Preparation and electrochemical properties of spherical LiFePO<Subscript>4</Subscript> and LiFe<Subscript>0.9</Subscript>Mg<Subscript>0.1</Subscript>PO<Subscript>4</Subscript> cathode materials for lithium rechargeable batteries

The spherical LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C powders were successfully prepared from spherical FePO₄ via a simple uniform-phase precipitation method at normal pressure, using FeCl₃ and H₃PO₄ as the reactants. The FePO₄, LiFePO₄/C, and LiFe_0.9Mg_0.1PO₄/C powders were characterized by scanning electron microscopies (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), and tap-density testing. The uniform spherical particles produced are amorphous, but they were crystallized to FePO₄ after calcining above 400 °C. Due to the homogeneity of the basic FePO₄, the final products, LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C, are also significantly uniform and the particle size is of about 1 μm in diameter. The tap-density of the spherical LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C are 1.75 and 1.77 g cm⁻³, respectively, which are remarkably higher than the non-spherical LiFePO₄ powders (the tap-density is 1.0–1.3 g cm⁻³). The excellent specific capacities of 148 and 157 mAh g⁻¹ with a rate of 0.1 C are achieved for the LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C, respectively. Comparison of the cyclic voltammograms of LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C shows enhanced redox current and reversibility for the sample substituting Mg on the Fe site. LiFe_0.9Mg_0.1PO₄/C exhibits better high-rate and cycle performances than the un-substituted LiFePO₄/C.     

Bi-modified SrTiO3-based ceramics for high-temperature energy storage applications

Dielectric capacitors with high energy storage performance are in great demand for emerging advanced energy storage applications. Relaxor ferroelectrics are one type dielectric materials possessing high energy storage density and energy efficiency simultaneously. In this study, 0.9(Sr_0.7Bi_0.2)TiO₃–0.1Bi(Mg_0.5Me_0.5)O₃ (Me = Ti, Zr, and Hf) dielectric relaxors are designed and the corresponding energy storage properties are investigated. The excellent recoverable energy density of 3.1 J/cm³ with a high energy efficiency of 93% is achieved at applied electric field of 360 kV/cm for 0.9(Sr_0.7Bi_0.2)TiO₃–0.1Bi(Mg_0.5Hf_0.5)O₃ (0.9SBT–0.1BMH) ceramic. High breakdown strength of 460 kV/cm in 0.9SBT–0.1BMH ceramic is obtained by Weibull distribution with satisfied reliability. In addition, 0.9SBT–0.1BMH shows outstanding thermal stability of energy storage performance up to 200°C, with the variation being less than 5%, together with satisfying cycling stability and high charge-discharge rate, making the 0.9SBT–0.1BMH ceramic a potential lead-free candidate for high power energy storage applications at elevated temperature.     

Mechanisms of ultralow and anisotropic thermal expansion in cordierite Mg2Al4Si5O18: Insight from phonon behaviors

Materials with negative or ultralow thermal expansion are of crucial importance for technological applications since they make it possible to tailor the coefficient of thermal expansion (CTE) of composite to a specific positive, negative or even zero value. In this work, first‐principle calculations were performed to investigate the thermal expansion behavior in cordierite Mg₂Al₄Si₅O₁₈, which is a representative silicate widely used in the ceramic industry and of promising application due to its ultralow CTE and good thermal shock resistance. According to the quasi‐harmonic approximation and the Grüneisen theory, temperature dependences of linear CTEs along a, b, and c directions were predicted. The transverse acoustic modes and low‐energy optic modes are identified to take the most of the responsibility for the negative CTE, especially at low temperatures while the high‐energy optic modes contribute positively to the thermal expansion, leading to increasing CTE at higher temperatures. The ultralow linear CTEs result from the weighted average of all the modal contributions with negative or positive Grüneisen parameters. In addition, the anisotropy of thermal expansion originates from its layered crystal structure containing rigid tetrahedron rings in a‐b plane staking along c direction. This work provides an insight into the mechanism of ultralow and anisotropic thermal expansion in Mg₂Al₄Si₅O₁₈ and further enriches the scope of material design for use in applications needing to control thermal expansion.     

