Transcript Synthesize of Li-intercalated ZrNCl and ZrNBr Superconductor (Dikti Sandwich Program in IMR Tohoku Unv.) Andhy Setiawan Bandung Institute of Technology (ITB)

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Synthesize of Li-intercalated
ZrNCl and ZrNBr Superconductor
(Dikti Sandwich Program in IMR Tohoku Unv.)
Andhy Setiawan
Bandung Institute of Technology (ITB)
Synthesize of Li-intercalated
ZrNCl and ZrNBr Superconductor
(Dikti Sandwich Program in IMR Tohoku Univ.)
Have been presented on January, 21st 2009 by
Andhy Setiawan
In IWASA Lab. IMR Tohoku University
Sendai, January, 29th 2009
Prof. Yoshihiro IWASA
Introduction
 Dikti Sandwich Program is purposed to facilitate graduate students
of Indonesia University to have a certain experience in overseas
university
 ITB<=>IMR
PECVD Lab.
(ITB)
IWASA Lab.
(IMR)
Getting new
experiences
 Synthesize of Li-intercalated ZrNCl and ZrNBr Superconductor
Synthesize Procedure and Its Apparatus
Synthesize of Li-intercalated ZrNCl and ZrNBr Superconductor
Material
Diamond wheel saw
Burner app.
cutting
Sealing
Preparation
Ultrasonic cleaner
Ultrasonification
Quartz tube
drying
Oven
Vacuum and burner app.
pumping and sealing
Step 1: Synthesize of ZrNCl and ZrNBr
Chemical vapor transport
-Vacuum and burner app.
-Furnace (double heater)
Step 2: Purification
Intercalation
Dispersing into
BuLi/hexane solution
Filtering and Collecting Sample
-Accurate pipette
-Stirrer
-Glove Box
-mesh, membrane, and filter app.
-glove box
-vacuum, He filler and burner app.
Superconductor
sample
Measurement and Its Apparatus
Measurement
Crystal Structure
x-ray diffraction
Magnetization :
M vs T
M vs H
SQUID PPMS
Resistivity :
Res. vs T
Some
Properties
Experiment
• Synthesize of ZrNCl :
– ZrH2 (1g) + NH4Cl (10 g)
• Synthesize of ZrNCl (NMR) :
– ZrH2 + NH4Cl (15N)
• Synthesize of ZrNBr :
– ZrH2 + NH4Br
• Purification of ZrNCl and
ZrNBr
• Intercalation (synthesize of
LixZrNCl, LixZrNBr)
• Measurement
Synthesize of ZrNCl
400 0C
600 0C
N2
NH4Cl
10 g
ZrH2
1g
700
NH4Cl
ZrH2
600
500
Step 1 :
400
Synthesize of
ZrNCl
300
200
100
0
0 1 2 3 4 5 220
240
260
t (minutes)
280
300
320
Purification of ZrNCl
750 0C
ZrNCl +
0.1NH4Cl
850 0C
Pure ZrNCl
800
600
Step 2 :
Purification
400
Left
Right
200
0
0
1
2
3
4 38.8
t (hours)
38.9
39
39.1
39.2
Synthesize and Purification of ZrNCl (NMR)
and ZrNBr
750 0C
850 0C
800
ZrH2 + 15NH4Cl
(ZrH2 + NH4Br)
600
Step 1 : Synthesize
400
Left
Right
200
Step 2 : Purification
0
0
1
2
3
4
5
6 40
40.2
t (hours)
40.4
40.6
40.8
750 0C
ZrNCl + 0.1 15NH4Cl
(ZrNBr + 0.1 NH4Br)
ZrNBr
850 0C
Pure ZrNCl
(ZrNBr)
Intercalation
• Intercalation Li to ZrNCl
Exp
ZrNCl
(mg)
ZrNCl
(mmol)
BuLi
(mL)
Li
(mmol)
x
141.3
1.00
400
0.40
0.40
Exp1
145.4
1.03
400
0.40
0.39
s-BuLi
140.5
1.00
500
0.50
0.50
137.9
0.98
500
0.50
0.51
140.3
1.00
125
0.20
0.20
Exp2
141.1
1.00
62.5
0.10
0.10
n-BuLi
139.9
0.99
36.25
0.058
0.06
140.2
1.00
12.5
0.02
0.02
Intercalation
• Intercalation Li to ZrNCl (NMR)
Exp
ZrNCl
(mg)
ZrNCl
(mmol)
BuLi
(mL)
Li
(mmol)
x
Exp4
246.8
1.75
87.5
0.14
0.08
n-BuLi
313.4
2.23
278.4
0.45
0.20
310.5
2.21
276.1
0.44
0.20
• Intercalation Li to ZrNBr (will be done)
x = 0.05 – 0.15
Measurement
Crystal Structure of ZrNCl (x-ray powder diffraction)
(003)
Cl
Zr
(110)
N
c
b
600
a
9.47
49.2
a = b = 3.602 Ǻ , c = 27.246 Ǻ
0.1
Measurement
Magnetization (emu/g)
0
Magnetization of LixZrNCl
15
-0.1
-0.2
-0.3
x = 0.51
x = 0.50
x = 0.40
x = 0.39
x = 0.20
x = 0.10
x = 0.06
x = 0.02
-0.4
90
-0.5
80
14
-0.6
6
70
Tc (K)
60
50
12
10
12
Temp. (K)
14
16
18
20
VF (%)
13
8
15
11
30
10
0
0.1
0.2
0.3
0.4
0.5
20
0.6
3
40
y = -4M (emu/cm )
10
5
0
y = 0.1362 + 0.76884H x= 0.51
y = 0.12265 + 0.84609H x= 0.50
y = 0.25383 + 0.81265H x= 0.40
y = 0.1144 + 0.76148H x= 0.39
y = -0.046203 + 0.51269H x= 0.20
y = 0.25603 + 0.43245H x= 0.10
y = -0.71144 + 0.51655H x= 0.06
y = -0.42102 + 0.26323H x= 0.02
-5
-10
x
-15
-20
-30
-20
-10
0
H (Oe)
10
20
30
Measurement
Resistivity of LixZrNCl
3
2
2
Resistivity (Ohm-m)
Resistivity (Ohm-m)
2.5
1.5
1
0.5
1.5
1
0.5
0
0
-0.5
0
50
100
150
200
Temperature (K)
250
300
0
4
8
12
16
Temperature (K)
20
24
Conclusion
I have learned to
• Synthesize of Li-intercalated ZrNCl and
ZrNBr superconductor.
• Measure the crystal structure,
magnetization, and resistivity.
Acknowledgment
• Prof. Yoshihiro IWASA
• Miho EUMURA
• Yuichi KASAHARA and Superconductor
Team in IWASA Lab. (Katsuki KOBAYASHI,
Tsukasa KISHIUME, Takumi TAKANO)
• IWASA Lab. Member (T. TAKENOBU, H.
SHIMOTANI, SATRIA ZB, H.T. YUAN, J. YE,
S. INOUE, Y. YOMOGIDA, H. OKIMOTO, S.
TSUDA, S. KIUCHI)
Thanks for Nice Moments