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Department of Physics and Department of Materials Science, University of Illinois, Urbana, Illinois 61801, United States
ABSTRACT: We develop a microscopic, force-level statistical dynamical theory for
the localization and activated hopping dynamics of dilute spherical particles, both
hard and soft, in polymer networks and entangled melts. The main factor
controlling localization is the connement a particle experiences from polymer
entanglements and/or chemical cross-links as characterized by the ratio of the
eective nanoparticle diameter to the mechanical mesh length, 2Reff/dT. Dynamical
localization occurs when the latter ratio is of order unity, and the activated hopping
mobility drastically decreases as the connement parameter even modestly increases
past threshold. Local packing correlations slightly enhance the tendency to localize
for hard particles and dramatically enhance mobility for soft repulsive particles. The
concept of an eective nanoparticle size largely, but not completely, collapses the
diverse dynamical results for hard and soft repulsive particles. For hard spheres in
entangled polymer melts we nd the exponentially slow hopping diusivity is
generally much smaller than transport via reptation-driven entanglement network
dissolution, except for a narrow window of connement parameters of 2R/dT 1.52 and long enough chains.
I. INTRODUCTION
Nanoparticle motion in diverse crowded environments is of
broad interest, with applications in physics, material science,
cell biology, and medicine. Understanding the motion of a
tagged nanoparticle can provide length-scale-dependent information about the properties of structurally and/or
viscoelastically complex matrix materials.14 In polymer
nanocomposites and lled elastomers, nanoparticles can
provide massive reinforcement of elastic and other mechanical
properties.57 In biology and medicine, molecular transport
underlies many cell functions and drug delivery applications.8,9
The problem has begun to be addressed theoretically, albeit
largely at a tentative and single particle diusion level.1016
Of specic interest in this article is how nanoparticles diuse
in cross-linked polymer networks and entangled polymer melts
in the dilute tracer limit. Yamamoto and Schweizer have
previously developed a microscopic statistical mechanical
theory at the level of forces for spherical one10 and two11
particle diusivity in unentangled and entangled polymer melts
built on a combination of Brownian motion, polymer physics,
and mode coupling theory (MCT) ideas. By adopting a
constraint release dynamical picture, appropriate when particles
are not too small compared to the entanglement tube diameter,
single particle mobility is driven solely by length-scaledependent collective relaxation of polymer density uctuations.
Their primary nding was nanoparticle diusivity can be
massively enhanced relative to the continuum StokesEinstein
prediction due to a gradual coupling of the particle to the
transient entanglement network constraints as its size increases.
A second, complementary advance extends the self-consistent
general Lengevin equation (GLE) framework developed in refs
17 and 18 to the case of small nanoparticles which decouple
2013 American Chemical Society
Macromolecules
Article
II. THEORY
A. Models. We consider spherical nanoparticles of core
radius Rcore larger than the polymer monomer size. The
polymer is described at the lightly coarse-grained level of a
freely jointed chain of hard sphere sites of diameter d (typically
nm).23,24 Monomers interact with the nanoparticle via a hard
core repulsion plus an exponential tail pair potential:
r < R core + d /2
Upn(r ) =
r (R core + d /2)
r R core + d /2
pn exp
pn
(1)
(4)
dr(1 eUpn(r))
(2)
hpn(k) = Cpn(k)Spp(k)
(5)
S
k
(
pp )
+
t
S0
k 2d 2
exp 2 T exp
Nx
rep
3 Spp(k)
(6)
(3)
Macromolecules
Article
cpp(k , t ) =
S0
k 2d 2
exp 2 T
Nx
3 Spp(k)
0 r < R core
gpn(r ) =
1 r R core
(7)
3
hpn(k) = 4R core
(8)
3 3
dk
Cpn 2(k)Spp(k)
ln 2
kBT
2 2r
(2 )3 p
2
S
d T 2
r
0 exp k 2 +
Nx
3 2Spp(k)
6
(10)
rB
dr e Fdyn(r)
dr eFdyn(r )
2
e FB
KLKB
(15)
(11)
For small barriers, FB 2kBT, hopping events become less welldened; however, eq 11 still accurately captures the average
time it takes the particle to move a jump distance, rB rL.
