Polymer Analysis

Chapter 1. Introduction/Overview

The focus of this course is analysis and characterization of polymers and plastics. Analysis of
polymeric systems is essentially a subtopic of the field of chemical analysis of organic materials.
Because of this, spectroscopic techniques commonly used by organic chemists are at the heart of
Polymer Analysis, e.g. infra-red (IR) spectroscopy, Raman spectroscopy, nuclear magnetic
resonance (NMR) spectroscopy and to some extent ultra-violet/visible (UV/Vis) spectroscopy. In
addition, since most polymeric materials are used in the solid state, traditional characterization
techniques aimed at the solid state are often encountered, x-ray diffraction, optical and electron
microscopy as well as thermal analysis. Unique to polymeric materials are analytic techniques
which focus on viscoelastic properties, specifically, dynamic mechanical testing. Additionally,
techniques aimed at determination of colloidal scale structure such as chain structure and molecular
weight for high molecular weight materials are somewhat unique to polymeric materials, i.e. gel
permeation chromatography, small angle scattering (SAS) and various other techniques for the
determination of colloidal scale structure. The textbook, Polymer Characterization covers all of
these analytic techniques and can serve as a reference for a general introduction to the analysis of
polymeric systems. Due to time constraints we can only cover a small number of analytic
techniques important to polymers in this course and these are outlined in the syllabus.

Structure/Processing/Property:

Generally people resort to analytic techniques when confronted with a problem which involves
understanding the relationship between properties of a processed material and the structure and
chemical composition of the system. Plastics are typically complex morphological systems being
composed of many phases and additives, even the polymer itself being disperse in molecular
weight, tacticity, crystallinity, orientation and sometimes chemical composition. Dispersion of
structure and chemical composition means that the best tools to describe polymeric materials are
always statistical in nature. For example, a low molecular weight organic has a specific melting
point, while a polymer displays a range of melting with an onset, a peak and a maximum melting
temperature. Such a melting spectrum might best be described by a Gaussian function with a
standard deviation and mean. Additionally, the complication of enormous macromolecular chains
means that simplified descriptions are often needed to characterize polymeric materials, for example
group contribution methods in spectroscopy where the chain structure is decomposed into chemical
groups which contribute to the absorption spectrum. A detailed understanding of many of the
analytic descriptions of polymeric materials is often precluded by the complexity of the situation.

Analytic Techniques:

All analytic techniques used in polymer characterization are based on specific physical principles
which serve as a guide to understanding the basic limitations of the techniques. Often multiple
techniques are available to describe the same property of a material and it is only through
understanding the physical basis of characterization techniques that one can pick the "right tool
for the job", the job being understanding the relationship between structure and chemical
composition and properties. For example, it is often found that blown films of polyethylene
display different tear strengths in the machine and transverse directions. This can lead to failure of
parts made from blown films such as plastic bags. It is often assumed that this directional nature
of the tear strength is related to orientation induced by processing of these plastics. There are
several analytic techniques available to describe orientation. These include construction of pole-
figures from x-ray diffraction scans, calculation of orientation functions from XRD data,
calculation of orientation functions from IR, NMR or Raman data, and measurement of the optical

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birefringence for the blown films using polarized light. Each of these techniques will yield a
different value for the orientation function!

Similarly, even the value for the degree of crystallinity in these blown films will depend on the
technique which is used, i.e. XRD, differential scanning calorimetry, density, or IR for example.
This makes a firm understanding of the physical basis of analytic techniques critical to their
application in polymeric systems.

Levels of Structure:

The analytic description of a complex material is strongly dependent on the size scale on which an
observation is made. For example, a semi-crystalline polymer such as polyethylene is composed
of chemical units similar to olefinic waxes. These chemical units give rise to spectroscopic
absorption patterns which are largely indistinguishable from their lower molecular weight
counterparts. Similarly, the crystalline structure, which is usually of low symmetry in polymers,
mimics the crystalline structure seen in lower molecular weight analogues such as waxes.

