Spark plasma sintering of (5RE.2)Ta3O9 high-entropy ceramics and their thermal properties

Six rare-earth tantalate high-entropy ceramics of (5RE_.2)Ta₃O₉ (RE represents any five elements selected from La, Ce, Nd, Sm, Eu, Gd) were designed and prepared by spark plasma sintering process at 1400°C in this study. The (5RE_.2)Ta₃O₉ ceramics only consist of a single-phase solid solution with perovskite structure. Their relative densities are all above 90%, and the average grain size is in the range of 1.47–2.92 μm. The thermal conductivity of (5RE_.2)Ta₃O₉ ceramics is in 2.24–1.90 W m⁻¹ K⁻¹ (25°C–500°C), which is much lower than that of yttria-stabilized zirconia. In six samples, (La_.2Nd_.2Sm_.2Gd_.2Eu_.2)Ta₃O₉ possesses a thermal conductivity of 1.90 W m⁻¹ K⁻¹, a thermal expansion coefficient of 3.47 × 10⁻⁶ K⁻¹ (500°C), a Vickers hardness of about 7.33 GPa, and a fracture toughness of about 5.20 MPa m^1/2, which are suitable for its application as thermal barrier coatings.     

High-entropy La(Fe0.2Co0.2Ni0.2Cr0.2Mn0.2)O3 ceramic exhibiting high emissivity and low thermal conductivity

A novel, high-entropy, perovskite-structured, solid solution La(Fe_0.2Co_0.2Ni_0.2Cr_0.2Mn_0.2)O₃ ceramic was successfully synthesized via high-temperature solid-state reaction. The crystal structure, microstructure, infrared emissivity, and thermophysical properties were investigated. The experimental results indicated that La(Fe_0.2Co_0.2Ni_0.2Cr_0.2Mn_0.2)O₃ exhibited an infrared emissivity as high as .92 in the near-infrared region of .76–2.50 μm. The thermal conductivity was 1.38–1.72 W m⁻¹ K⁻¹ in the temperature range of 25–1200°C.     

Functionalized few-layered graphene nanoplatelets for superior thermal management in heat transfer nanofluids

The superior thermal conductivity and lightweight of graphene flakes make them materials of choice for advanced heat transfer applications, especially for transport of electricity from sustainable power stations such as concentrating solar power plants. In view of the excellent thermal conductivity of graphene or graphene-like nanomaterials (3000–5000 W m⁻¹ K⁻¹), their dispersion into conventional host fluids such as water (0.613 W m⁻¹ K⁻¹) or ethylene glycol (0.25 W m⁻¹ K⁻¹) can significantly improve fluid heat transfer characteristics. The two-dimensional structure and high surface area as well as the cost-efficient carbon-based material make graphene nanoplatelets (GNPs) suitable for large-scale applications in colloidal thermal conductive fluids. For an efficient dispersion of GNPs in base fluids, intrinsically hydrophobic GNPs were acid treated to obtain highly concentrated (4 wt.%) graphene-based nanofluids. Investigations on various GNP sizes and reaction parameters showed significant influences on the resulting thermal conductivity values of the nanofluid. After 14 h measurements in a dormant system, the most efficient nanofluid reached a thermal conductivity of 0.586 W m⁻¹ K⁻¹ (the base fluid of 0.391 W m⁻¹ K⁻¹) and a low viscosity of 6.39 cP resulting in an overall efficiency improvement of 77%, when compared to the base fluid without particles.     

Thermophysical properties and cyclic lifetime of plasma sprayed SrAl12O19 for thermal barrier coating applications

