Flash Sintering Research Articles

Enhancing microstructure homogeneity and electrical conductivity in flash-sintered 8YSZ: Impact of electric-current ramp control and thermal insulation

Our study aimed to comprehend how variations in flash sintering parameters affect the evolution of microstructure and electrical properties of yttria-stabilised zirconia. For this purpose, cylindrical samples were sintered via a classic flash method (voltage-current control), with controlled increase in the current ramp, employing thermal insulation, and combining current ramp control with thermal insulation. The results demonstrated that the combination of current ramp control and thermal insulation yielded higher densification compared to other variations. Microstructural analysis revealed finer grain sizes and lower grain-boundary tensions on employing current ramp control, particularly when combined with thermal insulation. For all flash-sintering methods, greater electrical conductivity of grain boundaries was observed compared to conventional sintering, suggesting an enhancement in ionic conduction. This study underscores the potential of customised FS techniques in optimising sintering processes and enhancing material properties.

Static and dynamic open loop control of selective laser flash sintering conducted with direct current electric fields

AbstractSelective laser flash sintering utilizes a scanning laser as a heat source to locally initiate flash sintering in the regions scanned by the laser. A key challenge towards utilizing this process for additive manufacturing (AM) is the induced electrical current that arises during flash sintering. With traditional scan patterns conducted with static electric fields, electrical and thermal runaway and associated thermal shock cracking occur. In this study, several open‐loop control strategies with static and dynamic applied electric fields were utilized to control peak currents. These strategies were shown to be effective in reducing peak currents to below 1.0 µA and reducing the severity of, but not completely eliminating cracking. Alternative strategies are suggested that could lead to complete elimination of cracks.

Effects of limiting current density and current step rate on microstructure and hardness of flash sintered MgAl2O4 ceramics

This study investigates the effects of limiting current density and current step rate on the microstructure and hardness of current-step flash-sintered (CS-FS) disc-shaped MgAl2O4 ceramics. The results indicated that, unlike conventional flash sintering, the temperature of the sample during the current-step flash started at a lower initial value and subsequently increased gradually. Furthermore, the differences in oxygen vacancies between the positive and negative sides of the CS-FS-ed MgAl2O4 ceramics were significantly reduced. This led to the CS-FS samples exhibiting higher relative density, finer grain size, a more uniform microstructure, and increased hardness. The homogeneous microstructure resulted in consistent hardness across both sides of each CS-FS-ed sample. Additionally, as the limiting current density increased, the grain sizes near the positive and negative sides gradually enlarged, while the relative density initially increased before decreasing. A similar trend was observed when the current step rate decreased.

Flash sintering glass–ceramic treatment of Sr-contaminated soil waste

Effective disposal of radioactive waste is crucial for safe development of nuclear energy. In this study, flash sintering technology is used for the first time to quickly solidify simulated Sr-contaminated soil waste. The waste can be converted into a glass–ceramic phase by heating the waste at 1100 °C for 1 min during flash sintering. The phase evolution during flash sintering as a function of density and amorphous fraction was systematically investigated. Additionally, the microstructural evolution of the matrices and the leaching behavior of simulated waste elements (e.g., Sr) were evaluated. This study explores the feasibility of using flash sintering for treating radioactive contamination waste.

Flash sintering of UO2 pellets for nuclear fuel and wasteform applications

Flash sintering (FS) has been shown to enhance the sintering kinetics in UO2. Using a bespoke AC-FS furnace, high density UO2 pellets, >95% theoretical density (TD) have been produced followed by scale up and Gd2O3 doping trials. Increasing furnace temperature during FS increases pellet density to a plateau, however, increasing hold time and maximum current both increased the density of UO2 samples to >95% TD and grain size to ~4µm, close to conventional sintering (CS). The optimised FS program reduced sintering temperature and cycle time by ~50% compared to CS. Scale up trials showed >96%TD pellets could be achieved for 11.3 and 14.125mm diameter green bodies, demonstrating typical fuel pellet diameters are feasible with FS. Gd doping experiments showed with 1wt.% Gd2O3 addition, a ~92%TD pellet with ~2µm grain size was obtainable, highlighting further optimisation is required for mixed oxide (MOx) materials.

Flash sintering of AlN ceramics with Y2O3 additive

This study demonstrates the fabrication of dense AlN-based ceramics through the flash sintering technique for the first time. Flash sintering was performed at a furnace temperature of 1500 °C with 10 wt% Y2O3 as a sintering aid in a nitrogen atmosphere. The effects of the current density and holding time on the microstructure evolution and mechanical properties were investigated. The results show that the relative density, grain size and Vickers hardness of specimens increase with increasing current density and holding time. The specimen showed the highest relative density of 98.6% and a Vickers hardness of 12.68 GPa when a current density of 100 mA/mm2 and a holding time of 60 min were used. Additionally, the grain sizes at the positive side of the electrodes were found to be larger than those at the negative side. These findings suggest that dense AlN-based ceramics can be fabricated in a rapid and efficient way through the flash sintering technique.