Thermal expansion of bismuth magnesium tantalate and niobate pyrochlores

The thermal behavior of pyrochlores composing of Bi_1·5Mg_0.75M_1.5O_6.75 (M = Nb, Ta) (sp. gr. Fd-3m:2) was studied using the high-temperature X-ray powder diffraction in a wide temperature range of 30–1200 °C. At a temperature above 1080 °C both compounds thermally dissociate forming one of the reaction products MgMO₆ (M = Nb, Ta) whose reflexes are traced on X-ray diffraction patterns after cooling the sample down to room temperature. In the case of Bi_1·5Mg_0·75Nb_1·5O_6.75 orthoniobate α-BiNbO₄ forms at about 800–1020 °C as admixture. The thermal expansion analysis of Bi_1·5Mg_0.75M_1.5O_6.75 (M = Nb, Ta) showed that the compounds studied belong to slightly or moderately expanding materials. Thermal expansion for both compounds is isotropic. With a rise in temperature the unit cell parameter a and the thermal expansion coefficient (TEC) are increased uniformly and slightly for M = Ta (Nb): from 10.52822 (10.55325) Å (30 °C) up to 10.59181 (10.62801) Å (1050 °C) and from 3.8 (30 °C) up to 7.4 (8.9) × 10⁻⁶ °С⁻¹ at 800 °C respectively. The average TEC values in the range of 30–800 °C range are 5.6 (6.4) × 10⁻⁶ °C⁻¹ for M = Ta (Nb) respectively. Bi_1.5Mg_0.75Nb_1.5O_6.75 is characterized with the highest thermal expansion that may be related to the longer bond-length of Nb(Bi)–O in the polyhedra.     

Preparation and mechanical properties of β-Zr2O(PO4)2: A soft and damage tolerant ceramic with machinability and good thermal shock resistance

Damage tolerant and easily machinable ceramics play important roles in the field of thermal sealing and insulation. Herein, a soft and machinable β-Zr₂O(PO₄)₂ ceramic with excellent thermal shock resistance is reported through detailed investigation on its mechanical properties. β-Zr₂O(PO₄)₂ exhibits low hardness (5.9 GPa), low Pugh’s ratio (G/B = 0.36) and good thermal shock resistance. It also can be machined by WC tools and tolerant to damage. The damage tolerance is demonstrated by the residual strength versus indentation load curve as well as the load-displacement curve during compression strength test. From the crystal structure point of view, the mechanism that underpins the damage tolerance of β-Zr₂O(PO₄)₂ is the anisotropic chemical bonding within the crystal structure, which results in low and anisotropic shear deformation resistance. The possible slip systems of β-Zr₂O(PO₄)₂ are (010)[100] and (100)[010].     

Microstructure and electrical conductivity of La0.9Sr0.1 Ga0.8Mg0.2O2.85-Ce0.8Gd0.2O1.9 composite electrolytes for SOFCs

(100-x) wt.% La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 - x wt.% Ce_0.8Gd_0.2O_1.9 (x = 0, 5, 10, 20) electrolytes were prepared by solid-state reaction. The composition, microstructure, and electrical conductivity of the samples were investigated. At 300 ~ 600°C, the pure La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 electrolyte has a higher conductivity compared to the composite electrolytes, but at 650 ~ 800°C the 95 wt.% La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 - 5 wt.% Ce_0.8Gd_0.2O_1.9 composite electrolyte presents the highest conductivity, reaching 0.035 S cm⁻¹ at 800°C. The cell performances based on La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85-Ce_0.8Gd_0.2O_1.9 electrolytes were measured using Sr₂CoMoO₆-La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 as anode and Sr₂Co_0.9Mn_0.1NbO₆ -La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 as cathode, respectively. At 800°C, the measured open-circuit voltages are higher than 1.08 V, and the maximum power density and current density of the fuel cell prepared with 95 wt.% La_0.9Sr_0.1 Ga_0.8Mg_0.2O_2.85 - 5 wt.% Ce_0.8Gd_0.2O_1.9 electrolyte reach 192 mW cm⁻² and 720 mA cm⁻², respectively.     

