ARTICLE

Structural Relaxation of Polymer

Nanospheres under Soft and Hard
Confinement: Isobaric versus Isochoric
Conditions
Yunlong Guo,† Chuan Zhang,† Christine Lai,† Rodney D. Priestley,†,* Maria D’Acunzi,‡ and George Fytas‡,§
†
Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States, ‡Max Planck Institut für Polymerforschung,
Ackermannweg 10, 55128 Mainz, Germany, and §Department of Materials Science, University of Crete and F.O.R.T.H., Heraklion, Greece

U
nderstanding the dynamics of
nanoscopically confined polymer ABSTRACT We have measured the glassy-state structural relaxation of aqueous suspended
remains an intriguing scientific en- polystyrene (PS) nanoparticles (the case of soft confinement) and the corresponding silica-capped PS
deavor and one with significant technical nanoparticles (the case of hard confinement) via differential scanning calorimetry. Suspended and
motivation. Confined polymers are featured capped PS nanoparticles undergo physical aging under isobaric and isochoric conditions,
prominently in emerging applications ran-
respectively. With decreasing diameter, suspended and capped PS nanoparticles exhibited reduced
ging from nanostructured films for plastic
and bulk glass transition temperatures (Tg), respectively. To account for Tg changes with
solar cells to polymer nanocomposites for
structural applications, and to thin films for confinement, all physical aging measurements were performed at a constant value of Tg
Ta,
smart coatings, photoresists for patterning where Ta is the aging temperature. With decreasing diameter, aqueous suspended PS nanoparticles
of submicrometer features, and membranes exhibited enhanced physical aging rates in comparison to bulk PS. Due to differences in
for energy-efficient separations.1
5 When a thermodynamic conditions during aging and interfacial effects from nanoconfinement, at all values
polymer film (freestanding or substrate- of Tg
Ta investigated, capped PS nanoparticles aged at reduced rates compared to the
supported) is confined to the nanoscale,
corresponding aqueous suspended PS nanoparticles. We captured the physical aging behavior of
its glass transition temperature (Tg) and
all nanoparticles via the Tool, Narayanaswamy, and Moynihan model of structural relaxation.
associated dynamics can differ substantially
from the bulk.6
19 Factors that influence KEYWORDS: structural relaxation . confinement . nanoparticles . core
shell
the deviation in Tg with confinement in- nanoparticles . glass transition . physical aging . TNM model
clude geometry,20 strength of interfacial
interactions,14,21 sample preparation,22 and
chemical structure.23 of supported films (one free surface) with
The importance of confined polymers for similar thickness9 and direct measurements
nanotechnology, as well as scientific curios- of a reduced free surface layer Tg of single
ity, has motivated experimental studies to substrate support films.8,17,27 However, we
characterize and elucidate the cause of note that the impact of confinement on Tg is
the Tg confinement effect. Numerous still a subject of much debate.28
33
reviews9,15,24 highlighting the experimental Irrespective of deviations in Tg with con-
and computational studies have been writ- finement, confined glasses undergo structur-
ten. The initial work by Keddie et al.11 de- al relaxation (i.e., physical aging). Structural
monstrated the dependence of polymer
relaxation is the spontaneous relaxation of
substrate interactions on the deviation in Tg glasses toward equilibrium, which results in a
with confinement of thin films, which has been time dependence of end use properties.
subsequently confirmed by others.10,25,26 In Aside from investigations on submicrometer
essence, in the absence of strong poly- thick polymeric membranes,34,35 few studies * Address correspondence to
[email protected].
mer
substrate interactions, decreases in have characterized the structural relaxation
Tg with confinement presumably occur of confined polymer glasses.17,36
43 Reduc- Received for review December 21, 2010
due to free surface effects.6,8 This assertion tions in the rate-of-aging were reported for and accepted June 24, 2011.
was supported by measurements of free- supported thin polymer films of poly(methyl
Published online June 30, 2011
standing films (two free surfaces) in which methacrylate) (PMMA)38 and poly(2-vinyl 10.1021/nn201751m
the magnitude in Tg reduction due to con- pyridine) (P2VP),41 and polymer
silica
finement was significantly greater than that nanocomposites of PMMA and P2VP39,41,44 C 2011 American Chemical Society

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5365

www.acsnano.org
 ARTICLE
compared to the corresponding bulk polymer. Sup-
pressed aging with confinement has been attri-
buted to interfacial effects perturbing glassy-state
dynamics.38,39,41 This assertion was supported by local
interfacial aging measurements of PMMA films sup-
ported on silica that revealed a nearly complete sup-
pression of aging within the first 25 nm of the
interface.17 Recently, simulations also support the idea
that strongly impeded glassy-state dynamics at the
polymer
substrate interface can lead to suppressed
aging of confined polymer.45,46 In the absence of
interfacial effects, the rate-of-aging of ultrathin poly-
styrene films has been reported to be comparable to or Figure 1. Temperature protocol of aging test: (A) removal
enhanced relative to that of the bulk.37,38,40 of previous thermal history, (B) measurement of Tg prior to
aging step, (C) aging step, and (D) measurement of Tg after
Since glasses are non-equilibrium materials, their aging step.
properties depend on the path to formation.47 Differ-
ent thermal histories (e.g., cooling rate), environmental
conditions (e.g., humidity), and pressure during forma-
tion lead to glasses with different thermodynamic
properties. Given that their properties strongly depend
on the path to formation, it is easy to comprehend the
challenge of understanding confinement effects on
aging of glasses. Here, we advance the current under-
standing of how confinement impacts aging by inves-
tigating how different confinement conditions, such as
soft versus hard confinements, alter the rate of struc-
tural relaxation and the time required to reach equi-
librium. This is achieved via aging studies on aqueous
suspended polystyrene (PS) nanoparticles (the case of
soft confinement) and silica-capped PS core
shell nano- Figure 2. SEM images of 400 nm diameter PS nanoparticles
particles (the case of hard confinement) by calorimetry. and the corresponding silica-capped PS nanoparticles be-
fore and after aging (scale bars = 1 μm): (A) PS nanoparticles
For aqueous suspended PS nanoparticles, structural before aging, (B) PS nanoparticles after aging, (C) silica-
relaxation is under isobaric conditions, while for silica- capped PS nanoparticles before aging, and (D) silica-capped
capped PS nanoparticles, structural relaxation is under PS nanoparticles after aging.
isochoric conditions. We show that the type of confine- employed to measure physical aging. Similar SEM
ment has a significant effect on the deviation in structural images were obtained for 200 nm diameter PS/PS

