Review on the fabrication techniques of A-15 superconductors

This Paper reviews the present state-of-the-art of preparing multifilamentary A-15 superconductors. The most common types, Nb₃Sn and V₃Ga, are presently produced by the so-called bronze process. The highest J_c (overall) = 3.5 × 10⁴ cm⁻² (at 15 T and 4.2 K), obtained for bronze processed Nb₃Sn composites through Ti addition, has pushed the useful limit of this material from 12 to 16 T. Similarly a J_c of 1 × 10⁵ A cm⁻² (at 20 T and 4.2 K) for the A-15 V₃Ga has been attained through elemental additions to the core and the bronze matrix. To circumvent the problem of work-hardening of the bronze, several variations of the bronze process such as the internal tin method, the Nb tube method, the ECN method and jelly roll method have also been upgraded to commercial scale. Composites of Nb₃Sn and V₃Ga have been recently produced successfully on a laboratory scale following the so called in situ technique. These composites not only have a superior J_c value but display improved strain tolerance due to the ultrafine nature of the filaments formed in situ. In situ filamentary A-15 composites with high J_c values have also been produced by following the powder metallurgy technique. The infiltration technique has been found useful for producing high field Nb₃(Al, Ge), Nb₃(Al, Si) and Nb₃Sn composite conductors with high ε_irr. Superior materials such as Nb₃Al, Nb₃Ga and Nb₃(Al,Ge) with high J_c performance have been synthesized using the laser beam technique. Nb₃Ge tapes with T_c = 21 K and J_c = 10⁵ A cm⁻² (at 18 T and 4.2 K) have been successfully produced on a laboratory scale by following the CVD technique. Thus, there are several available options from which to choose a technique for fabricating filamentary composites of ubiquitous Nb₃Sn and V₃Ga. New techniques for fabricating superior materials like Nb₃Al, Nb₃Ga, Nb₃Ge and Nb₃(Al, Ge) also seem to be at an advanced stage of development.     

Superconductivity and Mössbauer effect of Nb3Sn produced by Sn implantation

We have implanted Sn, Ge, and Si into Nb films. The resulting Nb-Sn compounds and their annealing behavior have been analyzed by the Mössbauer effect and compared to samples obtained by diffusion of Sn into Nb foils. Mössbauer spectra show that Nb₃Sn is obtained just by implantation, but with a T _cof only 5 K. The 925°C annealing temperature necessary to form the A15 structure with long-range order of Nb chains and T _cvalues up to 17.8 K is at least 100 °C higher in implanted samples than in samples prepared by diffusion of Sn into Nb. This is explained in terms of implantation-induced lattice defects. The metastable A15 phases of Nb₃Ge and Nb₃Si could not be formed by Ge or Si implantation, regardless of target or annealing temperature. It is suggested that the high-energy ions only form phases stable at high temperatures and with low T _cvalues.On leave from North Dakota State University, Fargo, North Dakota.     

Superconductivity of Nb1−x Mg x B2: Impact of Stretched c-Parameter

We have performed a systematic study on the occurrence of superconductivity in Nb_1?x Mg _x B₂ (0.0≤x≤0.40). X-ray diffraction and magnetization measurements are carried out to determine the changes in lattice parameters, superconducting transition temperature (T _c ) and critical field (H _c1). The substitution of Mg at Nb site results in considerable stretching of c-parameter with only a slight change in a parameter. Rietveld analysis on X-ray diffraction patterns gives a=3.11 Å and c=3.26 Å for pure NbB₂ while a=3.10 Å and c=3.32 Å for Nb_0.60Mg_0.40B₂. This increased c-parameter introduces superconductivity in niobium diboride. Magnetization measurements though indicate the absence of superconductivity in NbB₂, the same shows a clear diamagnetic signal at about 10 K for Nb_0.60Mg_0.40B₂ sample. The magnetization M(H) plots exhibit weak superconductivity like hysteresis loops. The stretching of c-parameter from around 3.26 to 3.32 i.e. by 0.06 cannot be explained solely by substitution of Nb by Mg in the lattice. It seems that some Nb deficiencies are introduced in the Nb_1?x Mg _x B₂ as Mg is not substituted completely at the vacant Nb sites. This could be seen from XRD results, where one can clearly notice the presence of small amount of MgO in Nb_1?x Mg _x B₂ samples.     

