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CHARACTERIZATION, ANALYSIS AND TESTING

Polymer Characterization
Polymer characterization is the analytical branch of polymer science which is concerned
with the characterization of polymeric materials on a variety of levels. The characterization
typically has as a goal to improve the performance of the material. As such, many
characterization techniques should ideally be linked to the desirable properties of the material
such as strength, impermeability, thermal stability, and optical properties. These properties,
however is achieved through polymer-solvent interaction in a solution.

Solubility is and what it depends on..

It should be pointed out that not all polymers can be dissolved, and even though when
they can, the dissolution process may take up to several days or weeks. According to
Rosen (1982), there is an assembly of general rules for polymer solubility, based on

experimental observations, from which interesting conclusions can be obtained.


the dissolution of polymers depends not only on their physical properties, but also on

their chemical structure, such as:


polarity
molecular weight,
branching
crosslinking degree
crystallinity
The general principle that states like dissolves like is also appropriate in the case of
polymers. Thus, polar macromolecules like poly (acrylic acid), poly (acrylamide) and
polyvinyl alcohol, among others, are soluble in water. Conversely, nonpolar polymers or
polymer showing a low polarity such as polystyrene, poly(methyl methacrylate),
poly(vinyl chloride), and poly(isobutilene), are soluble in nonpolar solvents.

Molecular weight of polymers plays an important role in their solubility. In a given solvent
at a particular temperature, as molecular weight increases, the solubility of a polymer
decreases. This same behavior is also noticed as crosslinking degree increases, since
strongly crosslinked polymers will inhibit the interaction between polymer chains and
solvent molecules, preventing those polymer chains from being transported into solution.

How a polymer gets dissolved

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CHARACTERIZATION, ANALYSIS AND TESTING

The dissolution of a polymer is generally a slow process, which can take even several

weeks, depending on the structure and the molecular weight of a given polymer.
When a low molecular weight solute such as sucrose is added to water, the dissolution
process takes place immediately. The sugar molecules leave the crystal lattice

progressively, disperse in water, and form a solution.


But polymer molecules are rather different. They constitute long chains with a large
number of segments, forming tightly
folded coils which are even entangled
to each other. Numerous cohesive and
attractive both intra and intermolecular
forces hold these coils together, such a
dispersion,

dipole-dipole

induction,

and

interaction,

hydrogen

bonding

(Figure 1a).

Based on these features, one may


expect noticeable differences in the
dissolution

behavior

shown

by

polymers. Due to their size, coiled


shape,

and

between

the

them,

attraction
polymer

forces

molecules

become dissolved quite slowly than low


molecular weight molecules.

Billmeyer Jr. (1975) points out that


there are two stages involved in this
process: in the first place, the polymer
swelling, and next the dissolution
step itself.
Figure 1. Schematic representation of
the dissolution process for polymer
molecules

Thermodynamic Consideration for Polymer Solubility


1. Gibbs free energy

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CHARACTERIZATION, ANALYSIS AND TESTING

The evaluation of certain thermodynamic factors has allowed establishing if a


polymer in a given solvent will dissolve or not. Such factors are: the Gibbs free

energy (G) and the solubility parameters.


When a pure polymer is mixed with a pure solvent at a given temperature and
pressure, the free energy of mixing will be given by:

G = H - TS
Where:
G - the change in Gibbs free energy in the process

H - the change in enthalpy in the process


T- the absolute temperature in the process
S- the change in entropy in the process
According to equation, and from the thermodynamic point of view, the dissolution will
only take place if G sign is negative.

S is usually positive, since in solution, the molecules display a more chaotic


arrangement than in the solid state, and on the other hand, the absolute temperature must be
also positive.
However, H may be either positive or negative.

A positive H solvent and polymer prefer their own company, the pure materials

are in a lower energy state.


A negative H the solution is in the lower energy state, specific interactions are
formed such as hydrogen bonding between the solvents and polymer molecules.