About 6-8 wt% yttria-stabilized zirconia (YSZ) is the industry standard material for thermal barrier coatings (TBC). However, it cannot meet the long-term requirements for advanced engines due to the phase transformation and sintering issues above 1200°C. In this study, we have developed a magnetoplumbite-type SrAl₁₂O₁₉ coating fabricated by atmospheric plasma spray, which shows potential capability to be operated above 1200°C. SrAl₁₂O₁₉ coating exhibits large concentrations of cracks and pores (~26% porosity) after 1000 hours heat treatment at 1300°C, while the total porosity of YSZ coatings progressively decreases from the initial value of ~18% to ~5%. Due to the contribution of porous microstructure, an ultralow thermal conductivity (~1.36 W m⁻¹ K⁻¹) can be maintained for SrAl₁₂O₁₉ coating even after 1000 hours aging at 1300°C, which is far lower than that of the YSZ coating (~1.98 W m⁻¹ K⁻¹). In thermal cyclic fatigue test, the SrAl₁₂O₁₉/YSZ double-ceramic-layer coating undertakes a thermal cycling lifetime of ~512 cycles, which is not only much longer than its single-layer counterpart (~163 cycles), but also superior to that of YSZ coating (~392 cycles). These preliminary results suggest that SrAl₁₂O₁₉ might be a promising alternative TBC material to YSZ for applications above 1200°C.     

Reticulated open-cellular aluminum nitride ceramic foams: Effect of sintering aids on microstructural,thermal, and mechanical properties

Open-celled aluminum nitride ceramic foams were prepared by the polymer sponge replication technique involving aqueous dispersions of passivated AlN. The amount of the Y₂O₃ and Dy₂O₃ as sintering aid was varied, and the effects on the densification, microstructure formation, phase composition, and finally, the thermal conductivity were investigated. A typical thermal conductivity of 1.1 W m⁻¹ K⁻¹ was determined for foams at a porosity level of 94.3 vol.%, on average. This measured foam thermal conductivity was subsequently modeled using different porosity ↔ thermal conductivity relations considering the different hierarchical levels of porosity in these foams. From these models, the thermal conductivity of the bulk AlN strut material was determined, correlated with the strut microstructure and the phase composition, and compared to literature data.     

Enhanced thermoelectric properties of CNT dispersed and Na-doped Bi2Ba2Co2Oy composites

The thermoelectric properties of Bi₂Ba₂Co₂O_y and Bi_1.975Na_0.025Ba₂Co₂O_y+x wt% carbon nanotubes (CNT; x=0.00, 0.05, 0.10, 0.15, 0.5, and 1.0) ceramic samples synthesised by the solid-state reaction method were investigated from 300K to 950K. Na doping with a small amount played an important role in reducing resistivity and slightly reduced the Seebeck coefficients and the thermal conductivity. The CNT dispersant increased resistivity, but the thermal conductivity was reduced remarkably. In particular, the Bi_1.975Na_0.025Ba₂Co₂O_y+1.0wt% CNT sample exhibited an ultralow thermal conductivity of 0.39 W K⁻¹ m⁻¹ at 923K. This was attributed to the point defects caused by Na doping and the interface scattering caused by the CNT dispersant. The combination of Na doping and CNT dispersion had better effects on thermoelectric properties. The Bi_1.975Na_0.025Ba₂Co₂O_y+0.5wt% CNT sample exhibited a better dimensionless figure of merit (ZT) value of 0.2 at 923K, which was improved by 78.2%, compared with the undoped Bi₂Ba₂Co₂O_y sample.     

Processing and thermal properties of mayenite electride

A mayenite-based electride is being considered for field emitter applications where it will be critical to have a good understanding of processing repeatability and thermal properties. This paper focuses on the details of processing of mayenite compounds in a strongly reducing graphite environment to form an electride solid-solution phase as Ca₁₂Al₁₄O₃₂(C₂,O₂)_1-x(e₂)_x. The work reports, in addition to processing details, several thermal properties. The electride phase was found to have coefficient of thermal expansion (CTE) of 7e-6 K⁻¹, thermal diffusivity between 0.0063 and 0.0102 cm²/s, and thermal conductivity between 1.9 and 3.1 W m⁻¹ K⁻¹. Rattling motion of O²⁻ or C₂²⁻ ions in cage structure has been suggested to explain low thermal conductivity of the electride phase.     

