Sintering Of Ceramics Research Articles

Pressureless two-step sintering of ultrafine-grained high-entropy zirconate ceramics with excellent mechanical properties

The challenge of preparing dense ultrafine-grained high-entropy ceramics through conventional pressureless sintering is hereby addressed by a simple two-step sintering method. Ultrafine-grained (Ce0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 high-entropy zirconate with 99.2 % theoretical density and 135 nm grain size has been fabricated by pressureless two-step sintering for the first time. Compared to the conventional sintering, two-step sintering provides finer grain sizes and better microstructural uniformity, which yield excellent comprehensive mechanical properties with high hardness of 16.0 GPa, large elastic modulus of 262 GPa and high fracture toughness of 2.8 MPa·m1/2. It is believe that pressureless two-step sintering can be utilized to prepare other high-entropy ceramics with fine grain size and high quality.

Optical and mechanical properties of rutile TiO2 subjected to AC flash processing

Unusual physical properties associated with lattice defects induced by flash sintering and processing of oxide ceramics have attracted attentions. In this study, optical and mechanical properties of undoped and polycrystalline rutile TiO2 subjected to alternating current (AC) flash processing were characterized through diffuse reflectance spectroscopy and nanoindentation experiments at room temperature. The flashed sample exhibited substantial optical blackening and elastic softening but negligible changes in the hardness and crystal structure. The elastic softening demonstrated a significant rate dependence (i.e., elastic moduli decreased with testing rate), which was possibly caused by stress-induced reordering of point defects induced by AC flash processing. This elastic softening suggests that pronounced ionic mobility is obtained by flash processing even in undoped systems, which can potentially be extended to a general understanding of mass transport phenomena in transient metal oxides in strong electric fields.

Making the Case for Scaling Up Microwave Sintering of Ceramics

The densification and sintering of ceramics using microwaves is first reported in the mid‐1960s. Today, the reduced carbon footprint of this process has renewed interest as it uses less energy overall compared to conventional process heating/furnaces. However, scaling up and commercializing the microwave sintering process of ceramics remains a formidable challenge. As a contactless method, microwave sintering offers geometric flexibility over other field‐assisted sintering processes. Yet, the inability to address multiscale, multiphysics‐driven heterogeneities arising during microwave coupling limits discussions about a future scale‐up process. Herein, the case is made that unlike 60 years ago, new advances in multiscale computational modeling, materials characterization, control systems, and software open up new avenues for addressing these challenges. More importantly, the rise of additive manufacturing techniques demands the innovation of sintering processes in the ceramics community for realizing near‐net‐shaped and complex parts for applications ranging from medical implants to automotive and aerospace parts.

In-situ Li2O-atmosphere assisted solvent-free route to produce highly conductive Li7La3Zr2O12 solid electrolyte

Solid-state batteries have garnered attention due to their potentiality for increasing energy density and enhanced safety. One of the most promising solid electrolytes is garnet-type Li7La3Zr2O12 (LLZO) ceramic electrolyte because of its high conductivity and ease of manufacture in ambient air. The complex gas-liquid-solid sintering mechanism makes it difficult to prepare LLZO with excellent performance and high consistency. In this study, an in-situ Li2O-atmosphere assisted solvent-free route is developed for producing the LLZO ceramics. First, the lithium-rich additive Li6Zr2O7 (LiZO) is applied to in-situ supply Li2O atmosphere at grain boundaries, where its decomposition products (Li2ZrO3) build the bridge between the grain boundaries. Second, comparisons were studied between the effects of dry and wet routes on the crystallinity, surface contamination, and particle size of calcined powders and sintered ceramics. Third, by analyzing the grain boundary composition and the evolution of ceramic microstructure, the impacts of dry and wet routes and lithium-rich additive LiZO on the ceramic sintering process were studied in detail to elucidate the sintering behavior and mechanism. Lastly, exemplary Nb-doped LLZO pellets with 2 wt% LiZO additives sintered at 1,300 °C × 1 min deliver Li+ conductivities of 8.39 × 10-4 S cm-1 at 25 °C, relative densities of 96.8%, and ultra-high consistency. It is believed that our route sheds light on preparing high-performance LLZO ceramics for solid-state batteries.

