Investigation of thermal residual stresses during laser ablation of tantalum carbide coated graphite substrates using micro-Raman spectroscopy and COMSOL multiphysics

Laser ablation of high-temperature ceramic coatings results in thermal residual stresses due to which the coatings fail by cracking and debonding. Hence, the measurement of such residual stresses during laser ablation process holds utmost importance from the view of performance of coatings in extreme conditions. The present research aims at investigating the effect of laser parameters such as laser pulse energy, scanning speed and line spacing on thermal residual stresses induced in tantalum carbide-coated graphite substrates. Residual stresses were measured using micro-Raman spectroscopy and correlated with Raman peak shifts. Transient thermal analysis was performed using COMSOL Multiphysics to model the single ablated track and residual stresses were reported at low, moderate and high pulse energy regimes. The results showed that the initial laser conditions caused higher tensile residual stresses. Moderate pulse energy regime comprised higher compressive residual stresses due to off centre overlapping of the laser pulses. Higher pulse energy (250 μJ), higher scanning speed (1000 mm/s) and moderate line spacing (20 μm) caused accumulation of tensile residual stresses during the final stage of laser ablation. The deviation of experimental residual stresses from COMSOL numerical model was attributed to unaccounted additional stresses induced during thermal spraying process and deformation potentials in the numerical model.     

Stacking behavior of the close-packed Ta-atom planes and its effects on formation of “hybrid grains” in TaC0.66-0.7 ceramics

In previous works, it was found hard to synthesize “phase pure” ζ-Ta₄C_3-z at relatively low temperatures even by prolonged heating, though ζ-Ta₄C_3-z was believed stable till decomposition at ~2130°C. When the samples were subjected to TEM, vast richness of locally disordered structures in close relation with stacking of the close-pacted Ta-atom planes was observed. Although kinetic factors including diffusion of C atoms/vacancies and re-stacking of the Ta-atom planes explain the densely disordered structures, the richness of local disorders is a scenario that shows cohabitant of the cubic, rhombohedral, and hexagonal structures in a single grain, i.e. formation of a “hybrid grain” consisted of the three symmetries, indicating a transitional or intermediate stage before complete formation of the final phase of rhombohedral ζ-Ta₄C_3-z. This time tantalum carbide ceramics TaC_x with C:Ta atomic ratios x = 0.66 and 0.7 were prepared by reaction hot pressing of TaC and Ta powder mixtures. 5–30 mol% Cu/Ag additives and heat treatments were used to reproduce “hybrid grains” to facilitate further TEM and HRTEM observations on the disordered hybrid grains to argue for the transitional/intermediate stage. The cohabitant cubic, rhombohedral, and hexagonal structures in single grains may also help explain the difficulty in identification of the various phases by XRD in the transitional/intermediate stage of ζ-Ta₄C_3-z reaction. Microstructural evolution and fracture toughness of the composites were also investigated.     

Liquid gadolinium corrosion study of TaC coating on tantalum

Spectroscopic information of gadolinium isotopes is necessary to exploit the full potential of various isotopes in nuclear and medical applications. Container materials to handle liquid gadolinium during spectroscopic studies is an important aspect. Tantalum carbide (TaC) has excellent stability and also exhibits superior resistance to attack by various reactive actinide metals at high temperature for long durations. Tantalum crucibles with TaC coating were prepared and tested for compatibility against liquid gadolinium at 1673?K upto 14?h in vacuum. Optical microscopy and SEM/EDS investigations were done to evaluate the micro structural features of the coating and the liquid gadolinium attack. Experimental results show that TaC coating exhibits excellent corrosion resistance against liquid gadolinium at 1673?K.     

New environmental-friendly yellow pigments Y_(4-x)A_xMoO_(9+δ)(A =Ta,Tb)

A series of inorganic yellow pigments with general formula Y_(4-x)A_xMoO_(9+δ)(A = Ta, Tb), where x = 0,0.05,0.1,0.2, 0.4 for Ta and χ = 0, 0.005, 0.01.0.03, 0.05 for Tb,were synthesized by a conventional ceramic method at 1400 ℃ for 6 h in air. The samples were characterized by XRD,EDS,XPS,SEM,TG-DSC,UV-vis-NIR reflectance spectroscopy and CIE L*a*b* color scales. It is found that the substitution of A(A = Ta, Tb) for Y~(3+) in Y_4 MoO_9 decreases the NIR reflectance of the pigment samples, but the developed pigments Y_(4-x)A_xMoO_(9+δ)(A = Ta, Tb) still exhibit impressive NIR solar reflectance. The brighter yellow color of inorganic pigments Y_(4-x)A_xMoO_(9+δ)(A = Ta, Tb) is available when x is about 0.1 for Ta and 0.01 for Tb. The results make them a series of potential candidates as ecological yellow pigments because of their high reflectance, lightness, intense coloration and excellent thermal and chemical stability.     