Projected upper limits to the critical current density of superconducting Nb3Ge, Nb3Sn, and V3Ga

Applying a phenomenological theory of flux pinning developed by Kramer,¹ where the ultimate critical current density (J_c) of a superconductor is determined by plastic shearing of the flux lattice, approximate upper limits are put on J_c for Nb₃Ge, Nb₃Sn, and V₃Ga. At 4.2 K and for magnetic fields H < 100 kG, the J_c of V₃Ga is greater than that of either Nb₃Ge or Nb₃Sn and Nb₃Sn has somewhat higher values than Nb₃Ge. Above 200 kG Nb₃Ge has the highest J_c due to its having the highest upper critical field and at 14 K or above it probably has the largest J_c at all field values.     

Superconductivity in dilute Cu-Nb-Sn alloys containing Nb3Sn precipitates

The dilute Cu-Nb-Sn alloys containing small amounts of Nb and Sn less than 1 at % exhibited superconductivity after quenching from the liquid state and ageing. The best superconducting properties ( andJ _c=130 A cm^–2) in a Cu-0.30 at % Nb 0.15 at % Sn alloy were obtained when the sample was aged at 550° C for 384 h. This sample exhibited a structure of fine Nb₃Sn precipitates of 200 to 500Å diameter distributed homogeneously in the Cu matrix, and therefore it was concluded that superconductivity in these alloys resulted from the proximity effect of Nb₃Sn particles. In spite of the similar structure obtained by ageing at 800° C, the Cu-Nb-Sn alloys showed inferior superconducting properties compared to the Cu-0.4 at % Nb alloy and this would be explained qualitatively by the difference in the mean free path in the two alloys.     

Effects of H2/Cl2 ratio on CVD synthesis of superconducting Nb3Ge tapes

This Paper investigates the effects of H₂/Cl₂ ratio, R_g, [H₂/Cl₂(Nb,Ge)] in chemical vapour deposition processes on the synthesis and superconducting properties of Nb₃Ge tapes. Critical temperature, T_c, critical current density, J_c, and grain size of A15 Nb₃Ge vary considerably with the gas ratio, R_g. The lattice parameter of A15 Nb₃Ge and its volume ratio to Ge-rich Nb₅Ge₃ phases are also dependent on R_g. The volume ratio of A15 Nb₃Ge to Nb₅Ge₃ increases with increasing R_g, while the grain size of Nb₃Ge considerably decreases. The highest T_c, 19 K, (mid-point) was obtained for Nb₃Ge tape where the A15 Nb₃Ge compound coexisted with a small amount of tetragonal or hexagonal Nb₅Ge₃ compounds. The largest J_c was ≈ 4.5 × 10⁸ A m⁻² at 16 T and 4.2 K.     

The study on the critical temperature, composition, and microstresses in a Nb3Sn layer

Monofilamentary Nb₃Sn wires of large diameter with niobium tube, which were obtained by the method of solid-phase diffusion, are well suited for the study of the distribution of the critical temperature T_c in Nb₃Sn layers. Three regions with different gradients of Sn and Nb concentration and different Cu content can be distinguished in Nb₃Sn layer. In the central part of the layer, the Sn content comprises 24.5 at.% and the gradient of Sn concentration is negligibly small. Measurements on specimens of 1.2 mm in diameter with a slit cut along the cylinder generatrix showed that the critical temperature of the Nb₃Sn region adjacent to Cu(Sn) bronze is lower than the critical temperature of the central part of the layer. Fluctuations of T_c in the central part of the layer exceed the change of T_c related to the gradient of the Sn concentration, which is very small. These fluctuations spread both the R(T) curve and the high-temperature part of the temperature transition registered by the inductive method.     

