电阻焊接技术制备Nb3Sn-NbTi 混合超导接头

在强磁场超导磁体应用中,特别是具有高稳定度高场超导磁体,具有极低电阻的超导接头发挥着重要作用。通过电阻焊接方法制备了Nb₃Sn 和NbTi的异种材料超导接头。首先通过烧结法制备了Nb₃Sn的超导接头,然后通过电阻焊接将Nb₃Sn超导接头与NbTi超导体焊接成型。分析了Nb₃Sn超导接头制备过程中Nb₃Sn的微观组织结构和相变。利用无损检测CT对接头结构进行三维重构,分析了Nb₃Sn 和NbTi超导接头内部的缺陷和2种不同材料间的微观连接状态。最后,在背景磁场下对超导接头的电阻性能进行了测试和研究。结果表明,与传统超导焊料制备的超导接头相比,电阻焊接制备的超导接头显示出良好的耐磁场性能,在1.5 T背景磁场下具有较低的电阻值。     

A study of the effects of Hf and Sn additions on the microstructure of Nbss/Nb5Si3 based in situ composites

The phase stability and microstructures of Nb_ss/Nb₅Si₃ based in situ composites alloyed with Hf and Sn have been investigated. The Nb₅Si₃ silicide in the β and γ forms was the primary phase in the Nb–24Ti–18Si–5Cr–5Al–5Hf–2Mo and Nb–24Ti–18Si–5Cr–5Al–5Hf–5Sn–2Mo alloys studied in this work. In the as cast alloys, the formation of the Nb₃Si phase was suppressed by the addition of Hf. The structure of the Nb₅Si₃ phase was mainly affected by the Hf addition. The Hf-rich regions in the 5–3 silicide probably corresponded to the γNb₅Si₃. This silicide was stable up to 1500 °C in the presence of Hf. The Ti solubility in the Hf-rich Nb₅Si₃ was higher than that in the Nb₅Si₃. The Si concentration in the Nb₅Si₃ phase increased slightly and shifted closer to its stoichiometric composition by the addition of Hf. The alloying elements Hf and Sn preferentially substituted for Nb in the Nb₅Si₃ and Nb_ss, respectively. The Sn addition had a significant effect on the niobium solid solution leading to the formation of Sn-rich and Sn-poor parts in the solid solution in the as cast microstructure. In the presence of Sn, the Si solubility in Nb_ss increased considerably whilst the Cr solubility decreased. As a result of the decrease of the Cr solubility in Nb_ss, the Sn addition promoted the formation of Si-rich C14 Cr₂Nb Laves phase and stabilised this phase at 1300 °C. TiN and HfO₂ were formed below the surfaces of the heat treated alloys.     

Thermodynamic assessment of the Nb-Ge system

The Nb-Ge binary system has been thermodynamically assessed using the CALPHAD (Calculation of Phase Diagrams) approach on the basis of the experimental data of both the phase equilibria and the thermochemical properties. The reasonable models were constructed for all the phases of the system. The liquid and the terminal solid solution phases, Bcc-(Nb) and Diamond-(Ge), were described as the substitutional solutions with Redlich-Kister polynomials for the expressions of the excess Gibbs free energies. The intermediate phases (Nb₃Ge), (Nb₅Ge₃), (Nb₃Ge₂) and (NbGe₂) with homogeneity ranges were treated as the sublattice models Nb_0.75(Ge,Nb,Va)_0.25, Nb_0.5(Nb,Ge)_0.125(Ge,Va)_0.375, (Nb,Ge)_0.222(Nb,Ge)_0.333Nb_0.333(Ge,Va)_0.111 and (Nb,Ge)_0.333(Nb,Ge)_0.667 respectively based on their structure features of atom arrangements. A set of self-consistent thermodynamic parameters for the Nb-Ge system was obtained. Using the present thermodynamic data, the calculation results can reproduce the experimental data well.     

