Growth kinetics studies of multifilamentary Nb3Sn formed by the bronze process

A systematic study of growth kinetics of Nb₃Sn formation is reported for multifilamentary conductors in the bronze process. At all reaction temperatures studied, the rate controlling step is found to be the diffusion of tin through the grain boundaries of the layer. The growth law R = ktⁿ is obeyed and the measured values of the time exponent n are in accordance with growth kinetics models. The reaction rate constant k shows an optimum behaviour for samples annealed at 725°C. The results indicate that growth kinetics plays a significant role in determining T_C, the superconducting critical temperature of the Nb₃Sn layer.     

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.     

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.     

Growth and structural studies of multifilamentary Nb3Sn formed by solid state diffusion

Growth of Nb₃Sn layer formed in a multifilamentary composite of bronze matrix by solid state diffusion has been investigated and its T_c values are measured after different time periods of diffusion anneal. The grain boundary structures are also systematically studied with scanning electron microscopy. Results obtained beyond reasonable doubt conclude that the rate controlling process for growth of Nb₃Sn is via diffusion through grain boundaries of Nb₃Sn layer, and grain growth significantly affects the layer growth. Both T_c and the transition width ΔT_c change in a regular way as annealing progresses, and the variation of these parameters is related to changes in the grain structure and internal strains of the sample.     

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.     

Microstructure development in Nb3Sn(Ti) internal tin superconducting wire

The authors have studied the phase formation sequences in a Nb₃Sn ‘internal tin’ process superconductor. Heat treatments were performed to convert the starting materials of tin, Ti–Sn, copper and niobium, to bronze and Nb₃Sn. Specimens were quenched at different points of the heat treatment, followed by metallography to identify the phases present and X-ray microtomography (XMT) to investigate the void volume and distribution. An unexpected observation of the microstructure development was the uphill diffusion of tin during the Cu–Sn reactive diffusion. Some defects likely to affect the superconducting performance of the wires were observed. Microscopy revealed the presence of a Ti–Sn intermetallic compound displacing the niobium filaments, and XMT revealed the formation of long pores in the longitudinal direction. Two types of pore formation mechanism, in addition to Kirkendall pores, are proposed. The phase and microstructure development suggests that low-temperature heat treatment (below 415 °C) will have significant influence on optimising the final superconducting properties.     

The thermodynamics of A15 compound formation by diffusion from ternary bronzes

The formation of highT _c Nb₃Al, Nb₃Ga, Nb₃Ge and V₃ (Ga, Si) has been attempted by solid state diffusion from ternary bronzes. None of the desired compounds were formed. The results are explained in terms of the thermodynamics of compound formation by solid state diffusion. Diffusion follows two-phase tie-lines; only those phases which lie on tie-line routes, and which are the most stable as defined by the stability index, are able to form. The addition of the third element to the bronze in general has little significant effect. There is no evidence to indicate that highT _c Nb₃Al, Nb₃Ga or Nb₃Ge can be produced by solid state reaction.Work performed under the auspices of the US Department of Energy.     

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.     

Fabrication of Nb3Sn superconductors by the solid-liquid diffusion method using Sn rich CuSn alloy

Superconducting composite wires having thick Nb₃Sn layers (? 20 μm) and high current carrying capacities were fabricated by the diffusion reaction between Nb (solid) and Sn rich CuSn alloy (liquid): the solid-liquid diffusion method. Composite wires with a fine inner core of Cu 12 at % Sn alloy surrounded by Nb were produced by cold drawing and heat treated at about 700°C. The Sn rich intermetallic compounds which formed initially were transformed to Nb₃Sn in 50 ～ 100 h, as the Cu concentration in the CuSn alloy core increased due to the consumption of Sn. The process produced thick Nb₃Sn layers, in comparison with the bronze method, because of the high Sn content in CuSn alloy core. The mechanism of enhanced Nb₃Sn formation by Cu was also studied, and it was clarified that the Cu in CuSn alloy lowers the activity of Sn so that the formation of Sn poor intermetallic compounds Nb₃Sn becomes advantageous in the diffusion reaction as compared with other Sn rich compounds.     

The properties of surface diffusion processed V3Ga tape

The rapid growth of superconducting magnet technology is leading to many applications of superconductivity in science and industry. At present, the most widely used practical superconductors are NbTi alloys and Nb₃Sn compounds. Surface diffusion processed V₃Ga tape possesses an outstanding current carrying capacity in high magnetic fields. This paper is concerned with the properties of the V₃Ga tape which is produced by us on a commercial scale.     

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.     

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.     

Current-carrying capacities of small V3 Ga pancakes

As an intermediate step leading to the production of V₃Ga tapes long enough for magnets of practical size, we have produced by surface diffusion V₃Ga tapes ranging in length from 5 to 100 meters. These were wound into single pancakes and their current-carrying capacities were measured in external magnetic fields up to 180 kOe. Results indicate that it should be possible in the near future, to construct V₃Ga magnets capable of generating fields as high as 180 kOe, which exceeds by at least 30 kOe the maximum generated by an Nb₃Sn magnet. A further study in the area of stability, however, would be helpful.     

