Letter

Cite This: ACS Macro Lett. 2017, 6, 1104-1108 pubs.acs.org/macroletters

Solvent-Driven Infiltration of Polymer (SIP) into Nanoparticle

Packings
Neha Manohar, Kathleen J. Stebe,* and Daeyeon Lee*
Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
*
S Supporting Information

ABSTRACT: Despite their wide potential utility, the manufacture of

polymer−nanoparticle (NP) composites with high filler fractions presents
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significant challenges because of difficulties associated with dispersing and

mixing high volume fractions of NPs in polymer matrices. Polymer-
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infiltrated nanoparticle films (PINFs) circumvent these issues, allowing

fabrication of functional composites with extremely high filler fractions (>50
vol %). In this work, we present a one-step, room-temperature method for
porous PINF fabrication through solvent-driven infiltration of polymer
(SIP) into NP packings from a bilayer film composed of a densely packed
layer of NPs atop a polymer film. Upon exposure to solvent vapor, capillary
condensation occurs in the NP packing, leading to plasticization of the
polymer layer and subsequent infiltration of polymer into the NP layer. This
process results in a porous PINF without the need for energy-intensive
processes. We show that the extent of polymer infiltration depends on the
quality of solvent and the duration of solvent annealing as well as the molecular weight of the polymer. SIP can also be induced
using a slightly poor solvent, which offers a great advantage of inducing SIP via liquid solvent annealing, eliminating potential
hazards associated with solvent vapor annealing. The SIP process circumvents challenges associated with dispersing high
concentrations of nanoparticles in a polymer matrix to prepare a nanocomposite film with high filler fraction. Thus, SIP is a
potentially scalable method that can be used for the manufacturing of porous PINFs of a wide range of compositions, structures,
and functionalities for applications in structural and barrier coatings as well as electrodes for energy storage and conversion
devices.

T he infiltration of polymers into the interstices of dense

nanoparticle (NP) packings opens new opportunities for
fabrication of functional composites with extremely high
fractions of NPs (>50 vol %) and circumvents issues associated
with dispersal or mixing of NPs into polymers.1−6 Like
composite structures found in nature such as nacre, polymer-
infiltrated nanoparticle films (PINFs) have high strength and
toughness and also exhibit high scratch and wear resistance,
making them ideal protective and structural coatings.7−9
Moreover, many working electrodes in energy storage and
conversion devices such as fuel cells, lithium ion batteries, and
solid-state dye-sensitized solar cells exploit PINF struc-
tures;10−13 in these settings, a small volume of ion-conducting
polymers are dispersed in dense packings of NPs with catalytic
properties. PINFs also have great potential for producing gas
barrier layers.5,14 The introduction of nanoporosity in such
PINFs could further enhance their functionality by tuning their
optical properties, for example, to generate antireflection
coatings with high mechanical strength.9,15,16
Previous attempts to infiltrate polymer into porous structures
and NP packings have involved either immersion in a polymer
melt or solution,1,2 exposure to monomer vapor followed by in
situ polymerization,3,4 or infiltration with resin solutions that
are subsequently cross-linked.5,6 However, such approaches can
lead to low and inhomogeneous loadings or require multistep
complex methods that could result in the presence of residual
monomers and uncontrolled polymer fill fractions.1−6 Initiated
chemical vapor deposition also has been used for the generation
of PINFs for use in dye-sensitized solar cells; however, this
method requires vacuum processing.17 There is need, therefore,
for a scalable, facile technique for PINF fabrication that retains
polymer quality and consistent loading within the NP packings
to enable their use in a variety of applications.
Recently, a novel technique to overcome these obstacles has
been developed by depositing a packing of NPs atop a polymer
layer and, subsequently, thermally annealing the bilayer to
induce capillary-rise infiltration (CaRI) of the polymer into the
voids of the NP packing.7 Moreover, by varying the amount of
polymer relative to the void fraction in the NP film, it is
possible to manufacture nanoporous PINFs that can be
exploited for optical and mechanical applications.15 The CaRI
approach relies on the use of a polymer with a low or accessible
glass transition, which may not be the case for several glassy
polymers used in industrial applications.15 Such polymers can
decompose before reaching their Tg. Additionally, high
Received: May 29, 2017
Accepted: September 18, 2017
Published: September 20, 2017