Phase equilibria of the Sn–Ag–Ni ternary system and interfacial reactions at the Sn–Ag/Ni joints

There are no previous phase equilibria studies of the Sn–Ag–Ni ternary system, even though the phase equilibria information is important for the electronic industry. The isothermal section of the Sn–Ag–Ni ternary system at 240 °C has been determined in this study both by experimental examination and thermodynamic calculation. Experimental results show no existence of ternary compounds in the Sn–Ag–Ni system, and all the constituent binary compounds have very limited solubilities of the ternary elements. The binary Ni₃Sn₂ phase is very stable and is in equilibrium with most of the phases, Ag₃Sn, ζ-Ag₄Sn, Ag, Ni₃Sn₄ and Ni₃Sn phases. A preliminary thermodynamic model of the ternary system is developed based on the models of the three binary constituent systems without introducing any ternary interaction parameters. This ternary thermodynamic model is used with a commercial software Pandat to calculate the Sn–Ag–Ni 240 °C isothermal section. The phase relationships determined by calculation are consistent with those determined experimentally. Besides phase equilibria determination, the interfacial reactions between the Sn–Ag alloys with Ni substrate are investigated at 240, 300 and 400 °C, respectively. It is found that the phase formations in the Sn–3.5wt%Ag/Ni couples are very similar to those in the Sn/Ni couples.     

New data on phase equilibria in the Nb-rich region of the Nb-B system

The currently accepted Nb-B phase diagram shows Nb_ss (solid solution), Nb₃B₂, NbB, Nb₅B₆, Nb₃B₄, NbB₂, B, and liquid L as the stable phases in this system. There is a general agreement in the literature about the stability of the NbB, Nb₃B₄, and NbB₂ phases. However, the stability of Nb₃B₂, Nb₅B₆, and Nb₂B₃ phases is arguable. The aim of this work was to reevaluate the phase equilibria in the Nb-rich region (0-50at.% B) of the Nb-B system. The alloys were arc melted from high purity materials and heat-treated at 1700 °C under high vacuum. The samples were characterized by scanning electron microscopy/back-scattered electron image (SEM/BSE) and x-ray diffraction (XRD). The most important findings were: (1) no liquid formation was observed during heat-treatments of the alloys at 1700 °C; (2) the eutectic reaction in the Nb-rich region is L ↔ Nb_ss+ NbB with liquid eutectic composition close to 16 at.%B; and (3) the Nb₃B₂-phase is formed through the peritectoid reaction Nb_ss+ NbB ↔ Nb₃B₂. These results support the phase diagram proposed by Rudy [1969 Rud] for the Nb-rich region, which is not in agreement with the currently accepted Nb-B phase diagram.     

New data on phase equilibria in the Nb-rich region of the Nb-B system

The currently accepted Nb-B phase diagram shows Nb_ss (solid solution), Nb₃B₂, NbB, Nb₅B₆, Nb₃B₄, NbB₂, B, and liquid L as the stable phases in this system. There is a general agreement in the literature about the stability of the NbB, Nb₃B₄, and NbB₂ phases. However, the stability of Nb₃B₂, Nb₅B₆, and Nb₂B₃ phases is arguable. The aim of this work was to reevaluate the phase equilibria in the Nb-rich region (0-50at.% B) of the Nb-B system. The alloys were arc melted from high purity materials and heat-treated at 1700 °C under high vacuum. The samples were characterized by scanning electron microscopy/back-scattered electron image (SEM/BSE) and x-ray diffraction (XRD). The most important findings were: (1) no liquid formation was observed during heat-treatments of the alloys at 1700 °C; (2) the eutectic reaction in the Nb-rich region is L ↔ Nb_ss+ NbB with liquid eutectic composition close to 16 at.%B; and (3) the Nb₃B₂-phase is formed through the peritectoid reaction Nb_ss+ NbB ↔ Nb₃B₂. These results support the phase diagram proposed by Rudy [1969 Rud] for the Nb-rich region, which is not in agreement with the currently accepted Nb-B phase diagram.     

Effect of Sn on synthesis of nanocrystalline Ti-based alloy with fcc structure

The effect of the amount of Sn on the formation of fcc phase in Ti−13Ta−xSn (x=3, 6, 9 and 12, at.%) alloys was studied. The alloys were synthesized by mechanical alloying using a planetary mill, jar and balls of stabilized yttrium. Using Rietveld refinement, it was found that the obtained fcc phase has crystallite size smaller than 10 nm and microstrain larger than 10⁻³. Both conditions are required to form an fcc phase in Ti-based alloys. For all samples, the microstructure of the fcc phase consists of equiaxial crystallites with sizes smaller than 10 nm. The largest presence of fcc phase in the studied Ti alloy was found with 6 at.% Sn, because this alloy exhibits the largest microstrain (1.5×10⁻²) and crystallite size of 6.5 nm. Experimental data reveal that a solid solution and an amorphous phase were formed during milling. The necessary conditions to promote the formation of solid solution and amorphous phases were determined using thermodynamic calculations. When the amount of Sn increases, the energy required to form an amorphous phase varies from approximately 10 to approximately −5 kJ/mol for 3 and 12 at.% Sn, respectively. The thermodynamic calculations are in agreement with XRD patterns analysis and HRTEM results.     

