⊥ 

684 El60！名06h6ηzゑs！勿ソ

一Technical Paper一

Electrodeposition of Nb−Sn Alloy from SnCl2−NbCl5−EMIC
              Ambient Temperat皿e Molten Salts

Nobuyuki KOURA，Takayuki UMEBAYASHI，Yasushi IDEMOTO，＊and Guoping LINGa

Faculty of Science＆Technology，Tokyo University of Science（2641Yamazaki，Noda−shi，Chiba278−8510，
Japan）
aDepartment of Material Science＆Engineering，Zhejiang University（Hangzhou，310027，P．R China）

Received December7，1998； Accepted March l，1999

The electrodeposition of the Nb−Sn alloy from the SnCl2−NbCl5−EMIC melt was investigated．From the results
of the physical properties and cyclic vo］ltammetry，the possibility of electrodeposition of the Nb−Sn alloy was
suggested，which was subsequently obtained from the melt by electrodeposition．However，the Nb content in
the deposits was very low．The Iow Nb content was related to the low limiting current density of Nb。From
the results of bath temperature，melt composition and pulse electrolysis for increasing the Nb content in the
deposits，the Nb−Sn alloy containing69．l wt％Nb was obtained from the2．8mol％SnCl2−68．6mol％NbCl、一
28．6mol％EMIC melt at200mA cm 2with a pulse period of lO ms，duty ratio of O2at160℃．

κ￠y防眺：Electrodepositlon，Ambient Temperature Molten Salt，Nb−Sn Alloy，EMIC

              11ntro征uction
  Nb3Sn is one of the superconductor materials used
practically．However，it is very difficult to make the
Nb3Sn into linear shapes，because Nb3Sn is inter−
metallic compound and is very brittle．Therefore，
the powder method，1）初s吻method2）and vapor
deposition method3）were developed。These complex
process methods，4）however，require many steps．On
the other hand，it is considered that one can easily use
the electrodeposition method of Nb3Sn in one step
an（1continuously make it into various electro（ie
shapes．However，Nb is impossible to（leposit from
aqueous bath，because of the less noble reduction
potential of Nb（Nb（0）／Nb（皿）1−1，10Vvs．NHE）．
Hence，the halide molten salt at high temperature
（LiF−NaF，5）LiF−KF，6）LiF−NaF−KF，7）Na（⊃1−KC18）and
LiC1−KCI9））， 1iquid halogen and hydrogen halide，
such as HF，at low temperaturelo）and organic solvent
at room temperature11）have been used for electrode−
positing Nb．Moreover，it was reported that Nb3Sn
was obtained from a high temperature molten salt
melt．12）However，these baths require a high temper−
ature，therefore they are liable to cause corrosion，
ignition and are poisonous．
 On the other hand，the ambient temperature molten
salt using1−butylpyridinium chloride（BPC）and1−
ethyl−3−methylimidazolium chloride （EMIC）have
advantages such that the process is performed at
ambient temperature，and there is no fFear of igni−
tion．13）
 We clarified that the electrodeposition of Nb−Sn
alloy was possible from an SnC12−NbCI5−BPC melt
and the Nb−Sn alloy containing44．3wt％Nb was
obtained during pulse electrolysis．14・15）However，the
Nb content in the Nb−Sn alloy obtained from the BPC
system melt was low in comparison with the Nb
content of Nb3Sn having70．1wt％．Therefore，we
have to increase the Nb content of the Nb−Sn alloy．
  In this paper，we studied the electrodeposition from
the EMIC system ambient temperature molten salt
that has good physical properties，such as melting
point，viscosity and con（1uctivity，an（i stability under
high temperature in comparison with those of the
BPC system melt for increasing the Nb content in the
deposits．
             2 Experimental
  SnCl2，NbCl5and EMIC used special grade reagents
that had been dried under vacuum for48h．The
molten salt was prepared by slowly mixing SnCl2，
NbC15and EMIC with stirring until the desired molar
ratio was obtained in a glovebox containing a dry Ar
atmosphere．
  The conductivity was measure（i by a conductivity
meter（TOA Electronics，Ltd．，CM−40S），and the vis−
cosity was measured using a Ostwal（i viscometer．
The cyclic voltammetry（C。V．）was measured by a
three−electrode system in a glass ce1L A Pt wire was
used as the working electrode，and an Sn（99．99％）
plate or Nb plate（99．8％）were use（1as the counter
67，No．6（1999） 685

