The role of Sn and Ti additions in the microstructure of Nb–18Si base alloys

The effects of Sn and Ti on the microstructure and hardness of the as cast and heat treated Nb–18Si–5Sn (NV9) and Nb–24Ti–18Si–5Sn (NV6) alloys were studied. In both alloys the phases present in the as cast and heat treated microstructures were Nb_ss, Nb₃Sn and Nb₅Si_3. In NV9, Sn suppressed the formation of Nb₃Si, partitioned in Nb_ss stronger than in Nb₅Si₃ and did not affect significantly the solubility of Si in the Nb_ss. In NV6, the solubility of Ti in (Nb,Ti)_ss increased in the presence of Sn, the concentration of Ti in Nb₅Si₃ was sensitive to cooling rate and the solubility of Sn in Nb₅Si₃ decreased as the concentration of Ti increased. The Ti controlled the partitioning of Si between (Nb,Ti)_ss and Nb₃Sn and was considered responsible for the macrosegregation of Si in the as cast ingot. The transformation of β to Nb₅Si₃ was enhanced by the synergy of Sn and Ti. The addition of Ti did not destabilise the Nb₃Sn. Silicon increased the hardness of Nb₃Sn significantly, Sn did not affect the hardness of Nb₅Si₃ and Ti reduced the hardness of Nb₃Sn and Nb₅Si₃ significantly. The hardness of NV9 and NV6 decreased and increased, respectively, by heat treatment. The reduction of the hardness of NV6-AC compared to NV9-AC is attributed to the strong effect of Ti on the hardness of Nb₃Sn and Nb₅Si₃.     

Effects of ternary alloying on mechano-synthesis and nano-crystal stability of an iron-silicon alloy

This paper reports the effects of ternary alloying additions Al, Cu and Nb to Fe₇₅Si₂₅ in high energy ball milling to produce nano-crystalline alloy powder, and its microstructural stability during subsequent high temperature annealing. It is shown that all additions generally retard grain growth up to some temperature. Nb appears to amorphise the alloy. The binary base alloy and Al containing alloy forms the DO₃ ordered structure at high temperatures accompanied by rapid grain growth. The Cu and Nb containing alloys precipitate Cu and Nb₂Fe at high temperatures but do not become ordered.     

High temperature strength of Nb3Al-base alloys

High temperature strength was investigated as a function of volume percent of Nb₃Al using ternary alloys with controlled microstructures of equiaxed Nb₃Al and Nb_ss (Nb solid solution) grains. Creep strength was examined in Mo-added Nb₃Al-base alloy with two types of different microstructures, equiaxed grains and directionally elongated grains. Mo addition increases high temperature strength at all the volume percents of Nb₃Al, while Ta addition is effective only at high volume percents of Nb₃Al. Ti addition decreases high temperature strength at all the volume percents of Nb₃Al. Mo-added Nb₃Al-base alloy consisting of directionally elongated grains has high creep strength compared to other refractory intermetallic alloys such as MoSi₂ alloy and (Cr,Mo)₃Si/(Cr,Mo)₅Si₃ alloy. Creep strength is decreased under a low applied stress in Mo-added Nb₃Al-base alloy with equiaxed grains probably because of easy grain boundary sliding. The obtained results are discussed in terms of solid solution strengthening of the constituent phases.     

Phase diagram of the Nb–Al–Si ternary system

A high-efficiency diffusion-multiple approach was employed to map the phase diagram of the Nb–Al–Si ternary system which is very valuable for the design of niobium silicide-based composites. These composites have high potential as a replacement for Ni-base superalloys for jet engine applications. Aluminum is an alloying element for these composites, thus the Nb–Al–Si phase diagram, especially solubility of Al in Nb₅Si₃, is important information for the composite design. An isothermal section at 1000 °C was constructed from the results obtained from a diffusion multiple using scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). A ternary phase Nb₃Si₅Al₂ was observed. The solubility data of Al in Nb₅Si₃ and NbSi₂ as well as Si solubility in Nb₃Al, Nb₂Al and NbAl₃ were obtained. The new isothermal section helps to judge the reliability of the existing literature results and to add new data to the Nb–Al–Si phase equilibria.     

