Strong and tough laminated ceramics prepared from ceramic foams

Here, we present a novel strategy to prepare laminated ceramics by combining the ceramic foams and hot-pressing sintering. Al₂O₃ and ZrO₂ ceramic foams prepared by the particle-stabilized foaming method was cut into thin slices and then directly laminated and hot-pressing sintered. Al₂O₃/ZrO₂ laminated ceramics with various structures were prepared. Compared with the slices prepared by conventional process, ceramic foams can easily regulate the thickness of laminate to resemble the nacre-like structure. In addition, the grain in the ceramic foams have lower activity and shrinkage rate, thereby weakening the residual tensile internal stress caused by grain coarsening and differences in coefficient of thermal expansion. The effects of layer number and thickness ratio on residual stress and the structure-activity relationship between mechanical properties and microstructure were investigated. The fracture toughness, flexural strength, and work of fracture of the optimal Al₂O₃/ZrO₂ laminated ceramics are 8.2 ± 1.3 MPa·m^1/2, 356 ± 59 MPa, and 216 J·m^?2, respectively.     

Study on surface quality,precision and mechanical properties of 3D printed ZrO2 ceramic components by laser scanning stereolithography

Zirconia (ZrO₂) ceramic bars with three different printing sizes were fabricated by a stereolithographic (SLA) 3D-printing process and subsequent sintering. An anisotropic character of the ceramics surface quality was observed. The surface roughness of the horizontal surface was below 0.41 µm, whereas it reached 1.07 µm along the fabrication direction on the vertical surface. The warpage and flatness were utilized to measure the dimensional accuracy of the 3D printed ZrO₂. Furthermore, it was evaluated that the warpage and flatness were below 40 µm and 27 µm, respectively, even if the printed size of ceramic bar reached 3 mm × 4 mm × 80 mm. In addition, the flexural strength, the fracture toughness, the hardness and the density of ZrO₂ ceramics can reach to 1154 ± 182 MPa, 6.37 ± 0.25 MPa m^1/2, 13.90 ± 0.62 GPa and up to 99.3%, respectively. Moreover, the effects of scanning paths and printing size on properties of the sintered ZrO₂ samples were analyzed. The anisotropic character of surface quality was related to the various scanning paths. The warpage and flatness of 3D printed ZrO₂ bars were apparently affected by the various printed sizes. Also, the effects of special microstructure on the mechanical properties of sintered ZrO₂ samples were investigated.     

Effect of High‐Temperature Aging on the Fracture Toughness of 40 mol% Ceria‐Stabilized Zirconia

The 40 mol% CeO₂‐stabilized ZrO₂ ceramic was synthesized by the sol‐spray pyrolysis method and aged at 1400°C–1600°C. The effects of high‐temperature aging on its fracture toughness were investigated after heat treatments at 1500°C for 6–150 h in air. Characterization results indicated that the activation energy for grain growth of 40 mol% CeO₂‐stabilized ZrO₂ was 593 ± 47 kJ/mol. The average grain size of this ceramic varied from 1.4 to 5.6 μm within the aging condition of 1500°C for 6–150 h. The Ce‐lean tetragonal phase has a constant tetragonality (ratio of the c‐axis to a‐axis of the crystal lattice) of 1.0178 during the aging process. It was found that the fracture toughness of 40 mol% CeO₂‐stabilized ZrO₂ was determined to be 2.0 ± 0.1 MPa·m^1/2, which did not vary significantly with prolonging aging time. Since no monoclinic zirconia was detected in the regions around the indentation crack‐middle and crack‐tip, the high fracture toughness maintained after high‐temperature aging can be attributed to the remarkable stability of the tetragonal phase in 40 mol% CeO₂‐stabilized ZrO₂ composition.     

