Lin
Viscoelasticity
Basics, Molecular Theories and Experiments
Polymer
Viscoelasticity
Basics, Molecular Theories ma Experiments
YnHwang
Lin
Polymer
Viscoelasticity
Basics, Molecular Theories and Experiments
World Scientific
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ISBN 9812383948
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Contents
Preface
ix
1
2
5
7
10
11
13
15
16
2.1 Introduction
2.2 Entropy and Rubber Elasticity
2.3 Molecular Theory for Rubber Elasticity
References
3. Polymer Chain Dynamics
3.1
3.2
3.3
3.4
3.5
3.6
16
17
18
25
26
Introduction
The Smoluchowski Equation
The Langevin Equation
The Rouse Model
Diffusion Motion of the Rouse Chain
The Rouse Normal Modes of Motion
V
26
28
32
33
35
35
vi
Contents
40
43
43
46
49
49
50
55
56
58
59
63
69
71
71
76
83
85
87
90
91
6.1 Introduction
91
6.2 The Smoluchowski Equation for an Elastic Dumbbell . . .
92
6.3 Rheological Constitutive Equation of the
Elastic Dumbbell Model
97
Appendix 6.A Codeformational (Convected) Time Derivative 106
References
Ill
7. Molecular Theory of Polymer Viscoelasticity
The Rouse Model
7.1 The Smoluchowski Equation of the Rouse Model
7.2 Rheological Constitutive Equation of the Rouse Model
112
112
. . 120
Contents
vii
123
125
126
8.1 Introduction
8.2 The Primitive Chain
8.3 Diffusion Motion
8.4 Relaxation Modulus
8.5 Relaxation of Stress by Reptation
Appendix 8.A Tension in a Gaussian Chain Between
Two Fixed Points
Appendix 8.B Equivalent Expressions for Rubber Elasticity
References
9. Molecular Theory of Polymer Viscoelasticity
Processes in the Linear Relaxation Modulus
9.1 Intramolecular Processes
9.2 Contour Length Fluctuation of the Primitive Chain . . .
9.3 Relaxation Processes before t T eq
9.4 Universality of the G(t) Line Shape
9.5 ZeroShear Viscosity and SteadyState Compliance . . . .
Appendix 9.A Contour Length Fluctuations of the
Primitive Chain
Appendix 9.B Rouse Motions in an Entanglement Strand . .
References
10. Comparison of Theory and Experiment in Linear
Viscoelasticity and Diffusion
10.1 Effects of the MolecularWeight Distribution of
the Sample
10.2 Analysis of the G(t) Line Shape
10.3 ZeroShear Viscosity and SteadyState Compliance . . . .
10.4 Viscoelasticity and Diffusion
References
126
128
131
134
139
143
144
144
146
146
149
154
156
157
159
162
165
167
168
171
180
188
192
viii
Contents
194
11.1 Introduction
194
11.2 Entanglement Region
196
11.3 EntanglementFree Region and Onset of Entanglement . . 205
11.4 Tube Dilation
213
Appendix 11. A Basic Form of the Blending Law in a
Binary Blend
217
References
219
12. Molecular Theory of Polymer Viscoelasticity
Processes in the Nonlinear Relaxation Modulus
12.1 ChainTension Relaxation
12.2 Comparison of Theory and Experiment
References
13. Number of Entanglement Strands per Cubed
Entanglement Distance
13.1 Introduction
13.2 Number of Entanglement Strands per Cubed
Entanglement Distance
13.3 Concentration Dependence of n*
13.4 Packing of Polymer Chains
13.5 Some Comments
References
Index
221
222
228
235
236
236
237
238
241
243
244
245
Preface
IX
Preface
Preface
XI
Preface
Xll
Last but not least, I should mention that important concepts from early
studies of polymer viscoelasticity have not been used and described according to their historical developments. Here, I should like to refer to the
review by J. D. Ferry,a which covers the key research works in the period
from 1930 to 1970.
Y.H. Lin
July 2002
Chapter 1
1.1
Polymer
Viscoelasticity
1.2
Consider a stochastic variable X. If X has a countable set of realizations, {xi}, where i = 1,2,... ,n (n is either a finite integer or n = oo),
Conformation
of Polymer
Chains
PX{X) = Y,PiS(X ~ O
( L1 )
i=l
where 8(x x,) is the Dirac delta function (see Appendix l.A); and Pi is
the probability for finding the variable X at xit which must satisfy the
conditions Pi > 0 and T,n=1pi = 1. If X can take on a continuous set of
values, such as an interval on the real axis, we assume that there exists a
piecewise continuous function, Px(x), such that the probability that X has
a value in the interval {a < x < b} is given by
Prob(a < x < b) = j dxPx(x).
(1.2)
Ja
Then Px (x) is the probability distribution for the stochastic variable, and
Px (x) dx is the probability of finding the stochastic variable in the interval x > x + dx. The probability distribution must satisfy the condition
Px(x) > 0 and / ^ Px{x) dx = 1.
Often we wish to find the probability distribution for another stochastic
variable, Y = H(X), where H(X) is a known function of X. The probability distribution, PY(V), for the stochastic variable Y, is given by
oo
dx6(yH(x))Px(x).
(1.3)
oo
dxxnPx(x).
(1.4)
oo
The moment, (x), is also called the mean value of X; the combination,
(x2) (x)2, is referred to as the variance of X; and the standard deviation
of X, ax, is defined by
ax EE ((x2)  <*>2)1/2
(15)
The moments give us information about the spread and shape of the probability distribution Px(x).
The most important moments are the lowerorder ones since they contain the information about the overall shape of
the probability distribution.
Polymer Viscoelasticity
dx exp(ikx)Px
/
(x)
oo
The series expansion in the equation above is meaningful only if the higher
moments, (x"), are small so that the series converges. Prom the series
expansion, we see that it requires all the moments to completely determine
the probability distribution, Px{x). The characteristic function is a continuous function of k and has the properties that /x(0) 1, /x(&)l < 1)
and fx(k) = fx(ty (* denote complex conjugation). The product of two
characteristic function is always a characteristic function. If the characteristic function is known, the probability distribution, Px(x), is given by the
inverse Fourier transform
1
Px(x) =
27r
dkexp(ikx)fx(k).
(1.7)
Joo
dn
(1.8)
k> o
/oo
/
dx
oo
dyPx,Y{x,y)
= l.
(1.9)
Joo
dyPx,Y(x,y).
(1.10)
oo
OO
/
dx
oo
dy6(zG(x,y))Px,Y(x,y).
(1.11)
J oo
OO
dz
oo
fOO
dx
J oo
dyexp(izk)8(zG(x,y))Px,Y(x,y)
J oo
rOO
OO
/
dx /
oo
dyexp(ikG(x,y))Px,Y(x,y).
(1.12)
*/ oo
(113)
1.3
Let us consider a stochastic variable, Y}v, which is the deviation from the
average of the arithmetic mean of JV statistically independent measurements
of a stochastic variable, X. Yjv may be written as
YN={XI+X2+N
+ XN)
(X)=Z1+Z2
... + ZN
(1.14)
where
Zi =
(1.15)
(^L_M).
We want to obtain the probability distribution function of Y}v, Py,N{y)First, the characteristic function, fz(k; N), for the stochastic variable, Z^N,
can be written as
fz(k; N)=
= j
dz f
dxexp{ikz)5
dxexp {ik{X~N(x))^
k2a2
(z  ^ ~ ^ )
Px{x)
Px(x)
Polymer
Viscoelasticity
/oo
/oo
/
dy
= (/z(fc;W))"
dzi
dzN exp(iky)S I y  ^
zt J J  P ^ (z,)
AT
k22^2
a
1   X2^ +
2/V
e x
2_a_
27V
P (  ^ H
asiV^oo.
(1.17)
Thus, as N
I
PY,N{V)
(
dfcex
> 2 W
P(
_ifc
27T(T^ /
y)
ex
k2a2
P ( 2N^ )
2<TX
+  + XN=NYN
(1.19)
dy8(rNy)PY(y)
OO
1
2nN(x2)J
1/2
eXP
{2N&))
(L20)
Equation (1.20) has many applications in this book, such as the diffusion
motion of a Brownian particle and the probability distribution of the endtoend vector of a long polymer chain. The latter case will be studied in
this chapter. Essentially, (x 2 ) 1 / 2 in Eq. (1.20) can be regarded as the mean
projection of an independent segment (bond) vector in one of the three coordinate directions (i.e. x, y or z; all three directions are equivalent). As long
as the considered polymer chain is very long, we can always apply the central limit theorem, regardless of the local chemical structure. Because the
Conformation
of Polymer
Chains
1.4
(R1,R2,...,RN+I).
n = l,2,...,N.
(1.21)
Because all the segments are of fixed length b and are randomly oriented,
the segmental distribution function for the xth segment is given by
i>(bx) = ^5(\bx\b)
(1.22)
which means that finding the bond vector, bx, of the xth segment in the
region b x > hx + dhx has the probability ip(hx)dhx.
The distribution
Polymer
Viscoelasticity
rVb'
Fig. 1.1
fir
/oo
rP(bx)dbx =
l
= 1.
6(\bx\b)\bx\2d\bx(1.23)
\
d<f> sm6d6j
Since the orientations of all the segments in the chain are independent of
each other, i.e. all the segmental vectors are independent stochastic variables, the configurational distribution function ^ ( { b n } ) can be simply written as the product of the random distribution functions for the individual
segments. That is
N
(1.24)
*({bn = f t V>(bn).
n=l
Then the average value of any physical quantity A associated with the
molecular chain can be written as
(A) = J A({bn})*({bn})
dbi,db2,
...,dbN.
(1.25)
(L26)
Conformation
of Polymer
Chains
Then
N
<R) = ( b n ) = 0 .
(1.27)
n=l
<R2>
( L28 )
n>m
(1.29)
(K) = b2.
(1.30)
(R 2 ) = Nb2.
(1.31)
and
Thus,
(132)
(1.33)
<R 2 )=JV& 2 .
(1.34)
Thus,
10
Polymer
1.5
Viscoelasticity
(1.35)
/dRexp(ikR)$(R,iV)
N
[/
dbx exp(ik b x ) ^ ( b x )
(1.36)
With the substitution of Eq. (1.22) and the use of the spherical coordinates,
the term in brackets [ ] from Eq. (1.36) is rewritten as (with the direction
of k chosen as the z direction)
/
/00
= r /
47!^ J0
sin(fcfc)
kb
2TT
/Z7T
dbx I
J0
r7T
Thus,
/R(k) =
sin (k b)
kb
(1.38)
From the inverse Fourier transformation of Eq. (1.38), we obtain the probability distribution function for the endtoend vector R.
$(R,JV)= f^j
/dkexp(ikR)
sin(fcb)
kb
(1.39)
Conformation
of Polymer
Chains
11
1 eXP l
k2b2
Nk2b2\
^ )
(1.40)
I akexp
iK R
y
$(R,iV):
In) J
Nk2b2
(1.41)
2TT
.....
a=x,y,z
= {h) JL(i^)
3
ct=x,y,z
_Y3/2
2M2)
exp
(KI)
3R2\
6XP
Nklb2
(1.42)
~2Nb2)'
Thus, as given by Eq. (1.42), the probability distribution function for the
endtoend vector R is Gaussian. The distribution has the unrealistic feature that R can be greater than the maximum extended length Nb of the
chain. Although Eq. (1.42) is derived on the freely jointed chain model, it is
actually valid for a long chain, where the central limit theorem is applicable,
except for the highly extended states.
1.6
Here, we consider a chain where the length of each segment has the Gaussian
distribution, i.e.
3
V(bx)
\3/2
2^J
6XP
3b
2b2
(1.43)
Polymer Viscoelasticity
12
and
<b 2 >=& 2 .
(1.44)
Q \3/2
ou2
*M)=n(i) p()
3 \ 3N/2
exp
2nb2 )
(1.45)
n=l
3fcT
 R n ) =  ^  ( R n + i  Rn)2
(146)
= ~
( R + 1  Rn) 2 
(147)
n=l
Conformation
of Polymer
Chains
13
The Gaussian chain has an important property: the probability distribution of the vector R R m between any two beads n and m is a Gaussian
function, i.e.
$ ( R .  R
3(R R m )2 1
. (1.48)
2\nm\b2
, n  r n ) = ( ^ 
Equation (1.48) can be obtained from substituting Eq. (1.45) into an equation similar to Eq. (1.35) for the vector between any two beads. This
result is simply a special case of the theorem that the sum of any number of Gaussian stochastic variables is also a Gaussian stochastic variable.
As shown in the later chapters, this theorem finds applications in the study
of chain dynamics as well.7
Equation (1.42), derived on the freely jointed chain model for a long
chain (large N), is the same as Eq. (1.48) of the Gaussian chain model.
In other words, the freely jointed chain model and the Gaussian chain model
are basically the same in describing the physical properties associated with
a long section of a polymer chain. While the distribution (Eq. (1.42))
based on the freely jointed chain model is Gaussian only when iV is large,
the Gaussian distribution of the Gaussian chain model (Eq. (148)) can
be used between any two beads in the chain. Various calculations can be
greatly simplified by the use of the Gaussian chain model, as will be shown
in later chapters.
(l.A.l)
14
Polymer
Viscoelasticity
p(xx')dx = l.
(1.A.2)
oo
(1.A.3)
Then
OO
rOO
/
5(x x') dx = lim /
oo
p(x  x') dx 1
(1.A.4)
>0Joo
and
S(x x') = oo
= 0
for x = x'
for x ^ a;'.
(1.A.5)
oo
f(x)S(x
x') dx = lim /
lim /
f(x)p(x
x') dx
hr'a^
/x'e/2
= lim[/(x')+0(e2)]=/(x')
(1A.6)
(1.A.7)
27T J  o o
15
g(k)exp(ixk)dk
(1.A.8)
OO
1 f
g(k) = /
f{x)exp(ikx)dx.
2n
Joo
(1.A.9)
1.)
/exp[i(rr')k]dk
(1.A.10)
2K)
= f(r').
(l.A.ll)
References
1. Feller, W., An Introduction to Probability Theory and Its Applications (3rd
edn), Wiley, New York, (1968).
2. Reichl, L. E., A Modern Course in Statistical Physics (2nd edn), Wiley,
New York, (1998).
3. Lin, Y.H., and Luo, Z.H., J. Chem. Phys. 112, 7219 (2000).
4. Kuhn, W., Kolloid Z. 76, 258 (1936); Kolloid Z. 87, 3 (1939).
5. Yamakawa, H., Modern Theory of Polymer Solutions, Harper & Row,
New York, (1971).
6. Flory, P. J., Statistical Mechanics of Chain Molecules, Hanser Publisher,
New York (1989). To express the stiffness of a chain, the wormlike chain
is a useful model, which is characterized by two parameters: the persistence
length lp and the contour length L. In the limit of L/lv > oo, the Kuhn
segment length as defined by Eq. (1.32) is twice the persistence length.
7. Doi, M., and Edwards, S. F., The Theory of Polymer Dynamics, Oxford Univ.
Press, Oxford, (1986).
8. Dirac, P., The Principles of Quantum Mechanics (4th edn), Clarendon Press,
Oxford, (1958).
9. Wong, C. W., Introduction to Mathematical Physics, Methods and Concepts,
Oxford Univ. Press, New York, (1991).
Chapter 2
Rubber Elasticity
2.1
Introduction
The only difference between a polymer melt and a rubber material is that
the chains in the latter are crosslinked by chemical means. A rubber material can be regarded as a huge or macroscopic threedimensional network
formed of strands of polymer chain with both ends as crosslinks. Such a
material, maintaining the softness of a polymer above its melting temperature or glass transition temperature, will recover its original shape after
being released from a deformation. Materials of this nature, such as tire,
rubber, etc. are readily visible in our daily life. Because crosslinks in a
rubber keep the chain strands from moving away from their relative positions over a distance larger than the strand size itself, the chains do not
flow with the deformation and are able to recover their conformations once
the deformation is released. Thus, we only need to consider its elastic property. In contrast to this behavior, an uncrosslinked polymer exhibits the
elastic response only under momentary deformations; however, under a prolonged deformation, it cannot recover its original shape because the chain
molecules have flowed. For an uncrosslinked polymeric liquid, we need to
consider both the elasticity and viscosity of the materialthe main subject
of interest in this book. In Chapter 4, we shall study the viscoelastic behavior of the polymer in linear region phenomenologically. In Chapters 612,
we shall study the molecular theories that describe the viscoelastic properties of the polymers in the entangled and unentangled regions. The basic
physical mechanism that gives rise to rubber elasticity is also responsible
for the elastic aspect of the viscoelastic behavior of the polymer. 1 For our
purpose of studying the viscoelastic behavior of a polymer fluid, we discuss
the basic physics responsible for rubber elasticity here.
16
Rubber
17
Elasticity
2.2
(2.1)
(2.2)
\dlJT
\dlJT
\dl)T
(),*(),
where the Maxwell relation (dS/dl)r = (df/dT)i has been used. It is
observed that in maintaining a constant length I the tensile force / increases
with increasing temperature. (It is more correct experimentally to maintain a constant extension ratio l/l0 instead of simply constant length /,
where l0, denoting the length of the rubber piece in a strainfree state,
changes with temperature. The constant extension ratio is used to correct
for the socalled thermoelastic inversion effect 46 due to the change in volume of the rubber with temperature. To simplify our discussions here and
below, we use constant length with the understanding that the correction
18
Polymer
Viscoelasticity
(2.4)
and
#) r =(a +r $),
p5)
for a gas. For an ideal gas (dU/dV)T = 0. Thus, the pressure of a gas
arises from the entropy change caused by a change in volume.
2.3
exp
(^)
=(SP)
3 \
3 / 2
2^]
= W[X,Y,Z)
eXP
;(X2+Y2
27V6 2 '
+ Z2)
(2.6)
Rubber
Elasticity
19
jointed chain, all these individual configurations have the same energy and
the same probability of occurring. Thus, the number of configurations Q, at
a certain R is proportional to the probability distribution function $(R, N).
According to the Boltzmann equation, the entropy for the chain strand can
be written as
s =
fcln(fi).
(2.7)
As
n<xW(X,Y,Z)
(2.8)
"2^(X2
+ y 2+ Z2) + C
(2
9)
Fig. 2.1
20
Polymer
Viscoelasticity
(X0,Y0,Z0)
(X,Y,Z)
Fig. 2.2 Spatial configurations of a polymer strand in a piece of rubber before and after
the application of a deformation as shown in Fig. 2.1.
(2.10)
L%
L
(2.11)
A3
(2.12)
Furthermore, we assume that the density of the rubber does not change
with the deformation. Then we have the relation
A1A2A3 = 1.
(2.13)
Because of the symmetry of the deformation (A2 = A3), from Eq. (2.13),
we obtain
A2 A3 =
/Ax
(2.14)
According to Eq. (2.9), the entropies before and after deformation, denoted
by s0 and s respectively, are given by
s =
3fc
2Nb2
3k
{X2 + Y2 4 Z2) + C.
2Nb2
(2.15)
(2.16)
Rubber
Elasticity
21
Using Eqs. (2.10)(2.12) and (2.14), the entropy change associated with the
single chain strand due to the deformation can be written as
As = s s0 =
3fc
2Nb2
(A 2 1)X 0 2 +
1 17 +
(2.17)
If there are n chain strands in the total volume of the rubber piece V =
LLL = LxLyLz,
and the rubber is isotropic in its equilibrium state
before the deformation is applied, the total change in entropy AS can be
obtained by multiplying Eq. (2.17) by n and replacing X2, Y2, and Z2 by
their equilibrium average value, namely,
(R 2 )
Nb2
3 '
(2.18)
Thus, with the energetic contribution neglected, the total change in free
energy due to the deformation is given by
*f(* + h>
AA
(2.19)
=^{lt
t'
(2.20)
Then the force / applied to the piece of rubber in the x direction is given
by (Eq. (2.3))
/ =
'd(AA)'
dLx
= nkl
T,V
L2
Ll
(2.21)
f
LyL
nkT
V
*?fAi
(2.22)
In the literature, for practical purposes, the initial area of the cross section is
sometimes used to express the "stress" (often referred to as the engineering
22
Polymer
Viscoelasticity
LyLz
\\)
'
pNA
Mx
(2.24)
where p is the density of the rubber material and N& the Avogadro number.
Using Eq. (2.24), Eq. (2.22) can be expressed as
a = G (\\  i)
(2.25)
(2.26,
Rubber
Elasticity
"Theory
23
\ y\
\ j( i 
v\
1.0
2.0
3.0
4.0
Fig. 2.3 Comparison of experimental and theoretical (Eq. (2.23)) lengthforce relations for rubber in a typical case. The vertical scale has been adjusted for the best fit.
Reproduced, by permission, from Ref. 2.
(2.27)
Now, in a deformed state the entropy of the rubber is reduced; the entropy
change A 5 / involved in the firstorder transition from the deformed rubber to the crystalline state is also reduced. With AHf being basically
unchanged, the reduction of ASf leads to significant increase in the melting point Tm, when a large deformation is applied. In other words, crytallization in a rubber occurs much more easily when a large deformation
is applied. The crystallites in the rubber, formed at large deformations,
will act as additional "crosslinks" and will greatly enhance the observed
stress when additional deformation is applied. It is well known that natural
rubber has such an effect.5'6
Finally, it is interesting and helpful to make a comparison between rubber elasticity and gas pressure from the view point of statistical thermodynamics. A gas particle (atom or molecule) has more space to move about
in a large container than in a small one. In other words, the total number of the states available for the gas particle to occupy, all having the
same potential energy, is proportional to the volume V of the container.
Thus, corresponding to Eq. (2.9), the entropy of the gas particle can be
24
Polymer
Viscoelasticity
expressed as
s = kln{V) + C
(2.28)
(2.29)
which is the ideal gas law and is equivalent to Eq. (2.22) for the ideal rubber.
The basic physical effect responsible for rubber elasticity can be applied
to any length of polymer chain which is sufficiently long. In a polymeric liquid, whose concentration is high and whose polymer chains are
long, entanglements between polymer chains can occur. As we shall see
in Chapters 812, an entanglement can be treated as an impermanent
crosslink. Chain slippage through entanglement links will occur to equilibrate the uneven segmental distribution caused by the applied deformation.
Before the chain slippage mechanism has a chance to take place after a step
deformation is applied, the entanglement links can be regarded as fixed; the
measured modulus (in the linear region) can be used to calculate the entanglement molecular weight Me by using Eq. (2.26) (Mx is regarded as Me).
In a rubber, a chain strand can have an entanglement with another strand,
which cannot become freed because of the crosslinks; in other words, the
measured modulus receives contributions from both crosslinks and entanglements. Various models have been proposed to describe the additional
effect from entanglement in a rubber. 7 ' 8 The application of Eq. (2.26) to a
polymeric liquid to calculate Me from the measured modulus as mentioned
above is more exactly defined experimentally, as there is only the impermanent type of crosslink, namely, entanglement in the system. a As it turns
out, the obtained Me value plays a pivotal role in the universal behavior of
polymer viscoelasticity in the entanglement region; it is the basic structural
size in terms of which the molecular weight of a polymer can be expressed
"The socalled plateau modulus is often used to calculate Me In doing so, the equation
used is that of Eq. (2.26) multiplied by a factor of 4/5, which accounts for the effect of
chain slippage through entanglement links. See Chapters 811 for the details.
Rubber Elasticity
25
References
1. Mark, H., and Tobolsky, A. V., Physical Chemistry of High Polymeric Systems,
Interscience, New York (1950).
2. James, H. M., and Guth, E., J. Chem. Phys., 1 1 , 455 (1943).
3. James, H. M., and Guth, E., J. Polymer Sci., I V , 153 (1949).
4. Anthony, R. L., Caston, R. H., and Guth, E., J. Phys. Chem. 46, 826 (1942).
5. Treloar, L. R. G., Rep. Prog. Phys. 36, 755 (1973); Treloar, L. R. G., The
Physics of Rubber Elasticity (3rd edn), Clarendon Press, Oxford (1975).
6. Flory, P. J., Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca
(1979).
7. Mark, J. E., and Erman, B., (eds.) Elastomeric Polymer Networks, Prentice
Hall, New Jersey (1992).
8. Doi, M., and Edwards, S. F., The Theory of Polymer Dynamics, Oxford Univ.
Press (1986).
Chapter 3
3.1
Introduction
26
Polymer Chain
Dynamics
NMR relaxation
Brillouin scattering
Depolarized Rayleigh
scattering
Viscoelastic spectrum
Quasielastic neutron
scattering
Viscoelastic measurements
Diffusion measurements
28
Polymer
Viscoelasticity
3.2
Polymer Chain
flux, j(x,t),
29
Dynamics
= D
(3.1)
*D?
(33)
{Si)
dt ~udx*If an external potential field V(x) is applied to the particle, Fick's law needs
to be modified. As the potential V(x) exerts a force
* = %
on the particle, the average velocity of the particle v becomes nonzero.
If F is not large, v is proportional to F, i.e.
dV
<v = F =  
(3.5)
where is called the friction constant. Then the total flux becomes
J =
^dC
dC CdV
D+Cv
= D^.
..
(3.6)
(3.7)
<c^cirl^
(38)
(3.9)
30
Polymer Viscoelasticity
The Einstein relation states that, for particles (or a particle) undergoing
thermal motion, the quantity D which characterizes the diffusion process is
related to the quantity which specifies the response to an external force.
Substituting Eq. (3.9) into Eq. (3.6), one obtains
1 f,mdC
dV\
+ V)
(3.12)
(3.13)
Then the Smoluchowski equation (Eq. (3.11)) is derived from the continuity
equation
fs<^>
<314
>
Consider a particle undergoing thermal motion. If we denote the probability for finding the particle at x and t as \(a:, t), the above equations are
equally valid with C(x, t) replaced by ^(x, t). For noninteracting particles,
31
the only difference between C(x, t) and ^!(x, t) is that the latter is normalized while the former is not. Thus, the evolution equation for $(x,t) is
vn = ^2 Lnm({xs})Fm
(3.16)
where the coefficients Lmn are called the mobility matrix and can be
obtained using hydrodynamics. It can be proved that Lmn is a symmetric
positive definite matrix, 24 ' 27 i.e.
Lmn
= Lnm;
^^F
>0
forallir
n
( 3  17 )
= YJLnm^{kT\n<H
+ V).
(3.18)
dt
(3.19)
^ oxn
n
dt
2^2^dxn^m
n
(kTlnV + V) * .
(3.20)
32
3.3
Polymer
Viscoelasticity
or
dx
ldV
Physically, the random force f(t) = (g(t) represents the sum of the forces
arising from the ceaseless collisions with the fast moving small molecules
(including microstructural segments) in the fluid. As we cannot know the
precise time dependence of the random force, we regard it as a stochastic
variable with an assumed plausible distribution ^ [/(*)]. It can be shown
that if the distribution of f(t) is Gaussian characterized by the moments
</(*)> = 0
(322)
or
(9(t))=0
and
(f{t)f(t')) = 2(kT8{tt')
(3.23)
or
(g(t)g(t'))=2D6(tt')
the distribution of x(t) determined by Eq. (3.21) satisfies the Smoluchowski
equation (Eq. (3.11)).
The Langevin equation corresponding to the Smoluchowski equation
of multiple stochastic variables Eq. (3.20) with the condition
dLnm/dxm
= 0, which is often true, is given by 25 ' 27
TL(=:)+fcW
<3 24)
Polymer Chain
33
Dynamics
(3.25)
and
(9n(t)gm(t'))
= 2LnmkT8(t
 t').
(3.26)
The Langevin equation and the Smoluchowski equation represent the same
motion. Each of the equations has its advantages and disadvantages in
solving the dynamic problems of interest. One would choose one over the
other for its convenience in treating the problem of interest.
3.4
Fig. 3.2 Gaussian chain formed from N 1 "springs" and N "beads" at positions:
R i , R 2 , . , RAT relative to an arbitrary point in space. b n = R n + i R n is the bond
vector, and R c is the position of the center of mass (cm) for d n = R n R c and
? = 1 d = 0.
34
Polymer
Viscoelasticity
dt
dV
(kTlny)+
c?Rm
n=lm=l
9R
#.
(3.28)
When Eq. (3.28) is expressed in the form of Eq. (3.20), the mobility matrix
L for a chain of N beads will have the dimension 3N x 3JV.
In the Rouse model, the hydrodynamic interaction 29,30 and the excluded
volume interaction 3133 among beads are disregarded and the mobility tensor and the interaction potential are given by
"\kT
v
= ^ n= (2 *  ^i) 2 
(33); (L47)
OKI
dt
C.b2
( 2 R n  R n + 1  R _ 1 ) + g n (t)
(3.31)
(3.32)
(333)
for the end beads (n = 1 and N). The random fluctuation g n is Gaussian,
characterized by the moments which are given by substituting Eq. (3.29)
into Eqs. (3.25) and (3.26),
(gn(*)> = 0
2kT
{9na{t)9mf){t')) = ^Snm5a05(t
(3.34)
 t')
(3.35)
Polymer Chain
3.5
Dynamics
35
1 N
^)=7V^R
n W
"
(3 36)
'
n=l
T T  S S I .<>
<^>
n=l
Thus
((Rc(t)  Rc(0))2) 4 E E f
<(Rc(t)Rc(0))2) = .
(3.39)
(3.40)
=^
(341)
This result means that the diffusion constant for the whole Rouse chain is
simply 1/N of the diffusion constant for the individual bead {kT/Q.
3.6
Besides the diffusion motion, the dynamics of a polymer chain are also
characterized by its internal motions, which can be expressed in terms of
the normal modes.
36
Polymer
Viscoelasticity
b n = R n + i Rn.
Equations (3.31)(3.33) can be rewritten as
(
b2
b3
3kT
21 0 0
1 21 0
01
21
0\
bj
b2
b3
dt
bjv_ 2
\bNJ
/
0 0
0 0
1 2 1
01 2J
g2(*)gi(0
Si(t) 
t>W2
\bwJ
g3(0
(3.43)
+
gNi(t)SN2(t)
\
gjv(t)  g j v  i ( t )
TV  1
(3.44)
(3.45)
Here the normal procedure is to do the transformation from the bond vectors {b s } to the normal coordinates {q t } which will diagonalize the Rouse
matrix (Ast). As shown in Appendix 3.A, the Rouse matrix has the eigenvalues:
ap = 4 s i n 2 f ^  )
forp=l,2,...,JVl.
