Mesophase-isotropic liquid transition

The thermal behavior of liquid crystalline main chain polymers is more complicated. Depending on thermal history, different transitions may occur. The DSC curves of samples quenched from the melt may show the glass transition (positive ACp), cold crystallization (exotherm), melting (endotherm)and the mesophase-isotropic liquid transition (endotherm)[ Fig. I6]. ... 

Fig. 4. Entropy change for the mesophase isotropic liquid transition versus number of carbon atoms in the alkyl groups of diesters.

The hydrocarbon chain melting transition is facilitated by factors that reduce the polar headgroup network cohesion. The addition of water to cetyltrimethylam-monium tosylate produces a peak at 23°C, which is related to the melting of CTAT crystals (embedded in saturated aqueous solution below 23 C) to produce a liquid crystalline phase (in highly concentrated CTAT systems) or micellar solutions (in dilute systems). The peak is broad, probably due to the existence of a biphase transition zone. No melting peak related to the polar network was detected, probably because of the relatively weak cohesive forces in this particular polar network. The second peak detected in concentrated water-surfactant samples was due to the hexagonal mesophase-isotropic liquid transition [53]. 

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 thermotropic liquid crystal (mcsogen) is a compound that, on heating the crystal or on cooling the isotropic liquid, gives rise to mesomorphism. Liquid crystallinity occurs between the crystal and isotropic liquid states. The intermediate phases, or mesophases, can be either enantiotropic, i.e., thermodynamically stable, or monotropic, i.e., thermodynamically unstable. The solid to mesophase transition is referred to as the melting point, while the mesophase to isotropic liquid transition is referred to as the clearing point. 

One major conclusion that can be drawn from the presented results is related to the effect of the molecular structure of the rigid, anisotropic core of the polymers under investigation on their thermotropic behaviour. Thus, if one takes both the mesophasic-to-isotropic liquid transition temperature and the temperature range of persistence of such mesophase as a qualitative index of the effectiveness of the central group X in imparting liquid crystal properties to the polymer system, the following order can be established ... 

The way, or sequence, in which thermotropic transitions occur is defined in the following ways. The liquid crystal to isotropic liquid transition is called the clearing or isotropization point, and this transition, like those between liquid crystal phases, is essentially reversible and occurs with little hysteresis in temperature. The melting point of a material is usually a constant, but the recrystallization process can be subject to supercooling. Mesophases formed on the first heating cycle of a material are thermodynamically stable, and are called enantiotropic phases, whereas phases that are formed below the melt point on cooling cycles, and are revealed... 

The discussion of mixtures is worthy of further comment. It has been known for some time that mixtures of linear, nonmesomorphic molecules with nematic compounds are characterized by a sharp decrease in both the crystal-nematic and nematic-isotropic liquid transitions with increasing concentration of nonmesomorphic component. However, mixtures of two or more nematic compounds which possess subtle differences in molecular structure do not exhibit sharp decreases in the nematic-isotropic liquid transition temperatures with molar composition although eutectic points for the crystal-nematic transitions may be obtained. Thus, the nematic-isotropic liquid transition temperatures form a smooth curve over the entire range of molar composition. Similar smooth curve surfaces are observed in ternary mixtures. This remarkable stability of the nematic mesophase is undoubtedly due to the fact that all the molecules are oriented in the same direction resulting in the formation of a pseudo-lattice type structure. On the other hand, the molecules of a nonmesomorphic guest are randomly oriented in a nematic host and their presence results in the disruption of nematic order. 

FIG. 4 Concentration dependence of the heat capacity jumps in the dimethyldodecyl-phosphine oxide-water system at the transitions lamellar mesophase + isotropic liquid isotropic liquid (curves 1 and 2) and crystal -I- isotropic liquid —> isotropic liquid (curve 3). (From Ref. 2.)... 