Tough,strong, hard,and chemically durable enstatite-zirconia glass-ceramic

Strong glass-ceramics (GCs) have been envisaged and widely researched for various applications, including large architectural panels, ballistic impact protection, bioactive medical implants, and odontological prostheses. Here, we report on the development and characterization of a novel hard, strong and tough enstatite-zirconia (MgSiO₃-ZrO₂) glass-ceramic derived from a 51SiO₂–35MgO–6Na₂O–4ZrO₂–4TiO₂ (mol%) glass. The best GC was developed by treating glass samples for nucleation at 700°C for 12 hours, followed by crystal growth at 1090°C for 3 minutes. It was characterized by X-ray fluorescence (XRF), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM), and contained plate-like enstatite, zirconia, and Ti-containing crystals. We investigated the nucleating ability of ZrO₂ and TiO₂ in inducing internal nucleation. In the early stage of crystallization, enstatite spherulites were observed, which were precipitated by heterogeneous nucleation on previously nucleated ZrO₂ nano-crystals. At more advanced stages, at high temperatures, they transformed into plate-like crystals. The ball-on-three-balls strength, elastic modulus, and Vickers micro-hardness of the GC are 323 ± 26 MPa, 146 ± 13 GPa, and 6.9 ± 0.1 GPa (load = 5N), respectively. The indentation (K_C), single-edge notched beam bending (K_IC), and crack tip (K_tip) fracture toughness are 2.8 ± 0.6 MP.m^0.5, 2.2 ± 0.3 MP.m^0.5, 1.9 ± 0.3 MP.m^0.5, respectively. The crack propagation profile after a controlled Vickers indentation was quite intricate. The enstatite and zirconia crystals enhanced crack deflection, bridging and branching, hindering crack propagation. According to the ISO 6872 for dental materials, the chemical solubility of our GC is 80 ± 5 μg/cm². Due to this positive combination of high strength, toughness, hardness, and chemical durability, this new glass-ceramic is envisioned as a candidate for several applications and could be further developed for memory disc substrates, architectural cladding and tiles, ceramic glazes, and dental materials.     

Preparation and mechanical properties of the 2.5D ASf/ZrO2 composites after high-temperature heat treatment

In the paper, the aluminosilicate fiber-reinforced zirconia (AS_f/ZrO₂) ceramic composites were successfully fabricated by polymer impregnation and pyrolysis (PIP) method. The microstructure and high-temperature mechanical properties of the original composites were well studied. The results revealed that the composites could maintain the stability of microstructure at 1000 °C. The flexural strength increased from 58.82 ± 2.83 MPa to 88.74 ± 6.20 MPa and the flexural modulus increased from 29.26 ± 4.67 GPa to 40.76 ± 8.76 GPa. The thermal exposure improved the interfacial bonding and made the load transfer more effective. After heat treatment from 1200 °C to 1400 °C, the flexural strength gradually declined due to the crystallization of the AS fibers and ZrO₂ matrix, while the flexural modulus increased in a completely different trend. After heat treatment at 1400 °C, the composites could maintain a flexural strength of 66.95 ± 4.24 MPa with a flexural modulus of 60.42 ± 7.25 GPa. But the fracture mode gradually evolved to brittleness.     

Effect of ZrO2 content on the microstructure and flexural strength of Al2O3–ZrO2 composites with the stored failure energy-fragmentation relations

High flexural strength is an important mechanical property for a ceramic armor component to withstand high tensile stresses and protect its structural integrity against multiple hits. Also, larger fragments are required in fragmentation as larger fractured parts are harder to leave of the way for the penetrator and cause more abrasion and higher penetration resistance. In this study, the effect of different ZrO₂ content (0, 0.5, 1, 3, 5, 10, 20 vol%) on the flexural strength of Al₂O₃–ZrO₂ composites was investigated with relationship of the stored failure energy-crack length to evaluate the fragmentation behavior under possible impact conditions. Monotonic equibiaxial flexural strength test was used to measure the fracture strength. The highest strength was obtained for 20 vol% ZrO₂ containing composite as 435 ± 78 MPa, ~ 24% increase in comparison with the pure Al₂O₃. The transformation of tetragonal to monoclinic phase occurred during the strength test in the 10 and 20 vol% ZrO₂ content composites. 20 vol% ZrO₂ containing composite had the smallest total crack length accompanying the largest fragment size for a given fracture energy among all the composites due to the stress-induced transformation of ZrO₂ consumes energy that results in decreasing effective crack driving energy required for the crack branching.     

