Consolidation of undoped,monoclinic zirconia polycrystals by flash sintering

Consolidated, monoclinic ZrO₂ polycrystal was produced from undoped ZrO₂ powders in air by flash sintering at the sintering temperature of 1350°C for 5 minutes or 3 hours under an applied DC electric field of 175 V/cm. When the ZrO₂ was heated under the applied DC field, the electric current of the specimen steeply increased at the furnace temperature of 1335°C below the sintering temperature of 1350°C. When the furnace temperature was decreased from the sintering temperature of 1350°C to room temperature, volumetric expansion associated with tetragonal‐to‐monoclinic phase transformation gradually took place at the furnace temperature from 1000°C to 750°C, and monoclinic ZrO₂ body was remained consolidated even at room temperature in both specimens. In contrast, conventionally sintered ZrO₂ without applying DC field exhibited the abrupt volumetric expansion at about 1000°C, and shattered. SEM observation revealed the presence of grain‐boundary second phase in the flash‐sintered specimen for 3 hours, which is a possible origin of keeping a bulk body at room temperature. The thinner second phase is considered to be formed also in the flash‐sintered specimen for 5 minutes, although the formation of the phase could not be observed clearly by SEM observation. On the other hand, XRD measurements showed that <001> directions of the monoclinic ZrO₂ grains were oriented along the applied DC field after the isothermal flash sintering for 3 hours while the grain alignment could not be observed in flash‐sintered specimen for 5 minutes. The alignment of ZrO₂ grains observed in the isothermal flash sintering is considered to be closely related to the preferential direction of oxygen ionic conduction and the second phase formed along grain boundaries.     

Flash sintering feasibility study and localized densification in boron carbide

The feasibility of flash sintering boron carbide (B₄C) was investigated using a direct current (DC) electric field across different electrodes, field strengths, and thermal profiles. Flash behavior was observed at furnace temperatures as low as 386°C with field strengths of 68-278 V/cm, but only a small channel of the specimen was densified due to hot spot effects. Application of a 2.2 V/cm·s voltage ramp at a constant temperature of 550°C caused uniform heating, but at temperatures too low for sintering. Scalable densification of B₄C at low furnace temperatures with flash sintering is theorized to be possible by applying a higher current density through power supply or specimen modifications.     

In-operando synchrotron experiments of flash sintering carried out in current rate mode

We report first-time results for in-operando flash sintering synchrotron experiments carried out in current rate mode where the specimen, held at a constant temperature, is fed current that is increased at a constant rate. These experiments are unique because the time dependence of the sintering behavior can be stretched out over a longer period (by changing the current rate) than in voltage-to-current experiments in which sintering occurs in a burst at the onset of the flash. Two results are presented: (i) A comparison of temperatures measured with the platinum standard to those predicted by the black body radiation model leading to estimates of the emissivity as a function of porosity whereby emissivity increases from 0.65 to 0.9 as the sample sinters from its green state to full density, and (ii) measurements of the excess lattice expansion as a function of density as the sample sinters continuously while the current is increased. The present work highlights the promise of current rate experiments to obtain results while the sample sinters gradually from its green density to full density (somewhat akin to conventional sintering) for gaining further insights into the mechanisms of flash sintering.     

Shrinkage rate control during a flash state by current-ramping for 3 mol% Y2O3-doped ZrO2 polycrystals

3 mol% Y₂O₃-doped ZrO₂ green compacts with rectangular shapes were sintered by maintaining the shrinkage rates at constant values under alternating electric fields by ramping the electric current during flash states. Green compacts were furnace-heated under 40-100 V_rms/cm until current hits an initial current limit of 100 mA_rms. After then, current-ramping was started to keep the shrinkage rates constant by increasing the limit current value using a programmable power supply operating in a current control mode. Highly densified 3 mol% Y₂O₃-doped ZrO₂ polycrystals with a density of 6.05 g/cm³ as a bulk density and a grain size of about 0.4 μm were obtained at a furnace temperature of about 930℃, 50 V_rms/cm with 1000 Hz and shrinkage rate of about 120 μm/min (0.8%/min against initial lengths of green compacts). The Vickers hardness and indentation fracture toughness of the compact exhibit similar values to those obtained from thermally sintered compacts.     

