Macromolecular

Communication Rapid Communications

Effect of Nonsolvent on the Formation of

Polymer Nanomaterials in the Nanopores of
Anodic Aluminum Oxide Templates

Chih-Wei Lee, Tzu-Hui Wei, Chun-Wei Chang, Jiun-Tai Chen*

We study the effect of nonsolvent on the formation of polymer nanomaterials in the nano-
pores of porous templates. Water (nonsolvent) is added into a poly (methyl methacrylate)
(PMMA) solution in dimethylformamide (DMF) confined in the nanopores of an anodic alu-
minum oxide (AAO) template. Water forms a wetting layer on the pore wall and causes the
PMMA solution to be isolated in the center of the nanopore,
resulting in the formation of PMMA nanospheres or nanorods
after the solvent is evaporated. The formation of the polymer
nanomaterials induced by nonsolvent is found to be driven by
the Rayleigh-instability-type transformation. Without adding
the nonsolvent, PMMA chains precipitate on the walls of the
nanopores after the solvent is evaporated, and PMMA nano-
tubes are obtained.

1. Introduction nanomaterials have been fabricated using templates such

as the AAO template, only few studies have focused on the
In recent years, the fabrication of polymer nanomaterials formation mechanism of polymer nanomaterials using the
has aroused great interest because of their unique prop- template-based method.[14] For example, Russell and co-
erties and applications in areas such as sensors, actua- workers[15] studied the transition from partial to complete
tors, drug delivery, or photovoltaics.[1–4] Compared with wetting of polystyrene (PS) melts by using AAO templates.
other fabrication methods, the template method has been The wetting transition was found to be related to the
proved to be a powerful technique to prepare various kinds spreading coefficient, which is dependent on the annealing
of polymer nanomaterials.[5,6] Polymer melts or solutions temperature and the polymer molecular weight. Wendorff
are introduced into the nanopores of porous templates by and co-workers[16] also investigated the effect of polymer
wetting, and polymer nanomaterials are obtained after the molecular weight on the formation of PS nanomaterials
removal of the templates.[7] These polymer nanomaterials by wetting AAO templates with PS solution. They observed
possess unique properties and unusual morphologies, that the formation of PS nanorods, nanotubes, or void struc-
which are not accessible in the bulk.[8–11] One of the most tures can be controlled by changing the polymer molecular
widely used templates is the anodic aluminum oxide weight. Later, Feng and Jin[17] studied the effect of interfa-
(AAO) template, which is prepared by the electrochemical cial interactions on controlling the polymer nanostructures
oxidation of aluminum.[12] By using a two-step anodiza- using template wetting with PS solution. They demon-
tion process, developed by Masuda and Fukuda,[13] AAO strated that the nanorod morphology is dependent on the
templates with hexagonally packed nanopores and high solvents, which have preferential affinity to the pore wall
pore densities can be prepared. Although many polymer of the template. Despite these works, it is still a challenge
to fully understand the formation mechanism of polymer
C.-W. Lee, T.-H. Wei, C.-W. Chang, Prof. J.-T. Chen nanomaterials made by templates. The formation process
Department of Applied Chemistry, National Chiao Tung of these materials involves many interrelated factors, such
University, Hsinchu, Taiwan 30050 as the type of polymer, the polymer molecular weight,
E-mail: jtchen@mail.nctu.edu.tw the solution concentration, the type of solvent, the drying

