Deformation of single-walled carbon nanotubes under large axial strains

H.W. Zhang, K. Cai , L. Wang

State Key Laboratory of Structural Analysis for Industrial Equipment, Department of Engineering Mechanics, Dalian University of Technology, Dalian 116024, China
A B S T R A C T A R T I C L E I N F O
Article history:
Received 7 December 2007
Accepted 10 May 2008
Available online 25 May 2008
Keywords:
Nanostructures
Mechanical properties
Deformation and fracture
The deformations of single-walled carbon nanotubes (SWCNTs) under large axial strains are investigated. The
TersoffBrenner potential is adopted to describe the interactions between carbon atoms. Results show that
the changes of strain energies are dependent on chirality but independent of the tubes' radii. Under large
axial tension, abrupt changes of the congurations of SWCNTs may occur when the strains exceed 0.382 for
armchair patterns and 0.43 for zigzag patterns. The reason is that the changes of bond lengths and angles
lead to corresponding changes of many-body coupling interactions between atoms. Then the tubes reach
new equilibrium states. Such abrupt changes of congurations must trigger fracture of CNTs in a dynamic
deformation.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Since their discovery in the early 1990s [1], carbon nanotubes
(CNTs) have attracted more and more interests due to their excellent
properties such as low density, high strength and high stiffness. These
superior properties motivate intense research for the potential
applications of CNTs as structural materials [25]. For this reason,
understanding the mechanical behaviors of CNTs is critical [621].
Most of existing researches on Young's modulus of CNTs are under
rather small strains. A few studies on the mechanical behaviors of
CNTs under large strain have been reported [1214]. The main
objective of this paper is to explore deformations of CNTs under
large strain by mapping the tube to two-dimensional (2D), at and
unrolled sheet. Both chirality and radius dependency are considered.
Meanwhile, the congurations of the graphitic sheet under large
deformation along different directions are observed, as well. Different
from the modied Morse potential used by Belythchko et. al. [13] and
the REBO (reactive empirical bond order) potential by Liu et. al. [14],
the TersoffBrenner potential [22] is adopted for the interaction
between carbon atoms. It should be noted that the elongation strains
of the SWCNTs studied in the work [13] or [14] are less than 30%.
While, larger axial strains are considered in the current work.
2. Geometrical mapping between cylinder and plane
Since CNTcan be considered as a rolled graphitic sheet, one can map
it to the 2Dplanar sheet of carbonatoms as shown inFig. 1. The mapping
can be visualized by a cut of the CNTalong its axial direction followed by
the unrolling of the CNT to a plane without stretching. The distance
between each pair of carbon atoms in the unrolled plane (Fig. 1b) is
equal to the corresponding geodesic length on the CNT cylinder shell
(Fig. 1a). However, it should be noted that Fig. 1b is different from a
graphitic sheet since not only the bond lengths may not be identical, but
also the bond angles may deviate from 120. With the help of this
mapping, the computation and analysis onCNTcan be replacedby those
on the planar sheet. Fig. 1c shows a geometrical representative unit cell
including one central atomand its three nearest neighbor atoms, which
can ll the entire plane in Fig. 1b by repeating themperiodically. In such
a unit cell inplanar, unrolled sheet inFig. 1c, there are ve independent
geometric parameters: lengths l
1
, l
2
, l
3
and angles
12
,
13
. They
completely determine other lengths and angles in the planar cell. The
length of 01

is denoted by l
1
, and the lengths of 02

and 03

are denoted by
l
2
and l
3
, respectively.
12
represents the angle between 01

and 02

,
while
23
between 02

and 03

. C
h
is the chirality vector. a and b are
basis graphitic vectors dening the translations from one lattice point
to another.
i
, i =1, 2, 3 denotes the angle between line 0i

and C
h
.
The chirality vector can be expressed as an integral combination of
the two basis vectors,
C
h
n; m n a m b 1
where the set of two integers (n, m) is called as chirality index.
Three dimensional positions of the atoms in the geometrical unit
cell are marked as(x
i
y
i
z
i
), i =0, 1, 2, 3.
The distance between the ith neighboring atom and the central
atom can be expressed as follows,
r
i

x
i
x
0

2
y
i
y
0

2
z
i
z
0

2
_
R

2 1cost
i

2 l
i
sin
i
R
_ _
2

i 1; 2; 3 2
Materials Letters 62 (2008) 39403943
Corresponding author. Tel.: +86 411 84708751.
E-mail address: [email protected] (K. Cai).
0167-577X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2008.05.044
Contents lists available at ScienceDirect
Materials Letters
j our nal homepage: www. el sevi er. com/ l ocat e/ mat l et
The angle between vectors 0i

and 0j

(i, j =1, 2, 3) is,

/
ij
cos
1
r
2
i
r
2
j
r
2
ij
2r
i
r
j
_ _
i; j 1; 2; 3; ij 3
Where,
r
ij

x
i
x
j
_ _
2
y
i
y
j
_ _
2
z
i
z
j
_ _
2
_
R

2 1cos t
i
t
j
_ _ _ _

2 l
i
sin
i
l
j
sin
j
_ _
R
_ _2

4
is the distance between the ith and the jth atoms, R the diameter of
tube and t
i

