This is the authors version of a work that was submitted/accepted for publication in the following source:

Hu, Ning, Itoi, Takaomi, Akagi, Taro, Kojima, Takashi, Xue, Junmin, Yan,
Cheng, Atobe, Satoshi, Fukunaga, Hisao, Yuan, Weifeng, Ning, Huiming,
Surina, , Liu, Yaolu, & Alamusi,
(2013)
Ultrasensitive strain sensors made from metal-coated carbon
nanofiller/epoxy composites.
Carbon, 51, pp. 202-212.
This file was downloaded from: http://eprints.qut.edu.au/70083/

c Copyright 2012 Elsevier Ltd.

NOTICE: this is the authors version of a work that was accepted for publication in Carbon.
Changes resulting from the publishing process, such as peer review, editing, corrections,
structural formatting, and other quality control mechanisms may not be reflected in this
document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Carbon, [Volume 51, (January
2013)] DOI: 10.1016/j.carbon.2012.08.029

Notice: Changes introduced as a result of publishing processes such as

copy-editing and formatting may not be reflected in this document. For a
definitive version of this work, please refer to the published source:
http://doi.org/10.1016/j.carbon.2012.08.029

Figure 1. SEM images of M-Ni. a) Before acid-treatment. b) After acid-treatment

(a)

Ni

Agglomeration

(b)

Ni

20

Figure 2. SEM and TEM images of V-Ni before acid-treatment. a) SEM image and
elemental map. b) TEM images.

(a)

Ni

(b)

Ni

21

Figure 3. SEM and TEM images of V-Ni after acid-treatment. a) SEM image and
elemental map. b) TEM images.

(a)

Ni

(b)

Ni

22

Figure 4. SEM and TEM images of V-Ag. a) SEM image and elemental map (after
acid-treatment). b) TEM images (after acid-treatment). c) high magnification TEM
image (after acid-treatment). d) TEM and SEM images (before acid-treatment).

(a)

Ag

Ag

(b)

continued
23

(c)

Ag
0.24 nm
(111)Ag

VGCF

(d)

Ag

24

Figure 5. Piezoresistivity of various strain sensors. a) Resistance change ratio

versus applied strain (MWCNT). b) Resistance change ratio versus applied strain
(VGCF). c) Resistance change ratio versus applied strain (M-Ni). d) Resistance
change ratio versus applied strain (V-Cu). e) Log-Log plot of c) for M-Ni.

Resistance change ratio [%]

(c)

Resistance change ratio [%]

18
16
14
12
10
8
6
4
2
0
0

(b)
3.0wt.%
5.0wt.%
6.0wt.%
7.0wt.%
9.0wt.%
K=2

1000 2000 3000 4000 5000 6000

Micro-strain

30
25
20

2.5wt.%
3.0wt.%
5.0wt.%
K=2

15
10
5
0
0

1000 2000 3000 4000 5000 6000

40

3.0wt.%
5.0wt.%
6.0wt.%
7.0wt.%
9.0wt.%
K=2

20
0
0

1000 2000 3000 4000 5000 6000

Resistance change ratio [%]

Resistance change ratio [%]

60

25
20
15

3.0wt.%
5.0wt.%
6.0wt.%
7.0wt.%
9.0wt.%
K=2

10
5
0
0

1000 2000 3000 4000 5000 6000

Micro-strain

100
80
60
40

3.0wt.%
5.0wt.%
6.0wt.%
7.0wt.%
9.0wt.%
K=2

20
0
0

1000 2000 3000 4000 5000 6000

(f)

120

80

30

Micro-strain

Micro-strain

(e)
100

35

(d)
Resistance change ratio [%]

Resistance change ratio [%]

(a)

Micro-strain

54.60
20.09
7.39
2.72
1.00
0.37
0.14
0.05
0.02

2.5wt.%
3.0wt.%
5.0wt.%
K=2

148.4

403.4

1096.6 2981.0 8103.1

Micro-strain

25

Figure 6. Gauge factor of various strain sensors. a) Comparison of gauge factors

of various MWCNT based strain sensor. b) Comparison of gauge factors of various
VGCF based strain sensor.

140
MWCNT
M-Ni
M-Cu

Gauge factor

120
100
80
60
40
20
0
0

1
2
3
4
5
Nanofiller loading [wt.%]

200
VGCF
V-Ni
V-Cu
V-Ag

Gauge factor

160
120
80
40
0
0

2 3 4 5 6 7 8 9 10
Nanofiller loading [wt.%]

26

Figure 7. Dispersion states of nanofillers, and influences of internal conductive

network on strain sensor behaviors. a) Comparison of dispersion states between
pristine and metal-coated nanofillers. b) Working mechanisms of conductive network.
c) Influence of nanofiller length on sensor behaviors. d) Comparison of fractured
surfaces of V-Ni, V-Cu and V-Ag specimens (5wt.% loading)

(a)

MWCNT 3wt.%

M-Cu 3wt.%

Pristine
CNF/Epoxy composite

VGCF 3wt.%

Metal-coated

V-Cu 3wt.%

CNF/Epoxy composite

Relatively modest
aggregates
Relatively modest
aggregates

(b)

Sparse network

Intensive network

Breakup of conductive path

27

Continued

(c)
Nanofillers

(d)

V-Ni 5wt.%

V-Cu 5wt.%

V-Ag 5wt.%

28

Table 1. Property of MWCNT and VGCF, and mass ratio of carbon and metals
Properties
Fiber diameter [nm]
Fiber length [m]
Purity [%]
Mass ratio between C
and metals
C:Ni
C:Cu
C:Ag

MWCNT
40~90
10~30
>99.5
Before acid treatment

VGCF
150
8
>99
After acid treatment

1:2.5
1:1
1:1.5

1:0.5
1:0.5
1:0.82

Table 2. Gauge factor and conductivity of composite strain sensors

Nanofiller loading [wt.%]
MWCNT
M-Ni
M-Cu
VGCF
Gauge factor
V-Ni
V-Cu
V-Ag
MWCNT
M-Ni
M-Cu
Electrical
conductivity
(S/m)

VGCF

1
22.4

3.3
-2
X10

4.68
X10

V-Ni
V-Cu

2
11.6

104.05

1.13
-0
X10
1.90
-3
X10
1.54
-4
X10

Percolation
Threshold
(wt.%)

MWCNT
0.1

3
8.6
16.17
36.88
43.01

134.5
154.5
2.11
0
X10
2.96
-2
X10
1.65
-3
X10
8.28
-3
X10
8.36
-4
X10
3.31
-3
X10
4.01
-5
X10
V-Ni
1.78

4.86
X10

-3

-5

M-Ni
1.5

2.26
X10

V-Ag

2.5

42.46

-4

M-Cu
1.85

VGCF
0.95

29

4
7.6

34.56

5.44
0
X10

3.54
X10

-2

V-Cu
1.75

5
6.2
9.47
14.18
34.66

76.68
122.23
1.04
1
X10
7.58
-2
X10
7.79
-2
X10
3.31
-1
X10
1.66
-3
X10
1.95
-2
X10
1.17
-4
X10
V-Ag
1.8

34.13
76.5
69.08
107.87

21.92
64.42
53.78
97.35

20.58
48.55
43.7
92.52

3.95
X10

-1

8.76
X10

-2

2.54
X10

-2

3.39
X10

-4

1.54
X10

1.28
X10

-1

7.32
X10

-2

9.11
X10

-4

9.94
X10

3.34
X10

-1

2.89
X10

-1

1.27
X10

-3