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condition, the size of the nanopore, and the chemistry of purchased from Sigma–Aldrich with the weight-average
the pore wall.[18–25] These factors are important in control- molecular weight (Mw) of 35 kg mol−1. DMF and sodium
ling the properties, morphologies, and sizes of polymer hydroxide (NaOH) were obtained from TEDIA. The AAO mem-
nanomaterials made by templates, but they still require branes (pore diameter ≈ 150–400 nm, thickness ≈ 60 μm)
were purchased from Whatman. Polycarbonate filters (VCTP,
further investigation.
pore size: 0.1 μm) were obtained from Millipore. The wipers
Here, we study the effect of nonsolvent on the for-
(Kimwipes) were purchased from Kimberly-Clark.
mation of polymer nanomaterials made by templates.
Poly(methyl methacrylate) (PMMA) solution in dimethyl-
formamide (DMF) is first introduced to the nanopores of 2.2. Fabrication of Polymer Nanomaterials
AAO templates by capillary force. Without adding nonsol- PMMA and PS nanomaterials were made under similar condi-
vent, PMMA chains precipitate on the pore wall, and nano- tions. For making PMMA nanomaterials, for example, polymer
tubes are obtained after the solvent is dried by a vacuum solutions (PMMA in DMF) with different concentrations (5, 8, 10,
pump. By adding water (nonsolvent), the PMMA solution 16, and 32 wt%) were first prepared. To fabricate PMMA nano-
is isolated in the center of the nanopores of the templates, tubes, the AAO templates were immersed into the PMMA solu-
and PMMA nanospheres or nanorods are formed after the tion for 3 s. After the templates were taken out of the solution,
solvent is dried. The aspect ratios of the polymer nano- the residual solution outside the nanopores of the AAO tem-
materials are also found to be dependent on the polymer plates was removed by wiping with wipers (Kimwipes). Subse-
quently, the samples were dried with a vacuum pump, followed
concentration. The formation of these nanomaterials is
by immersing into NaOH(aq) to selectively dissolve the AAO
driven not only by the nonfavorable interaction between
template. Finally, the samples were filtered and washed with
the polymer and water but also by the confinement effect deionized water using polycarbonate filters. To fabricate PMMA
of the porous template. To demonstrate the versatility of nanospheres or nanorods, similar procedures were performed,
this work, another commonly used polymer, PS, is also but the AAO templates were dipped into a bottle of water before
studied, and similar results are obtained. the templates were selectively removed by NaOH(aq).[32]
By studying different drying times of the polymer solu-
tion in the nanopores before water is added, the forma-
2.3. Structure Analysis and Characterization
tion mechanism of the polymer nanomaterials is found
to be related to the Rayleigh-instability-type transforma- A JEOL JSM-7401F model scanning electron microscope (SEM)
tion. The Rayleigh instability was first studied by Plateau, with an accelerating voltage of 10 kV was used to investigate the
who investigated the instability in liquid cylinders.[26] He polymer nanostructures. Before the SEM measurement, the sam-
demonstrated that the free surface of a liquid cylinder ples were dried in a vacuum oven at 30 °C and were coated with
4 nm platinum. Bright-field transmission electron microscopy
first distorts, and the liquid cylinder then disintegrates
(TEM) studies were conducted with a JEOL JEM-2010 TEM oper-
into a chain of drops to reduce the surface energy. Later,
ating at an accelerating voltage of 200 kV. For TEM measurement,
Rayleigh showed that the wavelength of the distortion the samples were placed onto copper grids coated with Formvar
and the size of the drops are determined by the fastest dis- and carbon.
tortion mode.[27] Similar studies were further conducted
by Nichols and Mullins,[28] who extended Rayleigh’s
approach to solid cylinders. The Rayleigh-instability-type 3. Results and Discussion
transformation has been observed for different mate-
rials such as metals or polymers.[29–31] In this study, the To study the effect of nonsolvent on the formation of
polymer solution confined in a nanopore is first isolated polymer nanomaterials made by templates, we choose
by water and forms a cylindrical domain, which later water as the nonsolvent. First, we consider the Hildebrand
undulates and breaks into spherical domains, resulting solubility parameters (δ) of the polymers and solvents. The
in the formation of polymer nanospheres. When some Hildebrand solubility parameter is defined as the square
amount of solvent has been evaporated before adding root of the cohesive energy density and is often used as
water, the transformation process may not be completed, an indicator for solvation and swelling.[33] Polymers are
and intermediate structures can be observed. soluble in solvents with similar values of solubility para-
meters. The solubility parameters of PMMA, PS, DMF, and
water are 19.4, 18.6, 24.8, and 47.9 MPa1/2, respectively.
2. Experimental Section Consequently, PMMA and PS are soluble in DMF and are
insoluble in water. It is also important that DMF and water
2.1. Materials are miscible, so that water can diffuse into the polymer
Poly (methyl methacrylate) with weight-average molecular solution confined in the nanopores.
weights (Mw) of 97 and 557 kg mol−1 was purchased from The experimental scheme for preparing the polymer
Sigma–Aldrich and Polymer Source, respectively. PS was nanomaterials is shown in Figure 1, which is divided into