relaxation of confined glasses compared to the bulk. silica core
shell nanoparticles (shell thickness of
∼30 nm). As shown from the representative SEM
RESULTS
images, monodisperse, smooth PS nanoparticles
Figure 1 illustrates the temperature protocol employed were prepared by emulsion polymerization. Coating
for the aging test, which consisted of four major steps: PS nanoparticles with a thin silica shell via the Stöber
(A) sample equilibration (annealing at Tg þ 20
C for 20 method did not distort or alter the structure of the
min), (B) measurement of Tg prior to aging experiment, nanoparticles, as smooth, monodisperse silica-capped PS
(C) aging or annealing step, and (D) measurement of Tg nanoparticles were imaged. More importantly, the
after aging. The controlled heating rates (in steps B, C, images show that the nanoparticles were neither
and D) were 20 and 5
C/min (a lower heating rate is destroyed nor did aggregation take place during the
required for the MDSC technique) for the silica-capped thermal protocols employed for aging measurements.
PS and aqueous suspended PS nanoparticles, respec- Glass Transition Temperature. Glass transition tempera-
tively. The cooling rates were 40
C/min in all experi- tures were determined during segments B and D of the
ments. For MDSC measurements, the amplitude was aging protocol. Identical Tg values were determined for
0.2
C and the frequency was 0.05 Hz. Reported Tgs are both segments for all nanoparticle samples, which
midpoint values. indicated no coalescence of polymer nanoparticles
Figure 2 shows SEM images of 400 nm diameter PS during the aging protocol, in agreement with SEM
nanoparticles and the corresponding silica-capped images. For bulk PS, Tg,bulk = 384 K. Examination of
PS nanoparticles with a shell thickness of approxi- unaged scans for PS nanoparticles (see Figure 3)
mately 30 nm before and after the thermal protocol revealed that soft confinement of PS (nanoparticles

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5366

www.acsnano.org
Figure 3. Heat capacity versus temperature during aging at Tg
Ta = 8 K for (A) bulk PS, (B) 400 nm diameter PS nanoparticles
ARTICLE
and PS
silica core
shell nanoparticles, and (C) 200 nm diameter PS nanoparticles and PS
silica core
shell nanoparticles.

without silica shell) led to a Tg reduction (Tg,d=400 nm = Physical Aging. Figure 3 shows enthalpy recovery
370 K; Tg,d=200 nm = 357 K), while hard confinement curves at Tg
Ta = 8 K for different aging times for bulk
(nanoparticles with silica shell) resulted in nearly no PS, aqueous suspended PS nanoparticles, and silica-
change in Tg (Tg,d=400 nm = 383 K; Tg,d=200 nm = 378 K). capped PS nanoparticles. During aging, enthalpy recovery
These measurements are consistent with Tg confine- curves grew and shifted to slightly higher temperatures
ment effects previously reported for PS nano- until equilibrium was achieved. After an aging time of
approximately 40 min (2400 s), equilibrium was
particles48 and PS films in the freestanding10,19 and
achieved for bulk PS. In comparison, PS nanoparticles
capped geometries and support the assertion that
confined with and without a silica shell continuously
surface effects play a significant role in altering the Tg
exhibited aging at times greater than t = 320 min (19 200 s),
of confined polymer.6,8,13 To account for confine- suggesting a longer aging time to reach equilibrium for
ment-induced changes in Tg, aging was compared both soft and hard three-dimensional confinement.
at a constant value of Tg
Ta for all systems, where Ta This observation was further probed by plotting
was the aging or annealing temperature. Tf
Ta as a function of aging time at different values of

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5367

www.acsnano.org
 ARTICLE
Ta for bulk PS and PS nanoparticles. The quantity Tf
Ta
is a measure of the departure from equilibrium and by
definition equals zero at equilibrium; Tf, the fictive
temperature, is a measure of the glass structure.49
The fictive temperature was determined from DSC
heat capacity data using a method developed by
Moynihan50 in which Tf is defined as
Z T2 Z T2
(Cpl
Cpg )dT ¼ (Cp
Cpg )dT (1)
Tf T1

