Energetics and structure of SiC(N)(O) polymer-derived ceramics

This study presents new experimental data on the thermodynamic stability of SiC(O) and SCN(O) ceramics derived from the pyrolysis of polymeric precursors: SMP-10 (polycarbosilane), PSZ-20 (polysilazane), and Durazane-1800 (polysilazane) at 1200°C. There are close similarities in the structure of the polysilazanes, but they differ in crosslinking temperature. High-resolution X-ray photoelectron spectroscopy shows notable differences in the microstructure of all polymer-derived ceramics (PDCs). The enthalpies of formation (∆H°_{f, elem}) of SiC(O) (from SMP-10), SCN(O) (from PSZ-20), and SCN(O) (from Durazane-1800) are −20 ± 4.63, −78.55 ± 2.32, and −85.09 ± 2.18 kJ/mol, respectively. The PDC derived from Durazane-1800 displays greatest thermodynamic stability. The results point to increased thermodynamic stabilization with addition of nitrogen to the microstructure of PDCs. Thermodynamic analysis suggests increased thermodynamic drive for forming SiCN(O) microstructures with an increase in the relative amount of SiN_xC_4−x mixed bonds and a decrease in silica. Overall, enthalpies of formation suggest superior stabilizing effect of SiN_xC_4−x compared to SiO_xC_4−x mixed bonds. The results indicate systematic stabilization of SiCN(O) structures with decrease in silicon and oxygen content. The destabilization of PDCs resulting from higher silicon content may reach a plateau at higher concentrations.     

Synthesis,microstructure, physical and mechanical properties of phase-pure entropy-enhanced (Nb0.8Ti0.05Ta0.05V0.05M0.05)4AlC3 (M = Hf,Zr) ceramics

The first 413-phase entropy-enhanced (Nb_0.8Ti_0.05Ta_0.05V_0.05M_0.05)₄AlC₃ (M = Hf, Zr) (EEMAX_Hf and EEMAX_Zr) ceramics were successfully consolidated by spark plasma sintering (SPS) using Nb, Ti, Ta, V, Zr, Hf, Al and graphite as initial materials. The formation of solid solution with five transition metals at the M sites of hexagonal M₄AlC₃ unit cell was confirmed by elemental analyses. Compared with pure Nb₄AlC₃, both the electrical and thermal conductivities of the entropy-enhanced ceramics showed a slight decrease, which is attributed to the lattice distortion and the increasing lattice defects that prevents the transfer of electrons and phonons. On the other hand, the mechanical properties of entropy-enhanced ceramics were greatly enhanced compared to pure Nb₄AlC₃. The measured fracture toughness of EEMAX_Hf and EEMAX_Zr ceramics were 8.2 MPa·m^1/2 and 10.0 MPa·m^1/2, respectively, which were increased by 18.8% and 44.9% compared to Nb₄AlC₃. The compressive strength of EEMAX_Hf and EEMAX_Zr ceramics were 987 MPa and 1187 MPa, respectively, being 92.0% and 130.9% higher than that of Nb₄AlC₃, respectively. EEMAX_Hf and EEMAX_Zr ceramics also possessed the higher Vickers hardness of 6.8 GPa and 7.4 GPa, respectively.     

Thermogravimetric Study of the M-Co-O System: I, M = Ta and Nb at 1200°C

Phase equilibria in the Ta-Co-O and Nb-Co-O systems have been studied at 1200°C at oxygen partial pressures from 10^−0.68 to 10^−13.50 atm for the former and from 10^−0.68 to 10^−13.30 atm for the latter. In both systems, M₂CoO₆ and M₂Co₄O₉ are stable ternary compounds under the experimental conditions, and a new phase, Nb₅Co₂O₁₄, has been identified. The Ta-Co-O system is simple, whereas the Nb-Co-O system is somewhat more complicated because of the extra phase. The lattice constants of the ternary compounds have been determined and compared with previous values. The standard Gibbs energies of reactions have been determined using oxygen partial pressures in equilibrium with three solid phases.     