Porous Ca3Co4O9 with enhanced thermoelectric properties derived from Sol–Gel synthesis

Highly porous Ca₃Co₄O₉ thermoelectric oxide ceramics for high-temperature application were fabricated by sol–gel synthesis and subsequent conventional sintering. Growth mechanism of misfit-layered Ca₃Co₄O₉ phase, from sol–gel synthesis educts and upcoming intermediates, was characterized by in-situ X-ray diffraction, scanning electron microscopy and transmission electron microscopy investigations. The Ca₃Co₄O₉ ceramic exhibits a relative density of 67.7%. Thermoelectric properties were measured from 373 K to 1073 K. At 1073 K a power factor of 2.46 μW cm⁻¹ K⁻², a very low heat conductivity of 0.63 W m⁻¹ K⁻¹ and entropy conductivity of 0.61 mW m⁻¹ K⁻² were achieved. The maintained figure of merit ZT of 0.4 from sol–gel synthesized Ca₃Co₄O₉ is the highest obtained from conventional, non-doped Ca₃Co₄O₉. The high porosity and consequently reduced thermal conductivity leads to a high ZT value.     

Multi-component strategy for remarkable suppression of thermal conductivity in strontium diyttrium oxide: The case of high-entropy Sr(Y0.2Sm0.2Gd0.2Dy0.2Yb0.2)2O4 ceramic

Anti-spinel oxide SrY₂O₄ has attracted extensive attention as a promising host lattice due to its outstanding high-temperature structural stability and large thermal expansion coefficient (TEC). However, the overhigh thermal conductivity limits its application in the field of thermal barrier coatings. To address this issue, a novel high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic was designed and synthesized for the first time via the solid-state method. It is found that the thermal conductivity of Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ is reduced to 1.61 W·m⁻¹·K⁻¹, 53 % lower than that of SrY₂O₄ (3.44 W·m⁻¹·K⁻¹) at 1500 °C. Furthermore, reasonable TEC (11.53 ×10⁻⁶ K⁻¹, 25 °C ∼ 1500 °C), excellent phase stability, and improved fracture toughness (1.92 ± 0.04 MPa·m^1/2) remained for the high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic, making it a promising material for next-generation thermal barrier coatings.     

Super-insulating,ultralight and high-strength mullite-based nanofiber composite aerogels

Ceramic nanofiber aerogel is one of the most attractive insulation materials in recent years. However, its practical application ability is limited at high temperature due to high radiation heat transfer. Herein, we constructed a novel closed-cell/nanowire structured mullite-based nanofiber composite aerogel via electrospinning technology and solvothermal synthesis method. Hollow TiO₂ spheres were used as pore-making material and infrared opacifier to reduce fiber solid heat conduction and high temperature radiation heat transfer simultaneously. In addition, TiO₂ nanowires grown in-situ on the fiber surface further decrease the radiation heat transfer of aerogel and improve the mechanical properties. The unique structure endows the aerogel with high mechanical robustness (0.32–0.35 MPa, 10% strain), low density (39.2–47.5 mg/cm³) and ultralow thermal conductivity (~0.017 W m^?1 K^?1 at 25 ℃ and ~0.056 W m^?1 K^?1 at 1000 ℃). This work offers a novel strategy for the development of ceramic nanofiber aerogel at high temperature.     

Thermal expansion performance and intrinsic lattice thermal conductivity of ferroelastic RETaO4 ceramics

Ferroelastic RETaO₄ ceramics are promising thermal barrier coatings (TBCs) because of their attractive thermomechanical properties. The influence of crystal structure distortion degree on thermomechanical properties of RETaO₄ is estimated in this work. The relationship between Young's modulus and TECs is determined. The highest TECs (10.7 × 10⁻⁶ K⁻¹, 1200°C) of RETaO₄ are detected in ErTaO₄ ceramics and are ascribed to its small Young's modulus and low Debye temperature. The intrinsic lattice thermal conductivity (3.94-1.26 W m⁻¹ K⁻¹, 100-900°C) of RETaO₄ deceases with increasing of temperature due to an elimination in thermal radiation effects. The theoretical minimum thermal conductivity (1.00 W m⁻¹ K⁻¹) of RETaO₄ indicates that the experimental value is able to be reduced further. We have delved deeply into the thermomechanical properties of ferroelastic RETaO₄ ceramics and have emphasized their high-temperature applications as TBCs.     

