Rapid preparation of high-performance S0.4Co4Sb11.2Te0.8 skutterudites with a highly porous structure

In this study, S_0.4Co₄Sb_11.2Te_0.8 skutterudites with a highly porous structure inside grains are prepared by a one-step hot-pressing (OS-HP) method. The effect of the pressure relief treatment at the heating stage on the micro-morphology and thermoelectric properties of materials is investigated. When the temperature corresponding to the pressure relief treatment is less than 723 K, the grain size dramatically increases from ～1 to ～50 μm, and a large number of pores are distributed inside these large grains. Compared with those samples prepared by the conventional method, the thermal conductivity of samples prepared by the pressure relief treatment is significantly reduced due to the high porosity. The ZT values of samples prepared by the pressure relief treatment are greater than 1.6 at 825 K. This newly developed OS-HP method can be employed for the rapid fabrication of highly porous structured skutterudites with low-melting-point compositions as well as of other material systems.     

Thermoelectric properties and thermal stability of metal-doped cuprous sulfide thermoelectrics

Mn doping and S-evaporation are strategies used to improve the thermoelectric properties and thermal stability of cuprous sulfide thermoelectric materials. Cu_1.8S and Mn-alloyed Cu_1.8S powders were prepared via ball milling, and different samples were obtained via current-assisted sintering at different times. It was found that Mn and S-evaporation optimized the carrier concentration and thus improved the figure of merit (ZT) of the samples. The introduction of pore defects induced by S-evaporation also improved the ZT. The maximum ZT of the optimized sample reached 0.89 at 500 °C. Mn in the samples reacted with oxygen to form an oxide film on the surface of the block, which inhibited the kinetic process of Cu_1.8S decomposition and improved the thermal stability of the samples. However, the reaction between Mn and oxygen led to a continuous loss of metal cations in the material, resulting in changes in the thermoelectric properties.     

Enhancing the thermal stability of S/Se based thermoelectric materials using self-generated oxide films

This study focuses on the thermal stability of Cu_1.8S materials. During the ball milling process, metal powder is added to the milled Cu_1.8S powder, and then the obtained powder is sintered using current assisted sintering to obtain dense blocks. The aim is to enable the added metal elements to spontaneously grow an oxide film on the surface of the material block at high temperature, achieving protection of the material matrix. The thermal stability of materials is evaluated by utilizing changes in room temperature phase composition before and after high-temperature heat treatment, changes in material electrical conductivity during high-temperature processes, and cyclic electrical transmission performance testing. By observing the surface oxide film state of the material after high-temperature treatment, the commonalities and differences in the effects of different element additions on the thermal stability of the material were analyzed. The effects of different metal elements on material hardness and electrical transmission performance were evaluated. It is found that adding metal powder can effectively improve the thermal stability of Cu_1.8S, improve material hardness, and regulate the electrical transmission performance of the material. The characteristics of the oxide film formed by the spontaneous growth of metal elements and oxygen on the surface of the material substrate determine the effectiveness of the oxide film in protecting the material from high temperatures. The pure Cu_1.8S bulk can only maintain stability at 300 ^oC, and the addition of Cr, Al, 316L, Fe, and Mn powder respectively increased the stable temperature of the material to 400, 400, 450, 450, 500 ^oC. Adding metal elements to the material matrix to grow an oxide film on the surface of the material to prevent high-temperature oxidation or decomposition is an effective way to improve the thermal stability of S/Se compounds.     

Textured CaBi4Ti4O15 ceramics with large piezoelectricity,excellent thermal stability and high resistivity

The bismuth layer-structured ferroelectrics (BLSF) are promising high-temperature piezoelectric materials, in which large piezoelectricity, good thermal stability and high electrical resistivity are desired. Here highly textured CaBi₄Ti₄O₁₅ BLSF ceramics with orientation factor of 82% have been fabricated by spark plasma sintering technique. The piezoelectric coefficient d₃₃ is significantly enhanced by 250%, from 7.2 pC/N for the texture-less sample to 25.3 pC/N for the textured one, accompanied by a high Curie temperature T_C= 788 °C. The variation of d₃₃ is below 5% in the temperature range of 25–500 °C, showing excellent thermal stability. The textured sample exhibits high electrical resistivity ρ = 2.1 × 10¹¹ Ω·cm, an order of magnitude larger than that of the texture-less sample. At the temperature as high as 500 °C, the textured sample still maintains excellent electrical properties of d₃₃ = 24.2 pC/N, tanδ = 9.9% and ρ = 2.7 × 10⁶ Ω·cm, suggesting that the textured CaBi₄Ti₄O₁₅ ceramics could be a potential candidate for high-temperature piezoelectric sensor or detector applications.     