激光3D打印方法制备Nb/SiC体系梯度材料的微观组织及反应机理

采用激光3D打印的方法制备了Nb/SiC体系梯度材料,获得了从纯金属铌逐渐过渡到40%Nb+60%SiC(体积分数)复合层的梯度材料. 通过扫描电子显微镜(SEM)、电子探针(EPMA)和X射线衍射仪(XRD)分析了梯度复合层的微观组织. 结果表明,层与层之间结合良好,激光熔敷过程中铌和SiC之间发生了反应,生成了Nb₅Si₃,Nb₂C,NbC和NbSi₂等二元化合物,并且随着SiC含量的逐渐增加,梯度材料内部产物呈现如下变化趋势:Nb+Nb₅Si₃+Nb₂C+NbC→Nb₅Si₃+NbSi₂+SiC+NbC→NbSi₂+SiC+NbC. 当SiC含量达到30%时,梯度复合层中残留金属铌消失,且开始出现残余的SiC颗粒,随着原始SiC比例的增加,复合层中不仅残余SiC的含量增加,而且粒度也逐渐增大.     

X-ray diffraction study on formation of ErNbO4 powder

The formation of ErNbO₄ powder, prepared by calcining an Er₂O₃ (50 mol%) and Nb₂O₅ (50 mol%) powder mixture at 1100 and 1600 °C for different durations, was investigated by using X-ray diffraction. The experimental results have displayed that although the solid-state reaction had started to some extent when the mixture was pre-calcined at 1100 °C for a duration of 13 h, the two original phases Er₂O₃ and Nb₂O₅ still dominated the mixture. When the duration of the calcination reaction was increased to 120 h at the same temperature, the resultant mixture experienced a nearly complete phase transformation. Accordingly, the ErNbO₄ phase was dominant phase in the mixture. Nevertheless, a small portion of the raw powder still existed in the mixture. When the calcining temperature was elevated to 1600 °C, ErNbO₄ powder with higher purity could be obtained for a relatively much shorter duration (only up to several tens of hours). A simple formation mechanism of ErNbO₄, an elevated-temperature-assisted solid-state chemical reaction: Er₂O₃+Nb₂O₅2ErNbO₄, is suggested. In addition, the present experimental results offer important evidence for the formation of the additional phase ErNbO₄ induced in Er:LiNbO₃ crystals by vapour transport equilibration (VTE) treatment.     

New ternary aluminides T5M2Al having W5Si3-type structure

Six new ternary aluminides having W₅Si₃-type structure were found. These are: Zr₅Sn₂Al, Hf₅Sn₂Al, Ti₅Pb₂Al, Zr₅Pb₂Al, Hf₅Pb₂Al and Nb₅Sn₂Al.     

The role of Fe and Ti additions in the microstructure of Nb–18Si–5Sn silicide-based alloys

The effects of Fe and Ti on the microstructure and hardness of the as cast and heat treated Nb–24Ti–18Si–5Fe–5Sn (NV8) and Nb–45Ti–15Si–5Fe–5Sn (NV4) alloys were studied. The microstructure of NV8-AC consisted of (Nb,Ti)_ss, (Nb,Ti)₃Sn, (Nb,Ti)₅Si₃, (Nb,Ti)₃Si, FeNb₄Si, and Fe₂Nb₃ and a Ti rich oxide. The microstructure of NV8-HT consisted of (Nb,Ti)₃Si, (Nb,Ti)₃Sn and the Ti rich oxide. In NV8 the formation of Nb₅Si₃ was destabilised, the stability of Nb₃Si was enhanced and the eutectic between Nb₅Si₃ and the solid solution was suppressed. The microstructure of NV4-AC contained Ti rich and Nb rich solid solutions, 3-1 and 5-3 silicides. The FeNb₄Si and Fe₂Nb₃ phases and the Ti rich oxide observed in NV8-AC were not formed in NV4-AC. The microstructure of NV4-HT consisted of (Ti,Nb)₃Sn, β(Ti,Nb)_ss, (Ti,Nb)₃Si and (Ti,Nb)₅Si₃ phases. The solubility of Fe in the Ti-based 3-1 silicide was significantly lower than in the Nb-based 3-1 silicide. The β(Ti,Nb)_ss + (Ti,Nb)₅Si₃ → (Ti,Nb)₃Si transformation was enhanced in NV4. The effects of Fe and Ti on the hardness of Nb–18Si–5Sn-based alloys, and of alloying elements on the hardness of Nb₃Sn, Ti₃Sn, and Nb₃Si, Ti₃Si, and Ti and Nb base 5-3 silicides are discussed.     

