POLYMER

CHARACTERIZATION
Concept of Average Molecular
* Not only are polymer molecular weights very large, typically ranging from a few

thousand to a million or more; unlike conventional chemicals, the molecular weight within

any polymer sample is not uniform.

* Owing to this heterogeneity, the numerical value assigned to the molecular weight of a

polymer depends on the way in which the heterogeneity is averaged.

* Thus, if the molecular weight is computed by dividing the total mass by the total number of

molecules, which is equivalent to weighting the molecular weight of each species by its

mole fraction, then we obtain the number-average molecular weight M..

¢ Alternatively, the molecular weight of each species may be weighted by its weight fraction

to give the weight-average molecular weight M,,.

 el AAS oe et OOM La alae lee ela
Only for a homogeneous sample of a polymer are the two averages equal, and otherwise
No
* The principal methods for the measurement of the number-average molecular weight M,,
make use of the well-known properties of dilute solution, such as osmotic pressure,
elevation of the boiling point, and depression of the freezing point (i.e., the colligative
properties of solutions), since these properties are all proportional to the number of
dissolved solute molecules.
* Measurement of the turbidity of a dilute polymer
solution, i.e., the intensity of light scattered relative to

the intensity of the incident beam, is the standard

method for obtaining M,,.

Gel permeation chromatography is essentially a

process for the separation of polymer molecules

according to their size and affords determination of

both M, and M,. The most widely used

characterization procedure is, however, viscosity

because it is the easiest of the various methods and

requires no complicated instrument

Molecular Weight Averages
 The distribution of molecular weights in a

polymer sample is commonly expressed as

Arithmetic the proportions of the sample with particular

Mean molecular weights. The various molecular

weight averages used for polymers can

shown to be simply arithmetic me

molecular weight distributions.
 Let us assume that unit volume of a polymer sample contains a total of A molecules consist-
ing of a) molecules with molecular weight Mj, a2 molecules with molecular weight Mp, ..... aj
molecules with molecular weight M;. The arithmetic mean molecular weight M is then the total
measured quantity divided by the total number of molecules:

V- a,M, + a)M) + +++ + ajM;

a +2 ++ +4;
a,M, + a)M) + --- + ajM;
4
Mi + Mp + ++ + My
a a) a

A A A
 oo
4 On , ~ Pr
Pane

The ratio a;/A represents the proportion of molecules with molecular weight M;. Denoting this
proportion by fj, the arithmetic mean molecular weight will be given by

M = fiM, + fxM) + vee + FiMj = > AM (4.2)

i

Equation (4.2) gives the arithmetic mean of the distribution of molecular weights. Almost all
molecular weight averages can be related to this equation.
 Number-
Wal ge} oho
Molecular
Weight
 . . . ° ” ” i ]
If we substitute the proportion of species fj, which have molecular weight M;, by the corresponding v
mole fraction n; in Eq. (4.2), we obtain the deDhition of number-average molecular weight, M,,
representing the number distribution :

M = }inM = My (4.3)
_— i

The mole fraction n; is also the differential number function, and a plot of n; versus M; represents a
differential number distribution curve, as shown in Fig. 4.1(a). The distribution being normalized,
the scale of the ordinatein this Chure goes from.0.to.1, and the area under the.curve is unity.

3 : (a)

Mole fraction
Molecular weight, M,
 The cumulative number (or mole) fraction is deChed as

n(M;) = > nj (4.4)

i
where nt; is the mole fraction of molecules with molecular weight M; and n(M;) is the cumulative
mole fraction with molecular weight < M;. A plot of n(M,) against the corresponding M, yields an
integral number distribution curve, as in Fig. 4. 1(0). The units of ordinate are mole fractions and
extend from 0 to 1; the distribution is theref@sesaidsienbe normalized.
 ¢
hy

While Eq. (4.3) gives a simple deChition of the number average molecular weight M,, we
can derive other equivalent deChitions following a simple arithmetic. For this let us deChe the
following terms, some of which have already been used above.

mole fraction of species i (that is, m ne size

with molecular weight M;) in a sam
moles of species i
total of all N;’s
4: Weight fraction of speciesI
: weight of species i
sum of all W;’s
It now follows that mn = N/M = NIN
W; = NM,
w = Wi DW = NM/> NM,
Mn = YmM; = a
LW W l
DN 7 >(Wi/Mi) * D(wi/Mi)
The number-average degree of polymerization, DP, is deChed as

<x Number-average molecular weight

DP. a =
Mer weight
Mh yniM; ;
= Me = M = yi nix

which may also be written as DP, = y ny

where 7, is the number fraction of molecules containing x number of repeating units.

 Alternatively, from Eq. (4.6)

__ M, l l
DP, = — = =
, M, M, ¥(w;/M;) ¥(w;/X;)

which may also be written as

DP» = 1/ ¥ ovs/x)

where Wy is the weight fraction of molecules containing x number of repeating units.

Weight-Average Molecular Weight

The situation for weight distribution corresponds to that for a number distribution described in the
previous section. Thus recording the weight of each species in the sample, instead of the number
of molecules of each size, would give a weight distribution. The differential weight fraction is
simply the weight fraction w;, while the integral (cumulative) weight fraction w(M;) is given by

w(Mj) = yi (4.9)
i

and is equal to the weight fraction of all species with molecular weight not greater than Mj.
 A plot of w; against M; yields a normalized differential weight distribution curve, as in Fig.
4.2(a) and that of 1»(M;) against M, yields a normalized integral distribution curve, as in Fig. 4.2(b).
The scale of the ordinate in both these Chures goes from 0 to 1. Substituting w; for f in Eq.
(4.2) produces the following expression for the arithmetic mean of the weight distribution:

M = ywiM = My (4.10)
— i
My is the weight-average molecular weight. Combining Eqs. (4.10) and (4.4c) it can also be
expressed as

_ YNM? (4.11)
" "NM,

The weight-average degree of polymerization, DP,,, is deChed as

Weight-average molecular weight

DP
Mer weight
_ My _ ywM; _ > wins
= M, - M iAj