ARTICLE

pubs.acs.org/Macromolecules

Confinement Effects on Chain Entanglement in Free-Standing

Polystyrene Ultrathin Films
Jeremy M. Rathfon,†,‡ Robert W. Cohn,‡ Alfred J. Crosby,† Jonathan P. Rothstein,† and Gregory N. Tew*,†
†
Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive, Amherst,
Massachusetts 01003, United States
‡
ElectroOptics Research Institute and Nanotechnology Center, University of Louisville, Louisville, Kentucky 40292, United States
bS Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: A study of the confinement effects on chain

entanglements in free-standing ultrathin (<100 nm) polymer
films is presented. Chain entanglements are probed by deter-
mining the lifetime and breakup time scale of a branched
Downloaded via BOGAZICI UNIV on July 18, 2022 at 06:11:55 (UTC).

network of suspended fibers formed from the annealing of

these films. Films of polystyrene (between 50 and 100 nm) cast
via flow coating are suspended atop lithographically patterned
arrays of pillars. The films are then annealed above the glass
transition temperature, where holes are randomly formed. The
holes expand exponentially due to capillary forces and impinge
upon each other to form a suspended, branched network of fibers. The thinning of fibers as well as the lifetime and breakup of this
fiber network is observed via optical microscopy. A model for the viscoelastic-capillary thinning of fibers can be applied to determine
a time scale for the breakup of individual samples. The decay of this time scale, below a critical parent film thickness, shows a
transition between interchain and self-entanglements when crossing into a confined regime, illustrating a significantly decreased
interchain entanglement density and breakdown in the entangled network of the polymer melt. This analysis of confinement effects
on chain entanglement extends the understanding of ongoing studies into suspended fiber formation from the melting of free-
standing polymer thin films. A better knowledge of chain entanglements in confined systems will make future fabrication of
nanoscale suspended fibers, new architectures, and subsequent devices more controlled and accessible.

’ INTRODUCTION volume allowed for a chain’s conformation also decreases.

The dynamics of polymer chains in entangled melts has been a Because of increasing confinement, segments from other chains
major research focus for the past 40 years,1
9 but few reports are excluded from a specific chain’s pervaded volume, resulting in
directly investigate the entanglement of polymer chains in a a reduced interchain entanglement density despite a constant
confined regime.10
12 Placing polymer molecules into confined overall entanglement density.11 In this confined regime, changes
geometries provides a way to probe the effects of confinement on in polymer conformation can result in large deviations in phase
the conformation and mobility of chains and polymer
surface behavior and dynamics from the bulk.
interactions. In the bulk, entangled polymer melts are modeled as Confined systems can be explored by studying the formation,
ideal Gaussian chains where their random walk motion has a evolution, and breakup of suspended fibers formed from the
length scale dependent on the molecular weight, Mw, of the melting of free-standing polystyrene ultrathin films. Hole forma-
polymer.3 This characteristic length scale of a polymer chain can tion in viscous thin films has been studied in detail in the literature,
be expressed by the root-mean-squared end-to-end distance, Ree, as in the case of dewetting.13
20 The nucleation of holes in
where Ree ∼ Mw1/2. Because of random thermal motions, an ideal suspended polymeric films in the melt state has been studied by
chain will explore and occupy a pervaded volume, Vp ∼ Ree3. In Rathfon et al.21 as well as Croll et al.22 and is found to exhibit a
this volume a polymer chain will have specific interactions with classic free energy barrier relationship, in which hole density, Fh, is
itself and many other chains. Some of these interactions being proportional to the film thickness, h; thus Fh ∼ exp(
h2). The
entanglements or “knots” with other chains, which restrict chain holes expand exponentially under capillary forces and impinge
mobility. These entanglements are responsible for many impor- upon each other to form a branched network of suspended fibers.
tant characteristic polymeric properties including very high melt By applying a model for the viscoelastic-capillary thinning and
viscosities, toughness, and elastomeric viscoelasticity.3,11
In ultrathin polymer films (less than 100 nm in thickness) the Received: December 1, 2010
film thickness, h, approaches the natural length scale of a polymer Revised: April 21, 2011
chain (Ree), and as the film thickness decreases, the pervaded Published: June 08, 2011

r 2011 American Chemical Society 5436 dx.doi.org/10.1021/ma1026324 | Macromolecules 2011, 44, 5436–5442
Macromolecules ARTICLE

