Quasi crystallinity

A pecuhar sohd phase, which has been discovered not too long ago [172], is the quasi-crystalline phase. Quasi-crystals are characterized by a fivefold or icosahedral symmetry which is not of crystallographic type and therefore was assumed to be forbidden. In addition to dislocations which also exist in normal crystals, quasi-crystals show new types of defects called phasons. Computer simulations of the growth of quasicrystals [173] are still somewhat scarce, but an increasing number of quasi-crystalline details are studied by simulations, including dislocations and phasons, anomalous self-diffusion, and crack propagation [174,175]. 

Many workers have offered the opinion that the isokinetic relationship is confined to reactions in condensed phase (6, 122) or, more specially, may be attributed to solvation effects (13, 21, 37, 43, 56, 112, 116, 124, 126-130) which affect both enthalpy and entropy in the same direction. The most developed theories are based on a model of the half-specific quasi-crystalline solvation (129, 130), or of the nonideal conformal solutions (126). Other explanations have been given in terms of vibrational frequencies involving solute and solvent (13, 124), temperature dependence of solvent fluidity in the quasi-crystalline model (40), or changes of enthalpy and entropy to produce a hole in the solvent (87). 

Two types of swelling may occur. Surface hydration is one type of swelling in which water molecules are adsorbed on crystal surfaces. Hydrogen bonding holds a layer of water molecules to the oxygen atoms exposed on the crystal surfaces. Subsequent layers of water molecules align to form a quasi-crystalline structure between unit layers which results in an increased c-spacing. All types of clays swell in this manner. 

Au-substituted /U-Cu-Fe quasi crystalline alloys, a Au and Fe study Replacement of Cu by Au on BCl sites and strong hybridization of Au with A1 neighbors... 

All of the experiments in pure and mixed SSME systems, as well as in the Af-stearoyltyrosine systems, have one common feature, which seems characteristic of chiral molecular recognition in enantiomeric systems and their mixtures enantiomeric discrimination as reflected by monolayer dynamic and equilibrium properties has only been detected when either the racemic or enantiomeric systems have reverted to a tightly packed, presumably quasi-crystalline surface state. Thus far it has not been possible to detect clear enantiomeric discrimination in any fluid or gaseous monolayer state. 

Figure 2. These high-resolution micrographs show how a so-called x-ray amorphous, nonstoichiometric molybdenum sulfide catalyst exhibits structural (as well as compositional) heterogeneity. Amorphous, quasi-crystalline, and crystalline regions coexist at the ultramicro level (18,).

Na-cefazolin is instable in its amorphous state. Takeda [1.32J described a method to ensure complete crystallization in which micro crystalline Na-cefazolin were added to at 0 °C supersaturated Na-cefazolin solution, frozen and freeze dried. The product did not contain amorphous or quasi-crystalline components. 

Other antibiotics still require freeze drying, e. g. Na-Cephalotin (Na-CET). Takeda [ 1.32] showed, that thermal treatment of Na-CET was not sufficient to produce pure crystalline Na-CET, as the amorphous fraction discolors during storage and must be avoided. Takeda described the production of pure crystalline Na-CET by adding microcrystals of Na-CET to a saturated solution of Na-CET. If this mixture was frozen and freeze dried, then no amorphous or quasi-crystalline were found. Koyama et al. [3.35] described, that after thermal treatment for 24 h some parts remained incompletely crystallized. After adding 5 % (w/w) isopropylalcohol, a thermal treatment of 1 h was sufficient. Furthermore, the product could be dried at a higher pressure. Thus the drying time could be reduced and 100 % of the product could be used. 

Another characteristic point is the special attention that in intermetallic science, as in several fields of chemistry, needs to be dedicated to the structural aspects and to the description of the phases. The structure of intermetallic alloys in their different states, liquid, amorphous (glassy), quasi-crystalline and fully, three-dimensionally (3D) periodic crystalline are closely related to the different properties shown by these substances. Two chapters are therefore dedicated to selected aspects of intermetallic structural chemistry. Particular attention is dedicated to the solid state, in which a very large variety of properties and structures can be found. Solid intermetallic phases, generally non-molecular by nature, are characterized by their 3D crystal (or quasicrystal) structure. A great many crystal structures (often complex or very complex) have been elucidated, and intermetallic crystallochemistry is a fundamental topic of reference. A great number of papers have been published containing results obtained by powder and single crystal X-ray diffractometry and by neutron and electron diffraction methods. A characteristic nomenclature and several symbols and representations have been developed for the description, classification and identification of these phases. 

It may be mentioned that in 2D and 3D the possible rotations (the symmetry axes) that superimpose an infinitely periodic structure on itself are limited to angles 360°/n with n = 1, 2, 3, 4 or 6. Notice that for non-periodic, noncrystalline, quasi-crystalline structures, other symmetry axes are possible. See 3.11.3 and Fig. 3.45 on quasi-periodic crystals. 

Apart from deliberate or accidental introduction of tiny seed crystals to the system, and productive interactions between existing crystals and quasi-crystalline embryos or clusters in solution, the most influential mode of new crystal generation in an industrial crystalliser is contact secondary nucleation between the existing crystals themselves, between crystals and the walls or other internal parts of the crystalliser, or between crystals and the mechanical agitator. Secondary nucleation rates (in m-3 s 1) are most commonly correlated by empirical relationships such as ... 

Plansible explanations for the current experimental observations can provide the quasi-crystalline model proposed by Zhdanov et al. [28], Shimakawa et al. [29],... 

The discotic phases can show also a complex polymorphism. Nematic and cholesteric-like, low viscosity phases have been reported recently. In these, the director vector is perpendicular to the plane of alignment of the flat molecules56) in contrast to the normal nematics and cholesterics where it is parallel to the molecular axis. Most frequently, however, discotics form columnar arrangements as shown in Fig. 10. The order within the columns may change from liquid to quasi-crystalline. The columns are then packed in hexagonal or tetragonal coordination, but are free to slide in the direction parallel to their axes S7). The viscosity of these more ordered discotics is considerably higher than the nematic discotics. 

Silberberg47) used a quasi-crystalline lattice model for the adsorption of flexible macromolecules. If it is assumed that an adsorbed polymer chain with P segments consists of ma trains of length i and mBi loops of length i, the total number of configurations of the chains is given by... 

Plastic crystals The long-range orientational order is lost, the long-range positional order is preserved, i.e. a plastic quasi-crystalline lattice is still present. 

Figure 3.11 The complex quasi-crystalline transformations that occur when [NP(OCH2CF3)2], is heated or cooled. Derived from the work of Magill, Kojima, et al.

At present, a number of quasi-crystalline alloys with icosahedral, decagonal, and octagonal symmetry are synthesized by different methods. The quasicrystalline form of the solids turned out to be widespread in a great extent. The absence of the translation symmetry and the presence of numerous interstitial sites of the different types in the structure of icosahedral quasicrystals makes some of them interesting objects for hydride chemistry. We cannot wait for any sensational discoveries here, as the general laws of M-H interaction do not depend on matrix structure. However, encouraging results were obtained for icosahedral Ti45Zr38Nii7... 

Theoretical treatments for the energy of mixing have been evaluated based on several models (i.e., unexpanded gas, quasi-crystalline, distribution function). However, similar results can be obtained as ... 

Lutskii and Mikhailenko99 attempted a theoretical calculation of the correlation factor based on a quasi-crystalline model for liquids. To obtain a reasonable... 

According to X-ray investigation the lower alcohols also have partially a quasi-crystalline structure similar to that of water. 

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