Local glass transition temperature Tg(z) of polystyrene next to different polymers:

Hard vs. soft confinement

Roman R. Baglay and Connie B. Roth

Citation: J. Chem. Phys. 146, 203307 (2017); doi: 10.1063/1.4975168

View online: http://dx.doi.org/10.1063/1.4975168
View Table of Contents: http://aip.scitation.org/toc/jcp/146/20
Published by the American Institute of Physics

Articles you may be interested in

Influence of chemistry, interfacial width, and non-isothermal conditions on spatially heterogeneous activated
relaxation and elasticity in glass-forming free standing films
J. Chem. Phys. 146, 203301203301 (2017); 10.1063/1.4974766

Unexpected impact of irreversible adsorption on thermal expansion: Adsorbed layers are not that dead
J. Chem. Phys. 146, 203304203304 (2017); 10.1063/1.4974834

Interfacial interaction and glassy dynamics in stacked thin films of poly(methyl methacrylate)
J. Chem. Phys. 146, 203305203305 (2017); 10.1063/1.4974835

Reduced-mobility layers with high internal mobility in poly(ethylene oxide)silica nanocomposites

J. Chem. Phys. 146, 203303203303 (2017); 10.1063/1.4974768
 THE JOURNAL OF CHEMICAL PHYSICS 146, 203307 (2017)

Local glass transition temperature T g (z) of polystyrene next to different

polymers: Hard vs. soft confinement
Roman R. Baglay and Connie B. Rotha)
Department of Physics, Emory University, Atlanta, Georgia 30322, USA
(Received 1 November 2016; accepted 17 January 2017; published online 9 February 2017)

The depth to which the local glass transition temperature T g and alpha-relaxations are perturbed
near a boundary is believed to be related to the characteristic length scales associated with coopera-
tive dynamics in dynamically heterogeneous glasses. Following our recent work [R. R. Baglay and
C. R. Roth, J. Chem. Phys. 143, 111101 (2015)] that measured a very broad 350-400 nm local T g (z)
profile across a glassy-rubbery interface of polystyrene (PS)/poly(n-butyl methacrylate) (PnBMA),
we compare here how the T g (z) profile in PS varies when changing the neighboring polymer from
a lower T g material to a higher T g material. Here we report local T g (z) profiles for PS when in
contact with polysulfone (PSF), poly(methyl methacrylate) (PMMA), and poly(isobutyl methacry-
late) (PiBMA). We find that the distance from the interface before bulk T g of PS (Tg bulk = 101 C)
is recovered depends on whether PS forms the high-T g glassy component experiencing so-called soft
confinement, z 225-250 nm for PS next to PiBMA (Tg bulk = 62 C) and PnBMA (Tg bulk = 21 C),
or PS forms the low-T g rubbery component experiencing hard confinement, z 100-125 nm for PS
next to PSF (Tg bulk = 186 C) and PMMA (Tg bulk = 120 C). The depth to which these T g (z) pertur-
bations persist and the magnitude of the local T g perturbation at the interface are independent of the
difference in Tg bulk between the two polymers, the interaction parameter, and the chemical structure.
We demonstrate that these broad, extended T g (z) length scales appear to be universal across these
different systems but show that the strong dynamical coupling across the dissimilar polymer-polymer
interface only occurs when this interface has been annealed to equilibrium. We consider why dissim-
ilar polymer-polymer interfaces exhibit continuous local dynamics across the interface in contrast to
polymer-free surface, polymer-substrate, or polymer-liquid interfaces that show discontinuous local
dynamics. Published by AIP Publishing. [http://dx.doi.org/10.1063/1.4975168]

INTRODUCTION contributions of the regions near polymer-polymer interfaces

between the domains can be reasonably ignored. However,
Recent trends in polymer blends have been to drive the
when domain sizes become so small that the material becomes
domain sizes down into the sub-100 nm range to improve
dominated by interfaces, it is necessary to understand and
material performance, blend uniformity, and to create func-
incorporate the altered local properties at and near the inter-
tionality for particular applications.13 There are now a num-
faces. The results we present here demonstrate long length
ber of strategies for creating such nanostructured polymer
scales for the distance over which local glass transition tem-
blends: synthesis of multicomponent block copolymers,47
perature (T g ) perturbations propagate from polymer-polymer
novel cold-state processing methods,8 and nanolayer stacking
interfaces suggesting that nanostructured polymer blends with
and interweaving.913 Of particular interest are co-continuous
domain sizes of a few hundred nanometers likely have no
structures where domains of glassy, rubbery, and crystalline
regions where the local properties remain bulk-like. Instead,
components intertwine while percolating across the material
nanostructured blends likely exhibit more uniform properties
making ideal structures for applications such as filtration, ion
across the different domains and interfaces, which may explain
conduction, catalysis, photovoltaic technologies, and bioengi-
their typically enhanced performance over more traditional
neering applications.3,1417 These are materials whose func-
blends with large micron-sized domains.
tion and performance will be dictated by the properties of
We have recently mapped the local glass transition
the material near the polymer-polymer interfaces. Historically
temperature T g (z) profile across a glassy-rubbery interface
polymer blends have been treated as a patchwork of different
between polystyrene (PS) and poly(n-butyl methacrylate)
domains with separate properties, where it is often assumed
(PnBMA).19 Focusing on an idealized bilayer-style model sys-
that these domains retain the bulk properties of the individ-
tem, we used a localized fluorescence method to measure
ual components.18 Such approaches are appropriate for blends
the local T g (z) at different distances z from the PS/PnBMA
with large, micron-sized domains where the relatively small
interface. The T g (z) profile transitioned continuously from the
bulk T g value of PnBMA, Tg bulk PnBMA = 21 C, to that of PS,
a) Author to whom correspondence should be addressed. Electronic mail: Tg bulk PS = 101 C, far from the PS/PnBMA interface in either
[email protected] direction, as anticipated. However, unexpectedly, this T g (z)

0021-9606/2017/146(20)/203307/13/$30.00 146, 203307-1 Published by AIP Publishing.

203307-2 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

profile was found to be very broad, spanning 350-400 nm has been suggested that such differences are associated with
from one extreme to another.19 In addition, this dynamical what dynamical property is being measured.41,53,61 Here, we
T g (z) profile was asymmetric, being uncorrelated with the focus on the measurements of glassy dynamics and local T g .
local composition profile (z) tanh(2z/wI ), where the equi- Several studies both experimentally34,50,53,6265 and theoreti-
librium interfacial width of PS/PnBMA has been previously cally3745 suggest that such a length scale is likely related to
characterized at only wI = 7 nm.2022 These unexpected results the length scales involved in describing cooperative motion
demonstrate that the local glass transition dynamics are influ- and dynamic heterogeneity in glasses.
enced by factors much further away than simply the local Although the behavior of a polymer-free surface interface
composition, which has been the traditional viewpoint in poly- has been the most heavily studied, it is informative to make
mer blends.2325 These unexpected results of the T g (z) profile comparisons across different types of interfaces: polymer-
across a PS/PnBMA interface19 leave many open questions. substrate, polymer-liquid, and polymer-polymer interfaces. In
How universal is this to other polymer systems? What factors this regard, other groups have also begun looking at polymer-
are required to get this extraordinary coupling of cooperative polymer interfaces and investigating how they differ from
segmental dynamics across an immiscible polymer-polymer that of a free surface or liquid interface. Using MD sim-
interface? What controls the length scale over which these ulations, Simmons and coworkers have modeled the T g of
dynamics are perturbed away from the interface? Is this length a confined polymer layer in contact with a second different
scale a property of the polymer itself, perhaps related to its polymer layer.66 With periodic boundary conditions, this sys-
cooperatively rearranging region (CRR)? What properties of tem mimics nanolayered films made by coextrusion.10,11 They
the interface (degree of immiscibility, interaction parameter find that both the low-T g polymer under hard confinement
, interfacial width) influence this behavior? To what extent and the high-T g polymer under soft confinement exhibit a
do polymer-polymer interfaces behave similarly or differently shift in T g from their bulk value caused by the presence of
to other interfaces (e.g., polymer-substrate, polymer-free sur- the neighboring polymer.66 The magnitude of the shift for
face, and polymer-liquid)? Here we consider these various the low-T g polymer under hard confinement is additionally
factors. influenced by the interfacial energy, although in this simu-
We believe one way we can begin to understand these lation varying the interfacial energy also varies the amount
results is by analogy to the glass transition behavior in thin of interdiffusion at the interface, which we demonstrate in
films. For over two decades now, studies have found that the this work to be an important parameter. Interfacial energy
average glass transition temperature T g of thin polymer films, has also been considered an important factor for polymer-
supported on various substrates or free-standing with only air substrate6769 and polymer-liquid70 interactions. Tito, Lip-
interfaces, demonstrates large (tens of degrees Kelvin) devia- son, and Milner have modeled the local mobility profile next
tions in T g from their bulk values Tg bulk with decreasing film to a free surface or glassy-rubbery polymer-polymer inter-
thickness.2632 For a variety of polymers such confinement face using a kinetic limited-mobility model that encodes the
effects begin at film thicknesses of 100 nm.29,30,3335 The exchange of local mobility through different types of local
results of such studies have found that the phenomenon can free volume (mobile, dormant, and dense) where the
be understood as the presence of the interfaces (polymer-free interface in question becomes a source and sink of local free
surface or polymer-substrate interface) causing a perturba- volume and hence mobility.37 Evans and Torkelson have made
tion to the local dynamics that then propagates deep into the experimental comparisons between the magnitude of the shift
material leading to a gradient in local T g (z) as a function of in T g perturbation for PS with the value of the fragility of
depth from the interface over some distance before bulk-like the surrounding polymer matrix finding similarities between
properties of the material are recovered.26,3645 In general, thin 10-15 nm layers of PS and isolated chains of PS.71 The
the presence of a free surface tends to speed up (enhance) idea of differences between so-called hard vs. soft confine-
the local mobility, while the presence of a substrate inter- ment has been around for about a decade. Richert first intro-
face can slow down the local dynamics, typically depending duced the concept when comparing small molecule glass
on whether attractive interactions, such as hydrogen bonding, formers confined within soft emulsion drops instead of hard
are present between the polymer and substrate interface in nanoporous glasses,7274 where soft confinement referred to
question.28,35,4649 Such measurements of local T g near a PS- a liquid interface instead of that with a hard wall. However,
free surface, using the same localized fluorescence method recent studies on polymer-liquid interfaces70,7578 seem to sug-
mentioned above, found that a depth of 30-40 nm from the gest that, in some cases, a polymer-liquid interface may not
free surface is required before the bulk T g of PS was recov- actually behave that different compared to a polymer-substrate
ered.50 Some studies investigating polymer-substrate interac- interface. In contrast, experimental evidence22,35,7984 sug-
tions demonstrate even longer length scales spanning several gests that polymer-polymer interfaces may be distinctly dif-
hundred nanometers.51,52 Though, what factors control this ferent from that of polymer-free surface or polymer-liquid
length scale are still not well understood. There is also dis- interfaces.
agreement about the size of this enhanced mobility region Here we compare the local T g (z) profile of PS in con-
near a free surface, with studies measuring glassy dynamics tact with several different polymers: polysulfone (PSF),
well below bulk T g often reporting depths of a few tens of poly(methyl methacrylate) (PMMA), and poly(isobutyl
nanometers,36,50,52,53 while studies measuring liquid-like flow methacrylate) (PiBMA) with that of PnBMA from before.19
properties above or near bulk T g only reporting depths of a few We find that the depth to which the local T g (z) value is per-
nanometers5460 before bulk-like properties are recovered. It turbed from the polymer-polymer interface is strongly affected
203307-3 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