Prediction of solid solution characteristics of MC (M = Zr,Nb, and Ta) in TiC lattice using phase stability diagrams

Phase stability diagrams of Ti-M-O-C (M = Zr, Nb, and Ta, molar ratio of Ti and M = 1:1) systems at 1800 K were drawn as a function of the carbon activity, oxygen partial pressure, and solution formation characteristics. The solid solution characteristics were varied with the kind of M. The solid solution carbide, (Ti_0.5Zr_0.5)C, was less stable than the TiC-ZrC mixture while other solid solution carbides (Ti_0.5Nb_0.5)C and (Ti_0.5Ta_0.5)C were more stable than the mixtures of monocarbides. Thus, the (Ti_0.5Zr_0.5)C phase was not included in the phase stability diagram of the Ti-Zr-O-C system unlike the other solid solution carbides. The validity of the drawn stability diagrams was proved by experimental results. Thus, the conditions for synthesis of solid solution carbides by carbothermal reduction, or fabrication of TiC-based composites with solid solution phases, can be deduced using the phase stability diagrams.     

Phase stability,mechanical and thermodynamic properties of (Hf,Zr, Ta,M)B2 (M= Nb,Ti, Cr,W) quaternary high-entropy diboride ceramics via first-principles calculations

As the high-entropy design concept applied to the diboride ceramic system, high-entropy diboride ceramics with a wide range of composition control, is expected to become a new high-performance material for extreme high-temperature environments. Herein, the effects of four transition metal elements (Nb, Ti, Cr, W) on the phase stability and properties of (Hf, Zr, Ta)B₂-based high-entropy diboride ceramics are systematically investigated via the first-principles calculations. All components were identified as thermodynamically, mechanically and dynamically stable from enthalpy of formation, elastic and phonon spectrum calculations. Among these, compared with the (Hf, Zr, Ta)B₂ ceramics, the addition of Nb and Ti on the metal sublattice is beneficial to improve the mechanical properties of ceramics, including Young's modulus, hardness and fracture toughness, while the introduction of Cr and W weakens the strength of covalently and ionic bonds inside the material, reducing its mechanical properties. The predicted thermophysical properties show that the high-entropy diboride ceramics containing Nb and Ti have better high-temperature comprehensive performance, including higher Debye temperature, thermal conductivity and lower thermal expansion characteristics, which is conducive to the application in extreme high-temperature environments. This research will provide important guidance for the design and development of new high-performance high-entropy diboride ceramics.     

Phase content prediction in polymer-derived ceramics with metal additives

In this study, silicon oxycarbide (SiOC) is selected as the base polymer to derive a SiOC ceramic (PDC) matrix, and four transition metals M (M = Ni, Mo, Co, and Zr) are individually introduced into the SiOC base to form various SiOC/M systems. SiOC-Ni, SiOC-MoC_x, and SiOC-CoSi_x are obtained by pyrolysis at 1100°C, whereas SiOC-ZrO_x forms upon pyrolysis at 1400°C. The selected SiOC/M systems encompass four different types of phase separation pathways—pure metal, metal carbide, metal silicide, and metal oxide (SiC-SiO₂-C-Ni, SiC-SiO₂-C-MoC_x, SiC-SiO₂-C-CoSi_x, and SiC-SiO₂-C-ZrO_x). The driving force for crystallization has been analyzed using a Gibbs free energy minimization method and phase fractions of these different PDC systems are calculated based on the lever rule. This work also reveals the energetics related to the quaternary systems and provides guidance to synthesizing metal-containing PDCs with desired phase contents. In addition, we have examined the broad applicability of the phase content prediction method for a variety of other SiOC/M systems.     

