Porous TiO2/rGO nanocomposites prepared by cold sintering as efficient electrocatalyst for nitrogen reduction reaction under ambient conditions

Haber–Bosch process as the current dominant artificial NH₃ production process in industry, requires relatively high temperature (350–550 °C) and pressure (150–350 atm). Electrocatalytic nitrogen reduction reaction (NRR) as a green and sustainable strategy for ammonia production has raised intensive research interest in recent years but still remains a significant challenge because of the lack of high performance electrocatalysts. In this work, porous TiO₂-reduced graphene oxide (TiO₂/rGO) nanocomposite as self-supporting efficient electrocatalyst for NRR under ambient conditions were prepared by cold sintering associated with sacrificial template method. The porous TiO₂/rGO nanocomposite with grain size of ～40 nm were prepared by cold sintering process at 220 °C and 147 MPa. Given the 220 °C as cold sintering temperature, anatase TiO₂ were preserved as the final phase which exhibit much better NRR electrocatalytic performance than the rutile phase. The oxygen vacancy densities in the nanocomposites were also tuned by heat treatment at 450 °C under different atmosphere, while samples heat treated under H₂/Ar atmosphere gave the best electrocatalytic NRR performance with a FE of 8.88 % and an NH₃ yield of 7.75 μg h^?1 cm^?2 at ambient conditions. Experiments also shows that the addition of rGO significantly improved the electrocatalytic NRR performance especially the conductivity. This work not only designed a framework of ceramic nanocomposites based self-supporting and durable electrocatalysts system but also paves a feasible way towards preparing electrocatalysts that are sensitive to high temperature fabrication process.     

One-step cold sintering process towards translucent BaF2 ceramics

BaF₂ ceramics were prepared using a one-step cold sintering process with an ultra-low sintering temperature of 150 °C and uniaxial pressures ranging from 450 to 900 MPa. The relative density and microstructure improved steadily with the increasing pressure, and a fully densified microstructure with a relative density of 97.2% was achieved at 900 MPa. For BaF₂ ceramics with a thickness of 1 mm, the optimum in-line transmittance in the visible light region (58.5%) was achieved at a wavelength of 720 nm, and the maximum value (65.3%) was obtained at 1864 nm. The permittivity of the ceramics increased gradually from 6.18 to 7.09 with increasing pressure, and the dielectric loss was optimized from 0.01 to 0.003. Additionally, the mechanical properties improved continuously with the increasing pressure, and the optimal compressive strength (257 MPa), hardness (2.01 GPa), and Young's modulus (54.8 GPa) were achieved when cold sintered at 900 MPa.     

Preparation and properties of LiF transparent ceramics by cold sintering process

The development of optoelectronic devices depends on the development of optoelectronic materials such as transparent ceramics. LiF transparent ceramics are photoelectronic ceramics with excellent photoelectric properties. Still, the traditional preparation of LiF transparent ceramics generally needs a high temperature or high-pressure environment, and the cost is high. This paper adopts a cold sintering process to prepare high-density LiF transparent ceramics at low temperatures to reduce the preparation conditions. The effects of different cold sintering temperatures on microstructure, density, hardness, visible and near-infrared transmittance, and electrical properties of transparent ceramics were studied. The results show that using LiOH solution as the solvent, the relative density of LiF ceramics can reach up to 99.64% under the sintering condition of 375 °C/470 MPa, and the Vickers hardness is 1.34 GPa. Vickers hardness is 1.34 GPa. The transmittance in the visible and near-infrared regions is 60.45% and 85.31%, respectively. The dielectric constant and dielectric loss of 13 GHz are 4.36 and 1.11 × 10⁻³, respectively.     