Superconducting properties and microstructure of crystallized Hf-Nb-Si and Hf-V-Si amorphous alloys

Amorphous Hf-Nb-Si and Hf-V-Si alloys have been produced by rapidly quenching the melts using a melt-spinning technique. The silicon content in the amorphous alloys was limited to 14 to 20 at% and the niobium or vanadium content was limited to 0 to 45 at% and 0 to 35 at%, respectively. These amorphous alloys did not show any superconducting transition down to liquid helium temperature (4.2 K). However, a transition was detected above 4.2 K after inducing crystallization in these alloys by annealing at appropriate temperatures. The highest superconducting transition temperatures, T _c, attained were 8.9 K for the Hf₄₅Nb₄₀Si₁₅ alloy annealed for 1 h at 1273 K and 6.7 K for the Hf₅₀V₃₅Si₁₅ alloy annealed for 1 h at 1173 K. The upper critical magnetic field, H _c2, at 4.2 K and the critical current density, J _c, at zero applied field and 4.2 K were about 5.1×10⁶A m^–1 (6.4 T) and more than 1×10⁴ A cm^–2 for the Hf₄₅Nb₄₀Si₁₅ alloy and more than 8.0×10⁶ A m^–1 (10 T) and 5×10³ A cm^–2 for the Hf₅₀V₃₅Si₁₅ alloy. Detailed transmission electron microscopic studies of the annealed structure of these amorphous alloys established that, after crystallization, these alloys contain a body-centred cubic -Hf(Nb) solid solution and body-centred tetragonal Nb₃Si phases in the Hf₄₅Nb₄₀Si₁₅ alloy and hexagonal Hf₅Si₃, face-centred cubic HfV₂ and cubic V₃Si phases in the Hf₅₀V₃₅Si₁₅ alloy. Since Nb₃Si and Hf₅Si₃ are not superconducting above 4.2 K, it has been concluded that superconductivity in these crystallized alloys is due to the precipitation of -Hf(Nb) solid solution in the Hf-Nb-Si alloys and to the precipitation of HfV₂ and V₃Si compounds in the Hf-V-Si alloys.     

Critical current density and stability of Tube Type Nb3Sn conductors

The critical current densities (J_c) and stabilities of Tube Type Nb₃Sn conductors have been measured. The strands had superconducting subelement counts ranging from 192 to 744, and flat-to-flat filament sizes (for 0.7 mm OD wire) of from 35 μm down to 15 μm. These Tube Type conductors had a very simple structure: prior to heat treatment the filaments consist of a Sn core surrounded by a thin Cu tube, itself surrounded by a Nb or Nb alloy tube. Eight different strand types were investigated using various techniques including SEM, residual resistance ratio (RRR), transport J_c, and stability measurement. Most strands were studied at 0.7 mm OD, with one representative at 0.42 mm. The transport measurements were made at 4.2 K in fields up to 14 T. Numerous heat treatment schedules were investigated, with reaction temperatures ranging from 615 °C to 650 °C, and times ranging from 36–500 h. The highest J_cs were seen for the lowest reaction temperatures, with 12 T transport J_c values as high as 2450 A/mm² observed. The RRRs were lower for longer time and higher temperature reactions and ranged from 4 to 180. Strand stability was a strong function of the effective filament diameter, d_eff, and RRR. The most stable strands showed stability currents, J_s, of 8700 A/mm² and 15,300 A/mm² for 0.7 mm OD and 0.42 mm OD conductors, respectively.     