Crystal structure of the R3Si1.25Se7 (R = Pr, Nd and Sm) compounds

The crystal structure of new ternary R₃Si_1.25Se₇ (R = Pr, Nd and Sm) compounds (Dy₃Ge_1.25S₇ structure type, Pearson symbol hP22.5, space group P6₃, a = 1.05268 (3) nm, c = 0.60396 (3) nm, R_I = 0.0897 for Pr₃Si_1.25Se₇; a = 1.04760 (3) nm, c = 0.60268 (3) nm, R_I = 0.0891 for Nd₃Si_1.25Se₇; a = 1.04166 (6) nm, c = 0.59828 (6) nm for Sm₃Si_1.25Se₇) was determined using X-ray powder diffraction. The nearest neighbours of the R and Si atoms are exclusively Se atoms. The latter form distorted trigonal prisms around the R atoms, octahedra around the Si1 atoms and tetrahedra around the Si2 atoms. Tetrahedral surrounding exists for Se1 and Se3 atoms. Six neighbours surround every Se2 atom.     

Oxidation behavior of multiphase Mo5SiB2 （T2）-based alloys at high temperatures

Two MosSiB2 （T2）-based alloys with nominal compositions of Mo-12.5Si-25B and Mo-14Si-28B （molar fraction, %） were prepared in an arc-melting furnace, and their oxidation kinetics from 1 000 to 1 300 ℃ were studied. The microstructures of the alloys were characterized by X-ray diffractometry（XRD） and scanning electron microscopy（SEM） with energy dispersive spectroscopy （EDS）. The oxide scales of both alloys oxidized at 1 200 ℃ for l0 min, 2 h and 100 h were investigated by surface XRD and cross-sectional SEM-EDS. The results show that the matrix of both alloys consists of T2. The dispersions of Mo-12.5Si-25B alloy are Mo and Mo3Si, and the dispersions of Mo-14Si-28B alloy are MosSi3 （T1） and MoB. The cyclic oxidation kinetics data exhibit initial rapid mass loss followed by slow mass loss. The mass loss of Mo-12.5Si-25B alloy is much faster than that of Mo-14Si-28B alloy at 1 200 and 1 300 ~C. For l0 min exposure, both alloys form irregular and porous thin scale. For 2 h exposure, Mo-12.5Si-25B alloy forms irregular thin scale and the scale contains large cracks, and Mo-14Si-28B alloy forms sound and continuous scale. For 100 h exposure, Mo-12.5Si-25B and Mo-14Si-28B alloys form sound and continuous scale about 50-75 μm and 40-45 μm in thickness, respectively. The better oxidation resistance of Mo-14Si-28B alloy is due to a sound and continuous B-SiO2 layer formation in the early stage of oxidation.     

Crystal structures of new ternary rare earth silicides Sc3Pr2Si4, Sc1.26Pr3.74Si4 and Sc3.96Nd1.04Si4 with ordered and partially ordered rare earth sites

The crystal structures of three new ternary silicides Sc₃Pr₂Si₄, Sc_1.26Pr_3.74Si₄ and Sc_3.96Nd_1.04Si₄ were determined by single crystal X-ray diffraction. The title compounds crystallize with three different substitution derivatives of the Sm₅Ge₄ structure type (orthorhombic space group Pnma) containing various distributions of rare earth atoms on the three Sm sites. Crystal chemistry analysis shows that these distributions are controlled by the atomic size factor.     

Production of niobium carbide ceramic composites derived from polymer/filler mixtures: preliminary results

Studies have shown that Al₂O₃–NbC composites present a good potential to be used for metalworking. Manufacturing of composite ceramic material derived from polymer reactive filler mixtures were investigated. The present study reports the preliminary results of reaction bonded niobium carbide derived from polymer (polysiloxane), inert filler (Al₂O₃) and reactive filler (Nb). Niobium powder, alumina and polysiloxane mixtures were homogenized in a planetary ball milling and pressureless sintered in inert atmosphere at temperatures up to 1600 °C. Depending on the niobium content and pyrolysis conditions, ceramic materials with a porosity of 20–40%, a weight loss of 5–15%, a linear shrinkage of 2–4% and a flexural strength of maximum 80 MPa were obtained. X-ray diffraction (XRD) of a sample containing 60 wt% polymer + 40 wt% Nb showed the presence of new crystalline phases such as NbC, Nb₃Si and Nb₅Si₃.     

