Flash microwave pressing of zirconia

Microwave Pressing is a promising way to reduce microwave sintering temperatures and stabilize microwave powder materials processing. A multiphysics simulation was conducted of the regulated pressure-assisted microwave cavity. This simulation took into consideration resonance phenomena and the nonlinear temperature-dependent material parameters of zirconia. The intrinsic behaviors of microwave systems and zirconia make the regulation of the microwave pressing difficult. However, the same phenomena can be used to activate flash sintering. Flash microwave sintering uses high electric fields of the resonant microwave profile, the Negative Temperature Behavior (NTC) of zirconia resistivity, and the mechanical pressure applied to the powder via a die compaction configuration. The resulting flash microwave pressing still needs improvement in terms of the processed material structure homogeneity, but it has the capacity to become the fastest sintering treatment as it allows room temperature activation where the total process time only takes a few seconds. In addition, this 10-20 seconds processing technique has shown good potential for improving the transparency of alumina presintered specimens.     

The toughening mechanism and mechanical properties of graphene-reinforced zirconia ceramics by microwave sintering

ABSTRACT

The graphene/ZrO₂ composites were fabricated by impregnating graphene dispersion into the ZrO₂ ceramic matrix and sintered by microwave, and the microstructure and mechanical properties were investigated. The results showed that the graphene was well dispersed in the ceramic matrix and refined the grain size. The fracture toughness reached 8.62?MPa?m^1/2, confirmed by single-edge notched beam, which was 42% higher than that of the pure ZrO₂. Also, the toughening mechanisms were investigated by micro-hardness testing and showed that a combination of crack deflection, micro-crack and crack bridging increased the fracture toughness.     

Suppression of nitridation of yttria-doped zirconia during flash sintering

The effect of direct current (DC) and alternating current (AC) on nitridation of 3 mol% Y₂O₃-doped ZrO₂ (3YSZ) after keeping in a flash state for 1 hour was investigated. The inside of the DC-flashed compact was confirmed to exhibit blacking. Scanning transmission electron microscopy, electron energy loss spectroscopy, and X-ray diffraction analysis revealed that zirconium nitrides formed in the blackened area. In contrast, a uniformly densified compact without blackening was obtained by AC fields. No zirconium nitrides formed in the compacts exposed to AC fields even when the flash state was maintained for 1 hour. Therefore, AC fields are effective to suppress nitridation of 3YSZ during flash sintering.     

On the catalytic effect of zirconia on flash sintering of alumina

Flash sintering of alumina is more difficult than of yttria-stabilized zirconia (YSZ). Whereas (MgO doped) alumina requires fields greater than 1 kVcm^–1 and temperatures often significantly higher than 1000°C, YSZ can be flashed sintered at ∼100 Vcm^–1 at temperatures below 800°C. Mixed powders of such bi-phasic ceramics, on the other hand, can be flashed under conditions below those for alumina. This effect is usually subscribed to the influence of YSZ on the overall electrical conductivity of the composite. However, such rationalization leaves open the mechanism by which YSZ catalyzes the flash event in alumina. Here, we present results for the onset of flash in a layered structure of YSZ and alumina where both constituents extend from one electrode to the other. We find that the flash initiates, at first, exclusively in the YSZ layer, under conditions identical to those in usual voltage-to-current experiments in single phase YSZ, and then, after a brief incubation period, spreads transversely through the thickness of the alumina layer at a speed of ∼3.3 mm s^–1, while the power supply is held at constant current. This observation opens a new question as to how flash once initiated in an “easy” phase can migrate normal to itself into a second ceramic, which is nominally more-difficult-to flash. (In the present experiments, the alumina layer sintered to full density with all the shrinkage being accommodated in the thickness direction, consistent with an earlier study that articulated that flash obviates constrained sintering.) It is noteworthy that the catalytic effect depends not only on the volume fraction of YSZ, but also on the architecture of the green state (for example a two-phase powder mixture vs. layered structure), which may affect the initiation of the flash in YSZ but, likely, not its migration behavior into the second phase.     

