Crystallization preferred orientation

Bio-nanocomposite samples for XRD analysis should be well ground to a particle size of less than 50 pm. Uniform particle size and random orientation of crystals are very critical for accurate XRD analysis. A sample with well-defined orientation of crystals (preferred orientation) can give a different diffraction pattern than that of a sample with randomly oriented crystals. Preferred orientation is particularly a problem with plate like crystals because they tend to lie horizontal, rather than perpendicular, on the sample holder. For a film sample, the thickness of the film should be at least 0.5 nun in order to detect the intensity of diffracted X-rays. The XRD analysis should be sensitive enough to detect the crystalline structure of layered sihcates present in small amounts in bio-nanocomposites (Kasai and Kakudo, 2005). 

The stmcture of the polysihcon depends on the dopants, impurities, deposition temperature, and post-deposition heat annealing. Deposition at less than 575°C produces an amorphous stmcture deposition higher than 625°C results in a polycrystalline, columnar stmcture. Heating after deposition induces crystallization and grain growth. Deposition between 600 and 650°C yields a columnar stmcture having reasonable grain size and (llO)-preferred orientation. 

Fig. 1. Orientational order of the molecules in a liquid crystal. 9 is the angle between the long axis of a molecule and the direction of preferred orientation...

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. 

A summary of physical and chemical constants for beryUium is compUed ia Table 1 (3—7). One of the more important characteristics of beryUium is its pronounced anisotropy resulting from the close-packed hexagonal crystal stmcture. This factor must be considered for any property that is known or suspected to be stmcture sensitive. As an example, the thermal expansion coefficient at 273 K of siagle-crystal beryUium was measured (8) as 10.6 x 10 paraUel to the i -axis and 7.7 x 10 paraUel to the i -axis. The actual expansion of polycrystalline metal then becomes a function of the degree of preferred orientation present and the direction of measurement ia wrought beryUium. 

Here Pyj is the structure factor for the (hkl) diffiaction peak and is related to the atomic arrangements in the material. Specifically, Fjjj is the Fourier transform of the positions of the atoms in one unit cell. Each atom is weighted by its form factor, which is equal to its atomic number Z for small 26, but which decreases as 2d increases. Thus, XRD is more sensitive to high-Z materials, and for low-Z materials, neutron or electron diffraction may be more suitable. The faaor e (called the Debye-Waller factor) accounts for the reduction in intensity due to the disorder in the crystal, and the diffracting volume V depends on p and on the film thickness. For epitaxial thin films and films with preferred orientations, the integrated intensity depends on the orientation of the specimen. 

Crystallography is a very broad science, stretching from crystal-structure determination to crystal physics (especially the systematic study and mathematical analysis of anisotropy), crystal chemistry and the geometrical study of phase transitions in the solid state, and stretching to the prediction of crystal structures from first principles this last is very active nowadays and is entirely dependent on recent advances in the electron theory of solids. There is also a flourishing field of applied crystallography, encompassing such skills as the determination of preferred orientations, alias textures, in polycrystalline assemblies. It would be fair to say that... 

A separate study was the improvement of magnetic permeability in soft alloys such as are used in transformers and motors by lining up the orientations of individual crystal grains, also known as a preferred orientation this became an important subspeciality in the design of transformer laminations made of dilute Fe-Si alloys, introduced more than 100 years ago and still widely used. 

Metallurgists originally, and now materials scientists (as well as solid-state chemists) have used erystallographic methods, certainly, for the determination of the structures of intermetallic compounds, but also for such subsidiary parepistemes as the study of the orientation relationships involved in phase transformations, and the study of preferred orientations, alias texture (statistically preferential alignment of the crystal axes of the individual grains in a polycrystalline assembly) however, those who pursue such concerns are not members of the aristocracy The study of texture both by X-ray diffraction and by computer simulation has become a huge sub-subsidiary field, very recently marked by the publication of a major book (Kocks el al. 1998). 

Usually, crystallization of flexible-chain polymers from undeformed solutions and melts involves chain folding. Spherulite structures without a preferred orientation are generally formed. The structure of the sample as a whole is isotropic it is a system with a large number of folded-chain crystals distributed in an amorphous matrix and connected by a small number of tie chains (and an even smaller number of strained chains called loaded chains). In this case, the mechanical properties of polymer materials are determined by the small number of these ties and, hence, the tensile strength and elastic moduli of these polymers are not high. 

Liquid crystal behavior is a genuine supramolecular phenomenon based on the existence of extended weak interactions (dipole-dipole, dispersion forces, hydrogen bonding) between molecules. For the former two to be important enough, it is usually necessary for the molecules to have anisotropic shapes, able to pack efficiently so that these weak interactions can accumulate and co-operate, so as to keep the molecules associated in a preferred orientation, but free enough to move and slide, as they are not connected by rigid bonds. 

The term plastic crystal is not used if the rotation of the particles is hindered, i.e. if the molecules or ions perform rotational vibrations (librations) about their centers of gravity with large amplitudes this may include the occurrence of several preferred orientations. Instead, such crystals are said to have orientational disorder. Such crystals are annoying during crystal structure analysis by X-ray diffraction because the atoms can hardly be located. This situation is frequent among ions like BF4, PFg or N(CH3)J. To circumvent difficulties during structure determination, experienced chemists avoid such ions and prefer heavier, less symmetrical or more bulky ions. 

Films of CoB have been prepared by electroless deposition. Chang et al. [25] deposited magnetically soft amorphous films, which could be annealed to give materials with an Hc of 250 Oe. Depending on the annealing temperature, the films crystallized as the hep or fee modifications of Co. Matsui and co-workers [22] obtained crystalline materials in the as-deposited state, the crystalline characteristics being determined by processing conditions. A maximum HQ of 300 Oe was observed for films with 10.0 preferred orientation. 

All compositions were subject to preferred orientation. Pure Pd had a very strong and 74% Pd a less strong (111) orientation, whereas 39% Pd, 15% Pd, and pure Au films had a (110) orientation of increasing strength. It was inferred that these changes indicated differences in the relative extents of exposed crystal face, and this information was valuable in discussing the catalytic results (see Section IV). 

There are two major problems associated with the x-ray method. The first problem is encountered during sample preparation. At this step, preferred orientation of the particles must be minimized [1], Reduction of particle size is one of the most effective ways of minimizing preferred orientation, and this is usually achieved by grinding the sample. Grinding, however, can also disorder the crystal lattice. Moreover, decreased particle size can cause a broadening of x-ray lines, which in mm affects the values of /c and /a. The relationship between the crystallite size, t, and its x-ray line breadth, /3, (assuming no lattice strain) is given by the Scherrer equation [2] ... 

Preferred orientation of the particles must be minimized. One of the most effective ways to achieve this is to reduce the particle size by grinding the sample [1], As already discussed in Section III.A, however, grinding can disorder the crystal lattice. Grinding can also induce other undesirable transitions, such as polymorphic transformations [59]. In order to obtain reproducible intensities, there is an optimum crystallite size. The crystallites have to be sufficiently small so that the diffracted intensities are reproducible. Careful studies have been carried out to determine the desired crystallite size of quartz, but no such studies have been reported for pharmaceutical solids [60]. Care should be taken to ensure that the crystallites are not very small, since decreased particle size can cause a broadening of x-ray lines. This effect, discussed earlier (Eq. 9), usually becomes apparent when the particle size is below 0.1 jum. 

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