IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 29, NO.
5, AUGUST 2019
Microstructure and Superconducting Properties of
Brass Matrix Internal Tin Nb3Sn Wire With Ti
Doping to Nb Core
Taro Morita , Nobuya Banno , Tsuyoshi Yagai , and Kyoji Tachikawa
Abstract—Nb3 Sn superconducting wires are widely used for
high field applications. It is also expected to play a vital role for
high field application in the future, such as future circular col-
lider (FCC). Further improvement in Jc performance is required to
realize FCC. We have been studying the effect of element addition
into Cu matrix in the internal tin (IT) processed Nb3 Sn conductor.
In our previous brass method IT wire, where Ti is doped to cen-
tral Sn cores, Ti is accumulated between the sub-elements and is
inhomogeneously distributed across the wire after the heat treat-
ment. To solve this problem, we tried Ti doping to Nb cores on the
brass matrix IT wire. We prepared the specimens using Nb-0, 1,
1.54 at%Ti rod as Nb core. Nb3 Sn grain morphology and diffu-
sion reaction behavior of these specimens were compared and we
investigated the correlation between the microstructure and the su-
perconducting properties on the specimens with Ti doping to Nb
cores.
Index Terms—Diffusion reaction behavior, internal Sn,
microstructure, Nb3 Sn, Ti addition.
I. INTRODUCTION
Nb3 Sn conductors nowadays have become a crucial compo-
nent of high field applications such as International Thermonu-
clear Experimental Reactor (ITER), Nuclear Magnetic Reso-
nance (NMR) and so on. However, next generation high field
applications require very high superconducting performance:
for example, FCC requires Jc of ∼1500 A/mm2 at 16 T, 4.2 K.
Therefore, some drastic solution would be needed for further im-
provement of the Jc performance. We have studied so far on the
effect of element addition into Cu in internal tin (IT) processed
Nb3 Sn conductor, for example Zn addition, which is effective
for promotion of Nb3 Sn layer synthesis and improvement of
Manuscript received October 30, 2018; accepted March 27, 2019. Date of
publication April 19, 2019; date of current version July 1, 2019. This work was
supported in part by the JSPS KAKENHI under Grant JP18K04249. (Corre-
sponding author: Taro Morita.)
T. Morita is with the Sophia University, Tokyo 102-8554, Japan, and also with
the National Institute for Materials Science, Tsukuba 305-0047, Japan (e-mail:
morita0079@eagle.sophia.ac.jp).
N. Banno is with the National Institute for Materials Science, Tsukuba 305-
0047, Japan (e-mail: banno.nobuya@nims.go.jp).
T. Yagai is with the Sophia University, Tokyo 102-8554, Japan (e-mail:
tsuyoshi-yagai@sophia.ac.jp).
K. Tachikawa is with the National Institute for Materials Science, Tsukuba
305-0047, Japan, and also with the Tokai University, Hiratsuka 259-1292, Japan
(e-mail: tacsuper@keyaki.cc-u-tokai.ac.jp).
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Digital Object Identifier 10.1109/TASC.2019.2910020
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6001805
Jc characteristics. In our brass matrix (Cu-15wt%Zn) wire, Sn
cores are divided from the subelements consisting of Nb cores
and Ti is doped to central Sn cores so far. However, we found
some problem such that Ti diffusion is insufficient across the
matrix after heat treatment, resulting in the shortage of Ti in
outer Nb3 Sn filaments. For that reason, we tried Ti doping to
Nb cores on the brass matrix IT wire.
Ti is well known as an effective element to improve the crit-
ical magnetic field and Jc . Besides, E. N. Popova et al. have
studied in detail on the influence of Ti doping method for the
bronze processed Nb3 Sn wires. They reported that the highest
equiaxed Nb3 Sn grain zone thickness ratio is obtained by Ti
doping of the matrix and it is most promising for attaining the
best performance, because grain boundaries of equiaxed grains
are expected to act as the main pinning center [1], [2].
In this work, we prepared brass matrix IT wires using Nb-Ti
cores with different Ti amount. We investigated the effect of heat
treatment condition and amount of Ti on Nb3 Sn microstructure,
and diffusion reaction behavior of each element, using Field
Emission Scanning Energy Microscope (FE-SEM) and Energy
Dispersive X-ray spectrometry (EDX). We also measured criti-
cal current Ic by standard 4-probe resistive method and discussed
its correlation with microstructure.
II. EXPERIMENTAL
A. Samples
We prepared 3 kinds of specimens with (1) 1 at%Ti doped to
Nb core, (2) 1.54 at%Ti doped to Nb core and (3) no Ti doped
(named as NT-1. NT-1.54, 0Ti, respectively). Each specimen
was made by a typical double stacking rod-in-tube process; the
detail of the procedure is described in [3]. Fig. 1 shows the cross
sections of NT-1 and NT-1.54. After drawing process, the first
heat treatment was performed at 550 ◦ C × 100 h + 650 ◦ C ×
100 h and the additional heat treatment was performed at 670 ∼
750 ◦ C × 100 h at 1 atm. atmosphere. Although practical IT wire
adopts ∼650 ◦ C heat treatment for Nb3 Sn formation, this con-
dition is insufficient to grow the Nb3 Sn layer for our laboratory
scale brass matrix IT wires, because of a relatively large Nb3 Sn
filament size as one reason. That is, diffusion distance of Sn to
Nb filament is larger, compared to practical IT wires. Therefore,
we carry out the additional heat treatment (670 ∼ 750 ◦ C) for
the Nb3 Sn formation.