Figure 1. Process for fiber formation via flow coating and thin film melting and a representative image of fiber branching (h = 60 nm, 400 kDa PS). Some
fibers have thinned and necked beyond the point of being visible at 50 magnification, which appear as dangling ends. The red uniform circles in the
image are the supporting pillars, ∼15 μm in diameter with 75 μm spacing.

breakup of fibers in this network, a characteristic time scale can polystyrene standard samples were used (PS, Mn = 123, 400,
be derived. 2000, 6000 kDa, Mw/Mn = 1.08, 1.06, 1.20, 1.22, respectively,
In this study, fiber thinning as well as the branching lifetime Alfa Aesar). After flow coating, film thicknesses were measured
and breakup of suspended fibers is investigated via optical across the film’s gradient profile via a UV
vis interferometer
microscopy. Ultrathin polystyrene films (h = 50
100 nm), cast (Model F20, Filmetrics, Inc.). Films were then floated off the
via flow coating, are suspended atop lithographically patterned silicon substrate onto clean water (Milli-Q) and subsequently
arrays of pillars. The films are then annealed well above the bulk transferred atop a lithographically patterned array of pillars. The
glass transition temperature, Tg, of the polymer, randomly pillars have dimensions of 15 μm in diameter and 75 μm spacing.
forming holes which expand to form a branched network of Films were dried and annealed just below the Tg of the polymer
fibers. Details of hole expansion21,23
30 of polymeric thin films film under vacuum for 24 h to remove water and residual
have been researched thoroughly in the literature. In this report, solvents.
the thinning of fiber radius is measured as a function of time and Fiber Thinning. Ultrathin film samples with varying thick-
compared for samples of varying molecular weights and thick- nesses were thermally annealed using an enclosed Linkham
nesses. The fiber radius evolution is used as a tool to explore LTS350 microscopy thermal stage and imaged via a Zeiss Axio
rheological properties of these samples. The characteristic time Imager M2m optical microscope at 50 magnification. Film
scale for the decay of the branched structures is calculated and samples were taken from room temperature and heated at 30
C/min
compared across the range of film thicknesses. This breakup time to the annealing temperature, 130
C for 400 kDa PS, and held
scale is dependent on entanglement molecular weight; thus, a while hole formation, subsequent expansion, fiber formation, and
transition into a confined regime where interchain entangle- branching/fiber breakup occurred. Samples of other molecular
ments are greatly reduced is shown, evidenced by a correspond-
weights were annealed at temperatures to match the zero shear
ing drastic increase in the breakup time scale.
rate viscosity, η0, of this experiment (1.73  109 Pa 3 s), calcu-
lated using the empirical WLF equation (116, 161, and 196
C
’ RESULTS AND DISCUSSION for 123, 2000, and 6000 kDa, respectively). Previous studies by
Thin Film Preparation. “Flow coating” is a technique, devel- Rathfon et al. have shown a new approach toward the fabrication
oped by Stafford et al., to fabricate ultrathin polymer films with a of suspended fibers from the melting and breakup of suspended
gradient thickness in the submicrometer to nanoscale regime, in ultrathin, polymer films.21,33 Upon heating above the Tg of
which a bead of polymer solution is sandwiched between a blade the polymer film, random hole nucleation occurs spontaneously
and is drawn across a substrate.31,32 A schematic of thin film in the suspended films either through a process analogous to
sample preparation for this branching study is given in Figure 1. spinodal decomposition or from defects such as dust or density
Gradient thickness polystyrene films, from approximately inhomogeneities (<0.2 μm).23,34 Holes observed in this report
50
100 nm in thickness, were cast from 0.75
1.5 wt % solutions form spontaneously in the melt in random locations, consistent
in toluene using an acceleration of 6 mm/s2. Monodisperse with literature findings,23,26,30 and not at the pillar edges. These
5437 dx.doi.org/10.1021/ma1026324 |Macromolecules 2011, 44, 5436–5442
Macromolecules ARTICLE