by whether the neighboring polymer has a bulk T g value higher and chromophores. The washing procedure helps reduce
or lower than that of PS (i.e., whether the confinement is hard polydispersity, specifically biased towards eliminating low
or soft), with PS next to PSF behaving remarkably similar to MW PS-Py chains and unreacted monomer, while retaining
PnBMA next to PS. Following our previous analysis19 based the higher molecular weight chains. The label content of PS-
on the efforts of Butler and Harrowell,43 we characterize the Py was later characterized by ultraviolet-visible spectroscopy
depth to which the local T g (z) perturbation persists from the in spectroscopic grade THF. Unlabeled (neat) polystyrene
interface by 1/ 2 , the distance at which the local T g (z) perturba- (M w = 1920 kg/mol, M w /M n = 1.26), which was used to sand-
tion has dropped to half the value found at the interface. Butler wich the PS-Py 10-15 nm probe layers on the PS side
and Harrowell showed that for a simple two-spin facilitated of the structures, was purchased from Pressure Chemical
Ising model, such a dynamical length scale 1/ 2 (T ) exhib- and used as received. Polysulfone (M w = 85 kg/mol, Udel
ited the same temperature dependence as the mean relaxation P-3500 LCD MB8), poly(methyl methacrylate) (M w
time (T ) for dynamical heterogeneities in the bulk, suggest- = 1150 kg/mol, M w /M n = 1.06), and poly(isobutyl methacry-
ing that dynamical gradients near an interface can be used to late) (M w = 295 kg/mol, M w /M n = 1.83) were purchased from
probe the dynamical length scales associated with cooperative Solvay Advanced Polymers, Pressure Chemical, and Scientific
motion.43,85 We find that these 1/ 2 values are strongly grouped Polymer Products, respectively, and used as received.
around 1/ 2 = 55 5 nm for polymers next to a higher T g poly- Individual layers of PS-Py, PS, PMMA, and PiBMA
mer (hard confinement) compared with 1/ 2 = 115 5 nm for were made by spin-coating from toluene solutions either onto
polymers next to a lower T g polymer (soft confinement). We freshly cleaved mica or quartz slides, depending on whether
suggest that perhaps the distinctiveness of polymer-polymer the polymer was used as an underlayer or a PS/PS-Py/PS T g
interfaces may be associated with the extensive breadth (few reporting multilayer stack. All PSF films were prepared in
to several nanometers) of polymer-polymer interfaces in com- the same manner but from cyclopentanone solutions. Film
parison to the breath of polymer-air or polymer-liquid inter- thickness was determined via ellipsometry after the films
faces (0.5 nm86 ). As we will demonstrate, the extent to were either floated or spin-coated onto silicon wafers. The
which the two dissimilar polymers are allowed to interdiffuse spin speed and solution concentrations were adjusted to pro-
at the polymer-polymer interface is an important factor that duce films with known reproducible thicknesses and minimal
affects the extent of dynamical coupling across the interface. surface roughness (on the order of <1 nm). All individ-
If we restrict the amount of annealing done at the dissimi- ual layers were annealed under vacuum for at least 18 h at
lar polymer-polymer interface, we find the T g (z) profile to T g + >20 K to facilitate the removal of any residual sol-
be much shorter and not consistently stable as the interface vent and relaxation of spin-coating induced stresses. Mul-
continues to evolve. However, once the dissimilar polymer- tilayers were then assembled by successively floating each
polymer interface has been allowed to form to equilibrium, layer onto room temperature deionized water and capturing
we no longer see any evolution of the T g (z) profile with fur- the layer onto the multilayer sample starting from a given
ther annealing. Interestingly, despite this clear importance of base underlayer spun directly onto the quartz slide needed for
the breadth of interdiffusion of the interface, we do not observe fluorescence measurements. Between each successive float-
a correlation of the extent of the T g (z) perturbation from the ing, the sample is allowed to thoroughly dry. Bulk polymer
interface with the equilibrium interfacial width wI or equiva- underlayers and bulk PS capping layers were made >450 nm
lently the interaction parameter between the two polymers. in thickness to ensure that the pyrene-labeled probe layer
We also note that the breadth of these polymer-polymer inter- is unaffected by the free surface or underlying substrate
faces (5 nm) are all much smaller relative to the large extent interface.
of the T g (z) perturbations (many tens to hundreds of nanome- Multilayer structures with polymer underlayers contain-
ters). Thus, small differences in equilibrium interfacial width ing a polymer with a T g higher than that of PS were con-
do not seem to play a role in the dynamical coupling of coop- structed in a two-step annealing process, as illustrated in Fig-
erative dynamics across the interface provided that the dis- ure 1. This was done to limit the interdiffusion of the PS-Py
similar polymer-polymer interface has been able to anneal to probe layer into the surrounding neat PS matrix, while still
equilibrium. ensuring that the polymer-polymer interface of interest has
reached equilibrium and achieved good coupling of the cooper-
ative dynamics across the interface. The variable thickness PS
EXPERIMENTAL METHODS
z-layer was floated onto a PMMA or PSF coated substrate
High molecular weight pyrene-labeled polystyrene (PS (post-initial vacuum annealing of each layer) and annealed
-Py) with 1.4 mol. % pyrene content (M w = 672 kg/mol, to consolidate this bilayer and thereby form a PS/PMMA or
M w /M n = 1.3) was synthesized by bulk free-radical copoly- PS/PSF interface that had reached equilibrium prior to float-
merization of styrene with a pyrene butyl methacry- ing the remaining PS layers. The PS/PMMA and PS/PSF
late monomer that was synthesized via esterification of bilayers were annealed under vacuum at 150 C for 30 min
1-pyrenebutanol and methacryloyl chloride.22,50,87 Polymer- and at 210 C for 90 min, respectively. After these polymer-
ization was performed at 50 C for 24 h under a nitrogen polymer interfaces were consolidated, the remaining PS-Py
environment using azobisisobutyronitrile (AIBN) as initiator. and capping neat PS layers were floated atop the PS/PMMA or
Post-thermal termination, the PS-Py polymer was dissolved PS/PSF samples. The remaining PS/PS-Py/PS interfaces were
in tetrahydrofuran (THF) and subsequently re-precipitated in then annealed in an Instec HCS402 heater immediately prior
methanol at least seven times to remove unreacted monomer to the fluorescence measurements by heating to 170 C and
203307-4 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

FIG. 1. Exploded view of the two-

step annealing process for multilayer
samples containing PMMA or PSF as
the polymer underlayer that have a
T g higher than that of PS. The two-
step annealing process ensures that the
PS/PMMA or PS/PSF interface has
reached equilibrium without allowing
interdiffusion of the PS-Py reporting
layer.