Thermally induced crystallization of Fe73.5Cu1Nb3Si15.5B7 amorphous alloy

Thermally induced crystallization of Fe_73.5Cu₁Nb₃Si_15.5B₇ amorphous alloy occurs in two well-separated stages: the first, around 475 °C, corresponds to formation of α-Fe(Si)/Fe₃Si and Fe₂B phases from the amorphous matrix, while the second, around 625 °C, corresponds to formation of Fe₁₆Nb₆Si₇ and Fe₂Si phases out of the already formed α-Fe(Si)/Fe₃Si phase. Mössbauer spectroscopy suggests that the initial crystallization occurs through formation of several intermediate phases leading to the formation of stable α-Fe(Si)/Fe₃Si and Fe₂B phases, as well as formation of smaller amounts of Fe₁₆Nb₆Si₇ phase. X-ray diffraction (XRD) and electron microscopy suggest that the presence of Cu and Nb, as well as relatively high Si content in the as-prepared alloy causes inhibition of crystal growth at annealing temperatures below 625 °C, meaning that coalescence of smaller crystalline grains is the principal mechanism of crystal growth at higher annealing temperatures. The second stage of crystallization, at higher temperatures, is characterized by appearance of Fe₂Si phase and a significant increase in phase content of Fe₁₆Nb₆Si₇ phase. Kinetic and thermodynamic parameters for individual steps of crystallization suggest that the steps which occur in the same temperature region share some similarities in mechanism. This is further supported by investigation of dimensionality of crystal growth of individual phases, using both Matusita–Sakka method of analysis of DSC data and texture analysis using XRD data.     

A study of the microstructures and oxidation of Nb–Si–Cr–Al–Mo in situ composites alloyed with Ti,Hf and Sn

The effects of alloying on the microstructures, solidification path, phase stability and oxidation kinetics of Nb_ss/Nb₅Si₃ base in situ composites of the Nb–Ti–Si–Al–Cr–Mo–Hf–Sn system have been investigated in this study. All the studied alloys are classified as hyper-eutectic Nb silicide base in situ composites and have lower densities compared to nickel-based superalloys. The Nb₃Si silicide formed in the Hf-free alloys and transformed to Nb_ss and αNb₅Si₃ during heat treatment at 1500 °C. This transformation was enhanced by the addition of Ti. The Nb_ss and Nb₅Si₃ were the equilibrium phases in the microstructures of the Hf-free alloys. In the presence of Ti, the βNb₅Si₃ only partially transformed to αNb₅Si₃, suggesting that Ti stabilises the βNb₅Si₃ to lower temperatures (at least to 1300 °C). Furthermore, alloying with Hf stabilised the hexagonal γNb₅Si₃ (Mn₅Si₃-type) silicide in the Hf-containing alloys. The addition of Sn promoted the formation of the Si-rich C14 Laves phase and stabilised it at 1300 °C. This is attributed to the Sn addition decreasing the solubility of Cr in the Nb_ss of the Nb–Ti–Si–Al–Cr–Mo–Hf–Sn system whilst increasing the Si solubility. The Si solubility in the C14 Laves phase was in the range ∼6.6 to 10.5 at%. The lattice parameter of the Nb_ss in each alloy increased after heat treatment signifying the redistribution of solutes between the Nb_ss and the intermetallic phases. The oxidation resistance of the alloys at 800 °C and 1200 °C increased significantly by alloying with Ti and Sn. Pest oxidation behaviour was exhibited by the Nb–18Si–5Al–5Cr–5Mo (as cast), Nb–24Ti–18Si–5Al–5Cr–5Mo (as cast), Nb–24Ti–18Si–5Al–5Cr–2Mo (heat treated) and Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf (heat treated) alloys at 800 °C. Pesting was eliminated in the alloy Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf–5Sn at 800 °C, indicating that the addition of Sn plays an important role in controlling the pest oxidation behaviour at intermediate temperatures. The oxidation behaviour of all the alloys at 800 °C and 1200 °C was controlled by the oxidation of the Nb_ss and was sensitive to the area fraction of Nb_ss in the alloy.     

