Conversion of MAX phase single crystals in highly porous carbides by high temperature chlorination

We show that combining high temperature chlorination with the chemical sensitivity of the A-atom planes of single crystals of some nano-lamellar MAX phases allows one to synthesize highly porous and electrically conducting carbides. Focusing on the case of porous Cr₃C₂, we present the dependence of the layer morphology, structure and formation kinetics on processing parameters such as temperature and time. The determination of the Raman signature of Cr₃C₂ and Cr₇C₃ allows us to follow the creation and elimination of the various phases as a function of processing time. Electrical resistivity and magnetoresistance data versus temperature and magnetic field are also presented and analyzed.     

Determination of interdiffusion coefficients of Si and Al in Ti3SiC2–Ti3AlC2 diffusion couple at 1373-1673 K

In the diffusion couple of Ti₃SiC₂ and Ti₃AlC₂, only interdiffusion of Si and Al occurred during diffusion treatment process. Based on the concentration profiles of Si and Al measured by electron probe microanalysis (EPMA), the interdiffusion coefficients of Si and Al at 1373-1673 K in Ti₃SiC₂–Ti₃AlC₂ diffusion couple were determined by both the Boltzmann-Matano (B-M) method and the Saucer-Freise (S-F) method. At the position of Matano plane with the composition of Ti₃Al_0.5Si_0.5C₂, the interdiffusion coefficient could be expressed as D_int (m²/s) = 5.6 × 10⁻⁴⋅exp [−246 ± 14 (kJ/mol)/RT]. Based on the two methods, the calculated interdiffusion coefficients increased with increasing temperature, and the magnitudes of their absolute values were on the order of 10^–13-10^–11 m²/s at 1373-1673 K. At 1373-1573 K, the calculated interdiffusion coefficients decreased monotonously with the increase of Si concentration, that is, x_Si/(x_Al + x_Si). But at 1673 K, the variation trend of interdiffusion coefficients with x_Si/(x_Al + x_Si) was no longer monotonous, probably due to the presence of Ti₅Si₃ phase and voids on Ti₃AlC₂ side.     

Characterization of early transition metal carbides and nitrides by NEXAFS

Powder materials of a series of early transition metal (groups 4–6B) carbides and nitrides, including TiC, VC, NbC, Mo₂C, WC, TiN, VN and Mo₂N, have been characterized by nearedge X-ray absorption fine structure (NEXAFS). A comparison of the carbon and nitrogen K-edge features reveals systematic trends in the electronic properties of these materials. These results are compared to an earlier NEXAFS characterization of thin VC films produced on a single crystal V(110) surface. In addition, the NEXAFS data are also compared to existing band-structure calculations for carbides and nitrides of early transition metals.     

金属氮化物／碳化物加氢催化剂研究进展

过渡金属氮化物与碳化物是一类间充性化合物,其结构特点决定其在催化反应上具有独特的催化效果。本文介绍了过渡金属氮化物与碳化物基本性质与作为加氢催化剂的制备进展,综述了其在催化加氢,脱氢,脱硫等方面的研究进展,并展示了重要的理论研究意义和潜在的应用前景。     

Layered Structure Induced Anisotropic Low‐Energy Recoils in Ti3SiC2

Low‐energy recoil events in Ti₃SiC₂ are studied using ab initio molecular dynamics simulations. We find that the threshold displacement energies are orientation dependent because of anisotropic structural and/or bonding characteristic. For Ti and Si in the Ti–Si layer with weak bonds that have mixed covalent, ionic, and metallic characteristic, the threshold displacement energies for recoils perpendicular to the basal planes are larger than those parallel to the basal planes, which is an obvious layered‐structure‐related behavior. The calculated minimum threshold displacement energies are 7 eV for the C recoil along the direction, 26 eV for the Si recoil along the direction, 24 eV for the Ti in the Ti–C layer along the direction and 23 eV for the Ti in the Ti–Si layer along the direction. These results will advance the understanding of the cascade processes of Ti₃SiC₂ under irradiation and are expected to yield new perspective on the MAX phase family that includes more than 100 compounds.     