Thermal stability and thermal conductivity of stacked Cs intercalated layered niobate

Layered materials exhibit competitively low thermal conductivity along the out-of-plane direction. The solution process is a promising method for preparing stacked structures. However, the thermal stability of the layered materials is poor after processing in solution, thus hindering their applications at high temperatures. One of the solutions to improve the thermal stability of layered structures is to expand the interlayer distance by inserting large-size metal ions. In this work, we studied the thermal properties of Cs⁺ intercalated layered niobate obtained by the ion-exchanged process. The layered structure of the Cs⁺ intercalated layered niobate survives after thermal treatment even at 1200 °C. The room temperature thermal conductivity of as prepared stacked Cs–HCa₂Nb₃O₁₀ is as low as 0.11 W m⁻¹ k⁻¹. Upon thermal annealing, the thermal conductivity increases. After annealing at 1200 °C, the value is 0.90 W m⁻¹ k⁻¹. The finding suggests Cs⁺ intercalated layered niobate is a promising material for high-temperature insulation applications.     

Co-optimization of microwave dielectric properties in Ba(Mg1/3Ta2/3)O3 complex perovskite ceramics through ordered domain engineering

It is an important subject to improve the temperature coefficient of resonant frequency (τ_f) and thermal conductivity (κ) of microwave dielectric ceramics without reducing the Qf value. Ordered domain engineering was applied to realize the previous objectives in Ba(Mg_1/3Ta_2/3)O₃ ceramics. With the increasing ordering degree from 0.835 to 0.897, the optimized Qf value was obtained. Meanwhile, near zero τ_f from 11.9 to 5.6 ppm °C⁻¹ was achieved, together with increased κ from 5.5 to 7.6 W m⁻¹ K⁻¹, and enhanced dielectric strength from 801 to 921 kV cm⁻¹. The noticeable ordered domain structure with large ordered domains (∼100 nm) and low-energy domain boundaries was revealed in Ba(Mg_1/3Ta_2/3)O₃. The consequent weakened phonon scattering rises the thermal conductivity. The increased bond covalency and oxygen distortion in ceramics with higher ordering degree were suggested as a cause of enlarged bandgap, which enhanced the dielectric strength. The reduced τ_f is dominated by the less “rattling” space of the cations in the ordered state by inducing more positive τ_ε. The reduced τ_f, optimized thermal conductivity, and Qf value in the present work indicate that the ordered domain engineering could open up a new direction for the optimization of microwave dielectric ceramics.     

A new type of Sr(Zr0.2Hf0.2Ce0.2Yb0.2Me0.2)O3−x (Me = Y,Gd) high-entropy ceramics used in thermal barrier coatings

Seeking for new ceramics with excellent thermophysical properties as thermal barrier coatings candidate materials has become a hot research field. In this study, Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x high-entropy ceramic powders were successfully synthesized by the method of solid-state reaction, and the ceramics with single phase were prepared by pressureless sintering at 1600°C. The phase composition, microstructure, element distribution, high-temperature thermal stability, and thermophysical properties of the ceramics were studied. The results showed that Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x ceramics were composed of SrZrO₃ phase and the second phase of AB₂O₄ spinel (i.e., SrY₂O₄ and SrGd₂O₄). The content of the second phase was gradually increased after heat treatment at 1400°C, which significantly improved the thermophysical and mechanical properties of the ceramics. The microhardness and fracture toughness of the ceramics were improved compared with that of SrZrO₃. The thermal conductivities of Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x (Me = Y, Gd) ceramics were 1.30 and 1.28 W m⁻¹ K⁻¹ at 1000°C, which were about 35% and 40% lower than that of SrZrO₃ (1.96 W m⁻¹ K⁻¹) and yttria-stabilized zirconia (2.12 W m⁻¹ K⁻¹), respectively. The thermal expansion coefficients of Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x (Me = Y, Gd) ceramics were 12.8 × 10⁻⁶ and 14.1 × 10⁻⁶ K⁻¹ at 1300°C, respectively, which was more closer to the superalloys compared with SrZrO₃ ceramic (11.0 × 10⁻⁶ K⁻¹).     