Fabrication of ZrO2/rGO nanocomposites by flash sintering under AC electric fields

Ceramic matrix nanocomposites containing graphene possess superior mechanical properties. However, these nanocomposites are very difficult to be prepared using the conventional methods due to severe grain growth and simultaneous degradation of the graphene at high sintering temperatures and long dwell time. Herein, the dense ZrO₂/rGO (reduced graphene oxide) nanocomposites are successfully fabricated by flash sintering of the green compacts consisting of ZrO₂ nanoparticles and graphene oxide (GO) at 893–951℃ in merely 5 seconds under the alternating current (AC) electric fields of 130–150 V cm⁻¹. The GO can be in situ thermal reduced during the flash sintering. The as-prepared ZrO₂/rGO nanocomposites exhibit excellent mechanical properties. This study presents a green and simple approach to fabricate the dense ceramic matrix nanocomposites reinforced with graphene at low temperatures in a short time.     

Flash sintering of yttria-stabilized zirconia powders coated with nanoscale films of alumina by atomic layer deposition

The addition of small quantities of aluminum oxide (Al₂O₃) to 8 mol% yttria-stabilized zirconia (8YSZ) benefits conventional sintering by acting as a sintering aid and altering grain growth behavior. However, it is uncertain if these benefits observed during conventional sintering extend to flash sintering. In this work, nanoscale films of Al₂O₃ are deposited on 8YSZ powders by particle atomic layer deposition (ALD). The ALD-coated powders were flash sintered using voltage-to-current control and current rate experiments. The sintering behavior, microstructural evolution, and ionic conductivities were characterized. The addition of Al₂O₃ films changed the conductivity of the starting powder, effectively moving the flash onset temperature. The grain size of the samples flashed with current rate experiments was ~65% smaller than that of conventionally sintered samples. Measurement of grain size and estimates of sample density as a function of temperature during flash sintering showed that small quantities of Al₂O₃ can enhance grain growth and sintering of 8YSZ. This suggests that Al₂O₃ dissolves into the 8YSZ grain boundaries during flash sintering to form complexions that enhance the diffusion of species controlling these processes.     

In‐situ measurements of lattice expansion related to defect generation during flash sintering

We report results from in‐situ measurements of lattice expansion during flash sintering of 3 mol% yttria stabilized tetragonal zirconia taken at the Advanced Photon Source, Argonne National Laboratory. The expansion is anisotropic, with the relative expansion of the a‐lattice constant exceeding that of the c‐lattice constant. The anisotropic expansion cannot be explained by thermal expansion and is consistent with predictions from ab‐initio calculations based upon the generation of vacancy‐interstitial pairs of zirconium and oxygen.     

Onset of selective laser flash sintering of AlN

Flash sintering uses a combination of heating and electric fields to rapidly densify ceramics. Previously, it has been shown that a scanning laser can be used to initiate flash sintering in localized regions on an yttria-stabilized zirconia (YSZ) sample in a process known as selective laser flash sintering (SLFS). In this work, we show using a combination of measurements of electric current flowing through the sample and observations of necks formed between powder particles that aluminum nitride (AlN) can also undergo SLFS. Scan conditions required to initiate SLFS are characterized over a range of laser powers and laser scan speeds in a dry nitrogen environment. It is shown that initiation of SLFS in AlN is governed by both the local input energy density per scan and heat dissipation and a numerical model is developed to predict temperatures during SLFS. Assuming the minimum temperature along the conductive path determines the onset of SLFS, the minimum temperature and time required is 450–670 K in 2–0.25 s for the pressed AlN pellets used in this study for laser scan speeds of 33–300 m/s, laser powers of 10–30 W, and an applied electric field of 3000 V/cm.     