Li2+xZrO3Fx (0 ≤ x ≤1.25): A new high-Q × f and temperature-stable microwave dielectric ceramic system for LTCC applications

Here we report a new high-Q × f and temperature-stable oxyfluoride microwave dielectric ceramic system of Li_2+xZrO₃F_x (0 ≤ x ≤ 1.25) sintered at low temperatures (i.e., ≤950°C). The sintering characteristics, phase assemblage, microstructures, and microwave dielectric properties (MDPs) of the Li_2+xZrO₃F_x specimens were studied. The chemical bond theory calculations were employed to analyze the compositional dependence of the MDPs in the Li_2+xZrO₃F_x ceramic system. The optimal MDPs of ε_r = 15.8, Q × f = 65 100 GHz, and τ_f = 1.2 ppm/°C were achieved in the sample with x = 1. Besides, the ceramic samples exhibited high chemical compatibility with Ag electrodes. Therefore, the novel ceramic system of Li_2+xZrO₃F_x is confirmed to be a promising candidate as a low-temperature co-fired ceramic material.     

Fabrication of lightweight ZrO2 fiberboards using hollow ZrO2 fibers

ZrO₂ fiberboards with ultra-low densities (0.34–0.40 g/cm³) were fabricated using biomorphic ZrO₂ hollow fibers, which have a lower density and better thermal insulation than traditional ZrO₂ solid fibers. The effects of sol binder content, sintering temperature, and proportion of solid fibers on the density, microstructure, compressive strength, linear shrinkage, and thermal conductivity of lightweight ZrO₂ fiberboards were investigated. The results showed that the hollow features of biomorphic ZrO₂ fibers were successfully maintained after they were made into ZrO₂ fiberboards, which made them less dense and thermally conductive. The best conditions were found to be a sol binder content of 30 vol%, sintering temperature of 1400 °C, and 20 wt% sintered solid fibers to balance thermal insulation and compressive strength. The results show that the density and thermal conductivity of lightweight ZrO₂ fiberboard gives it obvious advantages as a heat-insulating ceramic. Specifically, when the sintering temperature was 1400 °C, the sample had an ultra-low density of 0.34–0.40 g/cm³, a thermal conductivity of 0.101–0.116 W/(m·K) (at 500 °C), a compressive strength of 0.05–0.24 MPa, and a linear shrinkage of 9.4–13%.     

Lamellar-interpenetrated Al−Si−Mg/Al2O3−ZrO2 composites prepared by freeze casting and pressureless infiltration

Using freeze casting and pressureless infiltration methods, we prepared lamellar Al−Si−Mg/Al₂O₃−ZrO₂ composites with initial ceramic loading of 30 vol% and different Al₂O₃:ZrO₂ weight ratios (Al₂O₃:ZrO₂=1:9, 3:7, 5:5, 7:3 and 9:1). The resultant composites inherited the lamellar structure of the Al₂O₃−ZrO₂ scaffolds, and the thickness of both metal and ceramic layers showed a trend of first increase and then decrease with increasing Al₂O₃ content. During pressureless infiltration, multiple chemical reactions took place between ZrO₂ and the Al−12Si−10Mg alloy and the main reaction products were (Al_1−m, Si_m)₃Zr, Al₂O₃ and ZrSi₂ phases. The degree of the reaction depended on the ZrO₂ content in the ceramic composition. In general, the compressive strength of the composites decreased with increasing Al₂O₃ content, but three-point bending strength showed a first decrease and then increase. When Al₂O₃:ZrO₂=1:9, the compressive and bending strength of the composites reached about 997±60 MPa and 426±10 MPa, respectively. A simple model was proposed to illustrate the fracture mode and toughening mechanism of the composites.     

Li2ZrO3 based Li-ion conductors doped with halide ions & sintered in oxygen-deficient atmosphere

All-solid-state batteries have recently attracted much attention for their high energy density and safety. Li₂ZrO₃-based Li-ion conductors with high electrochemical stability have potential applications for electrolytes in all-solid-state batteries. In this work, comparative investigations of Li₂ZrO₃ and halogen doped Li₂ZrO₃ ceramics were conducted by sintering at 700 °C in air or in oxygen-deficient atmosphere which was induced by a simple setup covering with corundum crucible. The analysis of phase composition reveals that the undoped Li₂ZrO₃ ceramic sintered in air contains pure monoclinic phase, while halogen-doped Li₂ZrO₃ sintered in air and all ceramics sintered in oxygen-deficient atmosphere are simultaneously composed of monoclinic and tetragonal phases. Li₂ZrO₃ ceramic with tetragonal phases has higher conductivity (0.28 mS cm⁻¹ for undoped Li₂ZrO₃) than the pure monoclinic Li₂ZrO₃ (0.07 mS cm⁻¹), and halogen doping can further enhance the conductivity of Li₂ZrO₃ ceramics higher than 0.5 mS cm⁻¹ at room temperature.     