© 2017 American Chemical Society 1104 DOI: 10.1021/acsmacrolett.7b00392

ACS Macro Lett. 2017, 6, 1104−1108
ACS Macro Letters Letter

temperatures can lead to loss of structural integrity of some

NPs that are made of metal or ceramics,18−20 creating a need
for viable room-temperature alternatives for porous PINF
fabrication, which would also significantly reduce the energy
requirement.
In this work, we present a method that induces the
infiltration of polymer into NP films without heating, but
rather, through solvent annealing. As shown in Figure 1, a

Figure 2. Percent filling (open symbols) of NP packing by condensed

solvent and NP film thickness (closed symbols) for SiO2 NP packings
on Si wafers upon exposure to toluene vapor. Two NP packings are
characterized by average particle radius 23 nm (red) and 77 nm
(black), respectively. Samples were purged in nitrogen for 10 min prior
to exposure to toluene vapor at the 5 min mark in this graph.

vapor exposure corresponds to near-complete filling of the

pores in the 23 nm particle packing for all the solvents used in
this study; for reference, the void fraction within the densely
Figure 1. Schematic illustration of solvent-driven infiltration of packed NP film is approximately 0.31. We also observe capillary
polymer (SIP) into a NP film. A polymer/NP bilayer is annealed condensation within the packing of 77 nm particles. However,
with solvent vapor, leading to capillary condensation of solvent in the owing to the larger pores in the packings of these larger
NP packing, followed by swelling and infiltration of polymer. particles, less than a quarter of the void space is filled with
liquid solvent, as shown in Figure 2.
bilayer, composed of a polymer layer and a layer of densely The bilayer samples are exposed to solvent vapor through an
packed NPs, is exposed to solvent vapor. The NP layer is apparatus that allows a nitrogen stream that is bubbled through
quickly flooded with condensed solvent,4,21 which then diffuses a liquid-state solvent to come in contact with the bilayer sample
into the polymer layer, leading to its plasticization. The (Figure S1). The SEM images of as-prepared bilayers are
plasticized polymer subsequently infiltrates into the voids compared to those of bilayers after solvent vapor exposure in
between the NPs. This process, solvent-driven infiltration of Figure 3. In the infiltrated sample, polymer within the
polymer (SIP), produces a composite layer that has an interstitial voids in the NP packing is evident in the SEM
extremely high filler fraction (i.e., a PINF) without the need images. Furthermore, in the infiltrated sample, one can observe
for thermal processing and also circumvents challenges a decrease in the thickness of the polymer layer, indicating
associated with dispersing high concentrations of NPs in polymer infiltration. The top-view SEM image of the infiltrated
polymers to form nanocomposite films with high filler fractions sample for the smaller NPs (Figure 3B, inset) also shows NPs
via conventional methods.22−31
Capillary condensation in NP packings occurs due to the
high negative curvature associated with the voids between two
small spheres in contact and has been shown to occur to a
greater extent as the size of the NP is decreased.4 We use SiO2
NPs with average diameters of 23 and 77 nm, which are small
enough that a significant driving force for condensation within
the respective packings exists. To show that capillary
condensation indeed occurs readily in this system, a 225 nm
thick film comprised of 23 nm SiO2 NPs and a 235 nm thick
film comprised of 77 nm SiO2 NPs are exposed to solvent
vapor after an initial nitrogen purge for 10 min and observed
using in situ ellipsometry.
Subsequently, the refractive index of the NP film increases
significantly upon exposure to the solvent vapor stream,
indicating capillary condensation of the solvent in the
interstices of the NP film. The thickness of the NP film does
not change upon exposure to solvent vapor as shown in Figure Figure 3. Cross-sectional SEM images of PS/23 nm SiO2 particles (A,
2. This indicates that the solvent is condensing within the film B) and PS/77 nm SiO2 particles (C, D). (A) and (C) show the bilayer
and not on top of the film, which allows for the use of a simple films before solvent exposure; (B) and (D) show the films after
mixing rule to estimate the percent of the voids filled with infiltration using SIP. Inset: top-down SEM images. All scale bars are
solvent (Figure 2). The change in refractive index upon solvent 100 nm.