Thermochemical model on the carbothermal reduction of oxides during spark plasma sintering of zirconium diboride

Carbon was used to reduce oxides in spark plasma sintered ZrB₂ ultra-high temperature ceramics. A thermodynamic model was used to evaluate the reducing reactions to remove B₂O₃ and ZrO₂ from the powder. Powder oxygen content was measured and carbon additions of 0.5 and 0.75 wt% were used. A C–ZrO₂ pseudo binary diagram, ZrO₂–B₂O₃–C pseudo ternaries, and Zr–C–O potential phase diagrams were generated to show how the reactions can be related to an open system experiment in the tube furnace. Scanning transmission electron microscopy identified impurity phases composed of amorphous Zr–B–O with lamellar BN and a Zr–C–O ternary model was calculated under SPS sintering conditions at 1900°C and 6 Pa to understand how oxides can be retained in the microstructure.     

Microstructural evolution of 3YSZ flash-sintered with current ramp control

The effect of a controlled current ramp during flash sintering (FS) on the densification and microstructural evolution of 3 mol% yttria-stabilized zirconia was investigated. The samples were flash sintered using a current ramp control with six different current ramp rates and compared with samples sintered by FS without current ramp control. In both cases, maximum electric current densities of 100 and 200 mA mm⁻² were used. The microstructure of cylindrical samples was observed, showing grain size heterogeneity between the curved surface and the core for the flash-sintered (FSed) samples regardless of the maximum current density used. By contrast, the current ramp FSed samples exhibited a homogeneous grain size when the electric current density of 100 mA mm⁻² was applied. Thus, controlling a current ramp during FS can be an alternative for avoiding grain size heterogeneity on ceramics sintered by this technique.     

Flame‐assisted flash sintering: A noncontact method to flash sinter coatings on conductive substrates

We present a novel and effective method for sintering ceramic coatings onto metallic substrates. This new technique, called Flame‐assisted flash sintering (FAFS), utilizes a flame as both a heating source and a conformal, current‐carrying top electrode to facilitate flash sintering. Using this method, Yttria‐stabilized Zirconia (8 mol% Y, 8YSZ) coatings are sintered onto stainless steel substrates to controlled degrees of porosity in rapid fashion. Flame‐assisted flash sintering utilizes a dynamic soft electrode for flash sintering and has commercial potential to sinter ceramic coatings on complex‐shaped substrates for a variety of applications including tribological or thermal protection coatings.     

Highly textured and strongly anisotropic TiB2 ceramics prepared using magnetic field alignment (9T)

Highly textured TiB₂ ceramics were prepared by slip casting an aqueous suspension in a magnetic field of 9 T, followed by sintering using Field Assisted Sintering Technology (FAST). Particle size refinement by ball milling improved both the degree of texturing and densification of the material (RD > 98 %). The sintered material exhibited a Lotgering orientation factor of 0.90, with the c-axis of TiB₂ oriented parallel to the magnetic field and FAST pressing direction. The texturing effect induced by the uniaxial pressing was negligible. The textured TiB₂ material exhibited a significant anisotropy in mechanical properties; the values of hardness and indentation elastic modulus measured along directions transverse to the c-axis of TiB₂ were 37 % and 13 % higher than the ones measured along the c-axis direction. Moreover, the specific wear rate of a surface of textured TiB₂ parallel to the field was one order of magnitude lower than a surface perpendicular to the field.     

