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6.1.5.

Analysis of Nonlinear Electrical and Optical Effects


Important technological applications are critically dependent on the influence
of light on the structure and dynamics of a polymer. For example, liquid crystalline sidechain
polymers are used for reversible optical data storage and
dielectric analysis has been successfully applied for investigating the mechanisms involved
in the storage procedure (Stracke et al. 2000 ).
6.1.6. Dielectric Characterization of Polymers for
Engineering Applications
At an industrial level, dielectric techniques have been implemented, among
others, in quality control (reliability and stability of the structure and performance, or for
studying mechanical and thermal treatment effects), in the
characterization of semiconductors, cable - insulating materials (polyethylene,
polypropylene, polytetrafluoroethylene, etc.), and passivation layers in microchips. Dielectric
heating of materials and remote sensing is another area of
interest. The latter application makes use of the change in the dielectric
response of certain materials when exposed to gases or liquids (Langlet et al.
2004 ). Dielectric results may also be used to solve questions arising from lack
of compositional information, such as uncertainties pertaining to the nature,
concentration, or spatial distribution of absorbed phases, dopants, or contaminants. The
piezoelectric, pyroelectric, and ferroelectric (Buixaderas et al. 2004 )
properties of polymeric materials (e.g., polytetrafluoroethylene, polyvinylidinefluoride, and
several of their copolymers) have also attracted considerable
attention.
6.1.7. Prelude to the Chapter
In the following sections, an introduction to dielectric theory and various
polarization/relaxation mechanisms observed in amorphous and semicrystalline polymers
(Section 6.2 ) is presented. This will equip undergraduate and
postgraduate students, as well as technicians, professionals, and academics,
with the theoretical background necessary for understanding the origin of
measured signals at the molecular level and for the correct interpretation of
dielectric data. Section 6.3 acquaints the reader with common isothermal and
nonisothermal techniques and related instrumentation, for dielectric measurements in the
frequency or time domain. The discussion focuses on two groups
of analytical techniques that make up the DEA family, involving dielectric
measurements performed using alternating [dielectric relaxation spectroscopy
(DRS)] or constant [thermally stimulated current technique (TSC)] electric
fields. A detailed description of experimental aspects (e.g., recommendations
for sample preparation and accurate measurements, errors), which are essential in
performing good measurements and extracting meaningful results for
the most common applications, is presented in Section 6.4 . In Section 6.5 the
reader is guided in performing routine data analysis, using thermoplastic
poly(methyl methacrylate) as a reference material that is readily available. The
knowledge acquired in these sections is sufficient to navigate through the
topics discussed in the following sections, dealing with the application of
dielectric analysis in representative thermoplastics (Section 6.6 ) and t6.1.1.
Establishment of Relationships between a Polymers
Configuration, Dynamic Properties, and Applications
The dynamics and energetics of a polymer can be explored by monitoring
structure - or composition - dependent changes in parameters (shape, position,
strength, etc.) characteristic of the glass transition and various secondary
signals. At the same time, the time, temperature, or pressure dependences of

properties related to translational motions of charges (DC conductivity, ion


mobility, trap energy depths, etc.) are sensitive to the diversity of the environ
ment provided by the polymer chains and the bonding state of the pertinent
ions. Several of these parameters can be used to appraise perturbations in the
strength of inter - and intramolecular interactions of a dipolar or ionic nature.
This information is fundamental in many areas of materials science, including
pharmaceutical science [e.g., for controlled drug delivery (Craig 1995 )] and
specialized applications in biochemistry and biophysics (body fluid hydromet
allurgy, protein stability, hydrophobic hydration, etc.). Interesting examples of
dielectric studies on liquids, liquid crystals, biopolymers, blends, copolymers,
and composites, can be found in excellent reference books [e.g., Runt (1997) ;
Kremer and Schnhals (2002) ].
6.1.2. Information on Surface and Bulk Properties in
Confining Environments
Dielectric techniques have proved particularly effective in the study of polymer
dynamics at interfaces and in confining geometries [polymers in ultrathin films
or within nanometric pores of oxide glasses, polymer in the galleries of clays,
etc. (Kalogeras 2008 )] because of their enhanced sensitivity with decreasing
size scale and the broad dynamic range, with an unparalleled range of fre
quency and temperature (Kremer et al. 2003 ; Hartmann et al. 2002 ). Probing
nanoconfinement - induced effects in the segmental relaxation dynamics of the

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