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Enhanced nanoflow behaviors of polymer melts using dispersed nanoparticles
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and ultrasonic vibration†
Wei Tian,*ab Kai Leung Yung,a Yan Xu,a Longbiao Huang,a Jie Kongb and Yunchuan Xiea
Received 28th May 2011, Accepted 15th August 2011
DOI: 10.1039/c1nr10545k
In the micro/nano fabrication of polymer nanostructures, a key
factor is the favorable nanoflow behavior of polymer melts.
Compared with the fluidic hydrodynamics of simple liquids through
micro- or macrochannels, the nanoflow behavior of polymer melts,
however, is affected much more by nanoscale effects and surface
interactions. Therefore, achieving a favorable nanoflow of polymer
melts in nanochannels is the key to fabricate high quality polymer
nanoproducts. In this paper, the improved nanoflow behaviors of
polystyrene melts in ordered porous alumina templates with the
addition of nanoparticles and ultrasonic vibration were reported for
the first time. Compared with bulk polystyrene (PS), the nanoflow
rate of PS melts was enhanced when nanoparticles, such as surface-
modified nano-silica (nano-SiO2) or b-cyclodextrin (b-CD), were
added in a dispersed phase into a polystyrene matrix due to the
decrease of the melts’ viscosity caused by interactions between
nanoparticles and PS segments. The enhancement action of b-CD
was observed to be more significant than that of nano-SiO2 based on
the adsorption and the supramolecular self-assembly interactions
between PS segments and b-CD. The enhanced nanoflow rate has
shown to be more pronounced under ultrasonic vibration than those
of the static condition and the low frequency vibration attributed to
the synergetic effects of mechanical vibration and ultrasonic oscil-
lation. The nanoflow rate of polymer melts increases with the
gradual increase of vibration frequency. The optimal nanoflow
behavior can be obtained by simultaneously adding b-CD as
dispersed phase into PS matrix and applying ultrasonic vibration in
one nanoflow system. These new findings will help the preparation of
polymer-based functional nanocomposites, ultrasonic vibration-
assisted nanofluidics, and micro/nano injection molding etc.
In the past decade, polymer nanostructures, including nanorods,
nanofibers, nanowires, and nanotubes have attracted increasing
interest for their broad applications in widely different areas such as
nanoreinforcement and nanofluidics, catalysis, sensors, photonics
a
Department of Industrial and Systems Engineering, The Hong Kong
Polytechnic University, Hung Hom, Kowloon, Hong Kong, P. R. China.
E-mail: happytw_3000@163.com; Tel: +852-34003248
b
Department of Applied Chemistry, School of Science, Northwestern
Polytechnical University, Xi’an, 710072, P. R. China
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c1nr10545k
4094 | Nanoscale, 2011, 3, 4094–4100
COMMUNICATION
and medicine.1,2 For the fabrication of these nanoproducts, lots of
micro-/nano-processing approaches, such as capillary lithography,
nanoimprint lithography, microstereolithography, electro-spinning,
and micro-/nano-injection, casting or extrusion have been devel-
oped.3–6 Recently, the fabrication of micro/nano structures by
applying ultrasonic vibration energy through a commercial ultrasonic
welding system has been reported.7,8 Amongst the micro/nano
fabrication technologies mentioned above, a key factor is the favor-
able nanoflow behavior of polymer melts. Compared with the fluidic
hydrodynamics of simple liquid through micro- or macrochannels,
however, the nanoflow behavior of polymer melts is affected much
more by the nanoscale effects and the surface interactions.9–11
Therefore, achieving a favorable nanoflow of polymer melts is the key
to fabricate high quality polymer nanoproducts.