Ultrafast high-temperature sintering and densification of ZrC-based ceramics

Zirconium carbide (ZrC) ceramics are promising candidates for high-temperature structural components and nuclear reactors. However, their poor sinterability has limited widespread application. This study explored the sintering and densification of ZrC-based ceramics with graphite or B4C additive using ultrafast high-temperature sintering (UHS). A nearly fully dense ZrC ceramic (> 98%) could be obtained by adding 2.5 wt% B4C additive via ultrafast high-temperature sintering at 2300 °C within 3 min. Additionally, the results revealed that adding graphite into ZrC was beneficial to reduce the grain size but detrimental to densification. Compared to ZrC ceramics sintered using conventional pressureless sintering (PLS) at 2400 °C for 60 min, ZrC-based ceramics with 2.5 wt% B4C sintered via UHS at 2400 °C for 30 s exhibited higher relative densities, smaller grain sizes, and greater Vickers hardness due to faster heating rates and shorter sintering processes.

Flash sintering of lead zirconate titanate ceramics under high voltage at room temperature

Flash sintering has been applied to various ceramics since it was first reported. However, the flash sintering of lead zirconate titanate (PZT) at room temperature has not been accomplished. In this study, flash sintering of PZT piezoelectric ceramics at room temperature was realised for the first time. Subsequent to surface treatment in a low-pressure environment, the sample was flash-sintered at a high voltage in air. The sample became dense rapidly during sintering. The results showed that after 300 s of sintering, the flash-sintered samples had a high density (98.1%) and d33 values (273 pC/N). The d33 is the highest compared with flash sintering of PZT through the furnace temperature of several hundred degree Celsius. Owing to the extremely short sintering time and the absence of heating devices, this method can greatly reduce energy consumption and lead to volatilisation, providing a new method for the rapid preparation of piezoelectric ceramics.

Synthesis and characterisations of clinoptilolite enriched hydroxyapatite nanoceramics by sol-gel route for bone regeneration

Hydroxyapatite (HA) has great bioactive potential in bone tissue engineering (BTE). However, the high crystalline stability of synthetic HA restricts its in-vivo bioresorbability which extends the healing time of bone defects. This study investigates doping HA with biocompatible Clinoptilolite (CLP) mineral rich in silicate and other biomimetic ions (Na+, K+, Ca+2, Mg+2 etc.). Sol-gel-based CLP doped HA nanoceramics are aimed to be exploited as bone filler substitutes with biomimetic morphology, composition, and improved biocompatibility and bioactivity. The pure and CLP (5%, 10% and 20%) doped HA ceramics were synthesised by sol-gel method to provide molecular level interactions of ions and sintered at different temperatures (800 °C, 950 °C, and 1100 °C). Morphological analyses by SEM and S-TEM showed biomimetic nano rod-like HA particles are attached to dispersed CLP sheets. Sintering of composite ceramics led to a cell-friendly interconnected porous microstructure even at 1100 °C, where the pure HA had a compact non-porous structure. The Ca/P ratio of CLP-doped HA samples was lower than the stoichiometric HA which indicates a partial reduction of stability that is supposed to induce bioresorption capacity. Cytotoxicity tests by WST-8 with Saos-2 cell lines showed that CLP addition into HA has significantly improved cell viability. The HA-CLP nanoceramics are expected to promote bone regeneration due to cell-friendly microstructure and biomimetic composition which can be supported by further in-vivo clinical studies.

Understanding the consolidation mechanism of selective laser sintering/powder bed selective laser process of ceramics: Hydroxyapatite case

PurposeThe consolidation process and morphology evolution in ceramics-based additive manufacturing (AM) are still not well-understood. As a way to better understand the ceramic selective laser sintering (SLS), a dynamic three-dimensional computational model was developed to forecast thermal behavior of hydroxyapatite (HA) bioceramic.Design/methodology/approachAM has revolutionized automotive, biomedical and aerospace industries, among many others. AM provides design and geometric freedom, rapid product customization and manufacturing flexibility through its layer-by-layer technique. However, a very limited number of materials are printable because of rapid melting and solidification hysteresis. Melting-solidification dynamics in powder bed fusion are usually correlated with welding, often ignoring the intrinsic properties of the laser irradiation; unsurprisingly, the printable materials are mostly the well-known weldable materials.FindingsThe consolidation mechanism of HA was identified during its processing in a ceramic SLS device, then the effect of the laser energy density was studied to see how it affects the processing window. Premature sintering and sintering regimes were revealed and elaborated in detail. The full consolidation beyond sintering was also revealed along with its interaction to baseplate.Originality/valueThese findings provide important insight into the consolidation mechanism of HA ceramics, which will be the cornerstone for extending the range of materials in laser powder bed fusion of ceramics.