Reactive flash sintering in a bilayer of zirconia and lanthana: Measurement of the diffusion coefficient in real time

Reactive flash sintering is a process where off-the-shelf powders of elemental oxides can be simultaneously sintered and reacted to form a multicomponent oxide in a matter of seconds at low furnace temperatures. The fact that several cation species, each residing within their own particles, can migrate over distances of several micrometers, and mix on the atomic scale to form multicomponent oxides, so quickly, is quite remarkable. The question arises as to the rate of this solid-state diffusion phenomenon. In this paper, we present measurements of this diffusion coefficient from live flash experiments. The results are obtained from millimeter scale bilayers of yttria-stabilized zirconia and lanthana where the flash initiates in the zirconia layer and then migrates into the lanthana layer, forming lanthanum zirconates. The velocities of migration of the flash-front, coupled with measurements of the length scale of the profile of zirconium and lanthanum interdiffusion, across the bilayer interface, provide an estimate of the effective diffusion coefficient. These measurements give a value for the cation diffusion to lie in the range of 2.5 × 10⁻¹⁰ m² s⁻¹ at 1380°C, with an activation energy of 200–250 kJ mol⁻¹. In comparison, the cation diffusion coefficient in yttria-stabilized zirconia, at 1350°C, is stated to be 1.1 × 10⁻²⁰ m² s⁻¹ with an activation energy of ∼550 kJ mol⁻¹. A pause for reflection.     

An oscillatory pressure sintering of zirconia powder: Rapid densification with limited grain growth

A novel oscillatory pressure sintering (OPS) process is reported to prepare high‐quality ceramics. The oscillatory pressure was applied at three stages (initial, intermediate, and final) during sintering process of zirconia ceramics for the first time. The microstructure of the samples prepared by OPS develops in a more homogeneous manner, leading to a higher final density, a smaller average grain size, and a narrower distribution of grain sizes compared with the samples prepared by conventional pressureless sintering (PS) and hot‐pressing (HP) processes. Remarkably, the OPS samples was obtained at relatively lower heating temperature and less soaking time for 1300°C and 0.5 hours than the samples prepared by other two techniques at 1450°C and 1 hour. The current results suggest that OPS is an effective technique for preparing high‐quality zirconia ceramics with low heating temperature and short sintering time, thus, it obviously reduces cost.     

DC electric field-assisted hot pressing of zirconia: Methodology,phenomenology, and sintering mechanism

Flash sintering (FS) is an important technique in the field of ceramic sintering. Nevertheless, conventional FS is less attractive for practical applications because of the complex shapes and small sizes of the specimens. In this study, using the novel electric field-assisted hot pressing (FAHP) technique, we successfully achieved FS during the net-shape hot pressing (HP) process for the first time. It was found that the 3 mol% yttria-stabilized zirconia (3YSZ) can be flash sintered at 909°C using a fairly low DC field of 33 V/cm under 30 MPa pressure. The grain sizes of the FAHP-sintered samples were 20% smaller than that of the HP-sintered sample. When the current density limit is ≥240 mA/mm², 3YSZ can be fully densified during the flash events. Careful analysis of the sintering curves suggests that although the carrier type or concentration is changed during flash events, it cannot explain the ultrafast densification. Additionally, we devised a qualitative method to analyze the densification mechanism. The results indicated that the ultrafast densification observed during flash events resulted from the synergistic effects of the rapid heating rate and peak sample temperature. Finally, the atomic force microscopy confirmed the lower grain boundary energy for the FAHP-sintered samples, which accounts for the smaller grain sizes than the HP-sintered sample. We believe that the FAHP technique could create new possibilities for theoretical and applied research on field-assisted sintering techniques.     

An oscillatory pressure sintering of zirconia powder: Densification trajectories and mechanical properties

The densification trajectories and mechanical properties of zirconia ceramics obtained by oscillatory pressure sintering (OPS) process were investigated, during the sintering process an oscillatory pressure was applied at three stages. Current results indicated that at intermediate stage the oscillatory pressure revealed a favorable improvement of mechanical properties compared with conventional hot pressing (HP) and pressureless sintering (PS) procedures, while the enhancement was not obvious at initial stage. When the oscillatory pressure was applied at final stage, the OPS specimens exhibited the highest bending strength and hardness of 1455 ± 99MPa and 16.6 ± 0.31GPa compared with the PS and HP specimens. Considering the high elastic modulus and Moiré patterns observed in the OPS specimen, the oscillatory pressure applied at intermediate and final stages was detected to facilitate the sliding of grain boundary, plastic deformation of monolithic grains, the removal of pores and the strengthening of atomic bonds.     