l
i
cos
i
R
.
CNTs have minimum potential energy in their equilibrium states.
So the ve independent geometric parameters in planar sheet can be
obtained by solving the following formulas,
Find l
i
;
12
;
23
i 1; 2; 3
to minimize V l
i
;
12
;
23

subject to g
j
l
i
;
12
;
23
V0 j 1; 2;
: : :

l
i
N0;
12
N0;
23
N0
5
Where V is the potential energy of a CNT in an equilibrium state. g
j
are constraint functions.
The TersoffBrenner potential has been adopted extensively in many
molecular dynamics simulations and continuum analysis and has
proven to be a reliable model for describing the interactions between
carbon atoms. So it is also adopted in the present work.
For carbon atoms i and j, Brenner [22] determined the interatomic
potential as
V r
ij
_ _
V
R
r
ij
_ _

B
ij
V
A
r
ij
_ _
6
where, r
ij
is the distance between atoms i and j, V
R
and V
A
are
repulsive and attractive pair terms given by
V
R
r
D
e
S1
exp

2S
p
d rR
e
_ _ _ _
f
c
r
V
A
r
S D
e
S1
exp

2=S
_
d rR
e
_ _ _ _
f
c
r
7
The function f
c
is merely a smooth cutoff function to limit the range
of the potential and is given by
f
c
r
1 r b R
1
1
2
1 cos
r
i
R
1
_ _
R
2
R
1
_ _ _ _
R
1
b r b R
2
0 r N R
2
_

_
8
which has cutoff values of R
(1)
=0.17 nm and R
(2)
=0.2 nm.
The term B
_
ij
is given by

B
ij

B
ij
B
ji
2
9
where B
ij
represents a multi-body coupling between the bond from
atom i to atom j and the local environment of atom i. Its form is given
by
B
ij
1
k i;j
G
ijk
_ _
f
c
r
ik

_ _

10
where r
ik
is the distance between atoms i and k,
ijk
is the angle
between bonds i j and i k, and the function G is given by
G a
0
1
c
2
0
d
2
0

