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