Cold sintering process for ZrO2‐based ceramics: significantly enhanced densification evolution in yttria‐doped ZrO2

We recently developed a novel technique of cold sintering process (CSP) to obtain dense ceramics at extraordinarily low temperatures. In this communication, we demonstrate the feasibility of applying CSP to zirconia‐based ceramics. As exemplified by 3Y‐TZP ceramics, a significantly enhanced densification evolution is observed. Water is simply utilized as a sintering aid to assist the ceramic densification under an applied external pressure. The low‐temperature advantage of CSP outstands in contrast to the densification curves compiled from other sintering techniques. A gradual monoclinic‐to‐tetragonal phase transformation is revealed in correspondence to the densification development, as well as contributes to the mechanical hardness evolution. A Vickers Hardness reaches ~10.5 GPa after annealing the cold‐sintered ceramics at 1100°C, which is comparable to those values reported in the previous studies at higher sintering temperatures. Such a sintering methodology is of significant importance as it provides a roadmap for cost‐effective processing of zirconia‐based ceramics and composites that enable broad practical applications.     

Effect of Ga2O3 on Sintering and Phase Stability of Sc2O3‐Doped Tetragonal Zirconia Prepared via Aqueous Solution Route

The effects of the presence of Ga₂O₃ on low‐temperature sintering and the phase stability of 4, 5, and 6 mol% Sc₂O₃‐doped tetragonal zirconia ceramics (4ScSZ, 5ScSZ, and 6ScSZ, respectively) were investigated. A series of zirconia sintered bodies with compositions (ZrO₂)_0.99?x(Sc₂O₃)_x(Ga₂O₃)_0.01, x = 0.04, 0.05, and 0.06 was fabricated by sintering at 1000°C to 1500°C for 1 h using fine powders that were prepared via the combination of homogeneous precipitation method and hydrolysis technique using monoclinic zirconia sols synthesized through the forced hydrolysis of an aqueous solution of zirconium oxychloride at 100°C for 168 h. The presence of 1 mol% Ga₂O₃ was effective in reducing sintering temperature necessary to fabricate dense bodies and enabled to obtain dense sintered bodies via sintering at 1100°C for 1 h. The phase stability, that is, low‐temperature degradation behavior of the resultant zirconia ceramics was determined under hydrothermal condition. The zirconia ceramics codoped with 1 mol% Ga₂O₃ and 6 mol% Sc₂O₃ (1Ga6ScZ) fabricated via sintering at 1300°C for 1 h showed high phase stability without the appearance of monoclinic zirconia phase, that is the tetragonal‐to‐monoclinic phase transformation was not observed in the 1Ga6ScZ after treatment under hydrothermal condition at 150°C for 30 h.     

Effects of sintering on the mechanical and ionic properties of ceria-doped scandia stabilized zirconia ceramic

The effect of conventional sintering from 1300 to 1550 °C on the properties of 1 mol% ceria-doped scandia stabilized zirconia was investigated. In addition, the influence of rapid sintering via microwave technique at low temperature regimes of 1300 °C and 1350 °C for 15 min on the properties of this zirconia was evaluated. It was found that both sintering methods yielded highly dense samples with minimum relative density of 97.5%. Phase analysis by X-ray diffraction revealed the presences of only cubic phase in all sintered samples. All sintered pellets possessed high Vickers hardness (13–14.6 GPa) and fracture toughness (~3 MPam^1/2). Microstructural examination by using the scanning electron microscope revealed that the grain size varied from 2.9 to 9.8 µm for the conventional-sintered samples. In comparison, the grain size of the microwave-sintered zirconia was maintained below 2 µm. Electrochemical Impedance Spectroscopy study showed that both the bulk and grain boundary resistivity of the zirconia decreases with increasing test temperature regardless of sintering methods. However, the grain boundary resistivity of the microwave-sintered samples was higher than the conventional-sintered ceramic at 600 °C and reduced significantly at 800 °C thus resulting in the enhancement of electrical conduction.     

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.     

