Thermotropic liquid crystal , structure

Figure 1 General structures of calamitic and discotic thermotropic liquid crystals. (A) Layered calamitic smectic liquid crystal. The structures of the various types depend on the local packing of the molecules, the extent of the packing, and the orientation of the long axes with respect to the layers. (B) Calamitic nematic liquid crystal. The molecules have no long-range order, and are only orientationally ordered. (C) Ordered columnar discotic liquid crystal. Disk-like molecules form ordered or disordered columns different column packings give rise to various mesophase structures. (D) Nematic-discotic liquid crystal phase. The disk-like molecules are only orientationally ordered.

The liquid crystal phases of a thermotropic material are generated by changes in temperature (see Chapter 3). However, lyotropic liquid crystal phases are formed on the dissolution of amphiphilic molecules of a material in a solvent (usually water). Just as there are many different types of structural modifications for thermotropic liquid crystals (see Chapter 3), there are several different types of lyotropic liquid crystal phase structures. Each of these different types has a different extent of molecular ordering within the solvent matrix. The concentration of the material in the solvent dictates the type of lyotropic liquid crystal phase that is exhibited. However, it is also possible to alter the type of lyotropic phase exhibited at each concentration by changing the temperature. 

There are several different phases in thermotropic liquid crystals. The structural nature of mesophases is influenced by the molecular shape and therefore depends on whether the liquid crystal is formed by rod-like or disc-like molecules. Thermotropics of rod-like molecules may be divided into two main categories nematic and smectic phases. There exist many types of smectic phases, labeled as 5, 5b, S /. When an ordered solid of a liquid crystal melts (see Fig. 1.1), it may melt into a nematic phase or a smectic A phase. Upon further heating, it eventually turns into an isotropic liquid. First, classical thermotropic liquid crystals are described, and then a group of more exotic liquid crystals like discotic thermotropics, lyotropics, and liquid crystalline polymers. 

Liquid crystals have structural order intermediate between conventional liquids and solids. Thermotropic liquid crystal phases form in pure compounds or homogeneous mixtures as the temperature is changed. Lyotropic liquid crystals form when amphiphilic molecules are dissolved in water, or another suitable solvent, and concentration is the main physical variable. Polymeric liquid crystalline order occurs in fluid polymer melts and solutions. We shall limit our discussion to thermotropic liquid crystals, for which the knowledge is most complete. 

Other interesting Langmuir monolayer systems include spread thermotropic liquid crystals where a foam structure forms on expansion from a collapsed state [23]. Spread monolayers of clay dispersions form a layer of overlapping clay platelets that can be subsequently deposited onto solid substrates [24]. 

In order to make polymers behave as liquid crystals it is necessary to introduce some structural rigidity. A typical polymer which has the required rigidity is poly(phenylenetetraphthalamide) (10.7). This material belongs to a class of polymer known as the aramids. Other liquid crystalline polymers are the thermotropic polyesters derived from /7-hydroxybenzoic acid, p, p -biphenol and terephthalic acid (10.8). 

Molecular Structure in Thermotropic Liquid Crystal Phases. 58... 

Most solid materials produce isotropic liquids directly upon melting. However, in some cases one or more intermediate phases are formed (called mesophases), where the material retains some ordered structure but already shows the mobility characteristic of a liquid. These materials are liquid crystal (LCs)(or mesogens) of the thermotropic type, and can display several transitions between phases at different temperatures crystal-crystal transition (between solid phases), melting point (solid to first mesophase transition), mesophase-mesophase transition (when several mesophases exist), and clearing point (last mesophase to isotropic liquid transition) [1]. Often the transitions are observed both upon heating and on cooling (enantiotropic transitions), but sometimes they appear only upon cooling (monotropic transitions). 

A review of the literature demonstrates some trends concerning the effect of the polymer backbone on the thermotropic behavior of side-chain liquid crystalline polymers. In comparison to low molar mass liquid crystals, the thermal stability of the mesophase increases upon polymerization (3,5,18). However, due to increasing viscosity as the degree of polymerization increases, structural rearrangements are slowed down. Perhaps this is why the isotropization temperature increases up to a critical value as the degree of polymerization increases (18). 

