reinforced with rGO exhibited lesser inversion parameter of 0.09 (for 0.2 wt% rGO) and 0.055 (for 0.4 wt% rGO), as compared to 0.145 obtained in non-reinforced composite, indicating lesser cation anti-sites formation in rGO-reinforced spinel composite.

Improved Performance of QDSSCs Can Be Achieved by Constructing a Transparent Anatase TiO2@MWCNT Photoanode Based on the Bionic Mountain Lotus.

In this research, the structural characteristics of the mountain holly leaf were emulated. It was observed that after the initially uneven surface of the petals is filled with infiltrated water, it exhibits a distinctive transparent beauty after rainfall. Furthermore, the presence of leaf veins enhances the structural strength of the petals and facilitates nutrient transport. Inspired by previous studies on double-layer spin-coated films, we further developed and designed the TA TiO2@MWCNT photocathode thin film. This innovative film incorporates multiwalled carbon nanotubes (MWCNT) into a previously established TA TiO2 photocathode thin film. The inclusion of MWCNT results in the formation of a three-dimensional highway structure, where MWCNT intertwines within the TA TiO2 film. Under the operational state of immersion in the electrolyte, it maintains a level of transparency similar to that of the TA TiO2 photoanode thin film. The high-temperature sintering process results in the oxidation and depletion of MWCNTs on the surface of the film, leaving behind uniformly dispersed concave defects, thereby greatly enhancing the specific surface area. The findings demonstrate that the optoelectrode of high transparency and high specific surface area, TA TiO2@MWCNT, comprehensively enhances the performance of the solar cells. The transparent QDSSC surpasses its counterparts for the first time, achieving a power conversion efficiency (PCE) of 6.335%. This sets the stage for new materials and innovative approaches in the field of solar cells and other titanium dioxide film-related areas.

Heterogeneous diamond–TiC composites with high fracture toughness and electrical conductivity

The concurrent enhancement of toughness, electrical conductivity, and thermal stability in polycrystalline diamond composites represents a formidable challenge. Here, a novel diamond-TiC composites (referred to as DTC) with high fracture toughness and conductivity were synthesized through a high-temperature and high-pressure reaction sintering process utilizing two precursors: diamond mixtures containing TiH2 and Ti-coated diamonds. On the one hand, the inherent bonding and encasing of TiC onto the diamond matrix form a heterogeneous structure, providing high strength and excellent fracture toughness up to 11.6 MPa·m1/2. On the other hand, the established oxygen barrier and current pathway offer a thermal stability of 765 °C and high conductivity up to 837 S·m−1. Remarkably, this rare combination of mechanical, electrical, and thermal properties has been realized within a single material under relatively moderate sintering conditions, thus positioning diamond-TiC composites as a promising ceramic for electrical applications in high-stress environments.

High-performance, stable buffer-layer-free La0.9Sr0.1Ga0.8Mg0.2O3 electrolyte-supported solid oxide cell with a nanostructured nickel-based hydrogen electrode

La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) with an extraordinary oxygen-ion conductivity has been extensively studied as an electrolyte material for intermediate temperature solid oxide cells (SOCs). However, the conventional high-temperature sintering process of electrodes results in detrimental reaction between LSGM and Ni-based hydrogen electrode and microstructural coarsening of the electrode. Herein, a buffer-layer-free LSGM electrolyte-supported single cell with a nanostructured Ni-Gd0.1Ce0.9O1.95 (GDC) electrode is developed using a sintering-free fabrication approach. The cell exhibits a peak power density of 1.23 W cm−2 at 800 °C and an electrolysis current density of 1.85 A cm−2 at 1.5 V with excellent operating stability. The good performance and durability is owing to the synergistic effects of the elimination of elemental interdiffusion at the electrode/electrolyte interface, polarization induced in situ formation of hetero-interfaces between Ni-GDC and LSGM, and remarkable structural stability of Ni-GDC. This study provides an innovative means for the development of efficient and durable buffer-layer-free LSGM-supported SOCs.