Neutron diffraction studies of LaMn2Ge2Si2 and LaMn2Si2 compounds: evidence of dominant antiferromagnetic components within the Mn planes

The magnetic properties of ThCr₂Si₂-type structure LaMn₂Ge₂ and LaMn₂Si₂ compounds have been reinvestigated by neutron diffraction experiments. The ferromagnetic ordering previously proposed to take place on the manganese sublattice is revised. At high temperature, both compounds are purely collinear antiferromagnets (not detected by magnetic measurements), characterized by a stacking of antiferromagnetic (001) Mn planes. Below T_c=310 and 325 K for LaMn₂Ge₂ and LaMn₂Si₂, respectively, both compounds exhibit an easy-axis ferromagnetic behaviour. However, the occurrence of a dominant antiferromagnetic component within the (001) Mn planes yields a conical magnetic structure for the germanide (cone semi-angle =58° at 2 K) and a canted magnetic structure for the silicide (φ=49°). At 2 K, the total Mn moments are about 3.0 and 2.4 μ_B for LaMn₂Ge₂ and LaMn₂Si₂, respectively. The results are compared with those of closely related RMnSi and RMnGe compounds and the magnetic properties of the ThCr₂Si₂-type structure RMn₂X₂ (XSi, Ge) compounds are discussed.     

Changes in the phase structure and magnetic characteristics of Gd5Si2Ge2 when alloyed with Mn

Gd₅Si₂Ge₂ parent compounds were alloyed with Mn in order to understand the underlying relation between the structural phases and the magnetic behavior of the pseudo ternary compounds formed. The alloying mechanism in Gd₅Si₂Ge₂ causes simultaneous substitution of the nonmagnetic Si and Ge atoms from the (Si + Ge) sublattice in equal amounts. No subsequent heat treatment was made on alloyed compounds. X-ray powder diffraction, magnetization versus temperature and isothermal magnetization measurements were carried out. X- ray diffraction patterns were used to qualitatively determine the existence of different structural phases in the alloys. It was observed that the starting, as-melted alloy with z = 0 has Gd₅Si₄-type orthorhombic structure at room temperature with traces of 1:1 stoichiometry phase which transforms totally to a Gd₅Si₂Ge₂-type monoclinic phase when heat treated. Similarly, increase in the Mn content leads to an increase in the monoclinic phase content of the originally orthorhombic compounds. Curie temperatures were determined from M(T) measurements and the magnetocaloric characterization was made using M(H) measurements by plotting the magnetic entropy change values against temperature. No giant magnetocaloric effect was observed for non heat treated samples.     

Direct synthesis of La9.33Si6O26 ultrafine powder via sol–gel self-combustion method

Single phase La_9.33Si₆O₂₆ ultrafine powder, as a kind of highly activated precursor to prepare medium-to-low temperature electrolyte for solid oxide fuel cells (SOFCs), has been successfully synthesized via a non-aqueous sol–gel and self-combustion approach from the starting materials: lanthanum nitrate (La(NO₃)₃·6H₂O), citric acid, ethylene glycol (EG), tetraethyl orthosilicate (TEOS) and ammonium nitrate. The details of gel's self-combustion were investigated by DTA–TG and the structural characterization of as-synthesized powder from self-combustion was performed by XRD and SEM. The results show that La_9.33Si₆O₂₆ single phase of apatite-type crystal structure can be directly synthesized by sol–gel self-combustion method without further calcinations on the condition that the molar ratio (R) of NO₃⁻ to citric acid and ethylene glycol being 6:1. Such powders composed of well-dispersed particles with an average size of 200 nm and a specific surface area of 5.54 m²/g. It can be sintered to 90% of its theoretical density at 1500 °C for 10 h, about 200 °C lower than the sintering temperature for the powder derived from traditional solid reactions. The sintered material has a thermal expansion coefficient of 9.2 × 10⁻⁶ K⁻¹ between room temperature and 800 °C.     