electrode．An Sn wire（99，99％，φ：1mm）immersed were less than100。C．The viscosity and the conduc−
in a66．7mol％SnCl2−33．3mo1％EMIC melt in a tivity for the various composition melts were also
pyrex tube（φ：10mm）separated by a G491ass frit measured（Fig．1）．The viscosity decreased with
was used as the reference electrode．The C．V．mea− increasing temperature；the viscosity of these melts
surement was carried oUt using a potentiostat／ was less than25cP above130。C．On the other hand，
galvanostat（Nikko Keisoku NPGS−305）connected to the conductivity increased with increasing tempera−
a function generator（Nikko Keisoku NFG3）an（1an ture；it was higher than75mS cm−1above130℃．
X−Y recorder（TOA Electronics，Ltd．，XYR−2B）． Hence，the SnCl2−NbC15−EMIC melt was used for the
 Electrodeposition was carried out by potentiostatic electrodeposition of the Nb−Sn alloy．
and galvanostatic electrolysis with stirring the melt． 3。1．2 Cyclic voltammetry   Cyclic voltammo−
ACuplate（99．99％）wasusedastheworkingelec− grams were obtained in order to investigate the redox
trode． The counter and the reference electrodes behavior（Fig．2）．For the SnC12−EMIC melt，a set of
were the same as used for the C．V．measurements． reduction and oxidation peaks related to the（leposi−
The pulse electrolysis was carried out using a current tion and dissolution of Sn was measured．On the
pulse generator（Nikko Keisok｝NCPG−10−10）。 The other hand，in the SnCl2−NbCl5−EMIC melt，new cath−
obtained electrodeposit’s composition was analyzed odic current peaks，CI and C2，apPeared in the acidic
by the ICP（inductively coupled plasma atomic emis− and basic melts，suggesting the possibility of
sion spectroscopy）method and structure was deter− electrodeposition of the Nb−Sn alloy．Moreover，the
mined by an X−ray diffraction method． CI and C2cathodic current peaks have different peak
  The catho（lic polarization curve for the partial potentials．The amount of ionic species changes
current of Nb and Sn was obtained by the composi− significantly by changing the melt composition based
tion of the electrodeposit determine（i by ICP after the
叩
200
potentiostatic electrolysis． 目              ダ（c）
の
  Electrodeposition and the measurements of physi− ＜ 100
…i                げノ
cal properties，C。V．，and polarizatiom curve were       ．一。／ジ：ノ’（b）
、
done in a glovebox containing a dry Ar atmosphere． h
，揖
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         3 Results and Discussion
qの 一100
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3．1 Properties of SnCl2・NbCl5−EMIC melt 自 ∼       acidic melt
5
3．1．1 Physical properties    Freezing point， り
一200
viscosity and conductivity were measured for obtain− 一〇．5  0．0  0．5  1．0  1．5

ing fundamental physical properties about the SnC12− Potential1Vvs．Sn（II）／Sn（0）
NbC15−EMIC melt and investigating the possibility of
its use as an electrodeposition bath before the 1QG
electrodeposition of the Nb−Sn alloy． The freezing ツ
iii ／を．、瀞4緯
50