holding for 5 min before dropping the temperature to 150 C T g values measured by fluorescence and ellipsometry are for
and holding for 2 min. This annealing protocol ensured that PMMA Tg bulk = 120 C, PiBMA Tg bulk = 62 C, and PSF
the PS/PS-Py/PS layers formed consolidated interfaces, while Tg bulk = 186 C.
still limiting the diffusion of the PS-Py probe layer. Multilayer
structures with polymer underlayers containing a polymer with
a T g lower than that of PS could be fabricated with a sin- RESULTS AND DISCUSSION
gle annealing process because the polymer-polymer interface
Comparing PS/PSF to PS/PnBMA: Hard vs. soft
of interest easily reaches equilibrium for annealing condi-
confinement
tions that are appropriate for the PS/PS-Py/PS interfaces.19
The PS and PS-Py films in multilayer samples containing In the present work, we demonstrate that the asymme-
PiBMA as the underlayer were floated directly atop each try and the extended length scale of the local glass transition
other in succession, and then only annealed together imme- T g (z) profile recently reported in the polystyrene/poly(n-butyl
diately prior to the fluorescence measurement for 20 min at methacrylate) (PS/PnBMA) system19 is not unique to this
120 C. single polymer-polymer system. We start by comparing our
Fluorescence measurements were performed using a Pho- previous PS/PnBMA system to one that is effectively reversed,
ton Technology International QuantaMaster spectrofluorome- where PS now forms the rubbery component next to a glassy
ter with samples mounted in an Instec HCS402 heater. The polymer, polysulfone (PSF). The bulk glass transition tem-
pyrene-labeled probe layers were excited at a wavelength of perature value of PSF is Tg bulk = 186 C resulting in an 85 K
330 nm using a xenon arc lamp with an excitation band- difference across the PS/PSF interface (Tg bulk = 101 C for
pass of 5.5-6.0 nm and an emission band-pass of 5.0 nm. PS). This PS/PSF system is analogous to that of PS/PnBMA,
After the final sample annealing as described above, the but reverses the role of the PS component. In the PS/PnBMA
sample temperature was ramped down at 1 C/min while system, the PS component was the hard glassy material that
pyrene fluorescence intensity was collected for 3 s every underwent soft confinement by the rubbery PnBMA, whereas
27 s, at an emission wavelength of 379 nm. All samples in the PS/PSF system, the PS component is the soft rubbery
were reheated to the starting temperature after each run to material undergoing hard confinement by the glassy PSF. In
ensure that the same initial fluorescence intensity was recov- both cases, there is an 80-85 K difference in bulk T g between
ered, verifying that the sample had remained stable during the the two components. A comparison between these two sys-
course of the experiment and no photobleaching occurred. This tems will allow us to test whether the penetration depth of
ramped fluorescence procedure for measuring T g was previ- the dynamical T g perturbation from the dissimilar polymer-
ously reported in the work of Rauscher et al.22 and utilized polymer interface is polymer specific (e.g., related to chemical
for the data collection in the work of Baglay and Roth.19 Bulk structure) or determined by the glassy vs. rubbery role played
203307-5 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

by the component (i.e., whether the confinement is soft vs. to equilibrium prior to the start of the fluorescence data
hard). collection.
Figure 2 illustrates the sample geometries of the two sys- Figure 3 shows the temperature-dependent fluorescence
tems being compared. Each geometry is comprised of four intensity measured for four different samples where the PS-Py
individually constructed films of designed thickness that were probe layer has been placed at specific distances z from either
assembled and carefully annealed to form a consolidated mate- a PS/PnBMA or PS/PSF interface. Vitrification in polymers is
rial with an effectively static geometry as illustrated. We characterized by the dynamic arrest of cooperative segmental
employ a temperature-dependent fluorescence method to mea- motion as the material enters the glassy state. It is well known
sure the local T g (z) at different distances z from the glassy- that pyrene is sensitive to the local density and rigidity of the
rubbery polymer-polymer interface. The multilayer sample surrounding polymer matrix.22,35,50,89 As the temperature is
geometries are constructed via a floating procedure where a lowered and the local polymer matrix surrounding the pyrene
10-15 nm pyrene-labeled PS probe layer (PS with a fluorescent
1-pyrenylbutyl methacrylate monomer chemically attached
to the PS backbone at a label content of 1:70 monomers,
designated PS-Py) is placed at a known distance z from the
dissimilar polymer-polymer interface in question by insert-
ing a neat (unlabeled) PS layer of thickness z between the
pyrene-probe layer and the dissimilar polymer layer (PSF
or PnBMA in Fig. 2). As previously discussed in the work
of Baglay and Roth,19 high molecular weight polystyrenes
are used to limit interdiffusion of the PS/PS-Py/PS interfaces
and keep the T g -reporting PS-Py layer localized a fixed dis-
tance z from the dissimilar polymer-polymer interface of
interest. One of the advantages of using polymers for this
type of study is that chain diffusion is effectively decou-
pled from more local cooperative segmental -relaxations
associated with T g in high molecular weight entangled poly-
mers such that the morphology of the layers assembled will
remain static during the course of the experiment. As we
will explore in more detail below, a key factor in measur-
ing a reproducible and reliable value of T g (z) is that the
dissimilar polymer-polymer interface has been annealed to
equilibrium. Immiscible polymer-polymer interfaces initially
interdiffuse quite readily by local Rouse modes but stabi-
1
lize quickly at an equilibrium interfacial width wI 2 of
only a few nanometers limited by the unfavorable interactions
between the two materials.88 Unless otherwise indicated,
all the T g (z) values presented are measured ensuring that
the dissimilar polymer-polymer interface has been annealed

FIG. 3. Normalized fluorescence intensity as a function of temperature col-

lected on cooling at 1 C/min for four different samples. (Top) PS/PSF system:
pyrene-labeled PS probe layer located at a distance z = 139 nm away from the
FIG. 2. Sample geometries comprised of four individually spin-coated layers PS/PSF interface reports a local T g (z) = 103 2 C in agreement with Tg bulk
of polystyrene (PS), and poly(n-butyl methacrylate) (PnBMA) or polysul- of PS, while at a distance z = 51 nm, the local T g (z) = 120 2 C significantly
fone (PSF), assembled and annealed to form a consolidated material with a increased by the presence of the PS/PSF interface. (Bottom) PS/PnBMA sys-
10-15 nm thick local T g -reporting pyrene-labeled PS layer. The neat PS tem:19 at a distance z = 356 nm, the local T g (z) = 99 2 C in agreement
z-layers varied the distance z of the pyrene-labeled PS layer relative to the with Tg bulk of PS, while at a distance z = 64 nm, the local T g (z) = 63 2 C
PS/PnBMA (7 nm wide) or PS/PSF (6 nm wide) interface. High molecu- significantly decreased by the presence of the PS/PnBMA interface. In both
lar weight polymers ensure that the assembled morphology remains static cases, the large perturbation in local T g (z) occurs at distances that are many
throughout the experiment. tens of nanometers away from the change in composition.
203307-6 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

dye becomes more rigid, the probability of radiative compared

with non-radiative decay of the pyrene fluorescence increases,
where a break in the slope of the signal intensity is manifested
when crossing from the liquid to glassy state as the tempera-
ture dependence of the density changes. Previous works have
demonstrated that this measure of T g via fluorescence matches
that by differential scanning calorimetry (DSC) in bulk mate-
rials and by ellipsometry in thin films.50,89 We measure the
fluorescence intensity on cooling at 1 C/min where the inten-
sity at a single wavelength (first emission peak of pyrene at
379 nm that is the most sensitive to its local environment90,91 )
is sampled every 30 s (averaging signal intensity over a 3 s
time window) resulting in a data point collected every 0.5 C,
with no additional smoothing performed to the temperature-
dependent intensity data.19,22 To facilitate comparisons, each
dataset shown in Fig. 3 is normalized and then vertically shifted
for clarity. The top panel graphs the temperature-dependent
intensity for PS-Py probe layers located at different distances
from a PS/PSF interface where PS forms the rubbery, lower
T g component: at a distance z = 139 nm (far from the PS/PSF FIG. 4. Experimentally measured local T g (z) profile of PS/PSF (open blue
interface), the local T g (z) = 103 2 C, consistent with the diamonds), compared with that previously measured19 for PS/PnBMA (open
red circles), as a function of z, the pyrene-labeled layers position from the
T g of bulk PS, but at a distance z = 51 nm (closer to the PS/PSF or PS/PnBMA interface. In the PS/PSF system, the PS layer is rub-
PS/PSF interface), the local T g (z) = 120 2 C, significantly bery relative to PSF undergoing hard confinement, while in the PS/PnBMA
increased relative to Tg bulk of PS. For comparison, the bottom system, and the PS layer is glassy relative to PnBMA undergoing soft con-
finement. Both PS/PSF and PS/PnBMA systems have a bulk T g difference of
panel graphs the temperature-dependent intensity for PS-Py
80-85 K between the two domains that the local T g (z) must transition between.
probe layers located at different distances from a PS/PnBMA We previously demonstrated19 that the PS/PnBMA T g (z) profile was well fit
interface where PS forms the glassy, higher T g component: by a hyperbolic tangent (solid black curve) demonstrating that the mobility-
at a distance z = 356 nm (far from the PS/PnBMA interface), gradient is broad and strongly biased toward the glassy PS side. Dashed curves
the local T g (z) = 99 2 C, consistent with the T g of bulk indicate the local composition profiles (z) with an equilibrium interfacial
width of 6 nm (PS/PSF) and 7 nm (PS/PnBMA), which appear nearly ver-
PS as expected, but at a distance z = 64 nm (closer to the tical on this scale unmistakably highlighting the breadth of the T g mobility
PS/PnBMA interface), the local T g (z) = 63 2 C, signif- gradient.
icantly decreased relative to Tg bulk of PS.19 Decreasing the
separation distance (z layer thickness) of the pyrene-labeled
PS layer in relation to the dissimilar polymer-polymer inter- profile behaves similarly to the full T g (z) profile collected
face drastically changes the local T g at that location relative previously19 for PS/PnBMA where the data are well fit by
to PS bulk T g . The magnitude of the T g perturbation is large a hyperbolic tangent function, which asymptotes to the bulk
(+19 K and 38 K) at a distance (51 and 64 nm) that is still T g values far from the interface on either side, with a broad
quite far from the dissimilar polymer-polymer interface. As mobility-gradient, strongly biased toward the glassy PS side.
discussed by Baglay and Roth,19 these perturbations in local The PS/PSF T g (z) data can be similarly fit to a hyperbolic
T g occur far from the polymer-polymer interface such that tangent showing the broad mobility-gradient is now strongly
locally only PS segments are present at the position z. The biased toward the glassy PSF side. The local T g -dynamics
local T g (z) near the PS/PnBMA interface is not at all cor- transition smoothly from one extreme to the other across the
related with the local composition (z), which has been the interface, in contrast to the composition. The dashed curves in
traditional view in understanding local T g in miscible poly- the figure represent the composition profiles of the two sys-
mer blends.2325 These distances (z = 51 and 64 nm) are also tems, (z) tanh(2z/wI ), with equilibrium interfacial width
quite large compared to the observed perturbation length scales wI = 7 nm for PS/PnBMA1922 and wI = 6 nm for PS/PSF
associated with the PS-free surface,50,53 but are comparable to (estimated based on solubility parameters9294 ). On the scale
systems with highly chemically interactive substrates.49,51,52 of Fig. 4, the two composition profiles look similar and nearly
To further investigate the length scale of the dynamical vertical, starkly defining the location of the interface. By com-
T g perturbation near the PS/PSF interface, Figure 4 graphs paring directly the T g (z) profiles of the PS/PSF system with
the local T g (z) values measured for many different samples that measured previously for the PS/PnBMA system, we can
where the thickness of the neat PS z-layer between PSF and observe two distinct behaviors: (1) The magnitude of the T g
the PS-Py probe reporting layer was varied. Error bars of 2 C reduction or enhancement from bulk T g dynamics is not depen-
were determined based on the standard deviation of multiple dent on the relative T g difference at the polymer-polymer
measurements at comparable z values as the largest experi- interface. In both the PS/PnBMA and PS/PSF systems, the dif-
mental error is associated with sample-to-sample variability. ference in T g is 80-85 K, yet the PS-Py probe layers close to
It is not possible to polymerize PSF with a pyrene label; thus, the PS/PnBMA interface experience more than twofold greater
we are restricted to only mapping the PS side of the PS/PSF deviation in local T g (z) from the bulk T g of PS for a given dis-
T g (z) profile. However, all data collected indicate that the T g (z) tance z, as compared to the PS-Py probe layers close to the
203307-7 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

