Thermal Properties of (Zr,TM)B2 Solid Solutions with TM = Ta,Mo, Re,V, and Cr

The thermal properties were investigated for hot‐pressed zirconium diboride containing solid solution additions of tantalum, molybdenum, rhenium, vanadium, and chromium. The nominal additions were equivalent to 3 at.% of each metal with respect to zirconium. Using 0.5 wt% carbon as a sintering aid, powders were hot‐pressed to near full density at 2150°C. Rietveld refinement of X‐ray diffraction data was used to measure lattice parameters and to ensure that the additives formed solid solutions. Thermal conductivities were calculated from measured thermal diffusivities and temperature‐dependent values for density and heat capacity. Thermal conductivities at 25°C ranged from 88 W·(m·K)^?1 for nominally pure ZrB₂ down to 28 W·(m·K)^?1 for (Zr,Cr)B₂. Electron contributions to thermal conductivity were calculated from electrical resistivity measurements using the Wiedemann–Franz law. Decreases in phonon and electron conduction correlated with the size of the metallic additive, indicating that changes in atom size in the Zr lattice positions reduced thermal transport.     

Thermal Properties of (Zr,TM)B2 Solid Solutions with TM = Hf,Nb, W,Ti, and Y

The thermal properties were investigated for hot‐pressed zirconium diboride—transition‐metal boride solid solutions. The transition‐metal additives included hafnium, niobium, tungsten, titanium, and yttrium. The nominal additions were equivalent to 3 at.% of each metal with respect to zirconium. Powders were hot‐pressed to nearly full density at 2150°C using 0.5 wt% carbon as a sintering aid. Thermal diffusivity was measured using the laser flash method. Thermal conductivity was calculated from the thermal diffusivity results using temperature‐dependent values for density and heat capacity. At 25°C, the thermal conductivity ranged from 88 to 34 W·(m·K)^?1 for specimens with various additives. Electrical resistivity measurements and the Wiedemann–Franz law were used to calculate the electron contribution of the thermal conductivity and revealed that thermal conductivity was dominated by the electron contribution. The decrease in thermal conductivity correlated with a decrease in unit cell volume, indicating that lattice strain may affect both phonon and electron transport in ZrB₂.     

Synergistically optimizing electrical and thermal transport properties of Bi2O2Se ceramics by Te‐substitution

Bi₂O₂Se oxyselenides, characterized with intrinsically low lattice thermal conductivity and large Seebeck coefficient, are potential n‐type thermoelectric material in the mediate temperature range. Given the low carrier concentration of ~10¹⁵ cm^?3 at 300 K, the intrinsically low electrical conductivity actually hinders further enhancement of their thermoelectric performance. In this work, the isovalent Te‐substitution of Se plays an effective role in narrowing the band gap, which notably increases the carrier concentration to ~10¹⁸ cm^?3 at 300 K and the electron conduction activation energy has been lowered significantly from 0.33 to 0.14 eV. As a consequence, the power factor has been improved from 104 μW·K^?2·m^?1 for pristine Bi₂O₂Se to 297 μW·K^?2·m^?1 for Bi₂O₂Se_0.96Te_0.04 at 823 K. Meanwhile, the suppressed lattice thermal conductivity derives from the introduced point defects by heavier Te atoms. The gradually decreased phonon mean free path reflects the increasingly intense phonon scattering. Ultimately, the ZT value attains 0.28 for Bi₂O₂Se_0.96Te_0.04 at 823 K, an enhancement by a factor of ~2 as compared to that of pristine Bi₂O₂Se. This study has demonstrated that Te‐substitution of Se could synergistically optimize the electrical and thermal properties thus effectively enhancing the thermoelectric performance of Bi₂O₂Se.     

High thermal conductivity of spark plasma sintered silicon carbide ceramics with yttria and scandia

A fully dense SiC ceramic with a room‐temperature thermal conductivity of 262 W·(m·K)^?1 was obtained via spark plasma sintering β‐SiC powder containing 0.79 vol% Y₂O₃‐Sc₂O₃. High‐resolution transmission electron microscopy revealed two different SiC‐SiC boundaries, that is, amorphous and clean boundaries, in addition to a fully crystallized junction phase. A high thermal conductivity was attributed to a low lattice oxygen content and the presence of clean SiC‐SiC boundaries.     