Illustration:

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CHARACTERIZATION, ANALYSIS AND TESTING

2. Solubility Parameter

H is given by an equation developed by Hildebrand:


H = s p ( s - p)2
Where

s and p are the volume fractions of solvent and polymer, respectively

s and p represent the cohesive energy density (CED) for solvent and polymer,
respectively. This magnitude is a measure of the strength of the intermolecular forces
keeping the molecules together in the liquid state, and it is known commonly with the
name of solubility parameter. Its units are (cal/cm3)1/2, and the equivalences to the SI
units are the following

The solubility parameters are particularly useful when studying how capable is a polymer to
being dissolved in a given solvent. However, it should be pointed out that above equation is
valid only for solutions where strong polymer-solvent interactions do not take place. Numerous
tables showing solubility parameters for both solvent and polymers have been published. Some
examples are detailed below.

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CHARACTERIZATION, ANALYSIS AND TESTING

For a polymer to be dissolved in a given solvent, the term ( s -

p ) in equation, must be

smaller than 4.0. Thus, for example, according to the data shown from the, if we are trying to
dissolve nylon 6.6 in water, we will see that it is not possible thermodynamically, since ( water -

nylon6.6) = (47.9 - 27.8) MPa1/2 = 20.1 MPa1/2 >> 4.0.

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CHARACTERIZATION, ANALYSIS AND TESTING

Polymer Interactions in Solutions

Example: Viscosity Control of Motor Oils


In order for motor oils to be effective year round they must have a viscosity that is
insensitive to temperature
Motor oils are much too sensitive to temperaturethe viscosity decreases exponentially
as the temperature increases
In order to reduce the temperature sensitivity, block copolymers of polystyrene
-hydrogenated polyisoprene are added

At low temperatures the


PS blocks phase separate
from the oil forming micelles,
while the H-PI blocks remain
dissolved in the oil. This is a
dilute
solution
and
the
viscosity
is
increased

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At high temperatures the PS


blocks become soluble in the
oil. This is a concentrated
solution and the viscosity is
increased significantly above
that of the oil

CHARACTERIZATION, ANALYSIS AND TESTING

Other Interactions in Solutions


1. Formation of polymer complexes. Some biological macromolecules reactions are
important especially on effects of drugs, viscosity
2. Binding of ions to macromolecules. E.g. calcium ions to polysaccharides
3. Adsorption of macromolecules. Stabilizers for suspension and emulsion

Industrial Applications of Polymer Solutions


Polymer

Solvent

Effect

Application

Sodium
carboxymethyl
cellulose

Soapy water

Selective precipitation
onto clothing
fibers

Diblock
copolymers

Motor oil

Colloidal suspensions
dissolve at
high temperatures,
raising viscosity

Poly(ethylene
oxide)

Water

Prevents oils from


redepositing on
clothing during detergent
washing:
antiredeposition agent
Multiviscosity (constant
viscosity)
motor oil. Example: IOW40
Heat exchange systems,
reduces
pumping costs

Proteins

Wine

Gels on reacting with


tannin

Clarification of wines,
removes
colloidal matter

Polystyrene,
various

Triglyceride oils

Viscosity control,
phase-separates
during oil
polymerization

Oil-based house paints,


makes
coatings harder, tougher

Poly urethane,
various

Esters, alcohols,
various

Varnishes, shellac, and


glues
(adhesives)

Poly(vinyl
chloride)
Polystyrene

Dibutyl phthalate

Solvent vehicle
evaporates, leaving
polymer film for glues,
solvent
enters mating surfaces
Plasticizes polymer

Poly(2,6-dimethyll,4-phenyl oxide)

Mutual solution;
toughens polystyrene

Reduces turbulent flow

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soften polymer,
makes "vinyl"
Impact-resistant objects,
such as

CHARACTERIZATION, ANALYSIS AND TESTING

Poly(methyl
methacrylate)

Poly(vinylidine
fluoride)

Increases PMMA oil


and solvent resistance

appliances
Automotive applications,
parts that might contact
gasoline

***

In many of these applications, the phase separation behavior of a polymer solution is manipulated in
order to create a desired effect.

References

Polymer Characterization. Retrieved from http://goo.gl/1fqGnh


Polymer Solutions. Retrievd from http://goo.gl/MLuh2b
Applicatons of Polymer Solutions. Retrievd from http://goo.gl/jIzWzU

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