Microstructure and radiation damage of commercially produced Nb3Sn tapes

The microstructure and fast neutron irradiation damage of Nb₃Sn tapes produced by a liquid tin diffusion method have been studied using electron microscopy, X-ray diffraction and secondary ion mass spectrometry.The Nb₃Sn layer consists of an outer region of clusters of Nb₃Sn grains, which have a high oxygen content, and an inner region of smaller equiaxed grains. The rate of growth of the Nb₃Sn layer and the kinetics of grain growth in these commercial tapes are compared with published results for a laboratory system and Nb₃Sn formed by the ‘bronze route’.In Nb₃Sn irradiated at 70°C to doses up to 5.4 10²³ neutrons m^?2 disordered regions and dislocation loops are observed; the latter dissappeared on annealing for short times at temperatures from 300 to 750°C Nb₃Sn tapes irradiated at higher temperatures only show dislocation loops which form pairs on annealing. These results are correlated with previously determined T_c measurements.     

Changes ofT c,J c,B c2 and the lattice parameter of the Nb3Sn phase formed at the initial stage of growth in a multifilamentary superconductive wire

Investigations were made of the superconducting transition temperature,T _c, the upper critical flux density,B _c2, and the critical current density,J _c, of Nb₃Sn layers in filamentary wire in a bronze matrix. The lattice parameter,a ₀, andT _c of Nb₃Sn layers in 259-filament wire were determined after removal of the bronze matrix. The microstructure and layer thickness were studied using scanning electron microscopy. The diffusion formation of Nb₃Sn phase at 1023 K was studied until the complete reaction of the niobium filaments. It was found that the Nb₃Sn layer begins to form in the manufacturing process during the intermediate annealing at 793 K, and that there is a considerable degradation of critical parameters due to the non-stoichiometry of the Nb₃Sn phase in layers thinner than 1m.     

New Fabrication Process of Cu–Nb Composite for Internal Reinforcement of Nb3Sn Wires

We developed Cu–20vol%Nb wires, for the reinforcement and stabilizing of Nb₃Sn wires, using a new Nb rod process. The electrical and mechanical properties of the CuNb wires prepared by different processes were measured to assess their suitability as reinforcing stabilizers for Nb₃Sn. All wires were heat-treated at 670 ^°C, which is the temperature required for formation of Nb₃Sn. After heat treatment, the mechanical properties of Nb-rod-processed CuNb were superior to those of in-situ-processed CuNb wires. The residual resistance ratio of the Nb-rod-processed CuNb was 64, and its magnetoresistivity was 0.16 μΩ?cm at 4.2 K and 15 T. These properties indicate that the new CuNb wire is suitable as a reinforcing stabilizer for using a high field, wide bore, superconducting magnet, such as the 20 T superconducting magnet with 400 mm room temperature bore being planned in Japan.     

Superconductivity and Ferromagnetism of the Ru-1232 Compounds in the (Ru1−x Nb x )Sr2(GdCe1.8Sr0.2)Cu2O z System

The Ru-1232 compounds have been synthesized in the (Ru_1?xNb _x )Sr₂(GdCe_1.8Sr_0.2)Cu₂O _z system, and effects of Nb substitution for Ru on superconductivity and ferromagnetism of the Ru-1232 compounds have been investigated. First, X-ray powder diffraction study shows that nearly the single 1232 phase samples can be obtained in the x composition range from 0.0 to 0.3. Then, from the electrical resistivity study, it is found that each of the samples shows resistivity dropping phenomenon at two temperatures of T _c ^l and T _c ^h, which originates from superconductivity of the Ru-1232 phase and the Ru-1222 one, respectively. Both of the starting temperatures are lowering with increasing Nb content x. Lastly, from the magnetic susceptibility study, it is found that superconducting transition temperature T _c is 20 K for the Ru-1232 sample with x = 0.0 and the ferromagnetic transition temperature T _m is about 90 K. This study also shows that both of the values of T _c and T _m become low with increasing x from 0.0 to 0.3.     

