MEKELLE UNIVERSITY

MEKELLE INSTITUTE OF TECHNOLOGY

Introduction to Polymer - Chapter 9

Presentation
 9.5 Diffusion Coefficient and Friction Factor
 We now turn our attention to the phenomenon of diffusion. This turns out to be

directly related to the viscosity through the friction factor, f. Most of us have a
sense of diffusion as a randomization process: place a drop of food coloring
into a glass of water, and before long the entire glass will be uniformly colored
even without stirring.
 The time it takes for the color to spread depends on two Diffusion Coefficient

and Friction Factor 347 things: how rapidly the dye molecules move, and the
size of the glass. The former is quantified by a diffusion coefficient, D, which
depends directly on the molecular friction factor.
 Diffusion is an important process to understand and control in many polymer

applications (e.g., how long will soda in a plastic bottle hold its fizz?
  How long does it take a drug in a skin patch to pass through the skin?), and

the diffusion coefficient itself is also a useful means of molecular

characterization.
 In this section we will emphasize the diffusion of polymers in

 dilute solution, but the development has a much broader range of

applicability.

9.5.1 Tracer Diffusion and Hydrodynamic Radius

Returning to our glass of water, imagine a single dye molecule some
where in the glass and further imagine that we could actually follow
its motion directly in time and space.
(This is not too far fetched, in fact, with recent developments in
single-molecule spectroscopy and microscopy). What would we see?
 The molecule is constantly buffeted by solvent molecules, and consequently

executes Brownian motion: it moves tiny distances between collisions, with the
instantaneous direction of motion fluctuating randomly.
 If we watch for a relatively long time interval, how far is the dye molecule likely

to move?
 We already have developed all the mathematics needed to answer this question,

when we considered random walks in Chapter 6.

 Namely, if the molecule executes a total of N random steps of average length b, the

mean square displacement (r2) will be s.

 We can formalize this as follows:
 The units of the diffusion coefficient are (length)2/time, or cmz/s in the cgs

system.
 if we define the location of a particle at time t: O as the origin, what is the

probability of finding it a distance r away after time t?

 This probability is known by a special name, the “van Hove space—time

self-correlation function,” but it is mathematically equivalent to Equation
6.7.12:
 The tracer diffusion coefficient is a property of an individual molecule or particle
undergoing Brownian motion.
 Its value, however, will generally depend on the size of the molecule and on the
medium in which it is diffusing.
 Einstein showed that there is a beautifully simple relationship between the friction
factor and Dt.

—Einstein relation As T increases, solvent molecules move more rapidly and are
more effective at jostling the tracer molecule, so Dt should increase.
At the same time, if the solvent viscosity increases, or if the particle increases in
size, then f should increase and Dt will be smaller.
If we now consider our tracer molecule to be a hard sphere and the solvent to be a
continuum, then we can incorporate Stokes’ law (Equation 9.2.4) to arrive at the
Stokes .
We can go an important step further, however. If our particle is not a hard
sphere, we can use Equation 9.5.4 to define an equivalent radius in terms of a
measured diffusivity, called the hydrodynamic radius, Rh:

9.5.2 Mutual Diffusion and Fick's Laws

Now we turn to the mutual diffusion coefficient, Dm, which describes how a
collection of Brownian particles will distribute themselves in space.
In the context of the food coloring analogy, Dt tells us how rapidly any
individual dye molecule explores space, but Dm describes how quickly the
entire droplet of food coloring disperses itself.
mutual diffusion acts to eliminate any gradients in concentration.
Fick’s first recognized that mass diffusion was analogous to thermal diffusion and
he proposed an adaptation of Fourier’s law of heat conduction for the transport of
material [1 1].
Specifically, the flux J (in units of mass per unit area per unit time) across a plane
is assumed to be proportional to the gradient in concentration (mass/volume) along
the direction perpendicular to the plane.
We will restrict ourselves to one-dimensional diffusion along the x-direction, and
therefore

The minus sign in Equation 9.5.6 recognizes the fact that the direction of the flow
is that of decreasing concentration.
• The incremental change in the total amount of solute dQ in the center volume element
per time increment (it can be developed in two different ways. In terms of fluxes,
whereas in terms of a concentration change dc in the element of volume A dx, dQ =
dc(A dx).

Figure 9.11 Schematic of diffusion with respect to a volume element of thickness dx

located at x = 0 between regions with concentration c1 and c2 > c1.
Diffusion Coefficient and Friction Factor
Under stationary-state flow conditions, Fdiff equals the force of viscous
resistance experienced by the particle.
The latter, in turn, equals the friction factor times the stationary velocity v0;

The product cvo defines the flux J, and therefore

 9.6 Dynamic Light Scattering
 light scattering in a dilute polymer solution arises from fluctuations In
concentration .
 However, each fluctuation must appear and disappear over some time interval
and this time interval is determined by Dm.
 As a consequence, the total scattered intensity also fluctuates in time
 and these fluctuations may be analyzed to extract a characteristic

 relaxation time, T. The magnitude of the scattering vector, q.