(3.46)
Polymer
Chain
37
Dynamics
Vm
NSm\
(3.48)
U? = Ul
or
AT1
(3.49)
22 UtsUtu = 5s
t=l
Using Eqs. (3.47) and (3.49), we can obtain from Eq. (3.44)
3kT
~~dT
N1N1N1
u=l
3kT
(3.50)
where
Nl
U
hp(t) = Yl
sP(Ss+i(t)  g,(t))
(351)
s=l
(3.52)
By using Eq. (3.35), the substitution of Eq. (3.48) into Eq. (3.51) gives
(hpa(t)hq0(t'))
4/cT
1 cos
8a0fipq$(t t').
(3.53)
Following the procedure shown in Appendix 3.B for solving the Langevin
equation of a particle in a simple harmonic potential, we obtain from
38
Polymer
Viscoelasticity
(3.54)
with
C62
3/cra p
(b2
12kTsin2(pn/2N)
(3.55)
The normal coordinate q p with p being a positive integer represents the pth
internal or intramolecular mode of motion of the polymer chain. Equation
(3.54) indicates that if p ^ q, the pth mode of motion is not correlated with
the qth. mode. Equation (3.55) can be expressed as
TpP = K
7T 2 M 2
 ^
12N2sm2(p^/2N)
K(3.56)
'
( 3  58 )
s=l
Substituting Eqs. (3.47) and (3.48) into Eq. (3.58), the time correlation
function of the endtoend vector, after some algebraic derivation, can be
expressed in terms of the normal modes as 34
(R(t)R(0))=
]T
ot
(^)exp()
(3.59)
where p's are odd integers, the largest of which is N 1 for N being an even
number and N 2 for N being an odd number. When N > oo, Eq. (3.59)
Polymer Chain
Dynamics
39
can be reduced as
26 2 47V 2
p=odd
Nb2
p=odd
with
{N2b2
Tp
Tt
(3.61)
~ 3 * T T I V ~~ p 2
where
C^2
Tl =
M 2
3fciv = * T
(3 62)
which is in agreement with the result obtained from the continuous Rouse
mode 27 (Appendix 3.C). Physically (R(t)R(O)) mainly represents the
reorientation motion of the polymer molecule with the rotational relaxation time Tr. Because of the strong 1/p2 dependence of the relaxation
strengths of the odd modes in Eq. (3.60), TT is basically equivalent to T\.
In summary, we have used the Rouse chain model to obtain the diffusion
constant of the center of mass and the timecorrelation function of the endtoend vector, which reflects the rotational motion of the whole polymer
molecule. Since N is proportional to the molecular weight M, and K is
independent of molecular weight, Eqs. (3.41) and (3.62) indicate that Do
and r r depend on the molecular weight, respectively, as
DG <X ^
(3.63)
TrT!txM2.
(3.64)
and
VM
(3 65)
r r oc M 3 / 2 .
(3.66)
"
and
40
Polymer
Viscoelasticity
1
0
0 0
1 0
1 X 1 0
0
(3.A.1)
Dz
0
0
0
0
0
0
0 1
0 0
where
x = a 2.
(3.A.2)
Polymer
Chain
Dynamics
41
(3.A.3)
>i = x
(3.A.4)
D2 = x2  1.
(3.A.5)
with
and
We may express x as
x = 2 cos 6> = exp(i0) + e x p (  i 0 ) .
(3.A.6)
(3.A.7)
A2 =
. ^ { i e \ ...
exp(t#)  exp(16)
XP(
(
" ? vv
(3.A.8)
(3A9)
exp(i^)  exp(ifr1)
Using the result from substituting Eqs. (3.A.8) and (3.A.9) into Eq. (3.A.7),
we have from Eq. (3.A.1)
sinf(z +1)01
Dz = l v . n ' J = 0.
sin 0
, k
3.A.10
Then the z eigenvalues of the Rouse matrix Ast are produced when
Eq. (3.A. 10) is satisfied, i.e. when
e=jrx
forp=1)2,...,z.
(3.A.11)
With x obtained from substituting Eq. (3.A.11) into Eq. (3.A.6), we obtain
from Eq. (3.A.2) the eigenvalues
* 2 + 2 o "(;Ti) 4 , r f G(jTij)
for p = 1,2,... ,z.
<3A 12)
'
42
Polymer
Viscoelasticity
^ =4sin2(^I))
(3.A.14)
cN_2 = (2  a p )c^_i.
exp
Ck1
ipn \
ipn
i\r; + e x p v N
(3.A.15)
cfc.
(3.A.16)
S l
e x p ( ^ )
e x p (  ^ )
(3.A.17)
(3.A.18)
J2 c*kck = 1
(3.A.19)
fc=i
Cfc
= /! sin (^r)
< 3  A  20)
Polymer Chain
43
Dynamics
= X
g{t)
(3.B.1)
with
(g(t)) = 0
(3.B.2)
{9(t)9(t')) = S(tt').
(3.B.3)
(3.B.4)
dt'exp l*^)
9(t')
(3.B.5)
where
T=.
(3.B.6)
Then
(x(t)x(0))=J
dt'J
dt"exp({t
'T
^Wt'M*"))
(3B.7)
exp (*).
(3.B.8)
44
Polymer
Viscoelasticity
R n + i + R n _ i  2 R n by d2Kn/dn2;
Then Eq. (3.31) is rewritten as
3kT 9 2 R
dUn
..
. ^ .
In rewriting Eqs. (3.32) and (3.33) in the continuous form, we note that
they are included in Eq. (3.C.1) if we define two hypothetical beads Ro and
R^v+i &s
Ro = R i ;
R N + I = RAT
(3.C.2)
= 0;
dn
= 0.
(3.C.3)
n=N
Equation (3.C.2) or (3.C.3) serves as the boundary condition for the differential Eq. (3.C.1), while the moments of the random forces are given in
the continuous limit by
<gn(*)> = 0
(3.C.4)
and
(9na(t)gm0(t'))
2kT
= r6(n
 m)Sa05(t
 t').
(3.C.5)
N.
( )
'
1/2
oo
E x "(*) c o s (^)
q=l
with q = 1,2,
(3c6)
Polymer Chain
45
Dynamics
j T R(t) cos ( ^ j dn
{(2/N)1/2
(3.C.7)
and the coordinate Xo() represents the position of the center of mass Hc(t),
i rN
Rc(t) = J Rn(*)dn = X0(t).
(3C.8)
\ 1/2 oo
/ 29 \ 1 / 2 ^ , 9 X g ( i )
/g7rn\
(*)
x
'
(  )
q=l
1 / 2
 ( f )
X , ) s ( ^ )
+ g
( t ) .
(3.C.9)
AT
Performing the integration JrQ dn on the both sides of Eq. (3.C.9) and
following a procedure similar to the discrete case, the same diffusion constant (Eq. (3.41)) can be obtained.
Multiplying both sides of Eq. (3.C.9) by (2/N)1/2 cos(pirn/N) and then
performing the integration JQ dn, we obtain
xp(*) = Z~ (jf)\(t)
+hp(t)
(3.C.10)
where
KM
=()
(3.C.11)
(3.C.12)
 t').
(3.C.13)
46
Polymer
Viscoelasticity
different modes are independent of each other (Eq. (3.C.13)), the motions
of the Xp's are also independent of each other. Thus,
(Xpa(t)Xq0(Q))
= Sa05pq^^
exp (~\
(3.C.14)
^rp=l,2,....
(3.C15)
where
CN2b2
^ = s k v
n
?
 Ro(*)
(3.C.16)
W =  2 (jj)
Using Eqs.
(3.C.14) and (3.C.17),
(R(i) R(0)) is then derived as
<R(i).R(0)> =  
v(t)
(3C17)
the timecorrelation
function
<Xp(t).Xp(0))
p=odd
p=odd
'
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
47
Lin, Y.H., and Wang, C. H., J. Chem. Phys. 66, 5578 (1977).
Wang, C. H., and Lin, Y.H., J. Colloid Interface Sci. 63, 270 (1978).
Lin, Y.H., Fyta, G., and Chu, B., J. Chem. Phys. 75, 2091 (1981).
Lin, Y.H., and Lai, C. S., Macromolecules 29, 5200 (1996).
Ewen, B., and Richter, D., Neutron Spin Echo Investigations on the Segmental Dynamics of Polymers in Melts, Networks and Solutions, in Advances in
Polymer Science 134, 1 (1997).
Doi, M., J. Polym. Sci., Polym. Phys. Ed. 18, 1005 (1980).
Lin, Y.H. (a) Macromolecules 17, 2846 (1984); (b) 19, 159 (1986); (c) 19,
168 (1986); (d) 20, 885 (1987).
Lin, Y.H., J. Rheology 29, 605 (1985).
Lin, Y.H., J. NonNewtonian Fluid Mech. 23, 163 (1987).
Bueche, F., J. Chem. Phys. 48, 1410 (1968).
Mills, P. J., Green, P. F., Palmstrom, C. J., Mayer, J. W., and Kramer, E. J.,
Appl. Phys. Lett. 4 5 , 958 (1984).
Green, P. F., Palmstrom, C. J., Mayer, J. W., and Kramer, E. J.,
Macromolecules 18, 501 (1985).
Antonietti, M., Coutandin, J., Grutter, R., and Sillescu, H., Macromolecules,
17, 798 (1984).
Callaghan, P. T., Principles of Nuclear Magnetic Resonance Microscopy,
Oxford Univ. Press (1991); Tirrel, M., Rubber Chem. Technol. 57, 523 (1984);
Lodge, T. P., Rotstein, N. A., and Prager, S., Advances in Chemical Physics
L X X I X (eds. I. Prigogine and S. A. Rice), Wiley, New York (1990), and
references therein.
Lin, Y.H., Macromolecules 18, 2779 (1985); 24, 5346 (1991).
Rouse, P. E., Jr., J. Chem. Phys. 21, 1271 (1953).
Einstein, A., Ann. Phys. 17, 549 (1905); 19, 371 (1906).
van Kampen, N. G., Stochastic Processes in Physics and Chemistry, NorthHolland, Amsterdam (1981).
Lax, M., Rev. Mod. Phys., 38, 541 (1966); Zwanzig, R., Adv. Chem. Phys.,
15, 325 (1969); Ermak, D. L., and McCammon, J. A., J. Chem. Phys. 69,
1352 (1978); Yang, D.J. and Lin, Y.H., Polymer 44, 2807 (2003).
Crank, J., The Mathematics of Diffusion, Oxford Univ. Press (1975).
Doi, M., and Edwards, S. F., The Theory of Polymer Dynamics. Oxford
Univ. Press (1987).
Zimm, B. H., J. Chem. Phys. 24, 269 (1956).
Batchelor, G. K., An Introduction to Fluid Dynamics, Cambridge Univ. Press
(1970).
Bird, R. B., Curtiss, C. F., Armstrong, R. C , and Hassager, O., Dynamics
of Polymeric Liquids, Vols. 1 and 2, (2nd edn) Wiley, New York (1987).
Flory, P. J., J. Chem. Phys. 17, 303 (1949).
Flory, P. J., Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca
(1953).
de Gennes, P. G., Scaling Concepts in Polymer Physics, Cornell Univ. Press,
Ithaca (1979).
Lin, Y.H., and Luo, Z.H., J. Chem. Phys. 112, 7219 (2000).
48
Polymer Viscoelasticity
35. King, T. A., Knox, A., and McAdam, J. D. G., J. Polym. Sci. Polym. Symp.
44, 195 (1974).
36. Han, C. C , and Crackin, F. L., Polymer 20, 427 (1979).
37. Nose, T., and Chu, B., Macromolecules 12, 590 (1979).
38. Schmidt, M., and Burchard, W., Macromolecules 14, 210 (1981).
39. Adachi, K., and Kotaka, T., Macromolcules 20, 2018 (1987).
40. Lin, Y.H., and Juang, J.H., Macromolecules 32, 181 (1999).
41. Ferry, D. J., Viscoelastic Properties of Polymers (3rd edn), Wiley, New York
(1980).
Chapter 4
Linear Viscoelasticity
4.1
Introduction
49
50
Polymer
Viscoelasticity
Stress and strain expressed in the tensorial forms, which are essential to
the molecular rheological theories as studied in the later chapters, will be
discussed in Chapter 5. For the phenomenological description in the linear
region, it is sufficient to discuss the stressstrain relation in terms of scalar
quantities.
4.2
Maxwell Equation
We begin by giving a simple explanation for the physical meaning of viscosity and elasticity. In Fig. 4.1, it is shown that a layer of simple liquid is
sandwiched between two parallel plates of area A, and of distance d apart.
If the upper plate under the application of a constant force / is moving at
a constant speed v relative to the lower plate in the direction parallel to
the plate surface, we can define the shear deformation rate by
<>
(43)
Here, the sign is chosen by defining a as the stress exerted by the system
to the external. If the viscosity value is independent of the shear rate, the
liquid is called a Newtonian fluid. Liquids of small molecules in general
belong to this category.
For elasticity, we consider a piece of solid material with top and bottom
areas A and height h as shown in Fig. 4.2. If a constant shear force, / ,
T
d
Fig. 4.1 Shear of a simple fluid sandwiched between two parallel plates, with a distance
d apart; and the upper plate moving at a velocity v relative to the lower plate.
Linear
Viscoelasticity
51
\\
Fig. 4.2 Shear of a rectangular material block, with a height h; and a displacement s
of the upper surface relative to the lower one.
is applied to the top and bottom surfaces, the relative position of the two
surfaces can be displaced by a certain distance, s. Then the shear strain is
defined by
A=
(4.4)
(45)
According to the definition for a Hookean solid, the stress is linearly proportional to the strain
G = l
(4.6)
where the proportional constant G is the modulus of the solid. Most metals
and ceramics behave as Hookean solids under small deformations.
Mechanically, we may use a dashpot to represent the viscous property
and a harmonic spring to represent the elastic property. In the Maxwell
model, the dashpot and the spring are connected in series as shown in
Fig. 4.3 to represent the viscoelastic nature of the system. When such a
combination is shortened or elongated under a pushing or pulling force, the
dashpot dissipates the energy while the spring stores the energy. We divide
the total length of the system D into two parts: D\ for the spring portion
and Z?2 for the dashport portion. Corresponding to Eq. (4.6), we write
(Di  D0)
(4.7)
52
Polymer
D,
Viscoelasticity
+
D,
tjmmmm?
Fig. 4.3
*F
(4.8)
dD2/dt
where F is the tensile force on the system to counteract the force applied
to elongate or to shorten the total length D of the system, and D0 is the
length of D\ at which the spring potential is at its minimum. Then from
Eqs. (4.7) and (4.8), it follows that
dD
d,
\_dF_ F
G~dt+~^
(4.9)
i}_dF_
G~dt ~
dD
^'dt
(4.10)
(4.11)
with
(4.12)
Equation (4.11) is called the Maxwell equation; and T, as given by
Eq. (4.12), is the relaxation time of the viscoelastic system. The relaxation
time plays an important role in determining whether the system behaves
more as a Newtonian fluid or as a Hookean solid. If r is very large and
Linear Viscoelasticity
r(da/dt)
53
= A
(4.13)
which, using Eq. (4.12), becomes the Hookean Eq. (4.6). On the other
hand, if r is small, and r(da/dt) <C a, Eq. (4.11) is approximated by the
Newtonian fluid Eq. (4.3). Thus, the Maxwell Eq. (4.11) is expected to be
capable of describing the viscoelastic behavior of a system which is between
the two limits: the Newtonian fluid and the Hookean solid.
Equation (4.11) is an inhomogeneous firstorder linear differential equation of cr{t). By multiplying both sides of Eq. (4.11) by an integration
factor exp(t/r), the Maxwell equation can be easily transformed into the
integration form
a(t) =  J
Gexp (zp\
x(t')dt'
(4.14)
= f*  exp (z?X\
X(t')dt'
(4.15)
where
\(t') = X(t,t')=
\(t")dt".
(4.16)
The total strain X(t,t'), as defined by the above equation, uses the time
t' = t as the reference point, i.e. X(t, t) 0.
Because of the large number of intramolecular degrees of freedom in a
longchain molecule, the polymer often contains many modes of motions
with different relaxation times. We have seen the expression in terms of
the normal modes for the time correlation function of the endtoend vector, (R(t) R(0)), in Chapter 3. As a result, it is often necessary to take
many relaxation times to adequately describe the viscoelastic behavior of
a polymer system phenomenologically. The Maxwell equation may be generalized to contain a distribution of relaxation times. Mechanically, the
generalization is equivalent to arranging many of the dashpotspring combinations with different values of 77 and G together in parallel, as shown
in Fig. 4.4. Corresponding to the arrangement of dashpots and springs in
54
Polymer
Viscoelasticity
> F
*
*
*
^m^Fig. 4.4 Generalized Maxwell model as represented by multiple dashpotspring combinations (Fig. 4.3) in parallel.
Ti
Ti
(4.18)
and
Vi
Gi
(4.19)
Just as Eqs. (4.14) and (4.15) were obtained, Eqs. (4.17)(4.19) can be
written in the integration forms:
(**') A(t')d*'
(4.20)
(**') A(t')dt' 
(4.21)
J oo
and
"O=r
Gi
exp
J oo
The arrangement of dashpotssprings shown in Fig. 4.4 represents a phenomenological model. We may write Eqs. (4.20) and (4.21) in the
Linear Viscoelasticity
55
general forms:
a(t) =  I
G{t t')X(t')dt'
(4.22)
J OO
and
a(t) = f
M(t t')\{t')dt'.
(4.23)
J OO
G(t) is often referred to as the relaxation modulus and M(t) as the memory
function; they are related as
M(t) = Git).
(4.24)
To build molecular models for obtaining the functional form of G(t) and
its relaxation times as a function of chain structure: molecular weight and
chain branching is a very challenging research field, and has been actively
pursued since the mid1900s. Nevertheless, successful models for the linear
polymer have been developed. In the later chapters, the Rouse theory for
the entanglementfree region, the DoiEdwards theory 5 for the entanglement region and the extended reptation theory 6 developed on the framework of the DoiEdwards theory will be studied.
4.3
Instead of using the generalized Maxwell picture, Eq. (4.22) can be obtained
from a more formal argument, namely Boltzmann's superposition principle.
It assumes that if the stress at the present time t is caused by a step
strain at an earlier time t', the stress is linearly proportional to the strain,
and the proportionality (the modulus) decreases with the separation of
the time, t t'. The modulus, a decaying function of t t', is denoted
by G(t t'). Consider a system which has been inflicted by small step
strains at different times, ti,*2, before the present time t. According to
Boltzmann's superposition principle, all the stresses as individually caused
by these small step strains are independent of each other. As a result,
the total stress at t is simply the sum of these stresses.
a(t) = ^G(tti)A\(ti)
(4.25)
56
Polymer
Viscoelasticity
where AA(<j) represents the small step strain applied at tt < t. We can
regard any strain history before t a s a sum of small strain changes, each
of which has occurred within very short intervals. Thus, Eq. (4.25) can be
rewritten as
a(t) = X>(it')^?At'.
(4.26)
In the limit of At' > 0, Eq. (4.26) can be written in the integration form
identical to Eq. (4.22).
We have used the generalized phenomenological Maxwell model or
Boltzmann's superposition principle to obtain the basic equation (Eq. (4.22)
or (4.23)) for describing linear viscoelastic behavior. For the kind of polymeric liquid studied in this book, this basic equation has been well tested
by experimental measurements of viscoelastic responses to different rateofstrain histories in the linear region. There are several types of rateofstrain
functions \(t) which have often been used to evaluate the viscoelastic properties of the polymer. These different viscoelastic quantities, obtained from
different kinds of measurements, are related through the relaxation modulus G(t). In the following sections, we shall show how these different
viscoelastic quantities are expressed in terms of G(t) by using Eq. (4.22).
4.4
Relaxation Modulus
 f
G(tt)dt
(4.27)
By applying the L'hospital rule or the property of the Dirac delta function
(see Appendix l.A) to Eq. (4.27)
a(t) = X0G(t).
(4.28)
Linear Viscoelasticity
57
Xo "
e o
time
<T(t)
e o
time
Fig. 4.5 Stepstrain stress relaxation experiment: (a) a constant strain Ao is applied
at time t = 0 (e 0) and maintained for all times t > 0; (b) the stress relaxation a{t)
responding to the applied step strain.
Polymer
58
"""1
'1
Viscoelasticity
' """1
' * """I
1 1 Nil
\*
^ s S T M t a i ^ v w . _
X"*.
=

3
T3
O
2
OS
X
JS
'f^SFP^y*"
CO
.= m
!

.*
r
~

P7
FA
4
F2
.
F10
NBS
L3
z
"

F40
10"'
i'
i t mil
I_IJ mil
10 u
1i i 11ml
il
i i.i j i i l l
10^
Time (sec)
1I_I_L
10"
ml
1 L _ l _U
IU
10u
Fig. 4.6 Relaxation modulus for nearly monodisperse polystyrene melts. Molecular
weight ranges from Mw = 1.67 x 10 4 (F2) to Mw = 4.22 x 10 5 (F40). Reproduced from
Ref. 6(b).
4.5
S t e a d y  S t a t e Shear Flow
The stress as defined by Eq. (4.3) corresponds to the stress arising from
a shear rate which has been maintained at a constant value Ao for a long
time. Thus, from Eq. (4.22) we obtain the steadystate shear stress as
a(t) = A 0 f
G(t  t')dt'
J OO
/OO
= Ao /
Jo
G{s)ds.
(4.29)
From the comparison of Eqs. (4.3) and (4.29), the viscosity is related to
G(t) as
/OO
V = Vo
/
Jo
G{t)dt.
(4.30)
Linear
Viscoelasticity
59
4.6
DynamicMechanical Spectroscopy
Rich and reliable viscoelastic data can be obtained from measuring the
dynamic mechanical response of the polymeric liquid to a rateofstrain
\(t) which is harmonically oscillatory:
\(t) =Xcos(ujt).
(4.31)
(4.32)
60
Polymer
Viscoelasticity
1.0
Poly(dimethyl
siloxane)
O
_
Poly(isobutylene]
Poly(ethylene)
Poly(butadiene)
Poly(tetramethyl
psilphenylene
siloxane)
Poly(methyl
methacrylate)
Poly(ethylene
glycol)
Poly(vinyl acetate
Ploy(styrene)
I
0
1
log 10,7X
Fig. 4.7 Steadystate viscosity of various polymers in melt, where Xw is a parameter
proportional to Mw. The curves are shifted vertically so as not to overlap each other.
Reproduced, by permission, from Ref. 7.
Linear Viscoelasticity
61
(4.33)
where
/OO
rf{w)=
l
Jo
G{s)cos(ojs)ds
(4.34)
G(s) sin(ws)ds.
(4.35)
and
/OO
f/"(a;)= /
T/'(W)
 tT/"(o;) = /
Jo
G(s) exp(io;s)ds.
(4.37)
As shown in Fig. 4.8, X(t) (Eq. (4.31)) and a[t) (Eq. (4.33)), both being
sinusoidal, have a phaseangle difference. We can express these two quantities, respectively, as
A(t) = Re[Aexp(twt)]
(4.38)
(4.39)
where Re indicates taking the real part of the complex variable in [...].
With Eq. (4.31) as the form for \(t), A0 in Eq. (4.38) is a real number.
In contrast to A0 being real, <J in Eq. (4.39) is a complex number for a
viscoelastic material. The relation between a0 and A0 can be obtained by
the following:
Given the definition of Eq. (4.37) for 77*(u>), Eq. (4.33) is equivalent to
a{t) = Re[rj*(Lj)X exp(iojt)}.
(4.40)
62
Polymer
Viscoelasticity
X(t) o
CT(t)
o
0
cot
Fig. 4.8 T h e oscillatory rateofstrain X(t) and stress <r(t) with a phase difference * for
a viscoelastic fluid.
(4.41)
In terms of the complex viscosity 77*, the phase difference between the
stress and the rateofstrain can be expressed. Generally the stress induced
by the rateofstrain given by Eq. (4.31) can be written as
a(t) = Acos(ut
 $)
(4.42)
(443)
(4.44)
.4sin$ = r/'A.
(4.45)
Thus, 77' represents the viscous contribution to the stress, i.e. the component in phase ($ = 0) with the rateofstrain, and is related to the
dissipation of energy. And, ry" represents the elastic contribution to the
Linear
63
Viscoelasticity
stress, i.e. the component out of phase ($ = 7r/2) with the rateofstrain,
and is related to the storage of energy. The combination of Eqs. (4.44) and
(4.45) can be expressed as
A = v V 2 + r]"2\
(4.46)
$ = tan1
(4.47)
.V.
Thus, it is clear that rf(u) and r)"(uj) contain the same information as
the oscillation amplitude A of the stress and the phase shift $ at the frequency ijj.
Another oftenused viscoelastic quantity, the complex modulus, is
defined by
G*(u) = iur]*(cj) = G'(u) + iG"(uj)
(4.48)
= u)T]"(u}) = u /
Jo
the loss modulus
G'{UJ)
and
G"(LJ)
G{s) sm(tjs)ds
(4.49)
TOO
G"(u>) =
G(S) cos(u:s)ds.
Jo
The ratio of G" to G' is often referred to as the loss tangent
(4.50)
OJT)'(LJ) =UJ
G"
tan6 =
n'
& r
{4 51)
The measured G' and G" (or equivalently r[ and rj") values, as a function
of the frequency u), can be displayed as a spectrum the viscoelastic spectrum. Figures 4.9 and 4.10 show the storage modulus spectra G'(w) and
the loss modulus spectra G"(ui), respectively, of a series of nearly monodisperse polystyrene samples. 10 The shape of a storage modulus spectrum is
basically the mirror image of its corresponding relaxation modulus G(t);
and a G'(u>) spectrum (or G"(ui)) contains the same information as its
corresponding G(t).
4.7
SteadyState Compliance
The scheme for carrying out the measurement of the steadystate compliance is shown in Fig. 4.11. Before t = 0, the polymeric liquid is in
Polymer
64
Viscoelasticity
160C
^
E
He
^y/
ID
c
>>5
/
/o
of
CD 4
^ 3
LI 1 '
/ / J L" U7
L15
L1
L5
uc
L12
1/
V
1
1
logcooj , sec'1
Fig. 4.9 Storage modulus vs. frequency for nearly monodisperse polystyrene melts.
Molecular weight ranges from Mw = 8.9 X10 3 (L9) to Mw = 5.8 x 10 5 (L18). Reproduced,
by permission, from Ref. 10.
J? = 
Ao
(4.52)
(4.53)
Linear
Viscoelasticity
65
160 L.
Pi)
E
o
"5 6
a>
c
>.
5
aP
vj$(y
L18 </flT
L19
b 4
o
jg
/
L5 '
' y'
L15
L37
L16
L27
I///
y3
ff
*f
*?
d.
L12
L14
4
.9
 3  2  1
0
1
logooa T , sec"1
Fig. 4.10
Thus
/oo
A0 = / (A(i') Jo
k^dt'
(4.54)
a0 =  f G(t  t')k(t')dt'.
Jo
(4.55)
G(tJ OO
t')Aoo dt'
(4.56)
where the lower limit of the integration is 00, because reaching the steadystate region requires time that lasts longer than the longest relaxation time
66
Polymer
(a)
Viscoelasticity
crm
T
o
time
^ x + xt
X(t)
(b)
X.
o
time
Fig. 4.11 Creep experiment: (a) a constant stress cro is applied at time t = 0 and
maintained for all times t > 0; (b) the strain measured relative to t = 0 increases with
time. The dashed line is extrapolated from the strain in the steadystate region, whose
intersection with the vertical axis at t = 0 gives AQ.
of the polymeric liquid, and waiting for such a long time is, in effect, equivalent to regarding the shear history as infinitely long.
Combining Eqs. (4.55) and (4.56), we have
Aoo /
Joo
t')X{t')dt'.
(4.57)
J0
Aoo /
Jo
ft
(4.58)
ft
/
G{s)ds = / G(s)[\{t  s)  \oo]ds.
(4.59)
67
Linear Viscoelasticity
( /
dt\ G(s)ds = I
G(s) ( f
[X(t  s)  * , ] * ) ds.
(4.60)
By substituting z = t  s and Eq. (4.54) into the right side of Eq. (4.60),
we obtain
*oo
Aoo /
Jo
/oo
sG{s)ds=
Jo
/oo
G(s)
[A(z)Aoo]dzds
Jo
/OO
= A0 /
G(s)ds
Jo
= Aoift)
(461)
0o = %Aoo
(462)
f0tG(t)dt
f0tG(t)dt
68
Polymer
Viscoelasticity
~
^
a(k
J^
6
E
o
O
O
7
*'
.o
0"
8 0
LOG Mw
O PlazekO'Rourke
3 Murakami ef a/.
Akovali
MillsNevin
) O'ReillyPrest
Tobolsky et al. Nemoto
CD Onogi ef al.
Q MierasRijn
in Chapter 10; the apparent agreement with the Rouse model shown in
Fig. 4.12 is a coincidence.
If we assume that the relaxation modulus has a certain distribution {Ai}
of relaxation times {T^}, i.e.
G(t)
G(0)
= 5>axp(i)
(4.64)
(4.65)
Linear
69
Viscoelasticity
and
jo
e_
g(0)^TJ
(G(0)E,^)
1 (r)
2
G(0)<r)"
Because zeroshear viscosity is related to the first moment of the relaxationtime distribution (T), while steadystate compliance is related to the
second moment of the distribution (T 2 ), the latter is much more sensitive to the molecularweight distribution of the polymer sample than the
former.
In summary, if G{t), which is contained in Eqs. (4.30), (4.34), (4.35),
(4.46), (4.47), (4.49)(4.51) and (4.63), is known, all the linear viscoelastic
quantities can be calculated. In other words, all the various viscoelastic
properties of the polymer are related to each other through the relaxation
modulus G(t). This result is of course the consequence of the generalized
Maxwell equation or equivalently Boltzmann's superposition principle. The
experimental results of linear viscoelastic properties of various polymers
support the phenomenological principle. 6 ' 8 Some viscoelastic properties
play more important roles than the others in certain rheological processes
related to polymer processing. Thus, in practical applications, it is more
convenient to measure them directly. In a nonlinear rheological process,
the linear viscoelastic relations as discussed in this chapter are no longer
applicable.
An important aspect of linear viscoelastic properties is their close relations to the molecular structure of the polymer, such as molecular weight,
molecularweight distribution, and chain branching. For linear polymers,
the molecular theories developed so far have been very successful in explaining the relations, as will be studied in Chapters 711. On the other hand,
linear viscoelastic behavior must gradually merge into nonlinear behavior as the strain or rateofstrain increases. Thus, the understanding of
linear viscoelastic behavior enlightens the study of the more complicated
nonlinear viscoelastic behavior. The major chain dynamic processes that
affect nonlinear viscoelastic behavior, and their relations with the dynamic
processes responsible for linear viscoelastic behavior, will be studied in
Chapter 12.