Influence of ordered carbon‐vacancy networks on the electronic structures and elastic properties of Nb4AlC3−x

Carbon‐vacancy‐bearing Nb₄AlC_3?x has the best high‐temperature mechanical robustness among MAX phases. The existing form of the vacancies has been long overlooked. Recently, the vacancies in Nb₄AlC_3?x have been identified to be ordered, establishing an ordered compound Nb₁₂Al₃C₈. Here, the spatial distribution of the ordered vacancies and their influences on bonding characteristics and elastic properties are unraveled by thoroughly comparing Nb₁₂Al₃C₈ and vacancy‐free Nb₄AlC₃. In Nb₁₂Al₃C₈, the carbon vacancies break only relatively weak Nb–C bonds and form ordered equilateral triangular carbon‐vacancy networks (OETCVNs) to maximize the bond strengthening effect. The networks slightly shift partial and total density of states toward the Fermi energy level, and bring about a feature of “de‐metallization”. Meanwhile, the presence of OETCVNs results in the softening of elastic modulus, decreasing of the anisotropy of Young's modulus, yet increasing that of shear modulus. These results shed lights on the carbon‐vacancy ordering behavior of MAX phases, and provide an opportunity to tailor their electronic structures and elastic properties through defect engineering.     

Ablation behavior of (Hf–Ta–Zr–Nb–Ti)C high-entropy carbide and (Hf–Ta–Zr–Nb–Ti)C–xSiC composites

The ablation behavior of (Hf–Ta–Zr–Nb–Ti)C high-entropy carbide (HEC-0) was investigated using a plasma flame in air for different times (60, 90, and 120 s) at about 2100°C. The effect of SiC content on the ablation resistance of HEC–xSiC composites (x = 10 and 20 vol%) was also studied. The linear ablation rate of HEC-0 decreases with increasing ablation time, showing the positive role of the oxide layer with a complex composition. The linear ablation rate of HEC–10 vol% SiC (0.3 µm s⁻¹) is only a 10th of that of HEC-0, showing a significant improvement in ablation resistance, probably due to the formation of a protective oxide layer containing melted SiO₂ and refractory Hf–Zr–Si–O oxides.     

Effects of 211 and 413 ordering on the corrosion behavior of V-Al-C MAX phases prepared by spark plasma sintering

In the present study, two V-Al-C based MAX phases, i.e., V₂AlC and V₄AlC₃ having two types of ordering were successfully manufactured by spark plasma sintering and the corrosion behavior of sintered samples was evaluated. Al, V and C metal powders were mixed with the desired molar ratios by a mixer mill, and sintered at 1300 °C. The relative density calculation revealed almost full densification for both prepared MAX phases. The measurements of mechanical properties showed a low increase in bending strength and Vickers hardness of V₄AlC₃ compared to V₂AlC MAX phase. Evaluation of corrosion behavior of developed MAX phases was carried out in 6.5 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests. Corrosion current density and corrosion potential of V₂AlC (5.3 ± 0.21 μA/cm² and -0.451 ± 0.01 V, respectively), and V₄AlC₃ (1.07 ± 0.22 μA/cm² and -0.091 ± 0.02 V, respectively) were measured and no passivation behavior was observed in their potentiodynamic polarization curves. However, EIS tests at open circuit potential confirmed more corrosion resistance of V₄AlC₃compared to V₂AlC. These tests also revealed the active dissolution of MAX phases in 6.5 M HCl solution at anodic potential of +0.1 V, while the impedance values of V₄AlC₃ were larger than those of V₂AlC. Microstructural investigation revealed the preferential dissolution of V₂AlC phase in grain boundaries after corrosion test. Moreover, the layered structure of V₂C MXenes was observed in some regions. After corrosion test, V₄C₃ MXene layers had larger thickness compared to V₂AlC. It was found that V₄AlC₃ with higher amount of Al₂O₃ and thicker layers has more corrosion resistance than V₂AlC MAX phase.     