Remarkably enhanced energy-storage density and excellent thermal stability under low electric fields of (Na0.5Bi0.5)TiO3-based ceramics via composition optimization strategy

High energy density and high thermal stability of energy-storage properties (ESP) under low electric fields are extremely crucial for the application of dielectric ceramics in miniaturized equipment. In present work, we use a composition-optimization approach to break the long-range ferroelectric order and modulate polar nanoregions (PNRs) in the local structure of (1-x)[0.7(Na_0.5Bi_0.5)TiO₃-0.3(Sr_0.7Bi_0.2)TiO₃]-xBi(Mg_0.5Ti_0.5)O₃ system. The large P_max value is maintained due to the existence of Bi ions in both the matrix and dopants. As a result, a high W_rec of 3.03 J/cm³ together with a moderate η of 79.5 % was obtained in x = 0.05 sample at a low electric field of 200 kV/cm. Meanwhile, the high W_rec (2.41–2.52 J/cm³) and excellent thermal stability of ESP (W_rec varying less than 4.3 % and η > 90 %) from 50 °C to 200 °C at 150 kV/cm were also observed. The current system will be a promising candidate in energy-storage capacitor applications under low-fields and high-temperature.     

Grain boundary segregation for enhancing the thermal stability of alumina-mullite diphasic fibers by La2O3 addition

Improved thermal stability of fibers is increasingly demanded for high-temperature applications. In this study, alumina-mullite diphasic fibers with 0–5 wt % La₂O₃ addition were synthesized via the sol-gel method. The precipitation of LaAl₁₁O₁₈ occurred when the content of added La₂O₃ exceeded a critical range. Subsequently, the effects of 1 wt % La₂O₃ on alumina-mullite diphasic fibers were systematically discussed in terms of pyrolysis removal, phase transition pathways, microstructure and thermal stability. The results indicated that alumina-mullite diphasic fibers consisted of γ, θ-Al₂O₃ and mullite phases. The spherical γ, θ-Al₂O₃ grains, ranging in size from 20 to 100 nm, were dispersed within the mullite matrix with an irregular shape. Additionally, the La element was segregated into the γ, θ-Al₂O₃ grain boundaries during the crystallization process. This resulted in stabilized γ, θ-Al₂O₃ and mullite grains and an improved strength retention rate of 84 % after thermal exposure at 1200 ℃ for 5 h.     

Highly enhanced thermal stability in quenched Na0.5Bi0.5TiO3-based lead-free piezoceramics

Unquenched and quenched ceramics of 0.85Na_0.5Bi_0.5TiO₃-0.11K_0.5Bi_0.5TiO₃-0.04BaTiO₃ have been prepared, and their crystal structure, temperature-dependent ferro-/piezoelectric properties and domain structure have been comparatively investigated. It is shown that quenching process can significantly improve the ferroelectric-relaxor transition temperature (T_F-R), which is 130 °C for unquenched ceramics and 198 °C for quenched one. As the result, the thermal stability of ferro-/piezoelectric properties is highly enhanced. These observations are mainly attributed to the quenching induced stable rhombohedral ferroelectric phase and the defect altered domain evolution. This work may deepen the understanding of the effect of quenching on crystal structure, domain structure and their contributions to thermal stability of NBT-based ceramics.     