When the barrier is large, FB 2kBT, eq 11 reduces to the
classic Kramers theory result:33
hop
(14)
(9)
kR core
Cij(r ) = (1 e Uij(r))gij(r )
j1 (kR core)
s r(t ) = Fdyn(r ) + fs (t )
t
r
(13)
2R 3
3 3
= ln
dT
2 2r 2
6 p
kBT
dT
[b1/2{2b1 3 + (1 2b1)eb} + erf( b )]
6(2R /dT )2
b=
(2R /dT )2 r 2 + 4/ 2S0
(16)
Fdyn(r )
(12)
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S0
(2R/dT)c
18
0.10
0.25
0.40
1.00
0.25
1.58
1.32
1.22
1.08
1.53
rL , c rL
R
0.24 0.09
2R
2R
dT
dT c
(17)
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1/2
2
rL
72
3
1/4 dT
(3
S
)
=
0
2
2R
R
p dT
(18)
2R
rB rL
2R
dT
R
dT c
Figure 4. Mean barrier hopping time in units of the particle short time
scale, s s(2R)2, as a function of the distance of the connement
parameter from its critical value for the analytic hard sphere model.
p2dT = 18 for all curves. The black, dot-dot-dashed curve is a t of
the low connement regime to the exponential form of eq 21 . (Inset)
Barriers for the same systems. The blue crosses are the barriers using
the PRISM structural model input and should be compared to the S0 =
0.25 curve.
(19)
which is robust to variations in the dimensionless compressibility except for S0 = 1.0. Equation 19 applies until 2R/dT
(2R/dT)c + 1. For 2R/dT (2R/dT)c, an analytic result can
again be derived. Since rL 0, the hopping distance is
dominated by the barrier location which obeys rB dT, and in
this limit we nd
2
1
1/3 2R
rB rL
r
B (6 )1/6 p 2dT
48
dT
dT
dT
(20)
2R
FB
2R
kBT
dT c
dT
FB
2R
2R
= 0.08 exp 16
dT
dT c
(23)
(21)
1
2
(2R )3 kBTp 2 = VnGx
6
dT
(22)
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N 3 2R 5 2
3
(p 2dT )
e FB
18
Nx dT KLKB
(24)
2d 1/3 5/3
1/3
T
2
R
2
F
e B
Nc = Nx
18 dT KLKB
(25)
D hop =
(rB rL)2
6hop
(26)
In the analytic model the short time diusivity, Ds, sets the
mobility scale. Since hopping is associated with escape from
entanglement constraints, we assume all relevant Rouse modes
rst relax, and thus obtain the N-independent result10
1
kBT
8 R3
= kBT
Ds =
3 R g 2 R
Rouse
(27)
DCR
= 1 + ent
Ds
Rouse
3
ent
d
1 N
=
3 3S0 T
Rouse
12 Nx
2R
2
2
2
2
+1
e3 S0(R / dT ) 1 +
2
2
2
2
3 S0(R /dT )
3 S0(R /dT )
(28)
410
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Macromolecules
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2Rcore/d
pn/d
2Reff/d
dT,c/d
(2Reff/dT)c
repulsive: constant
core size
pn
0
1
2
4
5
5
5
5
5.00
12.97
18.29
24.67
4.25
7.25
12.25
19.25
1.18
1.79
1.48
1.28
repulsive: constant
eective size
0.1
1
2.5
5
10
5
5
5
5
0
2.26
2.06
1.71
1.14
0.00
10
6.25
6.45
6.75
7.60
9.10
1.60
1.55
1.48
1.31
1.10
attractive
10
0.0
0.5
0.5
1.0
1.0
10
9.10
8.25
7.60
7.75
7.10
1.10
1.21
1.32
1.29
1.41
0
2
4
2
4
Calculations of the tube diameter at the onset of localization, dT,c, are shown for several dierent nanoparticle diameters, 2Rcore, and monomer
nanoparticle interfacial interaction strengths (ranges), pn (pn) (dened in eq 1). It is convenient to dene an eective particle size (via eq 2) and
compare it to the transition tube diameter (2Reff/dT)c. All length scales are expressed in terms of the polymer segment diameter d.
