1

Annealing effects on the magnetic properties of a

Cu-15vol% Nb composite conductor

M. J. R. Sandim1, H. R. Z. Sandim1, C. Y. Shigue1, M. Filgueira2, and L. Ghivelder3

1
Departmento de Engenharia de Materiais, FAENQUIL, 12600-000, Lorena-SP, Brazil
2
LAMAV, UENF, 28015-620, Campos dos Goytacazes-RJ, Brazil
3
Instituto de Física, UFRJ, 21945-970, Rio de Janeiro-RJ, Brazil

Abstract
In this paper, the annealing effects on the magnetic properties of a multifilamentary Cu-
Nb composite were investigated. During annealing, noticeable changes take place in the
microstructure, in special the partial spheroidization and further coarsening of the
niobium filaments. Results show that spheroidization becomes noticeable at about
700ºC and, even after annealing at severe conditions, e.g. 1050ºC for 32 h, the
continuity of the niobium-conducting path is partially preserved. The influence of these
microstructural changes on the magnetic properties of the multifilamentary Cu-
15vol%Nb composite conductor is discussed.

1. Introduction

Cu-Nb composites have been widely investigated due to their high strength, high

conductivity, and mechanical workability [1]. The combination of these properties

makes this particular material very attractive for applications in the high-field magnet

technology [2]. Furthermore, the Cu-Nb system reveals many interesting physical

aspects which help the understanding of proximity effects in heterogeneous systems

since both superconducting phase and normal matrix are very well known materials and

display very low mutual solubility.

Remarkable changes occur in the microstructure of Cu-Nb conductors during

annealing including recovery and recrystallization of copper and niobium depending on

the annealing temperature. It is well known that thermal instability mechanisms occur in

lamellar microstructures when exposed to elevated temperatures [3]. Regarding the

 2

multifilamentary Cu-Nb conductors, the former rod-like niobium filaments develop a

ribbon-like shape with increasing strain as well as the corresponding Cu-Nb interfacial

area. Most of the stored energy in the composite is due to the presence of geometrically

necessary dislocations at the Cu-Nb interface to compensate strain mismatches. The

high interfacial energy associated to these interfaces is the driving force for

spheroidization and, eventually, their coarsening [3,4].

Both the morphology of the filaments and the interfilament spacing have

considerable influence on the electrical [5-8] and magnetic properties [9-12] of the

multifilamentary superconducting conductors. The effects of annealing on the

microstructure and, consequently, on the electrical properties of the Cu-Nb

multifilamentary conductors have been addressed by several investigations [6,8,13,14].

In an earlier paper, we reported the annealing effects on the electrical and

superconducting properties of a Cu-15vol% Nb composite conductor with emphasis on

the spheroidization and further coarsening of the Nb filaments [14]. In the present work,

we focus on the microstructural evolution of the Nb filaments upon vacuum annealing

and the corresponding effects on the magnetic properties of the same composite. The

results are discussed in the framework of the proximity-effect-induced

superconductivity in the normal matrix of the multifilamentary conductor.

2. Experimental

The bundling-and-drawing process using high-purity niobium and OFHC-copper

was used to manufacture the multifilamentary Cu-15%vol Nb composite with 418,399

niobium filaments. The deformation process was carried out at room temperature.

Vacuum annealing of 0.6 mm-diameter composite conductors was carried out in the

300-1050ºC temperature range for 1 to 32 h. Microstructural characterization was

 3

performed using a 1450-VP LEO scanning electron microscope operating at 20 kV in

the secondary electrons mode. Some samples were deeply etched with an aqueous

solution of nitric acid to remove the copper matrix and expose the individual filaments.

AC and DC magnetization measurements were performed using a PPMS-Quantum

Design platform. The samples were 0.6 mm diameter and 15 mm long. The magnetic

measurements were taken with the applied magnetic field parallel to the wire axis. The

DC magnetization as a function of magnetic field was carried out at temperatures of 2 K

and at magnetic fields up to 1.7 x 104 Oe. The temperature dependence of AC

susceptibilitity was determined in the temperature range 2 to 12 K, at an AC magnetic

field of 1 Oe and frequency of 50 Hz. In this work, magnetization values are reported

per unit volume of total composite.