From previous experiments and literatures, it was found that
polymer melts can flow into nanochannels of anodized aluminum
oxide (AAO) due to the fact that high energy porous materials can
wet low energy polymer melts.12–14 Therefore, the nanoflow behavior
of polymer melts can be conveniently observed in AAO nano-
channels under different conditions and time ranges.15 However,
studies showed that the nanoflow rate through these AAO nano-
channels is low to some degree if it is only dependent on the wetting
actions. For example, the complete wetting of some polymer melts at
low temperature may take a long time ranging from several hours
even to several days.16–18 The above drawback will decrease produc-
tion efficiency, add extra cost, and further cause an obstruction for
developing micro/nano fabrication technologies. To overcome this
problem, increasing the wetting temperature above the polymer
melting point has been considered as the most effective method to
enhance the nanoflow rate of polymer melts.11,18 Unfortunately,
many nanoproducts may require the use of temperature-sensitive
functional nanomaterials, such as biological objects incorporated into
the resulting nanostructures that will fail in high-temperature.19
Alternatively, the nanoflow rate of polymer melts can also be
enhanced by altering some intrinsic parameters of polymers and
AAO nanochannel templates, such as the molecular weight of
polymers, the size of nanochannels and the polymer-to-wall interac-
tions.11,18,20,21 However, it is difficult to effectively adjust the nanoflow
rate of polymer melts by changing these parameters due to the
different wetting mechanisms (including precursor wetting and
capillary wetting),2 complicated wetting dynamics22 and flow
models23 as well as the synergistic action of various parameters.11
Therefore, it is very challenging and highly desirable to develop new
This journal is ª The Royal Society of Chemistry 2011

approaches to improve the nanoflow rate of polymer melts in AAO
nanochannel templates.
Herein, we propose two simple and efficient strategies to enhance
the nanoflow rate of polymer melts in AAO nanochannel templates
using polystyrene (PS) as model polymer, and then, determine the
optimal nanoflow behavior of PS melts by combining the two
methods into one nanoflow system. The first is to disperse nano-
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particles into PS matrix. In general, when hard nanoparticles, such as
silica (SiO2) dispersed in a soft polymer matrix which is so-called
nanocomposites, their high surface-to-volume ratio allows nano-
particles at relatively low volume fractions to strongly modify the
polymer matrix, resulting in improved rheological, mechanical,
optical, thermal, and other bulk properties.24–26 Some functional
nanoparticles, such as b-cyclodextrin (b-CD), may be influential on
the rheological behavior of polymers due to their spherical molecular
structure and supramolecular characteristics.27 However, to the best
of our knowledge, there has not still been reported an effect of
nanoparticles on the nanoflow rate of polymer melts in AAO
nanochannel templates. The second strategy is to apply dynamic
external forces to enhance the nanoflow rate of polymer melts, such
as ultrasonic vibration. It is well known that ultrasonic vibration
generates a large quantity of frictional heat for a very short processing
time and the heat-affected zone is very limited.28 Due to the several
benefits of ultrasonic vibration in processing, such as a short pro-
cessing time, small melting area, inexpensive equipment and an
environmentally friendly process, there has been growing interest in
using heat energy from ultrasonic vibration in the nano/micro
forming of thermoplastic materials,8 cleaning,29 and power disper-
sion/blending.30 Additionally, it was found that ultrasonic vibration
can control the flow velocity and patterning of fluid in a channel from
the outside,31,32 and affect the rheological behavior of polymer melts
in extrusion system.33 Recently, the enhanced flow behavior poly(3-
caprolactone) melts though nanoscale channels under vibration was
observed by our group.34 However, the study is preliminary and
limited to a simple low frequency vibration. Based on the benefits of
ultrasonic vibration discussed above, its application should be
considered to improve the nanoflow rate of polymer melts in AAO
nanochannel templates. What’s more, when the two methods above
are applied in one system, the nanoflow rate of polymer melts in
AAO nanochannel templates may be further enhanced due to the
synergistic actions from internal nanoparticles and external ultrasonic
vibration. Therefore, it is credible that our new findings will help the
preparation of polymer-based functional nanocomposites, ultrasonic
vibration-assisted nanofluidics, and micro/nano injection
molding etc.