where T1 is a temperature well below Tg at which the

measured heat capacity, Cp, and the glassy-state heat
capacity, Cpg, are the same and T2 is a temperature
well above Tg at which Cp is equal to the liquid heat
capacity, Cpl. Practically, Tf was determined by setting
the area (T2
Tf)(Cpl
Cpg) equal to the integral of
(Cp
Cpg) within the temperature interval [T1, T2].
Figure 4 illustrates aging isotherms for bulk PS and
aqueous suspended PS nanoparticles. All aging isotherms
asymptotically approached Tf
Ta = 0, which indicated
the attainment of (or approach to) equilibrium. For all
systems, increasing the quench depth (Tg
Ta) resulted in
longer aging times required to reach equilibrium. At
the same value of Tg
Ta, the time required to reach
equilibrium, teq, was significantly shorter for bulk PS
than aqueous suspended PS nanoparticles.
Figure 5 shows aging isotherms of PS nanoparticles
confined within a silica shell. Similar to bulk and
aqueous suspended PS nanoparticles, all aging iso-
therms asymptotically relaxed to or toward a value of
Tf
Ta = 0. At the same value of Tg
Ta, teq was shorter
for PS nanoparticles confined within a silica shell than
aqueous suspended PS nanoparticles. Then it follows
that teq,soft confinement > teq,hard confinement > teq,bulk. Yet,
we observe that teq is nearly identical for different sizes
of aqueous suspended and silica-capped PS nano-
particles. For the silica-capped PS nanoparticles,
this implies that PS and silica do not possess strong
attractive interactions, a premise consistent with direct
interfacial glass transition temperature measurements
Figure 4. Aging isotherms of (A) bulk PS, and (B) 400 nm
of PS supported on a silica substrate.8 In Figure 5, the diameter and (C) 200 nm diameter aqueous suspended PS
solid set of symbols are aging measurements performed nanoparticles aged at different quench depths (Tg
Ta).
at Tg
6 K using MDSC. The data points are consistent Solid lines are fits to the TNM model (see text). Error bars are
smaller than symbol sizes and were determined as the
with those determined by DSC (open symbols). Hence, standard deviation from multiple tests.
the mode of DSC employed should not affect the
observed aging isotherms. aqueous suspended PS nanoparticles. The percentage
We computed aging rates (R = d(Tf
Ta)/d log taging; reduction in aging rate (averaged over all aging tem-
with time in seconds) by fitting the linear portion of the peratures investigated) was similar for both 400 and
aging isotherms to a straight line; the results are sum- 200 nm PS nanoparticles with the addition of a silica
marized in Table 1. Over the aging temperatures probed, shell.
bulk PS and 400 nm diameter aqueous suspended PS Modeling Physical Aging of Polymer Nanoparticles. Aging,
nanoparticles exhibited similar aging rates. In contrast, a nonlinear and non-exponential relaxation process in
200 nm diameter aqueous suspended PS nanoparticles which enthalpy manifests time-dependent behavior, is
exhibited aging rates greater than bulk PS. All things often described by the Tool, Narayanaswamy, and
being equal, silica-capped PS nanoparticles underwent Moynihan (TNM) model51
53 and the Kovacs, Aklonis,
aging at reduced rates compared to the analogous Hutchinson, and Ramos (KAHR) model,54 which are

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5368

www.acsnano.org
 ARTICLE
TABLE 2. TNM Model Parameters of Δh/R, x, and β for
Fitting of Bulk PS and PS Nanoparticles

400 nm 200 nm
bulk PS 400 nm PS PS
silica 200 nm PS PS
silica

Δh/R (K) 83400 81300 83700 78700 83000

ln A (s)
212.49
215.04
215.17
215.75
214.91
x 0.18 0.19 0.07 0.27 0.13
β 0.43 0.84 0.83 0.86 0.89

where δh, the departure from equilibrium, is defined as

the difference between the equilibrium enthalpy loss
(ΔHa,¥) and the instantaneous enthalpy loss of the
glass (ΔHa), as such, δh0 is the initial enthalpy departure
from equilibrium. The parameter τ is the characteristic
relaxation time, and β is the non-exponential parameter
related to the width of the relaxation time distribution.
The relaxation time, which is dependent on temperature
and structure, is approximated by
xΔh (1
x)Δh
ln τ ¼ ln A þ þ (3)
RT RTf
where the parameter A is a material constant, x parti-
tions the structure and temperature dependence on τ,
and Δh/R is the relative activation energy. The relation-
ship between Tf and δh is given by
δh
Tf ¼ Ta þ (4)
ΔCp
Figure 5. Aging isotherms of (A) 400 nm diameter and (B)
200 nm diameter PS
silica core
shell nanoparticles aged where ΔCp is the change in heat capacity at Tg. When
at different quench depths (Tg
Ta). Solid lines are fits to the eqs 2
4 (TNM model) are applied, aging can be
TNM model (see text). Filled squares are data measured by
MDSC. Error bars are smaller than symbol sizes and were modeled by calculating the evolution of the fictive
determined as the standard deviation from multiple tests. temperature as a function of time.56
The relative activation energies (Δh/R) were deter-
mined experimentally for each sample as the slope from
TABLE 1. Aging Rates (R, unit: K) of Bulk and PS Arrhenius plots of ln(cooling rate) versus (1/Tf).37 The
Nanoparticles at Different Aging Temperaturesa parameters A, x, and β were identified by best fits to the
experimental data (see Table 2) via minimizing the sum
temperature (K)
of χ2 error between the desired fitting functions and the
size and structure Tg
4 Tg
6 Tg
8 Tg
10 data. The Levenberg
Marquardt algorithm was used to
search the parameter space for the minimum of χ2.57
d = 200 nm
core 1.996 2.491 2.824 3.077 The initial value of A was set according to ln A = ln τTg

core
shell 1.885 2.371 2.662 2.878 Δh/RTg, with τTg = 100 s; values of A determined by the
d = 400 nm fitting are comparable to those found in the literature.58
core 1.912 2.383 2.739 2.972 Solid lines in Figure 4 are fits to the TNM model
core
shell 1.818 2.302 2.573 2.786 using eqs 2
4. The model provided a good fit to the
bulk PS 1.679 2.312 2.699 2.895
experimental data for bulk PS and aqueous suspended
a
The error in aging rates is about (0.074 and was determined as the average PS nanoparticles. Activation energies for aqueous sus-
standard deviation in aging rates from multiple tests. pended PS nanoparticles were slightly lower than bulk
PS. The partition parameter, x, and stretched exponential
mathematically equivalent. The TNM model utilizes the parameter, β, were larger with soft confinement when
Kohlrausch
Williams
Watts (KWW)55 function to re- compared to bulk PS at identical values of Tg
Ta.
present structural relaxation during aging, and for At early aging time, the initial plateau was predicted to
enthalpy relaxation is given by be longer for aqueous suspended PS nanoparticles
2 3
Z t !β compared to bulk PS.
dt
δh ¼ ΔHa, ¥
ΔHa (t) ¼ δh0 exp4
5 (2) Capping of the PS nanoparticles with a thin silica shell,
0 τ
via the Stöber method, was accomplished at ∼296 K