References
1. Rouse, P. E. Jr., J. Chem. Phys. 21, 1271 (1953).
2. Maxwell, J. C , Phil. Trans. Roy. Soc. A157, 49 (1867).
70
Polymer Viscoelasticity
Chapter 5
In the last chapter we discussed the relation between stress and strain
(or instead rateofstrain) in one dimension by treating the viscoelastic
quantities as scalars. When the applied strain or rateofstrain is large, the
nonlinear response of the polymeric liquid involves more than one dimension. In addition, a rheological process always involves a threedimensional
deformation. In this chapter, we discuss how to express stress and strain in
threedimensional space. This is not only important in the study of polymer rheological properties in terms of continuum mechanics 13 but is also
essential in the polymer viscoelastic theories studied in the later chapters,
into which the chain dynamic models are incorporated.
5.1
Stress
(5.1)
Polymer
Viscoelasticity
Fig. 5.1 A plane cutting through a volume element dV at the point p. T h e direction
of the plane is represented by the unit vector n; and a surface force fn is exerted on the
plane.
where the stress components are expressed in terms of the symbol T with
two subscripts. The first subscript represents the direction of the plane
onto which the stress is applied and the second subscript represents the
direction of the stress component. If another plane with the direction c
cutting through the point p is chosen, a stress t c with the components
Tcc, Tc(, and Tca exerting on the new chosen plane can in the same way be
defined.
To any chosen plane, we can express the normal and shear stress components in terms of the symbol system given above. For any two chosen
planes at the point p, the stresses exerted on them are related. The stress
on any chosen plane at the point p can be obtained from a physical quantity called the stress tensor. The stress tensor is also a special device for
mathematical derivation which allows the stress state at any point in the
fluid body to be described. 4
The meaning and use of the stress tensor are discussed in the following:
In the close vicinity of the point p, three planes perpendicular to each other
can be erected as shown in Fig. 5.2. Let the directions of the three planes
be x, y, and z. The stresses on these three planes are denoted by t x , ty
and t z , respectively. Each of these three stresses has three components.
For instance, t x has Txx, Txy and Txz. Now we consider a plane which
cuts across the three planes and forms a tetrahedron with the three planes
enclosing the point p, as shown in Fig. 5.2. We denote the direction of the
plane as n. The total force experienced by the tetrahedron has to be zero;
otherwise, the body will accelerate.
Stress and
73
Strain
Fig. 5.2 Tetrahedron at the point p with three surfaces of directions x, y, z perpendicular to one another. T h e stresses on the four surfaces are denoted by t x , ty, tz and t n ,
respectively.
Let the areas of the four surfaces of the tetrahedron be Sn, Sx, Sy and
Sz respectively. From the balance of the forces from the four surfaces,
*"n&n *x&x ~r ZyOy r t,zDz
(5.2)
n xon .
(5.3a)
Similarly,
Sy = n ySn
(5.3b)
Sz = n zSn .
(5.3c)
(5.4)
By shrinking the size of the tetrahedron to zero at the point p, the stresses
contained in Eq. (5.4) become the fixed values at p. When both sides are
divided by Sn, Eq. (5.4) becomes
t = n (xt x + y t y + zt z )
(5.5)
74
Polymer
Viscoelasticity
With tx, ty, and tz expressed in terms of their components (Eq. (5.1)),
Eq. (5.5) is rewritten as
t n = n (xxT x x + xyTxy + xzTxz + yxTyx + yyTyy + yzTyz
+zxTzx + zyTzy + zzTzz).
(5.6)
(5.7)
0\
0 J
Pj
(5.8)
6 = J2Y, i i
i
=
\0
0 0\
X
<59)
0 1/
(5.10)
75
(5.11)
(5.12)
and
need be considered. As the third difference value (Tn T33 or Tn T33) can
be obtained from Eqs. (5.11) and (5.12), there are only two independent
difference values.
The stress tensor is expected to be symmetrical; i.e. Tij = Tji for i ^ j .
This can be shown by considering the two shearstress components, T13 and
T31, applied on a cube, as shown in Fig. 5.3. The two shearstress components must balance out, i.e. T13 = T31; otherwise the cube will start
accelerating around the 2 direction. Similarly, T12 = T21; and T23 = T32.
Thus, the stress tensor is symmetrical and has only six independent components. For expressing the symmetricity of the stress tensor, we write
T = TT
(5.13)
Fig. 5.3 If the two shearstress components T13 and T31 are not equal, the cube will
rotate about the S2 direction.
76
5.2
Polymer
Viscoelasticity
Finite Strain
(dX'dX')1/2
(5.14)
dX'
dX'
(5.15)
Here, we use the apostrophe mark " /" to indicate the state of the material
body at a certain time t' in the past. Let the material body be changed to
the shape shown in the right of Fig. 5.4. Both the p and q points change
their positions as a result of rotation and/or deformation of the material
body. The vector dX' between p and q is deformed to become dX. The
change in dX with respect to dX' is called the deformation gradient which is
expressed by the dyad ( V ' X ) T (see Appendix 5.A), and is often represented
at time t'
at time t
1
Fig. 5.4 T h e deformation between two neighboring points, p and q, in a piece of material
under deformation.
77
by a tensor symbol E:
\ T
E = (V'X)i =
ISMS
^#
(516)
or
dXi
dX'j '
E,13
X = X(X',t).
Then
dX = E dX'
dX = dX' E T .
(5.18)
Three examples are given below to illustrate the operations of the deformation gradient tensor. Consider a rectangular block of material with
dimensions Ax'lt Ax 2 , and Ax 3 , as shown in Fig. 5.5(a). A Cartesian
coordinate system can be chosen with one of the corners as the origin and
three unit vectors Si, S2, and S3 pointing in the three orthogonal directions of the block. In this coordinate system, the position vector of a point
p inside the material body is denoted by X ' = S\X[ + S2X2 + ^3X3.
(a)
Uniaxial
extension
In the uniaxial extension as shown in Fig. 5.5(b), the block (Fig. 5.5(a)) is
elongated Ai times in the ($1 direction. The block is transformed to have the
dimensions Ax\, Ax2, and AX3, and the position of the point p is changed
to X with three components given by
X!
Axi
jX1
x2
Ax2 ,
Ax^2
Axi
AX
x* =
= AiXj
A2X2
3 y, _ ;,
y,
(5.19)
78
Polymer
Viscoelasticity
Axi
Ax,
Axi
Fig. 5.5 (a) A rectangular block of material at rest, (b) T h e block under uniaxial
extension, (c) The block under simple shear deformation, (d) The block rotated.
E=
f\x
I 0
A2
(5.20)
\2)
(5.21)
79
Ai
0 \
1
(5.22)
E =
/AT/
Simple
shear
For a simple shear as shown in Fig. 5.5(c), the top plane of the block sliding
along the Si direction over a distance, a, with reference to the bottom plane
Xi = X1 +
X2 Xl + \X2
(5.23a)
X<2 = X2
(5.23b)
X3 = X3
(5.23c)
where A = a/Ax'2 is the simple shear strain. Substituting Eq. (5.23) into
Eq. (5.16), we obtain
(5.24)
E =
for simple shear.
(c)
Solidbody
rotation
Consider the rectangular block shown in Fig. 5.5(a) as a rigid (solid) body.
A rotation of the solid body around the 3 direction is shown in Fig. 5.5(d).
For a rotational angle 9,
Xj.
= X l C o s 0  X sin#
x2 = X[sm0
x 3 = x'z.
+ X2 cos 9
(5.25a)
(5.25b)
(5.25c)
J
(5.26)
80
Polymer
Viscoelasticity
For a solidbody rotation, the material body is not deformed; the distance
from the origin of the coordinate system to the p point does not change.
Yet for a solidbody rotation, E ^ 0, according to Eq. (5.26). The tensor
E describes a situation involving deformation [cases (a) and (b)], rotation
[case (c)], or both. A way to eliminate the rotational element needs to be
found.
Related to the deformation of the material body is the change in length
of dX'. We define the length ratio of the change from dX' to dX as
IdXI
" = i*
<527)
M =
dXdX
(ErfX')(ErfX')
dX'dX'
dX'ETEdX'
\dX'\2
= u' C u'
(5.29)
where Eq. (5.15) has been used for the last equality and C, called the
Cauchy tensor, is given by
C = E
E.
(5.30)
The Cauchy tensor is a device for describing the change in length at any
point of the material body. Equation (5.29) indicates that in performing
such a function the Cauchy tensor operates on the unit vector u' at some
time t' in the past. However, the stress tensor is always measured with
respect to the present form of the material body or the deformed state.
Thus, there is the need to find a deformation tensor that operates on the
unit vector at the present time. This can be done by using the inverse of
E, E _ 1 , to express dX' in terms of dX, namely,
dK' = H1dX
(5.31)
E  1 = (VX')T
(5.32)
where
81
2_
dXdX.
_
1
~dX.(Ei)rEi.dX = u . B  i . u
where
(5.35a)
or
B =E E
(5.35b)
A direct way for obtaining the Finger tensor, which also describes the
deformation, is to consider the change in a local area. In Fig. 5.4, we can
follow the change of either the area dA' or the length dX' to achieve the
same purpose. dA' and dX' are related by the volume dV
dV = dA' dX'.
(5.36)
Just as Eq. (5.27) defines the length ratio of the change from dX' to dX,
we can define the area ratio of the change from dA' to dA as
&
or
dAdA
dA' dA'
(5.39)
(5.40)
(5.41)
82
Polymer
Viscoelasticity
v2 =
(5.42)
Using the Finger tensor as defined by Eq. (5.35), Eq. (5.42) is rewritten as
1
(5.43)
nBn
where
dA
n
(5.44)
]dA\
(a)
Uniaxial
extension
Ai
0
C = B
/A?
o \
o \ Ai
/AT/
v/AT
0
/AT/
0\
(5.45)
Al
AT/
(b)
Simple
83
shear
With E given by Eq. (5.24), Eqs. (5.30) and (5.35) become, respectively:
(5.46)
'I A 0\ / l 0 0\
0 1 0j IA 1 0
t,0 0 1/ \ 0 0 1,
'1 + A2 A 0\
A
10).
0
0 1/
(c)
Solidbody
(5.47)
rotation
The substitution of Eq. (5.26) into Eqs. (5.30) and (5.35) gives
(5.48)
Both the Cauchy and Finger tensors are unit tensors. This means that, as
expected, the solidbody rotation does not deform the material.
5.3
A neoHookean Material
In Chapter 4, we discussed Hooke's law (Eq. (4.6)) for a small strain in one
dimension. As long as the applied strain is very small, Eq. (4.6) is valid
for a solid material. Here, we generalize it in three dimensions. It appears
logical that the stress tensor is linearly proportional to the deformation
tensor, 5 that is,
r = GB .
(5.49)
84
Polymer
Viscoelasticity
Here the sign is chosen by taking compression to be positive. For an incompressible material, the total stress tensor is given by
T = PS  GB .
(5.50)
IP  G\\
(5.51)
G
'33
= G[Xi Ai
(5.52)
e < 1.
(5.53)
(5.54)
e^0
(5.55)
(5.56)
85
Applying the neoHookean Eq. (5.50) to the simple shear deformation case,
we obtain from Eq. (5.47)
Ti2 = T 2 i = GX
(5.57)
Tn T22 GX
(5.58)
and
122
T33=0.
(5.59)
The above results indicate that the stressstrain relation is linear for
the shear component (Eq. (5.57)) while the first normalstress difference
becomes very large when the applied shear strain A is greater than 1
(Eq. (5.58)). The occurrence of the first normalstress difference is unexpected from the viewpoint of linear viscoelasticity (Eq. (4.6)). It is related
to the socalled rodclimbing phenomenon, 1 namely, the observation that a
polymeric liquid climbs a rotating shaft.
Comparing Eqs. (5.56) and (5.57), one sees that Young's modulus is
three times the shear modulus for an incompressible isotropic solid.
5.4
A Newtonian Fluid
For a fluid that does not possess any elastic property, what needs to be
measured is the deformation rate, instead of the total strain. Such a fluid
has no memory of past deformations. Thus, we need to express the present
changing rate of the Finger tensor B , while moving the past point position
X ' in B infinitely close to its present position X. Mathematically, these
two ideas can be expressed as
jij =
J
dBi
X ' ^ X dt
lim
lim
X'X
=E
it
=
dVj
dXj
d dXi \ dXj
dtdXi
d*'k
E
k
dVj
dXk
dXi ( d dXj
dtdXl
+ dX'k
dVj
Sjk + <5i
dVi
+ dXi
dXk
(5.60)
86
Polymer
Viscoelasticity
(5.61)
or
T = PS  rji
(5.62)
where the components of the rateofstrain tensor 7 are given by Eq. (5.60).
The application of the constitutive equation Eq. (5.62) to the simpleshear case gives
P
T]j 0 \
777 P
0 J
.0
O P /
(5.63)
where
1 =
dx2
dx;
(5 64)
From Eq. (5.63), the simpleshear result in one dimension (Eq. (4.3)) is
obtained, i.e.
T12 = rff.
(5.65)
We also see from Eq. (5.63) that the Newtonian fluid does not give rise to
a normalstress difference for simple shear.
In the case of uniaxial extension,
Vi = \iXi;
fori = 1,2,3.
(5.66)
\0
0
A2
0\
0 I.
(5.67)
0 kj
g__,.V,l:0.
(.68,
Thus,
Ai+A2 + A 3 = 0 .
(5.69)
87
(5.70)
A2 = A 3 .
Ai
0
0 \
Ai
"2
(5.71)
Ai
"T7
0
(5.72)
0
from which
Tii  T22
Tn
3r;Ai
'33
(5.73)
Prom the comparison of Eqs. (5.65) and (5.73), we see that the tensile
viscosity is three times the shear viscosity. This is Trouton's wellknown
rule, which is analogous to the relation of Young's modulus being three
times the shear modulus for an isotropic incompressible material.
Appendix 5.A Tensor Operations
Here, we use Eq. (5.7) as an example for discussing the operations related
to a tensor. The dot in Eq. (5.7) represents the multiplication of a tensor
by a vector, and the product is a vector. In Eq. (5.7), the unit vector n
forms a dot product with only the left unit vector in each dyad term of
the tensor T. With n  x = nx, n  y
and n  z = n z , Eq. (5.7) is
L
v>
rewritten as
"n X ( 7 l x J x x + Tlylyx
+ z{nxTxz+nyTyz
+ f^zlzx)
1 y\JlxJxy
+ nzTzz).
"T" nyyy
4"
TlzlZy)
(5.A.1)
iyx
1 zx
T
Jxy
x
T
yy
T
zy
'xz
iyz
Tzz
(5.A.2)
88
Polymer
Viscoelasticity
(
=
J xx
*xy
lx.
lyx
Lyy
*yz
Jzx
J zy
L zz ,
[yixL xx r Tlylyx
T TlzJ zz)
(5.A.3)
In Eq. (5.A.3) the vector n at the left of the dot is represented by a row.
The multiplication of the row with the matrix forms another row, which
represents a vector. In the matrix representation, the dot product between
two vectors is represented by the multiplication of a row on the left and a
column on the right.
The tensor T may also be concisely written as
T =
i
>*;!
(5.A.4)
(5.A.5)
n TilSl
= Yl ]C i
i
= Si(niTn
+ TI2T21 + n 3 T 3 i) + S2(niTi2
+ n2T22 + n3T32)
(5.A.6)
The result of Eq. (5.A.6) is the same as those of Eqs. (5.A.1) and (5.A.3).
89
(5.A.7a)
(5.A.7b)
If T is a symmetric tensor, T = T T .
(3) The components of a tensor can be formed from the components of
two vectors, two as a pair for one component. Take two vectors v and w.
The tensor formed from v and w is called the dyadic product of v and w.
The symbol to represent it is simply vw:
vw = Y^ Y^ SiSjViWj .
i
(5.A.8)
(5.A.9)
(4) If the components of the tensor are given by the Kronecker delta 5ij
(Sij = 1 if i = j ; Sij = 0 if i ^ j), the tensor is called the unit or identity
tensor, often denoted by
s = j2J2s^s^i
( 5  A1 )
' ^kSiSijTki
Y1Y1Y1Y16JkSiSiSijTkl
i
90
Polymer Viscoelasticity
where
Ru = J2SHTJi
(5. A. 12)
The product of two tensors with two dots between them (the double dot
product) is a scalar and is denned by the following:
S : T = 2_, E
i
*'*'
^kSiSijTki
= E E E E
i
3ktiiSijTki
= J2 "
(5.A.13)
References
1. Bird R. B., Armstrong, R. C , and Hassager, O., Dynamics of Polymeric
Liquids, Vol. 1 (2nd edn), Chapter 9, Wiley, New York (1987).
2. Astarita, G., and Marrucci, G., Principles of NonNewtonian Fluid Mechanics,
McGrawHill, New York (1974).
3. Malvern, L. E., Introduction to the Mechanics of a Continuous Medium,
PrenticeHall, Englewood Cliffs, NJ (1969).
4. Aris, R., Vectors, Tensors, and the Basic Equations of Fluid Mechanics,
PrenticeHall, Englewood Cliffs, NJ (1962).
5. Rivlin, R. S., Phil. Trans. Roy. Soc. (London) A240, 459; 491; 509 (1948).
6. Treloar, R. G., The Physics of Rubber Elasticity, (3rd edn) Clarendon Press,
Oxford (1975).
7. Anthony, R. L., Caston, R. H., and Guth, E., J. Phys. Chem. 46, 826 (1942).
Chapter 6
Introduction
91
92
Polymer
Fig. 6.1
6.2
Viscoelasticity
An elastic dumbbell.
For the dumbbell, as shown in Fig. 6.1, we assume that the two beads have
an identical mass m and radius a. Their position vectors are indicated by
R i and R2, respectively. Then the "configuration vector" between the two
beads is given by
R = R2  R i .
(6.1)
We assume that the fluid system under consideration has n such dumbbells
per unit volume. Each moving bead experiences a friction force which is proportional, with an opposite sign, to the velocity difference between the bead
and the fluid flow. The proportionality constant is referred to as the friction
constant . In Chapter 3, we studied the special case where there is no fluid
flow. Here, a nonzero fluid flow velocity needs to be included for the Theological study. If the polymer chain is surrounded by the solvent, Stoke's law
gives = 6irr]sa where T]s is the solvent viscosity.6 In a concentratedsolution
or melt system, is a parameter that has absorbed all the intermolecular
and intersegmental interactions, and depends strongly on temperature, as
noted in Chapter 3. In the usual theoretical study of a dynamic problem
in the concentratedsolution or melt system, where both the hydrodynamic
interaction and excluded volume effect are absent, 4 ' 7  9 the diameter of the
bead is ignored; the bead is treated as a point, and the friction constant
just as a parameter. For describing the viscoelastic properties, the elastic
dumbbell model and the Rouse model are meanfield theories. The bulk
viscoelastic quantity is simply the sum of the statisticallyaveraged values
Viscoelasticity
93
(6.2)
(6.3)
which does not change with position, but can change with time. We can
make the homogeneousfield assumption because the size of the fluid particle is much smaller than the macroscopic lengthscale. In the homogeneous
flow, the stress tensor is also independent of position. K is a traceless
tensor for an incompressible fluid (Eq. (5.68)).
As seen in Chapter 3, the force constant on the harmonic spring is of
entropic origin. The spring forces on bead 1 and bead 2, denoted by F i
and F2, respectively, are given by
dV
Fi =
3fcT
Mri^ =
dV
ft5JSS
. ,,
(6 4)
(6.5)
(6.6)
with R2 denoting the mean square distance between the two beads (R 2 ).
The centerofmass position of the elastic dumbbell is defined by
Re = ^
(67)
= <(RC)V>(R, t)dRcdR
(6.8)
94
Polymer
Viscoelasticity
(6.9)
/ '
ip(R,t)dR=l.
(6.10)
f M(R)ip(R,t)dR.
(6.11)
Let the fluid flow velocities at the positions R i and R2 be V i and V2,
respectively (Eq. (6.2)). Based on Eq. (3.18), we can write the equations
of motion for the two beads as
C(RiV1) =  ^  ( f c T l n * + y)
=  f c T l n * + F!
<(R2V2) =  f c T ln* + F2.
(6.12)
(6.13)
Oti.2
Substituting Eqs. (6.2), (6.4), and (6.5) into Eqs. (6.12) and (6.13); and
using Eqs. (6.1), (6.7), and (6.9), we can rewrite Eqs. (6.12) and (6.13) in
terms of R c and R as
R=K.R^Ai
n V
,_^
(6 . 14)
and
RC = V 0 + K  R C .
(6.15)
Equation (6.15) indicates that the center of mass follows the fluid flow. This
result is expected from the assumption made in Eq. (6.9). The continuity
(6 16)
ik^ik
where the second equality results from direct substitution of using Eqs. (6.1)
and (6.7). With the substitution of Eqs. (6.9) and (6.15), the first term on
the righthand side of Eq. (6.16) becomes
~ndR
( R )
(6.17)
Thus, Eq. (6.16)
am^.tM.
(, 18 ,
Substituting Eq. (6.14) into Eq. (6.18), we obtain the diffusion equation
the Smoluchowsky equation for tp(R)
<*>(
wHg).
dt
dR V
C 9R
(6.19)
This equation describes how the distribution function ip(R) changes with
time under the velocity field K. When K = 0, the form of Eq. (6.19)
becomes similar to that of Eq. (3.15).
To obtain the average value of a physical quantity (M), it is not necessary to first calculate the distribution function V(R) from Eq. (6.19) and
then substitute it into Eq. (6.11). Prom Eq. (6.11)
d(M)
= f M^dR.
dt
(6.20)
/4(RWR
R
OR)
/R^.^R
< 6  21 >
95
96
Polymer Viscoelasticity
In Eq. (6.21), we have used the Gauss divergence theorem and the condition
that ip(R) = 0 on the surface at R = oo.
Substituting Eq. (6.14) into Eq. (6.21) and by using integration by parts
and the Gauss divergence theorem, we obtain
d(M)
dt
=<K1)+X<MH<SM>
<>
(6.23)
 (RS).
Q
(6.24)
To get the last term of Eq. (6.24), we use the fact that R and S are in the
same direction (Eq. (6.4)).
Defining
<RR)m = ^
~
dt
 K (RR)  (RR) K T .
(6.25)
(6.26)
With the homogeneous flow assumption, whereby V ( R R ) = 0, the definition of (RR)(i) as given by Eq. (6.25) is the same as the codeformational
time derivative or convected time derivative shown in Appendix 6.A.
When K = 0 and the fluid system is in the equilibrium state,
d/dt(KR) = 0, and Eq. (6.24) gives
(RS) e = kTS.
(6.27)
6.3
Viscoelasticity
97
T.)
+ (Pp5 +
TP)
= P5 + T
(6.28)
(6.29)
and
T = TS+Tp
= ?y s 7 + Tp .
(6.30)
In Eq. (6.30), r]s is the solvent viscosity (see Eq. (5.61)), and
7 = VV + (VV)T.
(6.31)
Contribution
from tension
in the
connector11
Consider a plane which moves with the local velocity V in the fluid. Let
the direction of the selected plane be denoted by the unit vector n. Set up
a cube which contains an average of only one dumbbell and has a volume
of 1/n. The plane cuts across the middle of the cube as shown in Fig. 6.2.
If a dumbbell with the configuration vector R is randomly thrown into the
cube (in other words, its center of mass may, with equal probability, reach
Polymer
Viscoelasticity
Fig. 6.2 A dumbbell with bond vector R intersecting an arbitrary plane (shaded) of
area ( 1 / n ) 2 / 3 in a suspension of dumbbells. The plane is moving with the local velocity
and has the direction represented by the unit vector n. The () side of the plane exerts
a force S = F2 (Eq. (6.5)) to the (+) side through the bond. The dashed lines indicate
a cube of volume 1/n.
at any point inside the cube), the probability that the dumbbell will cross
the plane is
Projection o / R along the direction ofn
side length of the cube
nR
n1/3
(6.32)
At the same time, the probability that the configuration of the dumbbell is
in the range R to R + d R is ip(R, t)dR. Thus, the probability that a dumbbell in the range R to R+cR will cross the plane is n R(n 1 / / 3 )^(R, t) eR.
If bead 2 is on the (+) side of the plane,  n  R  = n  R and the force
exerted on the (+) side from the () side is S; if bead 1 is on the (+)
side,  n  R  = nR and the force exerted on the (+) side from the ()
side is S. Thus, the expectation value of the force exerted from the () side
to the (+) side of the cube (see Fig. 6.2) through the dumbbell is
 n 1 / 3 f(nK)Sip{B.,t)dH.
(6.33)
Dividing this value by the area of the plane (1/n) 2 / 3 gives the force per
unit area
 n / (n R ) S ^ ( R , t)dH =  n n / R S ^ ( R , t)dR
(6.34)
Viscoelasticity
99
stress tensor is
n
BSi/>(R,t)dR
(6.35)
n(RS).
(b)
Contribution
due to bead
motion
Because of the momentum it carries, any bead moving across a plane will
contribute to the stress tensor. To obtain the value contributed by this
mechanism, we first ask how many " 1 " beads with velocity R i will, in a
unit time, pass through any chosen plane of area S and direction n. This
value is the product of the number of dumbbells per unit volume n and the
volume of the parallelepiped, as shown in Fig. 6.3, namely,
n[(RiVi)Sn].
(6.36)
Then the momentum carried across the shaded plane (Fig. 6.3) is
n[(RiVi)Sn]m(RiVi).
(6.37)
 V i ) ( R i  Vi)]S(Ri,Ra)dR.idR2
(6.38)
RrV,
\*v
*A*
Fig. 6.3 A bead of a dumbbell carries its momentum in crossing an arbitrary surface
(shaded) moving with the local velocity, contributing to the stress tensor.
100
Polymer
Viscoelasticity
^(RiViXRiV;)
/ / 
S(Ri, R2)dRidR2
(6.39)
t=i
J^mfoViXRiVi)
" / /
Li=l
(6.40)
Substituting the Maxwellian distribution and R, Vj = v* into Eq. (6.40),
we obtain
n
b
2nfcT5.
(6.41)
Thus the motions of the beads only contribute to the normal stress.
Combining the contributions of T and Tp, as given by Eqs. (6.35) and
(6.41), we have
T p =  n ( R S ) + 2nkTS.
(6.42)
(6.43)
(6.44)
Thus P = Ps + nkT or
Pp = nkT.
(6.45)
(6.46)
and
T = TS+TP
nsi
 n(RS) + nkTS.
(6.47)
101
By eliminating the (RS) term between Eqs. (6.26) and (6.47), we obtain
( 1
,.
(6.49)
So far, in deriving Eqs. (6.26) and (6.47), we have only used the relation
that R and S are in the same direction. By substituting the Hooke relation,
Eq. (6.4), into Eq. (6.46), we obtain
T = TP =  ^ p  (RR) + nkTS.
(6.50)
3nkT
(D = R 2  < R R > ( i )
+nkTSw
^
T
_
=
( R R ) ( i )
n f c T ^ .
(651)
(6.52)
r? = nkTs
(6.53)
where
= 7 ^
12fcT
( 6  54 )
'
Equation (6.52) has the exact form of a "convected Maxwell model." Therefore, many results from continuum mechanics can be applied to Eq. (6.52)
directly. The relevant aspects of continuum mechanics are discussed in
Appendix 6.A. The rheological tensors in Eq. (6.52) are all evaluated by
following a particular fluid particle at any "current" moment t. Since a
particular fluid point is followed, t may be replaced by a past time t'.
102
Polymer
Viscoelasticity
For a certain fluid particle (X, t), we multiply each term in Eq. (6.52) by
E ( X , t , t ' ) , which is placed on the left side, and by E(X, t,t')T, which is
placed on the right:
E(i, t') r(f) E(*, t'f
(6.55)
(656)
(657)
which is
r
=  [
^exp{(tt')/s}1{1](t,t')dt'
nkTexp[(tt')/s]y{1](t,t')dt'.
(6.58)
Joo
nkT
exp[(t  t')/s\1[0]{t,t')dt'
(6.59)
where 7[oi(M') is given by Eq. (6.A.6). Equations (6.58) and (6.59) are
different from Eqs. (4.14) and (4.15) in that the former equations, involving
three dimensions, can be used for large deformations; the latter, with stress
and strain expressed as scalar quantities, are limited to small deformations.
We shall illustrate the applications of the constitutive Eq. (6.59) in two
cases: stress relaxation following a step shear deformation and steadystate
shear flow.
(a)
Stress
Viscoelasticity
103
relaxation
For a step shear deformation applied at t' = 0, the displacement functions are
X[ = Xi
X[=Xi
XX'2
X'2 = X2
for
X3 = X3
all t'
for all t'.
and
E=
/I
(I
A 0'
A0\
1 0
0 1
Vo
(6.60)
(6.61a)
(6.61b)
(6.62a)
and
7[0]
A2  A 0
= A
A 00 00
V 00
00 00 /
(6.62b)
r(i) =
r2l(t)
V 0
T12(t)
0
0
0\
0
0/
(6.63)
= T21(t) = AnfcTexp (J
(6.64a)
(6.64b)
104
Polymer Viscoelasticity
()
(6.65)
while the second normalstress difference T22(t) T33(t) is zero. The shear
relaxation modulus of the elastic dumbbel model (Eq. (6.64b)) does not
show a strain dependence and is equivalent to the linear viscoelastic result,
Eq. (4.28). However, Eq. (6.65) is a nonlinear result.
(b)
Steadystate
shear
flow
X0(t  t')X2
(6.66a)
X2 = X2
(6.66b)
X 3 = X3 .
(6.66c)
E =
Ao(tt')
1
0
0\
0 I.
1/
(6.67)
Ao(t')
0
0\
0 .
(6.68)
0/
Til
TVJI
T12
0
0\
0
0/
(6.69)
(6.70a)
or the viscosity
rjo = ?=
Xo
nkTs
(6.70b)
Viscoelasticity
105
(6.71)
K
while the second normalstress coefficient ^2 = (r22 T33)/^o ' s z e r o The viscosity result (Eq. (6.70b)) is the same as what will be obtained
from substituting the relaxation modulus (Eq. (6.64b)) into the linear viscoelastic relation (Eq. (4.30)). Similar to Eq. (6.65), Eq. (6.71) is a nonlinear result.