To study the influences of processing additives and dynamic
external forces, the nanoflow behavior of pure PS melts (Mn ¼ 100–
600) in AAO nanochannel templates was firstly investigated. A
simple and efficient characterization strategy was established,
according to our previous work.15 The displacement lt and rate dlt/dt
were used to describe the nanoflow behaviors of PS melts, and
deduced by statistical length of the PS nanorods/nanotubes formed in
AAO templates. The wetting driven force p is mainly generated from
partial or complete wetting of PS melts with low surface energy on the
walls of nanochannels of AAO template surfaces with high surface
energy. After wetting PS melts into AAO templates with the nano-
channel diameter of 200 nm and length of 60 mm (Fig. S1, Supporting
Information†), relatively short PS nanorods and long PS nanotubes
were generated at the wetting temperature of 160 and 180  C under
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the same wetting time, and aligned in a direction perpendicular to the
remaining bulk substrate as presented in Fig. 1. The corresponding
TEM images of PS nanorods/nanotubues are shown in Fig. 2. The
length or height of the generated PS nanorods/nanotubes can
represent the trace of polymer melts infiltrated into AAO templates
before they become condensed matter, which can be conveniently
determined from their cross-section (Fig. 1a and 1c). Furthermore,
the wetting displacement remarkably increases with the increase of
temperature and time as presented in Fig. 1e and 1f, indicating that
the higher nanoflow rate was achieved as the wetting temperature was
elevated (Fig. 1e). It may be ascribed to the decreased viscosity of the
melts with the increase of temperature. Correspondingly, prolonging
the wetting time can also increase the wetting displacement (Fig. 1f).
Though the increase of wetting temperature and time can enhance the
nanoflow of PS melts in AAO templates, the drawbacks of energy
consumption, long process cycle and problems as mentioned earlier
still exist. Therefore, processing additives and dynamic external forces
were considered in the next step.
For the investigation of influences of different nanoparticles on the
nanoflow rate of PS melts, a series of PS-based nanocomposites were
firstly prepared by using PS as polymeric matrix and nanoparticles
including surface-modified SiO2 and b-CD as dispersed phase. These
nanocomposites were denoted as PS-SiO2 and PS-b-CD. For
comparison, the mass ratio of polymeric matrix to dispersed phase
was fixed as 95 : 5, and the wetting temperature and time of these
nanocomposite melts in AAO templates were set to 170  C and 15
min hereinafter. The cross-section SEM images of pure PS, PS-SiO2
and PS-b-CD nanorods/nanotubes formed are presented in Fig. 3.
Compared with the displacement of pure PS melts (4.9 mm) (Fig. 3a),
the displacements of these nanocomposite melts evidently increase to
14.7 and 26.1 mm for PS–SiO2 (Fig. 3b) and PS-b-CD (Fig. 3c),
respectively. The result indicates that the nanoflow rate of PS melts
was enhanced in AAO templates when nanoparticles were added into
the PS matrix. This may be attributed to the interactions caused by
these nanoparticles in nanocomposite melts.24,35 These interactions
include PS segment–nanoparticle, nanoparticle–nanoparticle, and
nanoparticle–nanochannel wall in AAO templates. The PS segment–
nanoparticle interactions weaken the PS segment–segment interac-
tions, resulting in a decrease in entanglement among the segments.
Moreover, friction heating is generated due to the rigid nanoparticle–
nanoparticle interactions with hard structures, and nanoparticle–wall
with high surface energy, and as a result, the wetting temperature is
elevated. To sum up, the above interactions lead to the decrease of the
viscosity of melts, and subsequently give rise to a quicker nanoflow
according to the following Luacse–Washburn equation,36 which can
be used to describe the nanoflow rate of polymer melts in
nanochannels:18
dz/dt ¼ Rg cos qc/(4hz) (1)
Here z is the length of melt column, t is time, h is the viscosity of melt,
R is the hydraulic radius, g is surface tension, and qc is contact angle.
The equation shows the wetting rate depends on the surface tension,
liquid viscosity, diameter of micro/nano channels and the contact
angle. Therefore, the nanoflow rate of nanocomposite melts will
increase when the viscosity decreases.