The monomer structure combined with the topological arrangement of monomers in a polymer
chain give rise to helical coiling of polymer chains. This helical coiling and the weak chemical
associations related to it give rise to some mechanical and vibrational features which can often be
observed spectroscopically. Generally, the helical coiling of monomers in a chain are evidenced by
colloidal scale structure, chain persistence (local linearity) and enhancement of the ability of long
chain polymers to crystallize. NMR is a technique particularly suited for the characterization of the
topological arrangement of monomers in a chain (i.e. tacticity).

In polyethylene, local chain structure is sufficiently regular to give rise to a crystalline phase.
Entanglement of chains, chain branching and the presence of endgroups prevents complete
crystallization of a polymer. Polymeric materials which display crystallinity are always described
by a multi-phase model, i.e. semicrystalline, which includes an amorphous and crystalline phase in
coexistence. Low transport coefficients and chain folding give rise to nano-scale crystallites which
are best observed by TEM, small-angle x-ray scattering (SAXS) and to some extent by Raman
spectroscopy (Longitudinal Acoustic Modes, LAM).

Fibrillar crystallites in polymers lead to colloidal to optical scale structures, spherulites, which are
generally centro-symetric and which display radially oriented birefringence. These micron scale
structures are best observed using optical microscopy, SEM, small-angle light scattering (SALS)
and give rise to certain features in the mechanical and transport properties of semi-crystalline
polymers.

Thus, is one in interested in a specific analytic feature of a processing operation such as film
blowing on a polymeric material such as high density polyethylene (HDPE), one is immediately
faced with the issue of structural level, i.e. for transport properties one might need to characterize
the orientation of chains or crystallites (lamellae), for mechanical properties, orientation of
spherulites and the amorphous component of these biphase materials. Additionally, it is expected
that any analytic determination of these materials will be subject to a large range of statistical
variation between samples as well as an innate distribution associated with the polydispersity of the
material of itself.

Course Contents:

Statistics:

All properties of polymeric systems display dispersion due to 1) the limited ability of synthetic
chemistry to produce monodisperse and perfect chemical structure as well as 2) the dominance of
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kinetics in processing of high molecular weight materials. Statistical analysis is critical to
understanding and describing plastics. This course begins with a survey of the important tools to
describe statistically distributed systems which includes the major distribution functions and
mathematical descriptions of the propagation of error in data sets. Analytic descriptions of
polymers are of no use unless some description of the expected error associated with the analytic
results are presented.

Thermal and Mechanical Testing:

Thermal analysis is useful in describing solid state transitions in polymers and is of pivotal
importance to understanding mechanical properties and processing of plastics. The measurement
of the glass transition and crystalline transitions using typical analytic techniques will be discussed.
Polymeric systems are dominated by kinetics and this is emphasized in the use of dynamic
mechanical, thermal analysis techniques to describe mechanical absorption phenomena associated
with the glass transition and other mechanical transitions.

Absorption Spectroscopy:

The major techniques for the determination of chemical composition and molecular topology
involve the absorption of electro-magnetic radiation by polymers. The major techniques are IR,
Raman, and NMR spectroscopy and the bulk of this course will involve these major analytic
techniques. Absorption is a quantized inelastic phenomena involving the transfer of energy from
EM radiation to a material.

Diffraction and Scattering:

In addition to inelastic absorption phenomena, elastic interaction between EM radiation and a

Small-angle x-ray scattering is a critical technique for the description of polymeric materials since
diffraction at small angles is associated with the colloidal to nano-scales which is the size range of a
typical polymer chain. The colloidal scale is also associated with polymer crystallites (lamellae)
and microphase separated block copolymer structures. Further, light scattering has been widely
used in polymer science to describe disordered micron scale structure as well as a primary
technique for the determination of molecular weight from dilute solutions.