Growth rate of Nb<Subscript>3</Subscript>Sn for reactive diffusion between Nb and Cu–9.3Sn–0.3Ti alloy

In order to examine experimentally the growth behavior of Nb₃Sn during reactive diffusion between Nb and a bronze with the α + β two-phase microstructure, a sandwich (Cu–Sn–Ti)/Nb/(Cu–Sn–Ti) diffusion couple was prepared from pure Nb and a ternary Cu–Sn–Ti alloy with concentrations of 9.3 at.% Sn and 0.3 at.% Ti by a diffusion bonding technique. Here, α is the primary solid-solution phase of Cu with the face-centered cubic structure, and β is the intermediate phase with the body-centered cubic structure. The diffusion couple was isothermally annealed at temperatures between T = 923 and 1,053 K for various times up to 843 h. Owing to annealing, the Nb₃Sn layer is formed along each (Cu–Sn–Ti)/Nb interface in the diffusion couple, and grows mainly into Nb. Hence, the migration of the Nb₃Sn/Nb interface governs the growth of the Nb₃Sn layer. The mean thickness of the Nb₃Sn layer is proportional to a power function of the annealing time. The exponent of the power function is close to unity at T = 923 K, but takes values of 0.8–0.7 at T = 973–1,053 K. Consequently, the interface reaction at the migrating Nb₃Sn/Nb interface is the rate-controlling process for the growth of the Nb₃Sn layer at T = 923 K, and the interdiffusion across the Nb₃Sn layer as well as the interface reaction contributes to the rate-controlling process at T = 973–1,053 K. Except the effect of Ti, the growth rate of the Nb₃Sn layer is predominantly determined by the activity of Sn in the bronze and thus the concentration of Sn in the α phase. As a result, the growth rate is hardly affected by the volume fraction of the β phase, though the final amount of the Nb₃Sn layer may depend on the volume fraction.     

Microstructural factors important for the development of high critical current density Nb3Sn strand

Nb₃Sn is the primary candidate for the next generation of accelerator magnets as well as for NMR and other applications that require magnetic fields between 11 and 20 T. Since 1999 the layer critical current density available in long length accelerator quality strand has almost doubled. The microstructural and microchemical factors that are important for high critical current density Nb₃Sn are reviewed. The highest critical current density strands have a Nb₃Sn layer that minimizes chemical and microstructural inhomogeneities and has a high fraction of the layer close to stoichiometric Sn content. Only the internal Sn process has yielded critical current densities beyond 3000 A/mm² at 12 T (4.2 K) and only with interfilamentary Cu thicknesses that are too low to separate the filaments after the final reaction heat treatment. The result of the reaction heat treatment is to produce a continuous ring of Nb₃Sn from hundreds of Nb or Nb-alloy filaments and thus a major ongoing challenge of Nb₃Sn conductor design is to reduce the effective filament diameter to acceptable levels for intended applications. Recent successful attempts to reduce the cost of alloying the Nb₃Sn for high field application are also examined and the potential for future improvements discussed.     

Overview of Nb3Sn and V3Ga conductor development in Japan

In the early stage of high-field A15 conductor development in Japan, different type of V₃Ga conductors were fabricated. Then, Ti-doped Nb₃Sn conductors have been developed, and widely used for high-field generation. Increase of Sn concentration in the bronze produces an appreciable progress in the performance of bronze processed (Nb,Ti)₃Sn conductors. New internal Sn processed (Nb,Ti)₃Sn conductors with modified cross-sectional configurations have been produced, which exhibit large J_c in high fields as well as reduced AC loss. Both bronze processed and internal Sn processed (Nb,Ti)₃Sn conductors satisfy recent ITER magnet specifications. As for new type Nb₃Sn conductors, powder core and Jelly Roll processed (Nb,Ta)₃Sn wires with improved high-field performance have been fabricated.     