A thermo-gravimetric and microstructural study of the oxidation of Nbss/Nb5Si3-based in situ composites with Sn addition

The effect of Sn addition on the oxidation of the Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf–5Sn (at.%) alloy (JG6) in the as cast (AC) and heat treated (HT) conditions was studied at 800 °C and 1200 °C in static air using thermo-gravimetry and microstructural analysis. The oxidation kinetics, morphology and microstructure of the oxide scale and the microstructure of the bulk of the oxidised alloy were investigated. Oxidation occurred by inward oxygen anion diffusion. The oxidation of JG6 at 800 °C and 1200 °C is compared with the oxidation of Sn-free Nb–Ti–Si–Cr–Al–Mo–Hf alloys and is found to have been improved by the addition of Sn. At 800 °C pest oxidation, which was exhibited by the heat treated Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf alloy (JG4-HT), was eliminated by alloying with 5 at.% Sn. The elimination of pesting at 800 °C is attributed to the nature of the Nb solid solution in the alloy which consists of Sn-rich, Si-rich and Ti lean solid solution usually surrounded by Sn-poor, Si-poor and Ti-rich solid solution. The oxide scales that formed at 1200 °C on JG6 did not separate from the base metal and consisted of Nb₂O₅, TiO₂, SiO₂, HfO₂ and TiNb₂O₇. TiN, instead of TiO₂, and the (Nb,Ti)₅(Sn_1−xSi_x)₃ phase, which is considered as a ternary phase based on Nb₅Sn₂Si, are formed in the diffusion zone of the alloys JG6-AC and JG6-HT after oxidation at 1200 °C. The formation of these phases in the oxidised alloys JG6-AC and JG6-HT controlled the penetration of oxygen into the base material. The better oxidation performance of JG6-AC compared to JG6-HT at 1200 °C is attributed to the formation of Nb₃Sn in the former. It is suggested that the presence of the Sn-poor, Si-poor and Ti-rich Nb_ss in the microstructure is a key to the formation of the Nb₃Sn phase at the scale/diffusion zone interface in the JG6-AC oxidised at 1200 °C.     

The synthesis of nanocrystalline Ni75Nb12B13 alloys by high energy ball milling of elemental components

Ni₇₅Nb₁₂B₁₃ alloys were synthesized by mechanical alloying (MA) of individual Ni, Nb and B components. X-ray investigation showed the formation of Ni (Nb, B) solid solution and amorphous phase at the intermediate stage of milling. Metastable phases formed by MA turned into Ni (Nb), Ni₂₁Nb₂B₆ and Ni₃Nb stable phases during heating up to 720 °C. The exothermal effects on DSC curves were caused with these processes. The disintegration of Ni (Nb, B) solid solution and crystallization of an amorphous phase resulted in the stable phases formation during the milling prolongation as well as after thermal treatment.     

Isothermal Section of the Ti-Nb-Sn Ternary System at 700 °C

The phase equilibrium of annealed Ti-Nb-Sn alloys was investigated by means of x-ray diffraction, scanning electron microscopy and electron probe microanalysis. Isothermal section of the Ti-Nb-Sn ternary system below 50 at.% Sn at 700 °C was constructed according to the examinational analysis. The compositions of α-Ti, β(Ti, Nb), Ti₃Sn, Nb₃Sn and Ti₃Nb₃Sn₂ were confirmed. The solubility of Sn in β(Ti, Nb) region reaches up to 9.2 at.%, which is a relative large solubility, and that in α-Ti is small. The solubility in Ti₃Sn reaches up to 14.9 at.% Nb, and that of Nb₃Sn is 21.5 at.% Ti. The solubility range of Nb and Sn in Ti₃Nb₃Sn₂ is approximately 26.2-39.5 and 22.6-26.6 at.%, respectively.     

Ab-Initio Calculations and Thermodynamic Description of the Yb-Cd and Yb-Sn Systems

The phase diagrams of Yb-Cd and Yb-Sn systems were calculated by coupling the CALPHAD method and ab initio calculations. The enthalpies of formation of nine binary compounds (YbCd, αYbCd₂, Yb₂Sn, αYb₅Sn₃, βYb₅Sn₃, Yb₅Sn₄, YbSn, Yb₃Sn₅ and YbSn₃) were determined via ab initio density functional theory using the VASP code. Based on the available experimental data and the computed enthalpies of formation of the compounds, a thermodynamic assessment was carried out. The liquid phases and the γYb(bcc) and βYb(fcc) solid solutions were described by the Redlich–Kister polynomial model, while all the intermetallic compounds were treated as stoichiometric phases. A set of optimized model parameters were obtained for Yb-Cd and Yb-Sn systems. The calculated phase diagrams of these binary systems and their thermodynamic properties are presented and compared with the experimental data.     