Furthermore, the displacement of PS-b-CD (26.1 mm) (Fig. 3c)
increases more obviously than those of PS-SiO2 (14.7 mm) (Fig. 3b)
under the same wetting conditions, and pure PS at a high wetting
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Fig. 1 SEM images of PS nanorods/nanotubes arrays generated in AAO templates at the wetting time of 15 min: (a) cross-section at the wetting
temperature of 160  C; (b) top view at the wetting temperature of 160  C; (c) cross-section at the wetting temperature of 180  C; (d) top view at the
wetting temperature of 180  C. Dependence of displacements of PS melts in AAO templates on the wetting temperature at the wetting time of 15 min (e)
and on the wetting time at the wetting temperature of 170  C (f), respectively.

conditions. As can be seen from Fig. 4, PS-b-CD nanotube (Fig. 4b)

Fig. 2 TEM images of PS nanorods/nanotubes generated in AAO
templates at the wetting time of 15 min: (a) PS nanorods formed at the
wetting temperature of 160  C; (b) PS nanotubes formed at the wetting
temperature of 180  C.
temperature of 190  C (24.2 mm) (Fig. 1e) as well as at a long wetting
time of 120 min (25.1 mm) (Fig. 1f). What’s more, Fig. 4 shows TEM
images of pure PS and PS-b-CD nanotubes under the same wetting
displays a total different morphology compared with the pure PS
nanotube (Fig. 4a), although it is still not very clear for the distri-
bution of b-CD nanoparticles in a PS nanotube due to the very small
size of b-CD, with a diameter of about 1.6 nm. Based on the above
results, the influence of b-CD should be a key factor on the enhanced
nanoflow rate of PS-b-CD melts. Gonsior et al.27 gave the first
example concerning the influence of methylated b-CD on the rheo-
logical behavior of 1-ethyl-3-methyl imidazolium acetate solution,
however, the observation of this paper, that b-CD enhances the
nanoflow rate of PS melts in AAO nanochannel templates, is
described for the first time. It will be more challenging to explain its
mechanism. Here, we only give a preliminary analysis.
The first reason is the adsorption effect of PS segments on b-CD
nanoparticles. Large amounts of hydroxyl groups on the surface of
molecules supply a high surface energy to b-CD nanoparticles, and
further enhance the interaction between PS segments and nano-
particle surfaces. Similarly to the wetting behavior between low
surface energy polymer melts and high surface energy AAO

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Fig. 3 SEM images of cross-section of pure PS and PS-based nano-
composite nanorods/nanotubes arrays formed at the wetting time of 15
min and the wetting temperature of 170  C: (a) pure PS; (b) PS-SiO2; (c)
PS-b-CD.
Fig. 4 TEM images of pure PS and PS-b-CD nanotubes arrays gener-
ated in AAO templates at the wetting time of 15 min and the wetting
temperature of 170  C: (a) pure PS; (b) PS-b-CD.
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nanochannels, a favorable segment–particle interaction leads to the
PS segments wetting the b-CD surface,25 and forms an adsorbed layer
of PS segments that stabilizes b-CD nanoparticles in the melts26 as
presented in Scheme 1A(a). The other one is the host–guest supra-
molecular self-assembly between the benzyl groups in PS side chains
and the hydrophobic internal cavities of b-CD molecules. It is well
known that a b-CD molecule with a hydrophobic internal cavity
lined with alkyl groups and glycosidic oxygen atoms can act as a host
for a variety of smaller molecule guests through noncovalent inter-
actions.37 Since there is an inclusion interaction between the benzyl
group and the b-CD molecule, which has been well confirmed by the
literature38 and our previous work.39,40 This host–guest supramolec-
ular interaction may be attributed to the self-assembly of PS and
b-CD in the preparation process of nanocomposites as presented in
Scheme 1A(b). In fact, it is more reasonable that the adsorption and
supramolecular self-assembly interactions should be simultaneously
existent in the wetting process of PS-b-CD melts in the nanochannels
of AAO templates (Scheme 1A(c)). Consequently, the enhanced
nanoflow behavior of PS-b-CD melts under these interactions may be
similar to the function of a wheel, which is the so-called ‘‘wheel
effect’’. It is obvious that the b-CD units attached to the PS segments
are wheel-like (Scheme 1A(d)).