I
points of measured the various composition melts
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520
の （a）
o     暮
40 ℃   Potential！Vvs．Sn（II）／Sn（0）
    唱
  10     0
   9 Fig．2 Cyclic voltamograms for EMIC system melts at
   0 0 130℃．
           100   120   140   160
（a）：66．7mol％SnC12−33．3mo1％EMIC，（b）：64．5mol％
              Temperature！OC
SnCl2−3．2mol％NbC15−32．3mo1％EMIC，（c）：60．6mo1％
Fig．1Conductivity and Viscosity of SnC12−NbC15一一EMIC SnC12−9．1mo1％NbC15−30．3mol％EMIC．
melt． （a〆）：33．3mol％SnCl2−66．7mo1％EMIC，（b〆）：32．3mo1％
（a）●，○：66．7mol％SnC12−33．3mo1％EMIC melt，（b）▲， SnCl2−3．2moll％NbCl5−64．5mo1％EMIC，（c’）：30．3mol％
△：64．5mol％SnCl2−3．2mol％NbCl5・32．3mol％EMIC SnCl2−9．1mol％NbCl5−60．6mol％EMIC，Cathode：99．99
melt，（c）■，□：60．6mol％SnC12−9．1mol％NbCl5−30．3mol ％Pt，Anode：99，8％Nb，Scan rate：10mV sec−1without
％EMIC melt． stirring．
 686 EJ66ケooh6窺ゑs渉か

on the studies of the AICI3−BPC，CuC1−BPC and SnC12−
BPC16）systems．Since the peak potential changed by
the melt composition，it is considered that the ionic
species could be different． Consequently，the differ−
ence between CI and C2could be attributable to the
changing ionic species．
3．2 Electrodeposition of Nb鶴Sn alloy
 For the purpose of confirming the electrodeposit
from the SnCl2−NbCl5−EMIC melt，we examined the
electrodeposition of the Nb−Sn alloy using the60，6
mol％SnC12−9，1mo1％NbCl5−30．3mol％EMIC melt
that has a Iow viscosity and high conductivity．By
electrodeposition using the potentiostatic metho（1at
C1（Fig．2），the Nb−Sn alloy was obtained from this
increasing Nb content in the melt．
  From these results，the low Nb content is caused by
the low limiting current density of Nb compared with
Sn．Hence，an increase in limiting current density of
Nb is effective for increasing the Nb content in the
deposits．The value of the limiting current density，
歪1，is represented by the next equation．
       C
（3）
11二n皿）一
       δ
where n is the number of electrons，F is Faraday
constant，Z）is the diffusion coefficient，C is the bulk
concentration，and δ is the thickness of diffusion
layer。

melt．It is considered that C1，that appeared by
adding NbCl5to the SnC12−EMIC melt，is related to
the electrodeposition of the Nb−Sn alloy． Further−
more，the potentiostatic electrodeposition was perfor−
med in the range of−0．1to−1．O V vs．Sn（0）／Sn（II）．
This result is shown in Table L The Nb content of
the Nb−Sn alloy was the highest at−0．5V vs．Sn（0）／
Sn（II）．However，the Nb contents from this melt
were less than10wt％；these results we］re very low
compared with Nb3Sn（70．1wt％）．The cathodic
polarization curves for the partial current of Nb and
Snusingthe SnC12−NbC15−EMIC meltwas measured in
order to get the informations for increasing the Nb
content in the Nb−Sn alloy．
3．3 Polarization curves for the partial current of
Nb and Sn deposition
  The cathodic polarization curves for the partial
  From equation（3），the method of increasing the
limiting current density of Nb is（i）increasing the
diffusion coefficient Z）by increasing the bath temper・
ature，（ii）increasing the Nb（IV）species related to the
deposition，and （iii） decreasing the （1iffusion layer
thickness by pulse electrolysis．Then，we examined
these methods．
3．4 1ncrease in Nb content a皿ing Nb−Sn alloy
plating
3．4．1 Effects of bath temperat皿e   The
effect of bath temperature on the Nb content in the
Table l Nb content in the potentiostatic electrodeposited
Nb−Sn alloy from60．6mol％SnC12−9．1mol％NbC15・30．3
mo1％EMIC melt with stirring．（130℃）
    Potentia1 Nb content
V vs．Sn（II）／Sn（0）  （wt％）