3. Results and discussion

3.1. Microstructural characterization

The dimensions of the ribbon-like niobium filaments in the cross section are

about 2 µm-wide and 200 nm-thick. The interfilament spacing is calculated to be about

0.5 to 1 µm. Annealing at 300ºC/1 h promotes partial recrystallization in the copper

matrix. With increasing temperature, recrystallization occurs in full extent in the copper

matrix. Above 700ºC, recrystallization in the niobium filaments begins as well as

changes in their morphology. Fig. 1(a) shows the morphology of niobium filaments for

the Cu15%vol Nb conductor annealed at 800ºC for 1 h. From this figure it is evident the

development of thermal grooves along the surface of the filament. These grooves are

found parallel with the longitudinal direction of the filament. Spherical and elliptical

holes with sizes below 0.2 µm are also observed mainly at the edges of these filaments.

These features evidence the beginning of the fragmentation of the niobium filaments in
 4

several small cylinders at higher annealing temperatures (cylinderization). In theory,

diffusional processes might decompose them into a row of isolated spheres for longer

annealing times aiming to reduce the interfacial energy [3].

Evidences of the early stages of spheroidization promoted by boundary splitting

into a lamellar microstructure [3] are clearly seen in Fig. 1(b). This figure shows five

individual niobium filaments after annealing at 1000ºC for 1 h. In this figure, one can

clearly observe the occurrence of a pronounced fragmentation mostly along the lamellar

boundaries. In average, every individual ribbon-like filament is subdivided into four or

five 0.5 µm-wide rod-like structures. Individual spheres (as predicted by theory) are not

visible throughout these fragmented structures; however, the tendency for

cylinderization is very pronounced. While the fragmentation of the individual filaments

proceeds, new contact points formed by diffusional processes are also observed joining

the already fragmented parts with the very adjacent rod-like structures. These new

contact points aid filament coarsening at high annealing temperatures.

The recrystallization of niobium is clear and the filament morphology evolves to

a bamboo-like structure above 1000ºC as shown in Fig. 1(c). This figure displays the

morphology of niobium filaments for the Cu-15%vol Nb composite annealed at 1050ºC

for 32 h. This temperature corresponds to about 98% of the melting point of copper. At

this stage, cylinderization of niobium has occurred in a large extent. Transverse grain

boundaries are observed along the filaments. According to Sharma et al. [3], it is

plausible admit that filament break-up is somehow accelerated at high-angle boundaries

because of their higher diffusivity. After annealing at this severe condition (1050ºC for

32 h), filament break-up occurs in many regions, however, coarsening of the niobium

filaments is predominant.

Regarding the initial geometrical structure of the Cu15%vol Nb composite, the

 5

combination of spheroidization and coarsening of Nb filaments in the annealed state

leads to a very complicated system. In conductors annealed at high temperatures, such a

system is comprised by a collection of tiny normal regions surrounded by

superconducting material, as shown in Fig. 1(c).

3.2. Magnetic characterization

The remarkable changes in the microstructure of Nb filaments above discussed

exert a strong influence on the magnetic properties of the Cu15%vol Nb composite. Fig.

2 shows the temperature dependence of the real part of the AC susceptibility (χ’) for the

as-drawn and annealed samples at several temperatures in the range 700ºC < T <

1050ºC. All the χ’(T) curves display two major segments. These segments,

approximately in the temperature ranges 8 < T < 9 K and T < 8 K, correspond to

intrinsic and coupling superconducting transition, respectively. In multifilamentary

superconducting wires, such a double transitions are seen in χ’(T) curves as a

consequence of the proximity coupling (across the Cu matrix) between the filaments

[11,12]. From Fig. 2 it is evident that the superconducting transition is broader for the

sample annealed at 1050ºC. A deep insight in the annealing effects on the

superconducting transition is obtained by taking the first derivative of the χ’ vs T

curves.

