Stress fields around defects and fibers in a

polymer using carbon nanotubes as sensors

Cite as: Appl. Phys. Lett. 78, 1748 (2001); https://doi.org/10.1063/1.1357209
Submitted: 04 December 2000 . Accepted: 26 January 2001 . Published Online: 13 March 2001

Qing Zhao, Jonathan R. Wood, and H. Daniel Wagner

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Appl. Phys. Lett. 78, 1748 (2001); https://doi.org/10.1063/1.1357209 78, 1748

© 2001 American Institute of Physics.

APPLIED PHYSICS LETTERS VOLUME 78, NUMBER 12 19 MARCH 2001

Stress fields around defects and fibers in a polymer using carbon

nanotubes as sensors
Qing Zhao, Jonathan R. Wood, and H. Daniel Wagnera)
Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel
共Received 4 December 2000; accepted for publication 26 January 2001兲
Raman spectroscopy was used to map the stress distribution in the vicinity of discontinuities in a
polymer using single-wall nanotubes seeded in the specimen. In the case of a hole in a polymer
matrix subjected to unidirectional stress, the experimental stress field compared well with the
classical linear elasticity solution. For a single glass fiber embedded in a polymer, the tangential
thermal residual stress in the vicinity of the fiber was picked up by Raman spectroscopy and is in
satisfactory agreement with a standard two-phase concentric cylinder model. © 2001 American
Institute of Physics. 关DOI: 10.1063/1.1357209兴

It was recently demonstrated that the position of specific
bands in the Raman signature of single-wall carbon nano-
tubes 共SWNTs兲 strongly depends on mechanical 共or thermal兲
strain, and turns the nanotubes into sensitive nanoscale strain
gauges.1,2 Thus, when SWNTs are embedded in a polymer,
the hydrostatic compression due to specimen cooling shifts
the wave number of the disorder induced D * band upward,
from 2610 cm⫺1 in air to around 2628 cm⫺1 , depending on
the polymer used.3 Uniaxial strain applied to the polymer
causes a further shift of the D * band, which is linear with
applied strain in the elastic range of the matrix, the slope
being dependent on the orientation of the nanotubes.4,5 This
slope is the critical parameter for strain mapping by Raman
spectroscopy and it is affected by the matrix properties and
the orientation of the nanotubes with respect to the principal
strain axis. Using this concept, we show here that it is pos-
sible to measure the stress profile around a defect such as a
hole in a plate under far-field unidirectional stress, or an
embedded single glass fiber subjected to polymerization
stresses. In both cases, the experimental data are found to
compare well with existing classical theoretical models.
Single-wall nanotubes 共Dynamic Enterprises Ltd.兲 were
dispersed and mixed by ultrasound into a liquid urethane
acrylate polymer 共Ebecryl 4858, Radcure兲. The liquid mix-
ture was spread on a glass slide and a Doktor blade was then
employed to shear the film, thereby orienting the polymer
molecules and inducing nanotube orientation. Following the
shearing procedure, the resulting 150 ␮m thick viscous film
was immediately cured by exposure to an ultraviolet 共UV兲
source. The viscosity of the liquid polymer and its rapid
curing 共seconds兲 minimize the occurrence of molecular re-
laxation and therefore ensure that nanotube alignment is pre-
served. This assumption was recently verified using a series
of mechanical experiments in several orientations.5 The re-
sulting composite contained 0.1 wt % SWNTs, a quantity
small enough so as to produce no effect on the mechanical
properties of the matrix. Under tensile strain, the disorder-
induced Raman D * band of SWNTs, which reflects a breath-
ing vibrational mode in graphite,6 is observed to shift
a兲
Author to whom correspondence should be addressed; electronic mail:
daniel.wagner@weizmann.ac.il
linearly,3 the band shift being proportional to the elastic ma-
trix strain. When no polarizer and half-wave plates are used
in the laser beamline, to get a unambiguous correspondence
between strain 共or stress兲 and band shift the test should pref-
erably be conducted with oriented embedded nanotubes. The
reason for this is as follows. The diameter of the Raman laser
spot is 2–5 ␮m, thus several orders of magnitude larger than
the diameter of the nanotubes. The Raman signal therefore
represents an average response from the nanotube population
over the laser spot area. Assuming that the nanotubes are
randomly distributed rather than well oriented, under
uniaxial stress 共simple tension, for example兲, Poisson’s con-
traction occurs in the direction transverse to the loading axis
so some of the nanotubes undergo compressive strain while
others are under tension. This mixing of strain 共or stress兲
states does not occur if the embedded nanotubes are well
oriented. On the other hand, we recently showed4,5 that the
strain dependence of the Raman shift depends strongly on
the nanotube orientation and the polarization direction. Thus,
using the polarizer and half-wave plates, unoriented nano-
tubes can be used as strain sensors so that no tube alignment
is necessary and the strain can in principle be measured in all
directions using a single sample. In the present work, ori-
ented nanotube-based specimens were used, with no polariz-
ing plates. At room temperature, the ratio between the D *
band shift and the matrix elastic strain 共assuming equal ma-
trix and nanotube strains兲 is ⫺4.67 cm⫺1 per percent of
strain.4 Conversion of the Raman shift 共⌬␻兲 into matrix
stress ( ␴ m ) is obtained as follows:
E m⌬ ␻
␴ m⫽ , 共1兲
⫺4.67⫻100
where E m is the matrix Young’s modulus.
We have two cases of stress. Case I is the distribution of
stress about a circular hole.
The stress concentration which occurs around a circular
hole in an infinite, thin plate under uniaxial tension was ana-
lyzed by Kirsch.7 This was later generalized to the case of an
elliptical hole by Kolosoff7 and by Inglis.8 In Fig. 1共a兲, the
solution for a circular hole9 shows that the maximum value
of the ␴ y y stress component occurs at the boundary of the