current of Nb and Sn deposition were measured．It 一〇．1 9．2

was considere（1that Sn is electrodeposj．ted from a 一〇．3 9．8

bivalent ionic species，such as SnCl3−and Sn2Cl5一，and
一〇．5 10．2
the pentavalent Nb ion is reduced to the tetravalent
一〇．7 8．8
ionic species by oxidation of the bivalent Sn ion to
一〇．9 8．6
tetravalent ionic species． Hence，Sn and Nb are
electrodeposited from the bivalent and the tetravalent 一1．0 6．6

species，respectively．15）
9 ’

9Q100
S論

Sn（II）→Sn（IV）十2e− （1）
”
Sn
Nb（V）十e一→Nb（IV） （2）
＜
e ’幡’

   This assumption could be correct，because the ぺ
．わ ごNb

 current efficiency of electrodeposition of the Nb−Sn 暮10
 alloy was approximately100％based on the assump− 名
 tion． 揖
む
自
O  Cathodic polarization curves for the partial current づ   0．0   −0，1  −O．2 一〇．3 一〇．4
り
 of Nb and Sn deposition in SnCl2−NbCl5−EMIC are
Potential／Vvs．Sn（II）！Sn（0）
 shown in Fig．3．づNb and Jsn in the figure are the
 cathodic polarization curves for the partial current of Fig．3 Effects of the composition of the melt on the
 Nb and Sn deposition，respectively．The limiting Iimiting current density with stirring．

 current density of Nb was27to35mA cm 2and Sn ●濱Nb，■ら。：64．5mo1％SnC12−3．2mol％NbCl5−32．3mol

 did not reach the limitting current density from Fig．3． ％EMIC，O∫Nb〆，口乞s．〆：60．6mol％SnCl2−9．1mol％
 Moreover，the limiting current density in（）reased with NbC15−30．3mol％EMIC．
67，No．6（1999） 687

deposits was investigated in the60．6mol％SnC12−9．1
mol％NbCl5−30．3mo1％EMIC melt（Fig．4）．When
the bath temperature was increased from130℃to
160℃，the Nb content increased and the maximum
Nb content was obtained at160℃．However，the Nb
content in the deposits decreased with increasing
temperature above160℃，since the SnC12−NbCl5−
EMIC melt was decomposed at high temperature．
Accordingly，all experiments were performed at
160℃for which the maximum Nb content in the
deposits was obtained．
3．4．2 Effects of immersing Sn wire into the melt
 The method of increasing the limiting current den−
sity is increasing Nb（IV），from which Nb is deposited．
It is known that the decreased valence of the ionic
species in the melt is important for increasing the Nb
content in the deposits．Accordingly，the Nb ions
were reduced from pentavalent ionic species to
tetravalent by immersing Sn wire in the SnCl2−NbC15−
EMIC melt according to the following equations．
The electmdeposition carried out by changing the
proportion of NbC15and SnC12by keeping the total
molar amount of metal chloride（NbCl5and SnC12）
and EMIC in the melt constant．These results are
shown in Fig．5．The Nb content was significantly
increased with increasing amount of NbC15and
decreasing the amomt of SnC12．Particularly，the
Nb・Sn alloy containing60．8wt％Nb was obtained
from the2 ，8mol％SnC12−68．6mo1％NbCl5−28．6mol
％EMIC melt．It is thought that the limiting current
density of Nb had relatively increased by increasing
the limiting current density of Nb deposition and
decreasing that of Sn （1eposition by increasing the
Table2 Effect of immersing time of Sn wire on Nb
content in the Nb−Sn alloy from60．6mol％SnCl2−9．1mol
％NbCl5−30，3mol％EMIC melt at l60℃with stirring．
  ImmersingtIme
望time Current density Nb content
      （hou1））  （mA cm』2）  （wt％）
5 3．4