Fabrication and thermal stability of NH4HF2-etched Ti3C2 MXene

MXene, a new family of 2D transition metal carbides and carbonitrides, has been proved to possess excellent electrical conductivity and hydrophilicity. In this work, a single-step method to produce the larger interplanar spacing 2D MXene Ti₃C₂ by etching Ti₃AlC₂ with NH₄HF₂ was demonstrated, and the optimal reaction conditions between Ti₃AlC₂ and NH₄HF₂ were systematically researched. The morphology and microstructure of samples were characterized by scanning electron smicroscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD). The thermal stability of Ti₃C₂ was investigated by the thermogravimetry (TG) and differential thermal analyzer (DTA). It was found that the lattice parameter c of obtained Ti₃C₂ was up to 24.9 Å, and the larger interplanar spacing Ti₃C₂ was more stable than the sample exfoliated by HF. The transition temperature in air from NH₄HF₂-etched Ti₃C₂ to anatase TiO₂ thoroughly is more than 500 ℃, and the multilayered structure of Ti₃C₂ could be well retained even afer 900 ℃ heat treatment, while the value of HF-etched Ti₃C₂ is less than 350 ℃. This work is important for exploring a safe synthesis method and well understanding the thermal stability of 2D MXene materials.     

Influence of the chemical structure of PUR prepolymers on thermal stability

The thermal stability of adhesives for load-bearing construction has been one of their key parameters since engineered wood products were introduced in timber construction. In the case of one-component moisture-curing polyurethane (1C PUR) adhesives, knowledge about relationships between their chemical structure and the resulting bonding properties is limited, especially under high-temperature conditions. In this study the structure-property relationships of 1C PUR prepolymers were analyzed in the temperature range from 20 to 200 °C by means of mechanical and rheological tests. NCO-terminated urethane prepolymers were prepared from systematically varied MDI and polyether mixtures. The structural parameters investigated were the urea and urethane group content, cross-link density, ethylene oxide content and the adjustment of functionality via NCO or polyether component. Bonded wood joints were tested for their tensile shear strength and polymer films were analyzed by means of DMA and DSC. The results revealed a significant influence of hard segment content and cross-link density on the thermal stability of the prepolymers. Not all parameters that affect the film properties significantly influence bonding.     

A dispersed polycrystalline phase boundary constructed in CaZrO3 modified KNN based ceramics with both excellent piezoelectric properties and thermal stability

In this paper, the ceramics with composition of (0.98-x)(K_0.5Na_0.5)(Nb_0.96Sb_0.04)O₃-0.02(Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O_3-xCaZrO₃ (abbreviated as (0.98-x)KNNS-0.02BNZT-xCZ, x = 0, 0.01, 0.015, 0.02, 0.025, 0.03) were prepared by a traditional solid-state reaction method. The effect of the additional amount of CaZrO₃ on the phase structure, microstructure, dispersion index, domain structure and piezoelectric properties of ceramics was systematically studied. Finally, the piezoelectric properties and thermal stability of ceramics could be controlled by adding different amounts of CaZrO₃. The addition of CaZrO₃ transferred the phase structure of the ceramics from orthogonal-tetragonal (O-T) coexistence phase to rhombohedral-orthogonal (R–O) coexistence phase, which could be demonstrated by XRD test, temperature-dependent Raman spectra and ε_r‐T plot analysis. And when x = 0.02, the ceramics possessed the best piezoelectric and dielectric properties (d₃₃ = 253 pC/N, ε_r = 1185, tanδ = 0.044). Such excellent electrical properties could be originated from the heterogeneous domain structure and small-size nano-domains of the ceramics. Moreover, with the increase of CaZrO₃ doping amount, the dispersion index of ceramics gradually increased from 1.404 to 1.871, which showed more obvious dispersion phase transition characteristics and improved the thermal stability of ceramics. Particularly, when x = 0.02, after annealing at a high temperature of 220 °C (close to its Curie temperature), the d₃₃ tested at room temperature remained above 85% of that without annealing. The results indicated that (0.98-x)KNNS-0.02BNZT-xCZ ceramic was a promising lead-free piezoelectric ceramic system.     

Enhanced thermal stability of Bi2Te3-based alloys via interface engineering with atomic layer deposition

The ease of Te sublimation from Bi₂Te₃-based alloys significantly deteriorates thermoelectric and mechanical properties via the formation of voids. We propose a novel strategy based on atomic layer deposition (ALD) to improve the thermal stability of Bi₂Te₃-based alloys via the encapsulation of grains with a ZnO layer. Only a few cycles of ZnO ALD over the Bi₂Te_2.7Se_0.3 powders resulted in significant suppression of the generation of pores in Bi₂Te_2.7Se_0.3 extrudates and increased the density even after post-annealing at 500 °C. This is attributed to the suppression of Te sublimation from the extrudates. The ALD coating also enhanced grain refinement in Bi₂Te_2.7Se_0.3 extrudates. Consequently, their mechanical properties were significantly improved by the encapsulation approach. Furthermore, the ALD approach yields a substantial improvement in the figure-of-merit after the post-annealing. Therefore, we believe the proposed approach using ALD will be useful for enhancing the mechanical properties of Bi₂Te₃-based alloys without sacrificing thermoelectric performance.     