6001805
Fig. 1. Cross section of NT-1 (left) and NT-1.54 (right) (∅0.6 mm, non-
annealed).
TABLE I
DESIGN PECIFICATIONS OF FABRICATED NB3 SN WIRES
B. Microstructural Analysis
The fractured microstructures were observed using FE-SEM.
The average grain size was calculated as follows. Some area
inside the Nb3 Sn layer is chosen on a fractured Nb3 Sn fila-
ment and the area is measured. Then the number of the grains is
counted. The average grain size is calculated, assuming circular
grains [4]. We counted more than 600 grains to calculate average
grain size.
C. Ic Measurement
Critical current Ic was measured by a standard 4-probe resis-
tive method. Ic was determined with an electrical criterion of
1 μV/cm. Our laboratory samples have relatively larger Nb bar-
rier thickness, compared to practical IT wires. Hence, we used
an equivalent barrier fraction in the non-Cu area. Reffering to
some typical data in papers [5], [6] and [7], the barrier fraction
for the practical strands ranges from 6 to 8%, so that the equiv-
alent barrier fraction in our sample was assumed as 10% with a
slight overestimation.
III. RESULT AND DISCUSSION
A. Diffusion Behavior at Low Temperature
Fig. 2 shows microstructure of each specimen after 550 ◦ C ×
100 h heat treatment. In each sample, there can be seen some
void formation between the subelements. It is well known that
void is formed because the diffusion rate of Cu in Sn is much
faster than that of Sn in Cu [8]. Suppression of void would be
important to improve the Sn distribution and uniform Nb3 Sn
layer formation. In case that Ti is doped to Nb cores, Ti would
not affect the interdiffusion between Cu and Sn in the matrix.
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IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 29, NO. 5, AUGUST 2019
Fig. 2. Microstructure of 0Ti (top), NT-1 (middle), and NT-1.54 (bottom) after
550 ◦ C × 100 h heat treatment.
Then, the amount of void formation seems not to be different
each other so much.
When Ti is doped to central Sn cores, it has been pointed out
that some Sn-Ti intermetallic compound at the inner boundary
of the Nb filaments region is observed [9]. Although this com-
pound would dissolve after Nb3 Sn reaction heat treatment, it
does not completely disappear during the low temperature heat
treatment stage. This accumulation would prevent Sn diffusion
process, so that it should be avoided. Besides, it was reported
that Ti distribution is non-uniform after Nb3 Sn reaction heat
treatment [4]. In our previous brass method IT wire, Sn-Ti com-
pound exists after 550 ◦ C × 100 h heat treatment and also even
after 650 ◦ C × 100 h heat treatment. However, in Ti doping to
Nb cores, Sn-Ti intermetallic compound is absent.
B. Elements Distribution
Fig. 3 shows EDX mapping of Sn and Ti after 715 ◦ C × 100 h
heat treatment for NT-1 and NT-1.54 as well as 0Ti as a reference.
In NT-1.54, Sn diffusion is apparently accelerated, compared
with NT-1: many unreacted Nb cores are observed in NT-1. It
is believed that Ti doping to Nb cores promotes Sn diffusion
into Nb3 Sn layer [10], [11]. In NT-1 and NT-1.54, Ti was found
to move out of the filaments and segregate at the boundary of
the void. Fig. 4 shows Sn composition measured on a single Nb
filament located in an inner subelement of each specimen which
is fully reacted: the Sn compositions represented here do not
reflect ’partially’ reacted filaments located in outer subelements.
The average Sn composition in Nb3 Sn layer is 21.4%, 21.8% and
22.4% for 0Ti, NT-1 and NT-1.54, respectively. Although there
seems few un-reacted Nb filaments in 0Ti, Sn composition is
slightly smaller than the others.
In conventional brass method IT wire with Ti doping to central
Sn cores, it was found that Ti accumulated between the subele-
ments, and Ti distribution was inhomogeneous [4]. However
in NT specimens, Ti was found to be uniformly distrubuted in
Nb3 Sn layer.
MORITA et al.: MICROSTRUCTURE AND SUPERCONDUCTING PROPERTIES OF BRASS MATRIX INTERNAL TIN Nb3 Sn WIRE 6001805

Fig. 3. Sn and Ti distribution (EDX Mapping) for 0Ti (top), NT-1 (middle),
NT-1.54 (bottom) after 715 ◦ C × 100 h heat treatment.