PS/PSF interface. The local T g (z = 0) at the interface is con- kinetic correlations of glassy dynamics in bulk systems.43 In
sistently closer to the lower T g component in both systems: their simulations, Butler and Harrowell found values of 1/ 2 (T )
T g (z = 0) = 37 2 C for PS/PnBMA and T g (z = 0) = 130 up to 5-6 spin-layers as the glass transition was approached
3 C for PS/PSF. (2) The z-distance at which the perturbation from above, meaning deviations from bulk dynamics could
in local T g (z) begins on the PS side as the PSF or PnBMA persist to a depth of 10-12 spin-layers from the surface inter-
interface is approached is significantly different: at z 125 face of all up spins. Although there is no direct way to convert
nm as PSF is approached and at z 250 nm as PnBMA is n spin-layers to a physical size in nanometers, we can con-
approached. In addition, the propagation of the T g (z) pertur- sider that one spin-lattice site can flip (rearrange) from up to
bation is uncorrelated with the magnitude of the T g difference down, corresponding to a coarse-grained measure of a local
between the two polymers and is independent of the magni- arrangement of several physical units (polymer segments), rep-
tude in T g (z) perturbation at the interface. Below we discuss resenting a local region of the material. With only dynamical
separately these two factors: the magnitude of the perturba- correlations between nearest-neighboring spins, the influence
tion in local T g at the interface and the distance of propagation of the all-up spin interface persists to depths of many such spin
away from the interface that the dynamical perturbation per- sites.
sists. By comparing a series of polymer systems, we will show We recognize that this 1/ 2 length scale is a rather arbi-
that these behaviors of the broad T g (z) profile appear to be trary definition, but it has the advantage of being robustly
universal across different systems and are grouped in behavior quantifiable from the experimentally measured T g (z) values
by whether the neighboring interface has a higher or lower T g , and according to the work of Butler and Harrowell43,85 may
i.e., hard vs. soft confinement. provide insight into size-scales associated with glassy coop-
As it is difficult to precisely identify the location where erative dynamics. Thus, we proceed with this measure of
T g (z) begins deviating from bulk behavior, we have chosen quantification for the propagation distance of the dynami-
to quantify the propagation distance of the dynamical T g (z) cal T g (z) perturbation from bulk dynamics. We previously
perturbation from bulk dynamics by identifying the distance reported that for the PS/PnBMA system, 1/ 2 = 103 nm for
from the interface 1/ 2 at which the magnitude of the T g (z) glassy PS, while 1/ 2 = 50 nm for rubbery PnBMA.19 From
perturbation at the interface Tg (z = 0) Tgbulk  decays to half Figure 4 we find that in the PS/PSF system, 1/2 = 49 nm for
T (z)T bulk  rubbery PS. Thus, we see that the length scale over which
its value, 1/ 2 = z when  g g 
= 0.5. This quantifica-
| Tg (z=0)Tgbulk | the dynamical T g (z) perturbation persists depends on whether
tion of a length scale for the dynamical perturbation follows PS is next to PnBMA (soft confinement) or PSF (hard con-
from our previous work 19 and is based on an original def- finement), and that the length scale in PnBMA next to PS
inition of a kinetic correlation length in glassy systems put (hard confinement) is comparable to that for PS next to
forward by Butler and Harrowell.43 In 1991, Butler and Har- PSF (also hard confinement). This suggests that the propa-
rowell85 explored the temperature dependence of the mean gation of the dynamical T g (z) perturbation does not depend
spin relaxation times (T ) characterizing dynamical hetero- directly on some material property such as chemical struc-
geneity in the 2D two-spin facilitated Ising model (2FSM) of ture, but rather on whether the domain in question is in its
Fredrickson and Andersen.95,96 This simple facilitated kinetic glassy or rubbery state. As we will see in the next section,
Ising spin model exhibits heterogeneous dynamics, a broad PS glassy domains in contact with a rubbery interface (soft
spectrum of relaxation times, and undergoes dynamic arrest confinement) have their local T g (z) dynamics consistently
when the effective temperature is decreased. These character- perturbed out to a further distance from the interface than
istic hallmarks of the glass transition are achieved with only PS rubbery domains in contact with a glassy interface (hard
nearest-neighbor dynamical interactions; yet, this simple sys- confinement).
tem otherwise does not contain an equilibrium phase transition
or an inherent static correlation length. As a separate consider- Universal behavior: Local T g (z) of PS next to different
polymers
ation to their main work,85 Butler and Harrowell also explored
how the local relaxation time n for a given layer n would Next, we explore how universal this hard vs. soft con-
behave when next to a surface layer of all up spins.43 Butler finement behavior is by comparing profiles of the local T g (z)
and Harrowell43 characterized the dynamical influence of a dynamics in the PS domain next to a series of different poly-
surface of all up spins on the glassy kinetics of this simple mers with higher (hard) and lower (soft) T g in reference to PS.
Ising model as a function of layer distance n away from the By making this comparison across different systems, we are
surface by defining a kinetic correlation length 1/ 2 (T ) as the able to address possible factors and causes that could affect
distance from the surface (n = 1) at which the perturbation to the strong T g (z) coupling in cooperative segmental dynam-
the local relaxation time n relative to bulk decayed to half its ics between domains of dissimilar polymers. Again, for each
n bulk |
value, 1/ 2 (T ) = n when | |1 bulk | = 0.5. Having full access system presented here, we have made sure that the dissimilar
to the temperature-dependent relaxation time n (T ) from their polymer-polymer interface has been annealed to equilibrium.
simulations, Butler and Harrowell were able to determine the The section titled Varying annealing time of PS/PSF interface:
values of 1/ 2 (T ) for different temperatures. They found that Importance of reaching equilibrium will address what occurs
the temperature dependence of 1/ 2 (T ) matched the tempera- when the dissimilar polymer-polymer interface has only under-
ture dependence of the mean relaxation times (T ) previously gone limited annealing, demonstrating that the strong T g (z)
determined for the bulk system and argued that such a sur- coupling is significantly reduced or even eliminated if local
face decay kinetic correlation length 1/ 2 (T ) was a reflection of interdiffusion of the chains has not been allowed to occur.
203307-8 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