Phase transition behavior of Pb(Hf,Sn, Ti,Nb)O3 ceramics at morphotropic phase boundary

The phase transition and dielectric properties of Pb_0.988(Hf_0.945Sn_xTi_0.03-xNb_0.025)O₃ ceramics (0 ≤ x ≤ 0.03, correspondingly abbreviated as H1, H2, H3, and H4) at the morphotropic phase boundary were systematically investigated. X-ray diffraction results and P-E hysteresis loops show that the dominate orthorhombic antiferroelectric phase and a small amount of the tetragonal FE phase coexist in Pb_0.988(Hf_0.945Sn_xTi_0.03-xNb_0.025)O₃ ceramics. As the Sn content increases, the antiferroelectricity is significantly enhanced, accompanied with an increased Curie temperature and sharply reduced peak dielectric constant. H1 and H2 experience an irreversible field-induced AFE-FE phase transition at the ambient temperature, and the transition from a metastable FE phase to the original AFE phase is observed in H2 when heated to 60°C. H3 and H4 experience an invertible AFE-FE phase transition, along with an enhanced forward phase switching field E_F. Moreover a decreased backward phase switching field E_A for H4 is detected as the electric field increases due to the AFE/FE coexistence. These results reveal the unique phase transition characteristics of AFE materials near the phase boundary, which is helpful for better understanding of AFE/FE materials.     

Preparation of (Ti,Zr,Hf,Nb,Ta)C high-entropy carbide ceramics through carbosilicothermic reduction of oxides

Fully dense high-entropy carbide (HEC) ceramic has been prepared from a mixture of the group IV and V transition metal oxides by a two-step technique, which involved the vacuum carbosilicothermic reduction (VCSTR) synthesis of a composite powder containing 75 vol.% HEC, 20 vol.% (Nb_1-xMe_x)Si₂ (where Me = Ti, Zr, Hf, Ta), and 5 vol.% SiC followed by hot pressing of the as-synthesized product. It was found that the reaction between (Nb_1-xMe_x)Si₂ and HEC took place during hot pressing, thereby allowing effective sintering to occur. The mechanical properties of the obtained nearly single-phase HEC ceramic were comparable to or even slightly better than those of HEC ceramics prepared by other methods. The use of VCSTR synthesis as a key step in the preparation of fully dense HEC ceramic was concluded to be effective both in lowering the sintering temperature and in improving the mechanical properties.     

Fabrication of high-entropy carbide ceramics (Ti,Zr,Hf,Nb,Ta)C through low-temperature calcium-hydride reduction of oxides

High-entropy carbides (HECs) are paid great attention owing to superior properties, and various fabrication methods have been used to date to produce high-quality material. Here, a novel approach, in the case of HECs, is used to prepare powder and bulk (Ti,Zr,Hf,Nb,Ta)C: the calcium-hydride reduction (CHR) of oxides, followed by pressureless sintering (PS) and spark plasma sintering (SPS). The material obtained is characterized via TEM, SEM, and XRD. It has been shown that the CHR provides the formation of the nano-sized powder with a multiphase structure consisting of binary carbides. Subsequent PS and SPS lead to the formation of a single-phase structure; however, porosity differs significantly. As a bulk state, (Ti,Zr,Hf,Nb,Ta)C exhibits typical high hardness (20.4 GPa) and good fracture toughness (4.2 MPa∙m^1/2). The results have shown that calcium-hydride reduction process, with proper development, can provide a new cost-effective technology for the synthesis of nano and submicron powders of high-entropy carbides.     

Phase equilibria study and thermodynamic description of the BaO‐CaO‐Al2O3 system

A combined experimental investigation and thermodynamic assessment was performed for the BaO‐CaO‐Al₂O₃ system. By using a high‐temperature equilibration/quenching technique and scanning electron microscopy, electron probe microanalysis, and X‐ray powder diffraction analysis, the phase equilibria at 1500°C and phase stability of BaCa₂Al₈O₁₅ phase were determined. An extensive literature survey was conducted for the experimental and thermodynamic modeling data of the BaO‐CaO‐Al₂O₃ system. According to the literature data and the present measurements, a thermodynamic assessment was made in order to obtain a set of self‐consistent thermodynamic parameters to describe the BaO‐CaO‐Al₂O₃ system. Based on the thermodynamic parameters acquired in this work, isothermal sections at 1100°C, 1250°C, 1400°C, 1475°C, and 1500°C and the BaO·Al₂O₃‐CaO·Al₂O₃ and BaO·6Al₂O₃‐CaO·6Al₂O₃ joints were calculated and compared with the available experimental data.     