The molecular structure of arsphenamin is a typical representative of a thermotropic mesogen. With its symmetrical arrangement of the atoms the same holds for disodium cromoglycate, DNCG [20], which forms both thermotropic liquid crystals and lyotropic mesophases in the presence of water. Micronized DNCG powder applied to the mucosa of the nose or the bronchi absorbs water from the high relative humidity of the respiration tract and is first transformed into a lyotropic mesophase and then into a solution depending on the amount of water available. 

Liquid crystals are mainly used for decorative purposes in cosmetics. Cholesteric liquid crystals are particularly suitable because of their iridescent color effects, and find applications in nail varnish, eye shadow, and lipsticks. The structure of these thermotropic liquid crystals changes as a result of body temperature, resulting in the desired color effect. In recent times, such thermotropic cholesteric liquid crystals have been included in body care cosmetics, where they are dispersed in a hydrogel. Depending whether this dispersion requires stirring or a special spraying process, the iridescent liquid crystalline particles are distributed statistically in the gel (Estee Lau-... 

These structures are extensively described in the current literature (Fanum, 2008 Friberg, 1976 Birdi, 2002 Holmberg, 2004 Somasundaran, 2006). Even within the same phases, their self-assembled structures are tunable by the concentration for example, in lamellar phases, the layer distances increase with the solvent volume. Lamellar structures are found in systems such as the common hand soap, which consists of ca. 0% soap + 20% water. The layers of soap molecules are separated by a region of water (including, salts etc.) as a kind of sandwich. The x-ray diffraction analysis shows this structure very clearly. Since lyotropic liquid crystals rely on a subtle balance of intermolecular interactions, it is more difficult to analyze their structures and properties than those of thermotropic liquid crystals. Similar phases and characteristics can be observed in immiscible diblock copolymers. 

Our understanding of lyotropic liquid crystals follows in a similar manner. The action of solvent on a crystalline substance disrupts the lattice structure and most compounds pass into solution. However, some compounds yield liquid crystal solutions that possess long-range ordering intermediate between solutions and crystal. The lyotropic liquid crystal can pass into the solution state by the addition of more solvent and/or heating to a higher temperature. Thermotropic and lyotropic liquid crystals, both turbid in appearance, become clear when they pass itno the liquid and solution states, respectively. 

The mesogenic structures of glycolipids are due to the occurrence, on the same molecule, of a hydrophilic and a hydrophobic moiety often referred to as head and tail respectively. As a result, glycolipids are able to self-organize into a large variety of mesophases also called liquid crystals (Fig. 2) [ 10]. Supramolecular assemblies of mesogenic compounds can be caused by a rise in temperature (thermotropic liquid crystals) or by the addition of water (lyotropic liquid crystals) they result from different responses of the carbohydrate and the alkyl chain to temperature or solvent (water), respectively. 

Liquid crystal As the name implies, this is an ordered yet fluid phase in which water, surfactant, and solubilizate combine to form anisotropic, organized structures. These are called lyotropic mesomorphic phases, as opposed to thermotropic mesomorphs, which form when certain organic crystals are heated. 

Lyotropic Liquid Crystals, Some molecules in a sulvcni form phases with orientational antl/or positional order. In these systems, the transition from one phase to another can occur due to a change of concentration, so they arc given the name lyotropic liquid cry stals Of course temperature can also cause phase transitions in these systems, so this aspect of thermotropic liquid crystals is shared hy lyotropics. The real distinctiveness of lyotropic-liquid crystals is the fact that at least two very different species of molecules nttisl be present for these structures to form... 

A liquid crystal compound in more cases Ilian not takes on more than one type of mesomorphic structure as the conditions of temperature or solvent are changed. In thermotropic liquid crystals, transitions between various... 

Decher et al. [420] have developed the idea of using freely suspended smectic liquid crystals and have used it to form thin hlms on solid substrates. A thermotropic smectic liquid crystal is drawn across an aperture in a solid support and is capable of bridging the aperture (which can be up to 15 mm in diameter) with a him which can be between two and several hundred layers thick. The him consists of a smectic structure with the layers lying in the plane of the him. The him is formed a short distance above a solid substrate and the apparatus is constructed so that a difference of pressure between the two sides of the him can be used to force the him down in contact with the substrate. These authors have thus formed good quality hlms up to an area of about 1 cm2. In the work described the material used was ethyl-4 -n-octyloxybiphenyl-4-carboxylate. 

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