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 Macromolecular
Effect of Nonsolvent on the Formation of Polymer Nanomaterials . . . Rapid Communications
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route A and route B. The main difference between route when the samples are exposed to the aqueous NaOH solu-
A and route B is that water (nonsolvent) is not added in tion. For route B, the solution-containing templates are
route A to demonstrate the effect of the nonsolvent. For immersed into a bottle of water immediately after the
both routes, the polymer solution is introduced into the wiping step. The preferential interaction between water
nanopores of the AAO templates by capillary force. The and the pore wall causes the formation of a wetting
height at which the polymer solution can reach by cap- layer of water on the surface of the pore wall.[35] Conse-
illary force is inversely proportional to the radius of the quently, the polymer solution is isolated in the center of
nanopore, given by the Jurin’s law:[34] the pores. After the templates are selectively removed by
the aqueous NaOH solution, nanospheres or nanorods are
h = 2 ϒ cos θ /ρ g r (1) obtained, depending on the concentration of the polymer
solution.
where h is the maximum height, γ is the surface tension When water is introduced into the solution-containing
of the polymer solution, θ is the contact angle of the solu- nanopores, it is important to make sure that the solvent is
tion meniscus at the pore wall, ρ is the density of the not dried. If the solvent has already evaporated completely
polymer solution, g is gravity, and r is the radius of the before introducing water, then polymer nanotubes are
pore. The maximum height at which the polymer solu- obtained, because of the precipitation of the polymers on
tion can reach is higher than the length of the nanopores the pore wall. In this work, the solvent for the polymer is
(≈60 μm), mainly due to the small pore diameters DMF, which has relatively high boiling point (153 °C) and
(≈150–400 nm). The low viscosity of the polymer solution low vapor pressure (2.6 mmHg at 20 °C). Therefore, the
also causes the solution to be drawn into the nanopores polymer solution can stay longer in the nanopores of the
within a second. AAO template before the nonsolvent is added. For sol-
After the AAO templates are taken out from the pol- vents such as THF (boiling point: 66 °C, vapor pressure:
ymer solution, a wiping step using a wiper is performed 129 mmHg at 20 °C) or chloroform (boiling point: 61 °C,
to remove the polymer solution outside the nanopores of vapor pressure: 159 mmHg at 20 °C), also good solvents for
the AAO templates. This step is to ensure that the polymer PMMA at room temperature, they have much higher vapor
nanomaterials obtained after dissolving the templates are pressures than that of DMF and evaporate more quickly.
from the materials confined in the nanopores. Without Figure 2 shows the SEM and TEM images of PMMA
the wiping step, the obtained results are disturbed by the nanotubes. Without the nonsolvent, PMMA precipitate on
materials outside the nanopores. For route A, the solution- the pore wall of the AAO template after the evaporation
containing templates are dried using a vacuum pump, of the solvent.[36] The diameters (150–400 nm) and length
resulting in the precipitation of polymers on the pore walls. (≈60 μm) of the PMMA nanotubes correspond to those
After the templates are selectively removed by aqueous of the nanopores. Branched structures, indicating the
NaOH solution, polymer nanotubes are obtained. The branched pores in the AAO templates, can also be seen
vacuum pump is used to ensure that the solvent is dried from the side view of the nanotubes (Figure 2a). The
completely. Otherwise, the residual solvent in the nano- tubular nature of the structures is seen from the top view
pores may cause the morphology change of the polymers shown in Figure 2b. The top parts of the nanotubes are
observed to be inter-connected, demon-
strating that the polymer solution also
wets the top surface of the template
and forms a thin polymer film. Figure 2c
and d shows two typical images of a
single PMMA nanotube with low and
high magnifications, respectively. The
tubular structure is evident, and the wall
thickness of this nanotube is ≈100 nm
with an outer diameter of ≈300 nm. The
wavy structures with nonuniform thick-
ness on the tube wall may be caused by
the fast evaporation of the solvent by
the vacuum pump. Because the sample
Figure 1. The schematic illustration of the experimental processes, including route A and has been dried by the vacuum pump,
route B. For route A, the sample is dried directly using a vacuum pump without adding
water, and polymer nanotubes are obtained. For route B, the sample is dipped into water
the tubular polymer structures are
before the AAO template is selectively removed by NaOH(aq). Nanospheres or nanorods retained even after they are exposed to
are obtained, depending on the concentration of the polymer solution. the aqueous NaOH solution.

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the PMMA nanomaterials and the con-

