Crystal crystalline phase

Needham, D. and Evans, E. (1988) Struemre and mechanical properties of giant lipid (DMPC) vesicle bilayers from 20-degrees-C below to 10-degrees-C above the liquid-crystal crystalline phase transition at 24-degrees-C. Biochemistty, 27 (21), 8261-8269. 

This relationship is sketched in Fig. 4.7a, which emphasizes that P, must vary linearly with 6 and that P, ° must be available, at least by extrapolation. The heat of fusion is an example of a property of the crystalline phase that can be used this way. It could be difficult to show that the value of AH is constant per unit mass at all percentages of crystallinity and to obtain a value for AHj° for a crystal free from defects. Therefore, while conceptually simple, the actual utilization of Eq. (4.37) in precise work may not be easy. 

Research has led to alloys which undergo laser-induced crystallization within about 50 ns. This is possible, for example, with TeGe alloys, which also possess the necessary temperature stability up to 180°C and exhibit sufficient reflection (crystalline phase) and transmission characteristics (amorphous phase), respectively. TeGe alloys have not found a practical use because of the formation of depressions in the memory layer typical for them after repeated... 

Powder diffraction patterns have three main features that can be measured t5 -spacings, peak intensities, and peak shapes. Because these patterns ate a characteristic fingerprint for each crystalline phase, a computer can quickly compare the measured pattern with a standard pattern from its database and recommend the best match. Whereas the measurement of t5 -spacings is quite straightforward, the determination of peak intensities can be influenced by sample preparation. Any preferred orientation, or presence of several larger crystals in the sample, makes the interpretation of the intensity data difficult. 

Licjuid Crystals. Ferroelectric Hquid crystals have been appHed to LCD (Uquid crystal display) because of their quick response (239). Ferroelectric Hquid crystals have chiral components in their molecules, some of which are derived from amino acids (240). Concentrated solutions (10—30%) of a-helix poly(amino acid)s show a lyotropic cholesteric Hquid crystalline phase, and poly(glutamic acid ester) films display a thermotropic phase (241). Their practical appHcations have not been deterrnined. 

In the presence of excess fatty acid, different soap crystalline phase compounds can form, commonly referred to as acid—soaps. Acid—soap crystals are composed of stoichiometric amounts of soap and fatty acid and associate in similar bilayer stmctures as pure soap crystals. There are a number of different documented acid—soap crystals. The existence of crystals of the composition 2 acid—1 soap, 1 acid—1 soap, and 1 acid—2 soap has been reported (13). The presence of the acid—soaps can also have a dramatic impact on the physical and performance properties of the finished soap. The presence of acid—soaps increases the plasticity of the soap during processing and decreases product firmness, potentially to the point of stickiness during processing. Furthermore, the presence of the acid—soap changes the character of the lather, decreasing the bubble size and subsequently increasing lather stabiUty and... 

Analytical x-ray instruments ate used to characterize materials in several different ways. As with medical x-ray instmments there are analytical instmments that can produce images of internal stmctures of objects that are opaque to visible light. There are instmments that can determine the chemical elemental composition of an object, that can identify the crystalline phases of a mixture of soHds, and others that determine the complete atomic and molecular stmcture of a single crystal. These ate the most common appHcations for x-ray iastmments. 

X-ray diffraction consists of the measurement of the coherent scattering of x-rays (phenomenon 4 above). X-ray diffraction is used to determine the identity of crystalline phases in a multiphase powder sample and the atomic and molecular stmctures of single crystals. It can also be used to determine stmctural details of polymers, fibers, thin films, and amorphous soflds and to study stress, texture, and particle size. 

Bragg-Brentano Powder Diffractometer. A powder diffraction experiment differs in several ways from a single-crystal diffraction experiment. The sample, instead of being a single crystal, usually consists of many small single crystals that have many different orientations. It may consist of one or more crystalline phases (components). The size of the crystaUites is usually about 1—50 p.m in diameter. The sample is usually prepared to have a fiat surface. If possible, the experimenter tries to produce a sample that has a random distribution of crystaUite orientations. 

Crystallization kinetics have been studied by differential thermal analysis (92,94,95). The heat of fusion of the crystalline phase is approximately 96 kj/kg (23 kcal/mol), and the activation energy for crystallization is 104 kj/mol (25 kcal/mol). The extent of crystallinity may be calculated from the density of amorphous polymer (d = 1.23), and the crystalline density (d = 1.35). Using this method, polymer prepared at —40° C melts at 73°C and is 38% crystalline. Polymer made at +40° C melts at 45°C and is about 12% crystalline. 

The introduction of Hquid crystals as stabilizing elements for emulsions occurred in 1969 when it was found that the sudden stabilization at emulsifier concentrations in excess of 2.5% of a water—% xylene emulsion by a commercial octa(ethylene glycol) nonylphenyl ether was due to the formation of a Hquid crystalline phase in the emulsion (26). Later investigations confirmed the strong stabilizing action of these stmctures (27). 

The detection of Hquid crystal is based primarily on anisotropic optical properties. This means that a sample of this phase looks radiant when viewed against a light source placed between crossed polarizers. An isotropic solution is black under such conditions (Fig. 12). Optical microscopy may also detect the Hquid crystal in an emulsion. The Hquid crystal is conspicuous from its radiance in polarized light (Fig. 13). The stmcture of the Hquid crystalline phase is also most easily identified by optical microscopy. Lamellar Hquid crystals have a pattern of oil streaks and Maltese crosses (Fig. 14a), whereas ones with hexagonal arrays of cylinders give a different optical pattern (Fig. 14b). 

Liquid crystals stabilize in several ways. The lamellar stmcture leads to a strong reduction of the van der Waals forces during the coalescence step. The mathematical treatment of this problem is fairly complex (28). A diagram of the van der Waals potential (Fig. 15) illustrates the phenomenon (29). Without the Hquid crystalline phase, coalescence takes place over a thin Hquid film in a distance range, where the slope of the van der Waals potential is steep, ie, there is a large van der Waals force. With the Hquid crystal present, coalescence takes place over a thick film and the slope of the van der Waals potential is small. In addition, the Hquid crystal is highly viscous, and two droplets separated by a viscous film of Hquid crystal with only a small compressive force exhibit stabiHty against coalescence. Finally, the network of Hquid crystalline leaflets (30) hinders the free mobiHty of the emulsion droplets. 

The final factor influencing the stabiHty 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 Hquid 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 Hquid crystal (point B). The added surfactant, which at 2% would add a protective film of only 0.07 p.m to emulsion droplets of 5 p.m 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 p.m 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% Hquid crystalline phase. The stabilizing phase is now the principal part of the emulsion. 

Driving forces for solid-state phase transformations are about one-third of those for solidification. This is just what we would expect the difference in order between two crystalline phases will be less than the difference in order between a liquid and a crystal the entropy change in the solid-state transformation will be less than in solidification and AH/T will be less than AH/T . 

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