Densification of thermodynamically unstable tin monoxide using cold sintering process

SnO is a thermodynamically unstable phase and undergoes thermal decomposition into SnO₂ and Sn at a relatively low temperature when heating under ambient conditions. With the cold sintering process (CSP), SnO can be densified up to 89% of theoretical density within 100 min by applying uniaxial pressure of 350 MPa and transient liquid phase. 15-fold BET specific surface area reduction is observed between the ball-milled powder and the cold-sintered pellet, indicating experimental evidence of sintering. The temperature profiles of 70–265 °C show densification while maintaining the phase purity. Water and 2 M acetic acid solution are studied as transient liquid phases which promotes dissolution-precipitation on the particle surface and induces crystalline texture. Electrical properties of the cold sintered bulk, notably electrical conductivity and Seebeck coefficient, are measured as a function of temperature.     

Preparation of Na0.5Bi0.5TiO3 ceramics by hydrothermal-assisted cold sintering

A recently proposed novel technique, termed “cold sintering process” (CSP), can provide dense ceramic solids at remarkably low temperatures around 180?°C. In a recent work, we successfully obtained dense Na_0.5Bi_0.5TiO₃ ceramics by this method. Bismuth titanate sodium nanoparticles were prepared as the raw material powder by the hydrothermal synthesis route. A hydrothermal precursor solution was used as the transient solvent for cold sintering. Under the combined action of pressure and temperature, the Na_0.5Bi_0.5TiO₃ green body was densified by dissolution-precipitation, and a preliminary densified ceramic sheet was obtained. The amorphous phase in the ceramic sheet was then transformed into a crystalline phase by annealing. Finally, densified Na_0.5Bi_0.5TiO₃ ceramic sheets were obtained, with density of up to 99%, relative permittivity of 681, and dielectric loss of 0.08 at 10?kHz and room temperature. The piezoelectric coefficient d₃₃ of the sample was 52.5?pC/N. The properties of the prepared ceramics were comparable to those of the conventional sintered ceramics.     

Rutile TiO2 microwave dielectric ceramics prepared via cold sintering assisted two step sintering

In this work, a sintering route named cold sintering assisted two step sintering process (CSP-TS) is presented to prepare rutile TiO₂ ceramics with submicron grain sizes. Cold sintering process at 300 °C with tetrabutyl titanate and water as the liquid phase yields a ‘green body’ with a relatively high density of ～80 %, and finally dense (98.5–99.8 %) rutile TiO₂ ceramics with grain sizes of ～600 nm can be obtained in the second sintering process at 950?1000 °C. The microstructural analysis with SEM and TEM indicates that the CSP-TS samples sintered at 950 °C have an obvious phenomenon of recrystallization, accompanying by a decrease of amorphous phases and a formation of clear grain boundaries. Besides, the rutile TiO₂ ceramics prepared by CSP-TS possess excellent microwave dielectric properties with relative permittivity of 92.0–98.4 and Q × f values of 27,800?31,900 GHz. Therefore, it is feasible to utilize CSP-TS to prepare ceramics with small grain sizes at low sintering temperatures.     

Mechanism of densification of calcium carbonate by cold sintering process

In general, carbonates cannot be easily hardened by the conventional ceramic sintering process due to their thermal decomposition during heating. However, when the cold sintering process (CSP) is selected, carbonates can be hardened at lower temperatures. It has been demonstrated that calcium carbonate can be hardened by CSP, but the detailed densification mechanisms of cold sintering at various temperatures have not been fully clarified. In this study, the vaterite phase of calcium carbonate was selected as the starting material. As the cold sintering temperature for calcium carbonate powder increased, the bulk density of the hardened calcium carbonate body increased. The compressive strength was maximized when cold sintered at 80 °C due to the balance between the solubility of calcium carbonate and the reactivity of cold sintering. Almost no crystal phase transformation from vaterite to calcite occurred during cold sintering, and reprecipitation of the vaterite phase though dissolution-precipitation densified the body.     