Silver catalytic effect on flash sintering of ceramics

We investigated the use of metallic silver as a catalyst for flash sintering on hydroxyapatite/zirconia (HZ) composites. Adding 3 wt% of silver to the ceramic powder reduced the flash onset temperature (from 1084 °C to 925 °C) and also the electric field (from 300 V cm−1 to 150 V cm−1) used in the process. We attribute this behaviour to the formation of a silver percolation path that acts as a heat source, accelerating the thermal runaway. As a result, both the flash temperature and the required electric field were reduced. Furthermore, the results suggest that the temperatures along the percolation paths are high enough to reach the boiling point of silver, forming a gaseous phase that leaves the sample.

Analysis of the Luminescent Emission during Flash Sintering of 8YSZ and 20SDC Ceramics

Light-emission data were collected before, during, and after the occurrence of the flash event in pressureless electric-field-assisted (flash) sintering experiments on ZrO2: 8 mol% Y2O3 (8YSZ) and CeO2: 20 mol% Sm2O3 (20SDC) ceramic green pellets to analyze the luminescent emission from the samples. The experiments were performed at 800 °C with an applied electric field of 100 V·cm−1 at 1 kHz, limiting the electric current to 1 A. Luminescence data were obtained in the 200–1200 nm (ultraviolet–visible–near-infrared) range. The deconvolution of the optical spectra allowed for the identification of emission bands in the visible range due exclusively to the samples. The wavelength maxima of the emission bands in 8YSZ were found to be different from those in 20SDC. It is suggested that these bands might originate from the interaction of the electric current, resulting from the application of the electric field, with the depleted species located at the space-charge region at the grain boundaries of these ceramics. The main results represent a contribution to help to clarify the mechanisms responsible for the fast densification with inhibition of grain growth in electroceramics.

Influence of thermal cycling rate and sintering temperature of barium titanate and barium strontium titanate ceramics on their dielectric properties

One of the negative effects of ferroelectric applications, particularly for electrocaloric effect (ECE) applications, is temperature hysteresis (ΔT Hyst). Temperature hysteresis is the difference between the temperatures corresponding to the maximum dielectric permittivity in heating and cooling modes. The value of ΔT Hyst is commensurate with the value of the ECE temperature change. The ECE is a phenomenon in which a material shows a reversible temperature change under an applied electric field. The aim of this work is to study the possibilities of temperature hysteresis reduction by varying the ceramic sintering temperature, changing the stoichiometry of BaxSr1-xTiO3 solid solutions, and changing the rate of the heating-cooling cycle.

One-step synthesis and low-temperature rapid sintering of alumina-zirconia ceramics by flash sintering combined with phase transformation

High-performance alumina-zirconia ceramics are generally sintered above 1500 °C and consume lots of energy; rapid sintering at low temperature is an ideal technique due to its economy and low-energy consumption. For the first time, flash sintering combined with phase transformation-assisted sintering techniques was reported in this work. The alumina-zirconia amorphous precursor powder was used to replace the final product powder for ceramic processing, and the one-step synthesis and rapid sintering densification of alumina-zirconia ceramics at low temperature of 849 °C for 60 s were realized. The effects of electric field on the low-temperature sintering of amorphous powders are summarized into three aspects. Firstly, the electric field reduces the viscosity of the amorphous powder and promotes liquid phase sintering. Secondly, the electric field promotes the phase transition of the amorphous powder from metastable to stable phase, and accelerates the atomic migration. Thirdly, Joule heating and defect generation in the flash sintering promotes more effective material transport. Overall, this work reduces the energy for calcination of amorphous powders, reduces the sintering temperature of ceramics, well hinders the grain coarsening and shows excellent mechanical properties.

Flash sintering of ZnO ceramics with combined power supplies at room temperature

A flash sintering method at room temperature based on combined power supplies is proposed in this paper. Flash sintering is performed in two steps. First, a high voltage is used to break down the sample and then disconnect the power supply. Second, a low-voltage power supply is used to provide a large current to densify the sample. The method does not require changing the properties of the material or the sintering atmosphere. In addition to reducing the capacity of the required power supply, there is no need for external auxiliary equipment. Different types of high-voltage breakdown are also studied. The temperature and grain size corresponding to different currents of low-voltage flash sintering are studied. The results show that the sintered ZnO ceramics reach 98.5% relative density. A possible mechanism of flash sintering using combined power supplies is analysed.

