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Polymer Solutions
(8.1.1)
(8.1.2)
1
Light Waves A Brief Review
Notice that the wavelength in a medium is generally not equal to 0 .
They are related by
(8.1.6)
(8.1.4)
3
(8.1.5)
2
The Basis What is Scattering?
Scattering is the re-radiation of a traveling wave due to a change in the
character of the medium in which the wave is traveling. For light,
scattering will be caused by local changes in refractive index or
polarizability, due to, e.g. a dust particle in the air or a polymer in the
solvent. Note that we assume nonabsorbing media here. So, the
incident light intensity will either be transmitted or scattered. If there is
no energy exchange between the medium and the wave, the incident
and scattered wave frequencies are the same and we call the
scattering process elastic. If very small differences in energy is
involved, the scattering is quasielastic. When there is large change in
the energy of the wave upon scattering, the process is inelastic.
Representative inelastic scattering in polymers include Raman and
Brillouin scattering. The former involves vibrational excitations and the
latter propagating density waves (i.e., sound waves or phonons) in the
medium. Lastly, scattering is incoherent if the intensity is independent
of scattering angle, and coherent if it depends on the scattering angle.
We will elaborate the concept of coherent scattering in this context
later. 5
This should apply to the case of molecules in solution. We also anticipate larger
molecules to scatter proportionally more than smaller ones.
N.B. Suppose we scatter light from objects that are connected to one another, e.g.,
monomers within one polymer. Now the phases of the waves scattered from different
monomers should be related, because the distance rjk between any two monomers j
and k has some preferred value or range of values. This will lead to some
interference between these waves. Recall that interference between two waves is
constructive only if the difference in distance or path length difference (PLD) that the
two waves travel to the detector is some integral number of wavelengths, m, and
destructive if the PLD is an integer plus one half of . Because the PLD is on the
order of the distance between scatterers, we can therefore expect that in order to see
significant destructive interference we need the distance between scatterers to be a
significant fraction of , say a few percent. This will tum out to be the case. For visible
light with o 5000 , only for polymers that are larger than at least 100
(corresponding to polymers with Mn > ~ 105 g/mol) do we have to worry about this 6
kind of interference.
3
Basis Scattering from a Perfect Crystal
PLD =L -L = (/2)(k -k )r
1 2 s i
Consider a homogeneous array of
identical scatterers (e.g. atoms) that are k s ks
placed every 1 apart and shine light
with = 5000 on it. Every scatter will L1
re-radiate in all directions with the same L2 ki
amplitude and wavelength. For any
particular scatter and particular !
scattering direction k, we can always r Fig. 8.*
find another scatterer that produces a
scattered wave in the direction of k with path length difference (PLD)
exactly equal to /2 w.r.t. the first scatterer. This is possible because the
separation between scatterers is much less than so the array is
essentially a continuum. However, the above argument does not apply in
the forward direction (ki // ks) because the phase shift of the scattered
waves between two atoms is exactly canceled by the phase shift
between the incident waves arriving at the two atoms. Thus, the light
beam propagates through a homogeneous medium without any
scattering. 7
The second way of obtaining scattering from the hypothetical array would
be to make close to the distance between scatterers. Using x-rays with a
typical of 1.54, the pairing-off argument fails at specific incident angles
where the PLD between beams reflected from adjacent planes are
separated by integral multiples of , so the scattering from different atoms
will be in phase, i.e., coherent. This process is called Bragg diffraction (see
Fig. 8.3). In general, there will be coherent scattering when there is spatial
correlation between scattering objects on a distance comparable to . The
more spatial correlation between scatterers, the sharper the scattered peak
8
(scattering as a function of the scattering angle , see Fig. 8.3a) will be.
4
From Fig. 8.3b, one may see that the condition for Bragg diffraction is
(8.2.2)
(8.2.3)
!
ki
/2
9
Fig. 8.3 Fig. 8.4
(8.3.1)
(8.3.2)
10
5
Basis Scattering by an Isolated Small Molecule
(Rayleigh Scattering)
This shows that |Es* Es| ~ r- -2. Notice also that /e is the
displacement a charge e undertakes from the equilibrium position in
producing a dipole moment of . So we can write:
(8.3.3)
(8.3.4)
11
(8.3.5)
12
Fig. 8.5a Fig. 8.5b
6
Case 2: If the incident wave is unpolarized. We can view it as having
equal parts of vertically (// z) and horizontally (// y) polarized light.