Toward a size scale-up cold sintering process at reduced uniaxial pressure

Cold sintering is a low-temperature powder process methodology that enables the densification of ceramics and ceramic-based composites at significantly reduced times and temperatures. Although the general notion of required pressure for the cold sintering is in the hundreds MPa, some material systems were reasonably demonstrated to be densified in the pressure below 50 MPa, which allows to increase the sample size up to 25 cm² using a small tabletop laboratory press. Indeed, the pressure requirement has been a major constraint on promoting its application deployments, but this study is intended to propose a path to alleviate that limitation. Five different ceramic and composite systems (three ZnO-based composites, Li_1.5Al_0.5Ge_1.5(PO₄)₃, and zeolite Y) with applications in electronic, structural, and energy storage were investigated as a preliminary example of the size scale-up process. One of the observed challenges of the scale-up process was to obtain homogeneous microstructure all over the sample as the transient phase evaporation rate may be different upon the localization. In the case of ZnO, the inhomogeneous pellet translucency may pertain to partial anisotropic grain growth within the same sample.     

High density nano-grained Gd2Zr2O7 ceramic prepared by combined cold and microwave sintering

In this study, nano-grained Gd₂Zr₂O₇ (NGZO) ceramic with a high relative density was prepared by a novel cold sintering process (CSP) assisted by microwave sintering (CSP-MS). The CSP with water as the liquid phase at 280 °C yielded nano-grained ceramic with a relative density of 71.5%. NGZO with a high relative density of 97.1% and average grain size of 73 nm was obtained by subsequent microwave sintering of the cold-sintered sample at 1300 °C. Therefore, CSP-MS is feasible in preparing dense NGZO ceramics with small grain sizes at relatively low sintering temperatures.     

Cold sintering assisted CaF2 microwave dielectric ceramics for C-band antenna applications

A cold sintering process is adopted to pre-densify CaF₂ ceramics from 85.7% at 300 MPa to 91.7% at 750 MPa. Subsequent post-annealings at 1000–1150 °C lead to further improvements in densification, where great enhancements of grain size and crystallinity are also observed from the scanning and transmission electron micrographs. Significant advances in Qf values are achieved in the post-annealed CaF₂ ceramics. The optimum Qf value (80,522 GHz) is achieved after cold sintering at 750 MPa and post-annealing at 1000 °C, which is three times higher than the conventional sintered one at 1000 °C (26,448 GHz). Moreover, the obtained low-ε_r (5.9–6.5) of CaF₂ ceramics suggests broad application prospects in the high-band microwave communications. A microstrip patch antenna is fabricated using the CaF₂ ceramics as the substrate, which operates at 7.89 GHz in the C-band, with an S₁₁ of ?13.4 dB, simulated high gain and efficiency of 6.41 dBi and ?0.56 dB, respectively.     

The effect of yttrium nitrate addition on the densification behaviour of Y2O3 ceramics during the cold sintering process

The densification behaviour and phase development of Y₂O₃ ceramics were investigated as a function of yttrium nitrate (Y(NO₃)₃·6H₂O) solution addition during the cold sintering process at 200 °C. Second phases such as Y₄O(OH)₉NO₃ and Y(OH)₃ were observed after the cold sintering process. The amount of Y₄O(OH)₉NO₃ increased with increasing amount of yttrium nitrate, while the amount of Y(OH)₃ decreased. The second phases were transformed to fine sized Y₂O₃ (∼30 nm) particles smaller than those of the raw powder (<400 μm) by sintering at 600 °C. The fine sized Y₂O₃ particles were located in the voids between the larger Y₂O₃ particles, thus increasing the packing density and enhancing the densification of the Y₂O₃ ceramics after the final sintering process.     