Characterization and analysis of high-entropy boride ceramics sintered at low temperature

Multicomponent transition metal boride composite–sintered bodies were prepared by spark plasma sintering, and the composite sintered bodies prepared at different sintering temperatures (1500–1900°C) were characterized. The experimental results showed that several other compounds diffused into the TiB_x phase at lower sintering temperatures under the combined effect of temperature and pressure due to the nonstoichiometric ratio of TiB_1.5 vacancies. When the temperature reached 1900°C, only the hexagonal phase remained. With the continuous increase of sintering temperature, the Vickers hardness and fracture toughness of the sintered bodies had a trend of increasing first and then decreasing, due to the continuous reduction of the porosity of the cross section of the sintered bodies and the growth of the grain size. The Vickers hardness and fracture toughness of sintered body obtained at 1800°C are the best, which are 24.4 ± 1.8 GPa and 5.9 ± 0.2 MPa m^1/2. At 1900°C, the sintered body was a single-phase hexagonal high-entropy diboride. Its Vickers hardness and fracture toughness were 21.9 ± 1.5 GPa and 5.4 ± 0.2 MPa m^1/2, respectively; it showed a clear downward trend.     

Effect of temperature on the structure and mechanical properties of SiC–TiB2 composite ceramics by solid-phase spark plasma sintering

SiC composite ceramics have good mechanical properties. In this study, the effect of temperature on the microstructure and mechanical properties of SiC–TiB₂ composite ceramics by solid-phase spark plasma sintering (SPS) was investigated. SiC–TiB₂ composite ceramics were prepared by SPS method with graphite powder as sintering additive and kept at 1700 °C, 1750 °C, 1800 °C and 50 MPa for 10min.The experimental results show that the proper TiB₂ addition can obviously increase the mechanical properties of SiC–TiB₂ composite ceramics. Higher sintering temperature results in the aggregation and growth of second-phase TiB₂ grains, which decreases the mechanical properties of SiC–TiB₂ composite ceramics. Good mechanical properties were obtained at 1750 °C, with a density of 97.3%, Vickers hardness of 26.68 GPa, bending strength of 380 MPa and fracture toughness of 5.16 MPa m^1/2.     

Crystal structure and morphology of CeO2 doped stabilized zirconia ceramics under high-frequency microwave field sintering

Under high-frequency microwave irradiation, zirconia ceramics were prepared by sintering nano-CeO₂ (Ce = 7 mol%) doped zirconia powder. The different effects of temperature environment on the phase structure transformation, surface functional groups, microstructure, growth process, and density of doped zirconia were analyzed, and the optimized microwave sintering process for zirconia was determined. The experimental results reveal that the tetragonal phase of zirconia is positively correlated with the temperature when the temperature reaches about 1100 °C in the studied range. The reason is that the grain grows with the increase of sintering temperature, and the surface energy of grain decreases, which leads to the fluctuation of tetragonal phase content. The density of zirconia reaches 98.03% at 1300 °C, and the growth activation energy is 27.40 kJ/mol. There is no abnormal growth of zirconia particles, and the phase transition temperature decreases, which is attributed to the efficient heating of microwave and the incorporation of nano-ceria stabilizer.     

Pressureless low temperature sintering of nanocrystalline zirconia ceramics via dry powder processing

Pressureless sintering approaches provide a simple avenue to manufacture dense ceramic parts with minimal processing equipment, but current pressureless sintering techniques have yet to demonstrate capabilities of producing dense ceramics while maintaining sub-50 nm grain sizes. Nanocrystalline yttria stablized zirconia ceramics were process from 4 mol% yttria stablized zirconia (4YSZ) nanopowders with a crystallite size of 7.5 nm using dry cold isostatic pressing (CIP) where powders are dried immediately prior to green compact formation and CIP vacuum bagging. It is shown that CIP pressures >75 000 psi (517 MPa) effectively remove pores larger than 100 nm and that pressureless sintering occurs at reduced temperatures for green densities ≥50%. Though the sintering kinetics are shown to be similar to other zirconia nanopowder sintering studies, the small initial crystallize size and reduced sintering temperature allowed densities as high as 97.2%, while retaining a ceramic grain size at or below 40 nm. Produced nanocrystalline 4YSZ ceramics with a grain size of 30.3 nm and a density of 96.3% had Vicker's hardnesses as high as 14.2 GPa and Vicker's indentation fracture resistance of 3.43 MPa·, demonstrating that simple processing approaches can be refined to fabricate nanocrystalline ceramics while maintaining high hardness and indentation fracture resistance.     