The Effects of Substitution of Sn for Cu in Bi1.75Pb0.25Sr2CaCu2.3−x Sn x Sn x O y

The influence of Sn doping on superconductivity in the Bi-based 2212 phase is studied in this paper. For the samples R–T relations and magnetic hysteresis loops were measured. X-ray powder diffraction analysis was also performed. For Bi_1.75Pb_0.25Sr₂CaCu_2.3?x Sn _x O _y , the experimental results show that by adding the proper amount of Sn the superconductivity of the samples can be improved. As x = 0.15, the critical temperature T _c, the critical current density J _c, and the magnetic pinning force density F reach a maximum. At T = 11 K, the critical state parameters H _c1, H _c2, κ, λ, and ξ are calculated and compared with the results reported by other researchers. The experimental results also show that the Sn doping is able to speed up the growth of the 2223 phase. In brief, Sn doping is an effective way of improving the superconductivity in Bi-based superconductors.     

Microstructure and superconductivity in annealed Cu-Nb-(Ti,Zr, Hf) ternary amorphous alloys obtained by liquid quenching

Melt-quenched Cu-Nb-(Ti, Zr, Hf) ternary alloys have been found to be amorphous possessing high strength and good bend ductility. The niobium content in the amorphous alloys was limited to less than 35 at % and the titanium, zirconium or hafnium contents from 25 to 50 at %. The Cu₄₀Nb₃₀(Ti, Hf)₃₀ alloys showed a superconducting transition above the liquid helium temperature (4.2 K) after annealing at appropriate temperatures. The highest transition temperatures attained were 5.6 K for the Cu₄₀Nb₃₀Ti₃₀ alloy annealed for 1 h at 873 K and 8.4 K for the Cu₄₀Nb₃₀Hf₃₀ alloy annealed for 1 h at 1073 K. In addition, these alloys exhibited upper critical magnetic fields of 1.8 to 2.3×10⁶ Am^–1 at 4.2 K and critical current densities of 2×10³ to 1×10⁴ A cm^–2 at zero applied field and 4.2 K. Since the structure of the superconducting samples consisted of ordered phases based on a b c c lattice with a lattice parameter of 0.31 nm, it was concluded that the superconductivity in the Cu₄₀Nb₃₀Ti₃₀ and Cu₄₀Nb₃₀Hf₃₀ alloys was due to the precipitation of the metastable ordered b c c phases.     

Fabrication of sections of a Nb3Sn-based rigid superconducting cable

Using Nb₃Sn layers deposited onto the outer and inner surfaces of copper tubes 30 and 50 mm in diameter, we have fabricated sections of a rigid superconducting coaxial cable up to 1 m in length. The highest current-carrying capacity of the cable at 4.2 K was 800–850 A/mm, which corresponded to a critical current density of (5.0–5.5) × 10¹⁰ A/m² in the Nb₃Sn layer.     

Strain characteristics of Nb3Sn multifilamentary wires with CuNb reinforcing stabilizer

Bronze processed multifilamentary Nb₃Sn superconducting wires, with a CuNb reinforcing stabilizer instead of the conventional Cu stabilizer, were fabricated. The mechanical properties and the strain dependence of the critical current I_c were evaluated at 4.2 K and a magnetic field of 15 T. A remarkable increase in the yield stress (70%) and the plastic flow stress as compared to the values for the wire with Cu stabilizer was observed. The strain for the peak I_c was also increased by 0.2%. I_c on unloading was reversible within the strain range of 1.5%. The strain sensitivity of I_c in the CuNb/Nb₃Sn wire was almost the same as that of the Cu/Nb₃Sn wire. A decrease in the wire diameter from 0.8 to 0.5 mm resulted in a slight increase in the yield stress of the CuNb/Nb₃Sn wire, but no change in the strain dependence of I_c. An increase in the heat treatment temperature from 700 to 750°C resulted in a decrease in the flow stress of 15%, but no change in the strain dependence of I_c. A marked change in the morphology of the Nb filament in the CuNb reinforcing stabilizer was evidenced during heat treatment.