Polymer characterization
Polymer characterization is the analytical branch of polymer science.
The discipline 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.[1]
Characterization techniques are typically used to determine molecular mass, molecular
structure, morphology, thermal properties, and mechanical properties.
CONTENTS
1Molecular Mass
2Molecular Structure
3Morphology
4Thermal properties
5Mechanical Properties
Molecular Mass
The molecular mass of a polymer differs from typical molecules, in that polymerization reactions
produce a distribution of molecular weights and shapes. The distribution of molecular masses can be
summarized by the number average molecular weight, weight average molecular weight,
and polydispersity. Some of the most common methods for determining these parameters
are colligative property measurements, light scattering techniques, viscometry, and size exclusion
chromatography.
Gel permeation chromatography, a type of size exclusion chromatography, is an especially useful
technique used to directly determine the molecular weight distribution parameters based on the
polymer's hydrodynamic volume. Gel permeation chromatography is often used in combination
with Low-angle laser light scattering (LALLS) and orviscometry can be used to determine the
molecular weight distribution as well as the degree of long chain branching of a polymer, provided a
suitable solvent can be found.
Molar mass determination of copolymers is a much more complicated procedure. The complications
arise from the effect of solvent on the homopolymers and how this can affect the copolymer
morphology. Analysis of copolymers typically requires multiple characterization methods. For
instance, copolymers with short chain branching such as linear low-density polyethylene (a
copolymer of ethylene and a higher alkene such as hexene or octene) require the use of Analytical
Temperature Rising Elution Fractionation (ATREF) techniques. These techniques can reveal how the
short chain branches are distributed over the various molecular weights.
Molecular Structure
Many of the analytical techniques used to determine the molecular structure of unknown organic
compounds are also used in polymer characterization. Spectroscopic techniques such as ultraviolet-
visible spectroscopy, infrared spectroscopy, Raman spectroscopy, nuclear magnetic resonance
spectroscopy, electron spin resonance spectroscopy, X-ray diffraction, and mass spectrometry are
used to identify common functional groups.
Morphology
Polymer morphology is a microscale property that is largely dictated by the amorphous or crystalline
portions of the polymer chains and their influence on each other. Microscopy techniques are
especially useful in determining these microscale properties, as the domains created by the polymer
morphology are large enough to be viewed using modern microscopy instruments. Some of the most
common microscopy techniques used are X-ray diffraction, Transmission Electron
Microscopy, Scanning Transmission Electron Microscopy, Scanning Electron Microscopy,
and Atomic Force Microscopy.
Polymer morphology on a mesoscale (nanometers to micrometers) is particularly important for the
mechanical properties of many materials. Transmission Electron Microscopy in combination
with staining techniques, but also Scanning Electron Microscopy, Scanning probe microscopy are
important tools to optimize the morphology of materials likepolybutadiene-polystyrene polymers and
many polymer blends.
X-ray diffraction is generally not as powerful for this class of materials as they are either amorphous
or poorly crystallized. The Small-angle scattering like Small-angle X-ray scattering (SAXS) can be
used to measure the long periods of semicrystalline polymers.
Thermal properties
A true workhorse for polymer characterization is thermal analysis, particularly Differential scanning
calorimetry. Changes in the compositional and structural parameters of the material usually affect its
melting transitions or glass transitions and these in turn can be linked to many performance
parameters. For semicrystalline polymers it is an important method to measure
crystallinity. Thermogravimetric analysis can also give an indication of polymer thermal stability and
the effects of additives such as flame retardants. Other thermal analysis techniques are typically
combinations of the basic techniques and include differential thermal analysis, thermomechanical
analysis, dynamic mechanical thermal analysis, and dielectric thermal analysis.
Dynamic mechanical spectroscopy and Dielectric spectroscopy are essentially extensions of thermal
analysis that can reveal more subtle transitions with temperature as they affect the complex modulus
or the dielectric function of the material.
Mechanical Properties
The characterization of mechanical properties in polymers typically refers to a measure of the
strength of a polymer film. The tensile strength and Young's modulus of elasticity are of particular
interest for describing the stress-strain properties of polymer films. Dynamic mechanical analysis is
the most common technique used to characterize this viscoelastic behavior. Other techniques
include viscometry, rheometry, and pendulum hardness.