Low thermal conductivity of atomic layer deposition yttria-stabilized zirconia (YSZ) thin films for thermal insulation applications

Thermal insulation applications have long required materials with low thermal conductivity, and one example is yttria (Y₂O₃)-stabilized zirconia (ZrO₂) (YSZ) as thermal barrier coatings used in gas turbine engines. Although porosity has been a route to the low thermal conductivity of YSZ coatings, nonporous and conformal coating of YSZ thin films with low thermal conductivity may find a great impact on various thermal insulation applications in nanostructured materials and nanoscale devices. Here, we report on measurements of the thermal conductivity of atomic layer deposition-grown, nonporous YSZ thin films of thickness down to 35 nm using time-domain thermoreflectance. We find that the measured thermal conductivities are 1.35–1.5 W m⁻¹ K⁻¹ and do not strongly vary with film thickness. Without any reduction in thermal conductivity associated with porosity, the conductivities we report approach the minimum, amorphous limit, 1.25 W m⁻¹ K⁻¹, predicted by the minimum thermal conductivity model.     

Synthesis and thermophysical properties of ATa2O6 (A = Co,Ni, Mg,Ca) tantalates with robust CMAS resistance

A new family of ceramic environmental/thermal barrier coating (E/TBC) materials, that is, ATa₂O₆ (A = Co, Ni, Mg, Ca), for high-temperature applications, are investigated and reported in this study. We focus on the synthesis and features of crystal structures, and on the mechanical and high-temperature properties. ATa₂O₆ oxides have an extraordinary phase stability (up to 1300°C), and their thermal expansion coefficients (6.2–7.3 × 10⁻⁶ K⁻¹) match those of SiC fiber-enhanced SiC ceramic matrix composites (3–7 × 10⁻⁶ K⁻¹). Their low thermal conductivities (min: 1.15 W·m⁻¹·K⁻¹) root in the slow phonon spreading speed and fierce phonon-phonon scattering process, and they will provide exceptional thermal insulation. Moreover, their hardness (5.6–8.8 GPa), toughness (1.4–1.9 MPa·m^1/2), and moduli (100–210 GPa) have good comparability with current E/TBCs. We propose the 33CaO-9MgO-13AlO_1.5-45SiO₂ (CMAS) corrosion mechanisms of ATa₂O₆ ceramics, and their robust CMAS resistance relies on the phase stability of CaTa₂O₆ oxides. The excellent high-temperature properties ensure that ATa₂O₆ can be used as E/TBCs to provide thermal insulation and CMAS corrosion protection.     

Determining the thermal conductivity of ceramic coatings by relative method

Thermal conductivity is a crucial parameter for evaluating the quality and thermal effects of ceramic coatings, especially for thermal barrier coatings. However, measurement by conventional method involves two problems: (a) it is difficult to peel off a ceramic coating from a substrate; (b) even if the coating can be peeled off, it is still hardly used as standard specimen in test. Therefore, the relative method was proposed to evaluate the thermal conductivity of ceramic coating. An analytical relationship among the thermal conductivities of the coating, the substrate, and the coating/substrate composite was established. Experiments on TA4 coated with YSZ coatings were carried out to demonstrate the feasibility of this novel method and to investigate the impact of temperature on the thermal conductivity of YSZ coatings. The experimental results demonstrated the validity and convenience of the relative method. With the increasing testing temperature, the thermal conductivity value of YSZ coatings displayed nonlinearity feature, that is, decreased from 1.4 to 1.3 (W m⁻¹ K⁻¹) in the temperature range of 32-300°C and then increased up to 1.58 W m⁻¹ K⁻¹ at 1000°C.     