0003-6951/2001/78(12)/1748/3/$18.00 1748 © 2001 American Institute of Physics

Appl. Phys. Lett., Vol. 78, No. 12, 19 March 2001
FIG. 1. Specimens configurations used in the present study: 共a兲 circular hole
in a thin, infinite plate under unidirectional tensile stress, including SWNTs
embedded parallel to the loading axis; 共b兲 thin glass fiber embedded in a
thin, infinite plate, including SWNTs embedded perpendicular to the fiber
axis.
hole 共along the x axis, at the ends of the diameter perpen-
dicular to the direction of applied tensile stress兲 and that it is
three times larger than the applied stress:
␴ yy⫽
␴0
2 冉a 2 3a 4
2⫹ 2 ⫹ 4 ,
x x 冊 共2兲
where a is the hole radius and ␴ 0 is the applied stress. Figure
2 shows the normalized matrix stress data 共calculated from
the experimental Raman shift described above兲 along the x
axis, starting at the edge of a circular hole, under three levels
of applied stress. The hole had a 2 mm diameter and the plate
FIG. 2. Normalized stress along the x axis 关Fig. 1共a兲兴 from the edge of a
circular hole, based on the D * peak shift of SWNTs in an UV cured
urethane-acrylate polymer. Applied loads ( ␴ 0 ) of 4, 6, and 8 MPa were
employed. The solid line is the linear elastic solution.
Zhao, Wood, and Wagner 1749
dimensions were 20⫻8⫻0.15 mm3 . The loading direction,
y, was parallel to the average nanotube orientation. We ob-
serve that the wave number of the D * band shifts from a
constant 共far-field兲 value away from the hole edge down to
lower values nearer the edge. This reflects an increase in the
tensile stress due to the enhanced stress concentration in vi-
cinity close to the hole. It can be seen from Fig. 2 that be-
yond one hole radius from the edge, the hole looses its effect
on local stress 共in accordance with the Saint–Venant prin-
ciple兲. The fit between the experimental data and the theory
is excellent. Note however that at the highest applied stress
共8 MPa兲, the fit was slightly poorer due to localized yielding
of the polymer matrix under high local stress at the edge of
the hole.
Case II is the distribution of residual stress around a
cylindrical fiber.
A more complex problem is the case of a fiber embedded
in a matrix, because at the bimaterial interfaces the stress
state is three dimensional. Following polymerization at rela-
tively high temperatures, residual stresses set in and around a
cylindrical fiber embedded in a polymer matrix. These
stresses may be calculated by means of concentric cylinder
models,10–12 which lead to the following governing equa-
tions for the matrix stresses:
冉冊
R 2
␴ rr ⫽A⫹B ,
r
␴ ␪␪ ⫽A⫺B 冉冊R
r
2
, 共3兲
␴ zz ⫽C,
where ␴ rr , ␴ ␪␪ , and ␴ zz are the radial, tangential, and axial
stresses in the matrix, R is the radius of the fiber, r is the
radial coordinate, and A, B, and C are constants. Although
in the composites field Raman spectroscopy is routinely used
to measure the stress distribution in fibers,13–15 it has not
been applied to mapping of matrix stress distributions, for
which only birefringence or x-ray methods have been used.
The only significant stress component in a thin fiber is the
longitudinal stress, thus the assumption is implicitly made
that most of the measured Raman signal arises from that
stress component 共there is a clear one-to-one correspondence
between the Raman shift and the longitudinal stress compo-
nent in the fiber兲. The situation is more complex in the
present case: the Raman signal at the fiber–matrix interface
consists of a mixture of the stress components listed in Eq.
共3兲 and, thus, interpretation of the Raman shift is more dif-
ficult. Yet, the Raman signal is useful simply because such