Substances that show a liquid crystalline phase, or mesophase, are called mesogens. Several thousands of compounds, both with low molecular mass and polymeric, are now known to form mesophases. They are mainly highly geometrically anisotropic in shape, rodlike or disclike (hence the terms calamitic and discotic liquid crystals), or they are anisotropic in solubility properties, like amphiphilic molecules and, depending on their detailed molecular structure, they can exhibit one or more mesophases between the crystalline solid and the isotropic liquid. Transitions to these intermediate states may be induced by purely thermal processes (thermotropic liquid crystals) or by the action of solvents (lyotropic liquid crystals). Each of these two categories can be further divided according to the structure of the mesophases and/or molecules Scheme 1 shows the classification of thermotropic mesophases. 

The rapid rise in computer speed over recent years has led to atom-based simulations of liquid crystals becoming an important new area of research. Molecular mechanics and Monte Carlo studies of isolated liquid crystal molecules are now routine. However, care must be taken to model properly the influence of a nematic mean field if information about molecular structure in a mesophase is required. The current state-of-the-art consists of studies of (in the order of) 100 molecules in the bulk, in contact with a surface, or in a bilayer in contact with a solvent. Current simulation times can extend to around 10 ns and are sufficient to observe the growth of mesophases from an isotropic liquid. The results from a number of studies look very promising, and a wealth of structural and dynamic data now exists for bulk phases, monolayers and bilayers. Continued development of force fields for liquid crystals will be particularly important in the next few years, and particular emphasis must be placed on the development of all-atom force fields that are able to reproduce liquid phase densities for small molecules. Without these it will be difficult to obtain accurate phase transition temperatures. It will also be necessary to extend atomistic models to several thousand molecules to remove major system size effects which are present in all current work. This will be greatly facilitated by modern parallel simulation methods that allow molecular dynamics simulations to be carried out in parallel on multi-processor systems [115]. 

The conventional liquid state is described as the isotropic phase. The temperature at which the compound passes from the solid phase into a mesophase is described as the melting point and the transition temperature between a mesophase and an isotropic liquid is described as the clearing point. 

The complexes bearing one chiral substituent display a smectic A mesophase when the non-chiral chain is long, or an enantiotropic cholesteric and a monotropic SmA phase for shorter alkoxy chains. A TGBA phase is observed for the derivative which contains the chiral isocyanide combined with the diethyloxy, when the SmA to cholesteric transition is studied. The compound with two chiral ligands shows a monotropic chiral nematic transition. When this compound is cooled very slowly from the isotropic liquid it exhibits blue phases BP-III, BP-II, and BP-I. 

Poly (diethyl siloxane) was suggested by Beatty et al. 1651 based on DSC, dielectric, NMR, and X-ray measurements to possess liquid crystalline type order between about 270 and 300 K. The macromolecule shows two large lower temperature first order transitions, one at about 200 K, the other at about 270 K166 ll,7). The transition of the possible mesophase to the isotropic liquid at 300 K is quite small and irre-producible, so that variable, partial crystallinity was proposed 165) [measured heat of transition about 150 J/mole1S8)], Very little can be said about this state which may even consist of residual crystals. It is of interest, however, to further analyze the high temperature crystal phase between 200 and 270 K. It is produced from the, most likely, fully ordered crystal with an estimated heat and entropy of transition of 5.62kJ/mol and 28J/(Kmol), respectively [calculated from calorimetric data 1S6)... 

Depending on temperature, transitions between distinct types of LC phases can occur.3 All transitions between various liquid crystal phases with 0D, ID, or 2D periodicity (nematic, smectic, and columnar phases) and between these liquid crystal phases and the isotropic liquid state are reversible with nearly no hysteresis. However, due to the kinetic nature of crystallization, strong hysteresis can occur for the transition to solid crystalline phases (overcooling), which allows liquid crystal phases to be observed below the melting point, and these phases are termed monotropic (monotropic phases are shown in parenthesis). Some overcooling could also be found for mesophases with 3D order, namely cubic phases. The order-disorder transition from the liquid crystalline phases to the isotropic liquid state (assigned as clearing temperature) is used as a measure of the stability of the LC phase considered.4... 

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