Core–shell spherical graphite@SiC attenuating agent for AlN-based microwave attenuating ceramics with high–efficiency thermal conduction and microwave absorption abilities

A core–shell structured spherical graphite (SG)@SiC attenuating agent with a tunable silicon carbide (SiC) shell thickness was synthesized via in-situ solid-liquid reaction of SG and Si. Then, fully dense 10 wt%SG@SiC/AlN microwave attenuating composite ceramics were prepared through hot-pressing sintering, and the morphology of SG@SiC particle was well maintained. By moderately modulating the thickness of the SiC shell with relatively low complex permittivity and thermal conductivity, an effectively inhibited solid solution of SiC into AlN, weakened dipole and electron polarization, enhanced conduction loss, and an improved impedance matching, thermal conductivity and microwave loss capacity were simultaneously achieved. Thus, the SG@SiC/AlN composite exhibit excellent and impressive thermal conductivity of 63.92 W m⁻¹·K⁻¹ and minimum reflection loss of −34.2 dB. The outstanding performance of SG@SiC/AlN composite indicates that the composite is promising microwave attenuating ceramic with excellent thermal conduction and microwave absorption ability. This work opens up a new core–shell structure strategy for designing and developing a high-efficiency attenuating agent and microwave attenuating ceramic.     

Optimal Nb5+ doping for enhanced optical reflectivity and improved thermophysical properties of La0.9Sr0.1Ti1−xNbxO3+δ

Thermal protection materials with high optical reflectivity, low thermal conductivity, and good high-temperature stability are required for the development of laser technologies and the protection of the critical equipment components. Herein, we synthesize a novel thermal protective material, La_0.9Sr_0.1Ti_1−xNb_xO_3+δ (LSTN; x = 0.1, 0.125, 0.15), with different Nb⁵⁺-ion contents using solid-state sintering. Phase structure analysis demonstrates that LSTN (x = 0.1, 0.125, 0.15) presents a single-phase monoclinic structure with a uniform element distribution. In particular, the LSTN_0.125 ceramic exhibits ultrahigh optical reflectivity (96%, 2300 nm) and excellent thermophysical properties, such as a high thermal expansion coefficient (10.3 × 10⁻⁶ K⁻¹, 1000°C), an ultralow thermal conductivity (0.408 W (m K)⁻¹, 300°C), and excellent high-temperature stability. Aberration-corrected scanning transmission electron microscopy reveals that the disordered substitution of Nb⁵⁺ ions induces numerous lattice distortions and mass fluctuations, which decrease the thermal conductivity, and makes difference in the relative refractive indices of atomic layers causing the high reflectivity of the material. These remarkable properties render the LSTN_0.125 ceramic as an ideal alternative for near-infrared thermal protection applications.     

Screening rare-earth aluminates as promising thermal barrier coatings by high-throughput first-principles calculations

Thermal barrier coatings (TBCs) play an important role in gas turbines to protect the turbine blades from the high-temperature airflow damage. In this work, we use first-principles calculations to investigate a specific class of rare-earth (RE) aluminates, including cubic-REAlO₃ (c-REAlO₃), orthorhombic-REAlO₃ (o-REAlO₃), RE₃Al₅O₁₂, and RE₄Al₂O₉, to predict their structural stability, bonding characteristics, and mechanical and thermal properties. The polyhedron structures formed by the Al–O bonds are stronger and exhibit rigid characteristics, whereas the polyhedra formed by the RE–O bonds are relatively weak and soft. The alternating stacking of AlO₄ tetrahedra, AlO₆ octahedra, and RE–O polyhedra, as well as the selection of RE elements, shows intensive influences on the expected mechanical and thermal properties. The B, G, and E of these four types of aluminates decrease in the order of c-REAlO₃ > o-REAlO₃ > RE₃Al₅O₁₂ > RE₄Al₂O₉. REAlO₃ and RE₄Al₂O₉ are brittle and quasi-ductile ceramics, respectively, whereas RE₃Al₅O₁₂ is tailorable. The minimum thermal conductivity is in the range of 1.4–1.5 W m⁻¹ K⁻¹ for c-REAlO₃, 1.3–1.4 W m⁻¹ K⁻¹ for o-REAlO₃, 1.25–1.35 W m⁻¹ K⁻¹ for RE₃Al₅O₁₂, and 0.8–0.9 W m⁻¹ K⁻¹ for RE₄Al₂O₉. RE₄Al₂O₉ with low thermal conductivity and damage tolerance is predicted to be the potential candidates for next-generation TBC materials.