Increase ionic conductivity of a Zn2+/F− synergy Na3Zr2Si2PO12 solid electrolyte for sodium metal batteries

Na₃Zr₂Si₂PO₁₂ (NZSP) solid-state electrolyte is considered one of the most promising solid-state electrolyte because of their excellent electrochemical and thermal stability. Even though, the low conductivity of NZSP solid-state electrolytes hinders practical application. Therefore, an anions/cations co-assisting strategy is proposed by introducing the Zn²⁺ and F⁻. The influence of adding different amounts of Zn²⁺ and F⁻ on the Na⁺ conductivity of NZSP was investigated computationally and experimentally. The Zn²⁺/F⁻ co-assisting (Na_3.3Zr_1.85Zn_0.15Si₂PO₁₂) solid-state electrolyte exhibits the ionic conductivity of 0.722 mS cm⁻¹ at 30 °C, and the activation energy of ∼0.237 eV. Its applicability in a solid-state battery is tested, and the assembled Na/Na₃V₂(PO₄)₃ (NVP) battery exhibits an outstanding electrochemical performance of 98.4% capacity retention after being cycled at 0.5 C. Moreover, DFT calculations also have been used to demonstrate the effect of doping on the crystal structure and space migration energy barrier. This research provides new ideas for improving the electrochemical properties of inorganic solid electrolytes.     

Study on La2(Hf1-xTix)2O7 (x ≤ 0.20) pyrochlores for potential thermal/environmental barrier coating applications

Lanthanum hafnate (La₂Hf₂O₇) with a pyrochlore structure has excellent high temperature stability and low thermal conductivity, which is promising for thermal/environmental barrier coatings (T/EBCs) applications. To reduce its thermal expansion coefficient (TEC) so as to better match SiC_f/SiC composites, a smaller tetravalent dopant Ti⁴⁺ has been introduced in the Hf-sites to form La₂(Hf_1-xTi_x)₂O₇ (x ≤ 0.20). The phase composition and microstructure confirms that La₂(Hf_1-xTi_x)₂O₇ solid solutions possess a pure pyrochlore structure. With an increase of x, their TECs are decreasing consistently, whilst their thermal conductivities of La₂(Hf_1-xTi_x)₂O₇ are slightly increasing at high temperature but still much lower than those of meta-stable yttria partially stabilized zirconia, both of which are attributing to an increase of elastic modulus after Ti⁴⁺ doping on Hf-sites. The extremely excellent high temperature stability, relatively low thermal conductivities and low TECs suggest that La₂(Hf_1-xTi_x)₂O₇ is a prospective candidate material for T/EBC applications.     

On the way to understand the keys for the stabilization of the conductive phase in doped- NASICON-type materials

A family of doped-NASICON-type structures according to the chemical compositions: Li_1.2 Zr_1.9M_0.1(PO₄)₃ [with M = Ca²⁺, Mg²⁺, Zn²⁺]; Li_1.1 Zr_1.9Y_0.1(PO₄)₃ and Li_1.0 Zr_1.9Ce_0.1(PO₄)₃ have been synthesized by solid state reaction. The modification on the thermal treatment proposed in this work makes possible to obtain a high purity phase confirmed by XRD, SEM, microRaman-confocal and FTIR. Rietveld refinement evidences how the LZP lattice parameters are affected by each of those five different dopant cations incorporated into the pristine structure. Impedance spectroscopy proves how the relationship radius - charge of each dopant-ion affects the ionic conductivity. Unravelling that the partial replacement of Zr⁴⁺ in the LZP by a dopant improves the conductivity behavior. When the dopant cation has a lower charge and a larger size than the Zr⁴⁺ the developed structure favours the lithium-ion mobility at room temperature and the lithium conductivity increases.     

High-rate capability of three-dimensional CNTs-decorated NaTi2(PO4)3@C microspheres for sodium energy storage

One of the newest materials for sodium energy storage is NaTi₂(PO₄)₃, which is widely researched due to its considerable Na⁺ conductivity and excellent safety characteristics. However, NaTi₂(PO₄)₃ exhibits unfavorable electronic conductivity, restricting its application in sodium-ion batteries. Herein, three-dimensional CNTs-modified NaTi₂(PO₄)₃@C microspheres were synthesized by spray-drying method and solid-state high-temperature annealing. Within the designed composite, the NaTi₂(PO₄)₃@C nanoparticles were uniformly fixed on the CNTs surfaces, forming a three-dimensional CNTs-NaTi₂(PO₄)₃@C architecture. As an anode in a sodium-ion battery, the resulting CNTs-NaTi₂(PO₄)₃@C exhibited exceptional sodium storage potential, with a high reversible capacity, stable cycling properties, and a good rate capability. An excellent discharge capacity of about 128.5 mAh g^-1 was achieved with a low rate of 0.1C, and the anode displayed a reversible capability of 75.8 mAh g^-1 at 20C over 1000 cycles, with a low capacity fading rate of about 0.011% per cycle. Therefore, this novel strategy is highly effective and can be adopted to enhance the battery properties of other electrode materials.     