The influences of ultrasonic vibration on the nanoflow rate of PS
melts were studied by using an improved self-made apparatus
equipped with a high frequency piezoelectric transducer based on our
previous work.34 The vibration frequency was set from 10 to 100 kHz.
The cross-section images of pure PS nanorods/nanotubes formed
under vibration fields are presented in Fig. 5. Compared with the
static condition (4.9 mm) (Fig. 3a) and the low frequency vibration
(7.8 mm) (Fig. 5a), the displacement of PS melts in the ultrasonic
vibration fields with the frequency of 30 kHz (Fig. 5b) obviously
increases to 13.1 mm. Furthermore, with the change of ultrasonic
vibration frequency ranging from 30 to 100 kHz, the corresponding
displacement increases from 13.1 to 32.1 mm (Fig. 5d). These results
indicate that the nanoflow rate of PS melts in AAO nanochannel
templates under ultrasonic vibration is much faster than that without
ultrasonic vibration. In general, ultrasonic vibration is generated by
the synergetic effects of mechanical vibration and ultrasonic oscilla-
tion. Therefore, we try to explain the mechanism of the enhanced
nanoflow of PS melts under ultrasonic vibration from the two aspects
as follows.
From the viewpoint of mechanical vibration, the decreased
viscosity of PS melts gives rise to the enhanced nanoflow rate
according to the eqn (1). In general, the viscosity of melts obeys the
Arrhenius equation:
Inh ¼ InA + DEh/RT (2)
Where A is constant related with molecular structures, DEh is the
flowing active energy of polymer melts, R is gas constant, and T is the
melts temperature. For one thing, the motion of the polymer chain is
carried out through the wriggling motion of minor segments
according to the reptation model,41 and thus the wriggling motion of
PS chains in nanochannels can be activated under high-energy
mechanical vibration due to their short relaxation time and break
through the entanglements of PS chains. In this case, the DEh of PS
melts is reduced due to the decrease of melt elasticity and interaction
among polymer chains, as a result, directly causes the decrease of
viscosity of PS melts. For another thing, when high-energy
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Scheme 1 Schematic representation for the possible mechanisms of b-CD-enhanced (A), ultrasonic vibration-enhanced (B), and b-CD under ultrasonic
vibration-enhanced (C) the nanoflow behaviors of PS melts in AAO nanochannel templates.
mechanical vibration at an ultrasonic frequency range is applied to
PS melts, the mechanical energy is converted to heat energy between
molecules by friction,42 and against the walls of the nanochannels
(Scheme 1B(a)) which results in the increase of T, accompanied by the
decrease in PS viscosity. Additionally, mechanical vibration energy
can increase the shear rate and give rise to the decrease of shear stress
in PS melts by heating up the molecular boundaries. Thus, the
viscosity is reduced according to eqn (3):43
h ¼ sw/g (3)
Where sw is the shear stress in the nanochannels, g is the shear rate.
The above effects on the viscosity of PS melts can be further enhanced
by the increase of frequency resulting in the increase of wetting
displacement.