1105 DOI: 10.1021/acsmacrolett.7b00392

ACS Macro Lett. 2017, 6, 1104−1108
ACS Macro Letters Letter

Table 1. Flory−Huggins χ Parameters between PS and Different Solvents Used in This Study
solvent toluene cyclohexane 1,4-dioxane morpholine hexane diacetone alcohol ethanol
χ 0.35 0.53 0.55 0.80 1.03 1.90 2.37

that appear to be embedded in polymer. The average distance

between the NP centers for the infiltrated smaller NP film (⟨d⟩
∼ 26 nm) does not change significantly compared to the
uninfiltrated sample (⟨d⟩ ∼ 27 nm), but the visible portion of
the NPs shrinks, indicating polymer filling the spaces between
the NPs. We do not observe any polymer overlayer on top of
these NPs, which also agrees with our ellipsometry measure-
ments.
Solvent quality has a significant impact on the thermody-
namics and dynamics of polymers in solvents. To investigate
the effect of solvent quality on SIP (Table 1), PS-SiO2 NP
bilayers are exposed to seven different solvent vapors with
varying polymer−solvent Flory−Huggins interaction parameter
(χ). The polymer−solvent χ parameter ranges from that for
very good solvents (χ = 0.35) to nonsolvent systems (χ = 2.37),
where χc = 0.61 is the calculated critical value that indicates a θ
solvent for the polymer (Mn = 8000 g/mol).32 The Flory−
Huggins interaction parameter is calculated using the method
described by Hansen which emphasizes the dispersion
interactions between molecules (see eqs S2 and S3).33 The
volume fraction of PS in the NP film (φPS) upon SIP is
estimated based on changes in the thickness of the bottommost
PS layer (see eq S1). The top composite layer is modeled as a
homogeneous layer since there is no clear evidence of a
gradient and no clear infiltration front is observed based on
ellipsometry modeling.15 The thickness of the NP packing does
not change after SIP (see Figure S3).
The polymer volume fraction in the top layer (φPS) is also
dependent on the size of the nanoparticles in the packing, with
larger nanoparticles leading to less infiltration, irrespective of
solvent quality (Figure 4A). This is likely due to the decrease in Figure 4. Volume fraction of PS in the NP packing (φPS) (A) for PS
the extent of capillary condensation observed for larger (Mn = 8000 g/mol) into 23 nm particle packings (circles) and 77 nm
nanoparticle packings (Figure 2). From this we infer that, if particle packings (diamonds), after 30 min (closed) or 24 h (open) of
vapor exposure for various solvents at different χ, and (B) using
the interstitial voids of the nanoparticle packing are not different good solvents (χ < χc) as a function of PS molecular weight
completely filled with solvent, the polymer does not infiltrate after 30 min of vapor exposure.
into those voids. This can also be observed in the top-down
SEM images of the infiltrated sample for the larger nano-
particles (Figure 3D, inset). when the characteristic size of polymer chains is larger than the
The extent of infiltration depends on the solvent quality, as average pore size in the NP packing. To examine this
estimated by χ, the size of the nanoparticles, and the duration of possibility, we use bilayers composed of intermediate and
annealing. The poorer the solvent (i.e., the higher the χ), the high molecular weight PS (Mn = 21000 and 173000 g/mol; for
smaller φPS is found in the PINF for a constant annealing time both polymers PDI < 1.1) and 23 nm SiO2 NPs. The 21k and
of 30 min. When the samples are exposed to solvent vapors for 173k PS have estimated radii of gyration of 4 and 12 nm in
24 h, φPS is increased, as can be seen for the cases of cyclohexane, respectively, whereas the estimated average pore