0 50 8．2
Sn（0）→ Sn（II）十2e− （4）
100 16．2
Nb（V）十e一→Nb（IV） （5）

5 3．5

When Snwire immersedinthemelt andtheimmer− 3 50 9．2

sing time changed，the results of the galvanostatic 100 17．2

deposition showed in Table2．The Nb content in the
5 1．5
deposits increased with increasing immersion time of
the Sn wire．As a result，the immersion time of the
6 50 9．7

100 19．8
Sn wire was fixed at24h．
3．4．3 Effects of NbCl5content in the melt 5 3．8

  It was thought that the Nb content in the deposits 12 50 10．2

increased with increasing amount of NbCI5in the 100 22．3

melt because of the increasing Nb（IV）．As a result， 5 4．1

the Nb content in the deposits increased with increas− 24 50 14．2
ing NbCl5in the melt．However，the Nb content was 100 24．8
only slightly increased． So，for effectively increas−
ing the amount of NbC15in the melt，the amount of 70
NbC15increased and the amount of SnC12decreased． 60
尽
レの
3： 50
17 ＝1
40
琶i

16 岩 30
尽 15 8 20
3
り
14
‘）

z
≧ 10
5 13  0
砦
8
                 40    60    80   100
 20
12
              Current density／mA cm’2
ρ
z 11

10
 120  140  160  180 200
Temperature l oC
Fig．4 Effects of the bath temperature on the Nb content
in the Nb−Sn alloy from60，6mol％ SnCl、一9。1mol％
NbCl5−30．3mol％EMIC melt with stirring．
Fig．5 Relationship between current density and Nb
content in the galvanostatically deposite（i Nb−Sn alloy
from three kinds of melts，added Sn wire at160℃with
stirring．
（a）：57．1mol％SnCI2−14．3mol％NbCl5−28．6mol％EMIC，
（b）：28．6mol％SnCl2−42．8mol％NbCl5−28．6mo1％EMIC，
（c）：2．8mol％SnCl2−68．6mol％NbCl5−28．6mol％EMIC．

  