Realizing near-full density monophasic tetragonal 1.5-mol% yttria-stabilized zirconia ceramics via current-ramp flash sintering

This study demonstrates the successful fabrication of near-full density monophasic tetragonal 1.5-mol% yttria-stabilized zirconia (1.5YSZ) ceramics using current-ramp flash (CRF) sintering technique. The process involved regulating Joule heating in the samples by fine-tuning the input power through an alternating current field (nominal current density: 50 mA·mm−2) within a 3-minute timeframe at a furnace temperature of 1100°C. This approach effectively enhanced grain size uniformity, which is crucial for preventing sample cracking associated with spontaneous tetragonal-to-monoclinic (T→M) phase transformation, thereby promoting densification with average relative densities exceeding 99%. The highest average fracture toughness of the 1.5YSZ samples was measured at 9.2 MPa·m0.5 using the standardized single-edge pre-cracked beam method. This toughness is approximately double that of commonly used 3YSZ samples produced by CRF sintering, all of which exhibited comparable average grain sizes and relative densities. Additionally, the 1.5YSZ samples demonstrated nearly identical resistance to low-temperature degradation (LTD) compared to the 3YSZ samples after accelerated hydrothermal aging at 140°C for 15 hours, roughly equivalent to 60 years at 37°C. The reduced yttria concentration in 1.5YSZ facilitates T→M phase transformation at lower stress thresholds, enhancing toughness through increased crack shielding from a larger volume fraction of transformed grains. Furthermore, the uniform yttria distribution in 1.5YSZ, revealed by scanning transmission electron microscopy, compensates for the reduced tetragonal phase stability and contributes to improved LTD resistance. Notably, these exceptional properties were achieved at a furnace temperature 300°C lower and with a sintering duration several hours shorter than those of conventionally-sintered counterparts.

Rapid fabrication of Ba1–xSrxTiO3 ceramics via reactive flash sintering

Ba1–xSrxTiO3 (BST) ceramics are promising dielectric materials. However, their fabrication is usually laborious, requiring long preparation stages and high temperatures, which are not favorable for tuning the grain size and dielectric properties. In this study, (Ba1–xSrx)TiO3 (x = 0.1, 0.3, 0.5) ceramics were produced via reactive flash sintering (RFS) of a mixture of BaCO3, SrCO3 and TiO2 powders at 900 °C and relatively short times (15–90 s). The electric field (E-field) with a strength of 400 V/cm and the current densities of 25–75 mA mm−2 were applied during RFS. Once the Sr2+ content increased, the incubation time for the RFS decreased, suggesting that the addition of Sr2+ facilitated the RFS process. At the RFS time above 15 s, a single-phase Ba0.6Sr0.4TiO3 perovskite structure was formed. When the time and the applied current density increased, both the densities and grain sizes within the ceramics increased. This increased the real part (ε’) of the complex permittivity compared to that of the conventionally sintered (CS) ceramic. Moreover, the enhancement of mass transport by E-field-induced oxygen vacancies was considered the predominant mechanism of RFS in the production of BST ceramics.

Structural and electronic transformations in TiO2 induced by electric current

In-situ diffuse neutron scattering experiments revealed that when electric current is passed through single crystals of rutile TiO2 under conditions conducive to flash sintering, it induces the formation of parallel planes of oxygen vacancies. Specifically, a current perpendicular to the c-axis generates planes normal to the (132) reciprocal lattice vector, whereas currents aligned with the c-axis form planes normal to the (132) and to the (225) vector. The concentration of defects increases with incresing current. The structural modifications are linked to the appearance of signatures of interacting Ti3+ moments in magnetic susceptibility, signifying a structural collapse around the vacancy planes. Electrical conductivity measurements of the modified material reveal several electronic transitions between semiconducting states (via a metal-like intermediate state) with the smallest gap being 27 meV. Pristine TiO2 can be restored by heating followed by slow cooling in air. Our work suggests a novel paradigm for achieving switching of electrical conductivity related to the flash phenomenon.

Flash sintering of HUST-1 lunar regolith simulant: Effects of processing temperature on microstructure characteristics and mechanical properties

In-situ construction method is expected to be considered for lunar base construction because of its reducing transportation cost. Among the many in-situ construction processes, the flash sintering process can significantly reduce the processing time and become a potentially effective in-situ resource utilization (ISRU) technology. In this study, the flash sintering process was investigated for the first time to realize the sample forming of HUST-1 lunar regolith simulant (LRS). The effects of sintering temperature on the micro- and macrostructural characteristics and mechanical properties of the samples were systematically studied. The results showed that the densities and mechanical properties of the sintered samples were improved with the increase of the sintering temperature (from 1050 °C to 1290 °C) in a low vacuum environment for 4 min. Joule heating effect was investigated to cause rapid high-temperature solid-phase reactions between the LRS particles. At 1290 °C, the compressive strength of the sintered sample reached maximum 59.47 MPa. This study provides an efficient forming method for lunar construction in the future.