Figure 2. Model for the evolution as a function of time for an elastic fluid filament stretched between two surfaces (a), adapted from McKinley.36 The
dashed line represents the linear response of a Newtonian fluid. A representative plot of the exponential thinning of capillary fibers (b), from a parent film
of 100 nm thickness, (400 kDa PS) with an inset of a thinning fiber. Equation 3 was fitted to the data using least-squares-regression.

holes then expand at an exponential rate due to surface tension

driven capillary forces competing with viscous dissipation resist-
ing the flow of the polymer.23
28 As these holes expand,
eventually they impinge upon other holes, where the hole edges
meet, forming suspended “bridges” or fibers.
The elastocapillary thinning and breakup of slender viscoelas-
tic filaments or fibers has been studied in detail.35
38 For viscous
Newtonian fluids, the time scale for capillary thinning can be
expressed as the capillary time tcap = η0R/σ, where η0 is the
viscosity, R is the radius, and σ is the surface tension. However, in
elastocapillary thinning, fibers neck down and elongate due to
capillarity and undergo strong extensional flows which result in
large deformations of the polymer molecules leading to large
elastic stresses. The strain rate, ε·, for this capillary thinning, fluid
filament can be given as
d lnðRmid ðtÞ=R0 Þ Figure 3. Representative data for the evolution of fiber radius as a
ε_ ¼
2 ð1Þ function of time, in a semilog plot, exhibiting two regimes of thinning:
dt exponential at early times, as seen by the linear region at t = 0
300 s, and
where Rmid is the midfilament radius and R0 is the initial radius of transitions to linear at long times, with a different characteristic time
scale (h = 65 nm, 400 kDa PS). Note that at t > 500 s, a linear region
the filament. For an Oldroyd-B fluid, Entov and Hinch37 showed
should appear curved in a semilog plot; however, the slope of this region
that the resulting extension rate is constant and given by is small and imperceptible on the scale shown. Equation 4 was fitted to
ε· = 2/(3λ), where λ is the Oldroyd relaxation time constant. Anna the data using least-squares regression.
and McKinley35,36 later showed that this result is consistent for a
number of other viscoelastic constitutive models at moderate
strains before the onset of finite extensibility effects (FENE). This where G is the elastic modulus, and thus the prefactor in eq 3 can
includes multimode FENE models as well as the Rouse
Zimm be viewed as the dimensionless elastocapillary number GR0/σ.
model. However, in each case the Oldroyd relaxation time is This model for the evolution of a viscoelastic fluid filament as a
replaced by the longest (Zimm) relaxation time, λZ. The Rouse
function of time is shown in Figure 2a. The evolution of fiber
Zimm model predicts this relaxation time to scale with a depen- radius versus time was measured for fibers formed from films
dence on chain length with the well-known expression, λZ ∼ Mw3ν, with various molecular weights and thicknesses. A representative
which for a theta solvent (ν = 1/2) is stated λZ ∼ Mw3/2. plot of fiber evolution, showing the exponential decay of fiber
The total deformation at a given time can be given as the radius versus time, for a sample with 100 nm thickness and Mw =
Hencky strain: 400 kDa, is given in Figure 2b. Fiber radius, Rmid, was measured at
Z t the midpoint of each fiber from optical microscopy images with
εðtÞ ¼ ε_ ðt 0 Þ dt 0 ¼ 2 lnðR0 =Rmid ðtÞÞ ð2Þ an error of (0.2 μm. Initial fiber radius values measured were
0 typically 30 ( 3 μm. Each data point in the exponential decay
curves is from an average of fiber radii from a minimum of five
Equation 1 can be rewritten to obtain a prediction for how the representative fibers. The Rmid(t)/R0 curve is fitted via an
radius of a viscoelastic fluid filament will decay with time: exponential decay function and accurately depicts the exponen-
  tial decay of fiber radius for each sample.
Rmid GR0 1=3
¼ expð
t=3λZ Þ ð3Þ The exponential decrease in the fiber radius is well-described
R0 σ with the elastocapillary balance presented in eq 3. However,
5438 dx.doi.org/10.1021/ma1026324 |Macromolecules 2011, 44, 5436–5442
Macromolecules ARTICLE