cyclohexane (χ = 0.53) and hexane (χ = 1.03). For the case of radius in random close packing of 23 nm SiO2 NPs is 3−5
very good solvents such as toluene (i.e., low χ), infiltration nm.34,35 The 173k PS also represents a fully entangled system
occurs rapidly. Extended exposure of bilayers to some of these in its melt state. We find, remarkably, that these high molecular
very good solvents, however, can induce dewetting of PS from weight polymer chains are able to undergo SIP into the NP film
the substrate (i.e., the Si wafer), complicating precise sample provided that they are exposed to a good solvent vapor (Figure
characterization. For nonsolvents (e.g., diacetone alcohol), no 4B). Furthermore, even with a solvent of moderate quality such
infiltration is observed even after a 24 h exposure. The highest as cyclohexane (χ = 0.53), after 24 h of vapor annealing, the
calculated fill fraction of polymer possible in the NP film, found 21k PS infiltrates fully into the packing and the 173k PS begins
by completely filling the interstices of the NP film using CaRI, to infiltrate the packing (Figure S4). Additionally, for a poor
is φPS, max ∼ 0.31. Using SIP, the maximum volume fraction of quality solvent such as hexane (χ = 1.03), the 21k PS infiltrates
polymer in the composite is roughly φPS ∼ 0.25, indicating that to a small degree after 24 h (Figure S4). This result suggests
the SIP PINFs are porous. that while infiltration dynamics are slowed by molecular weight,
One intriguing question is whether polymers of high SIP is thermodynamically favored despite the increase in
molecular weight can be induced to undergo SIP, especially confinement within the NP packing.
1106 DOI: 10.1021/acsmacrolett.7b00392
ACS Macro Lett. 2017, 6, 1104−1108
ACS Macro Letters
The fact that even slightly poor solvents such as hexane can
induce SIP at long exposure times (Figures 4 and S4) could
provide a significant advantage; by using poor solvents instead
of good solvents, bilayers might be directly submerged in liquid
solvent without compromising sample integrity. The use of
liquids instead of vapors could also offer significant advantages
in manufacturing processes, since solvent vapors may pose
health and safety hazards. Furthermore, dipping processes are
far simpler to implement than are processes that rely on
annealing in vapor chambers. To test this possibility, a bilayer is
directly submerged in liquid hexane. PS indeed infiltrates the
NP packing, as shown in Figure 5. In contrast, direct
submersion in good solvents such as toluene leads to
immediate dissolution of the bilayer from the substrate.
Figure 5. Volume fraction of PS (8000 g/mol) in SiO2 NP packing
(φPS) after annealing with hexane (χ = 1.03) via vapor annealing
(black circles) and liquid annealing (blue squares) as a function of
time.
The dynamics of infiltration, as represented by the volume
fraction of polymer in PINF as a function of time, in vapor SIP
and liquid SIP are quite similar to each other, as shown in
Figure 5. These trends suggest that capillary condensation
occurs rapidly in the vapor annealing case and that the
condensed liquid in the interstices plasticizes the polymer and
induces SIP, making both systems essentially identical from the
perspective of the polymer layer. However, when the bilayers
are liquid-annealed in hexane for much longer times, loss of
polymer layer from the bilayer is observed, whereas the
refractive index changes indicate that the volume fraction of
polymer in the PINF layer (φps) stays constant around 0.25.
This result indicates that once polymer infiltrates the NP