Dense zircon (ZrSiO4) ceramics by high energy ball milling and spark plasma sintering

The addition of sintering additives has always been detrimental to the mechanical properties of sintered ceramics; therefore, methods to reduce or, as in this case, eliminate sintering additives are usually relevant. In this paper, dense zircon ceramics were obtained starting from mechanically activated powder compacted by spark plasma sintering without employing sintering additives.The high energy ball milling (HEBM) of starting powder was effective to enhance the sintering kinetics. The structural changes of the zircon powder introduced by the HEBM were evaluated. The phase composition and the microstructure of bulk zircon material were analyzed by SEM (EDAX) and XRD. The Vickers hardness and the fracture toughness were evaluated as well.Fully dense materials were obtained at 1400 °C with a heating rate of 100 °C/min, 10 min soaking time and 100 MPa uniaxial pressure. The zircon samples sintered at temperatures above 1400 °C were dissociated in monoclinic zirconia and amorphous silica. The dissociation was detrimental for the mechanical properties. Unlike conventional sintering methods (hot pressing, pressureless sintering) SPS permitted to overcome the dissociation of the zircon material and to obtain additive free, fully dense zircon ceramic with outstanding mechanical properties.     

Evaluating the role of uniformity on the properties of B4C–SiC composites

Fully dense boron carbide-silicon carbide composites were successfully produced by spark plasma sintering method at 1950 °C under 50 MPa applied pressure. The effect of dry and wet mixing methods on uniformity was observed. Density, elastic modulus, microstructure, Vickers hardness and fracture toughness were evaluated. The results showed that dry mixing did not provide uniformity on composites properties. On the other hand wet mixing provided uniformity in microstructure and consistency in material properties. The hardness of the sample containing 50 wt% B₄C was measured to be 30.34 GPa hardness value was found at 50 wt% B₄C content sample. The increase in the B₄C content of the composites decreased the Young's modulus, shear modulus, bulk modulus and fracture toughness. The highest values were found at 10 wt% B₄C sample which were 415 GPa (E), 177 GPa (G), 209 GPa (K), and 2.89 MPa m^1/2 fracture toughness (K_Ic).     

Sintering of zirconia ceramics by intense high-energy electron beam

A comparative analysis of the efficiency of zirconia ceramics sintering by thermal method and high-energy electron beam sintering was performed for compacts prepared from commercial TZ-3Y-E grade powder. The electron energy was 1.4 MeV. The samples were sintered in the temperature range of 1200–1400 °C. Sintering of zirconia ceramics by high-energy accelerated electron beam is shown to reduce the firing temperature by about 200 °C compared to that in conventional heating technique. Ceramics sintered by accelerated electron beam at 1200 °C is of high density, microhardness and smaller grain size compared to that produced by thermal firing at 1400 °C. Electron beam sintering at higher temperature causes deterioration of ceramics properties due to radiation-induced acceleration of high-temperature recrystallization at higher temperatures.     

Densification and enhancement of SiC particulate-reinforced fine-grain SiC ceramic

Dense sintering of SiC nanopowder under low temperature and pressure remains a big challenge, because of the great resistance caused by the severe agglomeration of nanopowder. A novel sintering strategy is proposed to prepare SiC composite ceramics by sintering the mixture of SiC nanopowder and SiC micron powder at low temperature and pressure. The SiC micron powder was in the size of 100 µm with little sintering activity, which was designed as a pressure conductor to promote the densification of SiC nanopowder. Experimental results showed that the SiC micron powder had a significant effect on increasing of the sintering density of nanopowder and improving the mechanical properties of SiC ceramics. An SiC composite ceramic with a relative density of 98%, a Vickers hardness of 22.6 GPa, and a fracture toughness of 5.43 MPa m^1/2 could be sintered by spark plasma sintering under 1700°C and 30 MPa by adding 30 wt.% 100 µm SiC micron powder as reinforcements.     

Electrical properties of reduced 3YTZP ceramics consolidated by spark plasma sintering

3 mol% Yttria doped zirconia ceramics were consolidated by spark plasma sintering (SPS) at two sintering temperatures with the aim of achieving two different reduction levels. Microstructural characterization of the ceramics was performed by scanning electron microscopy (SEM). Electrical properties were investigated by means of impedance spectroscopy from room temperature up to 500 °C. The two ceramics presented a remarkably different electrical behavior. The effect of the extra electrons introduced by reduction during SPS on both the bulk and the grain boundary conductivity was analyzed and discussed.     