c
2
0
d
2
0
1 cos
2
_ _
11
B
ji
has similar form with B
ij
.
Fig. 1. Geometrical mapping from 3D CNT to 2D plane: (a) a CNT, (b) a planar, unrolled CNT, (c) a geometrical unit cell including one central atom and its three nearest neighboring
atoms, (d) 13-point physical unit cell to show the potential environment of the central atom.
3941 H.W. Zhang et al. / Materials Letters 62 (2008) 39403943
The second set of parameters for carbon reported by Brenner [22]
is used and given by D
(e)
=6.000 eV, S=1.22, =21 nm
1
, R
(e)
=
0.1390 nm, =0.5, a
0
=0.00020813, c
0
=330 and d
0
=3.5.
3. Deformation analysis of CNTs
3.1. Strain energies of CNTs under large axial deformations
Commonly, thegraphitic sheet canbeconsideredas aCNTwithinnite
radius. Here the deformation of graphitic sheet is discussed, as well.
Fig. 2 shows the curves of strain energies of CNTs with different
chirality. For (10, 0) CNT, the energy density jumps from 2.232 eV/
atom at strain 0.446 to 2.089 eV/atom at strain 0.448. For (20, 0) CNT,
the energy density jumps from 2.219 eV/atom at strain 0.444 to
2.097 eV/atom at strain 0.446. Along zigzag direction, i.e., (, 0), of
graphitic sheet, the energy density jumps from2.103 eV/atomat strain
0.430 to 2.139 eV/atom at strain 0.432. For (5, 5) CNT, the energy
density jumps from 1.680 eV/atom at strain 0.344 to 1.372 eV/atom at
strain 0.346; for (10, 10) CNT, the energy density jumps from 2.101 eV/
atom at strain 0.378 to 1.514 eV/atom at strain 0.380. Along armchair
direction, i.e., (, ), of graphitic sheet, the energy density jumps from
2.193 eV/atom at strain 0.382 to 1.560 eV/atom at strain 0.384.
Energy jump of a CNT commonly implies the instability of its
conguration. This may trigger fracture of tube. Clearly, the failure
strains are larger than 34%, which is far more than the strains of the
CNTs in the work by Belytschko et. al. [13] or by Liu et. al. [14]. The
reason is that atoms in the current model do not vibrate (e.g. at 0 K)
when the TersoffBrenner potential is adopted to express its potential
environment. Thus, the tubes can be considered as periodic structures
with unit cells. It implies the local axial strain of a tube is identical to
its integral strain. However, when the atoms vibrate (at high
temperature) near their equilibrium positions, the local axial strains
are not uniform and are different from the integral strains. Although
the integral strain is far less than 34%, the local strain might be large
enough and even reaches failure strain.
3.2. Congurations of graphitic sheet under large axial deformation
From above, one can nd that the strain energy of a CNT shows
jump at critical strains. To gain more insights into the mechanical
deformations, we examine the changes of congurations near critical
stains, which is signicant to the fracture of CNT.
Since the changes of strain energies in CNTs with same chirality are
similar, only the deformation of graphitic sheet is studied here.
Meanwhile, r
i
=l
i
,
ij
=
ij
, i,j =1, 2, 3; i j.
When the deformation is along zigzag direction, abrupt change of
strain energy density occurs when strain is nearly 0.430 (See Fig. 2a).
Simultaneously, both the angle and the lengths of bonds change greatly
(See Table 1). Whenthe deformationis alongarmchair direction, sudden
decrease of strain energy density occurs when strain is nearly 0.382 (See
Fig. 2b). Meanwhile, the angle
12
changes obviously from 0.5438 to
0.5 (See Table 1).
Thus, the abrupt changes of the congurations may occur when the
deformations are large enough. The reason is that the changes of bond
lengths and angles lead to corresponding changes of many-body
coupling interactions between atoms. Then the tubes reach new
equilibrium states. However, the abrupt changes of tubes tend to
trigger fracture of CNTs in a dynamic deformation.
4. Conclusions
Strain energies and the corresponding congurations of the CNTs
under simple deformation are calculated. Results can be summarized
as follows:
The changes of strain energies are dependent on chirality and
hardly dependent of the tubes' radii.
To reach a new equilibrium state, abrupt change of the congura-
tion of the unit cell in a CNT may occur when strain is too large under
axial tension.
Fracture of CNTs must appear when abrupt changes of the
congurations occur in a dynamic deformation.
For armchair pattern CNTs, the fracture strain is no more than
0.384. The critical fracture strain of zigzag pattern CNTs is no more
than 0.448.
Acknowledgements
The nancial supports of the National Natural Science Foundation
of China (10225212, 10721062, 10332010, 10402005), the Program for
Changjiang Scholars and Innovative Research Team in University of
China (PCSIRT) and the National Key Basic Research Special Founda-
tion of China (2005CB321704) are greatly acknowledged.
References
[1] Iijima S. Nature 1991;354:568.
[2] Yakobson BI, Brabec CJ, Bernholc J. Phys Rev Lett 1996;76:25114. Fig. 2. Strain energy densities, i.e. energy per atom of CNTs, under axial deformation.
Table 1
Abrupt changes of the congurations of the unit cells in graphitic sheet deformed along
different directions
Direction Strain l
1
/nm l
2
(l
3
=l
2
)/nm
23
/
Zigzag 0.430 0.1711 0.1717 0.3928
0.432 0.1519 0.1803 0.3074
Armchair 0.382 0.1753 0.1542 0.9124
0.384 0.1739 0.1542 1.0000
3942 H.W. Zhang et al. / Materials Letters 62 (2008) 39403943
[3] Treacy MMJ, Ebbesen TW, Gibson JM. Nature 1996;38:67880.
[4] Wong EW, Sheehan PE, Lieber CM. Science 1997;277:19715.
[5] Yu MF, Files BS, Arepalli S, Ruoff RS. Phys Rev Lett 2000;84:55525.
[6] Krishnan A, Dujardin E, Ebbesen TW, Yianilos PN, Treacy MMJ. Phys Rev B
1998;58:140139.
[7] Salvetat JP, Briggs GAD, Bonard JM, Bacsa RR, Kulik AJ, Stckli T, et al. Phys Rev Lett
1999;82:9447.
[8] Liew KM, Wong CH, He XQ, Tan MJ, Meguid SA. Phys Rev B 2004;69:115429-8.
[9] Liew KM, He XQ, Wong CH. Acta Mater 2004;52:25217.
[10] Dereli G, zdoan C. Phys Rev B 2003;67:035416-6.
[11] Govindjee S, Sackman JL. Solid State Commun 1999;110:22730.
[12] Jiang H, Zhang P, Liu B, Huang Y, Geubelle PH, Gao H, et al. Computat Mater Sci
2003;28:42942.
[13] Belytschko T, Xiao SP, Schatz GC, Ruoff RS. Phys Rev B 2002;65:2354308.
[14] Liu P, Zhang YW, Lee HP, Lu C. Molec Simul 2004;30:5437.
[15] Arroyo M, Belytschko T. J Mech Phys Solids 2002;50:194177.
[16] Arroyo M, Belytschko T. Int J Numer Methods Eng 2004;59:41956.
[17] Arroyo M, Belytschko T. Phys Rev B 2004;69:115415-11.
[18] Zhang HW, Wang JB, Guo X. J Mech Phys Solids 2005;53:192950.
[19] Tu JP, Jiang CX, Guo SY, Fu MF. Mater Lett 2004;58:16469.
[20] Tong X, Zheng J, Lu Y, Zhang Z, Cheng H. Mater Lett 2007;61:17046.
[21] Arroyo M, Belytschko T. Meccanica 2005;40:45569.
[22] Brenner DW. Phys Rev B 1990;42:945871.
3943 H.W. Zhang et al. / Materials Letters 62 (2008) 39403943