packing, there is a continuous flux of polymer dissolving into
the solvent bath from the top of the packing.
In conclusion, solvent-driven infiltration of polymer (SIP) in
polymer/NP bilayers yields high filler-fraction nanocomposite
films of varying porosity, which can be tuned by controlling
solvent quality, nanoparticle size, and annealing time. Polymers
undergo SIP even when slightly poor solvents are used, and
high molecular weight polymers can also be induced to undergo
SIP upon extended exposure. The use of slightly poor solvents
provides a significant advantage in that they enable liquid
submersion (dip processing) to induce SIP, potentially
providing a route to a room-temperature, industrially viable
continuous fabrication process to prepare porous PINFs.
However, further optimization is required before the technique
can meet industrially relevant time scales.
1107
Letter
There are several outstanding questions regarding the
mechanism and dynamics of SIP, which are the focus of our
ongoing study. In particular, we are intrigued by two possible
mechanisms for SIP; polymer could infiltrate via a surface-
mediated pathway or via a solvation-mediated pathway. In the
first case, the polymer is driven into the confined NP packing
via surface interactions, somewhat analogous to the proposed
mechanism for the CaRI technique. The second route,
infiltration of polymer via dissolution directly in the solvent
condensed in the pores, might occur without significant surface
adsorption of the polymer on the NP surface. The results
presented in this work seem to point toward the dissolution
mechanism. It is likely that, depending on the quality of solvent
and the interactions between polymer and NPs, the mechanism
can switch from purely dissolution-driven to surface-driven,
which could result in PINFs with different morphology. This is
the focus of ongoing research. We will also address the
dynamics of SIP, which are likely determined by three key
steps: capillary condensation, polymer plasticization and
infiltration. The dynamics of SIP depends on the relative
time scales of these processes and may be dominated/limited
by one process, depending on the molecular weight of the
polymer and solvent−polymer−NP interactions.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsmacro-
lett.7b00392.
Experimental details and apparatus for solvent annealing,
NP layer thickness characterization, water condensate
removal, solvent quality determination, and longer
annealing studies (PDF).
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: kstebe@seas.upenn.edu.
*E-mail: daeyeon@seas.upenn.edu.
ORCID
Kathleen J. Stebe: 0000-0003-0510-0513
Daeyeon Lee: 0000-0001-6679-290X
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by NSF Grant Nos. CBET-1449337
and PIRE-1545884.
■ REFERENCES
(1) Flauder, S.; Sajzew, R.; Muller, F. A. ACS Appl. Mater. Interfaces
2015, 7, 845−851.
(2) Martínez-Vázquez, F. J.; Perera, F. H.; Miranda, P.; Pajares, A.;
Guiberteau, F. Acta Biomater. 2010, 6, 4361−4368.
(3) Zhang, H.; Popp, M.; Hartwig, A.; Mädler, L. Nanoscale 2012, 4,
2326−2332.
(4) Gemici, Z.; Schwachulla, P. I.; Williamson, E. H.; Rubner, M. F.;
Cohen, R. E. Nano Lett. 2009, 9, 1064−1070.
(5) Lan, Q.; Yan, N.; Wang, Y. J. Membr. Sci. 2017, 533, 96−102.
(6) Landi, E.; Valentini, F.; Tampieri, A. Acta Biomater. 2008, 4,
1620−1626.
(7) Huang, Y.-R.; Jiang, Y.; Hor, J. L.; Gupta, R.; Zhang, L.; Stebe, K.
J.; Feng, G.; Turner, K. T.; Lee, D. Nanoscale 2015, 7, 798−805.
DOI: 10.1021/acsmacrolett.7b00392
ACS Macro Lett. 2017, 6, 1104−1108
ACS Macro Letters Letter