Microstructure development and optical properties of Fe:ZnSe transparent ceramics sintered by spark plasma sintering

Fe:ZnSe transparent ceramics were prepared by spark plasma sintering. Fe:ZnSe powders synthesized via co-precipitation yielded well-dispersed particles with an average particle size of 550 nm. These powders were in the cubic phase Fe:ZnSe, indicating the successful substitution of Fe²⁺ for Zn²⁺. The highest relative density, 99.4%, was obtained by increasing the pressure and sintering time. The effects of sintering temperature, pressure, and time on the microstructure of SPS prepared ceramics were presented by micrographs. With increasing sintering temperature, from 600°C to 900°C, the average grain size increased from < 1 to 10 μm. The intergranular fracture indicated no neck formation in the sintering process. High pressure was essential for the densification process. The average grain size deceased from approximately 10 to 5 μm when the pressure was increased. Increasing the sintering time from 10 to 120 minutes lead to a change in the microstructure, from inter- to transgranular fracture, and eliminated the micropores. The as-prepared Fe:ZnSe ceramics were composed of single-phased cubic ZnSe. The sample sintered at 900°C under a pressure of 90 MPa for 120 minutes yielded a transmittance of approximately 60% at 1.4 μm and 68% at 7.5 μm and had residual micropores as its main scattering source. There was a strong characteristic absorption peak of Fe²⁺ ions at around 3 μm, which was red-shifted compared to Fe:ZnS transparent ceramics. Fe:ZnSe transparent ceramics have a reddish-brown color and it could be a promising mid-infrared laser material.     

Spark plasma sintering of UO2 nanopowders: Pressure,heating rate and current effects

We analysed with different methods the densification of UO₂ nanopowders in SPS under constant heating rate (CHR) and isothermal sintering conditions. The apparent activation energy of densification in SPS (75 kJ/mol with CHR method) is significantly smaller than in conventional sintering. It is shown that this is likely not an effect of the applied current. We also observed a threshold stress at 64 MPa for the transition from pressure-insensitive sintering (stress exponent n≈0) to pressure-assisted sintering, suggesting that the contribution of the capillary stresses in such nanopowders is comparable with the typical stress applied in SPS.     

Flash sintering of a three‐phase alumina,spinel, and yttria‐stabilized zirconia composite

Three‐phase ceramic composites constituted from equal volume fractions of α‐Al₂O₃, MgAl₂O₄ spinel, and cubic 8 mol% Y₂O₃‐stabilized ZrO₂ (8YSZ) were flash‐sintered under the influence of DC electric fields. The temperature for the onset of rapid densification (flash sintering) was measured using a constant heating rate at fields of 50‐500 V/cm. The experiments were carried out by heating the furnace at a constant rate. Flash sintering occurred at a furnace temperature of 1350°C at a field of 100 V/cm, which dropped to 1150°C at a field of 500 V/cm. The sintered densities ranged from 90% to 96%. Higher electric fields inhibited grain growth due to the lowering of the flash temperature and an accelerated sintering rate. During flash sintering, alumina reacted with the spinel phase to form a high‐alumina spinel solid solution, identified by electron dispersive spectroscopy and from a decrease in the spinel lattice parameter as measured by X‐ray diffraction. It is proposed that the solid solution reaction was promoted by a combination of electrical field and Joule heating.     

烧成温度和ZrO2含量对镁锆制品烧结性能的影响

以烧结镁砂和锆英石为原料,按烧结镁砂与锆英石的质量比分别为8812,8515,8020,7723进行配料,成型后在110 ℃下保温24 h干燥,然后分别在1550 ℃、1600 ℃、1650 ℃、1730 ℃下保温3 h烧成,采用扫描电镜和能谱分析及XRD分析方法,研究了烧成温度和锆英石加入量对镁锆制品烧结性能的影响.结果表明随着锆英石加入量的增加和烧成温度的提高,镁锆制品的理化性能也逐渐提高,当锆英石的加入量为20%(即ZrO2含量为12%),烧成温度为1650 ℃时,镁锆制品的理化性能最佳,MgO与SiO2反应形成的镁橄榄石相(M2S)最多,ZrO2则多以t-ZrO2形式存在于MgO颗粒的周围,还有一小部分与MgO形成固溶体.     