688
amount of NbCl5and decreasing the SnCl2in the melt，
and other reason is thought that ionic species of Sn
and Nb change by the melt composition．
3．5 Pulse electrolysis
  It has been reported that the composition of the
alloy can be changed by changing the pulse perio（1，
duty ratio and pulse current density．For example，
the various contents of the Nb−Sn alloy deposited
from SnC12−NbCl5−BPC and Sn−NbCl5−BPC by pulse
electrolysis15）were reporte（i．
  Based on Fig．3，the increase in the limiting current
density of Nb is required to increase the Nb content in
the（ieposits． In the case of pulse electrolysis，it is
expected that the Nb content in the（1eposits increased
because the thickness of the diffusion lay「er decreased
compared to the galvanostatic deposition．
  First，the pulse current density and duty ratio were
changed at the100ms pulse period from the2．8mol％
SnCl2−68．6mol％NbCl5−28，6mo1％EMIC melt which
produced the maximum Nb content by galvanostatic
deposition（Fig．6）。As a result，the highest Nb con−
tent in the deposits was of64．7wt％at200mA cm
for a duty ratio of O．2． The effect of duty ratio on the
Nb content depended on the current（1ensity． In the
case of50mA cm−2and100mA cm皿2，the Nb content
increased with increasing duty ratio which shows the
effect of a long on−time、The reason is that the
reaction rate at low current density is slow in com−
parison with a high current density，therefore，the Nb
deposition did not reach the limiting current density
at high duty ratio． On the other hand，in the case of
150mA cm2and200mA cm2，the Nb content in−
creased with decreasing duty ratio．It was thought
that since most of the Nb ions were consumed for
deposition， the concentration of the Nb ions de一
70
（d）
60 （c）
ぷ ま
と
50
き ≧
≧ 40
8 30
揖
8 20
』
（b）
    ▽
▽
A Q 20
z 10
（a）
0
            0．0  0．2  0．4  0．6  0．8  1．O
                    Duty ratio
Fig．6 Relationship between duty ratio and Nb colltent in
the deposits at the pulse electrolysis at160℃and100ms
with stirring．
Bath；2．8mol％SnCl2−68．6mol％NbCl5−28．6mo1％
EMIC melt added Sn wire．
（a）：C．D．50mA cm 2，（b）：C．D．100mA cm 2，（c）：C．D．150
mA cm 2，（d）：C．D．200mA cm
2．
一L＿
EJ66’706h召ηzZs’勿v
creased for a high（1uty ratio and the Nb ion is insuffi−
ciently supplied during the short off−time．Hence，
Nb easily reached its limiting current density，and Sn
deposition was preceded because Sn composition is
low in the melt。
 Fτom the former result of pulse period and duty
ratio for the Nb content in the deposits，it was inves，
tigated using a constant current density at200mA・
cm−2 Fig．7）．When the pulse period，T，decreased
from lOOO ms to10ms，the Nb content in the deposits
increased regardless of the duty ratio． The Nb con−
tent in the deposits obtained from the10ms pulse
period is larger than of lOOO ms because the thickness
of diffusion layer increased with（1ecreasing pulse
period and the deposition of Sn，which has a low
deposition current density，decreased．
  Finally，we obtained an Nb−Sn alloy containing
69．l wt％Nb from the2．8mol％SnC12−68．6mol％
NbCl5−28．6mo1％EMIC melt at200mA cm−2when
T二10ms and the duty ratio is O．2．Figure8shows
the X−ray diffraction pattems in the deposits．The
2
peaks of the Nb−Sn alloy apPeared and the peak
intensity of the Nb−Sn alloy increased with increasing
Nb content in the deposits． Therefore，it is expected
that the obtained deposit is the Nb−Sn alloy．The
Nb−Sn alloy is mainly Nb3Sn．The supercon−
ductivity property of the Nb−Sn alloy is now under
inveStigatiOn．
               4  Conclusion
  For the electrodeposition of the superconductor
Nb3Sn，the properties of melt，bath temperature，
composition of melt and current density during
galvanostatic deposition，and pulse current density，
pulse period and duty ratio during Pulse electrolysis
   70 （a）
A
   60
o
一 50
（b）
＼ 40
三
8 30
8 （c）
ゆ
回
乞 10
    0
0．0 0．2  0．4  0．6  0．8  1．O
    Duty ratio
Fig．7 Relationship between duty ratio and Nb content in
the deposits at the pulse electrolysis at l60℃and200mA・
cm−2with stirring．
Bath：2．8mol％SnCl2−68。6mol％NbCI5−28．6mo1％
EMIC melt added Sn wire．
（a）：Pulse period lO ms，（b）＝Pulse period100ms，（c）：Pulse
period1000ms
67，No．6（1999） 689

1000 ■
mol％SnC12−68．6mo1％NbC15−28．6mo1％EMIC melt
（a） ▲ ■
at100mA cm 2and l60。C、
  Moreover，the Nb content increased by pulse elec−
500   蓼 trolysis from the2．8mol％SnCl2−68。6mol％NbCl5−
  2 28．6mo1％EMIC melt．The Nb content in the
   ↑

     0    ♂ （1eposits changed with pulse current density，pulse

     20 30  40  50  60  70 80焉 ratio and dllty ratio．Finally，we obtained an Nb−Sn
ピ
i≡1000   あ alloy containing69．1wt％Nb from the2．8mo1％
コ ■ ■
（b）
  ム SnC12−68．6mo1％NbC15−28．6mo1％EMIC melt at200
の
お   Z
   Φ mA cm 2for a pulse period of10ms，duty ratio of O．2