Figure 4. Apparent extensional viscosity, η

happ, versus Hencky strain, for samples with varying molecular weights (a) and thicknesses (b). Samples
with varying Mw had a constant parent film thickness of h = 65 nm, whereas samples with varying thickness had a constant Mw = 400 kDa; pillar spacing
was 25 μm.

Entov and Hinch show that radius evolution will approach a consistent with Anna and McKinley’s findings for thinning of
linear behavior at late times due to polymer chains becoming fully elastocapillary filaments.35 It is apparent that a steady-state
stretched, no longer being capable of resisting the increasing extensional viscosity plateau was not observed in these fiber
capillary pressure.37 At this time, the filament thins similarly to a thinning experiments. A higher Hencky strain regime could yield
very viscous Newtonian fluid and approaches a steady-state these values; however, in the current report, fiber networks
extensional viscosity, ηh¥. In order to model the two regimes of typically began to fail before the observation of a steady-state
fiber radius evolution, the following equation is used: plateau. A recent technique by Arratia et al. shows the acquisition
of transient extensional viscosity for polymeric filament thinning
Rmid ðtÞ
¼ Ae
t=B
Ct þ D ð4Þ in a microfluidic channel, allowing for the attainment of the
R0 “elusive” steady-state extensional viscosity.39,40 The evolution in
where A, B, C, and D are fitting parameters. The value of B is ηhapp for samples of varying parent film thicknesses did not change
accordingly related to the longest relaxation time, λZ, and σ/C greatly, indicating fibers thinned similarly, for samples of the
determines the steady-state extensional viscosity, as will be seen same Mw, regardless of the differences in their initial strain
in eq 5. Equation 4 is fitted to each sample in order to better regimes. This observation is consistent with experimental ob-
model the radius behavior over the two thinning regimes. Figure 3 servation of capillary breakup of polymer solutions and melts and
shows a representative plot of fiber thinning behavior with the with the predictions of constitutive models like the Oldroyd-B
model eq 4 applied (see Supporting Information for all curves), and FENE dumbbell models discussed previously.
clearly showing both the initial exponential decay of fiber Branch Decay. To further probe the effects of confinement on
diameter then the linear response at long times. entanglements and the polymer dynamics in free-standing,
The transient extensional rheology of the PS samples is ultrathin PS films, the evolution of fibers with respect to
contained within the fiber radius evolution data and can be branching density was investigated. From the expression for
reexamined in the form of the transient extensional viscosity or the evolution of an elastic fluid capillary fiber (eq 3), the critical
apparent extensional viscosity, η time to breakup, tc, can be expressed as
happ. The forces on the filament  
form a balance of viscous and viscoelastic stresses with the 4
capillary pressure; thus, by substituting eq 1, η
happ is determined tc ¼ 3λ ln L2 ðGR0 =σÞ4=3 ð6Þ
to be 3