Influence of third elements on growth of Nb3Sn compounds and on global pinning force

The crystal growth of Nb₃Sn by the bronze method has been investigated by using diffusion couples consisting of niobium and bronze with the addition of third elements. When the specimens were annealed at temperatures between 973 and 1073 K, the time-dependence of layer thickness was represented approximately by the function ofd=kt ^m . The time exponent changed from 1/3 to unity depending on the annealing condition as well as on the nature of the third element. By the addition of titanium, hafnium, zirconium, indium and galium to the bronze, the growth rate of the compound layer increases. Faster layer growth corresponds to a larger time exponent. The following three processes are suggested to be important for controlling layer growth: diffusivity of tin atoms through grain boundaries in the compound layer, diffusivity of tin atoms through the matrix of the compound, and the rate of the chemical reaction to form the compound. Essentially these combined processes control the overall rate of layer growth. The grain size is found to be the most effective structural parameter to affect directly the maximum global pinning force. The critical current at a magnetic field of 5T can be scaled by both the layer thickness and the inverse grain size.     

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.     

Effects of the IVa element addition on the composite-processed superconducting Nb3Sn

The effect of the IVa element addition to the niobium core and that of gallium addition to the matrix on the composition, growth rate and superconducting properties of the composite-processed Nb₃Sn have been studied. The IVa elements added to the niobium core enhance the growth rate of Nb₃Sn, and prevent the grain coarsening of Nb₃Sn. A much larger amount of titanium is incorporated into Nb₃Sn than zirconium or hafnium. T_c shows a slight maximum against the IVa element concentration in the niobium core. J_c at high magnetic fields is more significantly increased by titanium addition than zirconium or hafnium additions. The gallium substitution for tin in the matrix is effective for increasing T_c and J_c in high fields, except for the specimen with Nb-Ti alloy core. The simultaneous addition of hafnium and gallium is most effective for the enhancement of J_c in high fields.     

Growth of Nb3Sn in multifilamentary bronze composites

Growth of Nb₃Sn layers in multifilamentary composites has been investigated and their superconducting critical temperatures are measured using both resistive and inductive techniques. The growth parameters are discussed in the light of the analytical models of Reddi et al. Results show that for the composites studied, the rate controlling step for Nb₃Sn growth is diffusion of tin through grain boundaries of Nb₃Sn with the time exponent n determined by both the initial grain size and grain growth. T _c measurements show that for composites with a higher filament number, the width of superconducting transition is broader with no significant change in the onset T _c.     

Room-temperature tensile behaviour of bronze-processed multi-filamentary Nb3Sn superconducting materials

Structure and its relation to fracture behaviour of multi-filamentary Nb₃Sn superconducting composite materials prepared by the bronze method were studied by tensile testing at room temperature. There were two types of fracture mode. Type I showed high elongation, accompanied by apparent plastic deformation of composites as a whole and the Nb₃Sn layer exhibited multiple fracture. Type II showed no apparent plastic deformation and the composites fractured in a brittle manner. Type I occurred when the fraction of the Nb₃Sn layer was small and the drop of load-bearing capacity due to fracture of Nb₃Sn layer could be compensated mainly by strain hardening of ductile constituents of Nb, Cu-Sn and Cu. On the other hand, Type II occurred when the fraction of Nb₃Sn layer was large and the fracture of the Nb₃Sn layer caused fracture of composites as a whole. To describe the tensile strength of composites for both types, a model was proposed, which explained well the experimental results. It was found that the strength of the Nb₃Sn layer decreases with increasing diameter of composites and with increasing annealing temperature and time.     

Pulsed magnetic field losses and critical current densities of V3 Ga and Nb3Sn multifilament superconductors

Pulsed magnetic field loss measurements have been performed on special V₃Ga filament superconductors, which are known to have very high critical current densities, and on a NB₃Sn filament superconductor.The dependence of the hysteresis losses on the diffusion heat treatment parameters for the V₃Ga layer formation is reported. To analyse the results, the hysteresis losses of hollow superconducting filaments in parallel and perpendicular magnetic fields were calculated.From E.J. Kramer's theory of flux pinning we postulate that, for a given material, upper and lower intrinsic limits of the hysteresis losses are due to the flux line shearing effect. A part of the results was presented at the ICEC 7.     

Studies on the formation of V3Ga and V3Si superconducting compounds by a new diffusion process

In the present work, diffusion between vanadium and Cu-20 at.% Ga alloy and that between vanadium and Cu-20 at.% Si alloy were studied. An intermetallic compound, V₃Ga, is formed easily by the selective diffusion of gallium from the Cu-Ga alloy to the vanadium. V₅Si₃ and V₃Si are formed also by the selective diffusion of silicon from the Cu-Si alloy to the vanadium. Copper scarcely dissolves either in V₃Ga, V₅Si₃ or V₃Si. Copper is not effective for enhancing the formation of V₃Si unlike the case of V₃Ga. A large super-conducting critical current density, J _c, is obtained in the V₃Ga formed at temperatures below 700° C while a much smaller J _c is obtained in the V₃Si formed at 800° C. Changes in J _c due to the heat-treatment can be interpreted by the grain growth of the compounds.