Influence of particle size and aggregates on translucent alumina ceramics fabricated by gelcasting

Three types of alumina powders and a polymer electrolyte Isobam system were used to fabricate translucent alumina ceramics via gelcasting, and each powder had the highest attainable solid loading. The effects of alumina particle size on slurry dispersion, microstructures and properties of green bodies and ceramics were investigated. All of the high-solid loading slurries contained strong aggregates, which could bridge with each other to form weak agglomerates. The smaller the initial particle size was, the more the contained particle number per aggregate. In addition, the smaller the aggregate size was, the lower the sintering activation energy of the ceramic and, finally, the higher the relative density. The initial particle size of the powder may not be the critical factor determining ceramic sintering, but the aggregate size and effective volume fraction of the aggregates may be the critical factors. Finally, the in-line transmittance of the ceramic with a higher density reached 22% at a wavelength of 650 nm and a thickness of 0.8 mm.

Heating-induced release of trapped bubbles from dead-end pore throats filled with nonvolatile liquid

The release of trapped bubbles from dead-end pore throats filled with nonvolatile liquid has widespread applications in gas–liquid reactors, radiators, foam flooding, ceramic sintering, and droplet microcarriers. As conventional pressure-driven flow cannot induce the transport of bubbles in dead-end pores, this paper explores the possibility of using heating to control the release of bubbles from dead-end pore throats. Visualization experiments of the microfluidics within a dead-end pore throat structure are conducted to address the release process of bubbles during heating. An increase in temperature causes dissolved gas in the solution to be transferred to the bubble, which enhances the bubble pressure and enables the bubble to pass through the pore throat. We analyze the effects of the initial bubble radius and initial temperature on the critical temperature Tcr at which the bubble passes through the pore throat. A larger initial radius does not necessarily make it more difficult for the bubble to pass through the throat, but there is a critical radius above which any increase in radius produces a lower value of Tcr. A theoretical model considering diffusion mass transfer, capillary forces, and corner film flows is developed, and this model is found to be in good agreement with the experimental results. Finally, we obtain three dimensionless numbers that can be used to predict Tcr. Our work provides guidance for the effective regulation of diffusive growth and the heating-induced release of bubbles from dead-end pore throats.

Physics-based neural network as constitutive law for finite element analysis of sintering

In the sintering of advanced ceramics, a digital twin consisted of a finite element model can predict the final shape and microstructure of a sintered ceramic. However, to minimise uncertainties, it is essential to continually update the mechanical properties in the digital twin using data collected from the manufacturing process. One promising approach for achieving this is through artificial neural networks (ANN). This study introduces a machine learning strategy to update the constitutive behaviour of advanced ceramics in finite element analysis of sintering deformation. A major challenge in implementing machine learning in material processing is the huge amount of data required by the training and validation of an ANN, which are often unavailable or incomplete in a real manufacturing process. This study demonstrates that the data requirement can be reduced by employing a two-step training technique. Firstly, the ANN is trained using a nonlinear constitutive law, which describes a general relationship between the strain rates and stresses. Subsequently, the weights and biases of the ANN are transferred for the retraining using limited experimental data for an actual ceramic. It is shown that such approach can successfully capture the nonlinear constitutive behaviour of fine-grained alumina without demanding for large amount of experimental data. A case study is provided, highlighting the feasibility of implementing the ANN in a commercial finite element package, to replace the constitutive law and predict the shrinkage and distortion of a sintering part. In particular, the sintered dumb-bell shape part, simulated using the retrained ANN, showed grain size and relative density that markedly different from those using the nonlinear constitutive law. It is important to note that the proposed methodology is generic and can be used to create ANNs to replace constitutive laws in finite element analysis in digital twins for a wide range of other engineering processes.