Interfacial reaction behavior and bonding mechanism between liquid Sn and ZrO2 ceramic exposed in ultrasonic waves

Ultrasound-assisted dipping of ZrO₂ ceramics into molten Sn solder was performed to realize the low-temperature joining of ZrO₂ ceramics in this study. Scanning electron microscopy with energy dispersive spectrometer, X-ray diffraction and X-ray photoelectron spectroscopy were employed to study the effects of ultrasonic vibration on the microstructure of Sn/ZrO₂ interface, and to elucidate the joining mechanism between Sn coating layer and ZrO₂ ceramic. Results showed that, after ultrasonically dipping in molten Sn for 1200 s, a pure Sn solder layer with a thickness of approximately 8–9 µm was coated on the ZrO₂ surface. The Sn coating layer exhibited excellent metallurgic bonding with ZrO₂ ceramic. A nano-sized ZrSnO₄ ternary phase, which was beneficial to the smooth transition of the lattice from Sn solder to ZrO₂ ceramic, was formed at the Sn/ZrO₂ interface. The formation of ZrSnO₄ interlayer was ascribed to the acoustic cavitation induced high-temperature reaction of Sn, O and ZrO₂ at the molten Sn/ZrO₂ ceramic interface. The tested average shear strength of ZrO₂/Sn/ZrO₂ joints was approximately 32 MPa, and the shearing failure mainly took place within the Sn solder layer.     

Fabrication and abrasive wear behavior of ZrO2-SiC-Al2O3 ceramic

In this paper, ZrO₂-SiC-Al₂O₃ ceramic was fabricated by as-prepared ZrO₂-SiC powders and commercial α-Al₂O₃ powders, sintered at 1450 °C for 1 h. ZrO₂-SiC composite powders were synthesized through carbothermal reduction with zircon as raw material and carbon black as the reductant. Through ZrO₂-SiC-Al₂O₃ ceramic mechanical properties measurements it was indicated that this ceramic had excellent properties in both bending strength and hardness. In addition, ZrO₂-SiC-Al₂O₃ ceramic abrasive wear property was measured. ZrO₂-SiC-Al₂O₃ ceramic mass loss increased along with the increase in both wheel rate and applied load. The type of wear particles had an important effect on abrasive wear resistance. ZrO₂-SiC-Al₂O₃ ceramic displayed excellent abrasive wear resistance in bentonite and quartz slurries in comparison with SiC slurry.     

Microstructural refinement and mechanical response of Al2O3–ZrO2 eutectics fabricated by a novel pulse discharge plasma assisted melting method

In the present work, microstructural refinement and mechanical response of Al₂O₃–ZrO₂ eutectics fabricated by a pulse discharge plasma assisted melting (PDPAM) method were investigated. The solidified microstructure evolves from polygonal eutectic colonies into irregular cellular colonies with increasing the superheating temperature of the melt from 1820 °C to 1900 °C. The average eutectic spacing inside the colonies decreases from 1.80 ± 0.10 μm to 0.25 ± 0.06 μm, and the coarse inter-colonial structure is refined, which is attributed to the increase in undercooling temperature. High-temperature microstructural stability of Al₂O₃–ZrO₂ eutectics is improved significantly as contrasted with the as-sintered ceramics. Besides, the load dependence of Vickers hardness for Al₂O₃–ZrO₂ eutectics is investigated.     