Negative thermal expansion properties of Cu1.5Mg0.5V2O7

Cu_1.5Mg_0.5V₂O₇ was prepared by a solid state method. Its phase, microstructure, thermal expansion property, and Raman spectra were analyzed in detail. Results show that Cu_1.5Mg_0.5V₂O₇ maintains a monoclinic crystal structure and exhibits an excellent linear negative thermal-expansion property with coefficient of thermal expansion of ?8.72?×?10^?6?K^?1 over a wide temperature range of 153–673?K. The mechanism underlying the negative thermal expansion of Cu_1.5Mg_0.5V₂O₇ involves the coupling effect of the tetrahedron caused by the lateral vibration of the bridge oxygen atom and the tensile effect of the tetrahedron, The partial collapse caused by the loss of the oxygen atoms also plays an important role in the mechanism.     

Electrochemical lithiation and delithiation of LiMnPO4: Effect of cation substitution

The electrochemical lithiation-delithiation reaction was examined for LiMnPO₄ in which different cations were substituted for part of Mn. The X-ray diffraction analysis indicated that LiMnPO₄ is tolerant, to some extent, to substitution of Mg²⁺, Ca²⁺ and Zr⁴⁺. The substitution of Mg²⁺ and/or Zr⁴⁺ led to an increased reversible capacity and a reduced polarization, whereas Ca²⁺ substitution had a detrimental effect on the electrochemical properties. The potential transient analysis showed that LiMn_0.88Mg_0.1Zr_0.02PO₄ has higher lithium diffusivities than pure LiMnPO₄, indicating facilitated diffusion kinetics in the substituted material. Upon the first charge-discharge cycle, LiMn_0.88Mg_0.1Zr_0.02PO₄ suffered less irreversible capacity loss when compared with LiMnPO₄, and smaller amounts of electrolyte salt-based species were detected on the electrode surface of LiMn_0.88Mg_0.1Zr_0.02PO₄.     

Temperature-dependent elastic and thermodynamic properties of ZrC,HfC, and their solid solutions (Zr0.5Hf0.5)C

Zirconium carbide (ZrC) and hafnium carbide (HfC) have been identified as ultrahigh temperature ceramics with excellent thermal conductivity performance. The temperature profiles of ZrC and HfC have been studied; however, the temperature-dependent of solid solution of (Zr_0.5Hf_0.5)C is still lacking. Herein, we report the temperature-dependent elastic and thermodynamic properties of (Zr_0.5Hf_0.5)C using first-principles calculations. The covalent characters of ZrC, HfC, and (Zr_0.5Hf_0.5)C are weakened at high temperatures by analyzing their respective electronic structures. In addition, the equilibrium volumes at different temperatures can be determined from the energy–volume (E–V) curves under the quasi-harmonic approximation. Throughout the temperature ranges studied, the HfC material shows the highest bulk modulus and lowest thermal expansion. When T > 1000 K, (Zr_0.5Hf_0.5)C exhibits better shear and Young's modulus performance close to HfC and shows the highest anisotropy. The lattice thermal conductivity decreased as temperature increased for ZrC, HfC, and (Zr_0.5Hf_0.5)C, and (Zr_0.5Hf_0.5)C has the smallest lattice thermal conductivity. These results provide fundamental and useful information for the practical application of ZrC, HfC, and (Zr_0.5Hf_0.5)C.     

Microstructures and electrochemical properties of Mg0.9Ti0.1Ni1−xMx (M = Co, Mn; x = 0, 0.1, 0.2) hydrogen storage alloys

Mg-Ni-Ti-based hydrogen storage alloys Mg_0.9Ti_0.1Ni_1−xM_x (M = Co, Mn; x = 0, 0.1, 0.2) were prepared by means of mechanical alloying (MA). The effects of partial substitution of Ni with Co or Mn on the microstructures and electrochemical performance of the alloys were investigated. The result of X-ray diffraction (XRD) shows that the alloys exhibit dominatingly amorphous structures. The electrochemical measurements indicate that the substitution of Ni can dramatically enhance the cycle stability of Mg-Ni-Ti-based alloys. After 50 charge/discharge cycles, the capacity retention rate of the alloy electrodes increases from 30% (Mg_0.9Ti_0.1Ni) to 59% (Mg_0.9Ti_0.1Ni_0.9Co_0.1), 58% (Mg_0.9Ti_0.1Ni_0.9Mn_0.1), 46% (Mg_0.9Ti_0.1Ni_0.8Co_0.2) and 53% (Mg_0.9Ti_0.1Ni_0.8Mn_0.2), respectively. Among these alloys, the Mg_0.9Ti_0.1Ni_0.9Mn_0.1 alloy presents better overall electrochemical performance. The cyclic voltammograms (CV) and anti-corruption test reveal that the electrochemical cycle stability of these alloys is improved by substituting Ni with Co or Mn.     