shifts are indeed observed. The nanotube sensors can still be
used to detect stress variations over measurable distances in
the vicinity of an interface. Since in this letter we focus on
showing a proof of principle for the nanotube sensing capa-
bility using different experimental systems, the more difficult
interpretation aspect in the specific case of a curved bimate-
rial interface is left for future investigation. The specimen
was similar to that of case I above, except for the fact that,
instead of a hole, a glass fiber was embedded in the liquid
matrix prior to curing, and it was perpendicular to the shear-
ing direction 关Fig. 1共b兲兴. Figure 3 shows the stress response
关calculated from the D * band shift using Eq. 共1兲兴 in the
1750 Appl. Phys. Lett., Vol. 78, No. 12, 19 March 2001
FIG. 3. Residual tangential stress distribution in the vicinity of an embedded
glass fiber. The data points are obtained from the wave number shift of the
embedded SWNTs.
vicinity of the embedded glass fiber, along the y axis. As can
be seen, a sharp stress increase close to the fiber–matrix
interface is detected by the Raman response of the SWNTs,
which could correspond to the tangential stress component
( ␴ ␪␪ , solid line in Fig. 3兲. The latter was calculated from the
concentric cylinder model using the matrix and fiber proper-
ties listed in Table I. Also in Fig. 3 is the 共negative兲 radial
stress component ( ␴ rr , dotted line兲. 共The longitudinal stress
is presumably not detectable because the nanotubes are ori-
ented perpendicular to the fiber’s axis.兲 The reason for the
better fit of the data in Fig. 3 to the tangential stress rather
than to the radial stress is as follows. The Raman data are
collected along the Y axis, from the fiber–matrix interface
outward. Along this axis, the nanotubes are oriented radial to
TABLE I. Mechanical and thermodynamic parameters for polyurethane
acrylate and glass fibers.
Polyurethane
Parameter acrylate
Young’s modulus, E 共GPa兲 1.2
Poisson’s ratio, ␯ 0.35
Thermal expansion coefficient ␣ (K⫺1 ) 110⫻10⫺6
Glass Transition Temperature, T g 共K兲 363
Diameter 共␮m兲 ¯ 15
Zhao, Wood, and Wagner
the fiber surface, except for those nanotubes that are very
close to the fiber. The specimen preparation procedure in-
volves lowering the fiber into the uncured oligomer, which
induces local realignment of the nanotubes around 共and par-
allel to兲 the fiber’s circumference. Without such realignment,
the nanotubes would experience matrix tangential stress
through their own radial direction, which would result in
practically no Raman shift at the relevant stress levels.3 Fur-
ther away from the fiber, the experimental data converge to a
constant, as predicted by the concentric cylinder model. Ad-
ditional experiments are currently being performed with
similar specimens at lower temperatures and preliminary re-
sults confirm the observations presented in this letter.
In summary, the unidirectional spreading of a small
amount of SWNTs inside a polymer matrix makes it Raman
active, and thus stress field variations in the matrix may be
revealed. This was demonstrated here by detecting the en-
hanced stress distribution around a hole and at a fiber–
polymer interface. In both cases, the experimental data were
found to compare satisfactorily with existing classical theo-
retical models.
This research was supported in part by a grant from the
Minerva Foundation, and in part by the Israel Science Foun-
dation founded by the Israel Academy of Sciences and Hu-
manities. One of the author holds 共H.D.W.兲 the Livio Norzi
Professorial Chair.
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