Liquid crystalline transformation

To date, there has been relatively little work reported on the mesophase pitch rheology which takes into account its liquid crystalline nature. However, several researchers have performed classical viscometric studies on pitch samples during and after their transformation to mesophase. While these results provide no information pertaining to the development of texture in mesophase pitch-based carbon fibers, this information is of empirical value in comparing pitches and predicting their spinnability, as well as predicting the approximate temperature at which an untested pitch may be melt-spun. 

Although the liquid crystalline phase of most polybibenzoates usually undergoes a rapid transformation into a three-dimensional crystal, the introduction of oxygen atoms in the spacer of polybibenzoates has been used to prevent or to slow down this transformation. The dynamic mechanical behavior of polybibenzoates with 2, 3, or 4 oxyethylene groups in the spacer (PDEB, PTEB, and PTTB, respectively) is determined by the composition of the spacer [24], as discussed in this section. 

One type of material that has transformed electronic displays is neither a solid nor a liquid, but something intermediate between the two. Liquid crystals are substances that flow like viscous liquids, but their molecules lie in a moderately orderly array, like those in a crystal. They are examples of a mesophase, an intermediate state of matter with the fluidity of a liquid and some of the molecular order of a solid. Liquid crystalline materials are finding many applications in the electronics industry because they are responsive to changes in temperature and electric fields. 

Many of the investigated mesogenic compounds show solid state polymorphism. In order to obtain useful information about the arrangement of the molecules in the mesophase from the X-ray data of the single crystals, it is important to investigate the crystal structure of those solid phase which transforms into the liquid crystalline phase. For instance, only the crystal structures of the low temperature solid phases of the compounds MBBA [138, 139], MHPOBC [159], and T15 [81] could be determined, but the... 

The chloroform solution of lipids (Solution A) is placed in a 50-mL round-bottomed spherical Quick-fit flask. Following evaporation of the solvent in a rotary evaporator at about 37°C, a thin lipid film is formed on the walls of the flask. The film is flushed for about 60 seconds with oxygen-free nitrogen (N2) to ensure complete solvent removal and to replace air. Two milliliters of distilled water and a few glass beads are added into the flask, the stopper is replaced, and the flask shaken vigorously by hand or mechanically until the lipid film has been transformed into a milky suspension. This process is carried out above the liquid-crystalline transition temperature (7/) of the phospholipid component of liposomes (> 7/) by prewarming the water... 

The reason why one chose to follow the main liquid-crystalline to gel phase transition in DPPC by monitoring the linewidth of the various or natural abundance resonance is evident when we consider the expressions for the spin-lattice relaxation time (Ti) and the spin-spin relaxation time T2). The first one is given by 1/Ti oc [/i(ft>o) + 72(2ft>o)] where Ji coq) is the Fourier transform of the correlation function at the resonance frequency o>o and is a constant related to internuclear separation. The relaxation rate l/Ti thus reflects motions at coq and 2coq. In contrast, the expression for T2 shows that 1/T2 monitors slow motions IjTi oc. B[/o(0) -I- /i(ft>o) + /2(2u>o)], where /o(0) is the Fourier component of the correlation function at zero frequency. Since the linewidth vi/2 (full-width at half-maximum intensity) is proportional to 1 / T2, the changes of linewidth will reflect changes in the mobility of various carbon atoms in the DPPC bilayer. 

The results are straight forward and the interpretation immediately evident. The liquid crystalline phase formed in these extremely water rich systems was destabilized by the dicarboxylic acid and transformed to an isotropic solution. The conclusion that the hydrotropic action of the dicarboxylic acid is intimately related to its capacity to destabilize a liquid crystalline phase also under the water-rich conditions during actual laundering conditions appears well justified. 

The interest in the conformation of the hydrotrope is primarily related to its behavior at an oll/water Interface in conjunction with surfactant molecules. In addition, molecules from an "oily dirt" may be present. Finally, it is essential to realize that the action of the hydrotrope is to destabilize a liquid crystalline phase and transform it to an isotropic liquid. 

This transformation of alkyl 2-chloro-2-cyclopropylideneacetates has been applied for the preparation of compounds of type 83 containing a czs-configurated disubstituted cyclopropane moiety [25] with potential liquid crystalline properties [52]. In the first approach to such compounds, 2-chloro-2-cyclopropylide-neacetic acids 2b-H, 2i-H were coupled with the linear diaryl components 81 fol-... 

If one follows the solution viscosity in concentrated sulfuric acid with increasing polymer concentration, then one observes first a rise, afterwards, however, an abrupt decrease (about 5 to 15%, depending on the type of polymers and the experimental conditions). This transition is identical with the transformation of an optical isotropic to an optical anisotropic liquid crystalline solution with nematic behavior. Such solutions in the state of rest are weakly clouded and become opalescent when they are stirred they show birefringence, i.e., they depolarize linear polarized light. The two phases, formed at the critical concentration, can be separated by centrifugation to an isotropic and an anisotropic phase. A high amount of anisotropic phase is desirable for the fiber properties. This can be obtained by variation of the molecular weight, the solvent, the temperature, and the polymer concentration. 