Equation (6.70) indicates that the viscosity is independent of the shear
rate Ao However, it is well known that the polymeric liquid exhibits
nonNewtonian behavior, namely, that the viscosity value decreases with
increasing shear rate after the rate reaches a certain value. This discrepancy is a weak point of the elastic dumbbell model and arises from an
inherent weakness in the Gaussian distribution assumed for the connector
vector. We can see the cause of this deficiency from the following analysis
of how the dumbbell configuration changes with shear rate.
Under steady shear at a certain rate, the mean square endtoend distance of an elastic dumbbell is given by
(R 2 ) = T r ( R R ) .
(6.72)
Taking the trace of Eq. (6.50) and substituting the result into Eq. (6.72),
we obtain
(R 2 )
(R 2 ) e g
Tr(r)
3nkT
= 1
, 2(sA 0 ) 2
(6.73)
where, for the second equality, Eq. (6.69) has been used. Equation (6.73)
indicates that the elastic dumbbell can be stretched to become infinitely
long by increasing the shear rate. Such a situation, of course, cannot occur
in reality as the endtoend distance of a polymer chain can at most be
stretched to its backbonecontour length, which is limited by very rigid
chemical bonds. The infinite extensibility of the elasticdumbbell connector
is related to the predicted constant viscosity value at all shear rates.
Theoretically, Eq. (6.58) is applicable in both the linear and nonlinear
regions, as Eqs. (5.49) and (5.61) are for the elastic and viscous limits, respectively. One can note that as the relaxation time s becomes
106
Polymer
Viscoelasticity
infinitely long or infinitely short, Eq. (6.58) reduces to Eqs. (5.49) or (5.61),
respectively.
In the linear region, the viscoelastic properties, G'(ui), G"(LJ), J etc.,
can be obtained from the relaxation modulus using Eq. (6.58) or (6.59)
just as they can from the linear viscoelastic relations given in Chapter 4.
The relaxation modulus of the elastic dumbbell model contains only a single relaxation time (Eq. (6.64)). This result is clearly too simple and is
inconsistent with the observed viscoelastic spectrum whose relaxationtime
distribution usually has a considerable width. However, the study of the
elastic dumbbell model in this chapter shows the basic theoretical steps
required to treat the Rouse chain, which consists of a finite large number
of beadspring segments. As the elastic dumbbell model gives a theoretical
form which is equivalent to the convected Maxwell model, the Rouse model
yields a form which is equivalent to the convected generalized Maxwell
model. In addition, all the relaxation times are expressed in terms of the
molecular parameters in the Rouse model.
(6.A.1)
which tells the position X ' of each particle (X, t) for all past times t'. The
displacement function is continuous and can be inverted to give
X = X(X',M')
(6.A.2)
C(X,i,0 = E E
B(X,*,t') = E  E T
(6.A.3)
(6.A.4)
(6.A.5)
Viscoelasticity
107
where (X,i, t') denotes a material point or particle (X, t) at a past time t'.
Corresponding to the role of the Finger strain tensor B described in
Chapter 5, we define the relative strain tensor 7r 0 i(X,t,t') as
y[0](X,t,t')
= SEET
= 6B
(6.A.6)
dX' = ^
i 'j
(6A7)
or as
dX.' = J2gidXi
(6.A.8)
i=\
where
_ dX!_
gt
~ dX*
dX1
dXt
D Si
(6.A.9)
108
Polymer Viscoelasticity
with D defined by
D(X,t,') = ( V X ' ) T
(6.A.10)
(6.A.11)
The stress tensor of the fluid particle (X, t) at time t', r ( X , t, t'), can be
expanded either in terms of unit vectors at the present time t and Cartesian
components r^ or in terms of the convected base vectors at position X ' and
time t' and contravariant components T%1 as shown in the following:
S S T
T(X, t, *') = E E
i j ij
= !>&**
= DT[0]Dr
(6.A.12)
ioi = E E w
i
( 6  A  13 )
whose components associated with the unit vectors at the present time t
are equivalent to the contravariant components of r ( X , t, t'). We need to
express the contravariant components TIJ in terms of the Cartesian components Tij. Using Eq. (6.A.11), this transformation can be obtained from
Eq. (6.A.12) as
T [ 0 ] (X, *, t') = E(X, t, t') r ( X , t, t') E r ( X , t, t').
(6.A.14)
109
for the time derivatives of 7 and T[Q] are derived in the following:
We shall first consider the changing rate of D and E with time, following
the fluid particle (X,i). Prom Eq. (6.A.10),
= EE^^E(VV)^i
= (VV)TD.
(6.A.15)
Here, it is understood that D and V V are evaluated at t' for the fluid
particle (X,t).
FromEq. (6.A.11),
(E.D) = f  D + E . f
=0.
(6.A.16)
V d? J
dt>
= _E.(VV)TDE
= E(VV)T.
(6.A.17)
7[i](X,M')
37[o]
&t'
()* m
<"">
110
Polymer
Viscoelasticity
(6.A.19)
where
7 ( i) (X, t, t') = ( V V ) T + V V = 7.
(6. A.20)
Similarly, using Eq. (6.A.17), the partial time derivative of Eq. (6.A.14) is
written as
HI] = ^ T = E  T
( 1 )
. E
(6.A.21)
 r (VV)  ( V V f r .
(6.A.22)
(6.A.23)
(6.A.24)
dA
A.VV(VV)r.A.
(6.A.25)
Viscoelasticity
111
(D =  7 ( i )
=  [ V V + (VV)T]
= 7.
(6.A.26)
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Chapter 7
R
C=
^ER
(71)
n=l
Relative to the center of mass, the positions of the beads are given by
{d} = {R  R c } .
(7.2)
s = l,2,...,Nl
(7.3)
Viscoelasticity
113
We shall need to go back and forth between the beads and the bonds
through Eq. (7.3). To avoid the confusion, we shall use the following index
convention:
n, m for numbering the beads from 1 to N
s,t,u...
1
d
" =
Sbs
(7 4)
'
s=l
Thus
Nl
Nl
Nl
From Eqs. (7.1), (7.3) and (7.5), the relations between {R} and ({b s }, R c )
can be expressed as
N
(76)
n=l
N
n=l
and
Nl
R n 2_^ Bnshs
+ Rc
(7.7)
s=l
JVl
d n = 2 ^ , ^nsl>s
s=l
where
CSn Os+l,n 0 S j
(78)
Polymer
114
Bns =
Viscoelasticity
for s < n
T;
= 4~r  1
for s > n.
(7.9)
Prom Eqs. (7.8) and (7.9), we obtain the following relations for any s:
N
Csn
J2
J2 (J+i.  *.) =
n=l
N
(710)
n=l
J2Bns = 0.
(7.11)
71 = 1
By using Eq. (7.10), the substitution of Eq. (7.7) into Eq. (7.6) gives
N
Nl
71=1
t=l
N  l
= 5 1 C'n^ntbt.
(7.12)
n=l t=l
/ ,CsnBnt
= <5sf.
(7.13)
71=1
Equation (7.13) can also be shown by carrying out the matrix multiplication with Csn and Bnt substituted by Eqs. (7.8) and (7.9), respectively.
Substituting Eqs. (7.1) and (7.6) into Eq. (7.7), we obtain
N
R
" = E
m
=l
/ ,
Nl
( jf + Yl B^Csm ) Rm
\
5=1
(7.14)
Thus
Nl
s=l
N
n=l
(716)
Viscoelasticity
115
p = 1,2,... ,7V  1.
(7.17); (3.46)
As discussed in Chapter 3, each bead of the Rouse chain, under ceaseless collisions with fast moving small molecules and/or microstructural segments, is undergoing Brownian motion. At the same time the bead at
R is affected by both the tensile forces on the nth and (n l)th bonds.
According to the same definition used in Eqs. (6.4) and (6.5), the total force
asserted on the nth bead by the springs is expressed as
*n
S n S_i = y ^(os+i)n
s=l
Nl
"s,n)Ss
= ~Y, cs>
(718)
s=l
where Eq. (7.8) is used for the last equality, and the tensile force on the
sth bond is given by
Ss = ^ f b s .
(7.19)
Similar to the elastic dumbbell case, the equation of motion for any bead
in the Rouse chain is written as
C ( R  V 0  K  R n ) =  f c T    l n * + F
(7.20)
where ^ ( { R } , t ) is the configurational distribution function. For a homogeneous flow with no concentration gradient, similar to Eq. (6.9) in the
elastic dumbbell case, the configurational distribution function of the Rouse
chain \P may be written as
*({Rn},t)=n^({ba},t)
(7.21)
where n is the number of Rouse chains per unit volume of the polymeric
liquid.
Summing Eq. (7.20) over n and then dividing the result by N, we obtain
n=\
n=l
n=l
116
Polymer
Viscoelasticity
Substituting Eqs. (7.1), (7.18) and (7.21) into Eq. (7.22), we obtain
n=l
N
AT n = l
Nl
aR
dlnV>V
\(dRc'\
dRn J\dRn)
kT
CRc = C(Vo + K . R c )  ]T
VJ (dlml>\(dbs\
^s = l V dbs AdRn)
Nl
(7.23)
s=l
dbs
Y2C*n=0
^dRn
n=l
(7.24)
n=l
Using the result of Eq. (7.24) and the assumption that ip({bs},t)
function of R c , Eq. (7.23) becomes
is not a
(7.25)
R c = VQ + K R c
which is equivalent to Eq. (6.15) in the elastic dumbbell case. This result
is expected from assuming Eq. (7.21). Substituting Eqs. (7.7), (7.18) and
(7.21) into Eq. (7.20), we obtain
Nl
Rc + 2_j
Nl
Bnsbs
s=l
= c V0 + K Rc + J2 Bnsbs
V
s=l
Nl
Nl
Nl
,.
s=l
Nl
 ^ ) Csn  Y. C S 
C Yl bs = CK J2 kTj2[
s=l
,,
s=l
'
s=l
(7.27)
Multiplying Eq. (7.27) by Ctn which is placed on the left side and summing
the result over n, we obtain
N
Nl
C 2 ^ , Z^i CtnBnsbs
n = l s=l
Nl
= K 2_j /_^
n=l s=l
Nl
kT 2_j
s=l
CtnBnsbs
,.
,v
I ~^r
^
N
) /
N
J
' n=l
CfnPsn /
Nl
j /
CtnCsnSs
n=l s=l
(7.28)
Viscoelasticity
117
bt = K bt  1 J2 Ast {kT^
+ S.) .
(7.29)
Equation (7.29) for the Rouse chain is equivalent to Eq. (6.14) for the elastic
dumbbell. However, Eq. (7.29) indicates that the motions of N 1 bond
vectors are coupled with each other through the Rouse matrix (Ast).
After the equation of motion for the bonds (Eq. (7.29)) is obtained,
we need to express the continuity equation for \& in terms of {b s } to obtain
the Smoluchowski equation. Similar to Eq. (6.16), we have
n=l
Using Eqs. (7.1), (7.6), and (7.7), which relate {R} and ({b s },R c ), and
Eqs. (7.10) and (7.11), Eq. (7.30) is rewritten as
dt>
dt
$
9RC ^  E
^ff f
9bl r ' ^
c
< 7  31 )
s=l
Similar to the first term of Eq. (6.16) being zero, the first term of Eq. (7.31)
disappears with the substitution of Eq. (7.21). Thus, Eq. (7.31) becomes
5=1
By using Eq. (7.19), the substitution of Eq. (7.29) into Eq. (7.32) gives
dtp
~di
T^
=
~ ^f dbs
S=l
iVl
1>
S
t=l
(7.33)
This equation is equivalent to Eq. (6.19) for the elastic dumbbell and is
the Smoluchowski equation for the Rouse chain under the flow field K.
In this equation, the Rouse matrix (Ast) couples the motions of the bond
vectors { b s } . Transforming to normal coordinates is the normal procedure
used to decouple the motions. As shown in Chapter 3, the transformation
118
Polymer
Viscoelasticity
*t1t
(7.34); (3.47)
t=i
where (Ust) is the orthogonal matrix (Eq. (3.48)) that diagonizes the Rouse
matrix, i.e.
Nl
Nl
E ^tu = E u^u^ = 5*
t=i
( 7  35 ); ( 3  49 )
*=i
and
Nl
Nl
s=l
t=l
psAstUtu
= ap6pu
(7.36)
q = E
ushs
(737)
s=l
X)(&)S'<:
p38)
at
EE^^{(KE^^V
t
u;
*"
tu
/J
EEfE^^)^^^
u
\ s
(7.39)
119
dqd
/T^
s,
u I ,m dib
3kT
(7.40)
(7.41)
tf({q.},*)= n^'^'*)
s=l
where ips(qs,t)
is normalized by
J'
(7.42)
i>s(<ls,t) dqs = 1.
9
(v
\ i  a
(K q)Vu
y fur
I kT^"
, h3kT
i u
 ^2 q u V
b
(7.43)
d
9q
(K q)V   r ( kT~Q
+ ~yT^uVu
1,2
+ Eu(t)ipu
JVl.
(7.44)
If Eq. (7.44) is integrated over the whole q u space, the left side becomes
zero because of the normalization condition (Eq. (7.42)), and the first term
on the right side becomes zero because ipu vanishes as q u > oo. Hence
Eu(t) must be zero. Then Eq. (7.44) becomes the same as Eq. (6.19) if ipu
is replaced by tp, q u by R, au by 2, and (3fcT/62)q by S.
Then, following the derivation steps from Eq. (6.19) to Eq. (6.26),
we obtain from Eq. (7.44) the following results, which are equivalent to
120
Polymer Viscoelasticity
= K (q u q u ) + (q u q) K J +  S
2aJtT
^ (qq)
6aukT/
qq)(i) = T o 2 (quq)
7.2
(7.45)
(7.46)
In Chapter 6, we derived the stress tensor for the elastic dumbbell model.
By following the derivation steps given there, one obtains the following
result for the Rouse chain model with N beads per chain, which is equivalent
to Eq. (6.50) for the elastic dumbbell model:
3nkTN
T = 
(7.47)
In Eq. (7.47), we have neglected the solvent contribution as we are mainlyinterested in the concentratedsolution or melt system. The first term
of Eq. (7.47) arises from the tensile force on the bonds, and the second
term from the momenta associated with the moving beads. Substituting
Eqs. (7.34) and (7.35) into Eq. (7.47), we obtain
r =
_^Y/J2J2ustUsu(qtqu)+n(Nl)kT6
s
N
3nkT
b2
J2 <i<i">+ n (^  l ) k T S 
( 7  48 )
Er"
< 7  49 )
with
3nkT
p(qq)+
n/cT($.
(7.50)
Viscoelasticity
121
Following the procedure for obtaining Eq. (6.52) from Eqs. (6.26) and
(6.50), one obtains the following result from Eqs. (7.46) and (7.50):
T"
ST^ 1 }
= nfcTs7 ( 1 ) = nkTsui
(7.51)
where su is the relaxation time for the uth Rouse mode of motion and is
given by
Following the steps for obtaining Eq. (6.57), we rewrite Eq. (7.51) as
rf0](t,t')
+ su Tf 0] (t,t') = nkTSuJ[1](t,t').
(7.53)
Just as Eqs. (6.58) and (6.59) were obtained in Chapter 6, the integral
forms of Eq. (7.53) can be obtained. Then, with Eq. (7.49), the integral
form of the constitutive equation for the Rouse chain model is given by
(with u replaced by p)
rt
Ni
JZexp
r(t) = nkT
Joo
/t_try
7[i]{t,t')dt'
(7.54)
or
rt
r(t) = nkT /
Nl
>
'oo
exp
(tt>)
1[0](t,t')dt'.
(7.55)
S
p=1
Cb2
24kTsm2{pn/2N)'
p = l,2,...,Nl
(7.56)
(7.57)
122
Polymer
Viscoelasticity
model contains only one relaxation time, while the Rouse model has multiple relaxation times, the number of which is equal to the number of bonds
(springs) in a single chain.
For the shear relaxation modulus, the Rouse model gives
N_1
/
G() = nfcT ^ exp I
\
P=i
t \
).
(7.58)
PJ
=nkT E 6kTap
^
2
P=I
2
nb (N l)
where for the last equality Eq. (7.A.5) is used. As in the elastic dumbbell
case, the Rouse model does not predict the nonNewtonian behavior of
viscosity.
Similarly, the steadystate compliance J is obtained as
Nl
P=I
^o
n(Cb2)2 EpJr
36fcT
2N2
1/4
rfc
+ 7
5nkT(N2  1)
(7.60)
where for the last equality Eqs. (7.A.6) and (7.59) are used.
For a polymer melt, n = pN^/M, where p is the density and NA the
Avogadro number. When the condition N ^> 1 holds, for easy comparison
Viscoelasticity
123
N2
36M
PNACb
10
fpm
K (^)
V
(7.61)
36
<  ?
<^>
The Rouse model has the same defects in the nonlinear region as the
elastic dumbbell model because they share the same basic assumptions.
However, in the linear region the Rouse model accurately describes the viscoelastic properties of the concentrated or melt system whose molecular
weight is not high enough for entanglements to form. The successful predictions of the theory include the most basic aspects: the molecularweight
dependence of the relaxation times and the line shape of the relaxation
modulus or equivalently the viscoelastic spectrum. In Chapter 11, we shall
compare measured spectra with the Rouse theory.
Bnt
Kst = J2
n=l
= J2 B^Bm
(7A.l)
n1
K. = ^
.<
124
Polymer Viscoelasticity
Using Eqs. (7.10), (7.11), (7.13), and (7.15), the matrix (Kst) is shown
to be the inverse of the Rouse matrix (Ast) as follows:
E C*rnCTmu
KstAtu = E E *2n*t=l
\n=l
t=l
AT
= 2 J L ^sn^mu
n=lm=l
/Nl
I 2  , ^ntCtm
\t=l
I
/
AT
\m=l
J CUnBns
'
~ JJ I / _, C u m I I y ^ Bns I
\ m
\ n
= <5S.
(7.A.3)
Denote the matrices obtained from diagonizing (Ast) and (Kst) by (Agt)
and (K'st), respectively. Then, using the traceinvariance property of a
matrix, the following relations are obtained:
s=l
= Y/ASS = 2(N1)
Ni
^1 ^ "
(7.A.4)
x
. "=
4sin2(s7r/2iV)
= E ^ = ^=i
(7A5)
XX* = E^ = E E ^
s=l
(JV l)(2iV 2 + 7)
180
(7.A.6)
where, for the last equality of Eq. (7.A.4), Eq. (7.16) is used, and for the
last equalities of Eqs. (7.A.5) and (7.A.6), Eq. (7.A.2) is used. Equations
(7.A.5) and (7.A.6) are used, respectively, in obtaining the expressions for
125
References
1. Rouse, P. E., Jr., J. Chem. Phys. 2 1 , 1271 (1953).
2. See Chapter 6 and references therein.
3. Kramers, H. A., Physica 1 1 , 1 (1944); Bird, R. B., Curtiss, C. F., Armstrong,
R. C , and Hassager, O., Dynamics of Polymeric Liquids, Vol. 2 (2nd edn.),
Wiley, New York (1987), p. 24.
Chapter 8
Introduction
Entanglement
(Reptation)
Model
127
(8.1)
As discussed below in this chapter, the DoiEdwards theory 9 models entanglements as sliplinks. Having taken the effects of chain slippage through
the links into account, the theory gives:
Experimental results of various polymers show that the critical molecular weight Mc is about 2.4 times the value of Me (determined according
to Eq. (8.2)). This observation indicates the close relation between Mc
and Me.
On the basis of the experimental results of polymer viscoelasticity as
explained above, it has long been believed that chain entanglements occur
in a concentrated longchain system.
The close relation between the viscoelastic properties and the chain
dynamics of a polymeric liquid has long been recognized. The Rouse theory describes the viscoelastic properties of an entanglementfree polymer in
terms of the Rouse normal modes of motion (Chapter 7). A promising way
to describe the entanglement effect for a highmolecularweight polymer had
not appeared until 1971 when de Gennes suggested the idea of reptation. 10
He suggested that a linear flexible chain moved in a network as if a "snake"
crawled in a "thin tube" and that the only motions allowed for the chain
128
Polymer
Viscoelasticity
8.2
Entanglement represents a nonpermanent structural interaction among different chains in a polymer. In general, at the most fundamental level,
a problem that involves many molecules is extremely difficult. Doi and
a
A s the theory is based on the theoretical framework of the DoiEdwards theory, it is
referred to as the extended DoiEdwards theory from the theoretical consideration; at the
same time, since the theory includes the intramolecular motions on top of the reptation
process, physically it is referred to as the extended reptation theory. Considering t h a t
the DoiEdwards theory covers t h e nonlinear region, while the extended reptation theory
is limited to the linear region, the term "extended reptation theory" is used throughout
this book instead of the extended DoiEdwards theory.
Entanglement
(Reptation)
Model
129
(a)
Feq<
t/
r\\
[^
(b)
Fig. 8.1 Equivalence of (a) the tube picture and (b) the sliplink picture with the
hypothetical tensile force F e q = 3fcT/a pulling at both chain ends in describing the
constraint effect of entanglement on the movement of a polymer chain.
130
Polymer
Viscoelasticity
its length, a, is regarded as a step length (also referred to as the entanglement distance) of the primitive chain. The segments of the real polymer
chain between two adjacent links wriggle in the direction perpendicular to
the primitive path. To use the sliplink picture, it is necessary to assume
that tensile forces of the magnitude F e q = 3kT/a (see Appendix 8. A) are
applied to both ends of the chain so that the amplitude of the segmental
wriggling motions will be basically kept within the tube diameter. Otherwise, the chain could "leak" out through the spaces between the links or,
so to speak, leak out of the tube, as shown in Fig. 8.2; and the sliplinks
would lose the effect of constraining the motions of the chain. The sliplink
picture with the tensile forces applied at both chain ends is equivalent to
the tube picture. 9 The primitive chain as defined above has the following
two characteristics:
(a) In the equilibrium state, the configuration of the primitive chain is
a sequence of random walks. Namely, the primitive chain can be regarded
as a freely jointed chain consisting of segments (steps) with length equal to
the distance, a, between two adjacent links (the links being equivalent to
the joints). Then the mean square endtoend distance of the polymer chain
denoted by R2 is equal to aL where L is the total contour length of the
primitive chain. As the polymer is a Gaussian chain by itself, R2 = N0b2
where iV0 is the number of Rouse segments per chain and b denotes the
root mean square length of a Rouse segment. Then the number of steps on
the primitive chain is
W(_)_i_*.
\
MeJ
(8.3)
Entanglement
(Reptation)
Model
131
This equation also implies that each entanglement strand is sufficiently long
to be described by a Gaussian chain model, i.e.
a2 = Neb2
(8.4)
where Ne is the number of Rouse segments per entanglement strand. Equation (8.3) is the most fundamental assumption in the DoiEdwards theory.
(Note: In the DoiEdwards papers, b was defined as the effective bond
length of the real chain. 9 b can be, as done here, regarded as the root mean
square length of the Rouse segment, with the corresponding changes in
meaning for N0 and iVe. The use of the Rouse segment, also later adopted
by Doi and Edwards, 16 ' 17 is more convenient for further development of the
theory and analyses of the experimental results in terms of the extended
theories in the later chapters.)
(b) The Brownian motion of the primitive chain is reptational. The
primitive chain moves along itself forward or backward randomly. In other
words, each point on the primitive chain follows its immediate neighbor
in movement. The important exception is the two chain ends. As the
primitive chain moves forward, the "head" can choose its direction randomly; in reverse, as the primitive chain moves backward, the "end" can
also choose its direction randomly. This random process of moving forward and backward can be described in terms of the curvilinear diffusion
constant defined by
<A52)
(**
Dcv
(8 5)
 ~2AT
where AS is the curvilinear length the primitive chain moves in a short
time interval At. At the same time, according to the Einstein relation
(Eq. (3.9)),
D
kT
Dcv =
(8.6)
where is the friction constant of the Rouse segment or bead (also see
Appendix 9.A).
8.3
Diffusion Motion
Here, we shall relate the translational diffusion motion of the center of mass
of a polymer chain to the curvilinear diffusion constant. Experimentally,
the translational diffusion constant can readily be measured. 1821
132
Polymer
Viscoelasticity
Doi and Edwards considered the primitive chain as a freely jointed chain
with step length a. The positions of the joints (or links) can be labeled as
{R n } = ( R i , R 2 , . . . , R J V ) .
(8.7)
Then R R n _ i  = a. Assume that in a time interval At, the primitive chain jumps forward or backward with equal probability one step of
length a. Then the curvilinear diffusion constant can be defined by
D
 = &f
(8 8)
"
(8.9)
for n = 2 , 3 , . . . , N  1
Rj(i + At) = R a ( t ) ( 1 + 2 $ ( t ) ) + [Ri(*) + r ( t ) ] ( 1 ~ 2 g ( t ) )
RN(t
^ ( f ) ) + RAfi(t) ( 1 ~^{t))
(8.10)
(8.11)
(8.12)
n=l
1
(8.13)
n=l
By subtracting Eq. (8.12) from Eq. (8.13), into both of which Eqs. (8.9)(8.11) have been substituted, we obtain
Rc(t + At)  Rc(t)
= ^ { [ R N ( 0  R i (*)](*) + r(t)}
= ^[R(*K(*)+r(t)]
(8.14)
where R(t) = R w (t)  R i (t) is the endtoend vector of the polymer chain.
Then the timecorrelation function of the centerofmass velocity can be
Entanglement
(Reptation)
133
Model
written as
(Vc(t) V c (f)>  ~([Rc(t
At 2 iV 21r[(W)R(*)R(0>+
<(*)'(*')>
\a2
]V "'
a2
(8.15)
AT 2 "'
For obtaining the above result, we have used the following relations:
(8.16)
(817)
and the condition that R(t) and r(i) are totally uncorrelated.
The second term of Eq. (8.15) is much smaller than the first term and
can be neglected. We can obtain the mean square displacement of the
center of mass from time 0 to t by integrating Eq. (8.15) over t and t'.
Then, by substituting the result of the double integration into Eq. (3.40),
we obtain
t"
a2\ t
AtjN
2Dcvt
~N~
(8 18)
'
Da = f
(8.19)
Using Eqs. (8.3), (8.4) and (8.6), Eq. (8.19) can be written as
kTNe
DG
=KNJ
(8 20)
'
This result shows that the diffusion constant of a long polymer chain
in a concentrated system, because of the constraint effect of entanglement, is inversely proportional to the square of the molecular weight.
This molecularweight dependence is distinctively different from the result,
DQ oc M  1 , given by the Rouse model (Chapter 3) and its observation is
often regarded as the indication of the reptational motion. 18 As shown in
134
Polymer
Viscoelasticity
Relaxation Modulus
^ =U*J
L=
SkT
(8 21)
This force should be equal to the tensile force on each entanglement strand
which, following the same arguments, is given by (3kT/Neb2)a = 2>kT/a.
Thus, the two are consistent.
In Chapters 6 and 7, we showed that the average contribution to the
stress tensor from a segment with length vector R and tensile force F
is (RF). For a particular entanglement strand with the length vector
denoted by r, and with n^ segments, the tensile force is Fj = (3fcT/rij62)rj.
Thus, for a polymer system where there are c identical chains per unit
volume and each chain has N entanglement strands, the stress tensor at a
certain time, t, is expressed as
)+Pt
(822)
Entanglement
(Reptation)
Model
135
Assume that, at time t < 0, the polymeric liquid system is in the equilibrium
state, and a particular chain constrained by the sliplinks in the system has
a configuration as shown in Fig. 8.3(a). At t = 0, a step deformation E
is applied to the system, and the configuration of the chain together with
the sliplinks is immediately changed to that shown in Fig. 8.3(b). At this
stage, the stress tensor is given by:
T = 3ckT^(^)+pS
(823)
r^Eri
(8.24)
where
and n't is the number of segments in the ith entanglement strand. (Note:
Following the notation of Doi and Edwards, the apostrophe mark "/" is
used to indicate the state after the application of the deformation E, which
is opposite to the way it is used in Chapter 5, where the apostrophe mark
indicates the state before deformation (Eq. (5.18))). Because the chain has
not had a chance to slide through the sliplinks, n\ is equal to its equilibrium
value, rij (i.e. the value before the deformation is applied). Thus, the tensile
force on the ith. entanglement strand becomes:
/3fcT
4
" W2
(8.25)
136
Polymer
Viscoelasticity
!W
ATV
>u
3)
3^
CVJE
dl
3L
,^/ WV
d2
V?'
Fig. 8.3 Schematic illustration of the entanglement configuration on a polymer chain
and its relaxation following a step deformation, (a) The equilibrium state before a
deformation is applied, (b) Immediately after the application of a step deformation
at time t = 0, entanglement strands of the chain are either stretched or compressed,
(c) At t ~ T e q , the readjustment of the segmental distribution balances the tensile force
along the primitive chain and recovers its equilibrium contour length. At this stage,
the conformation of the primitive chain is in a nonequilibrium state; the positions of
the sliplinks are not in a random configuration (the nonrandom sliplinks at this stage
are referred to as t h e original sliplinks). On the right, an equivalent deformed tube is
shown (shown as a straight tube to symbolize its anisotropy; the deformed tube at this
stage is referred to as the original tube), (d) By reptation, the chain disengages from
the original sliplinks. Illustrated in terms of the tube picture on the right, (dl) and
(d2): As the chain reptates right and left, those parts of the original tube which have
been reached by the chain ends disappears (indicated by the dashed lines), (e) Finally
the chain disengages from all the original sliplinks and forms a new set of sliplinks with
other chains, returning to the equilibrium state, which is statistically equivalent to (a).
On the right, the original tube vanishes or the chain is totally out of the original tube.
Entanglement
(Reptation)
137
Model
we obtain
n
(827)
i=^~^
At the same time, the contour length of the primitive chain, L", recovers
its equilibrium value, L. Thus,
L" =  r ;  = L = ^
(8.28)
i=f
where the limits of summation, / and I, represent the first and the last
entanglement strands of the polymer chain at t = T eq . Using Eq. (8.27),
the number of entanglement strands is obtained as
" *  <  '  $ >
= <
<8 29)
&
(8.30)
"
"
<
&
'
T = ~2,cN"kT ( 4 A ) + PS
= 3ciVfcr( (E g j ( g 1l) )<E.u)^
PJ.
(8. 32)
Prom Eq. (8.32), the modulus value at t = T eq , as a function of deformations E, can be calculated. The chainslippage mechanism involved in
the above modeling leads to two effects: one is the process of equilibrating the segmental distribution along the primitive chain; the other is the
reduction of the number of entanglement strands. In Eq. (8.32), the equilibration process of the segmental redistribution is related to  E  u  inside
the first (...), which is from Eq. (8.27); and the reduction of the number
of entanglement strands is related to (  E  u  ) _ 1 , which is from Eq. (8.31).