Fabrication and characterization of bioactive zirconia-based nanocrystalline glass-ceramics for dental abutment

Zirconia-based ceramics are becoming a popular biomaterial in dental implantology due to their natural silver-white color, excellent mechanical properties, and good biocompatibility. However, zirconia-based ceramics are biologically inert, which limits their ability to integrate with the surrounding human tissues. To solve this problem, the bioactive elements of calcium (Ca) and phosphorus (P) were doped in high-strength ZrO₂–SiO₂ nanocrystalline glass-ceramics (NCGCs) to overcome the biological inertness of ZrO₂-based ceramics. XRD results showed that tetragonal zirconia (t-ZrO₂) and monoclinic zirconia (m-ZrO₂) were the only two crystalline phases after spark plasma sintering. Ca and P dopants acted as destabilizer of t-ZrO₂, enhancing its transformability to m-ZrO₂ during sintering. The amount of t-ZrO₂ exerted significant effects on the average flexural strength of the NCGCs. The NCGC with 45 mol% ZrO₂ were composed of 64.5 vol% t-ZrO₂ and 35.5 vol% m-ZrO₂ after sintering at 1230 °C. And, the average flexural strength and Vickers hardness of the NCGC was 615 MPa and 1049 HV, respectively. In comparison, the NCGC with 65 mol% ZrO₂ were composed of 12.6 vol% t-ZrO₂ and 87.4 vol% m-ZrO₂ after sintering at 1150 °C. The average flexural strength and Vickers hardness of the NCGC was 293 MPa and 839 HV, respectively. Interestingly, the NCGCs exhibited a plastic deformation behavior during flexural strength test, which was different from traditional brittle ceramics. The ion release results demonstrated that Ca²⁺ and Si⁴⁺ ions kept on releasing from the surface of the material. The formation of hydroxyapatite in the in-vitro apatite formation test indicated that the NCGCs had good biological activity. The doped ZrO₂-based NCGCs combined moderate strength and good bioactivity. Hence, the NCGCs show promising potential to be used in sub-gingival regions, such as dental abutments.     

Rapid-sintered dental zirconia for chair-side one-visit application

To satisfy the requirement of dental chair-side clinical technique, zirconia ceramics is required to be sintered in 1 hour; the effect of rapid-speed sintering dwell time on dental zirconia was investigated. The relative density was measured through Archimedes method; Scanning electron microscopy and X-ray diffractometer were employed to characterize the microstructures; Universal mechanical test machine and Vickers indenter were used to evaluate the mechanical properties; Spectrophotometer was utilized to analyze the optical transmittance, and optical microscope was used to estimate the marginal adaptation of zirconia crown with abutment. Previous results indicated that rapid-speed sintering and dwelling at 1580°C for 20 minutes could help dental zirconia achieve adaptable clinical performances with bending strength of around 1151 MPa, hardness of 13.3 GPa, and fracture toughness of 5.92 MPa•m^1/2, as well as adaptable optical transmittance and marginal adaptation.     

Influence of sintering pressure on the microstructure and tribological properties of low temperature fast sintered hot-pressed Y-TZP

Contrarily to conventional sintering (CS) method where longer cycles and high temperature (1400–1500?°C) are applied to sinter yttria-stabilized tetragonal zirconia polycrystalline (Y-TZP) ceramics, this work presents a faster and low temperature (1175?°C) way through hot pressing (HP) to produce full densified zirconia with good mechanical and tribological properties. This work is concerned with the influence of sintering pressure on the microstructure and tribological properties of hot-pressed Y-TZP. For this purpose, four sintering pressures 5, 20, 60 and 100?MPa were tested. The wear tests were carried out by reciprocating ball-on-plate as a simplified test for tooth-to-restorative material contact under 37?°C using artificial saliva to mimic oral conditions. The results demonstrated that density, hardness and tribological properties are strongly influenced by the sintering pressure, namely an improvement with pressure increase was achieved. The highest density, hardness values and wear resistance were achieved for Y-TZP samples produced at P?=?100?MPa. Furthermore, it was revealed that a smaller grain size for Z100 samples (full densification condition) was achieved comparatively to conventional-sintered Y-TZP. This work proves that it is possible to produce dense Y-TZP materials under low sintering temperature and faster cycles with reduced grain size without compromise mechanical and tribological properties.     

