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Open Access Research Article Issue
Microstructure, elastic/mechanical and thermal properties of CrTaO4: A new thermal barrier material?
Journal of Advanced Ceramics 2024, 13 (3): 373-387
Published: 29 March 2024
Downloads:159

CrTaO4 (or Cr0.5Ta0.5O2) has been unexpectedly found to play a decisive role in improving the oxidation resistance of Cr and Ta-containing refractory high-entropy alloys (RHEAs). This rarely encountered complex oxide can effectively prevent the outward diffusion of metal cations from the RHEAs. Moreover, the oxidation kinetics of CrTaO4-forming RHEAs is comparable to that of the well-known oxidation resistant Cr2O3- and Al2O3-forming Ni-based superalloys. However, CrTaO4 has been ignored and its mechanical and thermal properties have yet to be studied. To fill this research gap and explore the untapped potential for its applications, here we report for the first time the microstructure, mechanical and thermal properties of CrTaO4 prepared by hot-press sintering of solid-state reaction synthesized powders. Using the HAADF and ABF-STEM techniques, rutile crystal structure was confirmed and short range ordering was directly observed. In addition, segregation of Ta and Cr was identified. Intriguingly, CrTaO4 exhibits elastic/mechanical properties similar to those of yttria stabilized zirconia (YSZ) with Young’s modulus, shear modulus, and bulk modulus of 268, 107, and 181 GPa, respectively, and Vickers hardness, flexural strength, and fracture toughness of 12.2±0.44 GPa, 142±14 MPa, and 1.87±0.074 MPa·m1/2. The analogous elastic/mechanical properties of CrTaO4 to those of YSZ has spurred inquiries to lucrative leverage it as a new thermal barrier material. The measured melting point of CrTaO4 is 2103±20 K. The anisotropic thermal expansion coefficients are αa = (5.68±0.10)×10−6 K−1, αc = (7.81±0.11)×10−6 K−1, with an average thermal expansion coefficient of (6.39±0.11)×10−6 K−1. The room temperature thermal conductivity of CrTaO4 is 1.31 W·m−1·K−1 and declines to 0.66 W·m−1·K−1 at 1473 K, which are lower than most of the currently well-known thermal barrier materials. From the perspective of matched thermal expansion coefficient, CrTaO4 pertains to an eligible thermal barrier material for refractory metals such as Ta, Nb, and RHEAs, and ultrahigh temperature ceramics. As such, this work not only provides fundamental microstructure, elastic/mechanical and thermal properties that are instructive for understanding the protectiveness displayed by CrTaO4 on top of RHEAs but also outreaches its untapped potential as a new thermal barrier material.

Open Access Research Article Just accepted
High-entropy rare earth stannate ceramics: Acid corrosion resistant radiative cooling materials with high atmospheric transparency window emissivity and high near-infrared solar reflectivity
Journal of Advanced Ceramics
Available online: 28 March 2024
Downloads:125

In response to the development concept of “carbon neutrality” and “carbon peak”, it is critical to develop materials with high near-infrared (NIR) solar reflectivity and high emissivity in atmospheric transparency window (ATW, 8-13 μm) to advance zero energy consumption radiative cooling technology. To achieve the regulation of emission and reflection properties, a series of high-entropy rare earth stannate ceramics (HE-RE2Sn2O7: (Y0.2La0.2Nd0.2Eu0.2Gd0.2)2Sn2O7, (Y0.2La0.2Sm0.2Eu0.2Lu0.2)2Sn2O7, (Y0.2La0.2Gd0.2Yb0.2Lu0.2)2Sn2O7) with seriously lattice distortion were prepared using the solid phase reaction followed by pressureless sintering method for the first time. The lattice distortion is accomplished by introducing rare earth elements with different cation radius and masses. The as-synthesized HE-RE2Sn2O7 ceramics possess high ATW emissivity (91.38%~95.41%), high NIR solar reflectivity (92.74%~97.62%), low thermal conductivity (1.080~1.619 W·m-1·K-1) and excellent chemistry stability. On the one hand, the lattice distortion intensifies the asymmetry of the structural unit to cause a notable alteration in the electric dipole moment, ultimately enlarging the ATW emissivity. On the other hand, through selecting excitation-difficult elements, HE-RE2Sn2O7 with a wide band gap exhibits high NIR solar reflectivity. Hence, the multi-component design can effectively enhance the radiative cooling ability of HE-RE2Sn2O7 and provide a novel strategy for developing radiative cooling materials.