138
Polymer Viscoelasticity
E =
(8.33)
the xy component of the stress tensor can be obtained from Eq. (8.32) as
+ \Uy)2 + Uy + u\ )
II
" ( 8  34 )
( l / ( I + XUy) + Uy + UjS
where ux, uy, and uz are the components of the unit vector u in the x,
y, and z directions. To calculate the shear stress Txy from Eq. (8.34)
at different values of the applied strain A, we make the transformation to
spherical coordinates (r, 6, <p):
ux > sin#cos</>
uy > sin 6 sin <j>
uz * cos 8
and perform averaging over all orientations for (...), i.e.
() > 7  /
4TT J0
JO
sm0ded<j>.
In the nonlinear region, Txy can only be calculated numerically (by a computer program). In the linear region, where all the second order terms and
beyond in Eq. (8.34) can be neglected, we obtain
4cNkTX.
(8.35)
5
We define the modulus GN by
GN =  % = ^cNkT.
(8.36)
A
5
Equation (8.36) becomes Eq. (8.2) for a polymer melt; and as mentioned
above, G^ is smaller by a factor of 4/5 than the result based on the theory
of rubber elasticity (Eq. (8.1)), where each entanglement is treated as a
permanent crosslink. The reduction factor 4/5 is entirely due to the the
segmental redistribution along the primitive chain. From Eq. (8.31), it can
be shown that N" = N in the linear region; in other words, the reduction
of the number of entanglement strands occurs only in the nonlinear region.
Entanglement
(Reptation)
Model
139
The chainslippage effects are responsible for the theoretical form given
by Eq. (8.32). For a comparison, we consider the situation where each sliplink is replaced by a permanent crosslink. In this situation, the equilibrium
time constant T eq is irrelevant, and n remains equal to n;. Using Eqs. (8.4)
and (8.30), we obtain from Eqs. (8.23) and (8.24)
T = 3cNkT((Eu)(Eu))+PS.
(8.37)
8.5
Equation (8.32) gives the stress, and thus modulus, of a well entangled
polymeric liquid at t = Teq, following a step deformation at t = 0. At this
stage, as shown in Fig. 8.3(c), the configuration of sliplink positions or the
distribution of entanglementstrand orientations is not random like that of
the equilibrium state before the application of the step deformation. Only
when the configuration has recovered from the nonrandom situation to the
equilibrium random state (statistically equivalent to that of Fig. 8.3(a)),
can the extra stress at t = T eq relax back to zero. To reach this stressfree
state, each chain in the polymeric liquid system needs to be totally out
of the nonrandom configuration of sliplinks, through which it has been
entangled with neighboring chains (or, equivalently, out of the deformed
or statistically anisotropic tube), and reforms a new random configuration
of entanglements with other chains (or, equivalently, reforms a new statistically isotropic tube). As described by the reptation mechanism in the
section on diffusion motion and as represented in Fig. 8.3(d) (Figs. 8.3(dl),
and 8.3(d2)), the polymer chain will move back and forth along itself and
eventually get out of the deformed tube totally and reach the equilibrium
state in which the orientations of the newly formed entanglement strands
are totally random (Fig. 8.3(e)). By considering the reptation mechanism,
the stress relaxation functional form is derived as follows: First, for the
physical quantity of interest, the equation of motion will be formulated.
The segmental distribution along the primitive chain has reached the
equilibrium state at t = T eq . In this state, by using Eq. (8.27), Eq. (8.32)
140
Polymer
Viscoelasticity
can be rewritten as
(8.38)
_oc^_
a
/ (u(s,t)u(s,t))ds
+ PS.
(8.39)
Jo
By absorbing the isotropic part of the integrand into the pressure term, Eq.
(8.39) can be expressed as
rL
SckT
'kT r
/ S(s,t)ds
a
Jo
+ PS
(8.40)
where
S(s,t) = (u(s,t)u(s,t)1\.
(8.41)
(8.42)
As As can be positive or negative and is random, its distribution is characterized by the moments
(As) = 0;
As S(s,t) is a function of u(s,t)
with As being random
(As 2 ) = 2DcvAt.
(8.43)
(844)
Entanglement
(Reptation)
Model
141
Using Eq. (8.43), the right hand side of Eq. (8.44) is expanded as
= S(M) + (A s ) ^M + i ( A s 2 ) ^ M
= S(M) + AAt^M .
(8.45)
That is
dS(s,t)
d*S(s,t)
^t~=Dcvd^
(8 46)
(8.47)
Equation (8.46), with the above boundary condition, describes the relaxation process from the state of Fig. 8.3(c) to the state of Fig. 8.3(d) and
then to that of Fig. 8.3(e). The relaxation from Fig. 8.3(b) to Fig. 8.3(c) is
finished in time T eq . Because T eq is in general much shorter than the characteristic time of the relaxation process described by Eq. (8.46), the state
of Fig. 8.3(c) is assumed as the initial state (t = 0); namely, S(s,t = 0)
(compare Eq. (8.32) with Eqs. (8.40) and (8.41)) is assumed as
S
M =
0) = ( ^ ^ } (  E . u 
  ^ Q ( E ) .
(8..48)
With this initial condition and the boundary condition given by Eq. (8.47),
the solution of the differential equation, Eq. (8.46), is derived in terms of
normal modes as:
< 8  49 >
podd
where
'=T?
(85O
>
142
Polymer
Viscoelasticity
T(^^Q
( E
^p(^)
(, 51 ,
p=odd
(8.52)
with
GN =
icJ^L = *cNkT
5
(8 53)
"WEjs?"^)
(854)
p=odd
The relaxation modulus G(t) that follows a step shear strain in the linear
region can be obtained from Eqs. (8.52)(8.54) as
G(t) = GNn(t).
(8.55)
It will be shown from analyzing the experimental results (Chapter 10) that
GN is the socalled plateau modulus.
Substituting Eqs. (8.3), (8.4), and (8.6) into Eq. (8.50), Td can be
rewritten as
CN3b2
M3
where K is the frictional factor that has been defined by Eq. (3.57). As
with the Rouse theory, the DoiEdwards theory has been developed on
the same frictionalfactor basis. The DoiEdwards theory, however, having
taken the constraint effect of entanglement into account, gives a structural
factor for the longest relaxation time quite different from that of the Rouse
theory. The former is proportional to M3 and inversely proportional to
M e ; the latter is proportional to M 2 . As the relaxationtime distributions
are also quite different, the line shapes of the relaxation modulus G(t)
predicted by the two theories are characteristically different. As we shall
see in Chapter 9, the DoiEdwards theory has provided the basic structural
element for the plateau in G(t) to appear.
Entanglement
(Reptation)
Model
143
Substituting Eqs. (8.53)(8.56) into Eqs. (4.30) and (4.63), one obtains
the zeroshear viscosity r?o and the steadystate compliance J , respectively, as
The 7}Q oc M 3 relation of Eq. (8.57) is still different from the experimental
observation TJQ OC M3A (Fig. 4.7), while Eq. (8.58) agrees with the basic
molecularweight independence of J^ in the highmolecularweight region
(Fig. 4.12). A detailed comparison of Eqs. (8.57) and (8.58) with the
Rouse theory and the extended reptation theory as well as experimental
results will be discussed in Chapter 10.
exp(j^).
(8Al)
where C is a constant. Define the tensile force on the Gaussian chain with
both ends fixed at positions 1 and 2 as
F = Fi =  F 2
(8.A.3)
dj4=
Gvf) R ' d R 
(8 A 4)

144
Polymer Viscoelasticity
(8.A.5)
n\
1
dR = 0
(8.A.6)
This scalar product must be equal to zero for any infinitesimal increment
dK. Thus,
F = ( f g ) R .
(8.A.7)
(8.B.1)
((EuMEu),) = /\TEikuk\
I^E.iiui
^2^2EikEji{ukui)
k
Y^^EikEji
k I
= x Y] EikEjk =  22 EikElj .
6
(8.B.2)
Using the definition of the Finger tensor (Eq. (5.35)), Eq. (8.B.1) is proven.
References
1. Fox, T. G., and Flory, P. J., J. Phys. Colloid Chem. 55, 221 (1951).
2. Berry, G. C, and Fox, T. G., Adv. Polym. Sci. 5, 261 (1968).
3. Mark, H., and Tobolsky, A. V., Physical Chemistry of High Polymeric Systems Interscience, New York (1950).
20.
21.
145
Chapter 9
Intramolecular Processes
Transition region
E to o
"
"
[IIII 1 1
11
Plateau region
""^"a
pI I I I 1 1
CD
t>
<5 10
.2
147
Modulus
Temiinal region
*
Tin
*>
1O
o
:
~E
10"'
10"
10'
Time (sec)
10"
10
Fig. 9.1 Relaxation modulus G(\,t) in the linear (A * 0; ooo) and nonlinear (A = 5;
AAA) regions of a nearly monodisperse polystyrene melt (Mw = 4.22 x 10 5 ). T h e
G(A = 5, t) curve was measured at a temperature different from the reference temperature (127.5C) of the shown G(A 0, i) master curve; as shown t h e G(A = 5,t)
curve has been shifted along both t h e time coordinate and t h e modulus coordinate t o
superpose on the G(A > 0, t) curve in t h e terminal region. (See Fig. 12.3 for t h e results
of G{\ = 0.2, t) and G(\ = 5, t), both measured at the same temperature.)
used in its theoretical study in Chapter 12) in the time region corresponding to the G{t) plateau. At the same time, the relaxation curves G(X,t)
at different A values are superposable onto the G(t) curve in the terminal
region by a vertical shift. Prom the superposition, the A dependence of the
shifting factor, h(X) = G(X,t)/G(X > 0,t), can be obtained, which is often
referred to as the damping function (also see Chapter 12). As shown in Fig.
9.2, 8 ' 9 and as reported by Osaki et o/.,4'5 Vrentas et al.,10 and Pearson, 11
the measured damping factors are in close agreement with the DoiEdwards
curve calculated using Eq. (8.34). It is important to point out that the
theoretical h(X) curve does not involve a single fitting parameter and, as
confirmed by experimental results, is independent of molecular weight and
the type of polymer. In other words, h(X) is universal for nearly monodisperse polymers in the entanglement region. This result, a very successful
148
Polymer
Viscoelastidty
o CM
10 _
10"
10'
10'
Shear Strain X
Fig. 9.2 Comparison of the damping functions: the measured values () and the curve
calculated from Eq. (8.34) (the lower line) and that calculated from Eq. (12.17) with
the independent alignment approximation (the upper line).
149
(denoted by HB(t) below) affecting G(t) in the linear region. This process was first theoretically studied by Doi 13 ' 14 and then by Lin. 15 Although
the the ^ B ( ) a n d fi*B(t,\) processes have the same dynamic origin, their
mechanisms for affecting the relaxation modulus are different. Because the
molecular dynamics for ^ s ( t ) is the same as that of nB(t, A), either /xs(t)
or n*B{t, A) occurs in the time region of the plateau in G(t).
Considering the transition of the stress level given by Eq. (8.37) to that
given by Eq. (8.32), Lin 15 has proposed that a minor process nx(t) exists
between the fiA(t) process region and the plateau region, namely, the /XB()
process region.
In summary, four processes in order of increasing relaxation time, /x^(i),
fj.x(t), fJB(t), and Hc{t), have been identified. Below, we shall follow Lin's
steps 15 in showing the molecular dynamics these four processes represent
and how they occur in G(t).
9.2
150
Polymer
Viscoelasticity
moves out of the tube due to a stretching of the contour length following a
shrink, it can pick a random direction. Thus, the size of the tubeend region
that can be affected by this relaxation process is determined by the fluctuation amplitude of the contour length. To include both the contour length
fluctuation process and the reptational process as causes for the stress relaxation, we need to consider two important aspects: (1) The contour length
fluctuation is a Rouselike motion with a characteristic relaxation time TB
which is much shorter than the characteristic time Td of the reptational
process because TB is proportional to M2 (Chapters 3 and 7) while T<j is
proportional to M3 (Td will be denoted by TQ below, standing for the pure
reptation). (2) Both the contour length fluctuation and the reptational
motion occur simultaneously. To obtain a theoretical expression for G(t)
which is simple in form, one hopes to separate the contributions of the two
kinds of motions. In other words, we hope to express the stress relaxation
as a sum of two decoupled processes. The decoupling of the two contributions can be achieved by following a scheme of "thought experiment" as
described below:
We first regard the fixed primitivechain contour length L in Eqs. (8.3)
and (8.51) as the time average of the fluctuating length L(t). In other
words,
L(t) = (L{t)) + SL(t) = L + 6L(t)
(9.1)
where SL(t) represents the fluctuation; (SL(t)) = 0. Thus, the length L(t)
plays two roles here. On the one hand, its average as defined in Eq. (9.1)
represents the original tube length (at t = T eq ) whose tube stress is to be
relaxed (in other words, the relaxation strength at t = T eq is proportional
to the average length L). On the other hand (see Eq. (9.2)), its length
fluctuation motion relaxes the tube stress in the tube end regions. As the
chain ends migrate because of the reptational motion, the contour length
fluctuation causes additional relaxation of the tube stress whenever the
fluctuation amplitude allows the chain ends to encounter the original tube
(Fig. 9.3).
To sort out such a complicated dynamic situation, we first assume that
the primitive chain is "nailed down" at some central point of the chain,
i.e. the reptational motion is "frozen"; only the contour length fluctuation
is allowed. This is equivalent to setting TQ oo while allowing the contour length fluctuation 5L(t) to occur with a finite characteristic relaxation
time TB In this hypothetical situation, the portion of the tube that still
possesses tube stress at t ta Tg is reduced to a shorter length L0, because of
Modulus
151
W//////M
y/////////////
ea(f)*;
Hi;
(b)
Fig. 9.3 T h e Brownian motion of a primitive chain: (a) with fixed contour length, and
(b) with fluctuating contour length. The oblique lines denote the region that has not
been reached by either end of the primitive chain. T h e length of the region a(t) decreases
faster in (b) t h a n in (a). AL ~ 5L  N5b (see Eqs. (9.4) and (9.8)). Reproduced,
by permission, from Ref. 13.
the fluctuation 6L(t). Then, at t < TB, the tube length that still possesses
tube stress can be defined by
L(t) =L0 + 8L(t).
(9.2)
In other words, 8L{t) relaxes to zero at < Tg. Because 5L{t) remains in
the original tube at t < TB, we can regard it as the length of 5L(t) that is
still correlated to its original 5L(0). In other words, we regard SL(t) as the
projection of 5L(t) to SL(0), i.e.
SL(t)
(SL(0)SL(t))
<*i(0)P)V2
(9.3)
^N~0bnB(t)
(9.4)
where
1^V
p=odd
V TB J
(9.5)
152
Polymer Viscoelasticity
with
TB
= *
* ^
(9.6)
re = %
(97)
Modulus
153
(9.8)
= >/N~0b.
(9.9)
Thus, L in the expression (Eqs. (8.53)) for the GN used in Eq. (8.55)
is separated into two parts: SL and L0. The tube stress on SL is to be
relaxed according to Eqs. (9.4)(9.6) while that on L0 is to be relaxed
by the reptational process with the time constant rc given by Eq. (9.7).
Instead of Eqs. (8.53)(8.56), the linear relaxation modulus G(t) for t > T eq
is now given by
< * >  ^
j;PB{t) + j^Vcit)
(9.10)
where Hs{t) ls given by Eqs. (9.5) and (9.6); and nc(t), equivalent to
Eq. (8.54) with Tj, or T replaced by TQ (Eq. (9.7)), is given by
McW= ^ e x p f ^ Y
(9.11)
Using Eqs. (8.3), (8.6) (8.56), (9.8) and (9.9), TC can be obtained from
Eq. (9.7) as
(9.12)
Using Eqs. (8.3), (9.8) and (9.9), Eq. (9.10) is rewritten as
G(t) = GN(BB(t)
+ Cnc(t))
(9.13)
154
Polymer
Viscoelasticity
= lB.
(9.15)
9.3
In general, the slower the mode of motion, the larger the lengthscale
involved. So far in this chapter, we have studied the /XB(<) and //c(*)
processes in G(t). /JB() represents an intramolecular motion that involves
the whole chain, and fic(t) is related to the diffusion motion of the whole
Modulus
155
chain. In G(t), besides these two processes, there are two readily identifiable faster processes, Hx(t) and / ^ ( t ) , as mentioned in the beginning of
this chapter. Either of these two fast processes involves only a section or a
part of the chain.
(a)
The /xx(*)
process
(9.17)
[BfiB(t) + Cnc(t)\.
(9.18)
The theoretical functional form for nx (t) is not known. It has been assumed
that the decay of \ix (t) is a single exponential. Because fix (t) affects the
G(t) line shape only in a minor way, such a simple assumption basically
does not affect the quantitative nature of the comparison of experimental
results with the whole G(t) equation, as will be discussed in Chapter 10.
156
(b)
Polymer Viscoelasticity
The / / A ( * )
process
In the whole process of obtaining Eq. (9.18), we have considered only the
deformation or orientation of entanglement strands along the primitive path
and the associated relaxation processes. In a time shorter than required for
the chain slippage through any entanglement link to have a chance to occur,
the deformation of the chain segments towards all directions, including the
directions perpendicular to the primitive path, adds values to the initial
modulus 5GAT/4 given in Eq. (9.18). Here, the relaxation process of the
additional modulus is the Rouse motion of an entanglement strand with
both ends fixed, which is treated in Appendix 9.B. The functional form of
the relaxation process is given by Eqs. (9.B.17)(9.B.20).
One sees that the end of relaxation in Eq. (9.B.17) occurs when HA{1)
diminishes to zero, and that the modulus value of Eq. (9.B.17) at the end
of relaxation matches the initial value of Eq. (9.18). Thus, we can combine
Eqs. (9.18) and (9.B.17) as
G(t) = GN[1 + M*)} [1 + 2/*x(*)] [BnB(t) + Cnc(t)]
(9.19)
where fiA(t) is given by Eqs. (9.B.18) and (9.B.20). Equation (9.19) covers the whole range of relaxation times from the transition region (the
AM()process region) to the terminal region (the /xc()~P rocess region). The
smallest structural unit involved in the theoretical development that leads
to Eq. (9.19) is the Rouse segment. Thus, it is expected that Eq. (9.19)
ceases to be applicable in the time region shorter than the characteristic time of local Rousesegmental motion, which is of the order b2/3kT.
As the comparison of theory with experiment shows in Chapter 10, this
limit is reached when the modulus value exceeds ~ 6 x 106 dynes/sqcm for
polystyrene.
9.4
As noted previously in this chapter, Eqs. (9.13)(9.16) indicate that the line
shape of the G(i) curve is a universal function of the normalized molecular
weight M/Me in the region covered by the /is(i) and nc(t) processes. The
relaxation times TB and TQ can also be normalized with respect to the
relaxation time of the lowest mode of the fJ.A(t) process, T\{=
KM^/6,
from Eq. (9.B.20) for a sufficiently large Ne). The relaxationtime ratios
Modulus
157
re J M \ 3
(9.20)
(9.21)
The fact that these two relaxationtime ratios are a universal function of
M/Me indicates that the universality of the G(t) line shape extends to the
HA(t) process region. (J,x(t) is situated between fiA(t) and the processes
HB(t) and nc(t) Thus, although we do not have the theoretical form for
Hx(t), its characteristic time T\ normalized with respect to T\ should also
be a function of the normalized molecular weight M/Me. Prom the G(t)
line shape analysis in terms of Eq. (9.19) as discussed in detail in Chapter
10, it has been found that TX is best described by
TX = 0.55KMeM
(9.22)
or
Equation (9.19) accurately describes the observed characteristics associated with the transformation of the G(t) line shape with changing molecular
weight. To illustrate the capability of the theory in describing these characteristics, the relaxation modulus curves calculated from Eq. (9.19) at
Mw/Me = 10, 20 and 40, all with the polydispersity of Mw/Mn = 1.05, are
shown in Fig. 9.4 for comparison with the experimental results, as shown in
Fig. 4.6. In Chapter 10, in terms of the theory, quantitative analyses of the
relaxation modulus curves of a series of nearly monodisperse polystyrene
samples will be described in detail.
9.5
Using the equations of linear viscoelasticity (Eqs. (4.30) and (4.63)), the
zeroshear viscosity, 770, and the steadystate compliance, J , can be numerically calculated from Eq. (9.19) by a computer program. If the molecular
weight is greater than ~ 5M e , the contributions of the / ^ ( i ) and Hx(t)
processes to 770 and J are negligible because of their relatively short relaxation times. From Eq. (9.19) with the / ^ ( t ) and ^ s ( t ) processes neglected
158
Polymer
Viscoelasticity
Fig. 9.4 Relaxation modulus G(t) curves calculated by convoluting Eq. (9.19) with
the Schulz molecularweight distribution for Mw/Mn
= 1.05 (i.e. Z = 20; see Eqs.
(10.3) and (10.4))) at molecular weights: Mw/Me = 10, 20, and 40 as they would be for
polystyrene (GN = 2 x 10 6 dyne/sq cm; Me = 13,500). The frictional factor K for the
A*xM> MB(*) a n d Vc{t) processes is set at 5 x 1 0  9 and the frictional factor (denoted
by K') for the /iyt(t) process is set at K' = 3.3 K (see Chapter 10 for details of the
ratio
K'/K).
J? =
3Me {ljMJMf
+ lJy/MJMf
2PRT [(i _ yfMJM? + \{,/MJMYY '
(9.24)
(9.25)
Equation (9.24) closely approximates the observed ??o <x M3A relation over
a wide region of molecular weight above 5Me. J is highly sensitive to the
molecularweight distribution. As a result, the measured values of nearly
monodisperse polymers in the highmolecularweight region (> 7Me) are
about 1.7 times greater than the values calculated from Eq. (9.25) which
is for ideal monodispersity. In Chapter 10, we shall further compare the
experimental results of T]0 and J with the theoretical results calculated
with and without both the HA(t) and Hx{t) processes.
159
The effect of the primitivechain contour length fluctuation was first considered by Doi. 13 In an approach which was meant to be an approximation,
Doi obtained the zeroshear viscosity and the steadystate compliance as
pRTM3
j 0 =
e
9Me
(9.26)
{ljMjMf
\{^QMf
+ i(v^7M)3]2'
Equations (9.26) and (9.27) are similar to Eqs. (9.24) and (9.25), respectively. Doi's calculation was mainly for the molecularweight dependence
of the zeroshear viscosity and the steadystate compliance. Because of the
approximations involved in his approach, Doi's results do not converge to
the DoiEdwards theory (Eqs. (8.57) and (8.58)) at infinitely high molecular weight as Eqs. (9.24) and (9.25) do.
Taking the contourlengthfluctuation effect into account, Doi 14
obtained another expression for the viscosity
(9.A.1)
160
Polymer
Viscoelasticity
(9.A.2)
(9.A.3)
(fn(t)fm(t'))
= 2(kT6(t  t')S(n  m)
(9.A.3')
161
~w~friSn{t)
= Feq
atn =
;Ar
(9A4)
or
d
Sn(t)=l
a t n = 0;ATo
(9.A.5)
on
with
b2
1=  .
(9.A.6)
Equation (9.A.2) has the following type of solution which satisfies the
boundary condition.
1 /*?
Xp(t) cos ( ^ )
for p= 1,2,...
(9.A.7)
where
i
X0(t) =
rN
/
Sn{t)dn
(9.A.8)
''o JO
represents the position of the "curvilinear center of the chain" along the
primitive path. To study the motion of X0(t) (the curvilinear diffusion
motion of the chain), Eq. (9.A.3') is to be used for the fluctuation force
in Eq. (9.A.2), as explained above. Using Eq. (9.A.8), we obtain from
substituting Eq. (9.A.7) into Eq. (9.A.2) the equation of the X0(t) motion
(9A9)
162
Polymer
Viscoelasticity
the fluctuation force. Substituting Eq. (9.A.7) into Eq. (9.A.2) and then
following the procedure as given in Appendix 3.C, we obtain
(Xp(0)Xp(t))
= H f ^ exp(Apt)
(9.A.10)
where
Xp = 
(9.A.11)
TB
with
2 2
Cb,2AT2
N
/ 2 \1/2
J2
P^
(9A13)
p=odd
and
(SL(0)SL(t)) = J2 (XP(0)XP(t)).
(9.A.14)
p=odd
]T
p=l,3... ^
exp(A p *).
(9.A.15)
163
Modulus
continuous form:12
(9.B.2)
R =E R
(9.B.3)
where {r} and R are the positions of the beads { r n } and R, respectively,
before the deformation E is applied. The motion of r n ( i ) is described by
the Langevin equation (see Appendix 3.C):
2>kT d2
Q
c
0i
rn(t) =
~Wdtfrn{t)
+ fn(t)
(9 B 4)
 '
{fna(t)fm0(t'))
(9.B.5)
*+(fl*<>(^)
with p= 1,2,3,... . (9.B.6)
Then, following a procedure similar t o that shown in Chapter 3.C,
Eq. (9.B.4) is transformed, giving
lxp(t)
= ~Xp(t)+hp(t)
(9.B.7)
where
_
p
<JV e 2 6 2
37r 2 fciy
(9.B.8)
{hpa(t)hp,/}(?))
2fcT
= S(p  p')S(t  t')5af}.
(9.B.9)
164
Polymer
Viscoelasticity
Jo
V P)
(tf)
hp(t') exp
dt'.
(9.B.10)
+ 5,Q/3
N*b2
37T 2 p 2
It
1 exp
(!)
(9.B.11)
N2b2
3TTV
(9.B.12)
we obtain
(Xpa(O)Xp0(O))
=
=
{(EXp)a(EXp)0)
Tr(Hpa0)((E.uUEu)0)u
N2b2
^((EuJ^Eu^u
(9.B.13)
ZkT
A^2
(RR) + ^ 7 V e 6 2
(E.u)(E.u,0op(!)4
(9.B.14)
(9.B.15)
165
1+
ZcNkT
?6XP(f)
? eXP ('l)
((E.u)Q(Eu)^)u
((E.uJaCE.u)^
(9.B.16)
where c is the number of polymer chains per unit volume, with N entanglement strands per chain. The relaxation modulus G(t) in the linear region
is obtained from Eq. (9.B.16) as
G(t) = cNkT[l + iiA(t)]
(9.B.17)
where
(9.B.18)
r>
with
2
TI P
AA
 TR
 {N?b
2
67r2fcTp2'
(9.B.19)
For a finite Ne which is not very large, the exact expression for rvA is 19
&
21kTsm2{Kp/2Ne)
KTT2M*
2AN^sm2(irp/2Ne)
forp=l,2,...,iVel
(9.B.20)
166
Polymer Viscoelasticity
6. Mark, H., and Tobolsky, A. V., Physical Chemistry of High Polymeric Systems, Interscience, New York (1950).
7. Lin, Y.H., Macromolecules 19, 159 (1986).
8. Lin, Y.H., J. NonNewtonaian Fluid Mech. 23, 163 (1987).
9. Lin, Y.H., J. Rheol. 28, 1 (1984).
10. Vrentas, C. M., and Graessley, W. W., J. Rheol. 26, 359 (1982).
11. Pearson, D. S., Rubber Chem. Tech. 60, 439 (1987).
12. Doi, M., J. Polym. Sci., Polym. Phys. Ed. 18, 1005 (1980).
13. Doi, M., J. Polym. Sci., Polym. Lett. Ed. 19, 265 (1981).
14. Doi, M., J. Polym. Sci., Polym. Phys. Ed. 2 1 , 667 (1983).
15. Lin, Y.H., Macromolecules 17, 2846 (1984).
16. Tobolsky, A. V., J. Apply. Phys. 27, 673 (1956).
17. Ferry, D. J., Viscoelastic Properties of Polymers (3rd edn), Wiley, New York
(1980).
18. Doi, M., and Edwards, S. F., The Theory of Polymer Dynamics, Chapter 6,
Oxford Univ. Press (1986).
19. Mooney, M., J. Polym. Sci. 34, 599 (1959).
Chapter 10
167
168
Polymer
Viscoelasticity
Only during and after the advent of the DoiEdwards theory, did meaningful quantitative comparison between theory and experiment become possible as for the damping function h(X). The extended reptation theory, whose
development on the theoretical framework of the DoiEdwards theory was
described in Chapter 9, provides a G(t) function which can be expressed
as a universal form in terms of the normalized molecular weight M/Me,
covering the whole range from the transition region to the terminal region.
It was pointed out in Chapter 9 that the extended reptation theory accurately describes the characteristics of transformation of the G(t) line shape
with changing molecular weight and that it explains the molecularweight
dependence of TJQ and J . In this chapter we shall describe and discuss
detailed aspects of the quantitative comparison between the extended reptation theory and experimental results.
10.1
The functional form of the relaxation modulus G(t) as given by Eq. (9.19)
together with Eqs. (9.5), (9.6), (9.11), (9.12), (9.14), (9.15), (9.B.18),
(9.B.20) and (9.22) is for an "ideally monodisperse sample" in the entanglement region. Equation (9.12) indicates that the relaxation time of the main
process in G(t) the terminal process nc(t) is strongly dependent on
the molecular weight. Thus, to compare the measured G(t) line shapes with
the theory, we need to take the molecularweight distribution into account,
even though the studied samples are nearly monodisperse (typically with
Mw/Mn < 1.1). This consideration involves the socalled blending law.
The simplest kind of blending law is the linear additivity of the contributions from the different molecularweight components in the distribution.
Assuming such a blending law is equivalent to the meanfield assumption
(in the sense that the bulk viscoelastic properties can be expressed in terms
of the behavior associated with a single chain) which the extended reptation theory as well as the DoiEdwards theory has been developed on. The
mean field assumed from the very beginning of the DoiEdwards theory is
represented by the clear definition of the primitive chain (Eq. (8.3)). Thus,
the mean field has much to do with the tube diameter a and its associated entanglement molecular weight Me (Eq. (8.4)) which is determined
from the plateau modulus (Eq. (8.2)). In addition, Eq. (8.3) plays a crucial role in the derivations of the expressions for TQ and TQ as studied in
Chapters 8 and 9. In a nearly monodisperse system of sufficiently high
Comparison
in Linear Viscoelasticity
and Diffusion
169
170
Polymer
Viscoelasticity
The unchanged tube diameter means that the terminal relaxation time associated with component two remains the same. But a small amount of tube
stress on componenttwo's chains will relax in a time much shorter than the
terminal relaxation time as the fastmoving componentone's chains reptate away from componenttwo's chains. This additional relaxation not
caused by the reptational motions of componenttwo's chains themselves
slightly enhances the declining rate in the plateau region. The relaxation
of the tube stress on the componentone chains also basically occurs in the
plateau region. Because there is only residual amount of component one,
the apparent effect of this relaxation would basically amount to enhancing
slightly the decline rate in the plateau region.
