Investigation of dipolar reorientation dynamics of pure bulk polymers using second harmonic generation

Second harmonic generation (SHG) in three corona‐poled, pure, bulk polymers is studied as a function of temperature. It is found that this technique readily yields dynamical information that is complementary to that obtained from the technique of dielectric relaxation (DR). The SHG results are compared to those from DR in the same temperature ranges above T_g. It is found that in the temperature ranges examined, the relaxation times obtained from SHG are several orders fo magnitude longer than those measured by dielectric relaxation. This is explained as being due to the strong correlation between oriented dipoles and to trapped charges injected by the poling process. Fitting measured data to the Williams‐Landau‐Ferry (WLF) equation indicates that more free volume is needed in SHG for dipolar reorientation than is needed in DR. An SHG relaxation elongation phenomenon at constant temperature is found to occur in the pure bulk polymers and is similar to that found in chromophore‐doped polymers previously studied. The SHG technique is developed as a new tool to directly study the reorientational dynamics of polar polymer segments. © 1994 John Wiley & Sons, Inc.