Open Access Research Article Issue
Electron-irradiation-facilitated production of chemically homogenized nanotwins in nanolaminated carbides
Journal of Advanced Ceramics 2023, 12 (6): 1288-1297
Published: 05 June 2023
Downloads:202

Twin boundaries have been exploited to stabilize ultrafine grains and improve mechanical properties of nanomaterials. The production of the twin boundaries and nanotwins is however prohibitively challenging in carbide ceramics. Using a scanning transmission electron microscope as a unique platform for atomic-scale structure engineering, we demonstrate that twin platelets could be produced in carbides by engineering antisite defects. The antisite defects at metal sites in various layered ternary carbides are collectively and controllably generated, and the metal elements are homogenized by electron irradiation, which transforms a twin-like lamellae into nanotwin platelets. Accompanying chemical homogenization, α-Ti3AlC2 transforms to unconventional β-Ti3AlC2. The chemical homogeneity and the width of the twin platelets can be tuned by dose and energy of bombarding electrons. Chemically homogenized nanotwins can boost hardness by ~45%. Our results provide a new way to produce ultrathin (< 5 nm) nanotwin platelets in scientifically and technologically important carbide materials and showcase feasibility of defect engineering by an angstrom-sized electron probe.

Open Access Research Article Issue
Fabrication of multi-anionic high-entropy carbonitride ultra-high-temperature ceramics by a green and low-cost process with excellent mechanical properties
Journal of Advanced Ceramics 2023, 12 (6): 1258-1272
Published: 29 May 2023
Downloads:572

As a new category of ultra-high-temperature ceramics (UHTCs), multi-anionic high-entropy (HE) carbonitride UHTCs are expected to have better comprehensive performance than conventional UHTCs. However, how to realize the green and low-cost synthesis of high-quality multi-anionic HE carbonitride UHTC powders and prepare bulk ceramics with excellent mechanical properties still faces great challenges. In this work, a green, low-cost, and controllable preparation process of (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)CxN1−x powders is achieved by sol–gel combined with the carbothermal reduction/nitridation method for the first time. The as-synthesized (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)CxN1−x powders possess high compositional uniformity and controllable particle size. In addition, the obtained bulk ceramics prepared at 1800 ℃ exhibit superior fracture toughness (KIC) of 5.39± 0.16 MPa·m1/2 and high nanohardness of 35.75±1.23 GPa, elastic modulus (E) of 566.70±8.68 GPa, and flexural strength of 487±41 MPa. This study provides a feasible strategy for preparing the high-performance HE carbonitride ceramics in a more environmentally friendly and economical manner.

Open Access Research Article Issue
Construction of hydrangea-like core–shell SiO2@Ti3C2Tx@CoNi microspheres for tunable electromagnetic wave absorbers
Journal of Advanced Ceramics 2023, 12 (4): 711-723
Published: 24 March 2023
Downloads:382

Ti3C2Tx MXene shows great potential in the application as microwave absorbers due to its high attenuation ability. However, excessively high permittivity and self-stacking are the main obstacles that constrain its wide range of applications. To tackle these problems, herein, the microspheres of SiO2@Ti3C2Tx@CoNi with the hydrangea-like core–shell structure were designed and prepared by a combinatorial electrostatic assembly and hydrothermal reaction method. These microspheres are constructed by an outside layer of CoNi nanosheets and intermediate Ti3C2Tx MXene nanosheets wrapping on the core of modified SiO2, engendering both homogenous and heterogeneous interfaces. Such trilayer SiO2@Ti3C2Tx@CoNi microspheres are "magnetic microsize supercapacitors" that can not only induce dielectric loss and magnetic loss but also provide multilayer interfaces to enhance the interfacial polarization. The optimized impedance matching and core–shell structure could boost the reflection loss (RL) by electromagnetic synergy. The synthesized SiO2@Ti3C2Tx@CoNi microspheres demonstrate outstanding microwave absorption (MA) performance benefited from these advantages. The obtained RL value was −63.95 dB at an ultra-thin thickness of 1.2 mm, corresponding to an effective absorption bandwidth (EAB) of 4.56 GHz. This work demonstrates that the trilayer core–shell structure designing strategy is highly efficient for tuning the MA performance of MXene-based microspheres.