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5369

www.acsnano.org
 ARTICLE
(room temperature). Therefore, at room temperature, the
TABLE 3. Change of Heat Capacity at the Glass Transition
nanoparticles should be considered in a stress-free state,
for Bulk PS and PS Nanoparticles
and the pressure within the core
shell nanoparticle
should be atmospheric. If the silica shell was rigid and 200 nm 400 nm
free of cracks, then upon heating, due to differences in bulk 200 nm PS PS
silica 400 nm PS PS
silica
thermal expansion coefficients between PS and silica, ΔCp, ΔCv (J/g 3 K) 0.304 0.311 0.247 0.334 0.266
glass formation and aging would be under nearly
isochoric conditions. Additionally, a positive pressure
would develop within the core
shell nanoparticles.
The condition of constant volume was confirmed by
comparing the constant pressure heat capacity, Cp, for
the aqueous suspended PS nanoparticles to the con-
stant volume heat capacity, Cv, of the silica-capped PS
nanoparticles at Tg to the thermodynamic relationship
TR2
Cp
Cv ¼ (5)
FK

where R is the coefficient of thermal expansion, κ is the

compressibility, and F is the density. Table 3 lists the
change in heat capacity at Tg for bulk and PS nanopar-
ticles. The differences in heat capacity between aqueous
Figure 6. Aging rates of aqueous suspended PS nanopar-
suspended and silica-capped PS nanoparticles are con- ticles, PS
silica core
shell nanoparticles, and bulk PS at
sistent with eq 5. different quench depths (Tg
Ta).
The expression between the Tf and δh (see eq 4) was
dependence of the aging rate (physical aging rate vs
modified to account for the isochoric relaxation of
temperature) was determined to be qualitatively differ-
silica-capped PS nanoparticles
ent and similar to the bulk, respectively.37,38 Addi-
δh
Tf;core
shell ¼ Ta þ (6) tionally, for PMMA, the maximum aging rate occurred
ΔCv
at ∼300 K for bulk and ∼380 K for a 20 nm thick film,38
The solid lines in Figure 5 are fits to the data using the while for PS, the maximum aging rate occurred at ∼340 K
TNM model, eqs 2, 3, and 6. The model provided a good for bulk and ∼350 K for a 30 nm thick film.38 From our
description of the experimental data. Silica-capped PS analysis of aqueous suspended and silica-capped PS
nanoparticles exhibited higher and lower values of nanoparticles, the temperature dependence of the aging
activation energies and x, respectively, compared to rate was qualitatively similar to that of bulk PS (see Figure 6)
aqueous suspended PS nanoparticles. Values of β and in agreement with the observation reported in refs
remained nearly unchanged for PS nanoparticles with 37, 38, and 40. We note that in Figure 6, a maximum in
and without a silica shell. aging rate was not observed due to the limited range
of aging temperatures probed below Tg. Therefore, we
DISCUSSION can conclude a similar temperature-dependent aging rate
This work presents a comparison of soft and hard (within the temperature range investigated) for bulk and
confinement effects on physical aging of polymer nanoparticles of PS. Regarding the second assumption,
glasses. Studies on polymer nanoparticles with and we gain insight into its validity by comparing the actual
without an outer inorganic shell allow for independent experimental Tg
Ta (measure of initial departure from
studies of confinement and interfacial effects on aging. equilibrium) values to Tf
Ta values predicted by the TNM
When investigating the impact of confinement on model in the early time of structural relaxation for bulk
physical aging, the importance of maintaining a con- and nanoparticles of PS. For bulk, suspended, and capped
stant quench depth is due to the strong nonlinear PS nanoparticles, the predicted values of Tf
Ta were in
dependence of aging rate on the aging temperature.59 agreement with the actual experimental values of Tg
Ta
The temperature dependence of the physical aging (=4, 6, 8, and 10 K), suggesting an equal departure from
rate is set by the synergism between the driving force equilibrium at the onset of aging.
for aging (Tg
Ta) and the mobility (Ta). Yet, two The work of Koh and Simon, who used DSC to measure
assumptions must still be made: (1) the temperature structural relaxation of stacked ultrathin PS films at
dependence of the aging rate is unaffected by confine- constant quench depths (Tg
Ta), provides the best
ment, and (2) a constant value of Tg
Ta for bulk and comparison to the present study.37 They found the time
confined polymer necessarily implies equal departures required to reach equilibrium was greater for a thin film
from equilibrium. Regarding the first assumption, for (h = 62 nm) compared to bulk and that the logarithmic
PMMA and PS films supported on silica, the temperature physical aging rate was independent of film thickness.

