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POLYMER CHARACTERIZATION

Introduction
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.
The field of polymer characterization is about answering that question: Have I made
anything, is it what I wanted to make, and is it the same as what I made last week. Along the
way, however, you can find ways to answer some other pretty cool questions that don't have
anything to do with the above.
Characterization techniques are typically used to determine molecular mass, molecular
structure, morphology, thermal properties, and mechanical properties.

Polymer Solutions
Three factors are of general interest
1. What Solvents will dissolve what polymer?
2. How does the polymer-solvent interaction influence the solution properties?
3. To what applications do the interesting properties of polymer solutions lead?

A. Basic Polymer Thermodynamics


Gm=Hm-TSm < 0
Where, Gm = the change in Gibbs free energy in the process
Hm = the change in enthalpy in the process
Sm = the change in entropy in the process
Only if Gm is negative will the solution process be feasible

A positive H solvent and polymer prefer their own company, the purematerials are in a
lower energy state. Imicible
A negative H the solution is in the lower energy state, specific interactionsare formed
between the solvents and polymer molecules.

A. Polymer dissolution
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 interaction, induction, and 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 the attraction forces
between them, polymer 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.

B. Polymer swelling

C. Viscosity of polymer solutions


For small molecular size, the solute does not swell when dissolving. Since molecular
mobility is not restricted, and therefore intermolecular friction does not increase
drastically, the viscosity of the solvent and the solution are similar

In the dissolution process of polymers, such big molecules swell appreciably, restricting
their mobility, and consequently the intermolecular friction increases. The solution in
these cases, becomes highly viscous. THUS VISCOSITY MODIFIER

D. Solubility factors

E. Gel
A three-dimensional crosslinked network

Drastic increase in viscosity

Rubber-like, elastic

At high concentration will yield a stress point

Defined by a critical concentration or temperature and depends on


Structure of polymer
Polymer-solvent interaction
Molecular weight
Chain flexibility

F. Interactions in polymer solutions


Formation of a gel layer upon immediate exposure of the hydrophilic polymer or the
water-soluble polymer to the aqueous medium, allow the slow release of drug into the
bulk medium.

Formation of polymer complexes


Some biological macromolecules reactions are important esp on effects of drugs,
viscosity

Binding of ions to macromolecules


E.g. calcium ions to polysaccharides

Adsorption of macromolecules
Stabilisers for suspension and emulsion

Interaction with solvents


Swelling and drug release

G. Solubility parameter

In absence of specific polymer-solvent interactions, it has been established that, for a polymer
to be dissolved in a given solvent, the term (ds - dp)2 must be smaller than 4.0.

Thus, for example, according to the data shown, if we are trying to dissolve nylon 6.6 in water,
we will see that it is not possible thermodynamically, (d water - dnylon6.6) = (47.9 - 27.8) MPa1/2 = 20.1
MPa1/2 >> 4.0.
However, nylon 6.6 will dissolve in toluene, since (d toluene - dnylon6.6) = (18.2 - 27.8) MPa 1/2 = -9,5
MPa1/2 << 4.0. Making similar calculations, we will see that nylon 6.6 can also be dissolved in nhexane and carbon tetrachloride.
It should be considered that the information the solubility parameters provide is based on a
thermodynamic rather than kinetic point of view.
It means that if a quick dissolution is what we are looking for, kinetically good solvents must be
employed.
Usually, solvent mixtures of kinetically good liquids with thermodynamically good liquids, assure
a quick and efficient dissolution.
In polar systems or when polymer-solvent interactions occur, for example hydrogen bonding, the
calculation of the solubility parameters is carried out by means of more complicated equations.

General
rules
for polymer solubility
1. Like dissolve like; Polar polymers- polar solvents Nonpolar polymer-nonpolar solvent. ex)
PVA in water, PS in toluene
2. Solubility will decrease with increasing molecular weight at const. temp.
3. Crystallinity decreases solubility.
4. Crosslinking eliminates solubility.
5. The rate of solubility increases with short branches, allowing the solvent
molecules to penetrate more easily.
6. The rate of solubility decreases with longer branches, because the
entanglement makes it harder for individual molecules to separate.
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