Δτ σ=Rmid ðtÞ
σ where λ is the longest relaxation time for the fluid fiber and L is
ηapp ¼ ¼ ¼ ð5Þ the finite extensibility parameter. Equation 6 is derived from eq 3
ε_ ε_ ðtÞ 2dRmid =dt
as the evolving fiber radius, Rmid, approaches zero; however, the
where Δτ is the tensile stress difference on the filament and ε· is finite extensibility of the polymer chain must be considered.35,36
the corresponding strain rate.35,36 Thus, η happ is inversely related Thus, tc gives a time based model for the breakup and decay of
to the first derivative of the fiber radius. Experimental data of fiber the fiber network. Equation 6 shows that the critical time to
radius over time were differentiated in order to determine the breakup is dependent upon the longest relaxation time, tc ∼ λ.
evolution of apparent extensional viscosity. In Figure 4, η happ is Because tc is proportional to λ, the breakup of fibers in the bulk is
plotted versus Hencky strain for samples with varying molecular dependent upon Mw, which relates directly to the previous
weights and parent film thicknesses, thus different initial strain statement of λ ∼ Mw3ν. Thus, there should be a strong correla-
regimes. These initial strain regimes were studied in a previous tion between the relaxation time and the effective molecular
report where shear viscosity values, for initial hole expansion weight of the chains, dictated by their interchain entanglements,
toward the formation of fibers, were on the order of 106 Pa 3 s with while in a regime with no confinement effects. With confinement,
shear strain rates of ∼0.5 s
1.33 The resultant Trouton ratio interchain entanglements can be reduced having an influence on
values for the present study would range between 101 and 104, the effective molecular weight and thus the relaxation time of the
5439 dx.doi.org/10.1021/ma1026324 |Macromolecules 2011, 44, 5436–5442
Macromolecules ARTICLE

Figure 5. Normalized branch density, Fb/Fb0, as a function of time, t,

showing the exponential decay of branching (h = 60 nm, 400 kDa PS)
with the initial portion fit with the linear expression, Fb(t)/Fb0 ∼
t/τb. Figure 6. Branching density time scale, τb, as a function of film
The inset shows finer detail of the initial linear region of branch thickness, h, Mw = 400 kDa. The red line is shown to illustrate the
density decay. deviation from bulk behavior. Thickness is plotted in terms of a
dimensionless ratio, h/2Ree, along the top axis.
fibers. As the breakup of the fiber network, relaxation time, and
the decay of branching in the bulk are all correlated, the following collected. The plot of linear branching time scales as a function of
expressions can be stated: thickness shows that below a critical film thickness the branching
Fb ðtÞ density time scale falls to far less than the expected bulk value
∼ expð
t=τb Þ ð7Þ (Figure 6). This critical thickness corresponds to the changeover
Fb0 to where the initial film is in a confined regime in which chains
have reduced interchain entanglements and thus the film thins,
τb ∼ λ ∼ Mw 3ν ð8Þ yields, and undergoes breakup more readily in the subsequent
flow, indicated by a decreased branching density time scale. In
where Fb(t) is the branching density as a function of time, the bulk, τb should be directly proportional to the relaxation time
normalized by the initial branching density, Fb0, and τb is the of the material, which correspondingly is proportional to the
characteristic branching density time scale. effective Mw. However, once chains have been confined, the
The decay of the branched fiber network is monitored via branching density time scale and thus the relaxation time deviate.
optical microscopy. From the images, the number of branches The decrease of the branching density time scale clearly shows its
and subsequently branching density can be calculated versus dependence on the effective entanglement molecular weight and
time. A representative plot of normalized branch density as a therefore the relative entanglement density at a given thickness,
function of time is shown in Figure 5. Branching density falls off ν(h), thus τb ∼ ν(h). Jones and co-workers illustrate this same
linearly in the initial stages of fiber network breakup, and then at confinement regime in their work.11 They report the same
long times, breakup slows and the time scale decays. As shown in transition to reduced interchain entanglements and increased
Figure 5, applying a linear fit to the initial linear portion of the yielding from films with initial thicknesses below ∼60 nm. This
branching data, the characteristic branching density time scale difference in yielding behavior between thick and thin films is
can be acquired, Fb(t)/Fb0 ∼
t/τb, as the inverse of the attributed to a network that is “more loosely entangled”.
tangential slope at t = 0 is equal to the exponential decay The amount of confinement of polymer chains in ultrathin
constant. A linear fit was chosen to analyze branching density films can be expressed as a ratio of film thickness versus the
decay due to the time frame of branching experiments at larger polymer length scale, Ree; thus h/2Ree, where h/2Ree = 1, would
thicknesses not completely encompassing the exponential decay represent a film with the thickness of one chain’s pervaded
of these slower yielding samples. The inset in Figure 5 shows the volume diameter. 2Ree was calculated to be ∼32 nm for 400 kDa
initial linear region in more detail. Because the branching density PS according to Ree = N1/2a, where N is the number of polymer
time scale is dependent upon tc (and thus λ and Mw), the slope of repeat units and a is the monomer length (approximated to be
the linear portion of the graph should be similar for samples of 2.55 Å).3 Considering the confined architecture of a thin film, a
the same molecular weight, unless the parent film thickness chain at an air/polymer interface is perturbed and reflected by
enters the confinement regime. In the confinement regime we this boundary such that the pervaded volume of a chain is
would expect a dramatic increase in the magnitude of this slope, reduced.1,11 This perturbation is approximated to be up to 1/2
thus a decrease in the branching density time scale, indicating less the bulk pervaded volume. As a chain is perturbed by an interface,
entangled chains, which would contribute to greater yielding and the interchain entanglements will be reduced due to the reduc-
breakup of the fibers. tion in the allowed pervaded volume. Thus, in a film with two
Confinement Effects on Chain Entanglement. Data for the interfaces, such as in a free-standing film, as a film gets thinner,
breakup of fiber networks from parent films with thicknesses chains will interact with both interfaces and the reduction in
varying from 50 to 100 nm were acquired. Branching time scales pervaded volume and entanglement density becomes more
for this series of films with constant Mw (400 kDa PS) were severe. Once a region is entered where films are sufficiently thin,
5440 dx.doi.org/10.1021/ma1026324 |Macromolecules 2011, 44, 5436–5442
Macromolecules ARTICLE