Zirconium Diboride with High Thermal Conductivity

Thermal properties were characterized for zirconium diboride produced by reactive hot pressing and compared to ZrB₂ ceramics that were hot pressed from commercial powders. No sintering additives were used in either process. Thermal conductivity was calculated from measured values of heat capacity, thermal diffusivity, and density for temperatures ranging from 298 to 2273 K. ZrB₂ produced by reactive hot pressing achieved near full density, but had a small volume fraction of ZrO₂, whereas hot‐pressed ZrB₂ contained porosity and carbon inclusions. Reactive hot pressing produced a ceramic with higher thermal diffusivity and heat capacity, resulting in thermal conductivities of 127 W·(m·K)^?1 at 298 K and 80 W·(m·K)^?1 at 2273 K, which were up to ~30% higher than typically reported for hot‐pressed ZrB₂.     

Effect of the addition of β-Si3N4 nuclei on the thermal conductivity of β-Si3N4 ceramics

Various microstructures of β-Si₃N₄ were fabricated, with or without the addition of β-Si₃N₄ seed particles to high-purity β-Si₃N₄ powder, using Yb₂O₃ and ZrO₂ as sintering additives, by gas-pressure sintering at 1950 °C for 16 h. The thermal conductivity of the specimen without seeds was 140 W·(m·K)⁻¹, and the specimen exhibited a bimodal microstructure with abnormally grown grains. The thermal conductivity of the specimen with 24 vol.% seed addition was 143 W·(m·K)⁻¹, and this specimen had the bimodal microstructure with finer grain size than that without the seeded material, but maintained the same amount of large grains (⩾2 μm in diameter) as in the specimen without the seeds. This finding indicates that the thermal conductivity of β-Si₃N₄ is controlled by the amount of reprecipitated large grains, rather than by the grain size of the β-Si₃N₄.     

ZrSi2–MgO as novel additives for high thermal conductivity of β-Si3N4 ceramics

A novel ZrSi₂–MgO system was used as sintering additive for fabricating high thermal conductivity silicon nitride ceramics by gas pressure sintering at 1900°C for 12 hours. By keeping the total amount of additives at 7 mol% and adjusting the amount of ZrSi₂ in the range of 0-7 mol%, the effect of ZrSi₂ addition on sintering behaviors and thermal conductivity of silicon nitride were investigated. It was found that binary additives ZrSi₂–MgO were effective for the densification of Si₃N₄ ceramics. XRD observations demonstrated that ZrSi₂ reacted with native silica on the Si₃N₄ surface to generate ZrO₂ and β-Si₃N₄ grains. TEM and in situ dilatometry confirmed that the as formed ZrO₂ collaborated with MgO and Si₃N₄ to form Si–Zr–Mg–O–N liquid phase promoting the densification of Si₃N₄. Abnormal grain growth was promoted by in situ generated β-Si₃N₄ grains. Consequently, compared to ZrO₂-doped materials, the addition of ZrSi₂ led to enlarged grains, extremely thin grain boundary film and high contiguity of Si₃N₄–Si₃N₄ grains. Ultimately, the thermal conductivity increased by 34.6% from 84.58 to 113.91 W·(m·K)⁻¹ when ZrO₂ was substituted by ZrSi₂.     

Thermal Properties of Hf‐Doped ZrB2 Ceramics

The effect of Hf additions on the thermal properties of ZrB₂ ceramics was studied. Reactive hot pressing of ZrH₂, B, and HfB₂ powders was used to synthesize (Zr_1?x,Hf_x)B₂ ceramics with Hf contents ranging from x = 0.0001 (0.01 at.%) to 0.0033 (0.33 at.%). Room‐temperature heat capacity values decreased from 495 J·(kg·K)^?1 for a Hf content of 0.01 at.% to 423 J·(kg·K)^?1 for a Hf content of 0.28 at.%. Thermal conductivity values decreased from 141 to 100 W·(m·K)^?1 as Hf content increased from 0.01 to 0.33 at.%. This study revealed, for the first time, that small Hf contents decreased the thermal conductivity of ZrB₂ ceramics. Furthermore, the results indicated that reported thermal properties of ZrB₂ ceramics are affected by the presence of impurities and do not represent intrinsic behavior.     