Insight into the vacancy effects on mechanical and electronic properties of Tantalum Silicide

The effects of the vacancies on the structural stability, elastic constants, elastic moduli, brittle-to-ductile transition and electronic properties of Tantalum Silicide (TaSi₂) are investigated in detail by first-principles calculations. The values of vacancy formation energy confirm that the perfect TaSi₂ and TaSi₂ with different atomic vacancies can exhibit the structural stability at ground state. It is found that Ta atom vacancies are more stable than Si atom vacancies in TaSi₂ with vacancies. The elastic constants and elastic moduli describe the mechanical behavior for TaSi₂ and TaSi₂ with vacancies. The different atomic vacancies weaken the elastic stiffness for TaSi₂. But the values of B/G confirm that the brittle-to-ductile transition occurs with different atomic vacancies for TaSi₂. Although these vacancies make the shear and volume deformation resistance of TaSi₂ weaker, they obviously improve the brittle behavior of TaSi₂. The difference charge density and electronic structures are calculated to discuss and analyze the structural stability and mechanical properties for the perfect TaSi₂ and TaSi₂ with vacancies.     

Strengthened interfacial bonding and its effects on fracture mode of TaC ceramics with addition of B

TaC ceramics with 0-0.237 wt% B addition were prepared by hot pressing. The effect of B addition on the phase constitution, interfacial chemistry/bonding and mechanical properties of the TaC ceramics were investigated. Upon B addition, the elimination of O impurity and segregation of B at grain boundaries were evidenced, accompanied by an increase in bonding strength of the TaC grains, to result in a fracture mode change from intergranular to transgranular and a reduced fracture toughness. Addition of excessive B resulted in the formation of TaB₂ and C within TaC ceramics. Further, TaC-TaB₂-SiC composites were prepared by Si addition. Coherent bonding between TaB₂ and TaC was preserved in the TaC-TaB₂-SiC composites, and residual stresses due to thermal expansion mismatch of the different phases increased flexural strength and fracture toughness of the composites.     

A novel ultra-high-temperature oxidation protective MoSi2-TaSi2 ceramic coating for tantalum substrate

To protect refractory metal against oxidation at ultra-high temperatures, a MoSi₂-TaSi₂ ceramic coating was prepared on a pure tantalum (Ta) substrate using a novel three-step process, which included dip-coating with a molybdenum slurry, vacuum sintering, and halide-activated pack cementation (HAPC). The original coating had a MoSi₂-TaSi₂ double-layer structure from the surface to the substrate. After oxidation at 1700°C for 8 h in air, the coating exhibited a complex multi-layer structure composed of SiO₂-Mo₅Si₃-MoSi₂-(Mo,Ta)₅Si₃-TaSi₂-Ta₅Si₃ from the outer layer to the inner layer, due to the high-temperature phase transition and diffusion of Si and O. The coating effectively protected the Ta substrate at 1700°C for 12 h without failure, thereby demonstrating great improvement to its service life in an ultra-high-temperature aerobic environment. The protective effect was attributed to the integrity of the ceramic coating and the formation of a dense, uniform SiO₂ film that effectively lowered the inward oxygen diffusion rate.     

钽表面铜掺杂Ta2O5纳米棒的制备及抗菌性能研究

本实验采用两步水热法在钽基体表面制备出掺杂Cu_²⁺的Ta₂O₅纳米棒薄膜。采用XRD、SEM、XPS等方法分析了材料的物相和表面微观结构。用ICP检测了样品在生理盐水中离子析出浓度,最后通过平板计数法检验了不同含量铜掺杂Ta₂O₅薄膜的抗菌能力。结果表明,通过两步水热处理,在钽表面生成了简单斜方晶体结构的Ta₂O₅纳米棒阵列,Cu_²⁺的掺杂不会对纳米棒薄膜的微观形貌和物相造成显著影响。随时间的增加,掺铜薄膜的铜离子析出速率逐渐趋于平缓。平板计数法表明,Cu_²⁺ 的掺杂量达到2.68At%时,铜掺杂Ta₂O₅纳米棒薄膜的抗菌性能最好,抗菌率达99.2%。     

电弧离子沉积钽膜及微结构研究

目的研究电弧离子沉积钽膜的沉积工艺及微观结构,分析钽膜生长机理。方法采用电弧离子沉积法在石墨基体上沉积钽膜,研究了沉积工艺(如弧电流、负偏压等参数)对钽膜的物相组成、沉积速率、表面形貌的影响。结果电弧离子沉积钽膜的物相由α-Ta相和极少量β-Ta相组成。弧电流、负偏压、靶间距等沉积参数对钽膜厚度、沉积速率和膜-基结合力的影响很大,在弧电流为220 A、负偏压为300 V、靶间距为200 mm时,钽膜沉积速率为0.1μm/min,沉积速率适宜,膜-基结合力达到69 N,结合力高。钽膜厚度均匀,在靠近基体侧形成了晶粒细小、组织致密的过渡层,厚度约0.6~0.9μm,其余为细小柱状晶结构。钽膜表面颗粒尺寸随负偏压的升高而减小,负偏压为300 V时,颗粒尺寸细小均匀(仅3~5μm),钽膜表面无细小孔隙和裂纹。结论电弧离子沉积法可以在石墨基体上沉积出组织致密、厚度均匀且膜-基结合力高的钽膜。沉积初期主要通过沉积、移动、扩散等过程形成稳定核,随着沉积时间的延长,稳定核逐渐长大成岛,并在三维方向以岛状生长形成连续膜,为典型岛状生长模式。