Processing of CaLa2S4 infrared transparent ceramics: A comparative study of HP and FAST/SPS techniques

The densification of CaLa₂S₄ (CLS) powders prepared by combustion method was investigated by the use of Field-Assisted Sintering Technique (FAST) and Hot Pressing (HP). CLS powders were sintered using FAST at 1000°C at different pressures and heating rates and sintered by HP under 120 MPa from 800°C to 1100°C for 6 hours with a heating rate of 10°C/min. Comparison of both techniques was further realized by use of the same conditions of pressure, dwell time, and heating rate. Complementary techniques (XRD, SEM-EDS, density measurements, FTIR spectroscopy) were employed to correlate the sintering processes/parameters to the microstructural/compositional developments and optical transmission of the ceramics. Both sintering techniques produce ceramics with submicrometer grain size and relative density of about 99%. Nevertheless, HP is more suitable to densify CLS ceramics without fragmentation and also reach higher transmission than FAST. Transmission of 40%–45% was measured out of a possible maximum of 69% based on the Fresnel losses in the 8-14 μm window when HP is applied at 1000°C for 6 hours under 120 MPa. In both techniques, ceramics undergo reduction issues that originate from graphitic sintering atmosphere.     

Thermal and electrical properties of additive-free rapidly hot-pressed SiC ceramics

The thermal and electrical properties of newly developed additive free SiC ceramics processed at a temperature as low as 1850 °C (RHP0) and SiC ceramics with 0.79 vol.% Y₂O₃-Sc₂O₃ additives (RHP79) were investigated and compared with those of the chemically vapor-deposited SiC (CVD-SiC) reference material. The additive free RHP0 showed a very high thermal conductivity, as high as 164 Wm⁻¹ K⁻¹, and a low electrical resistivity of 1.2 × 10⁻¹ Ω cm at room temperature (RT), which are the highest thermal conductivity and the lowest electrical resistivity yet seen in sintered SiC ceramics processed at ≤1900 °C. The thermal conductivity and electrical resistivity values of RHP79 were 117 Wm⁻¹ K⁻¹ and 9.5 × 10⁻² Ω cm, respectively. The thermal and electrical conductivities of CVD-SiC parallel to the direction of growth were ∼324 Wm⁻¹ K⁻¹ and ∼5 × 10⁻⁴Ω⁻¹ cm⁻¹ at RT, respectively.     

Effect of zirconia content and particle size on the properties of 3D-printed alumina-based ceramic cores

Alumina-based ceramic cores are used to manufacture the internal structures of hollow alloy blades, requiring both high precision and moderate properties. In this work, zirconia is regarded as a promoter to improve the mechanical properties of sintered ceramic. The effect of zirconia content and particle size on the microstructure and mechanical properties of ceramics was evaluated. The results indicate that the flexural strength of sintered ceramics reached the maximum of 14.5 ± 0.5 MPa when 20 wt% micron-sized (10 μm) zirconia (agglomerate size, consistent with the alumina particle size) was added, and 26.5±2.5 MPa when 15 wt% 0.3 μm zirconia was added. Zirconia with submicron-sized (0.3 μm) particles effectively filled the pores between alumina particles, thus leading to the maximum flexural strength with a relatively low content. The corresponding sintered ceramics had a bulk density of 2.0 g/cm³ and open porosity of 59.6%.     

Effect of sintering atmosphere on the grain growth and hardness of SiC/polysilazane ceramic composites

Silicon carbide (SiC) monoliths were synthesised using nano-size SiC powder mixed with/without polysilazane by hot pressing at 1750°C for 1?h under an applied pressure of 20?MPa in N₂ or Ar atmosphere. The effects of polysilazane and sintering atmosphere on the microstructure and hardness of SiC were examined. The grain sizes of the SiC ceramics sintered in N₂ atmosphere with and without the polysilazane were 161 and 605?nm, while the density for those samples were 96.5 and 98.1%, respectively. It was shown that Si₂N₂O was formed for the SiC/polysilazane composite and sintered in N₂. In addition, the sample mixed with polysilazane followed by sintering in N₂ atmosphere revealed a quite high hardness in spite of its relatively low density. It was suggested that Si₂N₂O phase played an important role for the inhibition of grain and subsequent high hardness.