Figure 5 graphs the T g (z) values within the PS domain To make quantitative comparisons between the various
next to interfaces with four different polymers: PSF (Tg bulk T g (z) datasets shown in Figure 5, we calculate the T g (z = 0)
= 186 C), PMMA (Tg bulk = 120 C), PiBMA (Tg bulk = 62 C), value at the interface between the two dissimilar polymers and
and PnBMA (Tg bulk = 21 C). The bulk T g of PS = 101 C is determine the distance 1/ 2 from the interface at which the
identified by the horizontal dashed black line clearly demar- T g (z) perturbation decays to half its value. These values are
cating which polymers have a higher T g than PS resulting in tabulated in Table I for the various systems, along with the
hard confinement, and which have a lower T g than PS result- bulk T g of the polymer in contact with PS, and the difference
ing in soft confinement. In addition, we added the T g (z) data Tg between the two bulk T g values. We clearly observe a
collected on the rubbery PnBMA side from the PS/PnBMA pattern where polymer domains under soft confinement (next
system,19 but in order to make a comparison of the extended to a polymer interface with a lower T g than itself) exhibit a
length scale of the T g (z) perturbation between hard and soft large decrease in T g (z) near the interface over an extremely
confined systems, we have plotted the magnitude of the T g (z) large length scale 1/ 2 = 115 5 nm, while polymer domains
perturbation measured in rubbery PnBMA next to PS (hard under hard confinement (next to a polymer interface with a
confinement of PnBMA), on the PS side and elevated it to higher T g than itself) exhibit a more modest increase in T g (z)
be referenced to the bulk T g of PS: T g (z) = T g (z) of PnBMA near the interface over a comparatively smaller length scale
Tg bulk PnBMA + Tg bulk PS , with z z. In this manner, we can 1/ 2 = 55 5 nm. For reference we also include values for
clearly see that the rubbery PnBMA T g (z) under hard confine- the equilibrium interfacial width wI between the two immisci-
ment next to glassy PS, behaves very similarly to the rubbery ble polymers and the fragility m of the neighboring polymer
PS T g (z) under hard confinement next to PSF and PMMA. next to PS. Although the equilibrium interfacial widths of the
It is clear from the data that the behavior of the T g (z) profile composition profile (z) vary between 5 and 7 nm, these are
near a dissimilar polymer-polymer interface primarily depends very small differences that appear to have little if any influ-
on whether the domain in question is experiencing hard con- ence on the T g (z) behavior. (Although there are no reports
finement next to a polymer with higher T g than itself or soft in the literature of PS/PiBMA equilibrium interfacial widths
confinement next to a polymer with lower T g than itself. For or even values, we suspect it is likely comparable to that
glassy polymers under soft confinement, the T g (z) perturba- between PS/PnBMA as the magnitude and temperature depen-
tion is much larger and extends to much greater distances dence of the surface tension of PiBMA is very similar to that
(z 225-250 nm before bulk T g of PS is recovered), compared of PnBMA.97 ) Perhaps this is unsurprising given the small
with rubbery polymers under hard confinement (z 100-125 size of the composition profile in comparison to the large
nm before bulk T g of PS is recovered). The depth from the range of the dynamical T g (z) profile. However, as we dis-
dissimilar polymer-polymer interface to which the local T g (z) cuss further in the section titled Varying annealing time of
is perturbed is independent of the magnitude of the T g differ- PS/PSF interface: Importance of reaching equilibrium, we do
ence between the two polymers in question and the magnitude believe that the broad nature of polymer-polymer interfaces,
of the T g (z) perturbation itself. The behavior depicted by the in comparison to the sharp (0.5 nm) polymer-air, polymer-
data appears to be universal to these various polymers, some liquid, or polymer-substrate interfaces plays some unique
with very different chemical structures. Note that we have not role in leading to the enormous dynamical T g (z) profiles we
indicated the composition profiles of the interface in Fig. 5, but observe.
if included they would resemble a nearly vertical step changes Evans et al. have recently measured the experimental T g
at z = 0 on this scale, given the enormous range of the x-axis. value of thin PS layers surrounded by large (500-nm thick)

FIG. 5. Local T g (z) profile in the PS domain as a func-

tion of distance z from the dissimilar polymer-polymer
interface with various neighboring polymers: PSF
(Tg bulk = 186 C) shown as blue diamonds, PMMA
(Tg bulk = 120 C) shown as red triangles, PiBMA (Tg bulk
= 62 C) shown as purple squares, and PnBMA (Tg bulk
= 21 C) shown as green circles. The behavior (magnitude
and penetration distance) of the T g (z) profile is primar-
ily dependent on whether PS (Tg bulk = 101 C, horizontal
dashed line) experiences hard confinement next to a poly-
mer with a higher Tg bulk (depth to which perturbation
decays to half its value 1/ 2 = 55 5 nm) or soft confine-
ment next to a polymer with a lower Tg bulk (1/ 2 = 115
5 nm). For comparison, previous data19 of the magni-
tude of the T g (z) perturbation in rubbery PnBMA next
to glassy PS (hard confinement) are added as gray stars
where the data have been shifted to the Tg bulk of PS as
reference.
203307-9 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

TABLE I. Tabulated values of the experimentally determined T g (z = 0) at the interface between the two dissimilar polymers, the distance 1/2 from the interface
at which the T g (z) perturbation decays to half its value, and for reference the T g bulk of the polymer in contact with the PS domain, along with the difference Tg
between the two bulk T g values of the system, the equilibrium interfacial width wI of the composition profile, and the fragility98 m of the neighboring polymer
next to PS. In the last row of the table are the corresponding values for PnBMA in contact with PS.

Polymer Tg bulk ( C) Tg (K) T g (z = 0) ( C) Penetration distance 1/2 (nm) Interfacial width wI (nm) Fragility m

PS/ PSF 186 85 130 49 6 (Ref. 92) 141 (Ref. 101)

PMMA 120 19 112 59 5 (Ref. 122) 145 (Ref. 102)
PiBMA 62 39 75 127 67 (Ref. 123)
PnBMA 21 80 37 103 7 (Ref. 20) 56 (Ref. 101)
PnBMA/ PS 101 80 37 50 7 (Ref. 20) 139 (Ref. 103)

bulk layers of different polymers.71 They found that as the PS a slab of a glassy or rubbery domain that was sandwiched
layer thickness decreased, the T g of the PS layer increased by material that had either a lower or higher mobility. Within
or decreased relative to Tg bulk PS and approached the bulk T g this kinetic lattice model, probabilities for mobility exchange
value of the surrounding polymer in their trilayer systems. For between neighboring lattice sites transitioned a given site
the thinnest films of 14-nm PS, the maximum shift in T g of between three different states (awake, sleep, or dense),
the PS domain was equivalent to previous measurements99,100 where a series of exchange parameters collectively governed
of the component T g of isolated PS chains (0.1 wt. % blends the dynamics of the system. Profiles of the local mobility as a
at near-infinite dilution) in a matrix of different polymer that function of position across the system showed different pene-
was the same as the surrounding polymer in the trilayer sys- tration depths to which the local dynamics were perturbed by
tem. Evans et al. argued that the magnitude of the perturbation the interface between the glassy-rubbery domains at different
to the PS T g in these trilayer and near-infinite dilution sys- temperatures. The Tito et al. work 37 predicted an asymmetric
tems was correlated with the fragility value of the neighboring mobility profile at the glassy-rubbery interface that extends
(surrounding) polymer.71,100 We consider now if our exper- further into the glassy (lower mobility side) than into the
imentally measured magnitude of the perturbation in local rubbery (higher mobility side). This prediction of an asym-
T g is correlated with the fragility of the neighboring domain. metric mobility profile is consistent with our experimental
Our maximum perturbation in local T g occurs at the dissimi- results shown in Fig. 5 for the various glassy-rubbery polymer-
lar polymer-polymer interface (z = 0). Following the work of polymer interfaces. This suggests that the observed asymmetry
Evans et al.,71 we calculate the relative shift in the magnitude of in the T g (z) profiles (i.e., the difference in penetration depth
the T g perturbation at the interface as Tg (z = 0) Tgbulk  /Tg of perturbed dynamics between the glassy and rubbery sides)
from the data presented in Table I. For the perturbation to the may reflect a property of how glassy dynamics behave near
PS component in our systems, we find at best only a loose interfaces.
correlation between fragility of the neighboring domain with Simmons and coworkers have investigated using bead-
the magnitude of the T g perturbation. However, it is not con- spring MD simulations the role that interfacial energy between
sistent with PSF and PMMA, which have comparable fragili- neighboring domains of a low T g and a high T g polymer
ties101,102 (141 and 145), but significantly different magnitudes influence each others dynamics.66,105 The high T g domain
in perturbation (35% and 60% of maximum, respectively). We under soft confinement by the lower T g polymer had its Tg high
can also estimate how universal this correlation with neigh- reduced relative to its Tg bulk, high and the low T g domain under
boring fragility might be by determining the magnitude of hard confinement by the higher T g polymer had its Tg low
the T g perturbation for the other polymers at the dissimilar increased relative to its Tg bulk, low . The T g shift in the low-T g
polymer-polymer interface caused by the presence of the PS domain under hard confinement was additionally influenced
domain. The magnitude of the T g perturbation at the interface by the magnitude of the interfacial energy between the two
(z = 0) varies from 20% to 65% for the different polymers pre- domains. One complicating factor in comparing these simu-
sented in Table I, while the fragility of the neighboring domain lations to our experimental results is that when the interfacial
(PS) is a fixed value (m = 139).103 Thus, for our systems, it energy was varied in the simulations, it also altered the degree
does not appear that fragility is a key parameter in controlling of chain interpenetration between the two domains. In the
the magnitude of the T g perturbation. However, we do have a section titled Varying annealing time of PS/PSF interface:
qualitatively different geometry of two semi-infinite domains Importance of reaching equilibrium, we demonstrate experi-
in contact, instead of isolated chains or small domains of PS mentally that the observed T g (z) profiles reported in Figures 4
surrounded by a dissimilar polymer. and 5 are strongly dependent on the amount of annealing of
Recently a number of theoretical and computational the dissimilar polymer-polymer interface and hence likely the
efforts have explored the dynamics of glassy systems in prox- extent of chain interpenetration across this interface. However,
imity to high mobility interfaces. Of particular interest to the of significance, the MD simulations found that the degree to
present study is a limited mobility model by Tito et al.37,104 which interfacial energy affected the T g shift was correlated
with the mean-square displacement u2 of the neighboring


where they have modeled exchanges in local mobility within a
heterogeneous glassy material and investigated local mobility domain, a quantity characterizing the hardness or shear
profiles near various interfaces. Their 2013 work 37 modeled modulus of the material.66 Starr and Douglas have also found
203307-10 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