High-temperature oxidation behavior of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics in air

High-entropy metal carbides have recently been arousing considerable interest. Nevertheless, their high-temperature oxidation behavior is rarely studied. Herein the high-temperature oxidation behavior of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy metal carbide (HEC-1) was investigated at 1573-1773 K in air for 120 minutes. The results showed that HEC-1 had good oxidation resistance and its oxidation obeyed a parabolic law at 1573-1673 K, while HEC-1 was completely oxidized after isothermal oxidation at 1773 K for 60 minutes and thereby its oxidation followed a parabolic-linear law at 1773 K. An interesting triple-layered structure was observed within the formed oxide layer at 1673 K, which was attributed to the inward diffusion of O₂ and the outward diffusion of Ti element and CO or CO₂ gaseous products.     

Vinylhydridosilsesquioxne: Synthesis and characterization of a potential filler material for vinyl-containing polysiloxanes

This paper reports the synthesis and characterization of an organic silsesquioxane (SQ) containing Si vinyl and Si H groups named as vinylhydridosilsesquioxane (SQVH-12). Detailed investigation of the structure of this organosilsesquioxane revealed that SQVH-12 has a highly cross-linked (polycyclic) Si O network of silsesquioxane with Si vinyl and Si H functional groups. Thermogravimetric analysis of the pyrolysis behavior of SQVH-12 yielded a high percentage of ceramic residue (~92%) at 1200°C under an argon atmosphere. The presence of functional groups in SQVH-12 and the high rate of ceramic residue highlights the potential usefulness of SQVH-12 as a filler for vinyl-containing polysiloxanes. Thus, further research of SQVH-12 can find applications in a wide variety of areas such as additive manufacturing, protective coatings, and advanced composites.     

Reentrant phase transition of poly(N‐isopropylacrylamide) gels in polymer solutions: Thermodynamic analysis

The swelling behavior of poly(N‐isopropylacrylamide) (PNIPA) gels in polymer solutions, particularly in aqueous solutions of poly(ethylene glycol)s, was investigated using the theory of equilibrium swelling. The volume of the PNIPA gel and the partition parameter of the macromolecules between the gel and the solution phases were calculated for various extents of the energetic interactions between the components. The simulation results were compared with the experimental data reported in the literature. It was shown that the PNIPA gel has a tendency to a reentrant phase transition in an aqueous solution of low molecular weight linear polymers. In such a transition, the gel first collapses, then reswells, if the linear polymer concentration is continuously varied. The necessary condition for the reentrant behavior of PNIPA gels was predicted in terms of the interaction parameters among the PNIPA network, the linear polymer, and water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 801– 813, 2002     

(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high‐entropy ceramics with low thermal conductivity

A novel high‐entropy carbide ceramic, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C, with a single‐phase rock salt structure, was synthesized by spark plasma sintering. X‐ray diffraction confirmed the formation of a single‐phase rock salt structure at 26‐1140°C in Argon atmosphere, in which the 5 metal elements may share a cation position while the C element occupies the anion position. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C exhibits a much lower thermal diffusivity and conductivity than the binary carbides HfC, ZrC, TaC, and TiC, which may result from the significant phonon scattering at its distorted anion sublattice. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C inherits the high elastic modulus and hardness of the binary carbide ceramics.     

高熵(Zr,Hf,Nb,Ta)C微米长方体的制备、吸波性能和抗氧化性研究

针对高熵碳化物制备困难,本文采用ZrC、HfC、NbC和TaC粉为原料,Ni粉为熔剂,通过低温无压烧结工艺成功制备出三种不同成分的高熵(Zr, Hf, Nb, Ta)C粉体。结果表明,三种粉体均为微米长方体,且暴露(100)晶面。(Zr_1/4Hf_1/4Nb_1/4Ta_1/4)C微米长方体因具有高介电常数而展现出优异的吸波性能,在厚度为3.5 mm、频率为6.16 GHz时,最低反射损耗值可达-48.86 dB。高熵(Zr, Hf, Nb, Ta)C微米长方体在800～1 200℃下展示出优异的抗氧化性,且氧化产物均由正交相(Nb_xTa_1-x)₂O₅固溶体、单斜相(Zr_xHf_1-x)O₂固溶体和正交相HfO₂所组成,与氧化温度和过渡金属的物质的量比无关。Zr、Hf、Nb和Ta的协同作用导致其氧化机制与单组元碳化物截然不同,Hf的存...     