self-entanglements will dominate and few interchain entangle- confined regime, below a critical film thickness, breakup in
ments will exist, resulting in a drastically reduced network of response to an exponential strain with a characteristic time scale
chains, and thus a more fragile film. Figure 6 shows this reduction in a manner consistent with a drastic reduction in the interchain
in entanglements corresponding to a dimension approximately entanglement density. The entanglement density was found to
twice the calculated diameter of a chain in the bulk. Below this decrease in a regime below a corresponding critical parent film
dimension perturbation of the pervaded volume of bulk chains is thickness, comparable to the dimensions of bulk polymers,
expected to have a significant contribution, as chains would have h/2Ree < 2. This model agrees with previous explorations and
to begin to pack into a confined regime with the influence of the experiments with models for the perturbation of the pervaded
two air/polymer interfaces. Thus, the entanglement density of volume of polymer chains when in contact with interfaces.1,11 As
the parent film and therefore the time scale for the breakup of the a film becomes sufficiently thin, interfaces dominate and the
fiber network will be greatly reduced. proportion of self-entanglements increases and interchain en-
The reduced interchain entanglement density seen can be tanglements decrease, resulting in a much less stable network of
compared to other studies where confinement is shown to affect chains. The presented analysis of confinement effects on chain
the chain order, mobility, and dynamics at the surface boundary entanglement extends the understanding of ongoing studies into
layer. Baumchen et al. show how interfacial entanglement density suspended nanoscale fiber formation from the melting of free-
affects boundary conditions in polymer flow.12 Slippage is standing polymer thin films.
directly linked to chain entanglements and a reduced interchain
entanglement density at the solid
liquid interface is found. The ’ ASSOCIATED CONTENT
onset of slippage correlates to the critical chain length for
entanglements where the slip length dependence on molecular bS Supporting Information. Fiber radii plots of exponential
weight corroborates the description by de Gennes for the sliding thinning for all samples; branch density versus time plot for all
chain end model.4 This reduced entanglement density at the samples; representative suspended fiber, branch decay movie.
boundary layer is similar to our study where a suspended film can This material is available free of charge via the Internet at http://
be thought of as having two boundaries and thus two surfaces pubs.acs.org.
with reduced entanglements. When a film becomes sufficiently
thin, these boundary layers can overlap, causing reduced en- ’ AUTHOR INFORMATION
tanglements throughout the film, leading to rapid breakup and a
reduced branching density time scale. Bodiguel et al. analyze the Corresponding Author
dewetting of thin polymer films on a liquid substrate and show a *E-mail: [email protected].
reduced viscosity in thin polymer films.41 Bodiguel et al. suggest
that reduced entanglements in the surface layer allow modes ’ ACKNOWLEDGMENT