Suppose again that the detector is in the x-y plane and is the
scattering angle as measured from the x direction (i.e., the propagation
direction of the EM wave). For the vertically polarized component (// z),
the scattered wave is the same for all . For the horizontally polarized
component (// y), is measured from the y-axis (see lower panel of
Fig. 8.5a). Clearly, sin can be written as sin(/2) = cos . So the
scattered field from the horizontally polarized part varies as cos , and
the scattered intensity as cos2. As a result, the total scattered
intensity varies as (1+cos2). Inserting this in (8.3.4), we get
(8.3.6)
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14
7
15
(8.4.1)
8
Scattering from a Dilute Polymer Solution
Because Is/Io ~ <2> by (8.3.4), the scattering is determined entirely by
the mean-square fluctuations in polarizability,<()2>. Consider:
(8.4.3)
Assume that the scattering from the p and T fluctuations is the same in
the neat solvent as in the dilute solution. In the following discussions, we
will only consider the excess scattered intensity, Iex = Issolution - Issolvent. One
may perceive that only the fluctuation in c would affect Iex. Substituting
(8.4.2) in (8.3.5) gives Iex due to Rayleigh scattering from one cell. Since
there are 1/ number of cells per unit volume, the excess scattering due
to a unit-volume of specimen is:
The key part is n/c, the refractive index increment (we drop the
reminder about constant T & P from now on), which can be measured or
looked up from tables. To find <(c)2>, write P(c) as the probability of a
given fluctuation c. So,
(8.4.7)
(8.4.8)
9
(8.4.9)
(8.4.11)
Recall that the condition for miscibility of a polymer solution is 2G/c2 > 0.
This can now be perceived from the Taylor expansion of G and the fact that
<c> = 0: For the solution to be stable, the energy change due to fluctuation
in c must be positive, so G > 0 2G/c2 > 0. With 2G/c2 > 0, the
quantity on the RHS of (8.4.11) is positive as required. Importantly, as the
spinodal is approached, 2G/c2 approaches zero. (8.4.11) implies that Iex
can get very large. Next, we relate 2G/c2 to a virial expansion. Suppose
that there are n1 moles of solvent and n2 moles of polymer in a solution that
has a volume of V (which we shall later set equal to the cell volume ):
(8.4.12a)
dV = 0 (8.4.12b)
19
(8.4.15b)
and
(8.4.16)
n1d1 + n2d2 = 0 at fixed T & P
So, (8.4.17)
But, (7.4.2)
So, (8.4.18)
20
10
and
(8.4.19)
(8.4.20)
So, (8.4.23) 21
(8.4.24a)
or (8.4.24b)
Note:
1. According to (8.4.24b), in the dilute solution limit c 0, Iex ~ R cM
which is proportional to (number of scatterers) x (scattering power of a
scatterer), as stated in (8.2.1).
2. In the dilute solution limit, light scattering measures M, and so does the
osmotic pressure. The two measurements are actually related: Light
scattering is determined by c, and their amplitude is related to the
associated osmotic cost (= [ (c + c) 0 ] / V ). One can imagine
semipermeable membranes around each of the fictitious cells. Any
fluctuations in a cells concentration will cause to change in such a way
that if c > 0, solvent in the neighboring cells wants to migrate there, and
vice versa. Essentially, thermal energy drives random fluctuations in c,
but the osmotic compressibility resists them.
22
11
3. The virial coefficient is obtainable from the
c dependence of (8.4.24b). Evidently, in a
good solvent where B > 0, the intensity will
Iex, a.u.
grow sublinearly when c is increased
sufficiently to make the second term of
(8.4.24b) significant. Conversely, for a bad
solvent with B < 0, the intensity will grow
faster than linear at large enough c. (see
c, a.u.
Fig. 8.6.)