Facile Route to Synthesize a Highly Sinterable Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolyte.

NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a widely used solid electrolyte in solid-state lithium batteries, owing to its excellent chemical stability against moisture and high total ionic conductivity. However, traditionally, densification of LATP has been achieved through a high-temperature sintering process (approximately 1000 °C) owing to its poor sinterability. Herein, we report a facile synthesis route to obtain highly sinterable LATP solid electrolyte using tetrabutyl titanate (C16H36O4Ti) as the titanium source and incorporating the traditional solid-state reaction method. The synthetic LATP powder mixed with a low ratio of LiTiPO5 exhibited a hybrid crystalline-amorphous phase structure, which facilitated grain fusion, promoted structural homogeneity, and facilitated structural densification under low-temperature sintering. The sintered LATP pellet, which exhibited an interconnected structure and indistinct grain boundaries, achieved a relative density of >90% and an ionic conductivity of 0.667 mS/cm at a sintering temperature of only 750 °C. Additionally, we systematically studied and demonstrated the synthesis reaction mechanism, sintering behavior, and ionic diffusion kinetics of LATP electrolytes. Our study paves the way for synthesizing highly sinterable LATP solid electrolytes using a simple, additive-free, and cost-effective method.

Cold sintering process for densification of Fe3O4 ceramic magnets with improved properties

Iron oxide-based ferrite ceramics, widely applied in high-frequency applications, are conventionally produced through high-temperature sintering processes, often resulting in grain growth and phase transformation. In this study, we used a cold sintering process (CSP) with oxalic acid (OA) as a solvent to consolidate iron oxide (Fe3O4) ceramics at a low temperature of 160 °C. The OA-assisted CSP technique has demonstrated a remarkable capacity to facilitate the dissolution and redeposition of iron oxide ions, leading to the interconnection of Fe3O4 particles, forming densely packed ceramics even at low-temperature sintering. Importantly, CSP maintained particle sizes and hindered phase transitions of Fe3O4. The OA concentrations in CSP had a minimal impact on crystal structure and magnetic properties, but it significantly enhanced microstructural features, density, hardness, and electrical resistance. Compared to reference samples prepared without an aqueous solution or with water alone, the CSP-prepared Fe3O4 ceramics with OA exhibited substantially improved density (a relative density of ∼80 %), mechanical properties (Vickers hardness of 3.5–4.0 GPa), magnetic properties (saturation magnetization >70 emu/g), and electrical resistance (electrical conductivity ∼10−3 S/cm at 102–106 Hz). These findings demonstrate a novel approach to fabricating Fe3O4 ceramics at significantly lower temperatures while still achieving properties comparable to those sintered at high temperatures.

Comparison between Lithium Substitution and Doping on the Physical and Piezoelectric Properties of Lead-Free BCZT Ceramics

Defects generation in ceramics by element substitution or doping may improve their properties. However, different results will be obtained even though the same element is involved due to different mechanisms. Ceramics Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCZT) is one of the potential candidates to replace lead-based material PZT. However, the conventional method requires high-temperature calcination and sintering process to synthesize this material. Thus, Lithium (Li) can act as the sintering aid to lower the temperature at the same time, the properties of piezoelectric can be enhanced. In this paper, the structural, physical, and piezoelectric performance of lead-free Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCZT) ceramics with Lithium Li substitution and doping, synthesized by the solid-state reaction method were studied. The substitution of Li increases the density, ρ and piezoelectric coefficient, d33 of BCZT which are 4.075 g/cm3 and 304.6 pC/N, respectively. These results demonstrate that Li substitution is more beneficial to the piezoelectric properties than doping because it produces higher grain boundary resistance and activation energy and has lower conductivity than doping. This can provide a definite strategy during the chemical composition design and manufacture of BCZT ceramics.