Factors influencing the thermal stability of buried protein mutants

Hydrophobic interaction is believed to be the most important factor for the stability of proteins upon buried mutations. In this work, we have analyzed the influence of different interactions to the stability of buried protein mutants by means of 49 various physical-chemical, energetic and conformational properties of amino acid residues. We found that the mutant stability is attributed with several factors including hydrophobicity. In lysozyme T4, the properties reflecting hydrophobicity, flexibility, turn and coil tendency, and long-range interactions show a strong correlation with stability. Entropy plays an important role and the contribution of hydrophobicity is minimal in barnase. The stability of human lysozyme is attributed with both hydrophobicity and secondary structure. The stability of buried mutants in staphylococcal nuclease is influenced by hydrophobicity and physical properties. Our results indicate that the stability of buried protein mutants are influenced not only with hydrophobicity but also other factors, such as, secondary structure, shape, flexibility, entropy and inter-residue contacts play an important role to the stability. We obtained the highest single property correlation of 0.83 between amino acid properties and thermal stability of buried protein mutants. The properties showing high correlation coefficient with thermal stability agree very well with experimental observations. Further, multiple regression technique combining three properties leads to the correlation in the range of 0.83-0.92 in the considered proteins.     

Catalyst-free in situ synthesis of ZrC nanowires with excellent thermal stability

No catalyst-assisted zirconium carbide nanowires (ZrCNWs) were successfully synthesized by thermal evaporation and in situ reaction using carbon nanotubes (CNTs) and ZrCl₄ as carbon and zirconium sources. Vapor-Solid (VS) mechanism was proposed to explain the growth process of ZrCNWs. The ZrCNWs prepared at 1400°C have a single crystal structure with the diameters of 130-290 nm. The axial growth direction of ZrCNWs is [111] and the yield is 76.5 wt%. After heat treatment at 1700°C, 2100°C, and 2450°C, the diameter of ZrCNWs increased and their aspect ratio decreased. By simulating the thermal stress of a single ZrCNW, it is speculated that the coarsening and fracture of ZrCNWs are caused by the overall slip of the atomic layers and the stress concentration at the dislocations.     

Carbon content-dependent microstructures,surface characteristics and thermal stability of mechanical alloying derived SiBCN powders

Three types of SiBCN: carbon-lean, -moderate and -rich powders with the same Si/B/N mole ratio were subjected to high-energy ball milling to yield an amorphous structure. The effects of carbon content on microstructures, solid-state amorphization, surface characteristics and thermal stability of the as-milled powders were studied in detail. Results showed that the increases in carbon content can drive solid-state amorphization accompanied by strain-induced, crystallite refinement-induced and/or chemical composition-induced nucleation of nano-SiC from an amorphous body. The specific surface area increases as carbon content increases. The amorphous networks of Si–C, C–B/C–C, C–N, B–N and C–B–N bonds that compose the amorphous nature, but the species and contents of the chemical bonds are carbon content-dependent. Carbon-moderate powders possess satisfying thermal stability while carbon-rich ones perform the worst. Mechanical alloying derived SiBCN powders have outstanding oxidation resistance below 800 °C; however only carbon-moderate powders show desirable anti-oxidation ability at higher temperatures. Thus, mechanical alloying of SiBCN appears a suitable technique for developing amorphous matrix materials for practical applications.     