Nitridation of Silicon Containing MgO and CeO2 Powders and SiC Whiskers

Processing and nitridation of MgO/CeO₂-doped silicon containing SiC whiskers was studied. The reaction time was dramatically reduced by incorporating MgO/CeO₂ dopants and SiC whiskers in silicon powders prior to nitridation. The decomposition of SiC whiskers depends on the nitriding temperature, sintering aids, and whisker surface composition.     

纳米碳酸钙在非等温条件下热分解动力学及机理研究

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-e     

Synthesis and characterization of quarternary Ti3Si(1−x)AlxC2 MAX phase materials

Ti₃Si_(1−x)Al_xC₂ (x=0–1) quarternary MAX phase materials were prepared by spark plasma sintering of TiC, Ti, Si and Al powder mixtures at 1200 °C. Effect of Al addition on lattice parameters, density and hardness were investigated. Impurities are limited to binary phases of TiC and Ti₅Si₃. No multinary compound other than Ti₃Si_(1−x)Al_xC₂ can be detected. TiC exists as impurity in all samples and trace amount of Ti₅Si₃ can be detected in Samples x=0.1–0.6. Oxidation of Al cannot be avoided although all sintering were performed under vacuum and trace amount of Al₂O₃ can be found in all samples with Al addition. Experimental results show that the lattice parameters a and c increase linearly with increasing Al content for x=0–1. The lattice variations are strongly anisotropic and follow Vegard׳s law. Both density and hardness decrease as Al content increases. The linear variation of lattice parameters, d spacings of crystalline faces and density against Al concentration suggest that continuous solid solutions of Ti₃Si_(1−x)Al_xC₂ (x=0–1) may have been formed between Ti₃SiC₂ and Ti₃AlC₂.     

Constructing hierarchical Ti3SiC2 layer and carbon nanotubes on SiC fibers for enhanced electromagnetic wave absorption

To enhance the absorption performance of silicon carbide fiber (SiC_f), hybrid fibers with a double shell structure (Ti₃SiC₂ and carbon nanotubes (CNTs)) on the SiC_f (CNT@Ti₃SiC₂@SiC_f) were successfully synthesized by the combination of molten salt method and floating catalytic chemical vapor deposition. A series of 10% weight fraction fibers reinforced paraffin samples was prepared to study the double coating influences on the electromagnetic wave (EMW) absorption performances. Coated by Ti₃SiC₂ and CNTs, the dielectric permittivity of hybrid fibers could be modulated in a quite wide range. The CNT@Ti₃SiC₂@SiC_f with a thickness of 3.8 mm showed a minimum reflection loss value of ?53 dB at 6.57 GHz, and the CNT@Ti₃SiC₂@SiC_f with a thickness of 2.5 mm presented a wide effective absorption bandwidth of 5.6 GHz (from 9 to 14.6 GHz). The highly improved EMW absorption performance of CNT@Ti₃SiC₂@SiC_f was attributed to the combination of conductive loss and dielectric loss aroused by interfaces. The excellent absorption performance provided the modified SiC_f with a high potential in the application of EMW absorbers.     

Medium-entropy (Ti,Zr, Hf)2SC MAX phase

Medium- and high-entropy alloys or ceramics for tuning the physicochemical properties of materials by the combination of multiple principal elements have received much interest. Herein, a medium-entropy (Ti, Zr, Hf)₂SC phase was synthesized attributing to the structural and chemical diversity of MAX phases. The crystal structure of (Ti, Zr, Hf)₂SC was determined by the Rietveld refinement of XRD, SEM, and atom-resolved TEM along with EDS elemental analysis. Phase evolution of X-ray diffraction patterns and TG/DSC curves were employed to reveal the synthesis mechanism of (Ti, Zr, Hf)₂SC from 2TiC–Zr–ZrC-2HfH₂-3.2FeS reactant system. The Vicker's hardness and the electrical resistivity of (Ti, Zr, Hf)₂SC were found higher than those of Ti₂SC, but the thermal conductivity of (Ti, Zr, Hf)₂SC was lower.