that local T g dynamics near an interface in bead-spring MD in the Experimental Methods section and Figure 1, when
simulations correlate with the relative stiffness of the under- measuring the T g (z) of a lower T g component (e.g., PS in
lying substrate.38 Perhaps this gives insight into why our PS/PSF), we first anneal the PS z-layer and underlying PSF
experimental results are separated into longer length scales layer together to ensure that this dissimilar polymer-polymer
(1/ 2 = 115 5 nm) for domains under soft confinement and interface has been annealed to equilibrium. Second, we add the
shorter length scales (1/ 2 = 55 5 nm) for domains under additional PS-Py labeled-probe layer and top (bulk) PS layer,
hard confinement, i.e., it is the softness or hardness of the performing a second annealing step of the PS/PS-Py/PS inter-
neighboring domain that influences how local T g -dynamics faces in order to obtain a consolidated material, while still
are perturbed near these interfaces. limiting interdiffusion of the probe layer, prior to the T g (z)
The role that local stiffness or local modulus plays in - measurement. We found that for a given location z from the
relaxations and T g has recently received renewed treatment interface, the measured T g (z) value varied with the length of
by Mirigian and Schweizer.106109 They have proposed that time of the first annealing step (that of the PS/PSF interface) up
the -relaxation event can be facilitated by a collective elastic to some saturation time scale, after which the measured T g (z)
distortion of the surrounding material, where the size of this value was reproducible and invariant to further annealing of
distortion field is related to the local elastic shear modulus. the PS/PSF interface.
This would suggest that the local -relaxations (T g ) would be
influenced by its local surroundings out to a greater distance
when the material is locally stiffer. Applying this reasoning to
our glassy-rubbery polymer-polymer interface systems might
suggest that the higher shear modulus of the glassy side would
be altered out to a greater extent than that of the softer rubbery
side. This reasoning perhaps provides a qualitative argument
for why the direction of the T g (z) asymmetry is biased towards
the glassy side of the dissimilar polymer-polymer interface.
Although the Mirigian and Schweizer theory has been success-
fully applied to model local T g changes near free surfaces,44,45
it has not yet been applied to dissimilar polymer-polymer
interfaces.
None of these theories address the large quantitative size
of the length scales we observe. This is still an outstanding
question. It is unclear why polymer-polymer interfaces alter
the local T g value out to hundreds of nanometers in contrast
to polymer-air interfaces which typically perturb the dynam-
ics out to only several tens of nanometers at most. We discuss
this in more detail in the section titled Varying annealing time
of PS/PSF interface: Importance of reaching equilibrium. We
do note that size scales typically associated with glass transi-
tion dynamics (CRR few nanometers) are much smaller
than the length scales of interfacial perturbations in con-
fined systems.19,50,52,53,110 However, a number of theoretical
models such as Random First Order Transition (RFOT) the-
ory42,111 and the Mirigian and Schweizer model just described
incorporate secondary longer-ranged factors where the local
cooperative dynamics are influenced by neighboring collective
dynamics. Experiments such as in this study demonstrating
long-ranged T g perturbations suggest that factors beyond a
single CRR size may be more important than we realize in
understanding glassy dynamics.
FIG. 6. (a) Fluorescence intensity at an emission wavelength of 379 nm col-
Varying annealing time of PS/PSF interface: lected on cooling at 1 C/min for PS-Py probe layers located at a fixed distance
Importance of reaching equilibrium of z = 50 nm from the PS/PSF interface. Data for three different samples are
shown where the PS/PSF interface was annealed for various lengths of time
Here we demonstrate the importance of annealing the dis- (20, 40, and 60 min) at a temperature of 210 C (above the bulk T g of both PS
similar polymer-polymer interface in establishing the observed and PSF) prior to the T g (z) fluorescence measurements. With progressively
longer annealing times leading to increasing local PS/PSF chain interdiffu-
T g (z) profiles. We find that the strong coupling in coopera- sion, the T g (z = 50 nm) increases from 100 2 C, essentially the bulk T g
tive segmental dynamics across the interface and the extended value of PS for only 20 min of annealing, to 110 2 C after 40 min and 118
length scales over which the T g (z) perturbation persists from 2 C after 60 min of annealing. (b) Local T g (z = 50 nm) as a function of
annealing time of the PS/PSF interface at 210 C demonstrating that the mea-
the interface only occur if the dissimilar polymer-polymer
sured T g (z) value saturates and becomes invariant after 60 min of annealing
interface is annealed to equilibrium. It is easiest to demonstrate when the PS/PSF interface reaches equilibrium. Dashed curve is a best fit to
this effect by focusing on the PS/PSF system. As described the data with a stretched exponential decay (see text for details).
203307-11 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

Figure 6 demonstrates the progression in T g (z) values at

z = 50 nm for the PS/PSF system, where we have varied the
annealing time of the PS/PSF interface (first annealing step)
during assembly of the multilayered structures. For very lim-
ited annealing of the PS/PSF interface, only 20 min, the T g
(z = 50 nm) = 100 2 C, equivalent to the bulk T g value of
PS, indicating that little to no dynamic coupling has occurred
across the PS/PSF interface. In contrast, for 40 and 60 min of
annealing the PS/PSF interface, the T g (z = 50 nm) increases
quickly to 110 2 C and 118 2 C, respectively. After
60 min, further annealing the PS/PSF interface does little
to change the T g (z = 50 nm) value further, with the T g (z
= 50 nm) reaching a limiting value of 121 2 C. It is impor-
tant to note that this annealing of the PS/PSF interface was
done at 210 C, above to the bulk T g values of both polymers.
Figure 6(b) plots these local T g (z = 50 nm) values as a
function of annealing time of the PS/PSF interface at 210 C. FIG. 7. Local T g (z) profiles on the PS side of the PS/PSF system. Data from
The data are reasonably well fit to a stretched exponential Figure 5, where the PS/PSF interface has been annealed for 90 min to equilib-
rium are shown as open diamonds. T g (z) data for z = 50 and 70 nm collected at
decay with an average relaxation time = 8 min and stretch- the different PS/PSF interface annealing times shown in Figure 6 are plotted
ing exponent of = 0.6. Such values are consistent with as colored symbols (same color coding as shown in Fig. 6): red diamonds
the idea that the local T g (z = 50 nm) values are saturating indicate that annealing for only 20 min leads to T g (z) values still close to that
because the PS/PSF interface is annealing further to equilib- of bulk PS with a nearly flat T g (z) profile, while 40 min of annealing (purple
diamonds) shows an intermediate T g (z) profile compared with that measured
rium. Polymer-polymer interface annealing occurs initially via for 60+ min of annealing.
Rouse modes, easily leading to equilibrium interfacial widths
of several nanometers.88,112 If the polymers are immiscible
such as is the case for the dissimilar polymer pairs in the present role in creating dynamical coupling of cooperative segmental,
study, the equilibrium interfacial width saturates at a maxi- T g -dynamics between the two dissimilar polymers.
mum value dictated by the unfavorable interaction parameter One of the major open questions that this work still does
, while in contrast, if the polymers were miscible, further not reveal is why polymer-polymer interfaces appear to be
annealing would lead to interdiffusion via reptation. Given the so qualitatively different than polymer-free surface, polymer
broad spectrum of relaxation times exhibited by the Rouse substrate, and even polymerliquid interfaces. As we demon-
modes of long chained polymers, it is not surprising that a strated, annealing of the dissimilar polymer-polymer interface
stretched exponential decay, rather than a single exponential, is necessary to cause the strong dynamical coupling observed.
was necessary to fit the data in Fig. 6(b). The T g (z) values What factors during polymer-polymer interface formation are
in Fig. 6(b) saturate after approximately 60 min of anneal- responsible? During annealing, the interfacial width broad-
ing, a time comparable to that required to obtain equilibrium ens, the dissimilar polymer chains interpenetrate locally, and
interfacial widths of 5-7 nm at temperatures of T g + 25 K the interface roughens, any one of which could be facilitat-
in literature studies.113116 We note that we have previously ing the dynamical coupling across the interface. Future work
addressed the possible suggestion that some small fraction of is required to disentangle these possible contributing factors.
low MW chains could diffuse across the weakly immiscible One interesting point is that the breadth or nature of the dis-
dissimilar polymer-polymer interface and possibly plasticize similar polymer-polymer interface is somehow requiring that
the PS component. We previously demonstrated that the T g (z) the local cooperative segmental dynamics become continuous
profile, when annealed to equilibrium, is independent of MW across the boundary, which may be responsible for creat-
and MW distribution of the neighboring polymer next to PS.19 ing the large breadth of the T g (z) profile. For only limited
Figure 7 illustrates how the T g (z) profile on the PS side of (20 min) amounts of annealing, we showed that the T g (z) pro-
the PS/PSF interface would evolve as a function of annealing file appears very narrow and could possibly be discontinuous at
time for the PS/PSF interface. The open diamonds plot the the dissimilar polymer-polymer interface. This would be more
data from Fig. 5 that was collected after annealing the PS/PSF like polymer-free surface, polymersubstrate, and polymer
interface for 90 min, ensuring that equilibrium was reached. liquid interfaces (all 0.5 nm) where the molecular dynamics
T g (z) data for z = 50 and 70 nm are included in the figure from one phase to another are locally discontinuous.
for the different annealing times shown in Fig. 6. The data
in Fig. 7 illustrate that the T g (z) profile would be nearly flat,
CONCLUSIONS
remaining at essentially the bulk T g of PS, at z-values quite
close the PS/PSF interface for only 20 min of annealing. In We have used a localized fluorescence probe to mea-
contrast, 40 min of annealing leads to an intermediate T g (z) sure local glass transition temperature T g (z) profiles in PS
profile, compared with the 60+ min of annealing required to domains near interfaces with different polymers. This work
obtain an equilibrium PS/PSF interface. From this we conclude builds on our recent measurements19 where we mapped the
that the amount of local interpenetration of the chains across full dynamical T g (z) profile across a PS/PnBMA polymer-
the dissimilar polymer-polymer interface plays a significant polymer interface finding that the dynamical profile does not
203307-12 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