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5370

www.acsnano.org
 ARTICLE
Our findings on aqueous suspended PS nanoparticles
were reasonably consistent with those of Koh and
Simon. As illustrated in Figure 7, longer aging times were
required for the attainment of equilibrium for aqueous
suspended and silica-capped PS nanoparticles compared
to bulk PS. In addition, as shown in Figure 6, we observed
similar logarithmic aging rates for bulk and silica-capped
PS nanoparticles, while aqueous suspended nanoparticles
exhibited slightly higher aging rates. A more direct com-
parison of confinement effects on aging between polymer
nanoparticles and freestanding films can be made by
defining a characteristic length, h*, which for nanoparti-
cles was the volume to surface area ratio equal to 1/6 of
the diameter, whereas for films, it was taken to be the
Figure 7. Time required for the attainment of equilibrium
thickness. For the 400 nm diameter PS nanoparticles, during aging for PS nanoparticles and bulk PS at different
h* ∼ 67 nm, while for the 200 nm diameter PS quench depths (Tg
Ta); teq is defined as the instant at
nanoparticles, h* ∼ 33 nm. Using this analysis, we which the value Tf
Ta e 0.1 K from the TNM model.
found our results to be in good agreement with that and presence of an initial aging plateau at short aging
of Koh and Simon, that is, an absence of an aging times (as predicted by the TNM model) for PS nano-
confinement effect on the aging rate for a thin film with particles with and without a silica shell, respectively.
h = 62 nm and nanoparticles with h* ∼ 67 nm. The In an early report, Simon et al.60 investigated the
slight enhancement in aging rate of the 200 nm dia- aging response of ortho-terphenyl (o-TP), a molecular
meter suspended PS nanoparticles was likely due to a glass former, under isochoric conditions. This was
greater extent of confinement. The consistency in size- achieved by confining the o-TP in controlled pore glass.
dependent aging rate of nanoparticles and thin films, Interestingly, the isochorically confined o-TP aged to a
when compared as a function of h*, suggests a com- nonzero value of Tf
Ta. That Tf
Ta 6¼ 0 at equilibrium
mon cause of the aging confinement effect irrespec- was due to the formation of a negative pressure during
tive of confining geometry (i.e., the free surface). A vitrification. Thus, at all aging temperatures (Ta < Tg), o-
recent study by Roth and co-workers, who used ellip- TP aged under tension, which led to a modification of
sometry to measure the physical aging rate of sup- the apparent equilibrium state. In the current study,
ported PS films, suggested a strong connection the state-of-affairs described above (i.e., aging under
between the free surface (gradient in dynamics away tension) would not occur unless Ta < Troom, an aging
from free surface) and aging confinement effects.40 condition not investigated in the current study.
Capping of the PS nanoparticles with a silica shell
should remove the soft interface by confining the polymer CONCLUSIONS
within a hard shell, that is, the case of hard confinement. In In summary, we have investigated the glassy-state
addition, the rigid shell layer created an isochoric structural relaxation of PS nanoparticles under soft and
condition for structural relaxation. Since the shell layer hard confinement. Aqueous suspended PS and silica-
was formed at room temperature, Troom, at Ta > Troom a capped PS nanoparticles aged under isobaric and
positive pressure, ΔP = Rgκg(Ta
Troom), would devel- isochoric conditions, respectively. We found that with
op within the core
shell nanoparticles. In comparison decreasing diameter aqueous suspended PS nanopar-
to the corresponding aqueous suspended PS nanoparti- ticles (soft confinement) exhibited higher logarithmic
cles, silica-capped PS nanoparticles confined within a silica physical aging rates in comparison to the bulk. Silica-
shell exhibited lower physical aging rates. This result is capped PS nanoparticles aged at reduced rates com-
consistent with there being an internal pressure within pared to the corresponding aqueous suspended PS
the capped nanoparticles; that is, the relaxation rate nanoparticles, in agreement with there being an inter-
should decrease with increasing pressure. Yet, the time nal positive pressure within the core
shell nanoparti-
required to reach equilibrium was smaller for capped PS cles. The aging behavior could be well captured via the
nanoparticles. This is presumably due to the absence TNM model of structural recovery.

EXPERIMENTAL SECTION pressure before use. All other chemicals were used as received:
Materials. Styrene was purchased from Acros Organics (99% sodium hydroxide (WTL La-borbedarf GmbH, 99%), divinylben-
extra pure, stabilized) and deinhibited by washing three times zene (Fluka, mixture of isomers ≈80%), ammonium persulfate
with a 2 M sodium hydroxide solution and three times with (Acros Organics, 98%), acrylic acid (Acros Organics, 99.5%,
Milli-Q water. Washed styrene was distilled under reduced stabilized), absolute ethanol (Sigma Aldrich), poly(allylamine