Bai [2] performed similar drop dissolution experiments with sodium oleate (NaOl) and Ci2(EO)4. For drops initially containing 7 and lOwt. % NaOl (particle size < 38 jim) the behavior was similar to that described above for drops having 8 wt. % SDS. However for drops with 15 and 17 wt. % NaOl dissolution was faster—comparable to that of the pure nonionics—and neither a surfactant-rich liquid immiscible with water nor emulsification was seen. Instead a concentrated liquid crystalline phase transformed directly into a micellar solution, as seen for the pure nonionics and nonionic mixtures well below their cloud points. 

Waigh, T. A., Gidley, M. J., Komanshek, B. U., Donald, A. M. (2000). The phase transformations in starch during gelatinisation a liquid crystalline approach. Carbohydrate Research, 328,165-176. 

Liquid-crystalline polymers with stiff backbones have many static and dynamic solution properties markedly distinct from usual flexible polymers. For example, their solutions are transformed from isotropic to liquid crystal state with increasing concentration. While very high in the concentrated isotropic state, their viscosity decreases drastically as the concentration crosses the phase boundary toward the liquid crystal state. The unique rheological properties they exhibit in the liquid crystal state are also remarkable. 

The appearance of tubular myelin-like structures in swollen lecithin was observed by light microscopy well before the systematic investigation of liposomes [351-352]. Similarly, it was also demonstrated some time ago that the addition of calcium ions converted phospholipid liposomes to cochleate cylinders [353]. Subsequent studies have, however, revealed that the system is extremely complex. For example, examination of the phase-transition behavior of synthetic sodium di-n-dodecyl phosphate [(C12H2sO)2PO2Na+ or NaDDP] and calcium di-n-dodecyl phosphate [Ca(DDP)2] showed the presence of many diverse structures [354]. In particular, hydrated NaDDP crystals were shown to form lyotropic liquid-crystalline phases which transformed, upon heating to 50 °C, to myelin-like tubes. Structures of the tubes formed were found... 

Reaction Cavities of Alkanophenones in Neat Solid and Liquid-Crystalline Phases. As mentioned previously, solid-state studies on the Norrish II processes of alkyl aryl ketones are unambiguous with respect to the triplet multiplicity of the reactive excited state. On the other hand, a bulky aryl auxochrome can create complications during the transformation of the excited triplet states to photoproducts in neat anisotropic phases. 

These examples indicate that the flexibility of the main chain, which is determined by its chemical constitution, directly influences the extent of the liquid crystalline state. With increasing rigidity of the main chain the motions of the mesogenic groups are more restricted. This can be noticed in an increase of the phase transformation temperature Tn. . 

We will discuss some preliminary results, which have been performed recently l01). In Fig. 39a the results for polymer No. 2d of Table 10 are shown, which were obtained by torsional vibration experiments. At low temperatures the step in the G (T) curve and the maximum in the G"(T) curve indicate a p-relaxation process at about 120-130 K. Accordingly the glass transition is detected at about 260 K. At 277 K the nematic elastomer becomes isotropic. This phase transformation can be seen only by a very small step in G and G" in the tail of glass transition region, which is shown in more detail in Fig. 39 b. From these measurements we can conclude, that the visco-elastic properties are largely dominated by the properties of the polymer backbone the change of the mesogenic side chains from isotropic to liquid crystalline acts only as a small disturbance and in principle the visco-elastic behavior of the elastomer... 

The final factor influencing the stability of these three-phase emulsions is probably the most important one. Small changes in emulsifier concentration lead to drastic changes in the amounts of the three phases. As an example, consider the points A to C in Figure 16. At point A, with 2% emulsifier, 49% water, and 49% aqueous phase, 50% oil and 50% aqueous phase are the only phases present. At point B the emulsifier concentration has been increased to 4%. Now the oil phase constitutes 47% of the total and the aqueous phase is reduced to 29% the remaining 24% is a liquid crystalline phase. The importance of these numbers is best perceived by a calculation of thickness of the protective layer of the emulsifier (point A) and of the liquid crystal (point B). The added surfactant, which at 2% would add a protective film of only 0.07 Xm to emulsion droplets of 5 im if all of it were adsorbed, has now been transformed to 24% of a viscous phase. This phase would form a very viscous film 0.85 Jim thick. The protective coating is more than 10 times thicker than one from the surfactant alone because the thick viscous film contains only 7% emulsifier the rest is 75% water and 18% oil. At point C, the aqueous phase has now disappeared, and the entire emulsion consists of 42.3% oil and 57.5% liquid crystalline phase. The stabilizing phase is now the principal part of the emulsion. 

Here % specify the transformation from coordinate system j to system i. In Equation 3 only Dq q (Qdm) varies with the molecular motion. Since amphiphilic liquid crystalline systems generally are cylindrically symmetrical around the director Dq q (nDM) = 0 if qf 0. If it also is assumed that a nucleus stays within a domain of a given orientation of the director over a time that is long compared with the inverse of the quadrupole interaction, one now obtains for the static quadrupole hamiltonian... 

As the name implies, liquid-crystalline materials combine the properties of a crystal with those of a liquid in a very special way and are therefore of interest for display and data storage technology. Liquid-crystalline compounds usually consist of rod- or disc-shaped organic molecules which preferentially adopt a mutually parallel orientation [33]. A change of molecular orientation caused by application of an electrical potential transforms the optical properties and can be utilised for display applications. 

---