Structural and Thermo‐Mechanical Properties of Nd: Y2O3 Transparent Ceramics

Various content of neodymia Nd: Y₂O₃ (Nd: 0.5–5.0 at.%) transparent ceramics were fabricated by vacuum sintering. The prepared Nd: Y₂O₃ ceramics exhibit high transmittance (~80%) at the wavelength of 1100 nm. It is found that the increase in Nd concentration enhances the grain size growth, while decreases the phonon energy, which is benefit for improving both the luminescence quantum and up‐conversion efficiency. The thermal conductivity and thermal expansion coefficient of the transparent 1.0 at.% Nd: Y₂O₃ ceramic is 5.51 W·(m·K)^?1 and 8.11 × 10^?6 K^?1, respectively. The hardness and the fracture toughness of the transparent ceramic is 9.18 GPa and 1.03 Mpa·m^1/2, respectively. The results indicate that the Nd: Y₂O₃ transparent ceramic is a potential candidate material for laser.     

Complex Effect of Sm3+/W6+ Codoping on α‐β Phase Transformation and Phonon Scattering of Oxygen‐Deficient La2Mo2O9

Lanthanum molybdate, La₂Mo₂O₉, has been attracted considerable attention owing to its high concentration of intrinsic oxygen vacancies, which could be reflected by enhanced phonon scattering and low thermal conductivity. A new series of La₂Mo₂O₉‐based oxides of the general formula La_2?xSm_xMo_2?xW_xO₉, where x ≤ 0.2, were synthesized by citric acid sol–gel process. The variation in thermal conductivity with Sm³⁺and W⁶⁺ fractions was analyzed based on structure information provided by X‐ray diffraction and Raman spectroscopy. The fully dense La_2?xSm_xMo_2?xW_xO₉ ceramics showed a minimum thermal conductivity value [κ = 0.84 W·(m·K)^?1,T = 1073 K] at the composition of La_1.8Sm_0.2Mo_1.8W_0.2O₉, which stems from the multiple enhanced phonon scatterings due to mass and strain fluctuations at the La³⁺ and Mo⁶⁺ sites as well as the high concentration of intrinsic oxygen vacancies embedded in the crystal lattice. The thermal conductivities present an abrupt decrease at the structural transition, which is due to the phase transformation from a low‐temperature ordered form (monoclinic α‐La₂Mo₂O₉) to a high‐temperature disordered form (cubic β‐La₂Mo₂O₉₎.     

Theoretical predictions on intrinsic lattice thermal conductivity of ZrB2

As a most important thermal management material, high thermal conductivity of ZrB₂ is expected. However, the reported values of thermal conductivity κ of ZrB₂ are quite scattering, and no consensus has been reached. The contribution from lattice separated by Wiedemann-Franz law is low and the relationship between electron and phonon contributions is still blurry. To explore the intrinsic κ of ZrB₂, in this work, two approaches, i.e. analytical Debye-Callaway model and iterative solution to the Boltzmann transport equation (BTE), are used to simulate the temperature-dependent theoretical lattice κ of ZrB₂. Our work demonstrates that the lattice thermal conductivity of ZrB₂ has been underestimated. The intrinsic lattice thermal conductivity of ZrB₂ is estimated to be 91 and 88 W m^?1 K^?1 at 300 K, by two different models, respectively. The effects of low lying optical phonon modes and grain boundary on the thermal conductivity of ZrB₂ are discussed. The thermal conductivity of ZrB₂ is controllable by designing effective grain size and microstructure. By casting light on the micro mechanism on lattice heat conduction of ZrB₂, our work will be constructive to the application of ZrB₂ as thermal management material.     

Highly porous Y2SiO5 ceramic with extremely low thermal conductivity prepared by foam‐gelcasting‐freeze drying method

Foam‐gelcasting‐freeze drying method is developed to fabricate porous Y₂SiO₅ ceramic with ultrahigh porosity of 92.2%‐95.8% and isotropous multiple pore structures. As prepared porous samples have quite low shrinkages of 0.8%‐1.9% during demolding and drying processes, lightweights of 0.19‐0.35 g/cm³, and extremely low thermal conductivities of 0.054‐0.089 W·(m·K)^?1. Our approach combines the merits of foam‐gelcasting method and freeze drying method. It is a simple and effective method to fabricate porous ceramics with very high porosity and extremely low thermal conductivity through low shrinkage of green body and near net complex shape forming.     