other than reptation, and thus, the viscosity would be reduced in
a single surface layer on the order of the coil size. This viscosity The authors thank the National Science Foundation’s Nano-
reduction, attributed to a reduced interchain entanglement scale Interdisciplinary Research Team (ECCS 0506941) for their
density, is found to depend only on the ratio of film thickness generous support of this work. This work utilized facilities
to coil size of the polymer chain. Thus, we would expect a film supported in part by the National Science Foundation Materials
with two surface layers, such as the free-standing films in this Research Science and Engineering Center (DMR 0820506) and
study, to show entanglement reductions near or below a thick- Center for Hierarchical Manufacturing (CMMI 0531171).
ness corresponding to two polymer coils as there are two free
surfaces. In free-standing films, Dalnoki-Veress et al. showed ’ REFERENCES
Tg reduction is dependent on Mw but with no direct link to coil (1) Brown, H. R.; Russell, T. P. Macromolecules 1996, 29, 798.
size,2 contradictory to the findings of Bodiguel et al. where (2) Dalnoki-Veress, K.; Forrest, J. A.; Murray, C.; Gigault, C.;
reduced viscosity and thus reductions of entanglements near the Dutcher, J. R. Phys. Rev. E 2001, 63, 031801.
surface were directly dependent on coil radius. These discrepan- (3) de Gennes, P. G. Scaling Concepts in Polymer Physics; Cornell
cies on coil dependence indicate that shifts in Tg and entangle- University Press: Ithaca, NY, 1979.
ment reductions are distinct phenomena which operate on (4) de Gennes, P. G. Eur. Phys. J. E 2000, 2, 201.
(5) Forrest, J. A.; Dalnoki-Veress, K. Adv. Colloid Interface Sci.
length scales affected differently by confinement.
2001, 94, 167.
(6) Graessley, W. W. Adv. Polym. Sci. 1974, 16, 1.
’ CONCLUSIONS (7) Keddie, J. L.; Jones, R. A. L.; Cory, R. A. Europhys. Lett. 1994,
27, 59.
The thinning of suspended fibers from the melting of free- (8) Mattsson, J.; Forrest, J. A.; Borjesson, L. Phys. Rev. E 2000,
standing polystyrene thin films was determined to obey the 62, 5187.
model for the capillary thinning of viscoelastic fluid fibers. The (9) Roth, C. B.; Dutcher, J. R. J. Electroanal. Chem. 2005, 584, 13.
technique of monitoring the evolution of viscoelastic free-stand- (10) Raegen, A.; Chowdhury, M.; Calers, C.; Schmatulla, A.; Steiner,
ing polymer fibers in the melt can prove to be a useful tool in the U.; Reiter, G. Phys. Rev. Lett. 2010, 105, 227801.
study of polymer rheological properties, such as the longest (11) Si, L.; Massa, M. V.; Dalnoki-Veress, K.; Brown, H. R.; Jones,
R. A. L. Phys. Rev. Lett. 2005, 94, 127801.
relaxation time of a polymer chain, the apparent extensional
(12) Baumchen, O.; Fetzer, R.; Jacobs, K. Phys. Rev. Lett. 2009,
viscosity, and the steady-state extensional viscosity. The decay of 103, 247801.
branching in suspended fiber networks formed by the melting of (13) Brochard-Wyart, F.; Debregeas, G.; Fondecave, R.; Martin, P.
free-standing polystyrene thin films was determined to be a Macromolecules 1997, 30, 1211.
useful tool in studying the effects of confinement on chain (14) Masson, J. L.; Green, P. F. Phys. Rev. Lett. 2002, 88, 205504.
entanglement. Fibers produced from thin films in an initial (15) Reiter, G. Phys. Rev. Lett. 1992, 68, 75.