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5371

www.acsnano.org
 ARTICLE
hydrochloride) (PAH, Aldrich, average Mw ≈ 15 000 g/mol), 7. Ellison, C. J.; Kim, S. D.; Hall, D. B.; Torkelson, J. M. Confinement
polyvinylpyrrolidone (PVP, Fluka, K 90, Mw ≈ 360 000 g/mol), and Processing Effects on Glass Transition Temperature and
ammonia (Fluka, 25 wt % in water), and tetraethoxysilane (TES, Physical Aging in Ultrathin Polymer Films: Novel Fluores-
Si(OEt)4) (Acros Organics, 98%). Milli-Q water was obtained from cence Measurements. Eur. Phys. J. E 2002, 8, 155–166.
a Millipore purification system operating at 18.2 MΩ cm. 8. Ellison, C. J.; Torkelson, J. M. The Distribution of Glass-
Synthesis of Polystyrene Nanoparticles. Soap-free emulsion po- Transition Temperatures in Nanoscopically Confined Glass
lymerization was carried out in a 500 mL three-necked flask Formers. Nat. Mater. 2003, 2, 695–700.
equipped with a condenser, a PTFE stirrer, and a gas inlet. Milli-Q 9. Forrest, J. A.; Dalnoki-Veress, K. The Glass Transition in Thin
water was put in the reactor, and nitrogen was bubbled for 20 Polymer Films. Adv. Colloid Interface Sci. 2001, 94, 167–196.
min. Ammonium persulfate was added to the water, and the 10. Forrest, J. A.; Dalnoki-Veress, K.; Stevens, J. R.; Dutcher, J. R.
system was heated to 75
C. A mixture of divinylbenzene, acrylic Effect of Free Surfaces on the Glass Transition Temperature
acid, and styrene was added dropwise within 1 h while stirring of Thin Polymer Films. Phys. Rev. Lett. 1996, 77, 2002–2005.
and reacted for 24 h. The resulting suspension was cleaned by 11. Keddie, J. L.; Jones, R. A. L.; Cory, R. A. Size-Dependent
centrifugation in water and ethanol at least six times. The Depression of the Glass Transition Temperature in Poly-
resulting PS nanoparticles were suspended in water. The PS mer Films. Europhys. Lett. 1994, 27, 59–64.
nanoparticles were slightly cross-linked with 0.4% and 1.3% 12. Keddie, J. L.; Jones, R. A. L.; Cory, R. A. Interface and Surface
w/w of divinylbenzene with respect to styrene for 200 and Effects on the Glass-Transition Temperature in Thin Poly-
400 nm PS nanoparticles, respectively. mer-Films. Faraday Discuss. 1994, 98, 219–230.
Synthesis of Silica-Capped PS Nanoparticles. Polystyrene spheres 13. Mattsson, J.; Forrest, J. A.; Borjesson, L. Quantifying Glass
were dispersed in water (concentration of 68 g/L) and pretreated Transition Behavior in Ultrathin Free-Standing Polymer
with polyelectrolytes according to the procedure outlined in ref 61. Films. Phys. Rev. E 2000, 62, 5187–5200.
Treated PS spheres were reacted with ammonia and TES at room 14. Park, C. H.; Kim, J. H.; Ree, M.; Sohn, B.; Jung, J. C.; Zin, W.
temperature (23
C) for 12 h while stirring, as previously des- Thickness and Composition Dependence of the Glass
cribed.62 The spheres were washed three times in fresh ethanol. Transition Temperature in Thin Random Copolymer Films.
The resulting PS
silica nanoparticles were suspended in water. Polymer 2004, 45, 4507–4513.
SEM Imaging. PS nanoparticles and PS
silica core
shell nano- 15. Priestley, R. D. Physical Aging of Confined Glasses. Soft
particles were first dried in a fume hood at room temperature for Matter 2009, 5, 919–926.
24 h then annealed at 50
C in DSC pans until a stable heat flow was 16. Priestley, R. D.; Broadbelt, L. J.; Torkelson, J. M. Transition
recorded. Dried samples were transferred onto black carbon tape Glass and Alpha-Relaxation Dynamics of Thin Films of
and coated by sputtering with iridium for 20 min and then imaged Labeled Polystyrene. Phys. Rev. E 2007, 75, 061806.
using a Philips XL30 FEG SEM. 17. Priestley, R. D.; Ellison, C. J.; Broadbelt, L. J.; Torkelson, J. M.
Calorimetry Measurements. Physical aging measurements were Structural Relaxation of Polymer Glasses at Surfaces, Inter-
performed using a TA Instruments Q2000 differential scanning faces and In Between. Science 2005, 309, 456–459.
calorimeter (DSC) in both standard mode (for PS
silica core
18. Roth, C. B.; Dutcher, J. R. Glass Transition Temperature of