Fig. 3 shows the dχ’/dT curves for the as-drawn and annealed samples at 800ºC

for 1 h and 1050ºC for 32 h. These curves show an evident peak close to 9 K,

corresponding to the intrinsic superconducting transition. It is evident that the highest

peaks correspond to the samples annealed at 700 and 800ºC for 1 h. By defining the

critical temperature, Tc, with reference to the maximum of dχ’/dT, Tc is about 8.5 K in

the as-drawn condition. Compared to the as-drawn sample, the samples annealed up to
 6

700°C show a little drop in Tc value. On the other hand, samples annealed at

temperatures above 800°C present a discrete increase in Tc value. Concerning the

behavior of Tc, these results are in very good agreement with those obtained from R(T)

measurements presented in an earlier investigation [14].

Fig. 4 shows the temperature dependence of the imaginary part of AC

susceptibility (χ”) for the as-drawn and annealed samples at 700, 800, and 1050ºC.

Corresponding to double transitions in χ’(T), the imaginary part χ’’ shows intrinsic and

proximity coupling loss peaks. All the χ’’(T) curves have a background signal, certainly

due the large volume of copper in the composite. Nevertheless, from Fig. 4 it is possible

to see that the samples annealed at 700 and 800°C for 1 h display the narrower intrinsic

peaks. Such a feature is in accordance with the characteristics of the peak close to 9 K in

dχ’/dT curves previously described. From Fig. 4 it is also evident that, for the most

severe annealing performed, i.e. 1050°C for 32 h, dissipation from coupling is

predominant because the intrinsic peak is not well defined. Coarsening and

spheroidization act in the opposite sense in terms of connectivity among niobium

filaments. Therefore, the features above described corroborate that the spheroidization

of niobium filaments becomes noticeable for annealing above 700°C for 1 h. For higher

annealing temperatures, mass diffusivity is enhanced and coarsening becomes the

predominant mechanism contributing for the coupling between the niobium filaments.

Further evidences for such a behavior can be obtained analyzing the DC magnetization

curves.

Fig. 5 shows the magnetic field dependence of the isothermal magnetization M

(H, T = 2 K) for the Cu15%vol Nb conductor in the as–drawn condition. In the

increasing field direction, the M x H curve deviates from linearity at about H ~ 157 Oe,

which corresponds to the breakdown field of the proximity coupled matrix. For a
 7

conductor in parallel field and in the thick limit (ξn << dn), the magnetic field necessary

to destroy the superconductivity in the normal matrix is given by [15]:

5φo
H = (1),
4πd nξ n

where φ0 is the quantum magnetic flux, dn is the normal metal thickness and ξn is the

coherence length in the normal metal. For H = 157 Oe, from eq. (1) we have calculated

dn ranging from 0.1 to 1 µm, respectively, in the limits for clean (ξn = 350 nm) and dirty

(ξn = 63 nm) copper [15]. These results are reasonable, because the observed

interfilament spacing in the as-drawn condition is in the range 0.5-1 µm, which is closer

to the value of dn obtained taking the dirty limit into account. There are two possibilities

to explain the deviation from clean-to-dirty behavior of the normal copper matrix:

a) Even using OFHC copper as starting material, the contamination of the copper matrix

with interstitial oxygen might occur during the manufacturing process. A thin layer of

oxides is present at the surface of the niobium rods [16,17] used to manufacture the

conductor, which might dissolve and diffuse into copper at high temperatures acting as a

source of oxygen.

b) Plastic deformation of Cu-Nb composites to very large strains might induce a slight

increase of the solubility of niobium in copper. Although the binary phase diagram of

this system indicate there is no mutual solubility of Nb and Cu at the equilibrium state

[18], atom probe measurements in a similar composite confirm the intermixing between

Nb and Cu mainly close to the interface forming a metastable substitutional solution

[19, 20].
 8

The magnetization curve of the Cu15%vol Nb sample annealed at 500°C for 1 h

(not shown) is formally similar to that obtained for the as-drawn condition. On the other

hand, the shape of the M x H curve is strongly affected when annealing is performed at

higher temperatures.