Microstructure and thermal conductivity of gas-pressure-sintered Si3N4 ceramic: the effects of Y2O3 additive content

Si₃N₄ ceramics were sintered at 1900 °C under a nitrogen pressure of 1 MPa using Y₂O₃-MgO additives. The effects of Y₂O₃ content (0.5-4 mol%) on microstructure and thermal conductivity were systematically investigated. The increasing Y₂O₃ content led to increases in amount and viscosity of liquid phase during sintering, which induced a “bimodal to normal” transition in distribution of grain size, decreased Si₃N₄/Si₃N₄ contiguity and enhanced devitrification degree of intergranular phase in sintered bulks. Moreover, the decreasing Y₂O₃ content was found to improve the elimination efficiency of SiO₂ impurity during sintering, resulting in lower lattice oxygen content in densified specimens. The microstructure had a strong effect on thermal conductivity. The samples sintered for 3 h gained an increase of thermal conductivity from 65 to 73 W·m^-1 K^-1 with increasing Y₂O₃ content, while the samples sintered for 12 h obtained a substantial increase of thermal conductivity from 87 to 132 W·m^-1 K^-1 with decreasing Y₂O₃ content.     

Effects of Y2O3–RE2O3 (RE = Sm,Gd, Lu) Additives on Electrical and Thermal Properties of Silicon Carbide Ceramics

In this study, we investigated the electrical and thermal properties of SiC ceramics with 2 vol% equimolar Y₂O₃–RE₂O₃ (RE = Sm, Gd, Lu) additives. The three SiC ceramics with 2 vol% equimolar Y₂O₃–RE₂O₃ additives showed electrical conductivities on the order of ~10³ (Ω·m)^?1, which is one order of magnitude higher than that of the SiC ceramics sintered with 2 vol% Y₂O₃ only. The increase in electrical conductivity is attributed to the growth of heavily nitrogen‐doped SiC grains during sintering and the confinement of oxide additives in the junction area. The thermal conductivities of the SiC ceramics were in the 176–198 W·(m·K)^?1 range at room temperature. The new additive systems, equimolar Y₂O₃–RE₂O₃, are beneficial for achieving both high electrical conductivity and high thermal conductivity in SiC ceramics.     

An Evaluation of the Thermophysical Properties of Stoichiometric CeO2 in Comparison to UO2 and PuO2

The thermal conductivity of stoichiometric CeO₂ was determined through measurement of thermal expansion from 313 to 1723 K, thermal diffusivity from 298 to 1473 K, and specific heat capacity from 313 to 1373 K. The thermal conductivity was then calculated as the product of the density, thermal diffusivity, and specific heat capacity. The thermal conductivity was found to obey an (A + BT)^?1 relationship with A = 6.776×10^?2 m·K·W^?1 and B = 2.793 × 10^?4 m·W^?1. Extrapolations of applied models were made to provide suggested data for the specific heat capacity, thermal diffusivity, and thermal conductivity data up to 1723 K. Results of thermal expansion and heat capacity measurements agreed well with the limited low‐temperature data available in the literature. The thermal conductivity values provided in the current study are significantly higher than the only high‐temperature data located for CeO₂. This is attributed to the tendency of CeO₂ to rapidly reduce at elevated temperatures given the available partial pressure of O₂ in air at ambient pressure. The CeO₂ data are compared to literature values for UO₂ and PuO₂ to evaluate its suitability as a surrogate in nuclear fuel systems where thermal transport is a primary criterion for performance     

Preparation,microstructure, and properties of GPS silicon nitride ceramics with β-Si3N4 seeds and nanophase additives

Si₃N₄ ceramics with high thermal conductivity and outstanding mechanical properties were prepared by adding β-Si₃N₄ seeds and nanophase α-Si₃N₄ powders as modifiers. The introduction of β-Si₃N₄ seeds enhanced the growth of β-Si₃N₄ grains. Owing to the interlocked structure induced by the β-Si₃N₄ grains, the fracture toughness of Si₃N₄ ceramics reached a high value of 7.6 MPa·m^1/2; also, the large-sized grains increased the contact possibility of Si₃N₄ grains, improving the thermal conductivity of Si₃N₄ ceramics (64 W/(m·K)). Because of the introduction of nanophase α-Si₃N₄, the flexural strength, fracture toughness, and thermal conductivity of the Si₃N₄ ceramics increased to 754 MPa, 7.2 MPa·m^1/2, and 54 W/(m·K), respectively. According to the analysis of the growth kinetics of Si₃N₄ grains, the rapid growth of Si₃N₄ grains was ascribed to the reduction in the activation energy resulting from the introduction of β-Si₃N₄ seeds and nanophase α-Si₃N₄.     