Comparison of a laboratorial scale synthesized and a commercial yttria-tetragonal zirconia polycrystals ceramics submitted to microwave sintering

Conventional sintering techniques of yttria-tetragonal zirconia polycrystals (Y-TZP) ceramics have presented limitations regarding the sintering time and temperature, increasing the cost of the final dental and biomedical products. Herein, microwave sintering comes to be an interesting alternative by providing fast heating, high densification, and grain-size control. The aim of this study was to compare the effect of microwave sintering of Y-TZP dental ceramics prepared from a pre-sintered commercial block and produced from powders synthesized in a laboratorial scale by the precipitation route. The synthetized and commercial discs were submitted to microwave sintering at 1450°C and 1350°C for 15, 30, and 60 minutes. Densification, fracture toughness, grain size, and crystalline phase quantification of the sintered groups were evaluated. Both synthetized and commercial groups sintered at 1450°C for 15 and 30 minutes showed the higher densification results (98% TD). XRD quantitative phase analysis indicates that samples present 89% tetragonal and 11% cubic phases, except for the group prepared from coprecipitated powders sintered at 1450°C for 30 minutes, that presented 79% and 21% of tetragonal and cubic phases. The microwave sintering at 1450°C allows hardness and fracture toughness values comparable to conventional sintering.     

Selective laser flash sintering of 8-YSZ

Flash sintering of ceramics is characterized by rapid sintering during simultaneous application of electric field and heat. Previous studies of flash sintering have been conducted in furnace environments, where sample temperatures are approximately uniform. In this work, we use highly dynamic heating from a scanning laser to initiate flash sintering while simultaneously applying a DC electric field. Onset of flash sintering is determined by a measurable increase in current through the sample. Our results show that stage I and stage II flash sintering can be initiated by laser heating. At low-to-moderate combinations of laser energies and applied electric fields, measured current rises slightly when the laser is scanned completely across the specimen from the positive to the negative electrodes. Microstructures for these samples show that powder consolidation is minimal in this regime (stage I flash sintering), and thus the observed current is likely due to onset of neck growth between powder particles rather than densification. At higher laser energies and fields, current rises steeply and microstructures show significant consolidation (stage II flash sintering). The demonstration that flash sintering occurs when ceramic is heated by laser-scanning supports future utilization of selective laser flash sintering as an additive manufacturing process.     

Fully coupled electromagnetic‐thermal‐mechanical comparative simulation of direct vs hybrid microwave sintering of 3Y‐ZrO2

Direct and hybrid microwave sintering of 3Y‐ZrO₂ are comparatively studied at frequency of 2.45 GHz. Using the continuum theory of sintering, a fully coupled electromagnetic‐thermal‐mechanical (EMTM) finite element simulation is carried out to predict powder samples deformation during their microwave processing. Direct and hybrid heating configurations are computationally tested using advanced heat transfer simulation tools including the surface to surface thermal radiation boundary conditions and a numeric proportional‐integral‐derivative regulation (PID). The developed modeling framework shows a good agreement of the calculation results with the known experimental data on the microwave sintering of 3Y‐ZrO₂ in terms of the densification kinetics. It is shown that the direct heating configuration renders highly hot spot effects resulting in nonhomogenous densification causing processed specimen's final shape distortions. Compared with the direct heating, the hybrid heating configuration provides a reduction of the thermal inhomogeneity along with a densification homogenization. As a result of the hybrid heating, the total densification of the specimen is attained without specimen distortions. It is also shown that the reduction of the sample size has a stabilization effect on the temperature and relative density spatial distributions.     

Flash spark plasma sintering of zirconia nanoparticles: Electro-thermal-mechanical-microstructural simulation and scalability solutions

Flash sintering is a very promising method with a great potential for the ultra-rapid production of objects with firing processes of mere seconds. However, the transition from few millimeters samples to larger scales is a key issue. In this study, we explore the spark plasma sintering approach allowing a stable hybrid heating in flash condition and producing near net shape sintered specimens. Two electric current configurations are employed for diameters of 15 and 30 mm to determine the effect of scale change and of electric current concentration. These experiments coupled with a Multiphysics simulation indicate that stable flash conditions can be reached for 30 mm specimens. However, even if the electrical current concentration is very effective at small sizes, it generates peripheral hot spots for large specimen dimensions. The blackening effect on zirconia flash specimens acts then as an indicator of the specimen thermal history.     