Influence of incongruent dissolution-precipitation on 8YSZ ceramics during cold sintering process

The incongruent dissolution-precipitation behaviors of 8YSZ (8 mol% yttria-stabilized zirconia) ceramics during cold sintering process is studied in this paper by changing the pH of liquid media. The different solubility of Y³⁺ and Zr⁴⁺ at the same lattice position causes the disparate dissolution behaviors, and results in incongruent precipitation. Compared with acidic or alkaline solution, neutral solution is more conducive to the incongruent dissolution-precipitation process, and the concentration ratio of dissolved Y³⁺ and Zr⁴⁺ can reach ～6385. The incongruent dissolution-precipitation process facilitates the formation of neck structure and promotes the ionic migration and diffusion at the subsequent high-temperature sintering process, which improves the mechanical properties and electrochemical properties of 8YSZ ceramics. This work reveals the principle of incongruent dissolution-precipitation process of zirconia-based ceramics, and it is of significance for selecting suitable liquid media to control the incongruent dissolution-precipitation behaviors in cold sintering process to prepare high-performance zirconia-based ceramics.     

Grain size effect on microwave dielectric properties of Na2WO4 ceramics prepared by cold sintering process

In this work, cold sintering was adopted to prepare Na₂WO₄ ceramics with different grain sizes ranging from 0.632 μm to 17.825 μm. Their microstructures, complex impedance, and microwave dielectric properties were studied in-depth. It was found that samples with relative densities higher than 92% can be successfully synthesized by cold sintering process at a low temperature of 240 °C. However, their electrical properties have strong dependence on the grain size. Specifically, the resistance of grain boundaries decreases dramatically with the increase of grain sizes, while the quality factor has a positive correlation with the grain sizes of Na₂WO₄ ceramics. Excellent microwave dielectric properties, including permittivity = 5.80, Q × f = 22,000 GHz, and TCF = −70 ppm/°C, are obtained for Na₂WO₄ ceramics with a grain size of 4.477 μm prepared by cold sintering process.     

Dense gypsum ceramics prepared by room-temperature cold sintering with greatly improved mechanical properties

Dense gypsum (CaSO₄·2H₂O) ceramics were successfully fabricated by a simple room-temperature cold sintering process with 5 wt% water. The relative density of gypsum ceramics increased from 89.6% to 96.8% with increasing the applied uniaxial pressure from 100 to 400 MPa during cold sintering. The relative density changed slightly for higher pressure, and microcracks were observed as well as abnormal grain growth. Both the compressive and flexural strengths reached the peaks at 98.5 MPa and 26.5 MPa for the uniaxial pressure of 400 MPa, which were improved by 2.6 and 2.0 times, respectively comparing with the bulk gypsum prepared by traditional method from α-plaster. Furthermore, the dry-pressed gypsum compacts were very fragile, and had relative densities 5–12 % lower than the cold-sintered ceramics, indicating that the slight solubility of gypsum in water (0.2 g/100 g) played a critical role in the densification, microstructural evolution and greatly improved mechanical properties of cold-sintered gypsum ceramics.     

Single-step densification of nanocrystalline CeO2 by the cold sintering process

This study reports the successful single-step cold sintering of nanocrystalline cerium dioxide (CeO₂) at temperatures ranging from 250°C to 400°C under 500 MPa, using molten hydroxides flux solvents. CeO₂ ceramics obtained were 82 to 91% of the theoretical density. Structural and microstructural investigations of the as-cold sintered CeO₂ ceramics were conducted to further understand this new approach to cold sinter ceramics. Electrical conductivity measured by two-point AC impedance demonstrated an activation energy for grain conductivity of 0.49 eV, with impedance spectra characteristic of nanoscale CeO₂.     

Sintering of a sodium-based NASICON electrolyte: A comparative study between cold,field assisted and conventional sintering methods

Scandium-substituted NASICON (Na_3.4Sc_0.4Zr_1.6Si₂PO₁₂) is a promising electrolyte material for sodium-ion solid state batteries, with the highest ionic conductivity reported to date for a NASICON material. Low-temperature densification and control of microstructure are important factors to enable the low-cost manufacturing of such new battery type. Non-conventional sintering techniques such as Field Assisted Sintering Technology / Spark Plasma Sintering (FAST/SPS) and Cold Sintering are therefore investigated and compared to conventional free sintering. FAST/SPS enables to get rapidly dense samples (99% TD) at lower temperatures than the ones required by conventional sintering routes and with similar electrical properties. Cold sintering experiments, involving the addition of aqueous solutions as sintering aids and high mechanical pressure, enable a moderate densification, but at temperatures as low as 250 °C. Further heat treatments still below the conventional sintering temperature increased the achieved density and ionic conductivity.     