5441 dx.doi.org/10.1021/ma1026324 |Macromolecules 2011, 44, 5436–5442

Macromolecules ARTICLE

(16) Reiter, G. Langmuir 1993, 9, 1344.

(17) Sharma, A.; Reiter, G. J. Colloid Interface Sci. 1996, 178, 383.
(18) Vilmin, T.; Raphael, E. Eur. Phys. J. E 2006, 21, 161.
(19) Reiter, G.; Al Akhrass, S.; Hamieh, M.; Damman, P.; Gabriele,
S.; Vilmin, T.; Raphael, E. Eur. Phys. J.—Spec. Top. 2009, 166, 165.
(20) Seemann, R.; Herminghaus, S.; Jacobs, K. Phys. Rev. Lett. 2001,
86, 5534.
(21) Rathfon, J. M.; Cohn, R. W.; Crosby, A. J.; Tew, G. N.
Macromolecules 2011, 44, 134.
(22) Croll, A. B.; Dalnoki-Veress, K. Soft Matter 2010, 6, 5547.
(23) Dalnoki-Veress, K.; Nickel, B. G.; Roth, C.; Dutcher, J. R. Phys.
Rev. E 1999, 59, 2153.
(24) Debregeas, G.; de Gennes, P. G.; Brochard-Wyart, F. Science
1998, 279, 1704.
(25) Debregeas, G.; Martin, P.; Brochardwyart, F. Phys. Rev. Lett.
1995, 75, 3886.
(26) Roth, C. B.; Deh, B.; Nickel, B. G.; Dutcher, J. R. Phys. Rev. E
2005, 72, 021802.
(27) Roth, C. B.; Dutcher, J. R. Phys. Rev. E 2005, 72, 021803.
(28) Roth, C. B.; Dutcher, J. R. J. Polym. Sci., Part B: Polym. Phys.
2006, 44, 3011.
(29) Roth, C. B.; Nickel, B. G.; Dutcher, J. R.; Dalnoki-Veress, K.
Rev. Sci. Instrum. 2003, 74, 2796.
(30) Xavier, J. H.; Pu, Y.; Li, C.; Rafailovich, M. H.; Sokolov, J.
Macromolecules 2004, 37, 1470.
(31) Stafford, C. M.; Roskov, K. E.; Epps, T. H.; Fasolka, M. J. Rev.
Sci. Instrum. 2006, 77, 023908.
(32) Meredith, J. C.; Smith, A. P.; Karim, A.; Amis, E. J. Macro-
molecules 2000, 33, 9747.
(33) Rathfon, J. M.; Grolman, J. M.; Crosby, A. J.; Tew, G. N.
Macromolecules 2009, 42, 6716.
(34) Brochard-Wyart, F.; Daillant, J. Can. J. Phys. 1990, 68, 1084.
(35) Anna, S. L.; McKinley, G. H. J. Rheol. 2001, 45, 115.
(36) McKinley, G. H. Annu. Rheol. Rev. 2005.
(37) Entov, V. M.; Hinch, E. J. J. Non-Newtonian Fluid Mech.
1997, 72, 31.
(38) Bhardwaj, A.; Miller, E.; Rothstein, J. P. J. Rheol. 2007, 51, 693.
(39) Arratia, P. E.; Cramer, L. A.; Gollub, J. P.; Durian, D. J. New
J. Phys. 2009, 11, 115006.
(40) Arratia, P. E.; Gollub, J. P.; Durian, D. J. Phys. Rev. E
2008, 77, 036309.
(41) Bodiguel, H.; Fretigny, C. Phys. Rev. Lett. 2006, 97, 266105.

5442 dx.doi.org/10.1021/ma1026324 |Macromolecules 2011, 44, 5436–5442