(8) Yeom, B.; Sain, T.; Lacevic, N.; Bukharina, D.; Cha, S.-H.; Waas,
A. M.; Arruda, E. M.; Kotov, N. A. Nature 2017, 543, 95−98.
(9) Mizoshita, N.; Ishii, M.; Kato, N.; Tanaka, H. ACS Appl. Mater.
Interfaces 2015, 7, 19424−19430.
(10) Bakangura, E.; Wu, L.; Ge, L.; Yang, Z.; Xu, T. Prog. Polym. Sci.
2016, 57, 103−152.
(11) Hudiono, Y.; Choi, S.; Shu, S.; Koros, W. J.; Tsapatsis, M.; Nair,
S. Microporous Mesoporous Mater. 2009, 118, 427−434.
(12) Croce, F.; Appetecchi, G. B.; Persi, L.; Scrosati, B. Nature 1998,
394, 456−458.
(13) Katsaros, G.; Stergiopoulos, T.; Arabatzis, I. M.; Papadokostaki,
K. G.; Falaras, P. J. Photochem. Photobiol., A 2002, 149, 191−198.
(14) Merkel, T. C.; Freeman, B. D.; Spontak, R. J.; He, Z.; Pinnau, I.;
Meakin, P.; Hill, A. J. Science 2002, 296, 519−522.
(15) Hor, J. L.; Jiang, Y.; Ring, D. J.; Riggleman, R. A.; Turner, K. T.;
Lee, D. ACS Nano 2017, 11, 3229−3236.
(16) De Oliveira, P. W.; Becker-Willinger, C.; Jilavi, M. H. Adv. Eng.
Mater. 2010, 12, 349−351.
(17) Nejati, S.; Lau, K. K. S. Nano Lett. 2011, 11, 419−423.
(18) Shao-Horn, Y.; Sheng, W. C.; Chen, S.; Ferreira, P. J.; Holby, E.
F.; Morgan, D. Top. Catal. 2007, 46, 285−305.
(19) Zhao, Y.; Qiu, X.; Burda, C. Chem. Mater. 2008, 20, 2629−2636.
(20) Liu, Y.; Mills, E. N.; Composto, R. J. J. Mater. Chem. 2009, 19,
2704.
(21) Lu, F.; Wu, S. H.; Hung, Y.; Mou, C. Y. Small 2009, 5, 1408−
1413.
(22) Kumar, S. K.; Jouault, N.; Benicewicz, B.; Neely, T.
Macromolecules 2013, 46, 3199−3214.
(23) Cheng, S.; Grest, G. S. ACS Macro Lett. 2016, 5, 694−698.
(24) Ge, T.; Kalathi, J. T.; Halverson, J. D.; Grest, G. S.; Rubinstein,
M. Macromolecules 2017, 50, 1749−1754.
(25) Hadzifejzovic, E.; Shkal, F.; Jurkschat, K.; Moghal, J.; Parker, E.
M.; Sawangphruk, M.; Slocombe, D. R.; Foord, J. S.; Moloney, M. G.
Langmuir 2016, 32, 7917−7928.
(26) Kumar, S. K.; Benicewicz, B. C.; Vaia, R. A.; Winey, K. I.
Macromolecules 2017, 50, 714−731.
(27) Lin, C.; Parrish, E.; Composto, R. J. Macromolecules 2016, 49,
5755−5772.
(28) Martin, T. B.; Jayaraman, A. Mater. Res. Express 2016, 3, 034001.
(29) Shen, J.; Li, X.; Shen, X.; Liu, J. Macromolecules 2017, 50, 687−
699.
(30) Xu, Q.; Chen, L. Soft Matter 2016, 12, 1385−1400.
(31) Zhang, R.; Lee, B.; Bockstaller, M. R.; Kumar, S. K.; Stafford, C.
M.; Douglas, J. F.; Raghavan, D.; Karim, A. Macromolecules 2016, 49,
3965−3974.
(32) Rubinstein, M.; Colby, R. H. Polymer Physics; Oxford University
Press, 2003.
(33) Hansen, C. M. The Three Dimensional Solubility Parameter and
Solvent Diffusion Coefficient; Danish Technical Press, 1967.
(34) Rouault, Y.; Assouline, S. Powder Technol. 1998, 96, 33−41.
(35) Fetters, L. J.; Hadjichristidis, N.; Lindner, J. S.; Mays, J. W. J.
Phys. Chem. Ref. Data 1994, 23, 619−640.

1108 DOI: 10.1021/acsmacrolett.7b00392

ACS Macro Lett. 2017, 6, 1104−1108