High-entropy yttrium pyrochlore ceramics with glass-like thermal conductivity for thermal barrier coating application

A₂B₂O₇-type oxides with low thermal conductivities are potential candidates for next-generation thermal barrier coatings. The formation of high-entropy ceramics is considered as a newly effective way to further lower their thermal conductivities. High-entropy Y₂(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)₂O₇ (5HEO) and Y₂(Ti_0.25Zr _0.25Hf_0.25Ta_0.25)₂O₇ (4HEO) ceramics were prepared by in situ solid reaction sintering, considering the important roles of B-site cations on thermal conductivities of the A₂B₂O₇-type oxides. Reaction process, phase structures, microstructures, and thermal conductivities of the as-sintered ceramics were investigated. Lattice distortion effects on their thermal conductivities were also discussed by using the proposed criterion based on the supercell volume difference of the individual compounds. Near fully-dense 5HEO and 4HEO ceramics were obtained after being sintered at 1600°C. The former one had a dual-phase structure containing high-entropy Y₂(Ti_0.227Zr_0.227Hf_0.227Nb_0.136Ta_0.182)₂O_7.318 pyrochlore oxide (5HEO-P) and Y(Nb, Ta)O₄ solid solution, while the latter one was a single-phase pyrochlore oxide (4HEO-P) with homogeneous element distribution. The formed 5HEO-P oxide has larger lattice distortion than 4HEO-P oxide due to the larger total amounts of Nb and Ta cations at B sites in the 5HEO-P oxide. It results in lower thermal conductivity of 5HEO ceramics (keeping at 1.8 W·m^–1·K^–1) than those of 4HEO ceramics (ranging from 1.8 to 2.5 W·m^–1·K^–1) at temperatures from 25°C to 1400°C. Their glass-like thermal conductivities were determined by the selection of B site cations and high-entropy effects. These results provide some useful information for the material design of novel thermal barrier coating materials.     

Optimized electrochemical performance of LiMn0.9Fe0.1−xMgxPO4/C for lithium ion batteries

A series of LiMn_0.9Fe_0.1−xMg_xPO₄/C (x = 0, 0.01, 0.02, 0.05) was synthesized by a solid state reaction, and the effect of synthesis temperature and Fe/Mg ratio on the electrochemical performance of the obtained materials was investigated by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and electrochemical measurements. The electrochemical performance of the Fe and Mg co-substituted LiMnPO₄ was obviously improved with increasing synthesis temperature from 650 to 800 °C, but further increase led to an abrupt capacity loss due to the impurity formation. The Fe and Mg co-substitution could remarkably enhance the electrochemical activity of LiMnPO₄ compared with the Fe substitution only, but too high level of Mg doping would worsen the rate capability. The LiMn_0.9Fe_0.09Mg_0.01PO₄/C synthesized at 800 °C demonstrated the optimum electrochemical performance with a high capacity and an excellent rate capability. Even discharged at the rate of 10 C, a capacity of 60 mAh g⁻¹ was still observed.     

Low‐Temperature Sinterable (1−x)Ba3(VO4)2–xLiMg0.9Zn0.1PO4 Microwave Dielectric Ceramics

The novel low‐temperature sinterable (1 ? x)Ba₃(VO₄)₂–xLiMg_0.9Zn_0.1PO₄ microwave dielectric ceramics were prepared by cofiring the mixtures of pure‐phase Ba₃(VO₄)₂ and LiMg_0.9Zn_0.1PO₄. The phase structure and grain morphology of the ceramics were evaluated using X‐ray diffraction, Raman spectra, and scanning electron microscopy. The results indicated that Ba₃(VO₄)₂ and LiMg_0.9Zn_0.1PO₄ phases can well coexist in the sintered body. Nevertheless, a small amount of LiZnPO₄ and some vanadate phases with low melting points were observed, which not only can influence the microwave dielectric properties of the ceramic but also can obviously improve the densification behavior at a relatively low sintering temperature. The near‐zero temperature coefficients of the resonant frequency (τ_f) could be achieved by adjusting the relative content of the two phases owing to their opposite τ_f values and simultaneously a desirable quality factor Q × f value can be maintained. No chemical reaction between the matrix ceramic phase and Ag took place after sintering at 800°C for 4 h. The ceramics with 45 vol% LiMg_0.9Zn_0.1PO₄ can be well sintered at only 800°C and exhibit excellent microwave dielectric properties of ε_r ~ 10, Q × f ~ 64 500 GHz, and τ_f ~ ?2.1 ppm/°C, thus showing a great potential as a low‐permittivity low‐temperature cofired microwave dielectric material.     