Redistribution of dopants between amorphous and crystalline phases in ZrO2–SiO2 nanoceramics

AbstractExtensive efforts have been devoted to investigate the distribution of dopants in ceramics. However, one critical question remained barely explored, which is the redistribution of dopants between amorphous and crystalline phases during fast sintering of ceramics. Here we address this gap by observing the redistribution of five selected dopants (Y, Ce, Yb, Hf, and Ta) in ZrO2–SiO2 nanoceramics during sintering. We designed two groups of experiments: In group one, dual‐phase amorphous particles were sintered with multicomponent crystalline ones. The former particles were ZrO2–SiO2 glass, whereas the latter ones consisted of ZrO2 solid‐solution nanocrystallites (SSNCs) embedded in an oxide glass containing Zr, Si, Y, Ce, Hf, Yb, and Ta. In group two, dual‐phase crystalline particles were sintered with multicomponent amorphous ones. The former particles were composed of ZrO2 nanocrystallites (NCs) embedded in an amorphous SiO2 matrix, whereas the latter ones were oxide glass containing Zr, Si, Y, Ce, Hf, Yb, and Ta. Redistribution of the dopants from the glass to ZrO2 NCs occurred in the two groups, that is, the five dopants migrated from the glass matrix into the ZrO2 NCs, forming ZrO2 SSNCs. The redistribution of the dopants not only increased the configuration entropy of the ZrO2 NCs but also benefited the network structure integrity of SiO2 glass. The dopant redistribution process was driven by the minimization of the studied material's free energy. The reported results are important for understanding the redistribution behaviors of dopants and are expected to provide new insights to design new ceramics via the multielement co‐doping strategy.

Vat Photopolymerization versus Conventional Colloidal Processing Methods in Structural Ceramics: Progress, Challenges, and Future Perspectives

Additive manufacturing (AM) has become a versatile and diverse technology that has a significant impact on manufacturing processes. Therefore, ceramic materials have been developed rapidly for use in AM processes. Vat photopolymerization (VPP) is an AM method that enables the production of dense ceramic components with increased dimensional accuracy. In particular, it facilitates the fabrication of small and intricately shaped parts. This review summarizes the research advancements in ceramics prepared via VPP. Special attention is paid to the current status of relevant areas, such as slurry preparation and process optimization, as well as the forming mechanisms, debinding, sintering, performance characterization, and use of VPP-based ceramics. Moreover, earlier studies performed by our research group on numerous VPP-based ceramic aspects are considered. In addition, a concise overview of the differences in forming principles, mechanical performance, advantages, and disadvantages between VPP-based ceramics and conventional colloidal-forming ceramics is presented. Finally, the challenges and prospects of VPP-based ceramics are discussed.

Effect of BPO4-B2O3 Composite Additive on Crystallization and Sintering of Silica Ceramics

BPO4-B2O3 composite additive enhanced silica ceramics were successfully prepared by solid phase sintering. The effects of BPO4-B2O3 addition and sintering temperature on the microstructure and phase composition and mechanical properties of silica ceramics were analysed by scanning electron microscopy and X-ray diffraction techniques. The results showed that at 1200°-1400°C, BPO4-B2O3 composite additive formed a glass phase in the sample, filled the pores, and improved the sintering densification of the sample. In addition, the addition of 9 wt% BPO4-B2O3 successfully inhibited the crystallization of fused silica, which significantly improved the mechanical strength of silica ceramics. After sintering at 1200°C for 3 h, the apparent porosity of silica ceramics with 9 wt% BPO4-B2O3 was only 1.33%, and the cold modulus of rupture reached a maximum of 60.99 MPa, which was about 35 times that of pure silica ceramics. It is shown that adding BPO4-B2O3 composite additive provides a feasible method for preparing silica ceramics with good mechanical properties.

Fabrication and magneto-optic property of infrared transparent gadolinium iron garnet (GdIG) ceramics by hot-press sintering process

A series of GdIG ceramics with good infrared transparency have been fabricated by a hot-press sintering process with vacuum/oxygen atmosphere. The effects of the powder synthesizing temperature and the ceramic sintering temperature on the phase structure and microstructure of the GdIG ceramics were examined and analyzed. The GdIG ceramic sample sintered at 1275 °C from the Gd2O3 and Fe2O3 powders pre-synthesized at 1000 °C demonstrated an exceptionally high infrared transmittance, it is ≥ 68% within the wavelength range of 1500–5000 nm (t = 0.5 mm). Furthermore, the magnetic and magneto-optic property of the GdIG ceramic samples were investigated and discussed. When a saturation external magnetic field of ∼50 mT acting on the GdIG ceramic sample, the specific Faraday rotation angles are about 104 deg./cm and 51 deg./cm at 1064 and 1550 nm wavelength respectively. It exhibits a good faraday effect of GdIG ceramics which is rarely reported until now.