correlate with the local composition profile (z). Unexpect- work will be needed to disentangle these possible factors. The
edly, the dynamical T g (z) profile spanned 350-400 nm in extent results presented here provide experimental data of a model
and was asymmetric with respect to the 7 nm wide composi- system for comparison to future theoretical efforts and have
tion profile. Here we demonstrate this broad, asymmetric T g (z) implications for how local properties should be considered in
behavior appears to be universal across a number of different polymer blends.
systems. Figure 5 shows that the distance from the interface
over which the T g (z) profile decays in PS varies depending ACKNOWLEDGMENTS
on if the neighboring domain has a higher T g (hard confine-
ment) or lower T g (soft confinement). In addition, we find that The authors gratefully acknowledge support from
the T g (z) profile in PS (Tg bulk = 101 C) next to PSF (Tg bulk National Science Foundation CAREER program (Grant No.
= 186 C) behaves similar to the T g (z) profile in PnBMA (Tg bulk DMR-1151646) and Emory University.
= 21 C) next to PS. This suggests that the propagation of this 1 C. Harrats, S. Thomas, and G. Groeninckx, Micro- and Nanostructured
dynamical T g (z) perturbation does not depend on some mate- Multiphase Polymer Blend Systems: Phase Morphology and Interfaces
rial property such as chemical structure, but rather on whether (CRC Press, Taylor & Francis Group, Boca Raton, FL, 2006).
2 L. Leibler, Prog. Polym. Sci. 30, 898 (2005).
the polymer has a higher or lower T g than its neighbor. 3 D. A. Bernards and T. A. Desai, Soft Matter 6, 1621 (2010).
We characterize the penetration depth by the distance 1/ 2 4 F. S. Bates, M. A. Hillmyer, T. P. Lodge, C. M. Bates, K. T. Delaney, and
from the interface at which the T g (z) perturbation decays to G. H. Fredrickson, Science 336, 434 (2012).
5 T. H. Epps, E. W. Cochran, C. M. Hardy, T. S. Bailey, R. S. Waletzko, and
half its value. Such a definition builds on previous work by
Butler and Harrowell43 who related a similar length scale to F. S. Bates, Macromolecules 37, 7085 (2004).
6 F. S. Bates, MRS Bull. 30, 525 (2005).
the temperature dependence of dynamical heterogeneities in a 7 W.-F. Kuan, R. Roy, L. Rong, B. S. Hsiao, and T. H. Epps III, ACS Macro
glassy model system. More recent theoretical efforts have also Lett. 1, 519 (2012).
8 Y. Tao, J. Kim, and J. M. Torkelson, Polymer 47, 6773 (2006).
tied dynamical perturbations near interfaces to glassy dynam-
9 M. F. Weber, C. A. Stover, L. R. Gilbert, T. J. Nevitt, and A. J. Ouderkirk,
ics and its associated length scales.3742,44,45 We find that PS
Science 287, 2451 (2000).
next to PSF and PMMA, so-called hard confinement of PS, 10 R. Y. F. Liu, Y. Jin, A. Hiltner, and E. Baer, Macromol. Rapid Commun. 24,
shows 1/ 2 = 55 5 nm, compared with PS next to PnBMA 943 (2003).
and PiBMA, soft confinement of PS, shows 1/ 2 = 115 5 nm.
11 R. Y. F. Liu, A. P. Ranade, H. P. Wang, T. E. Bernal-Lara, A. Hiltner, and

E. Baer, Macromolecules 38, 10721 (2005).

To within experimental error, we do not observe a difference 12 K. Arabeche, L. Delbreilh, R. Adhikari, G. H. Michler, A. Hiltner, E. Baer,
in 1/ 2 between the PSF and PMMA system, or the PnBMA and J.-M. Saiter, Polymer 53, 1355 (2012).
13 R. Casalini, L. Zhu, E. Baer, and C. M. Roland, Polymer 88, 133 (2016).
and PiBMA system, suggesting that the magnitude of the dif-
14 E. A. Jackson, Y. Lee, and M. A. Hillmyer, Macromolecules 46, 1484 (2013).
ference in Tg bulk between the two domains does not dictate the 15 V. Sethuraman, V. Pryamitsyn, and V. Ganesan, J. Polym. Sci., Part B:
propagation depth in PS. These systems also have slight dif- Polym. Phys. 54, 859 (2016).
ferences in equilibrium interfacial width, which does not seem 16 R. A. Segalman, B. McCulloch, S. Kirmayer, and J. J. Urban,

to change the length scale of the behavior. However, we find Macromolecules 42, 9205 (2009).
17 H. Sai, K. W. Tan, K. Hur, E. Asenath-Smith, R. Hovden, Y. Jiang, M. Riccio,
that these large length scales associated with the T g (z) behav-
D. A. Muller, V. Elser, L. A. Estroff, S. M. Gruner, and U. Wiesner, Science
ior are only observed when the dissimilar polymer-polymer 341, 530 (2013).
interface is annealed to equilibrium. We demonstrate using 18 L. H. Sperling, Polymeric Multicomponent Materials: An Introduction (John

PS/PSF that if the dissimilar PS/PSF interface is minimally Wiley & Sons, 1997).
19 R. R. Baglay and C. B. Roth, J. Chem. Phys. 143, 111101 (2015).
annealed for only 20 min at 210 C, compared with the 60+ min 20 D. F. Siqueira, D. W. Schubert, V. Erb, M. Stamm, and J. P. Amato, Colloid
required to reach equilibrium, strong dynamical coupling is Polym. Sci. 273, 1041 (1995).
not observed between the two dissimilar polymer domains and 21 J. A. Forrest and K. Dalnoki-Veress, J. Polym. Sci., Part B: Polym. Phys.

the T g (z) profile appears nearly discontinuous at the interface. 39, 2664 (2001).
22 P. M. Rauscher, J. E. Pye, R. R. Baglay, and C. B. Roth, Macromolecules
This important observation suggests that the strong dynamical
46, 9806 (2013).
coupling between dissimilar polymer domains, leading to the 23 T. P. Lodge and T. C. B. McLeish, Macromolecules 33, 5278 (2000).
broad continuous T g (z) profiles, are caused by some change 24 S. K. Kumar, S. Shenogin, and R. H. Colby, Macromolecules 40, 5759

that occurs during annealing. (2007).

25 Y. Y. He, T. R. Lutz, and M. D. Ediger, J. Chem. Phys. 119, 9956 (2003).
Comparing polymer-polymer interfaces to interfacial per- 26 M. D. Ediger and J. A. Forrest, Macromolecules 47, 471 (2014).
turbations near polymer-free surface, polymer-substrate, and 27 J. L. Keddie, R. A. L. Jones, and R. A. Cory, Europhys. Lett. 27, 59 (1994).
28 J. L. Keddie, R. A. L. Jones, and R. A. Cory, Faraday Discuss. 98, 219
polymer-liquid interfaces, we suggest three possible factors
that may be responsible for the long range effects. Polymer- (1994).
29 C. B. Roth and J. R. Dutcher, J. Electroanal. Chem. 584, 13 (2005).
polymer interfaces are typically much wider (5 nm) com- 30 J. A. Forrest and K. Dalnoki-Veress, Adv. Colloid Interface Sci. 94, 167
pared with the sharp (0.5 nm) composition profiles associated (2001).
31 M. Alcoutlabi and G. B. McKenna, J. Phys.: Condens. Matter 17, R461
with the other types of interfaces. Chain connectivity could be
also playing a modifying role to dynamical perturbations near (2005).
32 O. K. C. Tsui, in Polymer Thin Films, edited by O. K. C. Tsui and T. P. Russell
interfaces, as has been seen recently in a few studies.117119 (World Scientific, Singapore, 2008), pp. 267294.
Alternatively, interfacial roughness, which has been shown 33 J. E. Pye and C. B. Roth, Phys. Rev. Lett. 107, 235701 (2011).
34 C. J. Ellison, M. K. Mundra, and J. M. Torkelson, Macromolecules 38, 1767
in computer simulations to have a modifying effect on local
(2005).
dynamics,39,120,121 could also be a factor as polymer-polymer 35 C. B. Roth, K. L. McNerny, W. F. Jager, and J. M. Torkelson,
interfaces would be expected to experience increased interfa- Macromolecules 40, 2568 (2007).
cial roughness due to their reduced interfacial energy.97 Future 36 J. E. G. Lipson and S. T. Milner, Eur. Phys. J. B 72, 133 (2009).
203307-13 R. R. Baglay and C. B. Roth J. Chem. Phys. 146, 203307 (2017)