Transparent high-strength nanosized yttria stabilized zirconia obtained by pressure-less sintering

This work describes the development of transparent high-strength Yttria-Stabilized Zirconia (YSZ) ceramics with ultra-fine grain size utilizing conventional pressure-less densification. Starting with nanoparticles with diameter < 10 nm, it was possible to achieve full densification (>99.5% of theoretical density) at a sintering temperature of 1100–1200 °C. The average grain size of the resulting dense ceramics was 75 nm in 3 mol. % YSZ and 85 nm in 8 mol. % YSZ, showing in-line light transmission of 38% and 51% at a wavelength of 800 nm and average biaxial strength (piston on three balls test on samples of diameter 12 mm and thickness 1 mm) of 1980 MPa and 680 MPa, respectively. The nano-grained structure, absence of color centers, and miniaturization of residual pores enable the excellent light transmission. The high biaxial strength is attributed to the refined microstructure, but also to the martensitic tetragonal-to-monoclinic phase transformation that remains active even in nano-sized zirconia grains.     

Initial sintering mechanism and additive effect in zirconia ceramics

Y₂O₃-stabilized ZrO₂ (YSZ) ceramics have been used for various engineering applications because of their excellent mechanical properties or oxide-ion conductivity applicable to solid-electrolyte. The performance of YSZ depends on the sintered texture that is directly determined by sinterability of raw powders. A new kinetic analysis method of diffusion mechanism based on an initial sintering theory (grain-boundary or volume diffusion) is theoretically derived, the initial sintering mechanism of hydrolytic YSZ powder is experimentally determined, and the effects of powder characteristics on sinterability are discussed. Furthermore, the additive-enhanced sintering is proposed. A small amount of Al₂O₃ significantly enhances the densification. Using the additive effect, the low-temperature degradation that is the fault of zirconia ceramics can be improved by decreasing the sintering temperature.     

Intergranular amorphous films formed by DC electric field in pure zirconia

It is difficult to obtain pure ZrO₂ sintered compacts with a bulk style at room temperature because a large volumetric expansion from tetragonal to monoclinic phase (t/m) transformation occurs at around 1000°C, which is lower than the sintering temperature. In contrast, pure monoclinic ZrO₂ can be consolidated without shattering using flash‐sintering at 1350°C for 5 minutes under an applied DC electric field of 175 V/cm. High‐resolution transmission electron microscopy and electron energy loss spectroscopy have revealed that amorphous films are formed along grain boundaries after flash‐sintering at 1350°C for 5 minutes. Monoclinic ZrO₂ flash‐sintered compact including the amorphous films are able to survive without shattering through the t/m transformation, as the amorphous films partially absorb the large volumetric expansion arising from the t/m transformation. The formation of the amorphous films results from the severe reducing condition due to the applied DC electric fields during flash‐sintering.     

Controlled sintering and phase transformation of yttria-doped tetragonal zirconia polycrystal material

In this paper, 3 mol% yttria-doped tetragonal zirconia polycrystal material (3 mol% Y₂O₃–ZrO₂) was prepared using an optimised pressureless sintering process. The phase change and particle size distribution of Y₂O₃–ZrO₂ during sintering were studied, and the effect of sintering temperature on the properties of Y₂O₃–ZrO₂ was analysed. The raw materials and prepared samples were analysed using XRD, Raman spectroscopy, SEM, and Gaussian mathematical fitting. The results show that sintering encourages the transformation of the monoclinic phase into the tetragonal phase, thus improving the crystallinity of the sample. The relative content of the tetragonal phase in the sample increased from 57.43% to 99.80% after sintering at 1200 °C for 1 h. In the range of sintering temperatures studied in this paper (800–1200 °C), the zirconia material sintered at 1000 °C presented the lowest porosity and the best density.     