In the plateau region, since the absolute value of the reciprocal slope
At/AG is large, a small "wrong" additional decline of the modulus AG
in the plateau region can lead to a large error in time At. Thus, as the
relaxationtime scale is transformed to the molecularweight scale in the
analysis of the G(t) line shape, the presence of a small amount of component one can artificially broaden the molecularweight distribution if the
sample system is regarded as a nearly monodisperse system rather than a
binary blend. This effect somewhat contaminates the lineshape analysis
in one case discussed below, where the studied nearly monodisperse sample
contains a lowmolecularweight tail. This effect will be further discussed
when the comparison of theory with experiment is made for zeroshear
viscosity.
A stronger effect of different nature will occur if the amount of component one is not small. In this case the tube diameter felt by componenttwo's
chains becomes larger (this is referred to as the tube dilation effect) while
that felt by componentone's chains remains the same as in a monodisperse
situation. This effect is based on the observation that the terminal relaxation time associated with component two is shortened by the presence of a
significant amount of component one (as discussed in detail in Chapter 11,
corresponding to the tube dilation, an apparent larger entanglement molecular weight denoted by M" can be defined which leads to a smaller TC value
when Me in Eq. (912) is substituted by M"). As also pointed out by Doi
and Edwards, 4 the tube is a dynamic concept rather than static. In a system
of broad molecularweight distribution, chains of different molecular weights
feel different effective tube diameter sizes. A longer chain feels a larger tube
diameter because of relatively higher reptational mobility of the shorter
chains in its surroundings, while the shortest chain in the system feels the
same tubediameter size as in a monodisperse system. The distribution
Comparison
in Linear Viscoelasticity
and Diffusion
171
10.2
(10.1)
with
Mw = sjW%Mi
(10.2)
(M) =
r(z
i)M^
exp
ZM
~~MZ
(10.3)
172
Polymer
Viscoelasticity
Comparison
in Linear Viscoelasticity
and Diffusion
173
matching of the calculated and measured G(t) line shapes have the Z values
corresponding to a polydispersity of Mw/Mn < 1.04 in good agreement with
the values obtained from the characterization of the samples.
For two nearly monodisperse polystyrene samples of Mw = 1.79 x
105 and 4.22 x 105 (these two samples are denoted by NBS and F40,
respectively), 7 the G(t) lineshape analyses were made by doing the nonlinear, leastsquare fitting in terms of a distribution consisting of three discrete
molecularweight components (Eq. (10.1)). The polydispersity obtained
from the lineshape analysis for the NBS sample was Mw/Mn = 1.08, in
good agreement with the value 1.07 measured with the gel permeation
chromatograph (GPC); while that for F40 was Mw/Mn = 1.16, which is
somewhat greater than an apparent GPC value of 1.05. As explained above,
the discrepancy in the case of F40 is due to the lowmolecularweight tail in
the distribution as revealed by an independent GPC measurement. 7 This
discrepancy also has much to do with the "pitfalls" likely to occur in any
nonlinear, leastsquare fitting which would cause the uniqueness or exact
correctness of the obtained "best" set of the adjustable parameters to be
questioned. Here, the assumed distribution of three discrete components
cannot represent completely the true distribution which should be continuous. At the same time, the number of involved fitting parameters is
not small. This combination makes the obtained distribution easily distorted by errors in the measured curve. Here the main error source, as
explained above, is the additional declining rate in the plateau region due
to the lowmolecularweight tail in the studied sample. These factors lead
to the artificially larger polydispersity in the molecularweight distribution
obtained from the nonlinear, leastsquare G(t) fitting of F40. In support
of this explanation, the frictional factor K for F40 obtained from this G(t)
fitting is about 30% smaller than the average value obtained for the samples with molecular weight < 10M e . The smaller K value and the broader
molecularweight distribution in the case of F40 are both artificial outcomes of the nonlinear, leastsquare fitting of G(t). As explained further
in the comparison of theory and experiment for the zeroshear viscosity
below, these two artificial effects cancel each other out in the integration
of G(t) (Eq. (4.30)), giving a viscosity value which agrees closely with the
expected value. The 30% reduction of the K value in the case of F40
is unlikely due to the molecularweight error in the sample characterization. Based on Eq. (9.12), an error of 10% in the weightaverage molecular
weight can cause an uncertainty of ~ 30% in the K value obtained from the
G(t) curve analysis. The expected accuracy (a few percent at most) of the
174
Polymer
Viscoelasticity
Comparison
in Linear Viscoelasticity
and Diffusion
175
10'
Time (sec)
Fig. 10.1 Comparison of the measured (dots) and the calculated (line) relaxation modulus for the F40 sample. Also shown are the separate contributions of the /M(*)> M X M >
fiB{t) a n d McM processes (line A is calculated with all four processes in Eq. (9.19)
included, line X is calculated without / M ( < ) , line B is calculated without / i ^ W and
/ix(*)> a n d line C is calculated without /i/i(4), Hx(t) a n d M B M ; thus, the portion
between line A and line X is the contribution of the A M W process, and so forth).
176
Polymer
"v r 11 n i 
Viscoelasticity
rT]
i i i i
IIJ
w
0)
e
"5 <=
10
'
" '
2
Fig. 10.2
:
10"
'
'
'
'
10'
Time (sec)
10"
'
''
"
o
fX
~ )^
^^****
"
^
: C
O
=
:
 =
:
"=
,2
10 u
10
. . . ,\..i
.1
10'
Time (sec)
Fig. 10.3
10"
Comparison
in Linear Viscoelasticity
and Diffusion
177
_
:

^^N.
e O
u
.
>.<.
^S.
A \
_^2L_^
o
01
"a
c
o
>.
"B
CD
CO
3 m
o
3
T3 T
c
o
CO
X
CO
CD
~
'.
;
.
z.
\ \^ \ N
.
~
:
_
_
'.
'
cn
.
o
10'
10"
Fig. 10.4
Time (sec)
10"
10"
178
Polymer
Viscoelasticity
10
Molecular Weight
Fig. 10.5 K and K'/K values as a function of molecular weight Mw that have been
obtained from the lineshape analysis of the measured G(t) curves at 127.5C.
from the theory; however, the K (denoted by K' below) value in the /M()
process is different as will be explained and discussed below.
The K values of the F40 and NBS samples are about 30% smaller than
the average of the K values determined for the samples in the molecularweight region below 10M e . As explained above, this small yet noticeable
reduction of the K value is mainly related to the molecularweight distribution rather than caused by an error in the weightaverage molecular weights
of the samples. Above 10Me (> 135,000 for polystyrene), K' is independent
of molecular weight and is greater than K by a factor of about 4.2. Corrected for the 30% reduction in K in the case of NBS and F40, the K'/K
ratio becomes about 3.3 above 10M e . Below 10Me the ratio K'/K declines
gradually with decreasing molecular weight and reaches 1 as the molecular
weight approaches Me. From the close agreements between the calculated
and measured G(t) curves as shown in Figs. 10.110.4, the obtained K and
K' values as a function of molecular weight are uniquely determined.
That the obtained frictional factor K is, as expected, independent of
molecular weight is a vitally important result of the analysis of the G(t)
curves. The very good description of the line shapes of the G(t) curves by
Comparison
in Linear Viscoelasticity
and Diffusion
179
the theory would be totally meaningless if the obtained K values were not
independent of molecular weight. The significance will be further demonstrated when the comparison of theory with experiment is made for the
zeroshear viscosity.
What is surprising is the obtained molecularweight dependence of
K'. K'/K being greater than one indicates that the friction constant
for motions involving a lengthscale smaller than the tube diameter and
restricted inside the tube is greater than that for motions along the primitive path involving lengthscales greater than the tube diameter. Amazingly this difference disappears, i.e. K'/K > 1, as the molecular weight
approaches the Me value. This phenomenon is very significant as it indicates very reasonably that there is no difference between K and K' or
no motional anisotropy when the entanglement becomes absent. In other
words, the difference between the frictional factors K and K' has much
to do with the degree of entanglement per chain, i.e. M/Me. As shown
in Fig. 10.5, when the normalized molecular weight M/Me is sufficiently
large (> 10), the ratio K'/K reaches a plateau value. Such an effect can be
explained in terms of the extra free volume generally associated with the
chain ends. The extra free volume at either chain end is always available
to the motions along the primitive path. On the other hand, the portion of
the extra free volume available to the MA() modes of motions of a particular chain depends on the concentration of chain ends belonging to polymer
chains in its surroundings. Thus, the K' value extracted from the / M ( )
process is molecular weightdependent.
The G(t) curves shown in Figs. 10.110.4 were measured with the
System Four mechanical spectrometer manufactured by Rheometrics, Inc.
When oscillatory measurements for storage and loss moduli were made
with this instrument, both the strain signal of the servo system and the
stress signal from the transducer were correlated with a standard sine wave
to calculate the inphase and outofphase components. Because of these
correlation steps, the obtained storage and lossmodulus spectra as a function of frequency should be more free of noise than the relaxationmodulus
curves. To confirm the measurements and analyses of the G(t) curves as
shown above, the storage and lossmodulus spectra of the studied sample
were also measured. Consistent agreements between theory and experiment were obtained. The comparisons of the measured with the calculated
storagemodulus spectra G'{ui) corresponding to those comparisons shown
in Figs. 10.210.4 are shown in Figs. 10.610.8. Of course, the consistency between the results shown in Figs. 10.210.4 and those shown in
180
Polymer
10"4
'
Viscoelasticity
10"2
10
Frequency (rad/sec)
**
102
Fig. 10.6 Comparison of the measured (dots) and calculated (line) storagemodulus
spectra for the F10 sample. Also shown are the separate contributions of the fiA{t),
Mx(*)> M s M a n d A*c(*) processes (see Fig. 10.1 for the calculation of the A, X, B, and
C lines).
Figs. 10.610.8 also demonstrates the validity of the linear viscoelastic theory studied in Chapter 4.
10.3
Through Eqs. (4.30) and (4.63), the zeroshear viscosity ijo and the steadystate compliance J are related to the relaxation modulus G(t). In the high
molecular weight region ( > ~ 5M e ), both the /z>t() and Hx{t) processes
relax much faster than the Hc(t) process and contribute negligibly to 770
and J . With the /J,A{t) and Hx(t) processes neglected, the zeroshear viscosity and the steadystate compliance are given by Eqs. (9.24) and (9.25),
respectively. It is clear from Eqs. (9.24) and (9.25) that the viscosity value
is affected by the frictional factor K, which is strongly dependent on temperature, and a structural factor; while the steadystate compliance, being
independent of K, is only affected by a structural factor. The structural
factors of 770 and J^ are related to the functional form of the relaxation
modulus G(t), which is in turn determined by the structural factors of the
Comparison
"i
'
in Linear Viscoelasticity
i i mill
and Diffusion
i i iiii
, ,,.
IIM 1 1 1 "
V<
>
1 1 1 1 mi
//*
10
4
10"'
10u
Frequency (rad/sec)
Fig. 10.7
10*
E
u
N.
O
s/s
o
_x_
<D
2.
b
lus
'.
'.
'
~:
;
.
in
c"
=
S
sa
:
;

a
a
o
to
**
"
r
CO
'
" *
uL
1i i i H i d
10"'
10'
Frequency (rad/sec)
10'
Fig. 10.8
'
10
181
182
Polymer
Viscoelasticity
relaxation times (Eqs. (9.6) and (9.12)) and the relaxation strengths (B
and C as given by Eqs. (9.14) and (9.15)).
Both Eqs. (9.24) and (9.25) are for ideal monodispersity. As rjo is proportional to the first moment of the relaxationtime distribution (Eq. (4.65))
while J is proportional to the second moment (Eq. (4.66)), the former is
far less sensitive to the molecularweight distribution than the latter. If the
molecularweight distribution of a sample is nearly monodisperse, its rjo
value is little affected by the distribution while its J value is significantly
affected.
What has been said above about the effect of molecularweight distribution on r)o and J^ is similarly applicable to the lowmolecularweight
region where the contributions of the /i^(t) and Hx(t) processes cannot be
neglected. The analytical expressions for % and J cannot be obtained
from the full expression of the relaxation modulus (Eq. (9.19)). Yet theoretical values of 770 and J , including the contributions of / ^ ( t ) and /ux();
can be numerically calculated with a computer program.
(a)
Zeroshear
viscosity
For showing the main effect of molecularweight distribution on the viscosity value 770, especially in the high molecularweight region, it is sufficient to use the DoiEdwards equation (Eqs. (8.54)(8.56)) instead of
Eq. (9.19). Using the DoiEdwards equation, it can be easily shown by linearly adding the contributions from the different molecularweight components that 770 oc MwMzMz+i16
instead of 770 <x M As Mz+1 > Mz> Mw,
the width of the distribution of a nearly monodisperse polymer can lead to
a viscosity value slightly higher than that of an ideally monodisperse polymer at the same weightaverage molecular weight. If the studied samples
of different molecular weights are equally nearly monodisperse, the viscosity values for all the samples will increase more or less equally by a small
amount due to the narrow distribution of molecular weight; the obtained
molecularweight dependence of viscosity will be practically the same as
that obtained for "ideally monodisperse samples."
As shown above, the G(t) line shapes of a series of polystyrene samples
at different molecular weights above Me are well described by convolving Eq. (9.19) with a nearly monodisperse distribution. Furthermore, the
frictional factor K obtained from the analysis of the G(t) curves measured
at the same temperature is independent of molecular weight. Thus, we
expect to obtain good agreement between theory and experiment for the
Comparison
in Linear Viscoelasticity
and Diffusion
183
Molecular
Weight
Fig. 10.9 Comparison of the measured viscosity values (; without the socalled Tg correction) of nearly monodisperse polystyrene samples and those calculated from Eq. (9.24)
(solid line 1), from t h e DoiEdwards theory (solid line 2), from the Rouse theory (solid
line 3), and from integrating numerically Eq. (9.19) with K'/K = 1 (the bottom dashed
line), K'/K = 3 (the middle dashed line), and K'/K = 5.5 (the top dashed line).
184
Polymer
Viscoelasticity
numerical calculation. The difference between the viscosity curves calculated with K'/K = 3.3 and 5.5 is very small and is only barely noticeable
in the very lowmolecularweight region < Mc. Thus, the contribution of
internal viscosity to the bulk viscosity is negligibly small for the considered range of molecular weight, i.e. > Me. In the highmolecularweight
region, curve 1 (Eq. (9.24)) merges with the curves calculated numerically
with K'/K = 1, 3.3 and 5.5. The comparison of experimental results
with the extended reptation theory in Fig. 10.9 is made by allowing the
the experimental data points to shift along the vertical axis until the best
superposition on the theoretical curve is obtained in the highmolecularweight region (> 8 x 104 where no difference between curve 1 and curves
calculated with K'/K = 1, 3.3, and 5.5 can be discerned). As expected
from the results shown in Fig. 10.5 that K is independent of molecular
weight and that K'/K declines gradually from a plateau value of 3.3 in the
highmolecularweight region to 1 as the molecular weight approaches Me,
the experimental rjo results is in good agreement with curve 1 in the highmolecularweight region and gradually shifts from the curve of K'/K = 3.3
(or K'/K = 5.5) to the curve of K'/K = 1.
As shown in Fig. 10.9, the viscosity data points of the F40 and NBS
samples as well as those of the other samples are closely on the theoretical
curve, without showing a reduction of 30% which occurs to the K values (Fig. 10.5) obtained from the analyses of the G(t) curves of the two
samples. Due to the modification of the zeroshear viscosity by a narrow
molecularweight distribution as discussed above, the effect on the viscosity from the 30% reduction in K is largely cancelled out by the artificial
broadening of the molecularweight distribution extracted from the G(t)
lineshape analysis.
Because of the molecularweight dependence of the glass transition temperature Tg or free volume in the polymer melt, it has been a common practice to correct the measured isothermal viscosity data to the values corresponding to temperatures of equal distance from individual Tg values of the
samples (i.e. at the same AT = T Tg).1'18 This socalled Tg correction
allows the viscosity data to be compared under the condition of presumably
the same friction constant or frictional factor so that the structural factor
of r]o (i.e. a certain function of molecular weight) can be determined. As Tg
reaches a plateau value 19 ' 20 when the molecular weight is sufficiently high,
the correction is smaller with increasing molecular weight. The correction affects the 770 values noticeably mainly in the molecularweight region
below ~ 2MC. After the Tg correction, the molecularweight dependence of
Comparison
in Linear Viscoelasticity
and Diffusion
185
Molecular
Weight
Fig. 10.10 Comparison of the theoretical curve (solid line 1) obtained from integrating
numerically Eq. (9.19) with K'/K = 5.5 and the power law relations r/o oc M 3 4 above
Mc and ijoocAf below Mc (the dashed lines). Me = 13,500 is used in the calculation
giving Mc = 33,000. Also shown are the curves of the DoiEdwards theory (solid line 2)
and the Rouse theory (solid line 3).
186
Polymer
Viscoelasticity
(b)
Steadystate
compliance
Comparison
in Linear Viscoelasticity
and Diffusion
187
* 4k

^
^
Q.
X
~~3
'3
11
CO
10"
10
Molecular
Weight
10"
above M'c as predicted by the theory is not directly reflected by the data
points, whose molecularweight dependence appears flat. As revealed from
the G(t) lineshape analysis as well as the GPC characterization of the sample, the molecularweight distribution of a highermolecularweight nearly
monodisperse sample is broader than that of a lowermolecularweight one.
In fact the trend of molecularweight distribution broadening with increasing molecular weight is generally true for samples synthesized anionically.
The apparent flatness of the J that results in the molecularweight region
> M'c actually indicates that J for ideal monodispersity should decline
slightly with increasing molecular weight, as indicated by curves 1, 2 and 3.
Below M'c, both curves 2 and 3 are below the Rouse line. In the low molecular weight region, the inclusion of the G(t) relaxation component associated with the subRousesegmental motion would also make the J values
smaller. These two effects, cancelling out the broadening effect due to the
finite molecularweight distribution of the samples, make the J data points
below M'c very close to the Rouse line calculated for ideal monodispersity
188
Polymer
Viscoelasticity
(also see Fig. 4.12). This close agreement with the Rouse line is merely a
coincidence.
We can conclude that the extended reptation theory has accurately
explained the molecularweight dependence of the zeroshear viscosity and
the steadystate compliance and their respective transition points M c and
M'c. This success is indeed the logical consequence of the success of the
theory in analyzing the G(t) curves of the studied samples, a vitally important aspect of which is the molecularweight independence of the frictional
factor K. From the analysis of the G(t) curves, it is revealed that entanglements exist between Me and Mc. This point will be further confirmed
by the comparison of the diffusion data with the viscosity data through the
extended reptation theory as discussed below.
10.4
We can rewrite Eq. (8.20) as given by the DoiEdwards theory for the
diffusion constant DQ as
DG = KdM~2
(10.5)
(10.6,
with
< = W
where K^ is the ratio of the meansquare endtoend distance of the polymer chain to the molecular weight
which can be determined from the neutron scattering of the polymer melt
system with the probed chain labelled with deuterium. As the diffusion
constant of a polymer DQ characterizes the translational motion of the center of mass, it should not be affected by the intramolecular chain motions
that affect the viscoelastic behavior. Thus, in spite of the importance of the
intramolecular motions for the viscoelastic behavior as studied in Chapter 9
and above, DQ should remain described by Eqs. (10.5) and (10.6). Both
the Me and K values in Eq. (10.6) can be determined from the analysis of
the G(t) curves in terms of Eq. (9.19) as shown previously in this chapter.
Thus, the Kj, value can be predicted by using the values of K, Me and K^
Comparison
in Linear Viscoelasticity
and Diffusion
189
obtained from analyzing the experimental data of viscoelasticity and scattering for comparison with the value determined from direct measurements
of the diffusion constant on the basis of Eq. (10.5). This comparison would
give a very important test to the extended reptation theory.
The DQ oc M~2 scaling relation (Eq. (10.5)) has been extensively
observed. 23 ' 24 Kramer et a/.25'26 using the forward recoil spectrometry and
the marker displacement technique have obtained very consistent diffusion
results for polystyrene. Shown in Fig. 10.12 is the tracer diffusion constant
in a polystyrene matrix of molecular weight P = 2 x 107 obtained with
the two techniques at 174C. It has been experimentally shown by Green
and Kramer 27 that if the diffusingchain molecular weight M is sufficiently
high (> 100,000), the tracer diffusion constant is the same as the selfdiffusion constant (i.e. when P = M). The diffusion constant characterizes
the translational motion of the center of mass of the polymer chain, and
should not be affected by the intramolecular motions. Thus, while the stress
relaxation in the terminal region is much shortened by the primitivechain
10
10
u
10
10
10
10
10
10
10
M, MOLECULAR WEIGHT
Fig. 10.12 The molecularweight dependence of the tracer diffusion constant obtained
for the nearly monodisperse polystyrene samples in a polystyrene matrix of molecular
weight P = 2 x 10 7 at 174C. The solid line represents DG = 0 . 0 0 8 M  2 . Reproduced,
by permission, from Ref. 25.
190
Polymer
Viscoelasticity
contour length fluctuation if the molecular weight is not large, the diffusion constant, if not affected by the socalled constraint release processes, is
related only to the pure reptation time. For instance, at Af = 55,000, the
pure reptation time is longer than the terminal relaxation time by a factor of
3.9.28 Because of this difference, while, as shown previously in this chapter,
the linear viscoelasticity is not susceptible to the constraint release effect as
long as the sample is nearly monodisperse, the diffusion constant in the low
molecular weight region (< 100,000 for polystyrene) is somewhat enhanced
by the effect. Since we are interested in comparing the viscoelastic data
with the diffusion results, we consider the tracer diffusion data as shown
in Fig. 10.12. The diffusion constant for a highmolecularweight nearly
monodisperse polystyrene polymer was measured by Bueche using the radiolabeling technique. 29 After Bueche's result is corrected to 174C by using
the temperature dependence of viscosity data, 30 the obtained K& value is
in close agreement with the values obtained by Kramer et al. The average
of these studies gives Kd = 8 x 10 3 cm 2 g/(s mol 2 ) 13% at 174C. 31
Besides from the analysis of G(t) as shown in Sec. 10.2, the frictional
factor K can be obtained from the viscosity data using Eq. (9.24) in
the highmolecularweight region where the contributions of the [IA (t) and
Hx(,t) processes to viscosity are negligible. From the data of Plazek and
O'Rourke 30 at Mw = 0.94x, 1.89x, and 6.0 x 10 5 , one obtains K = 3.2x,
2.4x, and 2.7 x 10~ 12 , respectively, at 174C. As explained in Sec. 10.3,
the polydispersity of a nearly monodisperse polymer causes its viscosity to
be slightly higher than that of an ideally monodisperse one at the same
weightaverage molecular weight. Equation (9.24) being for ideal monodispersity, a correction should be made to the above obtained K values. The
bulk of correction can be made if the Mw/Mn values of the samples are
known. While being not given, the Mw/Mn values of the three samples
can be estimated from matching their measured steadystate compliance
J values 30 with those calculated from Eq. (4.63) wherein the G(t) is
first calculated from convoluting Eq. (9.19) with the Schulz distribution
(Eq. (10.3)) using the Z value as the only adjustable parameter. In this
way, Z = 23, 20 and 10 (correspondingly, Mw/Mn = 1.04, 1.05 and 1.1) are
obtained for the three samples, respectively. Then the correction factors for
K due to polydispersity can be obtained by comparing the viscosity values
calculated from Eq. (9.24) and from integrating numerically the G(t) calculated from convoluting Eq. (9.19) with the Schulz distribution using the
above obtained Z values, both kinds of calculations being done with the
same (weightaverage) molecular weight and K for each sample. The thus
191
obtained correction factors are 1.24, 1.22 and 1.34 for the three samples,
respectively. That the first sample, while having a Z value slightly larger
than the second one, has a slightly larger correction factor is due to the
fact that at its molecular weight the A*A(*) and Hx(t) processes can still
make a small noticeable contribution to viscosity. The K values corrected
by these factors are 2.6x, 2.Ox, and 2.0 x 1 0  1 2 , respectively. In the same
way, the K values of the three samples at 127.5C are obtained to be 5.7x,
4.9x, and 5.8 x 10~ 9 , respectively. Using the ratio of the average values of
the two sets of K values, we obtain K = 1.9 x 10~ 12 at 174C from the
K value at 127.5C obtained from analyzing G{t) (4.7 x 1 0  9 ; the average
over the samples with Mw between 3.4 x 104 and 1.1 x 10 5 as shown in
Fig. 10.5). The above obtained K values are in close agreement with one
another, at both 174 and 127.5C, further supporting K being independent
of molecular weight as shown in Fig. 10.5. Using the average of the K
values at 174C in Eq. (10.6) gives Kd = 9.2 x 10~ 3 , in close agreement
with the value 8 x 10~ 3 obtained directly from the diffusion measurements.
Shortly after the DoiEdwards theory was published, Graessley 16 proposed using the viscosity value at Mc to calculate the K value on the basis
of the Rouse theory
367ft (M = M c )
n*pRTMc
(10 8)
'
and then calculate through Eq. (10.6) the K^ value for comparison with
that obtained from the diffusion measurements. Since the diffusion measurements were made on samples in the molecularweight region where the
glass transition temperature Tg does not change with molecular weight, the
viscosity value at Mc to be entered into Eq. (10.8) has to be first corrected
for the Tg difference at Mc.
Graessley's approach for checking the validity of the diffusion constant
of the DoiEdwards theory (Eqs. 10.5 and 10.6) was based on the traditional belief that there was no entanglement at a molecular weight smaller
than Mc. However, the results as obtained previously in this chapter:
(1) the quantitative analysis of the G(t) curves in terms of Eq. (9.19) indicating that the factional factor K is independent of molecular weight to as
low as just above M e (Fig. 10.5) and (2) the molecularweight dependence
of the viscosity being well described by the extended reptation theory over
the whole molecularweight region above Me (Fig. 10.9) clearly indicate
that entanglement already occurs in the molecularweight region between
Me and M c . As shown in Figs. 10.9 and 10.10, the theoretical T]Q curve with
192
Polymer
Viscoelasticity
References
1. Ferry, D. J., Viscoelastic Properties of Polymers (3rd edn). Wiley, New York
(1980).
2. Ferry, J. D., Macromolecules 16, 5237 (1991).
3. Graessley, W. W., Adv. Polym. Sci. 16, 1 (1974).
4. Doi, M., and Edwards, S. F., The Theory of Polymer Dynamics, Oxford
Univ. Press (1986).
193
Chapter 11
Concentration Dependence of
Entanglement, Onset of
Entanglement, and Tube Dilation
11.1
Introduction
Dependence of Entanglement,
Onset of Entanglement,
195
segments (the molecular weight for a Rouse segment is about 850 7  9 ), serves
as a viscoelastic medium to componenttwo's chains rather than a viscous
one. At the same time, the identical segments of both components with the
same average surroundings have the same mobility (or friction constant).
Thus, the hydrodynamic interaction is not expected to occur in the blend
solution. Without both effects, the basic shortrange (shorter than the
entanglement strand) Rouse dynamic behavior of both components in the
blend solution is expected to be the same as that in the pure melt containing
a single component.
The DoiEdwards theory was built on the primitive chain concept which
is defined by Eq. (8.3). Its relation with the key physical quantities can be
summarized in the following equations:
aL = R2 = Na2 = N0b2 = ^a2
(11.1)
a2 = KQOMe
(11.3)
and
where K^ is given by Eq. (10.7). In other words, the tube diameter or the
entanglement distance, a, is related to the entanglement molecular weight
Me determined from the plateau modulus G^ The increase of the entanglement molecular weight with dilution will be reflected by the concentration
dependence of the plateau modulus. By simple argument, the entanglement
molecular weight of the blend solution M'e is given by
196
Polymer
Viscoelasticity
11.2
Entanglement Region
(a)
Theory
197
component two by Eq. (9.19), the theoretical form of the total relaxation
modulus G(t) is given by
G(t) = Wi f
Ax{M)GR(t,M)dM
JA2(M)
1+
exp(t/TX)
BVB{t/TB)
Cnc{t/TC) dM
(11.5)
where A\{M) and A2(M) are the nearly monodisperse molecular weight
distributions of components one and two, respectively; Gn(t) is the relaxation modulus of the Rouse theory, given by Eqs. (7.57) and (7.58); and
HA(t), Ats(i)) /*?(*), B, C, TVA, Tx, TB and Tc have the same functional
forms as given in Chapter 9 (Eqs. (9.B.18), (9.5), (9.11), (9.14), (9.15),
(9.B.20), (9.22), (9.6) and (9.12), respectively) but with all the M e quantities appearing in the equations replaced by M'e (Eq. (11.4)). When Wi = 0,
the second term of Eq. (11.5) becomes identical to Eq. (9.19), which can
be regarded as a special case of Eq. (11.5).
(b)
Comparison
of theory and
experiment
The linear relaxation moduli and viscoelastic spectra have been studied for
a series of concentrated polystyrene blend solutions consisting of two nearly
monodisperse components: F l (Mw = 1.03 x 104) as component one and X
(X = PI: Mw = 6.8 x 104; F10: Mw = 1.00 x 105; F35: Mw = 3.55 x 105;
F80: Mw = 7.75 x 105) as component two. 10 The blend solutions were prepared at the weightfraction ratios of P7/F1 = 50/50 and 75/25; F10/F1 =
50/50 and 75/25; F35/F1 = 50/50; and F80/F1 = 50/50. In these systems,
the componentone polymer with a molecular weight slightly below the
entanglement molecular weight Me is free of entanglement yet long enough
to be described by the Rouse theory while componenttwo polymers, which
all have a weightaverage molecular weight MW2 greater than M'e, are well
entangled. The viscoelasticspectrum line shapes of these blend solutions
have been analyzed in terms of Eq. (11.5) as shown below.
For convenience of discussion, the friction factor in the Gn(t) process
is denoted by K" (Eq. (7.57)), in the fiA(t) process by K' (Eq. (9.B.20)),
and in TX (Eq. (9.22)), rB (Eq. (9.6)), and TC (Eq. (9.12)) by K. In a
homogeneous blend, all components are in the same average environment.