Fig. 6 shows the M x H curves at T = 2 K for the samples annealed at 700, 800,

and 900ºC for 1 h. Note that in the ascending branch of the M x H curves two peaks are

evident below H = 2000 Oe. Starting from zero applied magnetic field, the M x H curve

deviates from linearity at Hc1n ∼ 200 Oe. Hc1n can be interpreted as the lower critical

field for the normal material, which becomes partially superconducting due to the

proximity effect. A close inspection in the inset shown in Fig. 6(a) reveals that for H >

Hc1n the magnetization curve displays a narrow plateau, followed by a small increase in

the absolute value of M at ∼ 400 Oe. With further increase of the magnetic field, M

reaches a second peak at Hc1s ∼ 1700 Oe. Hc1s has the same magnitude of the lower

critical field Hc1 for niobium at the same temperature (∼ 1800 Oe). Therefore, Hc1s can

be associated with the lower critical field of niobium. Once Hc1s is exceeded, flux lines

begin to enter the filaments, decreasing the absolute value of M. In addition, the

position of the peaks in the magnetization curves of the Cu15%vol Nb remains the

same, with Hc1n ~ 200 Oe and Hc1s ~ 1700 Oe, for increasing annealing temperature.

Although the position remains the same, there is a change in the relative magnitude of

such peaks. The absolute value of M at Hc1s is lower than at Hc1n for the sample

annealed at 700ºC, however, an opposite behavior is verified at 900ºC.

For the most severe annealing performed in this investigation (1050ºC/ 32 h),

the magnetization curve is shown in Fig. 7. Once H ∼ 50 Oe is exceeded, the

magnetization drops down to another line until the penetration field H ∼ 1200 Oe is

reached. The magnitude of such a field leads one to conclude that the excess of
 9

magnetization at H ~ 1200 Oe for the annealed sample at 1050 ºC comes from the

electromagnetic coupling between filaments. The coupled filaments behave as an

extended superconductor and consequently, the magnitude of M increases. Such a

behavior and the relative peak heights in the magnetization curves shown in Fig. 6

indicate that coarsening is the predominant mechanism above 900ºC as previously

demonstrated with aid of scanning electron microscopy.

Regarding the double peaks in the M x H curves displayed in Fig. 6, anomalies

with comparable appearances have been reported in a number of systems, for both high-

and low-temperature superconductors. In multifilamentary superconducting wires these

anomalies have to do with proximity coupling effects of different intensities [9,21,22].

For high-Tc superconductors, similar shapes of the magnetization curves have been

attributed to many reasons including granularity [23], different types of flux pinning

[24-26], vortex-dynamic characteristics [27], and decoupling between superconducting

layers in the single-crystals [28].

4. Conclusions

Based on an investigation of microstructure and magnetic properties of a

multifilamentary Cu-15%vol Nb conductor annealed at several temperatures in the

range 300ºC < T < 1050ºC, the following conclusions can be drawn:

(a) Vacuum annealing of Cu-15vol%Nb promotes noticeable changes in the

microstructure depending primarily on the annealing temperature. Recovery of niobium

and recrystallization of copper tend to occur at lower annealing temperatures whereas

spheroidization and further coarsening take place at higher temperatures (above 700°C).

(b) Spheroidization and coarsening of niobium filaments have strong influence on the

AC and DC magnetization of the Cu-15%vol Nb composite.

 10

(c) The combination of these phenomena affects the “double drop/double peak”

characteristics for the AC susceptibility and, at specific annealing conditions, produces

remarkable anomalies in the shape of the DC magnetization curve.

Acknowledgments

The authors thank to FAPESP (Sao Paulo, Brazil) for supporting this work.