Flash sintering mechanism in multiphase materials system of copper smelting slags

Flash sintering (FS) is of great interest today, as it allows the production of high-density ceramics in seconds at lower temperatures than conventional sintering. In this study, the effects of conventional sintering at 1250°C for 4 h and FS at various electric fields (12.5, 25, 50 and 75 V/mm) on copper smelting slag (CSS), which is a multiphase material system, are investigated. The results show that FS occurs at substantially lower temperatures with much shorter times than conventional sintering, in conjunction with improved density and hardness values for CSS. The optimum condition for better densification is observed for the sample applied the 25 V/mm electric field in 554 s, and the maximum power density of about 76.49 mW/mm3. On the other hand, the shortest FS duration is achieved with the sample applied 75 V/mm in 114 s. Flash sintering at lower temperatures also stabilizedthe magnetite-hematite the phase transition, which arouses at higher temperatures. Overall, FS has made a huge contribution to reducing sintering time and temperature while providing better microstructure integrity and mechanical properties in multiphase materials systems.

Plasma‐flash sintering: Metastable phase stabilization and evidence of ionized species

AbstractThe first demonstration of plasma‐flash sintering (PFS) is presented in this work. PFS is performed under a low‐pressure atmosphere that consecutively generates plasma and flash events. It is shown, by using several combined characterization techniques, that PFS stabilizes metastable phases on the surface of the material, which may be partially, but not solely, attributed to the generation of oxygen vacancies, and induces the absorption of ionized species, if a reactive atmosphere is employed. Even though additional research is required to understand the fundamentals of PFS, it is evidenced its potential to be used as a material surface engineering tool, which may widen the technological capabilities of flash sintering.

Flash Sintering of Rhenium in About 1 Minute with Electrical Current

Flash Sintering of Rhenium in About 1 Minute with Electrical Current

Microstructure and hardness of two-step reverse-polarity flash sintered high-purity Al2O3 ceramics

In this work, high-purity alumina ceramics were prepared by using two-step reverse polarity flash sintering (PR-FS). The effects of the time distribution between the first flash and the second flash on microstructure and hardness were studied. The results show that compared to the conventional DC flash sintered alumina, the RP–FS–ed samples exhibited more uniform-microstructure, finer grains, higher relative density, and higher hardness. The underlying mechanism for such more homogeneous microstructure was related to uniform distribution of point defects under effect of reverse polarity. Two-step reverse polarity flash sintering method offers a great potential in obtaining highly densified alumina ceramics with homogeneous microstructure.

Influence of the atmosphere on the formation of high-entropy oxides within the Co–Cu–Fe–Mg–Mn–Ni–O system via reactive flash sintering

In this study, the feasibility of preparing quinary equimolar high-entropy oxides within the Co–Cu–Fe–Mg–Mn–Ni–O system was explored using the reactive flash sintering (RFS) technique. Various compositions were tested using this technique under atmosphere pressure, leading to the formation of two primary phases: rock-salt and spinel. Conversely, a new high-entropy oxide was produced as a single-phase material with the composition (Co0.2,Cu0.2,Mg0.2,Mn0.2,Ni0.2)O when RFS experiments were conducted in nitrogen atmosphere. The reducing conditions achieved in nitrogen enabled the incorporation of cations with oxidation states different from +2 into the rock-salt lattice, emphasizing the critical role of the processing atmosphere, whether inert or oxidizing, in the formation of high-entropy oxides. The electrical characterization of this material was obtained via impedance spectroscopy, exhibiting a homogeneous response attributed to electronic conduction with a temperature dependence characteristic of disordered systems.

Flash sintering of tunable dielectric Ba0.6Sr0.4TiO3 electroceramics

Ba(1-x)SrxTiO3 (BST) is a crucial dielectric material in tunable devices for modern wireless communication technologies, owing to high dielectric tunability and low dielectric loss. However, the conventional processing of BST ceramics requires a high sintering temperature of about 1350 ºC. In this work, we demonstrate the feasibility of using Flash sintering (FS) and corresponding maps to process Ba0.6Sr0.4TiO3 ceramics, resulting in a 350 ºC decrease in sintering temperature and 7 h reduction in sintering process time. The Flash-sintered BST exhibits a finer grain microstructure, lower dielectric loss, and significantly higher K-factor (figure of merit for tunability) when compared to conventionally sintered BST, unequivocally meeting the application criteria for tunable materials. Our findings highlight the effectiveness of FS as an alternative method for the rapid sintering of BST, while also opening up possibilities for further research into more efficient sintering processes for electroceramics.