Thermodynamic Assessment of the Ti-Ir System

The thermodynamic assessment of the binary system Ti-Ir has been carried out by modeling the Gibbs energy of all individual phases using the calculation of phase diagrams approach based on the available literature data including the phase equilibria and thermodynamic properties. The Gibbs free energies of the liquid, bcc, fcc and hcp phases were described by the subregular solution model with Redlich-Kister formula, and those of the intermetallic compounds (Ti₃Ir, γTiIr, βTiIr and TiIr₃) in the Ti-Ir binary system were described by the two-sublattice model. The calculations are in good agreement with the literature data on both phase equilibria and thermodynamic properties in the Ti-Ir system.     

Influence of diffusion annealing on residual resistivity of Nb3Sn-based chromium-plated strands obtained by a bronze process

The residual resistivity ratio, R₂₇₃/R₂₀, is an important parameter for multifilament superconductors (strands) based on Nb₃Sn that are used to manufature cables of magnetic systems. High values of RRR impart stability to the cable with regard to thermal excitations. Nb₃Sn strands for magnetic system of the International Thermonuclear Experimental Reactor are manufactured from high purity oxygen-free copper with RRR > 250 units; however, after extended diffusion annealing intended to form superconducting phase Nb₃Sn, the residual resistivity ratio values of the strands decrease. This work investigates the influence of diffusion annealing for 55?C200 h during the final stage at 650°C on the residual resistivity ratio of chromium-plated Nb₃Sn strands. The contents of chromium and oxygen have been analyzed using X-ray spectral microanalysis of the strand surface and peripheral copper layers. Mass spectrometry with inductively coupled plasma (ICP mass spectrometry) has been used to determine the total chromium content in the copper shell. The influence of chromium and oxygen diffusion from coating during annealing at 650°C on the residual resistivity ratio has been demonstrated. Based on the data of ICP mass spectrometry, the depth of the penetration of chromium in a copper shell has been assessed.     

Thermodynamic assessment of the Gd–Sb system

A thermodynamic assessment of the binary Gd–Sb system was performed through the CALPHAD approach (CALculation of PHAse Diagram) based on the evaluation of all phase diagram data and available thermodynamic data in the literature. The liquid, hcp-A3 (αGd) and bcc-A2 (βGd) phases were described by a substitutional solution model. All the intermediate phases, Gd₅Sb₃, Gd₄Sb₃, βGdSb, αGdSb and Gd₁₆Sb₃₉, were treated as stoichiometric compounds. A set of self-consistent thermodynamic parameters of the Gd–Sb system has been obtained. A good agreement is obtained between the experimental and the calculated phase diagrams.     

Effect of annealing regimes on the structure of Nb<Subscript>3</Subscript>Sn superconducting layers in composites with internal tin sources

The structure and morphology of Nb₃Sn superconducting layers that are formed in multifilamentary conductors with distributed tin sources in different diffusion-annealing regimes have been investigated by transmission and scanning electron microscopy. The composites studied differ in the design (the number of Nb filaments and their final diameter, initial tin concentration, the presence of reinforcing Cu?Nb inserts in the stabilizing copper sheath, alloying of the copper matrix with manganese) and diffusion-annealing regime. In all of the conductors, superconducting layers arise with zones of different morphologies, namely, columnar grains are present along with fine equiaxed Nb₃Sn grains. Compared to Nb₃Sn-based conductors produced by the so-called bronze method, composites with internal tin layers are characterized by coarser Nb₃Sn grains with a greater spread of sizes. Nevertheless, the critical current density J_c of these latter can reach values 2276 A/mm² due to a higher Sn concentration in the superconducting phase and a larger relative amount of this phase in the conductor. Lower values of the critical current density (J_c = 850 А/mm²) were obtained in the conductor with a reduced tin concentration in the matrix and an enhanced number of Nb filaments with a smaller diameter, in which coarser Nb₃Sn grains with a wide spread of sizes and wider zones of columnar grains are formed.