Design and preparation of low-filled magnetic oriented BN@Fe3O4/EP insulating composite with improved thermal conductivity and thermal stability

As an excellent two-dimensional insulating material with high thermal conductivity, high temperature stability and high hardness, hexagonal boron nitride(h-BN) is widely applied in semiconductor manufacturing, aerospace, metallurgical manufacturing and other cutting-edge fields. However, the unique surface structure of h-BN leads to poor lubricity and easy agglomeration, which limits the application of h-BN especially in the field of electronic packaging. To address key issues boosted above, this study designed and prepared the BN@Fe₃O₄ magnetic insulating particles and doped it into the reduced viscosity epoxy resin to prepare the composites. By selecting appropriate external magnetic field strength and BN@Fe₃O₄ particles’ content, a novel 3D structure of fillers like dominoes in epoxy resin composite was successfully constructed. The microstructure of the BN@Fe₃O₄ particles and composites were analyzed, the thermal conductivity, the mechanical and the electrical properties of composites were simultaneously tested. Results manifested that the core-shell structures with BN as core and Fe₃O₄ as shell was successfully prepared, linking through the PDA middle layer between the BN core and Fe₃O₄ shell. Under the influence of magnetic orientation, the BN@Fe₃O₄ magnetic particles were preferred an out-of-plane oriented in the epoxy resin composites, resulted an enormously enhanced on thermal conductivity of composites. At a magnetic field strength of 60 mT and 25 vol% BN@Fe₃O₄ content, the thermal conductivity of BN@Fe₃O₄/EP composites is as lofty as 1.832 W/(m K), which is 1023.46% higher than that of pure epoxy resin. Meanwhile, the thermal stability has also been slightly improved, the elastic modulus and insulation performances remain at the same level.     

Coexistence of excellent piezoelectric performance and thermal stability in KNN-based lead-free piezoelectric ceramics

With close attention being paid to environmental issues and more legislation coming into force to limit the application of Pb-based materials, accelerating research on lead-free piezoelectric ceramics has become increasingly requisite and urgent. Herein, we have devised and synthesized (1-x)(K_0.5Na_0.5)_0.98Ag_0.02(Nb_0.96Sb_0.04)O₃-x(Bi_0.5Na_0.5)ZrO₃ [abbreviated as (1-x)KNANS-xBNZ, x = 0.01, 0.02, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06] Pb-free ceramics. Phase transition, microstructure, electrical properties, and temperature stability of the ceramics have been comprehensively investigated. The findings illustrate that optimizing BNZ content can give rise to a rhombohedral-tetragonal (R-T) phase boundary when x = 0.04, 0.045, 0.05. The specimens with x = 0.04 show improved piezoelectric properties (d₃₃ ~ 440 pC/N, k_p ~ 53%, T_C ~ 250 °C, d₃₃* ~ 553 pm/V) and good temperature stability. The overall performance is excellent and indicates that (1-x)KNANS-xBNZ ceramics have great potential for replacing their lead-based counterparts.     

Enhancing the thermal stability of switched domains in lithium niobate single-crystal thin films

Lithium niobate on insulator (LNOI) is widely used in optical, acoustic, domain wall current (DWC)-based integrated circuits and other domain engineering devices, enabling higher material performance, higher domain integration density and more advanced applications. However, there are hidden dangers of thermal failure in these highly integrated domain engineering devices. Therefore, maintaining thermal stability of domain structures in ferroelectric single-crystal thin films is an important and challenging task. Here, thermally induced structure reconstruction of tailored metastable switched domains was research in a 500 nm thick congruent lithium niobate (CLN) thin film, and a method for enhancing the thermal stability of switched domains was proposed. Piezoresponse force microscopy (PFM) and a polyheater are used to accurately monitor the thermal evolution of switched domains in CLN thin film sample. The results indicate the switched domain structures determine the thermal stability, and the enhanced thermal stability of the switched domains increases from 55 to 85 °C–150 °C. In this contribution, the thermal failure in domain engineering devices can be avoided effectively. The investigation paves the way for the development of domain engineering devices based on lithium niobate (LN) thin films.     