钎料中Ti元素含量对Si3N4/Si3N4接头界面结构及性能的影响

在900℃保温10 min的工艺条件下采用Ti含量不同的AgCu+Ti+nano-Si₃N₄复合钎料（AgCu_C）实现了Si₃N₄陶瓷自身的钎焊连接,并对不同Ti元素含量的接头界面组织及性能进行了分析.结果表明,接头典型界面结构为Si₃N₄/TiN+Ti₅Si₃/Ag_（s,s）+Cu_（s,s）+TiN_P+Ti₅Si_3P/TiN+Ti₅Si₃/Si₃N₄.随着复合钎料中Ti元素含量的增加,钎缝中团聚的纳米Si₃N₄颗粒逐渐减少,母材侧的反应层厚度逐渐增加后趋于稳定.当Ti元素含量高于4%时,钎缝中形成了类似于颗粒增强金属基复合材料的界面组织;当Ti元素含量达到10%时,有少量Ti-Cu金属间化合物在钎缝中形成;钎焊接头的抗剪强度随着Ti元素含量的增加而呈现先增加后降低的变化趋势,当Ti元素含量为6%时接头的抗剪强度达到最高值,即75 MPa.     

The crystal structure of the novel ternary silicide Sm4Pd4Si3

The crystal structure of the compound Sm₄Pd₄Si₃ was determined by the single-crystal method (KM-4 automatic diffractometer, Mo K radiation. Sm₄Pd₄Si₄ has the monoclinic Nd₄Rh₄Ge, type structure: space C2/c, mC44 (No. 15). a = 20.693(6), B = 5.584(1), C = 7.699(2) Å, β = 109.48(3)°, V = 838 Å, Z = 4, μ - 36.23 mm¹, R =_F = 0.0537, R _F = 0.0435 for 1652 unique reflections. The coordination numbers of samarium atoms are 17 and 18. For palladium and silicon atoms icosahedra and trigonal prisms with additional atoms are typical as coordination polyhedra. The structure of Sm₄Pd₄Si₄ is composed of fragments of the YPd₂Si and Y₁Rh₂Si₂ structure in a ratio 1:1.     

Phase relationships and crystallography in the pseudobinary system Gd5Si4---Gd5Ge4

A study of phase relationships and crystallography in the pseudobinary system Gd₅(Si_xGe_1−x)₄ revealed: (1) that both terminal binary compounds Gd₅Si₄ and Gd₅Ge₄ crystallize in the Sm₅Ge₄-type orthorhombic structure, and (2) the appearance of an intermediate (ternary) phase with a monoclinic crystal structure which is similar to both Gd₅Si₄ and Gd₅Ge₄. The formation of the monoclinic phase at 0.24≤x≤0.5 [between Gd₅(Si_0.96Ge_3.03)Gd₅(Si₁Ge₃) and Gd₅(Si₂Ge₂)] is probably due to the large difference in bonding characteristics of Si and Ge in the Gd₅Si₄-Gd₅Ge₄ pseudobinary system which limits the ability of the mutual substitution of Si for Ge and vice versa without a change of the crystal structure. For the composition Gd₅(Si₂Ge₂) the lattice parameters of the monoclinic structure (space group P112₁/a) are a=7.580865), b=14.802(1), c=7.7799(5)Å, γ=93.190(4)°. A distinct difference in the magnetic behaviors of the alloys from three different phase regions in this system follows the distinct difference in the crystal structures observed for the alloys from the three phase regions.     

Glass formation ability, structure and magnetocaloric effect of a heavy rare-earth bulk metallic glassy Gd55Co20Fe5Al20 alloy

The structure and magnetic entropy changes in melt-spun and annealed LaFe_11.8−xCo_xSi_1.2 (x = 0, 0.4 and 0.8) ribbons have been investigated. It is found that the value of T_c can be increased continuously up to 290 K for x = 0.8 and the phase transition, at T_c from paramagnetic to ferromagnetic, is changed from first- to second-order due to Co substitution. Large values of the magnetic entropy change are 31 and 13.5 J/kg K in the magnetic field change from 0 to 5 T at 201 K for the LaFe_11.8Si_1.2 and at 290 K for the LaFe₁₁Co_0.8Si_1.2 ribbons, respectively. The magnetic entropy change in the LaFe₁₁Co_0.8Si_1.2 ribbons is higher than that reported in the bulk counterpart and that of conventional MCE materials, such as pure Gd. The enhanced magnetic entropy change of ribbons compared to bulk counterpart is attributed to a more uniform microstructure and element distribution resulting from the high cooling rate by melt-spinning.