4. There is an important difference between Fig. 8.6
light scattering and osmotic pressure
measurement. Consider the polymer to be a collection of i-mers. So,
(8.4.25)
So, (8.4.26)
24
12
Kc/R, mol/g
25
c, g/mL
Fig. 8.7
(8.5.2)
26
13
Form Factor of a Homopolymer Chain
(8.5.3)
(8.5.4)
(8.5.5)
27
So,
n.b. q = ks ki, and q =
(8.5.6)
2kisin(/2), where is the
scattering angle, equal to
the angle measured from
with (8.5.7) ki to ks.
ki ks
where P(rjk) is the probability of monomers j and k
being separated by a vector rjk. For a chain in a
theta solvent, this function is Gaussian given by
(6.7.1). Assume that the solution is isotropic, which applies in most
cases. Then it is convenient to work in spherical coordinates (r,,)
because P(rjk) has no or dependence. Observe that
(8.5.8)
(8.5.9)
28
14
Then we can write
By looking
up tables
of integral:
Since , we have
! ! q2 q4
< exp[iq rjk ] >= 1 < rjk2 > + < rjk4 > ...
6 120
(8.5.13)
29
30
15
Zimm Equation
(8.5.16)
(8.5.17)
In the c 0 limit,
Zimm Plot
Recast (8.5.16) in the form of (8.4.24b). We get:
(8.5.19)
16
Zimm Plot
both series should converge to the same
y-intercept of 1/Mw when q 0 and c c 0 extrapolations,
0. For the first series, the slope should slope = (4k2Rg2)/(3Mw)
be the same and ~Rg . For the second
2
Kc/R
choice of is to space out the curves in
the first series, which are separated by
c, where c is the incremental amount
of c employed in the experiment.
Accordingly, suitable choices of are 0
~1/c (with which the curves are extrapolations,
slope =
separated horizontally by amounts of 2B/3000
~1.) To analyze the plots, one first fits
the data, as functions of sin2(/2) at sin2(/2) + 3000c
various fixed c, to straight lines and find Fig. 8.8 Zimm plot for a sample of
the = 0 intercepts from the fits for each methyl cellulose in water.
c. Next, one fits the data as functions
of c at various to straight lines and find the c 0 intercepts for each .
The two procedures result in two sets of (extrapolated) points as shown in33
Fig. 8.8 by solid circles. These points would from two lines that intersect
Zimm Plot
the Kc/R axis at the same point. The value of that intercept is 1/Mw. It
can be shown that the slopes of the c = constant parallel lines are
(2kRg)2/(3Mw) and those of the = constant parallel lines are 2B/.
34
17
Example 8.3 on Zimm Plot
35
Fig. 8.9
36
18
Example 8.3 on Zimm Plot
For the c = 0 data in Fig. 8.9c, one finds that
c=0
=0
For the = 0 data in Fig. 8.9c, one finds that
Scattering Regimes
Based on (8.5.13), i.e.,
we can delineate four general regimes of behavior, depending on the value of qRg
19
39
40
20
Form Factor of Several Shapes
Here, we state the form factor for three particularly important shapes: the Gaussian
coil, the rigid rod, and the hard sphere.
(8.6.1)
This function applies to chains in a theta solvent and in a melt. Note that it
doesnt apply when q-1 is small and comparable to the persistence length or
statistical segment length.
2. For a rigid rod of length L and zero width, the form factor is:
(8.6.2)
(8.6.3) 41
21
Light Scattering Experiments
One common application of light scattering is in dynamic light scattering
(DLS) (to be discussed in the next chapter), which setup can also be
used to measure I(q). Another common application is in size-exclusion
chromatography as an absolute Mw detector, which is in routine use
nowadays.
Fig. 8.12 shows the schematic of a light scattering setup. The index
matching fluid (e.g. silicon oil and toluene whose refractive indices are
close to that of glass) serves to reduce reflection of the incident light from
the sample, which is enclosed in a glass container. The index matching
bath also provides an effective medium for controlling the sample
temperature.
Fig. 8.12 43
Fig. 8.13
44
22
Samples and Solutions
Two main issues: (1) Choice of solvent (2) Need to prepare dust-free
samples.
For issue (1), one would like to have |n/c| as large as possible. It
may also be helpful to choose a solvent with a relatively small R of its
own, so that the polymer contribution to the excess scattering is
larger. (For pure solvent, scattering comes from density fluctuations,
which are determined by the isothermal compressibility of the solvent,
; the intensity is ~kT.) For issue (2), some solvents are easier to
make dust-free than others; for example, more polar solvents such as
water and THF are often trickier to clean than toluene or cyclohexane.
It is essential to remove dust, as stray particles that are significantly
larger than the polymer molecules will scatter strongly.
45
46
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