• the scattered intensity is analyzed via a time autocorrelation function, C(t),

defined as follows:
In the actual experiment, the scattered intensity is digitized and stored as a string of
numbers, which are then manipulated by a special computer called a correlator, to
generate the digital version of C(t).

Figure 9.13 (a) Scattered intensity as a function of time, with data digitized every
interval t. (b) Intensity autocorrelation function C(t) as a function of t.
Example 9.5 Estimate the range of time constants, 7, which would be extracted from
dynamic light scattering measurements of dilute aqueous suspensions of latex
particles ranging in size from 10 nm to 1 pm.

Solution: The time constants are determined by the product of q2 and Dm, so we
need to estimate both. For q, let us assume the light source is an argon

ion laser operating at 488 nm and that the instrument can access

scattering angles, q, from 30° to 150°. The refractive index of water is about 1.33.

We have emphasized here 1 /q is a length, and by taking the reciprocal of these

numbers we can see that the typical values for light scattering fall in the range 30
—120 nm.
The value of Dm can be estimated by assuming that the latex particles are
sufficiently dilute so that Dm = Dt and using the Stokes—Einstein relation .
For a hard sphere, remember that Rh = R.

In this calculation we have used cgs units, with the viscosity of water estimated to
be 0.01 P. In the final calculation of T we will need to convert these numbers to a,
nm2/s,which brings in a factor of 10^14 (nm^2/cm^2). The results are
 9.7 Hydrodynamic Interactions d Draining
 In this section we address a question that has played an important role in
interpreting the intrinsic viscosity and the diffusivity:.
 A detailed model for the dynamics of a flexible chain, called the bead—spring

or Rouse_Zimm model, will be discussed in Chapter 11. Its essence is to replace

the real polymer with a freely jointed sequence of N beads connected by elastic
springs of average length b,
 The springs resist deformation of the chain and act to restore random coil
conformations perturbed by the flow, but are otherwise “invisible.” Each bead
encounters frictional resistance as it moves relative to the solvent.
 The bead friction factor, g, is a parameter of the model but it should correspond
to the net friction of a few real monomer units.
 a) the solvent streamlines pass right through the coil, a limiting behavior termed
freely draining. In this case the total friction offered by the chain will be Ng
and thus f= M. In panel
b) the streamlines are totally diverted around the periphery of the coil, just as in
the hard sphere case

In particular, the number of beads N is proportional to the degree of

polymerization of the real chain.
This model is extremely successful in many respects, as we shall see in the next
chapter, but for now let us focus on the chain friction factor, f.
As the chain moves through the solvent, the total friction should just be the sum of
the friction experienced by each bead: f:Ng (9.7.1
Rh 2 0.271N1/2b = 0.66Rg
(a. This extreme of behavior is called non-draining,
and the friction varies as f Rh M.

Figure 9.15 Illustration of (a) a freely draining coil, (b) a non-draining coil.

all the other beads in the same direction so that there is a concerted element to
the chain motion. This cooperation among segments contributes to a reduction in
f, relative to Ng.
(c) the argument for the importance of (b) given in the text.

The cartoon in Figure 9.15c depicts a layer of pure solvent flowing with velocity v
past an infinite field of beads; the beads have a number density of n/V. There is
achracterstic penetration distance L, over which velocity varnishes.

Now we will estimate the force F required to maintain the solvent flowes over an
area of surface A by two separate routes; numerical prefactors will be omitted.
9.1). In this case the velocity gradient should be proportional to v/L, that is,
the velocity falls from v to 0 over the distance L. TherIn the second route, we
recognize that the force will be proportional to ∩s, A, and the velocity
gradient (recall the discussion accompanying Figure the force can be written
as

. In the first route, we add up the friction of each bead (i.e., as if the beads were
freely draining within the layer of thickness L). The number of beads is given by
(n/V) times the volume LA and thus the force would be
We now equate these two forces, and solve for L:

The key question is how does this penetration distance compare to the typical coil
size? If L >> Rg, then we expect freely draining behavior, but if L << Rg, non-
draining will be a better description. for big polymers Rg >>L and therefore the
coil will be non-draining. In real polymer solutions, the situation is more
complicated and tends to fall between these two extremes, albeit closer to the non-
draining limit. For example, as the solvent quality is improved beyond a theta
solvent, the chain expands and thus the average distance between beads increases.
Hydrodynamic interactions are therefore diminished.
 For chains in good solvents, part of the variation in the Markfl Houwink

exponent, a, can be attributed to variable degrees of draining.