shell nanoparticles and bulk PS) and modulated mode (MDSC) Freely-Standing Films of Atactic Poly(methyl methacry-
(for PS nanoparticles suspended in water). A nitrogen environ- late). Eur. Phys. J. E 2003, 12, S103–S107.
ment was employed in this study. The DSC was calibrated on
19. Sharp, J. S.; Forrest, J. A. Free Surfaces Cause Reductions in
heating at 20
C/min and isothermally calibrated at 75
C. The
the Glass Transition Temperature of Thin Polystyrene
MDSC was calibrated on heating at 5
C/min. Calibrations were
Films. Phys. Rev. Lett. 2003, 91, 23571.
performed using the modules in the Thermal Advantage soft-
20. Kranbuehl, D.; Knowles, R.; Hossain, A.; Hurt, M. Modeling
ware provided by TA Instruments.
the Effects of Confinement on the Glass Transition Tem-
Sample Preparation. PS nanoparticle (or PS
silica core
shell
perature and Segmental Mobility. J. Phys.: Condens. Matter.
nanoparticle) suspensions were added dropwise into aluminum
2003, 15, S1019–S1029.
DSC pans held at 50
C to partially evaporate water (core
shell
nanoparticle samples were completely dried). After partial 21. Priestley, R. D.; Mundra, M. K.; Barnett, N. J.; Broadbelt, L. J.;
evaporation of water, another drop of the suspension was Torkelson, J. M. Effects of Nanoscale Confinement and
added to the pan and the water allowed to evaporate. This Interfaces on The Glass Transition Temperatures of a Series
process was repeated twice to increase the mass of polymer in of Poly(n-methacrylate) Films. Aust. J. Chem. 2007, 60,
the sample pan. Samples were hermetically sealed, and as such, 765–771.
measurements were performed in an air (PS
silica core
shell 22. Fakhraai, Z.; Sharp, J. S.; Forrest, J. A. Effect of Sample
nanoparticles) or water (PS nanoparticles) environment in the Preparation on the Glass-Transition of Thin Polystyrene
DSC pan. Bulk PS was prepared from nanoparticle samples that Films. J. Polym. Sci. B: Polym. Phys. 2004, 42, 4503–4507.
were dried under vacuum and subsequently annealed at 423 K 23. Roth, C. B.; Dutcher, J. R. Glass Transition and Chain
for 20 h, which caused the particles to aggregate and form a Mobility in Thin Polymer Films. J. Electroanal. Chem.
bulk sample. SEM images (not shown) reveal the formation of 2005, 584, 13–22.
bulk polymer by the above annealing protocol. 24. Alcoutlabi, M.; McKenna, G. B. Effects of Confinement on
Materials Behavior at the Nanometre Size Scale. J. Phys.:
Condens. Matter. 2005, 17, R461–R524.
25. Forrest, J. A.; Dalnoki-Veress, K.; Dutcher, J. R. Interface
REFERENCES AND NOTES
and Chain Confinement Effects on the Glass Transition
1. Feng, W.; Patel, S. H.; Young, M. Y.; Zunino, J. L.; Xanthos, M. Temperature of Thin Polymer Films. Phys. Rev. E 1997, 56,
Smart Polymeric Coatings;Recent Advances. Adv. Polym. 5705–5716.
Tech. 2007, 26, 1–13. 26. Fukao, K.; Miyamoto, Y. Glass Transitions and Dynamics in
2. Lin, Q. Properties of Photoresist Polymers. In Physical Thin Polymer Films: Dielectric Relaxation of Thin Films of
Properties of Polymers Handbook; Mark, J. E., Ed.; Springer: Polystyrene. Phys. Rev. E 2000, 61, 1743–1754.
New York, 2007; p 965. 27. Papaleo, R. M.; Leal, R.; Carreira, W. H.; Barbosa, L. G.; Bello,
3. Mayer, A. C.; Scully, S. R.; Hardin, B. E.; Rowell, M. W.; I.; Bulla, A. Relaxation Times of Nanoscale Deformation on
McGehee, M. D. Polymer-Based Solar Cells. Mater. Today the Surface of a Polymer Thin Film near and below the
2007, 10, 28–33. Glass Transition. Phys. Rev. B 2006, 74, 094203.
4. Moniruzzaman, M.; Winey, K. I. Polymer Nanocomposites 28. Cheng, W.; Sainidou, R.; Burgardt, P.; Stefanou, N.; Kiyano-
Containing Carbon Nanotubes. Macromolecules 2006, 39, va, A.; Efremov, M.; Fytas, G.; Nealey, P. F. Elastic Properties
5194–5295. and Glass Transition of Supported Polymer Thin Films.
5. Stern, S. A. Polymers for Gas Separations: The Next Decade. Macromolecules 2007, 40, 7283–7290.
J. Membr. Sci. 1994, 94, 1–65. 29. Lu, H.; Chen, W.; Russell, T. P. Relaxation of Thin Films of
6. de Gennes, P. G. Glass Transitions in Thin Polymer Films. Polystyrene Floating on Ionic Liquid Surface. Macromole-
Eur. Phys. J. E 2000, 2, 201–205. cules 2009, 42, 9111–9117.