Figure 9. The two extrema lengths (main) and barrier height (inset)
of the dynamic free energy for soft particles of constant eective size
2Reff = 10d with various core sizes. For all cases pn = 5 and pn/d is
determined by the constant eective size condition of eq 2. The
2Rcore/d = 10 case represents a hard particle, and as the core size is
decreased the softness of the ller is increased. The barrier height
results are shown as a function of the inverse mesh length dT1
rendered dimensionless by the mesh length at the onset of localization
dT,c.
Figure 8. The two extrema lengths of the dynamic free energy for soft
repulsive systems with 2Rcore = 5d and pn = 5d and several dierent
repulsion strengths pn. Both the tube diameter and extrema lengths
are normalized by the eective particle size. (Inset) To exhibit the
extent of data collapse in the main frame, the uncollapsed results are
shown where dT is normalized by the particle core size and the extrema
lengths are normalized by the monomer diameter.
Macromolecules
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VI. DISCUSSION
We have developed a microscopic, force-level statistical
dynamical theory for the localization and activated hopping
dynamics of dilute spherical particles, both hard and soft, in
cross-linked networks and entangled polymer melts. Our
primary ndings and predictions are as follows. First and
foremost, the main factor controlling localization is the
connement the particle experiences from polymer entanglements and cross-links as characterized by the ratio of the
eective nanoparticle diameter to the mechanical mesh length,
2Reff/dT. Dynamic localization occurs when 2Reff dT, and the
hopping mobility drastically decreases as the connement
parameter even modestly increases past threshold. In addition
to this main eect, local packing correlations modestly enhance
the tendency to localize for hard particles, and for repulsive
particles increasing softness, even at xed eective particle
diameter, can enhance mobility. While the eects of soft
interfacial repulsions are small compared to those of particle
size (connement), they still have dramatic consequences for
the onset of localization and in turn the nanoparticle mobility.
For entangled melts, we nd the exponentially slow activated
hopping diusivity is ineective relative to particle transport
controlled by entanglement network dissolution for most cases.
The exception appears to be a narrow window of connement
parameters of 2R/dT 1.52 for suciently long chains.
Future experiments and simulations to test the regimes where
hopping is relevant for networks and melts would be very
valuable. Additionally, experimental evidence for the scaling of
the localization length and the hopping time with the
connement ratio would be an important test of our
predictions.
Our approach relies on two key theoretical assumptions
inherent to both MCT and NLE theory. First, we assume
particle hopping and polymer network uctuations are
isotropic. This, of course, is true in the context of ensemble
averaged results, but how much error it might incur at the level
of an individual hopping event is unknown. Second, we do not
allow the nanoparticle to actively (and perhaps nonlinearly)
modify the local network structure as part of the activated
hopping motion.13 Relaxing this assumption involves taking
into account higher order (greater than two body) static and
dynamical correlations in MCT and NLE theory, an open
problem for microscopic force-level approaches.
The theory presented here can be straightforwardly
generalized to treat particles in semidilute polymer solutions.
Nonspherical particles can also be studied, including the role of
translational versus rotational degrees of freedom in the
localization and hopping process. The present work provides
a foundation for attacking the very dicult nondilute
nanoparticle regime of high interest for polymer nanocomposites. However, this requires addressing several compli-
Figure 10. The two extrema lengths (main) and barrier height (inset)
of the dynamic free energy for particles with core 2Rcore = 10d and
various attraction ranges and strengths. The hard sphere case (solid
red) is shown for reference. The barrier heights are plotted as a
function of the inverse mesh length dT1 rendered dimensionless by
the mesh length at the onset of localization dT,c.
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AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENTS
This work was funded by Michelin-France. We thank Umi
Yamamoto and Sanat Kumar for helpful discussions.
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