Do-Yun Kim

Crystal structure, morphology and phase transitions in aromatic polyimide oligomers: 2. Poly(1,4-phenylene-oxy-1,4-phenylene-oxy-1,4-phenylene pyromellitimide)

Abstract Crystal structure, morphology and thermal effects of poly(1,4-phenylene-oxy-1,4-phenylene-oxy-1,4-phenylene pyromellitimide) (PMDA-TPE-Q), synthesized from N , N ′-dimethyl pyromellitic bisimide and 1,4-bis(4-aminophenoxy) benzene in the melt, have been studied by transmission electron microscopy (TEM), electron diffraction (ED) and wide angle X-ray diffraction (WAXD) measurements. The unit cell of PMDA-TPE-Q is determined by ED and WAXD to be a two-chain orthorhombic lattice with dimensions of a =0.823 nm, b =0.558 nm and c =2.209 nm. The observed crystal morphology from TEM is primarily lamellar with extended chain conformations. The thickness of the lamellar crystals varies with the polymerization conditions. Possible thermal effects on PMDA-TPE-Q have been studied by annealing the crystals at different temperatures. The results indicate that with increasing annealing temperature, the lateral dimensions of the lattice expand, primarily along the a -axis. The c -axis shrinks slightly with increasing the reflection intensities of (0 0 l ) planes when l =odd. This is confirmed by using order correlation changes along these directions measured by WAXD experiments. Crystal defects are found in dark field TEM observations.

Thermodynamic transition properties of highly ordered smectic phases

A series of polyethers have been synthesized from 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl)propane and α, Ω-dibromoalkanes having different numbers of methylene units [TPPs]. Both odd- and even-numbered TPPs [TPP(n=odd)s and TPP(n=even)s) exhibit multiple transitions during cooling and heating and they show little supercooling dependence, indicating close-to-equilibrium nature of these transitions. Combining the structural characterization obtainedvia wide angle X-ray diffraction powder and fiber patterns at different temperatures and the morphological observations from microscopy techniques, not only the nematic liquid crystalline phase but also highly ordered smecticF, smectic crystalG andH phases have been identified. The phase diagrams for both TPP(n=odd)s and TPP(n=even)s have been constructed [1–3]. Thermodynamic properties (enthalpy and entropy changes) during these transitions are studied based on differential scanning calorimetry experiments. The contributions of the mesogenic groups and methylene units to each ordering process can be separated and they indicate the characteristics of these processes thereby providing estimations of the transition types.