 The effect also depends on molecular weight. For shorter chains the degree of

draining increases simply because there are not enough monomers to shield the
inside of the coil from the solvent flow.
 In summary, the main qualitative effect of H is to make the chain friction factor

close to that of a hard sphere with radius Rh, but a full mathematical treatment
is extremely complicated.

9.8 Size Exclusion Chromatography (SEC)

 SEC is one of several modes of liquid chromatography in which a mixture of

solutes is separated by passing a solution through an appropriate column.

As the solution (mobile phase) passes through the column, different solutes are
retained to various degrees according to their interaction with the column packing
(stationary phase).
Surface adsorption and ion exchange are examples of interactions that serve as
the basis for other types of liquid chromatography. In SEC, the columns are filled
with porous particles and the separation occurs because molecules of different
sizes penetrate the pores of the stationary phase to varying degrees
Some other terminologies are noted below:
1. Gel permeation chromatography (GPC) is a very common name for this
method of separation; it is a less desirable term than SEC in that it emphasizes the
column packing material (the gel) rather than the supposed mechanism for the
separation (size exclusion).
2. Gel filtration chromatography (GFC) is a name often used in the biochemical
literature to describe this method of separation.

Under this heading, the method is primarily applied to aqueous solutions of

solutes of biological origin.

3. All three of these names (SEC, GPC. and GFC) are also modified by the term
high performance. or its acronym, to give HPSEC, HPGPC, and HPGFC.
 The additional feature implied by this terminology is the increased speed of

efficient separations due to rapid flow through the column under the influence
of relatively high applied pressures.
 At the time of writing. this prefix is generally omitted because “low

performance” instruments are little used.

 9.8.1 Basic Separation Process
 A cartoon of an SEC experiment is shown in Figure 9.16. The column is

packed with porous particles with some characteristic pore size, which should
correspond roughly to the typical sizes of the polymers to be analyzed. The first
rule of SEC is that the separation is based on size and not on molecular weight;
as we shall see the relevant size parameter is the hydrodynamic volume, Vh,
which1s roughly proportional to R3 .
 To use SEC for molecular weight determination, we must relate the volume of

solvent that passes through the column before a polymer of a particular M is

eluted, to M. This quantity is called the retention volume

Figure 9.17 Calibration curve for SEC as log M versus the retention volume VR,
showing how the location of the detector signal can be used to evaluate M. Also
shown are the void volume Vv and the internal volume Vi in relation to VR and
KVi as a fraction of Vi.
 At low M there is a region with no separation, when all polymers that are small

enough to enter all the pores will elute with the solvent.
 The intermediate range of M is the useful regime: a peak at a particular VR can

be related to a particular M, as shown in Figure 9.17.

 Note the curious fact that it is a common practice to plot the measured quantity,

or dependent variable, VR along the horizontal axis, and the independent

variable, log M, along the vertical axis.
 ∑h, is proportional to the cumulative weight of all polymers in all categories up

to the nth.
 The ratio hi/Mi is proportional to the weight of materials in the ith slice, wi is

divided by Mi, that is, to the number of moles in that class ni, Therefore Mn
can be evaluated as follows:
The product hiM, is proportional to ni, and Mw is evaluated as follows :

9.8.2 Separation Mechanism

To consider the origin of VR(M), begin by picturing a narrow band of
polymer solution being introduced at the top of a solvent—filled column.
The volume of this solvent can be subdivided into two categories: the
stagnant solvent in the pores (subscript i for internal) and the interstitial
liquid in the voids (subscript v) between the packing particles: Vsol vent
= Vv + Vi
 The entire interstitial volume moves through the column at the imposed flow

rate and must pass through the column before any polymer emerges.
 Then the first polymer that does appear is the one with the highest molecular

weight.
 This solute has spent all its time in the voids—not the pores—of the packing

and passes through the column with the velocity of the solvent.
 Progressively smaller molecules have access to successively larger fractions of

the internal volume.

 Therefore, as V, emerges, consecutive fractions of the polymer come with it.

Thus we can write the retention volume for a particular molecular weight
fraction as:
  where K is called the distribution coefficient. K is a function of both the pore

size and the molecular size and indicates what fraction of the internal volume is
accessible to the particular solute.
 When K = 0, the solute is totally excluded from the pores; when K = 1, it totally

penetrates the pores..

