Phase Identification in a Series of Liquid Crystalline TPP Polyethers and Copolyethers Having Highly Ordered Mesophase Structure. 3. Thin Film Surface-Induced Ordering Structure and Morphology in TPP(n = 7)

Abstract

A series of liquid crystalline polyethers has been synthesized from 1-(4-hydroxy-4′biphenylyl)-2-(4-hydroxyphenyl)propane and R,ω-dibromoalkanes [TPP(n)]. TPP(n)s show multiple phase transitions during cooling and heating. In TPP(n ) 7) bulk and fiber samples, three liquid crystalline phases have been identified: nematic phase and highly ordered smectic F and smectic crystal G phases. The detailed structures and morphology of TPP(n ) 7) thin films (with a thickness ranging from 10 to 100 nm) have been studied by electron diffraction and transmission electron microscopy experiments on three different types of substrates. These include silane-grafted, amorphous carbon-coated, and clean glass surfaces. The development of homeotropic molecular alignment in monodomains has been obtained by using substrates with silane-grafted and amorphous carbon-coated surfaces. Both surfaces can also induce structural ordering in TPP(n ) 7) to form an orthorhombic lateral packing which does not exist in the bulk and fiber samples and has only appeared in TPP(n g 11). This phase has been identified as a smectic crystal H phase. It has been found that the monodomain morphology of the highly ordered smectic crystal phases with the homeotropic molecular alignment depends strongly on the structural symmetry. Furthermore, the silane-grafted surface produces better homeotropic molecular alignment for TPP(n ) 7) than the amorphous carbon-coated surface, with the latter demonstrating a continuous change in the chain director between -30°and +30°. This change in the orientation results in observable striations in the monodomain morphology. The origin of this variation in the chain director may be associated with the fact that the vector normal to the layer of the smectic crystal phases is tilted about 32°away from the molecular direction (58°between the molecular direction and the layer surface). The clean glass surface does not induce orthorhombic packing and only polydomain structures can be found in which an in-plane homogeneous alignment of the chain directors exists. On the other hand, mechanically sheared thin films on glass surfaces show a uniaxial homogeneous molecular alignment.

Effects of Molecular Doping by Hydroquinones on Morphology and Optical Properties of Polyaniline

“…The presence of the solvent obviously benefits reorientation of the polymeric backbones, which is then fixed in dried film. It is logical to suppose that the liquid EB/HQ 1,2,3 substance possesses a lyotropic crystallinity similar to those of other liquid crystals …”

Phase Identification in a Series of Liquid Crystalline TPP Polyethers and Copolyethers Having Highly Ordered Mesophase Structures. 6. Structure Changes from Smectic to Columnar Phases in a Series of Copolyethers Containing Odd and Even Numbers of Methylene Units in Equal Molar Composition

“…In our previous reports on the phase identification in a series of main-chain liquid crystalline (LC) polyethers synthesized from 1-(4-hydroxy-4‘-biphenyl)-2-(4-hydroxyphenyl)propane and α,ω-dibromoalkanes [TPP( n )], the following phases were found: highly ordered smectic F (S F ), smectic crystal G (SC G ), and H (SC H ) phases. − The identification has been confirmed via molecular motion studies of each of these phases using solid-state carbon-13 nuclear magnetic resonance (NMR) . It has also been found that several new phases in some of these TPPs can be surface induced and stabilized, which are originally metastable in the bulk samples. , The phase structures and transition behaviors of TPPs with odd- and even-numbered methylene units are different. For example, TPPs( n = 5, 7, and 9) exhibit the following phase behavior: 1,2 whereas for TPP( n = 11), the phase transition sequence is as follows: 2 and the phase behavior of TPP( n = 12) is 3 …”

Phase Identification in a Series of Liquid Crystalline TPP Polyethers and Copolyethers Having Highly Ordered Mesophase Structures. 7. Phase Structures in a Series of Copolyethers Containing Odd and Even Numbers of Methylene Units of Different Compositions

“…Furthermore, TPP( m = 12) possesses two crystalline phases, K 1 and K 2 , which do not exist in TPP( n = 7). The transition thermodynamic properties (temperatures and heats of transitions) are also different in these TPPs. − Molecular dynamics in different phases, surface-induced phase structures, , and structural and morphological development in TPPs 8,9 have also been investigated.…”