37 N. B. Tito, J. E. G. Lipson, and S. T. Milner, Soft Matter 9, 9403 (2013). 83 M. Wubbenhorst, C. A. Murray, and J. R. Dutcher, Eur. Phys. J. E 12, S109
38 P. Z. Hanakata, J. F. Douglas, and F. W. Starr, Nat. Commun. 5, 4163 (2014). (2003).
39 P. Z. Hanakata, B. A. Pazmino Betancourt, J. F. Douglas, and F. W. Starr, 84 Y. Rharbi, Phys. Rev. E 77, 031806 (2008).
J. Chem. Phys. 142, 234907 (2015). 85 S. Butler and P. Harrowell, J. Chem. Phys. 95, 4454 (1991).
40 A. Shavit and R. A. Riggleman, J. Phys. Chem. B 118, 9096 (2014). 86 H.-J. Butt, K. Graf, and M. Kappl, Physics and Chemistry of Interfaces, 3rd
41 R. J. Lang and D. S. Simmons, Macromolecules 46, 9818 (2013). ed. (Wiley-VCH Verlag GmbH, Weinheim, Germany, 2013).
42 J. D. Stevenson and P. G. Wolynes, J. Chem. Phys. 129, 234514 (2008). 87 A. Kriisa, S. S. Park, and C. B. Roth, J. Polym. Sci., Part B: Polym. Phys.
43 S. Butler and P. Harrowell, J. Chem. Phys. 95, 4466 (1991). 50, 250 (2012).
44 S. Mirigian and K. S. Schweizer, J. Chem. Phys. 141, 161103 (2014). 88 R. A. L. Jones and R. W. Richards, Polymers at Surfaces and Interfaces
45 S. Mirigian and K. S. Schweizer, J. Chem. Phys. 143, 244705 (2015). (Cambridge University Press, 1999).
46 C. B. Roth and J. R. Dutcher, Eur. Phys. J. E 12, S103 (2003). 89 C. J. Ellison and J. M. Torkelson, J. Polym. Sci., Part B: Polym. Phys. 40,
47 R. D. Priestley, M. K. Mundra, N. J. Barnett, L. J. Broadbelt, and 2745 (2002).
90 B. Valeur, Molecular Fluorescence: Principles and Applications (Wiley-
J. M. Torkelson, Aust. J. Chem. 60, 765 (2007).
48 K. Geng and O. K. C. Tsui, Macromolecules 49, 2671 (2016). VCH, Weinheim, 2001).
49 R. S. Tate, D. S. Fryer, S. Pasqualini, M. F. Montague, J. J. de Pablo, and 91 K. Kalyanasundaram and J. K. Thomas, J. Am. Chem. Soc. 99, 2039 (1977).
92 Y. Du, Y. Xue, and H. L. Frisch, in Physical Properties of Polymers
P. F. Nealey, J. Chem. Phys. 115, 9982 (2001).
50 C. J. Ellison and J. M. Torkelson, Nat. Mater. 2, 695 (2003). Handbook, edited by J. E. Mark (AIP Press, New York, 1996), pp. 227239.
51 P. Rittigstein, R. D. Priestley, L. J. Broadbelt, and J. M. Torkelson, Nat. 93 T. Matsuura, P. Blais, and S. Sourirajan, J. Appl. Polym. Sci. 20, 1515

Mater. 6, 278 (2007). (1976).

52 R. D. Priestley, C. J. Ellison, L. J. Broadbelt, and J. M. Torkelson, Science 94 R. Y. F. Liu, T. E. Bernal-Lara, A. Hiltner, and E. Baer, Macromolecules 38,

309, 456 (2005). 4819 (2005).

53 J. E. Pye, K. A. Rohald, E. A. Baker, and C. B. Roth, Macromolecules 43, 95 G. H. Fredrickson and H. C. Andersen, Phys. Rev. Lett. 53, 1244 (1984).
96 G. H. Fredrickson and H. C. Andersen, J. Chem. Phys. 83, 5822 (1985).
8296 (2010).
54 Z. Yang, Y. Fujii, F. K. Lee, C.-H. Lam, and O. K. C. Tsui, Science 328, 97 A. Falsafi, S. Mangipudi, and M. J. Owen, in Physical Properties of Polymers

1676 (2010). Handbook, edited by J. E. Mark (Springer, New York, 2007).

55 K. Paeng, S. F. Swallen, and M. D. Ediger, J. Am. Chem. Soc. 133, 8444 98 We caution the reader that fragility values are rarely known to better than

(2011). 10%, but choose to quote here values from the literature as they were
56 K. Paeng and M. D. Ediger, Macromolecules 44, 7034 (2011). previously cited.
57 K. Paeng, R. Richert, and M. D. Ediger, Soft Matter 8, 819 (2012). 99 C. M. Evans, R. W. Sandoval, and J. M. Torkelson, Macromolecules 44,
58 Z. Fakhraai and J. A. Forrest, Science 319, 600 (2008). 6645 (2011).
59 C. R. Daley, Z. Fakhraai, M. D. Ediger, and J. A. Forrest, Soft Matter 8, 100 C. M. Evans and J. M. Torkelson, Macromolecules 45, 8319 (2012).
101 D. Huang and G. B. McKenna, J. Chem. Phys. 114, 5621 (2001).
2206 (2012).
60 Y. Chai, T. Salez, J. D. McGraw, M. Benzaquen, K. Dalnoki-Veress, 102 A. P. Sokolov, V. N. Novikov, and Y. Ding, J. Phys.: Condens. Matter 19,

E. Raphael, and J. A. Forrest, Science 343, 994 (2014). 205116 (2007).

61 C. B. Roth, J. E. Pye, and R. R. Baglay, in Polymer Glasses, edited by 103 R. Bohmer, K. L. Ngai, C. A. Angell, and D. J. Plazek, J. Chem. Phys. 99,
C. B. Roth (CRC Press, Taylor & Francis Group, 2016), pp. 181204. 4201 (1993).
62 J. A. Forrest and J. Mattsson, Phys. Rev. E 61, R53 (2000). 104 N. B. Tito, J. E. G. Lipson, and S. T. Milner, Soft Matter 9, 3173 (2013).
63 J. Mattsson, J. A. Forrest, and L. Borjesson, Phys. Rev. E 62, 5187 (2000). 105 D. S. Simmons, Macromol. Chem. Phys. 217, 137 (2016).
64 C. G. Campbell and B. D. Vogt, Polymer 48, 7169 (2007). 106 S. Mirigian and K. S. Schweizer, J. Phys. Chem. Lett. 4, 3648 (2013).
65 C. M. Evans, H. Deng, W. F. Jager, and J. M. Torkelson, Macromolecules 107 S. Mirigian and K. S. Schweizer, J. Chem. Phys. 140, 194506 (2014).
108 S. Mirigian and K. S. Schweizer, J. Chem. Phys. 140, 194507 (2014).
46, 6091 (2013).
66 R. J. Lang, W. L. Merling, and D. S. Simmons, ACS Macro Lett. 3, 758 109 S. Mirigian and K. S. Schweizer, Macromolecules 48, 1901 (2015).
110 Y. Zhang, E. C. Glor, M. Li, T. Liu, K. Wahid, W. Zhang, R. A. Riggleman,
(2014).
67 J. Torres, P. F. Nealey, and J. J. de Pablo, Phys. Rev. Lett. 85, 3221 and Z. Fakhraai, J. Chem. Phys. 145, 114502 (2016).
111 V. Lubchenko and P. G. Wolynes, Annu. Rev. Phys. Chem. 58, 235
(2000).
68 D. S. Fryer, R. D. Peters, E. J. Kim, J. E. Tomaszewski, J. J. de Pablo, (2007).
112 Physics of Polymer Surfaces and Interfaces, edited by I. C. Sanchez
P. F. Nealey, C. C. White, and W. L. Wu, Macromolecules 34, 5627 (2001).
69 O. K. C. Tsui, T. P. Russell, and C. J. Hawker, Macromolecules 34, 5535 (Butterworth-Heinemann, Reed Publishing, 1992).
113 A. Karim, A. Mansour, G. P. Felcher, and T. P. Russell, Phys. Rev. B 42,
(2001).
70 D. Christie, C. Zhang, J. Fu, B. Koel, and R. D. Priestley, J. Polym. Sci., 6846 (1990).
114 S. Huttenbach, M. Stamm, G. Reiter, and M. Foster, Langmuir 7, 2438
Part B: Polym. Phys. 54, 1776 (2016).
71 C. M. Evans, S. Kim, C. B. Roth, R. D. Priestley, L. J. Broadbelt, and (1991).
115 M. Stamm and D. W. Schubert, Annu. Rev. Mater. Sci. 25, 325 (1995).
J. M. Torkelson, Polymer 80, 180 (2015).
72 R. Richert, Annu. Rev. Phys. Chem. 62, 65 (2011). 116 D. W. Schubert, M. Stamm, and A. H. E. Muller, Polym. Eng. Sci. 39, 1501
73 L. M. Wang, F. He, and R. Richert, Phys. Rev. Lett. 92, 095701 (2004). (1999).
74 F. He, L. M. Wang, and R. Richert, Phys. Rev. B 71, 144205 (2005). 117 E. C. Glor and Z. Fakhraai, J. Chem. Phys. 141, 194505 (2014).
75 H. Bodiguel and C. Fretigny, Macromolecules 40, 7291 (2007). 118 E. Glynos, B. Frieberg, H. Oh, M. Liu, D. W. Gidley, and P. F. Green, Phys.
76 J. Wang and G. B. McKenna, Macromolecules 46, 2485 (2013). Rev. Lett. 106, 128301 (2011).
77 J. Wang and G. B. McKenna, J. Polym. Sci., Part B: Polym. Phys. 51, 1343 119 L. Zhang, R. Elupula, S. M. Grayson, and J. M. Torkelson, Macromolecules

(2013). 49, 257 (2016).

78 H. Lu, W. Chen, and T. P. Russell, Macromolecules 42, 9111 (2009). 120 B. A. Pazmi no Betancourt, P. Z. Hanakata, F. W. Starr, and J. F. Douglas,
79 C. B. Roth and J. M. Torkelson, Macromolecules 40, 3328 (2007). Proc. Natl. Acad. Sci. U. S. A. 112, 2966 (2015).
80 C. M. Evans, S. Narayanan, Z. Jiang, and J. M. Torkelson, Phys. Rev. Lett. 121 P. Scheidler, W. Kob, and K. Binder, Europhys. Lett. 59, 701 (2002).
122 Polymer Handbook, 4th ed., edited by J. Brandrup et al. (Wiley, New York,
109, 038302 (2012).
81 Y. P. Koh, G. B. McKenna, and S. L. Simon, J. Polym. Sci., Part B: Polym. 1999).
123 K. L. Ngai, T. R. Gopalakrishnan, and M. Beiner, Polymer 47, 7222
Phys. 44, 3518 (2006).
82 H. Yoon and G. B. McKenna, Macromolecules 47, 8808 (2014). (2006).