On the other hand, ultrasonic oscillation may change the nanoflow
pattern of PS melts in AAO nanochannel templates. From the view
of polymer rheology,44 the high hydrodynamic resistance caused by
the elastic turbulence, being considered as a unstable flow, should be
the major obstacle to increase the nanoflow rate of PS melts in the
wetting process. However, ultrasonic oscillation promotes the tran-
sition from unstable flow to stable flow, such as the laminar flow, and
further increases the nanoflow rate of PS melts. A suggested
4098 | Nanoscale, 2011, 3, 4094–4100
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explanation is that acoustic cavitation bubbles induced by the effect
of acoustic nonlinearity (Scheme 1B(b)) increase heat transfer coef-
ficients for heating elements in PS melts.45,46 In this case, the nanoflow
pattern of PS melts may be greatly changed by the perturbation of
heat transfer coefficients, and result in the transition from unstable
flow to stable flow. Nomura et al. reported that it was possible to
control the flow pattern and rate of fluid in a channel during appli-
cation of ultrasonic vibration.31,32 The effects of ultrasonic oscillation
on die pressure, productivity of extrusion, melt viscosity, and melt
oscillating flow of PS were also studied by Chen et al.33 The results of
these references further support our analysis above.
Based on the above discussion, both nanoparticles and ultrasonic
vibration can improve the nanoflow rate of PS melts in AAO
nanochannel templates. Therefore, it is worth considering that
combining of the two methods into one nanoflow system may further
optimize the nanoflow behavior of PS melts. Thus, b-CD nano-
particles dispersed in PS matrix with a ratio of 5 wt% was still selected
for optimizing experiments due to the clear superiority compared
with surface-modified SiO2, while ultrasonic vibration with the
frequency of 30 kHz was also applied. Fig. 5c shows the cross-section
image of PS-b-CD nanorods/nanotubes formed under ultrasonic
vibration fields. Compared with PS-b-CD (26.1 mm) (Fig. 3c) and
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Fig. 5 SEM images of cross-section of pure PS and PS-based nanocomposite nanorods/nanotubes arrays formed under vibration fields at the wetting
time of 15 min and the wetting temperature of 170  C (a) pure PS with vibration at the frequency of 10 kHZ; (b) pure PS with ultrasonic vibration at the
frequency of 30 kHZ; (c) PS-b-CD with ultrasonic vibration at the frequency of 30 kHZ. Dependence of displacements of PS melts in AAO templates on
the vibration frequency (d).
pure PS under ultrasonic vibration with the frequency of 30 kHz
(13.1 mm) (Fig. 5b), the displacement of PS-b-CD under ultrasonic
vibration with the frequency of 30 kHz increases to 30.2 mm. This
result may be due to the synergistic actions of internal nanoparticles
and external ultrasonic vibration (Scheme 1C). For one thing, the
adsorption and the supramolecular self-assembly of PS melts on
b-CD nanoparticles are further enhanced under ultrasonic vibration.
This may be attributed to the improvement of interfacial adhesion
and compatibility between PS matrix and b-CD dispersed phase as
well as the decrease of nanoparticles distribution in matrix when
ultrasonic vibration is added.43,44,47,48 For another thing, the thermal
motion of b-CD nanoparticles in PS melts further gives rise to the
generation of acoustic cavitation bubbles, accelerates the trans-
mission of ultrasonic waves, and enhances the efficiency of ultrasonic
vibration. Consequently, the optimal nanoflow behavior of PS melts
in AAO nanochannel templates is obtained by adding b-CD nano-
particles as a dispersed phase under ultrasonic vibration.
In conclusion, the nanoflow behavior of PS melts in AAO nano-
channel templates can be improved with the addition of nanoparticles
and ultrasonic vibration. Compared with the polymer bulk, the
nanoflow rate of polymer melts can be enhanced when surface-
modified SiO2 or b-CD as nanoparticles dispersed phase were added
to the polymer matrix. More importantly, the enhancement action of
b-CD in polymer matrix on the nanoflow rate was observed for the
first time to be more significant than those of other nanoparticles. The
adsorption and the supramolecular self-assembly interactions
between polymer segments and b-CD were proposed to explain the
new phenomenon. Moreover, the enhancement was found to be
much higher with ultrasonic vibration due to the synergistic actions of
mechanical vibration and ultrasonic oscillation. The nanoflow rate of
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polymer melts increased with the increase of vibration frequency. The
optimal nanoflow behavior can be obtained by simultaneously add-
ing b-CD nanoparticles as a dispersed phase into polymer matrix and
applying ultrasonic vibration into one nanoflow system. The tech-
nique developed in this work can be readily extended to the prepa-
ration of polymer-based functional nanocomposites, ultrasonic
vibration-assisted nanofluidics, and micro/nano injection molding
etc.