Hyperdoping: doping TiO2 beyond thermodynamic limits using Flash sintering

For the first time, it has been demonstrated that TiO2 optical properties can be improved by doping Fe using flash sintering. Hyperdoped TiO2 (doped with 10 at% Fe) fabricated using flash sintering, exhibited remarkable improvements in optical characteristics. Hyperdoping (exceeding the equilibrium solubility limit), induces charge trap centers or inhibits charge recombination in semiconductors. By employing XPS and UV-Vis spectroscopy, surface species alterations including oxygen vacancies, Ti4+, Ti3+, and optical characteristics were investigated. With varying holding periods, flash sintering unveiled substantial enhancements in optical absorbance and absorption regions by generating Ti3+ and oxygen vacancies. Notably, a 10-second hold time during flash sintering displayed the highest redshift among the investigated samples, indicating superior optical improvement. Oxygen vacancies and Ti3+ increased with decreased holding time during flash, suggesting the influence of flash sintering parameters on forming a metastable phase, signifying the pivotal role of flash sintering's time parameter in modulating material properties.

Structural, Mössbauer and magnetic study of (Mn0.2Co0.2Ni0.2Cu0.2X0.2)Fe2O4 (X=Fe, Mg) spinel high-entropy oxides fabricated via reactive flash sintering

Herein, it is reported the concomitant synthesis and sintering in a single step of (Mn0.2Co0.2Ni0.2Cu0.2X0.2)Fe2O4 (X=Fe, Mg), a spinel-structured high-entropy oxides, by the reactive flash sintering technique. A single phase, identified with a spinel crystal structure Fd3̅m, was obtained in just 30 min at a furnace temperature of 1173 K. The structural and magnetic properties of the prepared compounds were assessed by the combined use of various techniques, aiming to understand the correlations between functional properties and crystal structure. Characteristic features of the Mössbauer spectra prove the existence of different nonequivalent Fe environments . Both compositions display soft magnetic behavior, characterized by low coercive fields and saturation magnetization reached at low fields. Thus, the substitution of nonmagnetic Mg2+ for magnetic Fe2+ results in a decrease in magnetic parameters due to the weakening of the super-exchange interaction among the magnetic moments.

Effects of amorphous phase and yttrium on flash sintering and microstructures of ZrO2–SiO2 ceramic nanocomposites

AbstractFlash sintering has been used to consolidate a wide range of ceramics and ceramic composites. However, flash sintering of ceramic nanocomposite with a substantial amorphous phase is rarely studied. Meanwhile, the effects of yttrium addition on the flash sintering behaviors and microstructures of ZrO2‐based ceramic nanocomposite remain unknown. Herein, ZrO2‐SiO2 crystalline‐amorphous ceramic nanocomposites (CACNs) with different contents of amorphous phase and two types of yttrium dopants were sintered by flash sintering. Results showed that the content of amorphous phase (SiO2) had significant effects on the flash sintering behavior. The CACN with 65 mol% SiO2 was nonflash sinterable due to the high electric resistivity of SiO2, whereas, the CACN with 45 mol% SiO2 can be flash sintered to high densification within 35 seconds. The flash‐sintered CACNs consisted of ZrO2 nanocrystallites distributed in an amorphous SiO2 matrix. Flash sintering enhanced the tetragonal‐to‐monoclinic phase transformation of ZrO2. In addition, influences of yttrium dopant on CACNs were also investigated. Yttrium dopants can rapidly dissolve in ZrO2 lattices and show a tetragonal phase stabilization effect during flash sintering. Firework‐like ZrO2 microcrystallites formed by dendritic growth were observed close to the cathode region, which was attributed to athermal electric field effects and the formation and aggregation of oxygen vacancies at the cathode region. The results would provide guidance for fabricating CACNs via flash sintering.

Flash sintering of silicon carbide at room temperature

Although flash sintering (FS) is an effective method for rapidly preparing ceramics, FS of non-oxide ceramics at room temperature (RT) has not yet been achieved. In this study, we developed a feasible method for FS of SiC at room temperature (RT). A dog-bone-shape SiC sample prepared without using any sintering aid achieved a relative density of 96.5 % after sintering in a low-pressure Ar atmosphere for 60 s. Arc heating, which was constrained by the height of an alumina plate fixed above the sample, increased the conductivity of the sample, which then reached the stable stage of FS. The sintered sample exhibited a typical 6H–SiC crystal structure, which was consistent with that of the raw powder. The proposed FS method, based on constraining the arc using an alumina plate under a low-pressure inert gas atmosphere, provides a reference for developing further advanced RT FS strategies for non-oxide ceramics with low conductivities at RT.