Effect of sintering regimes and thickness on optical properties of zirconia ceramics for dental applications

In dentistry, monolithic zirconia restorations have been preferred over all-ceramic restorations in recent years. Translucency is an aesthetic demand in dental restorations, and it can be identified with translucency parameter (TP). Zirconia thickness, Y₂O₃ content, and sintering conditions are important parameters that influence the translucency of the restorations. It is crucial to investigate monolithic zirconia ceramics under different sintering regimes and reveal the critical parameters for dental restorations. The aim of this study was to determine the optical and microstructural behaviors of monolithic zirconia ceramics containing different amounts of yttria depending on various sintering regimes and thicknesses. Therefore, a conventional zirconia CopranZri (CZI) and two monolithic zirconia materials, CopraSupreme (CSP), CopraSmile (CSM) were used. Slow, normal, speed, and translucency sintering regimes with thicknesses of 0.7, 1.0, 1.3 mm were selected. TP of the specimens was calculated, and statistical analyses were performed by using one-way ANOVA and Tukey-Kramer post hoc tests. Characterization of the specimens was performed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) techniques. The results showed that the effect of different sintering programs is more critical for CSP and CSM in terms of translucency variations and translucency program led to the most grain growth.     

Study of the densification and grain growth mechanisms occurring during spark plasma sintering of different submicronic yttria-stabilized zirconia powders

Densification and grain growth mechanisms of Yttria-Stabilized Zirconia sintered by Spark Plasma Sintering are investigated. Sintering trajectories of four commercial submicronic powders with different average particle sizes and yttria amounts have been established and sintering regimes determined. Densification mechanisms are determined in the regime where densification is occurring without grain growth using a model derived from hot-pressing. Grain growth mechanisms are determined using the conventional power law in the regime where ceramics are fully densified. Densification occurs by grain boundary sliding accommodated by an in-series interface-reaction/lattice diffusion of cations or by an overlapping of surface diffusion and grain boundary sliding mechanisms for tetragonal stabilized zirconia and by dislocation climbing for fully stabilized zirconia. A normal grain growth occurs for each ceramic, all composed of a single phase, contrary to the two-phased ceramics obtained in literature where grain growth occurs by segregation at grain boundaries.     

The controlled preparation and stability mechanism of partially stabilized zirconia by microwave intensification

Partially stabilized zirconia (PSZ) occupies an important application portion in ceramics materials and refractories materials. In this work, calcium oxide-partially stabilized zirconia (CaO-PSZ) ceramics were prepared from fused zirconia by microwave sintering, with its microstructure and stability properties characterized by XRD and SEM. Results indicated that the heating rate, cooling rate, quenching temperature and isothermal treatment time rendered different influence on the stability properties, which was mainly ascribed to the reversible martensitic transformation of zirconia ceramics. Additionally, a mixed-phase composed by cubic phase ZrO₂ (c-ZrO₂) and monoclinic phase ZrO₂ (m-ZrO₂) appeared after fused zirconia treated by microwave sintering at 1450 °C for 2 h, indicating the formation of CaO-PSZ ceramics, which the finding was consistent with the SEM and EDAX analysis. Meanwhile, CaO stabilizer precipitated behavior at the crystal boundary, with the formation of acicular grains and fine particles, further rendering a toughening effect to CaO-PSZ ceramics. This work can provide important theoretical and practical significance for applications of microwave sintering to prepare CaO-PSZ ceramics material, even extending further applications in functional materials and structural materials.     

Flash microwave sintering of zirconia by multiple susceptors cascade strategy

In the field of flash sintering, microwave energy represents an interesting way to densify ceramics complex shapes, thanks to a contactless volumetric heating. Attaining a fast and homogeneous heating is a critical parameter and hybrid heating, using silicon carbide susceptors, is generally used. In this study, an original multiple susceptors cascade strategy is developed, using both SiC and 3D-printed ZrO₂ susceptors. This novel configuration follows perfectly the flash heating scheme, even for high heating rates up to 1000 K.min^-1 and leads to a high stability of the “flash” hybrid heating. Flash microwave sintering produced dense (97 % relative density) microstructures within 45 s. Based on comprehensive multiphysics simulations of the overall process, in-situ dilatometry measurements, kinetics method analysis and microstructural characterizations, this work highlights the sintering behavior of zirconia and the temperature distribution during flash microwave sintering.