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Sandim, IEEE Trans. on Appl. Superconductivity 12, 1195 (2002).
 11

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 12

(a)
)

2µ
µm

(b)

5µ
µm

(c)

2µ
µm

Fig. 1: Niobium filaments of the conductor Cu15%volNb annealed in vacuum at

(a) 800 ºC/ 31 h, (b) 1000ºC/ 1 h, and (c) 1050ºC/ 32 h (SEM/BSE). The copper matrix
has been etched away. In (c) the bamboo-like structure of the coarsened filaments is
evident. The white arrow marks a region where boundary-assisted splitting is evident.
 13

0.0
as-drawn
o
500 C/1h
o
-7.0x10
-3 700 C/1h
o
800 C/1h

χ' (emu/Oe.cm )
o

3
900 C/1h
-2 o
-1.4x10 1050 C/1h

-2
-2.1x10

-2
-2.8x10

-2
-3.5x10
2 4 6 8 10
T (K)

Fig. 2: Temperature dependence of the real part of ac susceptibility for Cu15%vol Nb

conductor in the as-drawn condition and annealed at several temperatures in the range
500ºC < T < 1050ºC.

-2
6.0x10

as-drawn
-2 o
5.0x10 500 C/1 h
o
700 C/1 h
o
800 C/1 h
dχ'/dT (emu/Oe.cm .K)

-2
4.0x10 o
900 C/1 h
3

o
1050 C/32 h
-2
3.0x10

-2
2.0x10

-2
1.0x10

0.0

7.0 7.5 8.0 8.5 9.0 9.5

T (K)

Fig. 3: dχ’/dT curves for Cu15%vol Nb conductor for as-drawn and annealed samples
at several temperatures in the range 500 < T < 1050ºC. The correspondent curves of
χ’(T) are shown in Fig. 2.
 14

-4
2,2x10
as-drawn
o
1,8x10
-4 700 C/1 h
o
800 C/1 h

χ'' (emu/Oe.cm )
3
o
1050 C/32 h
-4
1,3x10

-5
9,0x10

-5
4,5x10
χ

0,0
2 4 6 8 10

T (K)

Fig 4: Temperature dependence of the imaginary part of ac susceptibility for

Cu15%vol Nb for as-drawn and annealed samples at T = 700, 800 and 1050ºC.

1.0

as-drawn

0.0

-1.0
M (emu/cm )
3

0.0
-2.0

-1.5

-3.0 -3.0

-4.5
0 200 400 600 800 1000
-4.0
0 2000 4000 6000 8000 10000
H (Oe)

Fig. 5: Field dependence of magnetization, at T = 2 K, for Cu15%vol Nb conductor in

the as-drawn condition. The inset shows the magnetic behavior in the field range
0 < H < 1000 Oe.
 15

2.0

o
700 C/1 h (a)
1.0

0.0

M (emu/cm )
-1.0
3

2.0
-2.0 1.0

0.0

-1.0
-3.0
-2.0 H c1n
Hc1S -3.0
-4.0 -4.0

-5.0
0 250 500 750 1000

-5.0
0 2000 4000 6000 8000 10000
H (Oe)

1.5

(b)

0.0
M (emu/cm )
3

-1.5

-3.0

o
800 C/1 h

-4.5
0 2000 4000 6000 8000 10000
H (Oe)
 16

2.0

1.0 (c)

0.0

-1.0

M (emu/cm )
3
-2.0

-3.0

-4.0

o
-5.0 900 C/1 h

-6.0
0 2000 4000 6000 8000 10000
H (Oe)

Fig. 6: Field dependence of magnetization, at T = 2 K, for Cu15%vol Nb conductor

annealed for 1 h at (a) 700ºC, (b) 800ºC and (c) 900ºC. The inset in (a) shows the M x H
curve for the sample annealed at 700ºC/1 h in the field range 0 < H < 1000 Oe. Hc1n and
Hc1s are defined in the manuscript.
 17

1.2
o
1050 C/ 32 h
0.0

-1.2

-2.4

M (emu/cm )
3
-3.6 0.0

-1.5
-4.8 -3.0

-4.5
-6.0 -6.0

-7.5
-7.2
-9.0
0 500 1000 1500 2000

-8.4
0 2000 4000 6000 8000 10000
H (Oe)

Fig. 7: Field dependence of magnetization, at T = 2 K, for Cu15%vol Nb conductor

annealed for 32 h 1050ºC. The inset shows the magnetic behavior in the field range
0 < H < 2000 Oe.