Fig. 5. Grain morphology of Nb3 Sn filament of 0Ti (up-left), NT-1 (up-right)

Fig. 4. (a) Example of analysis points for Sn composition, (b) Sn composition
in Nb3 Sn layer after 715◦ × 100 h heat treatment for each specimen.
C. Nb3 Sn Grain Morphology
Past study indicates columnar grain zone does not contribute
to superconducting current transfer well [12]. To further im-
provement superconducting performance, it is needed to de-
crease the columnar grain zone and increase the fine equiaxed
grain zone [13], [14].
and NT-1.54 (bottom) after 715 ◦ C × 100 h heat treatment.
Fig. 5 shows Nb3 Sn grain morphology of each specimen
after 715 ◦ C × 100 h heat treatment. In 0Ti specimen, columnar
grain zone is found to occupy large area in the center of Nb3 Sn
filament. In NT-1, columnar grain zone significantly decreases
and whole area is mainly composed of equiaxed grains.
Fig. 6 shows correlation between the additional heat treat-
ment temperature and the average grain size: the pre-annealing
condition was 550 ◦ C × 100 h + 650 ◦ C × 100 h, but for
650 ◦ C, the average grain size just after the pre-annealing was

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6001805 IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 29, NO. 5, AUGUST 2019
Fig. 6. The correlation between the average grain size and the additional heat
treatment temperature (duration: 100 h) after the pre-annealing of 550 ◦ C × 100
h + 650 ◦ C × 100 h (for 650 ◦ C, the value just after the pre-annealing is plotted).
Fig. 7. Jc characteristics of specimens as function of magnetic field.
plotted. The analyzed grain sizes for NT-1 fluctuated so much.
The grain morphology of NT-1 consists of larger columnar and
smaller equiaxed grains, and perhaps the area ratio of the colum-
nar/equiaxed grain region may have changed from filament to
filament, which is attributed to the irregular filament shape. The
grain size of the Ti-doped wires has a tendency to decrease,
compared to non-Ti-doping.
In NT-1.54, the Nb3 Sn grain size is slightly larger than that
of NT-1. Some researchers have reported that the grain size
becomes larger by increasing the amount of Ti doping to Nb
cores [2], [10].
D. Jc − B Characteristics
Fig. 7 shows Jc − B characteristics of each specimen at 4.2 K:
the best characteristics were here chosen for each specimen.
Jc − B characteristics in high field increase with increasing
amount of Ti doping of the Nb core. Especially in NT-1.54, the
characteristics in high field is significantly improved. As pointed
out in the previous studies, the upper critical field Bc2 would be
enhanced due to increase of normal state resistivity ρn with Ti
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addition to Nb cores [15], [16]. According to [10], the Nb3 Sn
layer thickness and thus Jc property increase rapidly, when Ti
doping amount exceeds 1 at%. The higher Jc performance in
NT-1.54 would be due to increase of the area of the Nb3 Sn
layer, increase of the equiaxed grain region and probably also
enhancement of the stoichiometry. In addition, this Jc perfor-
mance is much higher than that of our previous brass matrix IT
wire with Ti doping to Sn cores [10]. This is apparently due to
improvement of Ti distribution across the filamentary region.
Although the grain size of NT-1 was smaller than that of
NT-1.54, Jc of NT-1 was much smaller, compared to NT-1.54.
Smaller Jc performance of NT-1 seems to be attributed to the
smaller Nb3 Sn layer formation (Fig. 3), smaller area fraction
of the equiaxed grain region and smaller Bc2 due to the insuf-
ficient Ti amount in the Nb3 Sn phase. As previously pointed
out, the grain boundary of the equiaxed grains gives a signif-
icant impact on the Jc performance with respect to the coarse
grains [17]–[20]. Increase of Ti amount rapidly enhanced both
Bc2 and Nb3 Sn layer formation [10].
IV. CONCLUSION
We have studied the effect of Ti addition to Nb cores on brass
matrix internal tin Nb3 Sn wire. Sn diffuses smoothly across the
filamentary region in the brass matrix wire with Ti addition to
Nb cores. Ti-doping to Nb cores is attractive in terms of activa-
tion of Nb3 Sn layer formation and uniformity of Ti distribution.
At 1.54 at%Ti addition to Nb cores, Nb3 Sn layer can trans-
form to fully equiaxed grain microstructure. NT-1 has a mixed
grain morphology consisting of columnar and equiaxed grains,
while in the no-Ti-doping wire, columnar grain morphology is
dominant.
The higher Jc performance in NT-1.54 would be due to in-
crease of the area of the Nb3 Sn layer, increase of the equiaxed
grain region and also increase of the stoichiometry. The Jc per-
formance is much higher than that of our previous brass matrix
IT wire with Ti doping to Sn cores. This is apparently due to
improvement of Ti distribution across the filamentary region.
In the wire fabrication process, despite the differential flow
strength between NbTi filaments and matrix material causing
some non-uniform deformation of composite, there were no se-
rious problems experienced during the drawing process down to
0.6 mm in diameter of the laboratory scale wire.
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