Microstructure and thermal expansion of Al2TiO5–MgTi2O5 solid solutions obtained by reaction sintering

Solid solutions Mg_0.1Al_1.8Ti_1.1O₅ and Mg_0.5AlTi_1.5O₅ were obtained by reaction sintering of mixtures of the binary oxides at 1350–1600 °C using different precursor powders. For the composition Mg_0.1Al_1.8Ti_1.1O₅, ceramics sintered at 1400–1500 °C have high relative density (⩾90%), reduced grain size (2–6 μm), low thermal expansion (−0.8 to 0.3×10⁻⁶ K⁻¹ in the range 200–1000 °C) and reproducible expansion behaviour. At higher temperature, grain size rapidly increases owing to anisotropic and exaggerated grain growth (EGG) resulting in severe microcracking. Microstructure evolution is affected by the nature of the starting oxides, in particular for what concerns the onset temperature of EGG, the size and the fraction of abnormal grains. For the composition Mg_0.5AlTi_1.5O₅, EGG already takes place at 1350 °C and materials with grain size < 5 μm are difficult to obtain by conventional reaction sintering. Large grained samples (>10 μm) of both compositions show a reduced hysteresis and complex thermal expansion behaviour. In particular, heating to 1000 °C results in a significant increase in specimen size on return to room temperature. Repeated thermal cycling leads to an increase of the hysteresis.     

Mechanical and thermal properties of δ-RE4Hf3O12 (RE = Yb,Lu)

Rare-earth (RE) hafnates are promising thermal and environmental barrier coating (TEBC) materials for SiC_f/SiC ceramic matrix composites. In this study, pure-phase and dense δ-RE₄Hf₃O₁₂ (RE = Yb, Lu) bulk ceramics have been fabricated via a hot-pressing method. The crystal structure, microstructure, mechanical, and thermal properties of δ-RE₄Hf₃O₁₂ were systematically investigated in order to probe their potential application as TEBCs. The high-temperature elastic moduli of δ-Yb₄Hf₃O₁₂ and δ-Lu₄Hf₃O₁₂ are measured to be 185 and 188 GPa at 1673 K, respectively, which are over 85% values of room temperature. The coefficients of thermal expansion are 7.64 × 10⁻⁶ and 7.46 × 10⁻⁶ K⁻¹ for δ-Yb₄Hf₃O₁₂ and δ-Lu₄Hf₃O₁₂, respectively. The relatively low coefficient of thermal expansion and thermal conductivity as well as their excellent high-temperature stability endow these hafnates as potential TEBC candidates.     

Low-temperature synthesis and oxidation resistance of random combination of Hf,Nb, and Ta carbides microcuboids

Based on the dissolution-precipitation mechanism, this article successfully synthesized binary and ternary transition metal carbide microcuboids with random combinations of Hf, Nb, and Ta by annealing monocarbides/cobalt powders. Accelerated mass transport rate through the flow of molten alloys (Co-Hf-Nb-Ta) instead of slow solid diffusion made the low-temperature pressureless sintering technique (1500°C) a reality. Furthermore, the equilibrium morphology was driven by the gradient Gibbs potential of carbides induced by the different local curvature of powders and anisotropic interfacial energy. (Hf_0.5Ta_0.5)C possessed the optimal oxidation resistance among all mentioned carbides, even competed with (Hf_1/3Nb_1/3Ta_1/3)C. During the isothermal oxidation at 800∼1200°C, the doping of Nb and Ta in carbides assisted the monoclinic-orthorhombic HfO₂ transition at ambient pressure, besides, TaC can also restrain the orthorhombic-monoclinic transition of Nb₂O₅. Moreover, oxidation kinetics parameters concluded that the addition of HfC and TaC contributed to the decreasing reaction order and the increasing activation energy, respectively.