Effect of manganese addition on sintering behavior and mechanical properties of alumina toughened zirconia

The effect of MnO₂ additives on the sintering behavior and mechanical properties of alumina-toughened zirconia (ATZ, with 10 vol% alumina) composites was investigated by incorporating different amounts of MnO₂ (0, 0.5, 1.0, and 1.5 wt%) and sintering at various temperatures ranging from 1300 to 1450 °C. The addition of MnO₂ up to 1.0 wt% improved the sintered density, hardness, flexural strength, and fracture toughness of the composite. However, the addition of 1.5 wt% MnO₂ degraded the relative density, hardness, and flexural strength of the composite due to the transformation of the ZrO₂ phase from tetragonal to monoclinic and grain coarsening. Optimal results were obtained with 1.0 wt% MnO₂ and sintering at 1450 °C, which improved the mechanical properties (hardness: 13.5 GPa, flexural strength: 1.2 GPa, fracture toughness: 8.5 MPa m^1/2) and lowered the sintering temperature compared to the conventional sintering temperature of ATZ composites (1550 °C). Thus, the ATZ composite doped with MnO₂ is a promising material for structural engineering ceramics owing to its improved mechanical properties and lower sintering temperature.     

Microwave Sintering of Zirconia Materials: Mechanical and Microstructural Properties

Commercially, 3 mol% Y₂O₃‐stabilized tetragonal zirconia (70–90 nm) compacts were fabricated using a conventional and a nonconventional sintering technique; microwave heating in a resonant mono‐mode cavity at 2.45 GHz, at temperatures in the 1100–1400°C range. A considerable difference in the densification behavior between conventional (CS) and microwave (MW) sintered materials was observed. The MW materials attain a full density of 99.9% of the theoretical density (t.d.) at 1400°C/10 min, whereas the CS reach only 98.0% t.d. at the same temperature and 1 h of dwelling time. Therefore, the MW materials exhibit superior Vickers hardness values (16.0 GPa) when compared with CS (13.4 GPa).     

Structural parameters and oxygen ion conductivity of Y2O3–ZrO2 and MgO–ZrO2 at high temperature

The oxygen ion conductivity of zirconia-based solid electrolytes doped with 8 mol% Y₂O₃–ZrO₂ (YSZ) and 9 mol% MgO–ZrO₂ (Mg-PSZ) at high temperature was investigated in terms of their thermal behavior and structural changes. At room temperature, YSZ showed a single phase with a fluorite cubic structure, whereas Mg-PSZ had a mixture of cubic, tetragonal and some monoclinic phases. YSZ exhibited higher ionic conductivity than Mg-PSZ at temperatures from 600 °C to 1250 °C because of the existence of the single cubic structure and low activation energy. A considerable increase in the conductivity with increasing temperature was observed in Mg-PSZ, which showed higher ionic conductivity than YSZ within the higher temperature range of 1300–1500 °C. A monoclinic-to-tetragonal phase transformation was found in Mg-PSZ and the lattice parameter of the cubic phase increased at 1200 °C. The phase transformation and the large lattice free volume contributed to the significant enhancement of the ionic conductivity of Mg-PSZ at high temperatures.     

In-situ synthesis and low-temperature fabrication of B4C/TiB2-based multilayer graded composites with B4C and Ti–Al intermetallics mixtures through transient liquid phase sintering

The seven-layer B4C/TiB2-based graded composites was prepared with B4C and Ti–Al intermetallics through stepped laminating processing and transient liquid phase spark plasma sintering. The sintering strategy of the graded composites was proposed based on the sintering products of monolayer materials with different contents of Ti–Al intermetallics from 5 wt% to 60 wt%. The top three layers and bottom three layers were sintered respectively at 1650 °C and 1500 °C, and then the middle layer was used as the binder to joint the as-preserved two sections at 1550 °C. The apparent density of the as-prepared B4C/TiB2-based multilayer graded composites was 2.94 g/cm3, which was lower than that of most advanced ceramics. With the increase in the addition of Ti–Al intermetallics, the hardness of B4C/TiB2-based multilayer graded composites decreased from 31 GPa (B4C-riched) to 25 GPa (TiB2-riched), whereas the fracture toughness increased from 3.8 MPa·m0.5–6.02 MPa·m0.5. The compressive strength was up to 1100 MPa, displaying the jagged stress-strain curve. Crack propagation resistance mechanisms such as deflection and bridging enhanced the fracture toughness. The B4C/TiB2-based multilayer graded composites fabricated at low temperature possess high front hardness, high rear toughness, high overall strength and low density, and has promising applications in impact-resistant fields such as lightweight ceramic armor.