Laser synthesis of silicon carbonitride nanopowders; structure and thermal stability

Si₃N₄/SiC nanocomposite materials are of great interest for structural applications at high temperature. In silicon nitride based ceramics, the small size and the spherical shape of the grains constituting the material are two important parameters in favour of high temperature deformation. Therefore, SiCN nano-sized powders are real candidates as starting materials to elaborate dense Si₃N₄/SiC nanocomposites exhibiting the microstructure required for ductility at high temperature. SiCN nanopowders with different chemical compositions and characteristics can be prepared by CO₂ laser pyrolysis of organosilicon precursors. Laser pyrolysis of gaseous precursors is able to produce partly crystallised SiCN nanoparticles exhibiting a reasonable thermal stability and suitable for elaboration of ceramic materials. In order to reduce the cost and to improve the safety of the process, an aerosol generated from a liquid precursor, hexamethyldisilazane (HMDS), has also been used to synthesised SiCN nanopowders. However, in this latter case the powders obtained exhibit a high weight loss during heat treatment at high temperature. Therefore, in this study the effects of various synthesis parameters (chemical nature of the precursor and laser power) on the degree of crystallisation and on the thermal stability of nanopowders are investigated. Characteristics of powders such as chemical composition, morphology, structure and thermal stability are reported. A correlation between the synthesis conditions of powders and their thermal stability is established, and the synthesis parameters enabling improvement of thermal stability are determined.     

Effect of sintering temperature on the thermal expansion behavior of ZrMgMo3O12p/2024Al composite

A 2024Al metal matrix composite with 10?vol% negative expansion ceramic ZrMgMo₃O₁₂ was fabricated by vacuum hot pressing, and the influence of sintering temperature on the microstructure and thermal expansion coefficient (CTE) of alloys was investigated. Experimental results showed that all ZrMgMo₃O_12p/2024Al composites sintered at 500–530?°C had a similar reticular structure and exhibited different linear expansion coefficients at 40–150?°C and 150–300?°C. The addition of 10?vol% ZrMgMo₃O₁₂ decreased the CTEs of 2024Al by ~ 16% at 40–150?°C and by ~ 7% at 150–300?°C. This addition also increased the hardness of 2024Al by ~ 23%. The density of the composites and the content of Al₂Cu in ZrMgMo₃O_12p/2024Al increased as the sintering temperature increased. The CTEs of the composites decreased, whereas hardness increased. Thermal cycling from 40?°C to 300?°C caused the CTEs of the composites to decrease gradually and reach a stable value after seven cycles. The lowest CTEs of 15.4?×?10^?6 °C^?1 at 40–150?°C and 20.1?×?10^?6 °C^?1 at 150–300?°C were obtained after 10 thermal cycles and were reduced by ~ 32% and ~ 17%, respectively, compared with the CTE of the 2024Al. Among the current reinforcements, ZrMgMo₃O₁₂ negative expansion ceramics showed the highest efficiency to decrease the CTE of Al matrix composites.     

Luminescence properties of Ca2GdNbO6: Sm3+, Eu3+ red phosphors with high quantum yield and excellent thermal stability for WLEDs

A series of Ca₂GdNbO₆: xSm³⁺ (0.01 ≤ x ≤ 0.15) and Ca₂GdNbO₆: 0.03Sm³⁺, yEu³⁺ (0.05 ≤ y ≤ 0.3) phosphors were synthesized by the traditional solid-state sintering process. XRD and the corresponding refinement results indicate that both Sm³⁺ and Eu³⁺ ions are doped successfully into the lattice of Ca₂GdNbO₆. The micro-morphology shows that the elements of Ca₂GdNbO₆: 0.03Sm³⁺, 0.2Eu³⁺ phosphor are evenly distributed in the sample, and the particle size is about 2 μm. The optical properties and fluorescence lifetime of Ca₂GdNbO₆: 0.03Sm³⁺, Eu³⁺ phosphors were detailedly studied. The emission peak at ⁵D₀→⁷F₂ (614 nm) is the strongest and emits red light under 406 nm excitation. The increase of Eu³⁺ concentration causes the energy transfers from Sm³⁺ to Eu³⁺ ions, and the transfer efficiency reaches 28.6%. Ca₂GdNbO₆: 0.03Sm³⁺, 0.2Eu³⁺ phosphor has a quantum yield of about 82.7%, and thermal quenching activation energy is of 0.312 eV. The color coordinate (0.646, 0.352) of Ca₂GdNbO₆: 0.03Sm³⁺, 0.2Eu³⁺ phosphors is located in the red area. The LED device fabricated based on the above phosphor emit bright white light, and CCT = 5400 K, Ra = 92.8. The results present that Ca₂GdNbO₆: 0.03Sm³⁺, Eu³⁺ phosphors potentially find use in the future.