Acknowledgements
The authors are grateful to the Research Grants Council of Hong
Kong Special Administrative Region (PolyU 5347/08E) for funding
support.
References
1 R. Dersch, M. Steinhart, U. Boudriot, A. Greiner and J. H. Wendorff,
Polym. Adv. Technol., 2005, 16, 276–282.
2 M. Steinhart, Adv. Polym. Sci., 2008, 220, 123–187.
3 P. G. Conrad, P. T. Nishimura, D. Aherne, B. J. Schwartz, D. M. Wu,
N. Fang, X. Zhang, M. J. Roberts and K. J. Shea, Adv. Mater., 2003,
15, 1541–1544.
4 M. Vogler, S. Wiedenberg, M. Muhlberger, I. Bergmair, T. Glinsner,
H. Schmidt, E. B. Kley and G. Grutzner, Microelectron. Eng., 2007,
84, 984–988.
5 X. F. Wang, I. C. Um, D. F. Fang, A. Okamoto, B. S. Hsiao and
B. Chu, Polymer, 2005, 46, 4853–4867.
6 H. Y. Li, Y. C. Ke and Y. L. Hu, J. Appl. Polym. Sci., 2006, 99, 1018–
1023.
7 K. A. Janes, M. P. Fresneau, A. Marazuela, A. Fabra and
M. J. Alonso, Microsyst. Technol., 2008, 14, 1325–1333.
Nanoscale, 2011, 3, 4094–4100 | 4099

8 C. H. Lee, P. G. Jung, S. M. Lee, S. H. Park, B. S. Shin, J. H. Kim,
K. Y. Hwang, K. M. Kim and J. S. Ko, J. Micromech. Microeng.,
2010, 20, 035018.
9 Y. Cui, M. T. Bjork, J. A. Liddle, C. Sonnichsen, B. Boussert and
A. P. Alivisatos, Nano Lett., 2004, 4, 1093–1098.
10 F. Hennrich, R. Krupke, K. Arnold, J. A. Rojas Stutz, S. Lebedkin,
T. Koch, T. Schimmel and M. M. Kappes, J. Phys. Chem. B., 2007,
111, 1932–1937.
11 S. Ahadian, H. Mizuseki and Y. Kawazoe, Microfluid Nanofluid,
Published on 08 September 2011. Downloaded by University of Illinois at Chicago on 26/10/2014 14:45:30.
2010, 9, 319–328.
12 M. Steinhart, J. H. Wendorff, A. Greiner, R. B. Wehrspohn,
K. Nielsch, J. Schilling, J. Choi and U. Gosele, Science, 2002, 296,
1997.
13 M. Steinhart, S. Senz, R. B. Wehrspohn, U. Gosele and
J. H. Wendorff, Macromolecules, 2003, 36, 3646–3651.
14 M. Steinhart, R. B. Wehrspohn, U. Gosele and J. H. Wendorff,
Angew. Chem. Int. Ed., 2004, 43, 1334–1344.
15 K. L. Yung, J. Kong and Y. Xu, Polymer, 2007, 48, 7645–7652.
16 M. Steinhart, J. H. Wendorff and R. B. Wehrspohn, Nanotubes a la
Carte: ChemPhysChem, 2003, 4, 1171–1176.
17 Y. M. Sun, M. Steinhart, D. Zschech, R. Adhikari, G. H. Michler and
U. Gosele, Macromol. Rapid Commun., 2005, 26, 369–375.
18 M. F. Zhang, P. Dobriyal, J. T. Chen, T. P. Russell, J. Olmo and
A. Merry, Nano Lett., 2006, 6, 1075–1079.
19 S. Schlitt, A. Greiner and J. H. Wendorff, Macromolecules, 2008, 41,
3228–3234.