Open Access Research Article Issue
Zr2SeB and Hf2SeB: Two new MAB phase compounds with the Cr2AlC-type MAX phase (211 phase) crystal structures
Journal of Advanced Ceramics 2022, 11 (11): 1764-1776
Published: 05 November 2022
Downloads:108

The ternary or quaternary layered compounds called MAB phases are frequently mentioned recently together with the well-known MAX phases. However, MAB phases are generally referred to layered transition metal borides, while MAX phases are layered transition metal carbides and nitrides with different types of crystal structure although they share the common nano-laminated structure characteristics. In order to prove that MAB phases can share the same type of crystal structure with MAX phases and extend the composition window of MAX phases from carbides and nitrides to borides, two new MAB phase compounds Zr2SeB and Hf2SeB with the Cr2AlC-type MAX phase (211 phase) crystal structure were discovered by a combination of first-principles calculations and experimental verification in this work. First-principles calculations predicted the stability and lattice parameters of the two new MAB phase compounds Zr2SeB and Hf2SeB. Then they were successfully synthesized by using a thermal explosion method in a spark plasma sintering (SPS) furnace. The crystal structures of Zr2SeB and Hf2SeB were determined by a combination of the X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The lattice parameters of Zr2SeB and Hf2SeB are a = 3.64398 Å, c = 12.63223 Å and a = 3.52280 Å, c = 12.47804 Å, respectively. And the atomic positions are M at 4f (1/3, 2/3, 0.60288 [Zr] or 0.59889 [Hf]), Se at 2c (1/3, 2/3, 1/4), and B at 2a (0, 0, 0). And the atomic stacking sequences follow those of the Cr2AlC-type MAX phases. This work opens up the composition window for the MAB phases and MAX phases and will trigger the interests of material scientists and physicists to explore new compounds and properties in this new family of materials.

Open Access Research Article Issue
Electronic structure, bonding characteristics, and mechanical behaviors of a new family of Si-containing damage-tolerant MAB phases M5SiB2 (M = IVB–VIB transition metals)
Journal of Advanced Ceramics 2022, 11 (10): 1626-1640
Published: 27 September 2022
Downloads:106

MAB phases are layered ternary compounds with alternative stacking of transition metal boride layers and group A element layers. Until now, most of the investigated MAB phases are concentrated on compounds with Al as the A element layers. In this work, the family of M5SiB2 (M = IVB–VIB transition metals) compounds with silicon as interlayers were investigated by density functional theory (DFT) methods as potential MAB phases for high-temperature applications. Starting from the known Mo5SiB2, the electronic structure, bonding characteristics, and mechanical behaviors were systematically investigated and discussed. Although the composition of M5SiB2 does not follow the general formula of experimentally reported (MB)2zAx(MB2)y (z = 1, 2; x = 1, 2; y = 0, 1, 2), their layered structure and anisotropic bonding characteristics are similar to other known MAB phases, which justifies their classification as new members of this material class. As a result of the higher bulk modulus and lower shear modulus, Mo5SiB2 has a Pugh’s ratio of 0.53, which is much lower than the common MAB phases. It was found that the stability and mechanical properties of M5SiB2 compounds depend on their valence electron concentrations (VECs), and an optimum VEC exists as the criteria for stability. The hypothesized Zr and Hf containing compounds, i.e., Zr5SiB2 and Hf5SiB2, which are more interesting in terms of high-temperature oxidation/ablation resistance, were found to be unfortunately unstable. To cope with this problem, a new stable solid solution (Zr0.6Mo0.4)5SiB2 was designed based on VEC tuning to demonstrate a promising approach for developing new MAB phases with desirable compositions.

Open Access Research Article Issue
Tunnel-structured willemite Zn2SiO4: Electronic structure, elastic, and thermal properties
Journal of Advanced Ceramics 2022, 11 (8): 1249-1262
Published: 25 July 2022
Downloads:71