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5372

www.acsnano.org
 ARTICLE
30. Sasaki, T.; Shimizu, A.; Mourey, T. H.; Thurau, C. T.; Ediger, M. D. 51. Moynihan, C. T.; Macedo, P. B.; Montrose, C. J.; Gupta, P. K.;
Glass Transition of Small Polystyrene Spheres in Aqueous Debolt, M. A.; Dill, J. F.; Dom, B. E.; Drake, P. W.; Easteal, A. J.;
Suspensions. J. Chem. Phys. 2003, 119, 8730–8735. Elterman, P. B.; et al. Structural Relaxation in Vitreous
31. Serghei, A.; Huth, H.; Schellenberger, M.; Schick, C.; Kremer, Materials. Ann. N.Y. Acad. Sci. 1976, 279, 15–35.
F. Pattern Formation in Thin Polystyrene Films Induced by 52. Narayanaswamy, O. S. Model of Structural Relaxation in
an Enhanced Mobility in Ambient Air. Phys. Rev. E 2005, 71, Glass. J. Am. Ceram. Soc. 1971, 54, 491–497.
061801. 53. Tool, A. Q. Relation between Inelastic Deformability and
32. Tress, M.; Erber, M.; Mapesa, E. U.; Huth, H.; Muller, J.; Thermal Expansion of Glass in Its Annealing Range. J. Am.
Serghei, A.; Schick, C.; Eichhorn, K.-J.; Voit, B.; Kremer, F. Ceram. Soc. 1946, 29, 240–253.
Glassy Dynamics and Glass Transition in Nanometric Thin 54. Kovacs, A. J.; Aklonis, J. J.; Hutchinson, J. M.; Ramos, A. R.
Layers of Polystyrene. Macromolecules 2010, 43, 9937– Isobaric Volume and Enthalpy Recovery of Glasses: A
9944. Transparent Multiparameter Theory. Macromolecules
33. van Zanten, J. H.; Wallace, W. E.; Wu, W. Effect of Strongly 1979, 17, 1097–1162.
Favorable Substrate Interactions on the Thermal Proper- 55. Kohlrausch, F. Ueber die Elastiche Nachwirkung Bei der
ties of Ultrathin Polymer Films. Phys. Rev. E 1996, 53, Torsion. Poogendorff’s Annalen der Physik und Chemie
R2053–R2056. 1863, 119, 337–368.
34. Dorkenoo, K.; Pfromm, P. H. Accelerated Physical Aging of 56. Simon, S. L.; Sobieski, J. W.; Plazek, D. J. Volume and
Thin Poly[1-(trimethylsilyl)-1-propyne] Films. Macromole- Enthalpy Recovery of Polystyrene. Polymer 2001, 42,
cules 2000, 33, 3747–3751. 2555–2567.
35. Huang, Y.; Paul, D. R. Physical Aging of Thin Glassy Polymer 57. Guo, Y.; Wang, N.; Bradshaw, R. D.; Brinson, L. C. Modeling
Films Monitored by Gas Permeability. Polymer 2004, 45, Mechanical Aging Shift Factors in Glassy Polymers during
8377–8393. Nonisothermal Physical Aging: Experiments and KAHR-ate
36. Kawana, S.; Jones, R. A. L. Effect of Physical Ageing in Thin Model Prediction. J. Polym. Sci. B: Polym. Phys. 2009, 47,
Glassy Polymer Films. Eur. Phys. J. E 2003, 10, 223–230. 340.
37. Koh, Y. P.; Simon, S. L. Structural Relaxation of Stacked 58. Badrinarayanan, P.; Zheng, W.; Li, Q.; Simon, S. L. The Glass
Ultrathin Polystyrene Films. J. Polym. Sci. B: Polym. Phys. Transition versus the Fictive Temperature. J. Non-Cryst.
2008, 46, 2741–2753. Solids 2007, 353, 2603–2612.
38. Priestley, R. D.; Broadbelt, L. J.; Torkelson, J. M. Physical 59. Greiner, R.; Schwarzl, F. R. Thermal Contraction and Vo-
Aging of Ultrathin Polymer Films Above and Below the lume Relaxation of Amorphous Polymers. Rheol. Acta
Bulk Glass Transition Temperature: Effects of Attractive vs 1984, 23, 378–395.
Neutral Polymer
Substrate Interactions Measured by 60. Simon, S. L.; Park, J. Y.; McKenna, G. B. Enthalpy Recovery of
Fluorescence. Macromolecules 2005, 38, 654–657. a Glass-Forming Liquid Constrained in a Nanoporous
39. Priestley, R. D.; Rittigstein, P.; Broadbelt, L. J.; Torkelson, Matrix: Negative Pressure Effects. Eur. Phys. J. E 2002, 8,
J. M. Evidence for the Molecular-Scale Origin of the 209–216.
Suppression of Physical Aging in Confined Polymer: Fluo- 61. Graf, C.; Vossen, D. L. J.; Imhof, A.; van Blaaderen, A. A
rescence and Dielectric Studies of Polymer
Silica Nano- General Method To Coat Colloidal Particles with Silica.
composites. J. Phys.: Condens. Matter. 2007, 19, 205120. Langmuir 2003, 19, 6693–6700.
62. Zhang, L.; D'Acunzi, M.; Kappl, M.; Auernhammer, G. K.;
40. Pye, J. E.; Rohald, K. A.; Baker, E. A.; Roth, C. B. Physical Aging
Vollmer, D. Hollow Silica Spheres: Synthesis and Mechan-
in Ultrathin Polystyrene Films: Evidence of a Gradient in
Dynamics at the Free Surface and Its Connection to the ical Properties. Langmuir 2009, 25, 2711–2717.
Glass Transition Temperature Reductions. Macromolecules
2010, 43, 8296–8303.
41. Rittigstein, P.; Priestley, R. D.; Broadbelt, L. J.; Torkelson,
J. M. Model Polymer Nanocomposites Provides an Under-
standing of Confinement Effects in Real Nanocomposites.
Nat. Mater. 2007, 6, 278–282.
42. Wu, J.; Huang, G.; Wang, X.; He, X.; Lei, H. Confinement Effect
of Polystyrene on the Relaxation Behavior of Polyisobuty-
lene. J. Polym. Sci. B: Polym. Phys. 2010, 48, 2165–2172.
43. Zhou, C.; Chung, T.; Wang, R.; Goh, S. H. A Governing
Equation for Physical Aging of Thick and Thin Fluoropo-
lyimide Films. J. Appl. Polym. Sci. 2004, 92, 1758–1764.
44. Rittigstein, P.; Torkelson, J. M. Polymer
Nanoparticle In-
terfacial Interactions in Polymer Nanocomposites: Con-
finement Effects on Glass Transition Temperature and
Suppression of Physical Aging. J. Polym. Sci. B: Polym. Phys.
2006, 44, 2935–2943.
45. Liu, A. Y. H.; Rottler, J. Physical Aging and Structural
Relaxation in Polymer Nanocomposites. J. Polym. Sci. B:
Polym. Phys. 2009, 47, 1789–1798.
46. Mukherji, D.; Muser, M. H. Glassy Dynamics, Aging in
Mobility, and Structural Relaxation of Strongly Adsorbed
Polymer Films: Corrugation or Confinement?. Macromole-
cules 2007, 40, 1754–1762.
47. Debenedetti, P. G.; Stillinger, F. H. Supercooled Liquids and
The Glass Transition. Nature 2001, 410, 259–267.
48. Zhang, C.; Guo, Y.; Priestley, R. D. The Glass Transition
Temperature of Polymer Nanoparticles under Soft and
Hard Confinement. Macromolecules 2011, 44, 4001–4006.
49. Debolt, M. A.; Easteal, A. J.; Macedo, P. B.; Moynihan, C. T.
Analysis of Structural Relaxation in Glass Using Rate Heat-
ing Data. J. Am. Ceram. Soc. 1976, 59, 16–21.
50. Moynihan, C. T.; Easteal, A. J.; Debolt, M. A. Dependence of
the Fictive Temperature of Glass on Cooling Rate. J. Am.
Ceram. Soc. 1976, 59, 12–16.

GUO ET AL. VOL. 5 ’ NO. 7 ’ 5365–5373 ’ 2011 5373

www.acsnano.org