〉500
・錺 ▲  ●  ●
  ‘
  ト
   ⊆
and at160℃。

毎   ゲ
   ⊆
芒    Φ                 References
一   〇   り
   ⊆
     20 30  40  50  60  70  80 o 1）R．Bormam，H．C．Freyhardt，and H．Bergmann，∠4勿」。
の
  P勿s．L観．，35，944（1980）．
  1000
      （c）
菱 2）H．Kumakura，K．Togano，and K．Tachikawa，
●
≦   ！44∂α％66s わz C勿ソog6π6ガ6E多z8ゴπ667Jng，28，515（1982）．
．9）
3）S．Gonda・，S銘吻06，19，474（1981）（in Japanese）．
500 ▲ 工
● 4）Y．Tanaka，Cho46n40鋸 渉o so％0 0妙o％，Sangyou
   Tosyo，p．57（1989）（in Japanese）．
5）Q．Zhiyu and T．Pierre，1．El66渉706hωn．So6．，15，259
0
          20  30  40  50  60  70  80
   （1985），

6）U．Cohen，∫．El60ケooh6別．506。，128，731（1981）．
                  20（Cu−Kα）
7）G。P．Capsimalis，E．S．Chen，and R．E。Peterson，∫．
Fig．8 XRD diffraction pattems of deposits（2．8mol％    ノ1、ρブ）」．El‘36孟γ06h6簿z．，17，253（1987）．

SnCl2−68．6mo1％NbC15−28．6mol％EMIC melt at200mA
 
cm−2
（a）10．2wt％Nb（丁二1000ms，duty ratio：0．8），（b）24．8wt
％Nb（丁二10ms，duty ratio二〇．8），（c）69．1wt％Nb（丁二10  
 
ms，duty ratio：0．2），●：Nb−Sn Alloy（mainly Nb3Sn），▲：
10）V．Taranenko，K．D．Sienerth，N．Sato，A．G．Edwards，
Sn，■：Cu
 
 
8）1。Nakagawa and Y．Hirabayashi，P6％h診καgα肋（pres−
  ently El66か06h6ηz乞s耽y），51，256，（1983）（in Japanese）．
9）K．Zhou，T．Takenaka，N．Sato，and M．Nanjo，1）6nh乞
  κ‘zgαhz6（presently El66か06h6錫πs疏y），59，981 （1991）（in
  Japanese）．
  and G．Mamantov，〃1鷹7翅s S6勿n66Fo7％解，73−75，
  595（1991）．

were investigated．
 The SnCl2−NbC15−EMIC melt could form a molten
salt，and the melt煽as useful for the electrodeposition
of the Nb−Sn alloy．The Nb−Sn alloy was obtained
from the melt by electrodeposition．
11）N．S．Chong，J．L．Anderson，and M．L．Norton，∫．
   El雄706h翻．So6．，136，1245（1989）．
12）R．Gel，（｝．Drobotenko，and V．Kolosov，〃「．S，3動’．
   8y”zρ．〃り1渉。Sα1．，Paris，P．11（1991）．
13）S．Takahashi and N．Koura，T6孟梛一！〇一施g召彫，77，921
   （1991）（in．Japanese）．

 The methods of increasing the Nb content in the
deposits from the melt were investigated by increas−
ing the bath temperature，the addition of Sn wire，
increasing the NbCl5 content an（1 decreasing the
SnCl2content． For these results，an Nb−Sn alloy
containing60．8wt％Nb was obtained from the2．8
14）N．Koura，G．Ling，and H．Ito，∫．S鋸4FJ痂sh．So6．〃銘．，
   46，1162（1995）（in Japanese）．
15）G．Ling and N．Koura，∫．S％4Fガn乞sh．So6．ヵ）％．，48，454
   （1997）（illl Japanese）．
16）G．Ling；and N．Koura，P6πhJκ㎎αhκ（presently五ll66一
   ケ06h6ηz奮耽y），65，149（1997）（in Japanese）。

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