Willemite Zn2SiO4 crystallizes in such a way that Zn and Si are tetrahedrally coordinated with O in an ionic-covalent manner to form ZnO4 and SiO4 tetrahedra as the building units. The tetrahedra are corner-sharing, of which one SiO4 tetrahedron connects eight ZnO4 tetrahedra, and one ZnO4 tetrahedron links four ZnO4 tetrahedra and four SiO4 tetrahedra. The unique crystallographic configuration gives rise to parallel tunnels with a diameter of 5.7 Å along the c-axis direction. The tunnel structure of Zn2SiO4 definitely correlates with its interesting elastic and thermal properties. On the one hand, the elastic modulus, coefficient of thermal expansion (CTE), and thermal conductivity are low. Zn2SiO4 has low Vickers hardness of 6.6 GPa at 10 N and low thermal conductivity of 2.34 W/(m·K) at 1073 K. On the other hand, the elastic modulus and CTE along the c-axis are significantly larger than those along the a- and b-axes, showing obvious elastic and thermal expansion anisotropy. Specifically, the Young’s modulus along the z direction (Ez = 179 GPa) is almost twice those in the x and y directions (Ex = Ey = 93 GPa). The high thermal expansion anisotropy is ascribed to the empty tunnels along the c-axis, which are capable of more accommodating the thermal expansion along the a- and b-axes. The striking properties of Zn2SiO4 in elastic modulus, hardness, CTE, and thermal conductivity make it much useful in various fields of ceramics, such as low thermal expansion, thermal insulation, and machining tools.

Open Access Research Article Issue
High-entropy spinel ferrites MFe2O4 (M = Mg, Mn, Fe, Co, Ni, Cu, Zn) with tunable electromagnetic properties and strong microwave absorption
Journal of Advanced Ceramics 2022, 11 (5): 754-768
Published: 20 April 2022
Downloads:565

Ferrites are the most widely used microwave absorbing materials to deal with the threat of electromagnetic (EM) pollution. However, the lack of sufficient dielectric loss capacity is the main challenge that limits their applications. To cope with this challenge, three high-entropy (HE) spinel-type ferrite ceramics including (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)Fe2O4, (Mg0.2Fe0.2Co0.2Ni0.2Cu0.2)Fe2O4, and (Mg0.2Fe0.2Co0.2Ni0.2Zn0.2)Fe2O4 were designed and successfully prepared through solid state synthesis. The results show that all three HE MFe2O4 samples exhibit synergetic dielectric loss and magnetic loss. The good magnetic loss ability is due to the presence of magnetic components; while the enhanced dielectric properties are attributed to nano-domain, hopping mechanism of resonance effect and HE effect. Among three HE spinels, (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)Fe2O4 shows the best EM wave absorption performance, e.g., its minimum reflection loss (RLmin) reaches −35.10 dB at 6.78 GHz with a thickness of 3.5 mm, and the optimized effective absorption bandwidth (EAB) is 7.48 GHz from 8.48 to 15.96 GHz at the thickness of 2.4 mm. Due to the easy preparation and strong EM dissipation ability, HE MFe2O4 are promising as a new type of EM absorption materials.

Open Access Research Article Issue
Achieving ultra-broadband electromagnetic wave absorption in high-entropy transition metal carbides (HE TMCs)
Journal of Advanced Ceramics 2022, 11 (4): 545-555
Published: 17 March 2022
Downloads:405

Electronic devices pervade everyday life, which has triggered severe electromagnetic (EM) wave pollution. To face this challenge, developing EM wave absorbers with ultra-broadband absorption capacity is critically required. Currently, nano-composite construction has been widely utilized to realize impedance match and broadband absorption. However, complex experimental procedures, limited thermal stability, and interior oxidation resistance are still unneglectable issues. Therefore, it is appealing to realize ultra-broadband EM wave absorption in single-phase materials with good stability. Aiming at this target, two high-entropy transition metal carbides (HE TMCs) including (Zr,Hf,Nb,Ta)C (HE TMC-2) and (Cr,Zr,Hf,Nb,Ta)C (HE TMC-3) are designed and synthesized, of which the microwave absorption performance is investigated in comparison with previously reported (Ti,Zr,Hf,Nb,Ta)C (HE TMC-1). Due to the synergistic effects of dielectric and magnetic losses, HE TMC-2 and HE TMC-3 exhibit better impedance match and wider effective absorption bandwidth (EAB). In specific, the exclusion of Ti element in HE TMC-2 endows it optimal minimum reflection loss (RLmin) and EAB of -41.7 dB (2.11 mm, 10.52 GHz) and 3.5 GHz (at 3.0 mm), respectively. Remarkably, the incorporation of Cr element in HE TMC-3 significantly improves the impedance match, thus realizing EAB of 10.5, 9.2, and 13.9 GHz at 2, 3, and 4 mm, respectively. The significance of this study lays on realizing ultra-broadband capacity in HE TMC-3 (Cr, Zr, Hf, Nb, Ta), demonstrating the effectiveness of high-entropy component design in tailoring the impedance match.

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