198
Polymer
Viscoelasticity
Thus, the first and second terms of Eq. (11.5) are expected to have the same
frictional factor, i.e. K" = K. If the second term of Eq. (11.5) behaves
the same in the concentrated blend solution as in the puremelt system
(i.e. when W\ = 0 in Eq. (11.5)), whose study was described in the last
chapter, the same molecularweight dependence of K'/K (Fig. 10.5) should
be followed with the molecular weight expressed in terms of the normalized
molecular weight: Mw/Me for the melt and MW2/M'e for the blend solution. Indeed, as shown in Fig. 11.1, the molecularweight dependences of
the melt and blendsolution systems have been observed to be the same. 10
The dependence of K'/K on M/Me (or M2/M'e) can be described by the
empirical equation:
0L
K
2.525
+ 0.769.
exp[0.643[(M/M e )  4.567]] + 1
~l
1I I I I
(11.6)
1I I I I I J ' 
i^A.^
K 7K
O o
K'/K
*s
J?
 T "
i i i i 11
10
M/M orM/M
I I I I
100
Fig. 11.1 A"(A) for the nearly monodisperse (polystyrene) melts (from Ref. l i b ; same as
shown in Fig. 10.5), K"/K (a) for the X / F l blend solutions (from Ref. 10), and K'/K:
() for the nearly monodisperse melts (from Ref. l i b ; same as shown in Fig. 10.5) and
(o) for the X / F l blend solutions (from Ref. 10) as a function of the normalized molecular
weight: Mw/Me for the melt and Mw/M'e for the blend solution.
Dependence
of Entanglement,
'"H
 v j>*
Onset of Entanglement,
199
:I
%
: A \<\
"=
rx
"
C
"
;
:
;:
:
V.
\ \*
o
OH
10',2
10"
Time (sec)
10'
10^
Fig. 11.2 Comparison of the measured (dots) and the calculated (line) relaxation modulus, G(t), for the P 7 / F 1 = 50/50 sample. Also shown are the separate contributions
of the freeRousechain process of F l (the portion between lines R and A; line A is calculated by setting W\ = 0), and the / ^ ( t ) , /Jx{t), AB(*)> a n d M c M processes of P7
(see Fig. 10.1 for the calculation of lines A, X, B and C). The calculation is made with
K = 1 0  8 , K'/K = 1.4, and K"/K = 1.
200
Polymer
\ '
'i
'
>
Viscoelasticity
''
, , M
'"i
IJ
C3
>//
rx
:B
o
2
\*

0)
":
ec
'
"
i
'
10"
10'
10*
10'
Time (sec)
Fig. 11.3 Same as Fig. 11.2 for the F 1 0 / F 1 = 50/50 sample. T h e calculation is made
with K1 IK = 1.8 and K"/K = 1.
ni
i i iiriii)'
t i IMIII
i i i 1111
10"*
10"'
Frequency (rad/sec)
i i T mri
'
10"
i i iiini
w*
"
10'
Fig. 11.4 Same as Fig. 11.2 for the storagemodulus spectrum, G'(u)), of the F 3 5 / F 1 =
50/50 sample. T h e calculation is made with K'/K = 4.1 and K"/K = 1.2.
Dependence of Entanglement,
Onset of Entanglement,
201
Frequency (rad/sec)
Fig. 11.5 Same as Fig. 11.2 for the storagemodulus spectrum, G'(w), of t h e F 8 0 / F 1 =
50/50 sample. The calculation is made with K'/K = 4.2 and K"/K = 1.3.
202
Polymer
Viscoelasticity
I
b 3
b
00
...
7/
Dependence of Entanglement,
Onset of Entanglement,
203
(11.7)
The agreement between the experimental results and Eq. (11.7) is within
5% for the studied blendsolution samples. 10 The second point is the diminishing of the modulusplateau zone with decreasing W2 The increase in
entanglement molecular weight M'e with decreasing W2 affects the line
shape of the viscoelastic spectrum through the relaxation strengths B and
C (Eqs. (9.14) and (915)) and the relaxationtime ratios TC/T\,
TB/T\,
TX/T\ (Eqs. (9.20), (9.21), (9.23)). As W2 decreases, the relaxationtime
ratios decrease and bring all the relaxation processes closer in time; particularly, the separation between the transition zone and the terminal zone
is narrowed by the decrease in the ratio TC/T\. While the decrease in W2
reduces the width of the modulus plateau, B increases and C decreases,
both changes enhancing the importance of the /is(t) process. These changes
reduce the flatness of the modulus plateau. As shown in Fig. 11.7, the
comparison of the viscoelastic spectra of pure F10, F10/F1 = 75/25, and
F10/F1 = 50/50, all quantitatively described by Eq. (11.5) (including
Eq. (9.19) for pure F10), clearly illustrates the effects of dilution on the
spectrum line shape.
A very important result of the lineshape analysis of the viscoelastic
spectra in terms of Eq. (11.5) for the concentrated blend solutions is that
the obtained K" and K values are, as expected, the same (Fig. 11.1). The
sensitivity of the determination of the K"/K ratio is rather high. As shown
in Fig. 3 of Ref. 10, a 50% change in the K"/K ratio value can cause a
clearly noticeable difference between the measured and calculated spectra;
the possible error of the shown K"/K ratio values in Fig. 11.1 should be
no more than about 20%. The close agreement between K" and K means
that the extended reptation theory, developed on the framework of the
DoiEdwards theory (Chapter 9), has bridged the gap between the DoiEdwards theory and the Rouse theory. One may think that the linkage
is quite miraculous because the tube (or the primitive chain denned by
Eq. (8.3)) introduced in the DoiEdwards theory is an assumed mean field
which is structurally one level larger than the mean field assumed in the
Rouse theory (i.e. the Rouse segment and its associated friction constant).
The linkage not only supports the validity of the primitivechain idea, but
204
Polymer
Viscoelasticity
Frequency (rad/sec)
Fig. 11.7 Comparison of the storagemodulus spectra (both the calculated (lines) and
the measured) of the F10 ( A ) , F 1 0 / F 1 = 75/25 () and F 1 0 / F 1 = 50/50 () samples.
The arrows indicate t h e frequencies uic = 1/TC where the TC values are calculated from
Eq. (9.12) with K = 1 x 10~ 8 and M e replaced by M'e = Me x W 2  1 . The dashed lines
indicate the separations of the contributions of the freeRousechain process of F l and
the HA{t) process from those of t h e fix(t), / i s M and Hc{t) processes; in other words,
the high frequency limits of the dashed lines occur at (5/4)GjvW^ (see Eq. (11.5)).
also supports that the DoiEdwards theory has provided the right theoretical framework in which the additional dynamic processes can be properly
incorporated.
In this section, we have shown the results of the quantitative analysis of the viscoelastic spectrum in the concentrated region where chain
entanglements are extensive. These results, as well as those described in
Chapter 10 for the melt system, give the molecularweight dependence
of K'/K shown in Fig. 11.1, suggesting that entanglements start at the
molecular weight Me for the melt system and M'e for the blend solution.
It is important to observe directly whether this is indeed so. To show the
onset of entanglement, we shall first study the lowconcentration region of
the blendsolution system and the lowmolecularweight region of the onecomponent melt system where the whole system is expected to be free of
entanglement.
Dependence
11.3
of Entanglement,
Onset of Entanglement,
205
As discussed above, the entanglement molecular weight M'e in a concentrated blend solution is given by Eq. (11.4). If the concentration W2 is
smaller than the critical concentration Wc, denned by
w
(1L8)
'  &
then MW2 < M'e and the solution should be free of entanglement for both
the low and highmolecularweight components. 13 The relaxation modulus
of such an entanglementfree blend solution may be described by a linear
combination of two Rouse relaxation processes corresponding to the two
components.
Git) = WX f A1(M)GR(t,M)
dM + W2 f A2(M)GR(t,
M) dM
(11.9)
where GR(1,M) is the relaxation modulus given by Eqs. (7.57) and (7.58)
and A\{M) and A2(M) are the nearly monodisperse molecularweight distributions of component one and component two, respectively.
A series of polymer blend solutions, denoted by samples A, B, C and D,
were prepared by blending two nearly monodisperse polystyrene polymers:
G10 (component two with Mw = 1.03 x 105 and Mw/Mn = 1.01) and G l
(component one with Mw = 9.1 x 10 3 and Mw/Mn = 1.02) at the weightfraction ratios W1/W2 = 95/5, 80/20, 70/30 and 60/40, respectively.13
Shown in Fig. 11.8 are the molecularweight distributions for the G1/G10
blend solutions calculated using the Schulz function (Eqs. (10.3) and (10.4))
with Z = 50 for G l and Z = 90 for G10. Z = 50 and Z = 90 for
the two separate components were chosen to give the Mw/Mn values in
agreement with the values obtained from the sample characterizations of G l
and G10, respectively. The entanglement molecular weights Me (= 13,500
for polystyrene) and M'e (Eq. (11.4)) for all the blendsolution samples
are indicated in Fig. 11.8. Figure 11.8(a) shows that both components in
sample A are free of entanglement. Figures 11.8(b)(d) indicate that while
the G l component remains free of entanglement, the degree of entanglement
among GlO's chains (namely, Mw2/M'e) increases with the increase in W2
from sample B to sample D.
As shown in Fig. 11.9, the storagemodulus spectrum of sample A is well
described by the Rouse theory: Eq. (11.9) with the molecular weight distributions shown in Fig. 11.8(a) for A\{M) and A2(M). In the calculation
206
Polymer
Viscoelastidty
A.. A
(d)
" A. . A
(c)
(b)
'I
0A
(a)
/..A10 3
10 4
^
10 s
10 6
molecular weight
Fig. 11.8 The molecularweight distribution
(Eqs. (10.3) and (10.4) with Z = 50 for G\ and
(a), 80/20 (b), 70/30 (c), and 60/40 (d) blend
blend solution are indicated by and o points,
of the spectrum, the number of Rouse segments per chain N is taken as the
integer of the ratio M/m where m, set to be 850 for polystyrene, 79 ' 13 is the
molecular weight for a Rouse segment. Due to the weak molecularweight
dependence of the relaxation times, and of the relaxationtime distribution in the Rouse model, the calculated spectrum is very insensitive to
the molecularweight distribution of either of the two nearly monodisperse
components as long as it is sufficiently narrow. For instance, as long as
Z > 50, virtually no change in the spectrum can be discerned as the Z
value varies. This insensitivity removes any concern that some difference
in the calculated spectrum might be caused by a small uncertainty in the
molecularweight distribution.
No shift along the modulus coordinate is involved in obtaining the very
good superposition of the measured and calculated spectra as shown in
Fig. 11.9. This indicates that the force constant on the Rouse segment,
Dependence of Entanglement,
Onset of Entanglement,
10 8  a r  n
10 7
TT
1rrriTTT]
1rTxmq
1rrivrn]
207
1n iyu
10B 
104
10 3 
102
I
10^
10" 3
10"2
'
i
10"1
10
101
'
i
10 2
1Q3
FREQ (rad/sec)
Fig. 11.9 Comparison of the measured storagemodulus spectrum (o and ) and that
calculated from the Rouse theory (solid line) for sample A. The dashed line indicates the
separation of the contributions from the G l and G10 components. T h e arrow at 1 / T I ( 1 )
indicates the frequency t h a t is the reciprocal of the relaxation time of the first Rouse
mode of the G l component calculated from Eq. (7.57) with K = 1 x 1 0  8 , whereas the
arrow at 1 / T I ( 2 ) indicates the same for the G10 component.
which gives rise to the modulus, is of entropic origin as it is defined statistically. In Fig. 11.9, the dashed line (calculated by setting Wx = 0) indicates
the separation of the contributions from the G10 and Gl components. It is
clear that the two "bumps" on the storagemodulus spectrum correspond to
the main viscoelastic responses of the two components in the blend solution:
the highfrequency one for the Gl component and the lowfrequency one for
the G10 component. The accurate prediction by the theory of the relative
positions of the two bumps and their shapes clearly illustrates that, in the
entanglementfree region, the molecularweight dependence (i.e. n ex M 2 )
and the p dependence (i.e. TV OC l/sin 2 (p7r/2iV)) of the viscoelastic relaxation times in the blend solution are well described by the Rouse theory.
Entanglements among componenttwo's chains will eventually occur as
W2 increases above a certain point. As they occur, the constraint effect due
to entanglement will render the spectrum in the lowfrequency region where
the main viscoelastic response of component two occurs no longer described
by the Rouse theory. Assuming that entanglements never did occur to
208
Polymer
Viscoelasticity
fTTTIl]
io
103
1 I l
102
101
10
101
102
103
FREQ (rad/sec)
Fig. 11.10 Comparison of the measured storagemodulus spectra of samples A (o and
) , B ( D and ) , C ( A and A ) , and D (<> and ) with those calculated (solid lines) using
the Rouse theory for both the G l and G10 components. In calculating the spectra,
the frictional factor K is set to be 1 0  8 for sample A (line 1); 1 0  9 for sample B (line
2); 1 0  1 0 for sample C (line 3); and 1 0  1 1 for sample D (line 4) to avoid overlapping
of the lines and the data points. T h e comparison is made for each sample by shifting
the measured spectrum along the frequency coordinate to match the calculated in the
highfrequency bump region.
Dependence
of Entanglement,
Onset of Entanglement,
209
calculated are parallel with each other in the lowfrequency region (both the
calculated and measured lines of log(G') versus log(o;) are straight and have
the expected slope of 2; see Chapter 4). The measured line is more remote
toward the lowerfrequency side from the calculated as W2 increases. The
shift factor obtained from superposing the two parallel lines by moving only
along the frequency coordinate can be used to characterize the degree of
deviation. Because of the use of the internal reference, the frequencyshift
factor determined this way for component two is free of any change of the
frictional factor due to any outside influence, such as a change in temperature or concentration; in other words, it reflects entirely the change in the
structural factor of relaxationtime (mainly of the slowest mode) which is
caused by the occurrence of entanglements. In Fig. 11.11, the frequencyshift factors at different concentrations W2 are shown. By extrapolating the
shift factors towards the smaller W2 region, the point where the extrapolation line crosses the noshift line can be determined. This point, denoted
by W, can be regarded as the highest concentration where a change in
the structural factor of relaxationtime due to entanglement has not yet
occurred, or as the onset point of entanglement. W occurs in the close
neighborhood of Wc calculated according to Eq. (11.8). This means that,
3.5
3.0
'
"5 2.0
1.5
1.0
0.0
0.1
0.2
0.3
0.4
0.5
W2
Fig. 11.11 Frequencyshift factor as caused by the entanglement effect versus the weight
fraction of component two, Wi The arrow indicates the expected Wc value from
Eq. (11.8).
210
Polymer
Viscoelasticity
if MW2 is the variable, and Wi is kept at a fixed value in the blend solution,
entanglements start to occur within the experimental error at M'e given by
Eq. (11.4).
Equation (11.9) includes the special case of pure melt containing only
one nearly monodisperse component (i.e. by setting either W\ or W2 = 1)
whose molecular weight Mw is smaller than Me. Shown in Fig. 11.12 is
the comparison of the storagemodulus spectrum of a nearly monodisperse polystyrene polymer F l whose molecular weight is 0.76Me (Mw =
1.03 x 104; Mw/Mn = 1.01), with that calculated from Eq. (11.9) using
the Schulz molecularweight distribution with Z = 90. 14 As long as Z is
above 50, no change in the calculated spectrum can be discerned with
a change in Z. Except for the veryhighfrequency region where the subRousesegmental dynamic process has a significant contribution to the measured spectrum, the measured and calculated spectra are in close agreement over the whole range of modulus (i.e. below ~ 5 x 106 dynes/sqcm;
the small molecular weight of the F l sample makes the highermodulus
(or frequency) region particularly susceptible to the contribution of the
subRousesegmental process). On the other hand, it is very clear from
105 r
lo
rn
10"1
10"
101
10z
103
Frequency (rad/sec)
Fig. 11.12 Comparison of the measured (dots) storagemodulus spectrum and the
calculated (line) from the Rouse theory for sample F l .
Dependence of Entanglement,
10
I I 1 I llll
Onset of Entanglement,
I I I I llll
I I I Mill
TTJ
211
I I IITl
107
10
105
104
103
10 J
''
10 2
10"1
10
101
10z
103
Frequency (rad/sec)
Fig. 11.13 Comparison of the measured (dots) storagemodulus spectrum and the
calculated (line) from the Rouse theory for sample F2.
Fig. 11.13 14 that such a close agreement between the measured spectrum
and the Rouse theory (calculated with Z = 50) cannot be obtained for
a nearly monodisperse polystyrene melt F2 whose molecular weight is
1.24Me (Mw = 1.67 x 104; Mw/Mn = 1.02). Similar to the results shown
in Fig. 11.10, Fig. 11.13 shows that the measured spectrum in the lowfrequency region deviates toward the lowerfrequency side from the calculated while both spectra match in the highfrequency region. This slowdown phenomenon, occurring mainly to the slowest Rouse mode of motion,
is a sign of entanglement. In fact, as shown in Figs. 10.4 and 10.8, the
spectrum of F2 can be well described by Eq. (9.19), which contains the constraint effect of chain entanglement (the fic(t) process). From the results
shown in Figs. 11.12 and 11.13, the initial deviation from the Rouse theory,
signifying the onset of entanglement, should occur at a molecular weight
between those of F l and F2, namely, between 10,300 and 16,700. In other
words, the onset of entanglement should occur at a point very close to
the entanglement molecular weight Me (= 13,500 for polystyrene) for the
onecomponent melt. This result is in agreement with the finding that the
onset of entanglement occurs in the close neighborhood of M'e for the blend
solution.
212
Polymer Viscoelasticity
213
for obtaining the viscosity can even out vital entanglementrelated details
in the relaxation modulus or equivalently in the viscoelastic spectrum.
11.4
Tube Dilation
214
Polymer
Viscoelasticity
frictional factor K for the terminal relaxation remains the same; any time
shift in the terminal region between a binary blend and its pure componenttwo melt should be entirely due to a change in the entanglementrelated
structural factor.
If the frictional factor K in a blend solution were the same as that in
its pure componenttwo melt, the terminalrelaxationtime ratio of the two
systems could be obtained from Eq. (9.12) as
TC
Me
ML
11
(M'e/Mw2y/2
(Me/Mw2y/*
,2
(11.10)
where T'C is for the blend solution and TQ for the pure melt. In Fig. 11.14,
the measured and calculated relaxation curves of the pure F80 melt are
compared with the curves of the F80/Y binaryblend series (Y = NBS,
F10, F4 and W2/Wi = 0.5/0.5), measured at the same temperature, and
the theoretical curve of the blend solution with F80 as component two
Time (sec)
Fig. 11.14 Comparison of the calculated and measured relaxation modulus G(t) curves
in the terminal region: the upper solid line is the calculated for the F80 melt, which has
been multiplied by a factor of l / 4 ( = W%) for comparison with other curves; the lower
solid line is calculated for the concentrated solution of F80 at W2 = 0.5 (M'e = M e /0.5);
(. .) is the measured G(i) of the F80 melt multiplied by 1/4; (  ) is the measured
G(t) of the F80/NBS = 50/50 blend; (
) is the measured G(t) of the F80/F10 blend;
and (
) is the measured G(t) of the F80/F4 blend.
Dependence
of Entanglement,
Onset of Entanglement,
215
216
Polymer
Viscoelasticity
Fig. 11.15 The apparent timeshift factor, T'Q/TC, as a function of the molecular weight
(MW) of the low M W component (denoted by Y) in the binary blends: F80/Y = 75/25
(); F80/Y = 50/50 (o); F35/Y = 75/25 (*); and F35/Y = 50/50 ( A ) . The horizontal
lines on the vertical axis indicate the theoretical T'C/TC values calculated from Eq. (11.10)
as the limiting values for the four series of blend samples.
217
e
2
J
0
10 s
2x10 5
3x10 5
MW of the Low MW Component
I
4x10 5
Fig. 11.16 The apparent M"/Me values as a function of the molecular weight of the
low MW component (Y) in the F80/Y = 50/50 blends.
218
Polymer Viscoelasticity
() + Cmc
B\HB
+ GNW2[W1T(t)
TCI
+ W2] B2^B
\TB2j
+ C2(J.C
T~C2
(11.A.1)
where B\, C\, TBI, and TCI are for component one and B2, C2, TB2, and
rc2 for component two; and B, C, /XB(), Hc(t), TB and re have the same
definitions as given by Eqs. (9.14), (9.15), (9.5), (9.11), (9.6) and (9.12),
respectively. In the above equation, T(t) is a decaying function for the
tuberenewal process that takes place on a componenttwo chain as the
componentone chains originally entangled with it disentangle and reptate
away. Prom the analysis of measured spectra in terms of Eq. (ll.A.l), T(t),
assumed to be a single exponential, is found to have a characteristic time
rt that is about seven times larger than TQ\ At the same time, while Bi,
C\, TBI and TCI are not affected by the presence of component two and
keep their respective values in the pure melt state, B2, C2, TBI and TCI
are affected by the tube dilation due to the much faster reptation motions
of the componentone chains. The tubedilation effect can be accounted
for by changing the Me quantity that occurs in the expressions for B2, C2,
TB2 and TCI to an apparent effective value M" (> Me) as discussed in the
section on tube dilation of this chapter. For two components which are
actually nearly monodisperse in an experiment, the convolution over their
respective molecularweight distributions can be done to Eq. (ll.A.l) in
the same way as done to Eq. (11.5), however, without including the effect
of componentone's molecularweight distribution on T(t).
When componentone's molecular weight is below Me, the viscoelastic response of component one is described by the Rouse theory, and r t
(proportional to TCI if the componentone chain reptates) can be equated
to zero as the componentone chains lose the reptational mechanism. Then
Eq. (ll.A.l) is transformed to
G(t) = W1GR(t,M1)
where GR(t,Mi)
+ G'N B2flB
\TB2j
(11.A.2)
+ C2nc
TC2
^ ' W2
5ML
(11.A.3)
Dependence
of Entanglement,
Onset of Entanglement,
219
with
M'e = .
(11.A.4)
References
1. Doi, M., and Edwards, S. F., The Theory of Polymer Dynamics, Oxford
Univ. Press (1986).
2. Bird, R. B., Curtiss, C. F., Armstrong, R. C , and Hassager, O., Dynamics
of Polymeric Liquids, Kinetic Theory, Vol. 2 (2nd edn.), Wiley, New York
(1987).
3. Zimm, B. H., J. Chem. Phys. 24, 269 (1956).
4. Flory, P. J., Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca
(1953).
5. de Gennes, P. G., Scaling Concepts in Polymer Physics, Cornell Univ. Press,
Ithaca (1979).
220
Polymer Viscoelasticity
6. Kirste, R., and Lehnen, B., Makromol. Chem. 177,1137 (1976); Westermann,
S., Willner, L., Richter, D., and Fetters, L. J., Macromol. Chem. Phys. 201,
500 (2000).
7. Ballard, D. G. H., Rayner, M. G., and Schelten, J., Polymer 17, 349 (1976);
Norisuye, T., and Fujita, H., Polymer 14, 143 (1982).
8. Inoue, T., Okamoto, H., and Osaki, K., Macromolecules 24, 5670 (1991);
Inoue, T., and Osaki, K., Macromolecules 29, 1595 (1996).
9. Lin, Y.H., and Lai, C. S., Macromolecules 29, 5200 (1996); Lai, C. S., Juang,
J.H., and Lin, Y.H., J. Chem. Phys. 110, 9310 (1999); and Lin, Y.H., and
Luo, Z.H., J. Chem. Phys. 112, 7219 (2000).
10. Lin, Y.H., Macromolecules 20, 885 (1987).
11. Lin, Y.H., (a) Macromolecules 17, 2846 (1984); (b) 19, 159 (1986).
12. Watanabe, H., Sakamoto, T., and Kotaka, T., Macromolecules
18, 1436
(1985).
13. Lin, Y.H., and Juang, J.H., Macromolecules 32, 181 (1999).
14. Lin, Y.H., Macromolecules 19, 168 (1986); as shown in Figs. 11.12 and 11.13,
the theoretical curves are recalculated with m = 850 for each Rouse segment.
15. Lin, Y.H., Macromolecules 24, 5346 (1991).
16. Ferry, D. J., Viscoelastic Properties of Polymers (3rd edn.), Wiley, New York
(1980).
17. Berry, G. C., and Fox, T. G., Adv. Polym. Sci. 5, 261 (1968).
18. Graessley, W. W., J. Polym. Sci., Polym. Phys. Ed. 18, 27 (1980).
19. Lin, Y.H., Macromolecules 22, 3075 (1989); 22, 3080 (1989).
20. Klein, J., Macromolecules 11, 853 (1978).
21. Daoud, M., and de Gennes, P.G., J. Polym. Sci., Polym. Phys. Ed. 17,
1971 (1979).
22. Graessley, W. W., Adv. Polym. Sci. 47, 67 (1982).
23. Marrucci, M., J. Polym. Sci., Polym. Phys. Ed. 2 3 , 159 (1985).
24. Viovy, J. L., J. Phys. (Les Ulis, Fr.) 46, 847 (1985).
25. Rubinstein, M., Helfand, E., and Pearson, D. S., Macromolecules 20, 822
(1987).
26. des Cloizeaux, J., Macromolecules 23, 3992 (1990).
Chapter 12
222
12.1
Polymer
Viscoelasticity
ChainTension Relaxation
Y,Ni
= N0.
(12.1)
(12.2)
where
Ti(t)=Ri(t)Ri1(t).
(12.3)
Letting the index n represent the nth Rouse segment in the entanglement
strand between Ri_i and Rj, Doi assumes
Ri(t)  Rii(t)
= <(*W(t)<(t)>
(12.4)
Modulus
223
62
b2
f dn(Vn(t)vn(t))(ln(t))2+P5.
Jo
(12.5)
In making the assumption of Eq. (12.4), one has allowed the averaging
over orientation for v n v to be separated from the tensilestress magnitude (oc {ln(t))2) on each Rouse segment as expressed in Eq. (12.5). Furthermore, in changing the summation over the entanglement strands to
the integration over the whole chain segments J0 " dn in Eq. (12.5), Ni(t)
is replaced by its average. Applying these assumptions is equivalent to
making the socalled independent alignment approximation. 2 With these
assumptions, the local differences among entanglement strands have been
ignored. These assumptions lead to some small discrepancies from the exact
situation, as can be seen in the following:
Let Sn be the point on the primitivechain contour corresponding to the
nth Rouse segment. Denote the positions of Sn in threedimensional space
before and after a step deformation E is applied as R ( 5 n ) and R(Sn(t)),
respectively. Then, before the application of E, the length vector Z v along
the primitive chain corresponding to the nth Rouse segment is given by
lnvn = J;R(S)
(12.6)
with
dTL(Sn)
rn =  ^
(i2.7)
224
Polymer
Viscoelasticity
and
(dR(Sn))/dn
v = \(dR(S ))/dn\n
(12.8)
And at time t following the initial application of E, the length vector corresponding to the nth Rouse segment is given by
d
(12.9)
dn R(S(t))=V n (t)in(t)
Since R(S n ()) changes affinely with the deformation E, the initial value
of ln(t) and v() (i.e. the values at t TA and denoted by l'n and v^) are
I'
^E.R(5n)
(12.10)
KIEvfl
and
Ev
Ev
"
(12.11)
(12.12)
and
'(E.v)(E.v)'
Ev2
(Eu)(Eu)
Eu2
(v' v ' ) =
(12.13)
(12.14)
m:
for Nel = a. Substituting Eqs. (12.12) and (12.13) into Eq. (12.5), one then
has the stress at t ss TA
T(t rA)
3cfcr
E u)
AW ( E ;5
: ')
Eu2
62
a{Er+PS
=  3 c W ( E ; " ) ( E ; u ) \ a(E? + PS
\
Eu
where, for the last equality, Eqs. (8.3) and (12.14) have been used.
(12.15)
Modulus
225
The discrepancy between Eq. (12.15) and the exact result, Eq. (8.37),
is not large as
(Eu)(Eu)
IEu 2
(Eu)2((Eu)(E.u))u.
(12.16)
/(Eu)(Eu)
\
E'u2
pS
(12.17)
Strain X
Fig. 12.1 Comparison of <(E u ) ( E u ) /  E u  2 ) a ( E ) 2 (denoted by A; solid line) and
( ( E  u ) ( E  u ) ) (denoted by B ; dashed line) as a function of strain A for simple shear
deformation (E given by Eq. (5.24)).
Polymer
226
ju
Viscoelasticity
/
/
/
/
1
/
1
1
20
m
i
a
m
/
/ 1
10 
/ /
/ /
/ /
^^^^
0 
* ^ ~
10 
1 1 T T"1
0.1
I'T
10
Strain X
Fig. 12.2 Comparison of <(E u ) ( E  u ) /  E  u  2 ) a ( E ) 2 (denoted by A ; solid line) and
((E u ) ( E u)} (denoted by B ; dashed line) as a function of strain Ai for uniaxial extension/compression deformation (E given by Eq. (5.22)).
2^><.*Q<.>4
(12.18)
at n = 0; N0.
(12.20)
227
Modulus
<l(<)> = I
l + (a(E)l)
p=odd
sin
np
pnn\
tp2
(12.21)
C&X2 _ K n/f2
ZK2kT
(12.22)
+ PS.
(12.23)
Substituting Eq. (12.21) into Eq. (12.23) and carrying out the integration,
one obtains
%rN kT
T(t) =  ^ v N^RQ ' ( E ) ^ ( t , E ) + P5
(12.24)
where
/(t,E)= Y,
p=odd
7T 2 p 2
l + (a(E)  l ) e x p
pH
(12.25)
(12.26)
228
Polymer
Viscoelasticity
As pointed out above, /i#(*) and /j,B(t,Fi) have the same dynamic origin. However, nB(t,Fi) relaxes the extra tension residing in every part of
the primitive chain while ^ s ( t ) relaxes the tube stress only in the tube end
regions. In the linear region, a(E) = 1; thus, the n*B{t, E) process is not
observable (see Eq. (12.25)). In the nonlinear region, the contribution of
the chain tension to the total stress is very large; the /JB() process (see
Eq. (9.13)) is "wiped out" or overshadowed by the n*B{t, E) process. Particularly in the highmolecularweight region, where the relaxation strength
of the HB(t) process (Eq. (914)) is relatively small in comparison with
that of the /ic() process (Eq. (9.15)), the /is(t) process can be ignored.
By neglecting the contribution of the ^ s ( i ) process, the stress relaxation
in the terminal region can be obtained from Eq. (8.52) with fi(t) given by
Eq. (8.54) to be replaced by fic{t) given by Eqs. (9.11) and (9.12)
T(i) = 3cNkTQ(E)nc(t)
+ PS.
(12.27)
Since Q(E) Q'(E), one may combine Eqs. (12.26) and (12.27) as
T(t) = 3cNkTK(E)nmB(t,E)itc(t)
+ PS
(12.28)
with
K(E) = Q(E)
(12.29)
K(E) = Q'(E)
(12.30)
or
12.2
io z
Modulus
229
I I ITTII
102
10
Time (sec.)