20 K. Shin, S. Obukhov, J. T. Chen, J. Huh, Y. Hwang, S. Mok,
P. Dobriyal, P. Thiyagarajan and T. P. Russell, Nat. Mater., 2007,
6, 961–965.
21 S. Ahadian and Y. Kawazoe, Colloid Polym. Sci., 2009, 287, 961–967.
22 G. McHale, M. I. Newton and N. J. Shirtcliffe, J. Phys.: Condens.
Matter, 2009, 21, 464122.
23 A. Johner, K. Shin and S. Obukhov, EPL, 2010, 91, 38002.
24 B. J. Anderson and C. F. Zukoski, Macromolecules, 2007, 40, 5133–
5140.
25 B. J. Anderson and C. F. Zukoski, Macromolecules, 2008, 41, 9326–
9334.
26 B. J. Anderson and C. F. Zukoski, Langmuir, 2010, 26, 8709–
8720.
4100 | Nanoscale, 2011, 3, 4094–4100
View Article Online
27 N. Gonsior, M. Hetzer, W. M. Kulicke and H. Ritter, J. Phys. Chem.
B, 2010, 114, 12468–1272.
28 H. W. Yu, C. H. Lee, P. G. Jung, B. S. Shin, J. H. Kim, K. Y. Hwang
and J. S. Ko, J. Micro/Nanolith., 2009, 8, 021113.
29 B. Niemczewski, Ultrason. Sonochem., 2007, 14, 13–18.
30 A. W. Patwardhan, A. B. Pandit and J. B. Joshi, Chem. Eng. Sci.,
2003, 58, 2951–2962.
31 S. Nomura, Y. Sasaki and K. Murakami, Jpn. J. Appl. Phys., 2000,
39, 4987–4989.
32 S. Nomura, K. Murakami and M. Kawada, Jpn. J. Appl. Phys., 2002,
41, 3217–3222.
33 G. S. Chen, S. Y. Guo and H. L. Li, J. Appl. Polym. Sci., 2002, 84,
2451–2460.
34 J. Kong, Y. Xu, K. L. Yung, Y. C. Xie and L. He, J. Phys. Chem. C,
2009, 113, 624–629.
35 J. B. Hooper and K. S. Schweizer, Macromolecules, 2005, 38, 8858–
8869.
36 G. Martic, F. Gentner, D. Seveno, D. Coulon, J. De Coninck and
T. D. Blake, Langmuir, 2002, 18, 7971–7976.
37 R. Villalonga, R. Cao and A. Fragoso, Chem. Rev., 2007, 107, 3088–
3116.
38 M. V. Rekharsky and Y. Inoue, Chem. Rev., 1998, 98, 1875–1917.
39 W. Tian, X. D. Fan, J. Kong, T. Liu, Y. Y. Liu, Y. Huang, S. J. Wang
and G. B. Zhang, Macromolecules, 2009, 42, 640–651.
40 W. Tian, X. D. Fan, J. Kong, Y. Y. Liu, T. Liu and Y. Huang,
Polymer, 2010, 51, 2556–2564.
41 R. P. Wool, Ed. Hanser Publishers Munich/Vienna/New York 1995,
pp, 41–60.
42 M. N. Tolunay, P. R. Dawson and K. K. Wang, Polym. Eng. Sci.,
2004, 23, 726–733.
43 G. S. Chen, S. Y. Guo and H. L. Li, J. Appl. Polym. Sci., 2002, 86, 23–
32.
44 J. P. Ibar, Polym. Eng. Sci., 1998, 38, 1–20.
45 S. Nomura, K. Murakami and Y. Sasaki, Jpn. J. Appl. Phys., 2000,
39, 3636–3640.
46 K. A. Park and A. E. Bergles, Int. J. Heat Mass. Trans., 1988, 31, 664–
667.
47 W. L. Feng and A. I. Isayev, Polymer, 2004, 45, 1207–1216.
48 Y. Z. Chen and H. L. Li, Polymer, 2005, 46, 7707–7714.
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