centration of the polymer solution is
plotted in Figure 4c. The aspect ratio of
the nanomaterials increases with the
polymer concentration.
To understand the formation mech-
anism of the polymer nanomate-
rials induced by nonsolvent and the
concentration-dependent morphology,
we try to study the intermediate states
of the formation process by controlling
the amount of solvent in the nanop-
ores. The above results are obtained
by immersing the solution-containing
templates into water without any
drying process. The solution-containing
(5 wt% PMMA in DMF) templates are
also dried in ambient conditions for dif-
ferent periods of time before immersing
into water. Figure 5b, c, d, and e are
the SEM images of the water-induced
PMMA nanomaterials by drying for 30,
20, 10, and 0 min, respectively. Undu-
lated PMMA structures are observed
at longer drying time, while PMMA
nanospheres are obtained without the
drying process. Based on these results,
Figure 2. SEM and TEM pictures of PMMA (Mw: 97 kg mol−1) nanotubes. (a–b) SEM we propose a simple model to explain
images of PMMA nanotubes from 5 wt% (a) and 10 wt% (b) PMMA solution.
the possible formation mechanism
(c–d) TEM images of PMMA nanotubes from 10 wt% PMMA solution with low (c) and
high (d) magnifications. of the water-induced polymer nano-
materials, as shown in Figure 5a. When
By adding water into the PMMA solution confined in water enters the solution-containing nanopore and wets
the nanopores of AAO templates, PMMA nanospheres the pore wall, the polymer solution is isolated and forms
or nanorods are obtained. Figure 3a is the SEM image of a cylindrical domain. The cylindrical solution then undu-
PMMA nanostructures by adding water into 5 wt% PMMA lates and breaks into spherical domains, driven by the
solution. Water wets the surface of the pore wall and Rayleigh instability.[26,27]
causes the PMMA solution to precipitate in the center of When the Rayleigh instability is applied to viscoelastic
the nanopores, resulting in the formation of PMMA nano- materials, the viscosity resists the breakup of the mate-
spheres and short nanorods. When the PMMA concen- rials.[37] The characteristic time for the material breakup is
tration increases to 10 wt%, longer PMMA nanorods are
observed (see Figure 3b). The internal structures of the τ m = η R0 / σ (2)
PMMA nanomaterials from 5 and 10 wt% PMMA solu-
tion are further examined by TEM (Figure 3c and d), and where τm is the characteristic time for the fastest growing
the solid nature of the materials is confirmed. The results mode, η is the viscosity of the material, R0 is the radius
from 5 and 10 wt% PMMA solution exhibit the depend- of the cylinder, and σ is the surface tension of the inter-
ence of the polymer morphology on the polymer concen- face.[37,38] When the sample is not dried before immersing
tration. The PMMA concentrations are further increased into water, more solvent is present in the nanopores.
to 16 and 32 wt% (Figure 4a and b), and PMMA nanorods Therefore, the characteristic time for the transforma-
with longer lengths are observed. The highest concentra- tion process is shorter because of the lower solution vis-
tion used in this work is 32 wt% because of the solubility cosity. Consequently, the cylindrical solution domain
issue and the high viscosity of the polymer solution. When undulates and breaks into spherical domains before the
the polymer concentration is too high, the viscous solu- solvent is completely dried, resulting in the formation of
tion is difficult to be processed. The relationship between polymer nanospheres, as shown in Figure 5e. When some
the aspect ratio (the length divided by the diameter) of amount of solvent is dried before immersing the sample

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Effect of Nonsolvent on the Formation of Polymer Nanomaterials . . . Rapid Communications
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viscosity. For example, PMMA with high

molecular weight (Mw: 557 kg mol−1) is
used, and undulated PMMA structures
are obtained, as shown in the Supporting
Information.
Even though most of the results can
be explained by this simple model, the
mechanism of the formation of the
polymer nanomaterials induced by
nonsolvent is considered to be more
complicated. This complexity is due to
the fact that water is soluble in DMF,
so the interface between water and the
polymer domain is not well defined. If
water wets the pore wall and diffuses
into polymer solution by Fickian diffu-
sion, a broad interface is expected.[39] If
some amount of solvent is dried, water
may diffuse into the concentrated
polymer solution by non-Fickian dif-
fusion (Case II), in which the diffusion
constant is also a function of the con-
centration, and a sharp interface may be
formed.[40] In addition, the rate of pre-
cipitation of the polymers is controlled
by the diffusion rate of water molecules.
To address these issues, a more compli-
Figure 3. SEM and TEM pictures of PMMA (Mw: 97 kg mol−1) nanospheres and nanorods. cated model may be required to better
(a–b) SEM images of PMMA nanospheres from 5 (a) and 10 wt% (b) PMMA solution.
reflect the formation process.
(c–d) TEM images of PMMA nanorods from 5 (c) and 10 wt% (d) PMMA solution.
The sizes of the polymer nanomate-
rials made by templates are also com-
into water, the characteristic time for the transformation pared with the original pore sizes of the AAO templates.
process is longer because of the higher solution viscosity. The nanopores can be seen from the top view of the AAO
Therefore, the transformation process may not be com- templates, as shown in the Supporting Information. The
pleted before the solvent is completely dried, resulting in size distribution of the nanopores in the AAO templates
the formation of undulated structures (see Figure 5b, c, is plotted in Figure S3a (Supporting Information). The dia-
and d). The undulated structures can also be observed by meters of the nanopores range from 150 to 400 nm, and
using polymers with higher molecular weights without the average pore size is 237 nm. Since the pore diameter
any drying process because of the higher solution near the surface is generally larger than the pore diameters
away from the surface, the measured
values are slightly larger than the actual
values. The size distribution of the diam-
eters of the PMMA nanotubes is shown
in Figure S3b (Supporting Information).
The average diameter of the PMMA
nanotubes is 219 nm, which is close to
the average pore size of the AAO tem-
plates. This result confirms that nano-
tubes are formed by the precipitation of
polymers on the pore walls. But the size
distribution of the nanotubes is broader
Figure 4. SEM images of PMMA (Mw: 97 kg mol−1) nanomaterials prepared from (a) 16
and (b) 32 wt% PMMA solution. (c) Plot of the aspect ratio of the nanorods versus the
than that of the nanopores of the AAO
polymer concentration. The closed boxes indicate the average values of the aspect ratios, templates. The broadness may be due to
and the error bars represent the standard deviation. the fact that the nanotubes are not rigid