Pressureless sintering and properties of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics: The effect of pyrolytic carbon

A novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic was successfully prepared by pressureless sintering at 2200 °C. With increasing content of resin-derived-carbon, the density, and mechanical and thermal properties increased up to a maximum content of 2～4 wt% resin addition, after which further addition was detrimental. All specimens showed high strength (≥347±36 MPa), with the highest value achieving 450±64 MPa, and fracture toughness significantly higher (>20 %) than those of the corresponding monocarbides and Ta_0.5Hf_0.5C, (Ta_1/3Zr_1/3Nb_1/3)C. The thermal conductivity was approximately equivalent to the lowest value of the corresponding mono-carbides, which was assumed to be due to the lattice distortion effect.     

Thermal and electrical properties of a high entropy carbide (Ta,Hf, Nb,Zr) at elevated temperatures

The thermal and electrical properties were measured for a high entropy carbide ceramic, consisting of (Hf, Ta, Zr, Nb)C. The ceramic was produced by spark plasma sintering a mixture of the monocarbides and had a relative density of more than 97.6%. The resulting ceramic was chemically homogeneous as a single-phase solid solution formed from the constituent carbides. The thermal diffusivity (0.045–0.087 cm²/s) and heat capacity (0.23–0.44 J/g•K) were measured from room temperature up to 2000°C. The thermal conductivity increased from 10.7 W/m•K at room temperature to 39.9 W/m•K at 2000°C. The phonon and electron contributions to the thermal conductivity were investigated, which showed that the increase in thermal conductivity was predominantly due to the electron contribution, while the phonon contribution was independent of temperature. The electrical resistivity increased from 80.9 μΩ•cm at room temperature to 114.1 μΩ•cm at 800°C.     

Mechanical properties,thermal expansion performance and intrinsic lattice thermal conductivity of AlMO4 (M=Ta,Nb) ceramics for high-temperature applications

The vital thermo-mechanical properties of thermal and environment barrier coatings (TBCs/EBCs) include high hardness, low Young's modulus, matching thermal expansion coefficients (TECs) with substrate and low thermal conductivity. The effect of distortion degree of crystal structure on thermo-mechanical properties of AlMO₄ (M=Ta, Nb) ceramics are assessed in this work. AlMO₄ ceramics display modest TECs and no phase transformation is detected from room temperature to 1200?℃. The experiment thermal conductivity can be dropped further as the theoretical minimum thermal conductivity of AlTaO₄ and AlNbO₄ is 1.48?W?m^?1 K^?1 and 1.05?W?m^?1 K^?1, respectively. The temperature dependent phonon thermal diffusivity of AlMO₄ ceramics has been confirmed; the intrinsic lattice thermal conductivity is determined. The extraordinary thermo-mechanical properties make it clear that AlMO₄ ceramics are suitable for high-temperature applications.     

The effect of Nb or Ta substitution into the M1 phase of the MoV(Nb,Ta)TeO selective oxidation catalyst

We use aberration corrected high-angle annular dark field (HAADF) imaging to systematically study, atomic column by atomic column, the effects of substituting Nb or Ta into the M1 phase of the MoV(Nb,Ta)TeO propane (amm)oxidation catalyst. The HAADF results indicate that the x,y coordinates of the metal sites within the M1 framework are unaffected by the substitution of either Nb or Ta for Mo. The HAADF analysis of the Ta-substituted catalyst demonstrated that the Ta preferentially substitutes into the pentagonal bipyramidal site, and by analogy, we anticipate that Nb substitutes similarly. Compositional analysis of the entire framework suggests that Ta/Nb behaves as a director of V among the octahedra that link the pentagonal rings, and the variable V occupancy may be correlated with variations in catalytic activities and selectivities. Finally, HAADF imaging provided evidence of coexistence of Ta-rich and Ta-poor domains. Similar phase segregation behavior may be present in Nb-substituted specimens, but would be very difficult to detect.