Direct ink writing of 3Y-TZP ceramics using PEG-Laponite® as additive

This study investigated a new colloidal ink, containing Laponite® nanoclay as additive, to develop ZrO₂-based ceramic prototypes by Direct Ink Writing (DIW). The ink developed contained 31 vol% 3Y-TZP as solid load and 69% v/v of gel containing 7.5% (w/w) Laponite®, polyethylene glycol (PEG), and dibutyl phthalate. The rheologyical behavior of this ceramic ink was analyzed and its extrudability was optimized. The samples were DIW 3D-printed at a speed of 10 mm/s with nozzle diameter of 0.41 mm. After drying for 24 h, the zirconia samples underwent debinding and were pre-sintered at 1100 °C under a heating rate of 1 °C/min. After pre-sintering, the samples were sintered at 1550 °C for 2 h. Subsequently, the sintered samples were characterized by Scanning Electron Microscopy and X-ray diffractometry. Fracture toughness was measured by Vickers indentation, whereas nano-hardness and Young’s modulus were assessed by dynamic Vickers nanoindentation (250–1960 mN loads). A relative density of 89.3 ± 0.5% was found. The following crystalline phases were observed: monoclinic-ZrO₂ (34%), tetragonal-ZrO₂ (31%), and cubic-ZrO₂ (35%). This behavior is probably due to the segregation of Y⁺³ between the zirconia grains, favored by the presence of Laponite® nanoclay during the sintering process. The microstructure of the prototypes showed two distinct populations of ZrO₂ grains with average particle sizes of 1 μm (monoclinic and tetragonal phases) and >5 μm (cubic phase). Vickers hardness (HV_1000gF) was 952 ± 40 HV and fracture toughness was 4.6 ± 1.1 MPa m^1/2. A Young’s modulus of ∼200 GPa and hardness values of 1837.9 and 1943.3 HV were found for loads of 250 and 1960 mN, respectively.     

Seed-mediated growth of ZrC whisker and its toughening effect on ZrB2-SiC-C ceramic

ZrC whiskers (ZrC_w) hold great promise in improving the strength and toughness of ultra-high temperature ceramics (UHTCs) without reducing their high-temperature stability. However, obtaining high quality ZrC_w has been challenging. Herein, we propose a novel method for easily synthesizing catalyst-free ZrC_w by seed-mediated growth technique, in which single crystal ZrC nanoparticle (ZrC_np) was used as seed crystal and ZrO₂-C-NaF mixture was used as precursor system. The effect of ZrC_np, NaF, and, synthesis temperature on the growth of ZrC_w was studied and the reaction process was analyzed based on the experimental results. The vapor-solid (V-S) growth mechanism was proved to be the dominating growing mechanism. Subsequently, the synthesized ZrC_w were added to a ZrB₂-SiC-C ceramic. Compared with the baseline, ZrC_w reinforced ZrB₂-SiC-C exhibited a remarkable combination of high strength and high toughness (592 ± 30 MPa and 7.1 ± 0.8 MPa·m^1/2). This novel synthesis method of ZrC_w may be applicable to the synthesis of other carbide ceramic whiskers and enrich the design of high performance ultra-high temperature ceramics.     

Microstructure evolution and bonding mechanism of ZrO2 ceramic and Ti-6Al-4V alloy joints brazed by Bi2O3-B2O3-ZnO glass paste

Ceramics and metal joinings have been widely employed in aerospace, dental implants, and the electronic packaging industry for fabricating multifunctional components. In this study, the 35Bi₂O₃-50B₂O₃-15ZnO (mol.%) glass has been employed for joining the ZrO₂ ceramic and Ti-6Al-4V alloy. The effect of brazing temperature on the microstructure evolution, mechanical properties, and bonding mechanism of brazed joints has been analyzed. The microstructure of the ZrO₂/glass/Ti-6Al-4V joints and the content of Bi₄B₂O₉, Bi₂O₃ and Bi₂₄B₂O₃₉ precipitated crystals in glass were found to be dependent on the brazing temperature. The reaction product of Bi₄Ti₃O₁₂ was identified in the glass/Ti-6Al-4V interface because of the chemical reaction between the oxidized layer of Ti-6Al-4V alloy and glass. A maximum shear strength as high as 48.8 ± 5.2 MPa was obtained. Our work, thus, demonstrates that the 35Bi₂O₃-50B₂O₃-15ZnO glass is an effective bonding material for joining ZrO₂ ceramic and Ti-6Al-4V alloy under low temperature in an ambient atmosphere.     