Fig. 12.3 Comparison of the relaxation modulus G(t, A) at A = 0.2 (in the linear region)
and at A = 5 (in the nonlinear region) of nearly monodisperse polystyrene sample F40
(Mw = 4.22 x 10 s ), both measured at the same temperature (~ 167C).
the shorter time is required for moving the linear curve to superpose on the
nonlinear curve in the case of A = 5).
(a)
Damping
function
In making the superposition of two relaxationmodulus curves in the terminal region, the shift factor along the modulus coordinate defined by
h(\)
G(,A+0)
(12.31)
230
Polymer
Viscoelasticity
obtained by allowing such a time shift. A greater time shift is required for
a greater strain. At the strain A = 5, a time shift of about 15% can be
observed. Although this effect has not been clearly expected in the DoiEdwards theory, some disentanglement caused by a large deformation (see
Eq. (8.29)) may lead to a small shortening of the reptation time. This effect
can be seen by replacing Me of Eq. (9.12) by a greater effective value due
to disentanglement caused by a large deformation. Except for the small
time shift involved at a very large strain, the agreement between the calculated and measured h(X) values is very good. The successful prediction of
the damping function by the DoiEdwards theory is very significant as no
fitting parameter is involved in the calculation. In other words, the damping function is universal. Indeed the close agreement between theory and
experiment for h(X) has been observed for different polymers. 38
(b)
modulus
The nonlinear relaxation modulus as shown in Fig. 12.3 contains two distinctive relaxation processes. It is both interesting and important to see how
well the relative positions of the two relaxation processes are described by
Eq. (12.28) together with Eqs. (9.11), (9.12), (12.22) and (12.25). In Figs.
12.412.7, we compare the measured relaxation moduli at A = 3 and 5 with
those calculated from Eq. (12.28) for two nearly monodisperse polystyrene
samples: F40 and F80 (Mw = 7.75 x 10 5 ). The molecularweight distributions of the two samples included in the calculation are identical to those
that have been extracted from the analyses of their respective linear viscoelastic spectra as described in detail in Chapter 10. The decrease in the
modulus from the linear G(t) in the terminal region is determined by the
damping factor h(X), for which the close agreement between theory and
experiment has been shown in Fig. 9.2. As shown in Figs. 12.412.7, the
comparisons of the measured nonlinear relaxation curves with the calculated are made by matching in the terminal region to obtain the actual
damping factors shown in Fig. 9.2. Overall, the agreement between theory and experiment is good; however, some discrepancies can be observed.
At A = 3, the theoretical curves in the /i^(,E)process region underestimate the measured, by about the same degree for both the F40 and F80
samples. These discrepancies may arise from assumptions made in deriving Eq. (12.25) as discussed in the last section. The difference between
theory and experiment appears related to the a(E) value, calculated from
Eq. (12.12) at A = 3, being too small.
dynes/sq cm)
11 1 1 I I I ]
T'TTMIII
rrrmi
r i i i 11 i i 
111 1 1 l
231
Modulus
CO
~
^
.
^ ^ ~  t * j
1
Relaxation Modulus
CD
O
ii
":
;
ii
CN
,2
imil
>
10"
Time (sec)
10
'
10'
Fig. 12.4 Comparison of the measured (dots) and the calculated (line) relaxation
modulus G(t, A) at A = 3 for sample F40. The curves are calculated from Eq. (12.28);
the portion between line B* and line C is the contribution of the ii*B (t, E) process, while
below line C is the contribution of the nc(t) process.
E
'
'
TTTTTT[
es/s
r
;c
>
11 1 1 I I I ]
~I
1 1 1 1 1 ll
^ ~ ^ ^ . : . .
^^*^"4*
o o LiLs^~***i
V
1r I I 1111
^
E to
<x
'
*>
CD
CO
3
Z3
o
\
*
o
2
c
_o
to
X
to
<u
CC
~
;
"
::
;
.
\\ ::
\ V:
.
CM
O
J
2
10 u
Time (sec)
10
Fig. 12.5
'
1 1 1 Hi
10'
232
Polymer
Viscoelasticity
T*B
Mey
which is obtained from Eqs. (9.12) and (12.22). Equation (12.32) is the
same as Eq. (9.16) for the relaxationtime ratio between ^ B ( ) and fJ,c(t)
in the linear G(t). As the role of the /xs(i) process in the linear G(i) has
been well proven in Chapter 10, the observation that Eq. (12.32) is well
followed in the nonlinear G{t) supports that TB = TB and that /x#() and
/ig(i,E) have the same dynamic origin. This conclusion is expected from
the modeling that leads to Eq. (12.25).
For making a comparison of the roles of the various dynamic processes
in the linear and nonlinear regions, we show in Fig. 12.8 the linear and
nonlinear (at A = 5) G(t) curves, both calculated and measured, for the
F40 sample. In this figure, the nonlinear G(t) curve is shifted upward along
the modulus coordinate (by a factor that is equivalent to the reciprocal of
the damping factor) so that its terminal region is superposed on the linear
G(t) curve. The theoretical curve for the linear G(t) is calculated using
Eq. (9.19) while that for the nonlinear G(t) is calculated using Eq. (12.28).
The comparison illustrates the relative positions (or roles) of the involved
processes: fi*B(t,Ei) nonlinear, jUs(t) linear, nc(t) linear and nonlinear, HA(t) linear, and fix{t) linear. The linear and nonlinear G()'s
are linked in the terminal region (the nc(t) process) by the damping factor.
Finally, we shall mention the slipstick melt fracture phenomenon 9
a phenomenon often observed in polymer extrusion which is much
related to the relative positions of the nB(t, E) and Hc(t) processes. The
phenomenon is a wellknown problem in the polymer processing industry
because it limits the output of polymer through an extruder. In a capillary
flow, the decline of the viscosity observed as the shear rate (or flow rate)
increases from the Newtonian region is much related to the damping factor
i i i r 11
i i I ii ii
I I I iii[
1 i
i i 11 ii]
CO
233
in 1 1 n
Modulus
"
"j
^r
<>
/
. c
>,
o
"* *.
^
o*
CO
.
nes
er
"
:
'
:
;
.
.2
^CXO
CD
a>
a:
CM
L_ i i n i
10',2
Fig. 12.6
"I
1_
'
_i
10'
iii 11 i i i 
1
1 1 1 1III
mi i i i
CO
m i l l
r
E
o
iLI
10 u
Time (sec)
'
"=
i
"
r
*~
:
c
' c
>,
D
Or
tn
"co
CD
^ ^ ^ ^v?^
^" rv "*"^
CI
o
CO
3
3
"O
O
;
.
o
CD
X
CD
CD
DC
CM
O
~
\
:

\\ .
:
:
10"'
Fig. 12.7
'
i_
i i i n i
10"
Time (sec)
'
L_
'
10'
1 .I.JLLLL
234
Polymer
Viscoelasticity
Time (sec)
Fig. 12.8 Comparison of the linear and nonlinear (at A = 5) G(t) line shapes, measured
(o for the linear; A for A = 5) and calculated (lines), for sample F40. Also shown are
the separate contributions of the HAW> Hx{t), Ms(*)> / ^ B C ^ E ) and Hc{t) processes (see
Figs. 10.1 and 12.6).
associated with the nc(t) process. In a high, but not extremely high, shearrate region where still only the contribution of the Hc{t) process needs to
be considered, the shear stress will eventually decline with the increasing
shear rate because of the damping factor. In this rate region, the "viscosity" is negative, indicating instability. As the shear rate increases further
to become comparable to l / r ^ , the chain tension begins to contribute to
the total shear stress significantly and causes the stress to rise again. Thus
a dip in the flow curve is created. When the two processes /ig(,E) and
Hc(t) grow further apart with increasing molecular weight according to
Eq. (12.32), the dip becomes wider and deeper, and more observable. The
maximum point before the dip in the flow curve represents the onset of
instability. It has been shown that the instability point corresponds to the
onset of the slipstick melt fracture phenomenon. There is the tendency
for the dip to be smeared out by the molecularweight distribution of the
sample. The wider and deeper dip for a larger molecular weight has a
higher chance to survive the smearingout effect. Thus, the slipstick melt
fracture phenomenon is more prone to occur at a higher molecular weight
235
References
1. Doi, M., J. Polym. Sci., Polym. Phys. Ed. 18, 1005 (1980).
2. Doi, M., and Edwards, S. F., J. C. S. Faraday II 74, 1802 (1978); II 74,
1818 (1978).
3. Osaki, K., and Kurata, M., Macromolecules 13, 671 (1980).
4. Osaki, K., Nishizawa, K., and Kurata, M., Macromolecules 15, 1068 (1982).
5. Vrentas, C. M., and Graessley, W. W., J. Rheol. 26, 359 (1982).
6. Lin, Y.H., J. Rheol. 28, 1 (1984).
7. Lin, Y.H., J. NonNewtonian Fluid Mech. 2 3 , 163 (1987).
8. Pearson, D. S., Rubber Chem. Tech. 60, 439 (1987).
9. Vinogradov, G. V., Malkin, A. Ya, Yanovskii, G. Yu, Borisenkova, E. K.,
Yarlykov, B. V., and Berezhnaya, G. V., J. Polym. Sci. Part A2 10, 1061
(1972).
10. Edwards, S. F., Rheol. Acta 29, 493 (1990).
11. Lin, Y.H., J. Rheol. 29, 605 (1985).
12. McLeish, T. C. B., and Ball, R. C., J. Polym. Sci., Phys. Ed. 24, 1735 (1986).
13. Lin, Y.H., Makromol. Chem., Macromol. Symp. 56, 1 (1992).
Chapter 13
Introduction
236
Number of Entanglement
13.2
Distance
237
GN
kT
= I ? = r*
(13 2
>
with
PNA
" = ~M;
,,>
(13 3
>
where p is the polymer density, Nj\ the Avogadro number, and k the
Boltzmann constant. Because of the universality of chain entanglement
as summarized above, a certain onetoone correspondence should exist
between the entanglement distance a and nv. A logical way is to calculate
238
Polymer
Viscoelasticity
(13.4)
should be a universal constant. 2 Every quantity in Eq. (13.4) can be independently determined by experimental measurements: Me from the measured value of the plateau modulus (Eq. (13.2)), and Koo from the R2 value
obtained mainly from the smallangle neutron scattering (SANS) measurement on the polymer melt or from the light scattering measurement or the
intrinsic viscosity measurement of the dilute solution system under the 6
condition. Shown in Tables 13.1 and 13.2 are the measured p, K^, and
Me (or GN) values of two sets of polymers at two different temperatures,
413 K and 298 K, which have been compiled by Fetters et al.3 Also shown
in the two tables are the calculated values of a (according to Eq. (13.1))
and nt (according to Eq. (13.4)). The abbreviations in the first column of
the tables denote polymers shown in Table 13.3. The two tables show that
while the plateau modulus GN, a key viscoelastic property, can differ by a
factor as large as 38 (between PE and PVCH), the nt value is constant. The
averages of nt in Tables 13.1 and 13.2 are 19.14 and 17.02 with only 5.7%
and 6.6% for the standard deviation S, respectively. The two average nt values differ by about 13%, which, though still small, is somewhat larger than
their standard deviations. Thus nt appears to have a very weak temperature dependence, which may arise from a small deviation from the ideal
fundamental assumptions (Eqs. (13.1) and (13.2)) involved in obtaining
Eq. (13.4). Nevertheless, the results clearly indicate that nt is a universal
constant, regardless of the great diversity in microstructure.
13.3
C o n c e n t r a t i o n D e p e n d e n c e of nt
(13.5)
Number of Entanglement
Distance
239
Table 13.1 Molecular and Theological characteristics for polymers at 413 K. See Table
13.3 for the polymers denoted by the abbreviations. As defined in the text, p in g/cm 3 ;
GN in MPa; Koo in n m 2 / m o l g ; and a in nm. Reproduced, by permission, from Ref. 3.
Polymer
PE
PEB2
PEB4.6
PEO
PEB7.1
PEB9.5
PEB10.6
1,4PBd
PEB11.7
altPEB
PEB17.6
PEB24.6
altPEB
HHPP
aPP
PEB32
1,4PI
PIB
PMMA
PEB39.3
PEB40.9
H 2 3,4PI
PS
PDMS
PEE
PVCH
Kx
GN
0.78
0.79
0.79
1.06
0.79
0.79
0.79
0.83
0.79
0.79
0.80
0.80
0.80
0.81
0.79
0.80
0.83
0.85
1.13
0.81
0.81
0.81
0.97
0.90
0.81
0.92
2.60
2.21
1.90
1.80
1.55
1.40
1.30
1.25
1.20
0.95
0.90
0.67
0.52
0.52
0.47
0.43
0.42
0.32
0.31
0.30
0.29
0.22
0.20
0.20
0.20
0.068
x 10 2
1.25
1.21
1.15
0.81
1.05
1.05
1.06
0.88
0.95
0.83
0.91
0.80
0.69
0.69
0.67
0.69
0.63
0.57
0.43
0.65
0.60
0.53
0.43
0.46
0.51
0.32
Me
nt
3.22
3.44
3.62
3.62
3.83
4.04
4.21
3.99
4.16
4.36
4.71
5.12
5.41
5.44
5.57
5.95
5.83
6.45
6.52
6.90
6.80
7.31
7.60
7.50
7.50
11.2
828
976
1139
1624
1398
1552
1674
1815
1815
2284
2433
3276
4226
4279
4623
5124
5429
7288
10013
7371
7652
10114
13309
12293
11084
38966
18.98
19.65
19.74
18.64
19.11
20.18
21.29
17.37
18.89
17.31
20.65
19.66
18.02
18.32
17.76
19.81
18.19
18.78
18.86
21.55
19.90
18.87
19.24
18.46
18.46
20.07
Av. 19.14 5 . 7 %
4 4>pRT
5 ML
4 pRT
5 MP
(13.6)
Using Eqs. (13.1), (13.3), and (13.5), the number of entanglement strands
per unit volume and entanglement distance in the blend solution, denoted
by n'v and a' respectively, are obtained as
,
4>pNA
2
n = ML
, = nvd>
(13.7)
a'2 = KxM'e
(13.8)
240
Polymer
Viscoelasticity
Table 13.2 Same as Table 13.1 . For polymers at 298 K. Reproduced , by permission,
from Ref. 3.
Polymer
1,4PEB
altPEP
PEB17.6
PEB14
PEB24.6
altPEB
HHPP
aPP
PEB32
PEB39.3
H 2 50PI
1.4PI
PIB
PEB40.9
PDMS
H 2 3,4PI
PEE
1,41,2PBd
62PBd
cisPBd
PPOX
cisPI
PVE
50PI
1,4PEB
PMA
H 2 1,4MYRC
1,4MYRC
H 2 64MYRC
64MYRC
GJV
tfoc X 10 2
Me
nt
0.90
0.86
0.86
0.86
0.86
0.86
0.88
0.85
0.86
0.86
0.86
0.90
0.92
0.86
0.97
0.88
0.87
0.84
0.89
0.90
1.00
0.91
0.89
0.89
0.89
1.11
0.85
0.89
0.85
0.89
1.15
1.15
1.12
1.12
0.69
0.58
0.52
0.48
0.44
0.38
0.35
0.35
0.32
0.30
0.20
0.19
0.18
0.87
0.81
0.76
0.70
0.58
0.57
0.41
0.29
0.25
0.14
0.10
0.10
0.07
0.88
0.92
0.93
0.93
0.80
0.73
0.69
0.66
0.64
0.62
0.63
0.60
0.57
0.55
0.42
0.46
0.49
0.80
0.73
0.76
0.60
0.68
0.66
0.55
0.54
0.44
0.43
0.40
0.41
0.37
3.68
3.70
3.75
3.75
4.46
4.62
4.81
4.83
4.99
5.30
5.56
5.51
5.69
5.59
6.37
6.52
6.80
3.87
3.98
4.22
4.12
4.60
4.53
4.85
5.75
6.19
7.24
8.39
8.30
9.65
1543
1475
1522
1522
2482
2942
3347
3518
3888
4507
4876
5097
5686
5709
9613
9160
9536
1880
2178
2347
2832
3120
3091
4317
6090
8801
12077
17681
16828
24874
17.35
17.58
18.00
17.97
18.54
17.36
17.56
16.45
16.62
17.17
18.23
17.80
17.93
15.90
15.70
15.99
17.20
16.24
15.50
17.32
14.85
17.18
16.10
14.25
16.79
18.05
16.13
17.93
17.34
19.35
Av. 17.02 6 . 6 %
(13.9)
By using Eq. (13.4), the substitution of Eqs. (13.7) and (13.8) intoEq. (13.9)
gives
n't = nt^4>.
(13.10)
Thus, due to the presence of the solvent molecules, the number of entanglement strands per cubed entanglement distance decreases with dilution.
Number of Entanglement
Distance
241
Table 13.3 Polymers represented by the abbreviations used in Tables 13.1 and 13.2.
Reproduced, by permission, from Ref. 3.
PE
PEBx
PEO
62PBd
cisPBd
1,4PBd
1,41,2PBd
cisPI
1,4PI
a/PEP
1,4PEB
aftPEB
HHPP
aPP
PIB
PMA
PMMA
H 2 3,4PI
PS
PVCH
PDMS
PVE
PEE
50PI
H 2 50PI
1,4MYRC
H 2 1,4MYRC
64MYRC
H 2 64MYRC
13.4
The fact that nt is a universal constant for the puremelt system indicates
that the constraint effect of entanglement on the viscoelastic behavior is
242
Polymer
Viscoelasticity
mainly due to the long length of the polymer chain and basically has nothing
to do with the microstructure of the polymer. Regarding each segment as
a Kuhn segment, we can assume that each segment is cylindricalshaped,
with length b and diameter d. The size of a Kuhn segment considered here
contains the average contribution of free volume, which necessarily exists
among segments. Taking the average nt to be 18 and by considering the
packing of the Kuhn segments in a volume a3, we have
\d%Ne
= g.
(13.11)
(13.12)
which indicates that the number of Kuhn segments per entanglement strand
Ne is solely determined by and very sensitive to the aspect ratio d/b of
the Kuhn segment; the thinner the freely jointed chain (or the Gaussian
chain), the smaller the number of segments in one entanglement strand.
Physically, this relation is indeed a very reasonable expectation. Although
the microstructural details are ignored in using the Kuhn segment and
Ne to obtain Eq. (13.12), whether both the aspect ratio b/d and Ne are
universal constants remains to be seen. As discussed extensively in the
previous chapters, the viscoelastic behavior of an entangled polymer is universal as expressed in terms of the normalized molecular weight M/Me
(or M/M'e). Whether universality can extend into the size scale below Me
(for instance, iVe being a universal constant) is not now known. We may
say that there is currently a not wellunderstood gap existing between the
Rousesegment size scale and the entanglementstrand size scale. Any further understanding in this area will depend on how one defines the Rouse
segment experimentally. Such a definition has to be in accordance with
the statistical meaning of a Rouse segment. Related to this subject are the
early studies of the Kuhn segment based on the determination of the persistence length by neutron scattering. 4 ' 5 In recent years, there has been much
research interest in the subject; and different approaches have been used:
(1) The Rouse segment size was calculated from the highfrequency rubbery
modulus determined by analyzing the measured dynamic viscoelastic and
birefringence spectra with the assumption of a modified stressoptical rule
for a glassy polymer. 6 ' 7 (2) Through a theoretical analysis interrelating
the depolarized photoncorrelation and viscoelastic results of polystyrene
Number of Entanglement
Distance
243
13.5
Some Comments
From the view point that a plateau modulus GN can only be clearly measured in a nearly monodisperse highmolecularweight sample, the number
of entanglement strands per cubed entanglement distance nt, which is calculated using the GN value, has a clear definition only in the highmolecularweight region. However, the extensive analysis of the viscoelastic behavior
in terms of the extended reptation theory shows that Me does not change
with molecular weight decreasing to as low as just above Me (Chapters 10
and 11). Furthermore, it has been shown in Chapter 11 that, within a
small experimental error, the onset of entanglement M is equivalent to
the entanglement molecular weight Me determined from the plateau modulus according to Eq. (13.2). n ' 1 2 These results suggest that Eq. (13.4) for
nt remain applicable in the molecularweight region where a clear modulus
plateau is not visible, as long as M > Me. What really affects the polymer viscoelasticity as the molecular weight decreases (such as the gradual
disappearance of a clear modulus plateau as M becomes less than about
7M e ) is not an entanglementrelated structural change which would affect
nt, but the decline of the reptation influence and the simultaneous increase
in the importance of the primitivechaincontourlengthfluctuation effect
(Chapters 9 and 10).
When Fetters et al. reported the voluminous data covering a wide range
of G ^ (Tables 13.1 and 13.2), they offered another interpretation for nt as a
universal constant. They started with the idea that the larger the dimension
of a chain coil, the greater the volume it sweeps out, and the greater the
number of other chains it will encounter with which it might entangle. They
defined the volume pervaded by the chain as
j/
V,p = A(Ry'*
= A
6m 0
(13.13)
VspPNA
M
(13.14)
244
Polymer
Viscoelasticity
Then, they denned M e (which they also linked with the plateau modulus
GN according to Eq. (13.2) as described below) as the molecular weight of
a chain at which N = 2, that is, when there is just one other chain in the
spanned volume. Since Vsp is proportional to o 3 at M = Me, the argument
naturally leads to an equation equivalent to Eq. (13.4), disregarding the
difference in the proportional constant. The arbitrariness of setting N = 2
at M = Me is absorbed in the proportional constant as well. Fetters et al.
started by setting N equal to 2 at the onset of entanglement, which they
assumed to be Me, and then they moved on to link this Me with the plateau
modulus GN according to Eq. (13.2), which is really experimentally denned
in the highmolecularweight region. In view of the result that the onset of
entanglement M is equivalent to the entanglement molecular weight Me
as shown in Chapter 11 and further pointed out above, the argument of
Fetters et al. might appear equivalent to Lin's. Since entanglement in a
monodisperse polymer melt involves many chains, even in the region where
entanglements have just begun to occur, it seems somewhat arbitrary to
set N = 2, i.e. only involving two chains, at the onset of entanglement.
In effect, as long as AT is held to be a constant, an equation equivalent
to Eq. (13.4) will be obtained. Then, what should N be at M = M e ?
As pointed out above, nt is only related to the structural aspect which
remains the same as long as M > Me = M.
References
1. Lin, Y.H., and Luo, Z.H., J. Chem. Phys. 112, 7219 (2000).
2. Lin, Y.H., Macromolecules 20, 3080 (1987).
3. Fetters, L. J., Lohse, D. J., Richter, D., Witten, T. A., and Zirkel, A., Macromolecules 27, 4639 (1994).
4. Ballard, D. G. H., Rayner, M. G., and Schelten, J., Polymer 17, 349 (1976).
5. Norisuye, T., and Fujita, H., Polymer 14, 143 (1982).
6. Inoue, T., Okamoto, H., and Osaki, K., Macromolecules 24, 5670 (1991).
7. Inoue, T., and Osaki, K., Macromolecules 29, 1595 (1996).
8. Lin, Y.H., J. Polym. Res. 1, 51 (1994).
9. Lin, Y.H., and Lai, C. S., Macromolecules 29, 5200 (1996).
10. Lai, C. S., Juang, J.H., and Lin, Y.H., J. Chem. Phys. 110, 9310 (1999).
11. Lin, Y.H., Macromolecules 19, 159; 168 (1986).
12. Lin, Y.H., and Juang J.H. Macromolecules 32, 181 (1999).
Index
246
Polymer Viscoelasticity
247
Index
number of entanglement strands
per a 3 , 237243
values of various flexible linear
polymers, 239, 240
entanglement molecular weight, 24,
127, 158, 185, 188, 195, 204206,
237, 239, 240
comparison with onset molecular
weight of entanglement,
209, 210, 212
concentration dependence,
195197, 205, 219, 238
determination from plateau
modulus, 24, 127, 154, 175,
177
effective value in binary blend, 216,
217
relation to critical molecular
weight, M c , experiment and
extended reptation model,
183185
relation to critical molecular
weight, M'c, experiment and
extended reptation model,
186, 187
values of various flexible linear
polymers, 239, 240
entanglement strand, 27, 136,
236242
Rouse motions of, 156, 162, 178,
179, 185, 197
see entanglement distance
entropic force constant, 34, 93, 96,
160
equilibrium tensile force, 129, 130,
134, 143, 161, 226
extended reptation model, 55, 57, 59,
67, 128, 143, 146165, 167192,
194204, 212, 219, 221, 237, 243
consistency with Rouse model, see
Rouse model
theoretical development, 149157,
159165
universality in, 154, 156
viscoelasticity equations, 156158
248
Polymer Viscoelasticity
joint probability, 4
Kramers matrix, 123
Kuhn segment, 9, 15, 237, 242
Langevin equation, 28, 37, 45, 91
general form, 32, 33
particle in a harmonic potential, 43
Rouse model, 34, 43
of primitive chain, 160
of entanglement strand, 163
linearadditivity rule as blending law,
169, 171, 182, 219
loss modulus, 63, 65, 202
loss tangent, 63
marker displacement technique, 189
material time derivative, 110
Maxwell equation, 52, 53
Maxwellian distribution, 99, 100
mean square endtoend distance, 7,
9, 93, 105, 112, 130, 188, 237
memory function, 55
microstructure of polymer, 1, 238
mobility matrix, 31
mobility tensor, 34
modulus plateau, 126
molecular weight of a chain strand
between two crosslinks, 22
moments of a stochastic variable, 3
HA{t) process, 146, 149, 156158, 172,
174, 175, 178180, 182, 186, 197,
199, 218, 221, 222, 234
fiB(i) process, 149, 151, 153156, 161,
172, 174, 175, 177, 189, 197, 199,
203, 221, 228, 232, 234
\iB * (t,E) process, 146, 148, 227,
228, 231234
Index
primitive path, 140
see primitive chain
probability distribution function, 25,
18, 19
freely jointedchain segment, 7
endtoend vector of freely jointed
chain, 10, 11
vector between two beads in
Gaussian chain, 13
pure reptational time, 142, 152, 153,
190
rateofstrain, 52
rateofstrain tensor, 86, 101, 110
ratio of K'/K, 158, 178, 179, 183,
184, 191, 198, 204
ratio of K"/K, related to consistency
between Rouse model and extended
reptation model, 197201, 203, 212
ratio of mean square endtoend
distance to molecular weight, Kco,
188, 195, 236240
values of various flexible linear
polymers, 239, 240
relative strain tensor, 102, 107
reptation model,
see DoiEdwards model
relaxation modulus (linear), 40,
5559, 63, 6569, 126, 146148,
153157, 167, 168, 180, 214, 218,
221, 229, 234
comparison with relaxation
modulus in nonlinear
region, 147, 229, 234
curves calculated from extended
reptation model, 158
DoiEdwards model, 142
elastic dumbbell model, 103
equation for binary blend, 217218
equation for blend solution,
combining extended
reptation model and Rouse
model, 196, 197
experimental results, 58
extended reptation model, 153158
Rouse model, 122
249
universality in terms of extended
reptation model, 154, 156,
197204
see viscoelastic spectrum lineshape
analysis
relaxation modulus in nonlinear
region, 146148, 221
comparison of theory and
experiment, 228234
comparison with relaxation
modulus in linear region,
147, 229, 234
experimental results, 147, 229
extended reptation model
incorporated with chain
tension relaxation, 222228
see chain tension relaxation,
damping function
relaxation strength,
of Mfi(t) process, 154
of fiB * (, E) process, 227
of fic(t) process, 154
of nx(t) process, 155
relaxation time, see frictional factor,
structural factors of relaxation
times
relaxationtime distribution, 69
rheological equation of state, see
constitutive equation
rodclimbing phenomenon, 85
rotational motion, 39
Rouse matrix, 36, 114, 115, 117, 118
eigenvalues and eigenvectors, 4042
inverse of, 123, 124
Rouse model
consistency with extended
reptation model, 191192,
197204, 212
constitutive equation, 120, 121
continuous model, 4346
diffusion constant, 35, 45
discrete model, of finite number of
beads, 33, 34, 112123
timecorrelation function of the
endtoend vector, 38, 46
validity of the model, 205207, 210
250
Polymer Viscoelasticity
experimental results, 68
extended reptation model, 157,
158, 186188
Rouse model, 122, 123, 125
see critical molecular weight
steadystate shear flow, 58, 104, 122
step strain, 56, 57, 103, 135, 146, 221,
222
stochastical variable, 2
Stoke's law, 92
storage modulus, 63, 64
see viscoelastic spectrum lineshape
analysis
stress, 71
stress relaxation, see relaxation
modulus, relaxation modulus in
nonlinear region
stress tensor, 80, 8287, 93, 97100,
108, 120, 134, 137, 139, 163, 222,
223, 225, 228
beadspring model, 120
contravariant component, 108
contravariant convected derivative,
101, 110
definition, 7174
DoiEdwards model, 134137
elastic dumbbell model, 97100
Giesekus expression, 101
Kramers expression, 100
neoHookean material, 84
rubber network, 139, 144
symmetry of, 75
see constitutive equation
structural factors of relaxation times
elastic dumbbell model, 101
Rouse model, 38,39, 46, 121
pure reptation, 142
TA.
165
TB, 152
TB*, 227
re, 153
rx, 157
subRousesegmental dynamic
process, 210
251
Index
tensile viscosity, 87
tensor, 74
operations, 87
see Cauchy tensor, deformation
gradient tensor, Finger
tensor, stress tensor
terminal process or region, 145, 147
Tg correction, see freevolume
correction
thermoelastic inversion effect, 17
0 solutions, 39, 238
timecorrelation function,
of a particle in a harmonic
potential, 43
of endtoend vector of a Rouse
chain, 38, 39, 46
of primitivechain contourlength
fluctuation, 151, 162
timetemperature superposition
principle, 152, 194
topological interactions, see
entanglement
tracer diffusion constant, 189
transition process or region (from
glasslike to rubberlike consistency),
146, 147
see f*A(t) process
translational diffusion, see diffusion
Trouton's rule, 87
tube diameter, 129, 130, 160, 179,
195, see entanglement distance
tube model, see primitive chain
tube stress, 170
tubedilation effect, 170, 194, 196,
213219
tuberenewal process, 218
WilliamsLandelFerry (WLF)
equation, 40
wormlike chain, 15
Young's modulus, 84
zeroshear viscosity, see viscosity
Viscoelasticity
Basics, Molecular Theories
and Experiments
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ISBN 9812383948
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