Thermotropic textures

Thermotropic liquid-crystalline properties of different metal alkanesulfonates are studied by microscopy and X-ray diffraction [59]. Sodium soaps show smectic polymorphism of smectic A and smectic B phases. Ammonium soaps only show smectic A phases but polymorphism in the crystalline state. Calcium soaps show columnar mesophases. In Figs. 32 and 33 some textures and x-ray diffraction patterns are depicted. 

Figure 7.1 Illustration of different aggregation states obtained (from left to right) by increasing temperature crystal (K), smectic C (SmC), nematic (N) and isotropic (I). Row a shows macroscopic appearance of samples in row b, short-range microscopic ordering is represented (each bar represents a molecule) thermotropic phase diagram of row c illustrates relevant transition temperatures (Tm melting temperature Tsmc-N transition temperature between SmC and N Tc clearing temperature) row d shows different texture of different states as seen through polarizing microscope (with crossed polars, isotropic phase appears black).

FIG. 2. Schematic representation of different calamitic and discotic thermotropic liquid crystals (a) nematic, (b) cholesteric, (c-e) smectic, (f) columnar hexagonal, (g) columnar hexagonal tilted a-e adapted from Demus, D., and Richter, L., Textures of Liquid Crystals, Verlag Chemie, Weinheim, Germany, 1978 f,g adapted from Eidenschenk, R., Flussige Kristalle, Chem. Unserer Zeit, 18, 168-176 (1978). 

The smectic mesophases of the thermotropic liquid crystals show a variety of textures but resemble mainly the fan-shape texture of the lyotropic hexagonal meso-phase. For further reading more comprehensive literature is recommended [11]. 

It was first reported in the early 1970s that these melt processible polymers could best be described as thermotropic systems which usually display an nematic texture in the melt phase [5]. Subsequently, a number of additional phases have been reported ranging from discotic structures to highly ordered smectic E G systems with three dimensional order. In the last several years an IUPAC sponsored study on nomenclature on thermotropic LPCs has been underway. A more complete set of definitions will be available shortly as a result of Recommendation No. 199 IUPAC [6]. 

This study has concentrated on the defects observed in lyotropic lamellar phases, and it has put into evidence the specific character of the textures compared to classical thermotropic smectic phases. In leci-... 

One of the most classic examples of chiral expression in thermotropic liquid crystals is that of the stereospecific formation of helical fibres by di-astereomers of tartaric acid derivatised either with uracil or 2,6-diacylamino pyridine (Fig. 9) [88]. Upon mixing the complementary components, which are not liquid crystals in their pure state, mesophases form which exist over very broad temperature ranges, whose magnitude depend on whether the tartaric acid core is either d, l or meso [89]. Electron microscopy studies of samples deposited from chloroform solutions showed that aggregates formed by combination of the meso compounds gave no discernable texture, while those formed by combinations of the d or l components produced fibres of a determined handedness [90]. The observation of these fibres and their dimensions makes it possible that the structural hypothesis drawn schematically in Fig. 9 is valid. This example shows elegantly the transfer of chirality from the molecular to the supramolecular level in the nanometer to micrometer regime. 

Tazuke, Ikeda, and their co-workers [53,54] were the first to use phenylene-diacrylate (PDA) as a mesogen and chromophore to explore the possibility of forming two-dimensionally reinforced polymer materials by photochemical cross-linking of a thermotropic LC polymer. Polyesters, 23, of para-phenylene-diacrylic acid and several diols were synthesized and found to exhibit LC behavior upon annealing above Tg. Polymer 23a exhibited [53] the texture of a N meso-... 

However, only 65a exhibits thermotropic nematic behavior if amorphous thin films are heated to 155 °C, at which a Schlieren texture develops. The material decomposes above... 

Above 110 °C, this arrangement becomes mobile, and a smectic C liquid-crystalline phase is entered. Samples cooled down from the isotropic melt (140 °C) show Schlieren and banded textures when viewed under crossed polarizers (Figure 8). These textures look similar to nematic Schlieren textures, but from the X-ray diffraction data it is clear that 12c forms a homeotropically oriented smectic C phase. In a nematic phase, the small-angle diffraction peak would be absent, and a broad scattering feature, a nematic streak , would be observed. Polymer 12c was the first example of a PPE derivative for which three states of matter, i.e. crystalline, thermotropic liquid crystalline, and a highly viscous isotropic liquid, were accessible [46]. 

The mesophase exhibiting a homeotropic texture can still shew stir opalescence, which is a method of identification particularly suited for thermotropic polymers. This somewhat crude method of characterizing a liquid crystalline material is performed by shearing a thin film of the mesophase and looking for momentary appearances of turbidity in the otherwise transparent melt. No microscope is need to observe stir opalescence, but simple shearing of the homeotropic melt between crossed-polars can also reveal the mesophase. 

The rheology of low molecular weight thermotropic compounds has been a subject of considerable theoretical and experimental analysis In general, liquid crystals are easily oriented by surfaces, electromagnetic fields and mechanical stress or shear, and the degree of orientation, in turn, affects their melt viscosity. The rheological behavior of a liquid crystal is known to be greatly dependent on the nature and also on the texture of its mesophase. 

The smectic mesophases of the thermotropic liquid crystals show a variety of textures but resemble the... 

Figure 6.6 (Left ) Stained section of a crab cuticle Carcinus maenas), showing the single twist of protein fibres (some indicated by red lines), characteristic of the chiral thermotropic cholesteric mesophase. (Right ) Schematic relation between nested arc texture in the micrograph and the cholesteric mesostructure. Micrograph and drawing adapted from (9. ...

The thermotropic liquid crystalline PECs could be synthesized from HBA, DHBP, DPC. Threaded textures of PECs, a characteristic of the nematic phase, were observed over the investigated composition range. 

Harrison, P. Navard, P. Cidade, M.T. Investigation of the band texture occurring in acetoxy-propyl cellulose thermotropic liquid crystalline polymer using rheo-optical, rheological, and light scattering techniques. Rheol. Acta 1999, 38 (6), 594-605. 

A second noteworthy series is that of the dirhodium tetraalkanaotes (Figure 80 above) which have been extensively studied as thermotropic mesogens (see 5. 2. above). However, in solution in hexadecane, nematic phases are formed as evidenced by the schlieren textures observed [188],... 

Gao et al. have recently prepared a number of thermotropic liquid crystalline main-chain fer-rocenes exhibiting fluorescent properties.182 The reaction of 1,1 -bisf functionalized)ferrocenes, 95, with 1,4-dibromobutane, 97a, or a,a -dibromo-p-xylene 97b generated polyelectrolytes 97a,b with Mn ranging from 5400-14,700 (Scheme 2.29). These polymers were highly thermally stable with the first weight loss occurring between 172 and 330°C. The liquid crystalline properties showed these materials formed smectic liquid-crystal phases and displayed batonnet textures. 

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