An Improved Internal Gelation Process for Preparing ZrO2 Ceramic Microspheres Without Cooling the Precursor Solution

ZrO₂ microspheres were prepared with an improved internal gelation process without cooling the precursor solution. The stability of the broth for internal gelation process has been systematically investigated, and the results show that the preparation and storage temperature, the concentration of NO₃^? and the urea in the broth have important effects on the stability of the broth. Through optimizing the broth formulation the broth prepared can be stable for 14 h at 25°C. The prepared ZrO₂ ceramic microspheres have uniform size and good sphericity, with a density of 5.87 g/cm³.     

Ablative property and mechanism of SiC-CuxSiy modified C/C-ZrC composites prepared by a rapid method

A rapid method was developed to fabricate C/C-ZrC-SiC-Cu_xSi_y composites with low open porosity by precursor infiltration and pyrolysis combining with pressure assisted reactive melt infiltration. Dominant phases of ZrC and SiC with scattered Cu_xSi_y inclusions were present in continuous infiltrated matrix, in which the dimension of submicron ZrC particles displayed gradient change. At ablation test, the heat absorbing effect of Cu_xSi_y-phase and formation of protective ZrO₂-SiO₂ cover enhanced the ablative property of composites for short-time ablation, causing ablation rates of 30 s ablation reached 1.7 ± 0.1 µm/s and 1.3 ± 0.1 mg/s, respectively. As ablation time extends to 60 s, the massive consumption of Si-phase damaged the integrity of surface oxide cover, but the partial melted ZrO₂ improved the viscosity and self-healing ability of ZrO₂-SiO₂ mixture, protecting substrate from further erosion. Thus, ablation rates were increased and decreased to 3.8 ± 0.2 µm/s and 1.2 ± 0.1 mg/s, respectively.     

Effect of the crystalline layer on the electrical behaviour of 17.7Li2O·5.2ZrO2·68.1SiO2·9.0Al2O3 glass ceramic monoliths

Li₂O–ZrO₂–SiO₂–Al₂O₃ (LZSA) glass ceramic systems are usually obtained from powder technology to obtain materials with a low thermal expansion coefficient (CTE). However, in these cases, there is a high residual porosity. An alternative to reduce the porosity involves the production of monoliths. Nevertheless, there is still a lack of crystallisation kinetics and the final properties of glass ceramic monoliths are affected such as electrical properties. This study aims to evaluate the electrical behaviour as function of the crystalline layer thickness formed on the monolith surface of a 17.7Li₂O·5.2ZrO₂·68.1SiO₂·9.0Al₂O₃ (molar basis) glass ceramic LZSA composition. Monoliths thermally treated at 750, 800, and 850 °C were chosen to evaluate based on the range of the crystalline layer growth. Electrochemical impedance spectroscopy was used for the electrical characterisation of LZSA glass and the glass ceramics. The resistivity increased with increasing thermal treatment temperature due to the formation of lithium-based crystalline phases. The electrical conductivity at 25 °C of the glass ceramic thermally treated at 850 °C decreased to 1.4 × 10^?13 S cm^?1 from 8.7 × 10^?11 S cm^?1 for LZSA glass. Based on the electrical behaviour, monoliths thermally treated at 850 °C can be considered potential for dielectric industrial applications.     

Mechanical properties and pre-oxidation behavior of spark plasma sintered B4C ceramics using (Ti3SiC2+CeO2/La2O3) as sintering aid

B₄C ceramic with the addition of 5 wt % (Ti₃SiC₂+ CeO₂/La₂O₃) as sintering aids was fabricated by spark plasma sintering at a relatively low temperature of 1650 °C for 5 min at 80 MPa. The phase composition, microstructures, and comprehensive mechanical properties of the ceramics were studied in detail. The existence of reinforced second phase particles, the refinement of the matrix grains, the formation of residual stress along the grain boundaries and the appearance of the mixed fracture mode had a synergetic strengthening effect on the mechanical properties. The flexural strength, fracture toughness and Vickers hardness of B₄C ceramics reached 565.2 ± 21.8/551.0 ± 25.2 MPa, 6.28 ± 0.01/6.41 ± 0.12 MPa·m^0.5, and 28.51 ± 0.86/27.23 ± 1.08 GPa, respectively. In addition, to reduce the crack sensitivity of the ceramic, the ceramics were pre-oxidized at 800 °C for different durations. The flexural strength was increased by approximately 13.4% after the ceramic was oxidized at 800 °C for 45 min due to the crack-healing effect induced by the oxide glass B₂O₃ on the ceramic surface.