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Figure 5. (a) The proposed model of the formation mechanism of polymer nanomaterials induced by nonsolvent. (b–e) SEM images of
PMMA (Mw: 97 kg mol−1) nanomaterials from 5 wt% PMMA solution under different periods of drying time before immersing into water:
(b) 30, (c) 20, (d) 10, and (e) 0 min.

and may be distorted after they are removed from the (Supporting Information) shows the SEM images of
template. Such distortion causes the discrepancy of the PMMA and PS aggregates that are formed by dropping
measured diameters from the real diameters. The size dis- 1 wt% polymer solution into water without the presence
tribution of the diameters of the nanospheres made from of the AAO templates. Without the confinement from the
5% PMMA solution is shown in Figure S3c (Supporting template, polymer aggregates with irregular shapes are
Information). The average diameter of the nanospheres is obtained from both PMMA and PS solution in DMF.
159 nm, which is considerably smaller than the average
pore size. The reduction in diameters is reasonable because
the polymer chains aggregate in the center of the nanop- 4. Conclusion
ores instead of precipitating on the pore walls.
PS, another commonly used polymer, is also studied to In conclusion, we have studied the effect of nonsolvent
demonstrate the effect of nonsolvent on the formation of (water) on the formation of polymer nanomaterials made
polymer nanomaterials made by templates. As shown in by templates using PMMA and PS. Without using the
Figure S4 (Supporting Information), the results obtained nonsolvent, polymer precipitate on the pore walls after
from PS are similar to those from PMMA. Without adding the evaporation of the solvent, resulting in the forma-
water, PS nanotubes are obtained. By adding water, PS tion of polymer nanotubes. When water (nonsolvent) is
nanospheres or nanorods are prepared. The lengths of the added to the polymer solution confined in the nanopores
PS nanorods, however, are shorter than the lengths of the of AAO templates, water wets the pore walls and causes
PMMA nanorods, when the same polymer concentration the polymer solutions to be isolated in the central part
is used. For example, the length of the PS nanorods from of the nanopores, resulting in the formation of polymer
30 wt% PS (Mw: 35 kg mol−1) solution is ≈1.5 μm, while the nanospheres or nanorods. The aspect ratios of the nano-
length of the PMMA nanorods from 30 wt% PMMA (Mw: materials induced by nonsolvent can be controlled by the
97 kg mol) solution is ≈3.5 μm. Several factors may cause polymer concentration. This study demonstrates that the
the length difference of the polymer nanorods, including morphology and sizes of polymer nanomaterials can be
the molecular weight, the solubility of the polymer in simply controlled by using nonsolvent. Studies are cur-
DMF, or the interaction between the polymer and the rently being pursued to apply this simple method to other
pore wall. polymer–solvent systems. This concept can also be used to
To further clarify the confinement effect of the AAO prepare nanomaterials from conjugated polymers or inor-
template on the formation of water-induced polymer ganic materials.[41]
nanomaterials, we also study the precipitation of poly-
mers when they are dropped into a beaker of water
without the presence of the AAO template. PMMA or Supporting Information
PS solution is dropped into water under sonication
using a micropipette. The sonication process is to keep Supporting Information is available from the Wiley Online
the polymers from forming large aggregates. Figure S5 Library or from the author.

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Effect of Nonsolvent on the Formation of Polymer Nanomaterials . . . Rapid Communications
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