Figure 9.19 Schematic illustration of size exclusion in a cylindrical pore: (a) for
spherical particles of radius R and (b) for a flexible chain, showing allowed (solid)
and forbidden (dotted) conformations.
spherical solute molecule from approaching any closer than a distance R from the
walls of the pore. This effectively decreases the volume accessible to the solute to
a smaller cylinder of radius (a —R).
 The fraction of the external concentration found in the pore is given by the

ratio of the accessible volume to the actual volume of the cylindrical pore:

 This fraction gives K for the case of spherical solute molecules in cylindrical

cavities. If we assume that the pore is long enough to neglect end effects, we
have.

Note that the fraction is zero when R : a and unity when R = 0. This simple model
illustrates how the fraction K and, therefore, VR are influenced by the dimensions
of both the solute molecules and the pores.
9.8.3 Two Calibration Strategies
•take a series of polymers of known M, referred to as calibration standards, run
them through the column, and generate an empirical plot of log M versus VR.
• This approach is in common practice and it is appealingly simple.
•The calibration should be repeated at regular intervals because column
performance will drift with time, but as only minuscule amounts of the standards
are required for each run, this is not particularly expensive.
•What are the limitations of this approach?
9.8.3.1 Limitations of Calibration by Standards
1. Separation is based on the hydrodynamic volume, Vh,, and not on M directly.
Consequently, accuracy in M requires the use of standards of the same polymer
as the analyte. to produce standards of a variety of polymers, there are, of course,
a much larger number of polymer structures for which standards are simply not
available. One expedient often encountered in the literature is to quote “an
apparent M, based on polystyrene standards,” which gives some very
approximate idea of the real M.

2. The absolute M of a given stand may not be known to an accuracy better than 5%
——10%, which ultimately limits the accuracy achievable with this mode of
SEC.
 9.8.3.2 Universal Calibration
 The second mode of calibration in routine use is known by the optimistic name

of universal calibration.
 The hypothesis is that in SEC, VR depends solely on the hydrodynamic

volume, Vh, which itself will be proportional to R^3g.

•The hydrodynamic volume, therefore, should be proportional to the product

9.8.4 Size Exclusion Chromatography Detectors

To conclude this discussion of SEC we offer a brief discussion on the four classes
of detectors in common use:
the refractive index (RI), absorption (uv—vis), light scattering (LS), and
viscometer (V) detectors.
.
9.8.4. 1 RI Detector
 the central role that the refractive index increment, , plays in light
scattering.
 For a dilute polymer solution (which is almost always the case in SEC), the

refractive index of the eluent may be written:

•where c is the concentration in g/mL of the eluting polymer and n3 is the

refractive index of the solvent.
•The response of the detector (e.g., in volts) can then be assumed proportional to c
and the proportionality factor determined by injection of known quantities of
material (assuming no adsorption on the column and that is known).
 9.8.4.2 UV—Vr's Detector
 This approach takes advantage of Beer’s law, whereby the transmittance of the

solution (ratio of transmitted light intensity to incident light intensity, is

Is related to the concentration of the absorbing species by,

absorptivity of the solute at the wavelength of interest.

• Thus, as with the RI detector, the signal is arranged to be proportional to c.
• The uv—vis detector is less general than the RI detector because many polymers
do not absorb at sufficiently long wavelengths to avoid solvent absorption.
•On the other hand, when dealing with mixtures, for example copolymers, it may be
possible to choose a wavelength in the uv— vis detector that favors only one
component, whereas the RI detector is likely to respond to both.
• here A is the absorbance, b is the path length through the capillary, and
In this case both detectors in series can be used to establish the average
composition of the sample at each VR

9.8.4.3 Light Scattering Detector

 The crucial advantage of the LS detector is the possibility of obtaining an

absolute MW, of each slice of the chromatogram without any column

calibration.
 This makes use of the theoretical machinery developed in Chapter 8. If M is

sufficiently low that the form factor, P(q), is effectively 1, then a single angle
detector is adequate.
 On the other hand, for larger polymers multiple angle detectors are desirable.
 9.8.4.4 Viscometer
 This detector takes advantage of the direct relation between the hydrodynamic

volume, which determines VR and : Vh~M ..

 Consequently by estimating at each slice, M can be calculated. The detector
itself is a kind of “Wheatstone bridge,” or null detector, for viscosity.
 The eluting solution passes across one face of a sensitive pressure transducer.

Pure solvent is circulated against the other face.

 If both liquids are flowing at the same rate, any difference in viscosity between

them will be transformed into a differential shear force and thus a pressure on the
transducer.
This could be measured, but a more effective approach is to increase the pure
solvent flow rate to null out the pressure drop.
The amount the flow rate needs to be increased is directly proportional to
The intrinsic viscosity is then estimated by
 ou
k y
a n
T h