Theoretical Prediction and Experimental Investigation on the Thermal and Mechanical Properties of Bulk β‐Yb2Si2O7

The thermal and mechanical properties of β‐Yb₂Si₂O₇ were investigated using a combination of first‐principles calculations and experimental investigations. Theoretically, anisotropic chemical bonding and elastic properties, weak interatomic (010) and (001) planes in the crystal structure, damage tolerance, and low thermal conductivity are predicted. Experimentally, preferred orientation, superior mechanical properties, and damage tolerant behavior for hot‐pressed bulk β‐Yb₂Si₂O₇ are approved. Slipping along the weakly bonded {010}, {001}, or {100} planes, grain delamination, buckling, and kinking of nanolaminated grains are identified as main mechanisms for damage tolerance. The anisotropic linear thermal expansion coefficients (CTEs) are: α_a = (3.57 ± 0.18) × 10^?6 K^?1, α_b = (2.49 ± 0.14) × 10⁶ K^?1, and α_c = (1.48 ± 0.22) × 10^?6 K^?1 (673–1273 K). A low thermal conductivity of ~2.1 W (m·K)^?1 at 1273 K has been confirmed. The unique combination of these properties endow it a potential candidate for thermal barrier coating (TBC)/environmental barrier coating of silicon‐based ceramics.     

Theoretical Investigations on the Structural,Electronic, Mechanical,and Thermal Properties of MP2O7 (M = Ti,Hf)

A systematical ab initio analysis on MP₂O₇ (M = Ti, Hf) is presented in this work. Density functional theory (DFT) computations were performed for the electronic, mechanical, and thermal properties of MP₂O₇. Heterogeneous bonding nature of MP₂O₇ was revealed by examining the structural and electronic properties, M–O bonds were weaker than P–O bonds. The elastic constants and polycrystalline mechanical properties of MP₂O₇ were reported. Based on the low shear‐modulus‐to‐bulk‐modulus ratios and positive Cauchy pressure, MP₂O₇ ceramics were predicted to be “quasi‐ductile”. In addition, the minimum thermal conductivities were estimated to be 1.52 and 0.99 W·m^?1·K^?1 for TiP₂O₇ and HfP₂O₇, respectively. The ultra‐low thermal conductivities were contributed to the lattice phonon scattering due to the heterogeneous bonding nature. Our theoretical results emphasize the importance of weak M–O bonds in the determination of mechanical and thermal properties of MP₂O₇.     

Enhanced Thermoelectric Properties of Bi2O2Se Ceramics by Bi Deficiencies

Polycrystalline Bi_2?xO₂Se ceramics were synthesized by spark plasma sintering process. Their thermoelectric properties were evaluated from 300 to 773 K. All the samples are layered structure with a tetragonal phase. The introduction of Bi deficiencies will cause the orientation alignment and change of effective mass. As a result, a significant enhancement of thermoelectric performance was achieved. The maximum of Seebeck coefficient is ?568.8 μV/K for Bi_1.9O₂Se at 773 K, much larger than ?445.6 μV/K for pristine Bi₂O₂Se. Featured with very low thermal conductivity [~0.6 W·(m·K)^?1] and an optimized electrical conductivity, ZT at 773 K is significantly increased from 0.05 for pristine Bi₂O₂Se to 0.12 for Bi_1.9O₂Se by introducing Bi deficiencies, which makes it a promising candidate for medium temperature thermoelectric applications.     

Microstructure and Thermal Conductivity of Silicon Carbide with Yttria and Scandia

A fully dense SiC ceramic with high thermal conductivity was obtained by conventional hot pressing, with 1 vol% Y₂O₃–Sc₂O₃ additives. The ceramic had a bimodal microstructure consisting of large and small equiaxed SiC grains. Observation with high‐resolution transmission electron microscopy (HRTEM) showed two kinds of homophase (SiC/SiC) boundaries, that is crystallized and clean boundaries, and a fully crystallized junction phase. The thermal conductivity of the SiC ceramic was 234 W (m·K)^?1 at room temperature. The high thermal conductivity was attributed to a clean SiC lattice and good contiguity between SiC grains.