Highly dense 0.3CaCeNbWO8-0.7LaMnO3 composite ceramics fabricated by cold sintering process

The cold sintering process (CSP) has been used for fabricating functional ceramics at a low sintering temperature. In this study, highly dense 0.3CaCeNbWO₈-0.7LaMnO₃ composite ceramics have been successfully fabricated by CSP. The phase structure, microstructure, and electrical properties of composite ceramics have been investigated. The composite ceramic is mainly composed of a tetragonal CaCeNbWO₈ phase with scheelite structure and an orthorhombic LaMnO₃ phase with perovskite structure. The relative density of composite ceramic is 94.5%, and is higher than that of single phase ceramic. The resistivity of composite ceramic exhibits negative temperature coefficient characteristics, with an aging coefficient less than 2%. Such a sintering methodology is of great significance, since it provides a feasible idea for preparing composite ceramics.     

Microstructural evolution of ZnO via hybrid cold sintering/spark plasma sintering

In this work, we demonstrate a hybrid cold sintering/spark plasma sintering (CSP-SPS) process to densify ZnO ceramic with controlled grain growth. The densification of ZnO is initially activated at 85 °C, and high densities (>98%) are achieved at 200–300 °C in only 5 min with a low assisted pressure of 3.8–50 MPa. The microstructure of ZnO grains experiences a mild coarsening from ~205–680 nm during the CSP-SPS. In comparison, a much higher temperature (>770 °C) is required to sinter ZnO ceramic via SPS, and the grain size exhibits an obvious overgrowth to ~10 µm. The calculated apparent activation energy of grain growth using CSP-SPS is 69.3 ± 6 kJ/mol, which is much lower than that of SPS samples with 296.8 ± 59 kJ/mol. In addition, the conduction mechanism of the CSP-SPS and SPS samples is investigated using impedance spectroscopy. Overall, CSP-SPS is promising for the fabrication of fine ceramics with mild sintering conditions.     

The cold sintering process: A review on processing features,densification mechanisms and perspectives

Since its first introduction in 2016, cold sintering process (CSP) has gained worldwide interest from the scientific community as green and innovative fabrication route due to the dramatic reduction of processing time, energy, and costs. Cold sintering resembles the geological formation of rocks where a ceramic powder is densified with the aid of a liquid phase under an intense external pressure and limited heating conditions (below 350 °C). Up to date, tens of different materials, including composites, have been successfully processed through CSP and extraordinary results in terms of densification, microstructure and final properties have been achieved. In the present review, processing features and variables, possible densification mechanisms and issues also for the realization of ceramic-based composites are explored. Advantages with respect to existing techniques are analysed and current challenges are described to lay the ground for new processing opportunities to be faced in the near future.     

Fabrication and properties of C/SiC porous ceramics by grinding-mould pressing-sintering process

High temperature resistant porous ceramics are considered to be prime candidates for applications in the transpiration cooling system of a hypersonic vehicle. This paper describes a new preparation process including grinding-mould pressing-sintering process, which is successfully used to fabricate C/SiC porous ceramics with high compressive strength and excellent permeability. The effects of carbon fiber content on the microstructure, mechanical property, pore size distribution and permeability of this porous ceramic are investigated in detail. The results indicate that this porous ceramic prepared in this study exhibits high compressive strength (～270.82 MPa) and excellent permeability (～3.937 × 10^?8 mm²). The C/SiC porous ceramics fabricated in this study will have potential application in active thermal protection systems.