Crystals, perfect

Systems involving an interface are often metastable, that is, essentially in equilibrium in some aspects although in principle evolving slowly to a final state of global equilibrium. The solid-vapor interface is a good example of this. We can have adsorption equilibrium and calculate various thermodynamic quantities for the adsorption process yet the particles of a solid are unstable toward a drift to the final equilibrium condition of a single, perfect crystal. Much of Chapters IX and XVII are thus thermodynamic in content. 

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

Bikerman [179] has argued that the Kelvin equation should not apply to crystals, that is, in terms of increased vapor pressure or solubility of small crystals. The reasoning is that perfect crystals of whatever size will consist of plane facets whose radius of curvature is therefore infinite. On a molecular scale, it is argued that local condensation-evaporation equilibrium on a crystal plane should not be affected by the extent of the plane, that is, the crystal size, since molecular forces are short range. This conclusion is contrary to that in Section VII-2C. Discuss the situation. The derivation of the Kelvin equation in Ref. 180 is helpful. 

The mechanism of crystal growth has been a topic of considerable interest. In the case of a perfect crystal, the starting of a new layer involves a kind of nucleation since the first few atoms added must occupy energy-rich positions. Becker and Doring [4],... 

Issues associated with order occupy a large area of study for crystalline matter [1, 7, 8]. For nearly perfect crystals, one can have systems with defects such as point defects and extended defects such as dislocations and grain... 

Defining order in an amorphous solid is problematic at best. There are several qualitative concepts that can be used to describe disorder [7]. In figure Al.3.28 a perfect crystal is illustrated. A simple fonn of disorder involves crystals containing more than one type of atom. Suppose one considers an alloy consisting of two different atoms (A and B). In an ordered crystal one might consider each A surrounded by B and vice versa. 

Because it is necessary to exclude some substances, including some crystals, from the Nemst heat theorem, Lewis and Gibson (1920) introduced the concept of a perfect crystal and proposed the following modification as a definitive statement of the third law of themiodynamics (exact wording due to Lewis and Randall (1923)) ... 

Since shallow-level impurities have energy eigenvalues very near Arose of tire perfect crystal, tliey can be described using a perturbative approach first developed in tire 1950s and known as effective mass theoiy (EMT). The idea is to approximate tire band nearest to tire shallow level by a parabola, tire curvature of which is characterized by an effective mass parameter m. ... 

Deep-level defects cannot be described by EMT or be viewed as simple perturbations to tlie perfect crystal. Instead, tlie full crystal-plus-defect problem must be solved and tlie geometries around tlie defect optimized to account for lattice relaxations and distortions. The study of deep levels is an area of active research. 

Materials that contain defects and impurities can exhibit some of the most scientifically interesting and economically important phenomena known. The nature of disorder in solids is a vast subject and so our discussion will necessarily be limited. The smallest degree of disorder that can be introduced into a perfect crystal is a point defect. Three common types of point defect are vacancies, interstitials and substitutionals. Vacancies form when an atom is missing from its expected lattice site. A common example is the Schottky defect, which is typically formed when one cation and one anion are removed from fhe bulk and placed on the surface. Schottky defects are common in the alkali halides. Interstitials are due to the presence of an atom in a location that is usually unoccupied. A... 

In Section 1.3 it was noted that the energy of adsorption even for a perfect crystal differs from one face to another. An actual specimen of solid will tend to be microcrystalline, and the proportion of the various faces exposed will depend not only on the lattice itself but also on the crystal habit this may well vary amongst the crystallites, since it is highly sensitive to the conditions prevailing during the preparation of the specimen. Thus the overall behaviour of the solid as an adsorbent will be determined not only by its chemical nature but also by the way in which it was prepared. 

Melting occurs over a range of temperatures, as in Fig. 4.1. The range narrows as the crystallization temperature increases. This is probably due to a wider range of crystal dimensions and less perfect crystals under the lower temperatures of formation. 

Density, mechanical, and thermal properties are significantly affected by the degree of crystallinity. These properties can be used to experimentally estimate the percent crystallinity, although no measure is completely adequate (48). The crystalline density of PET can be calculated theoretically from the crystalline stmcture to be 1.455 g/cm. The density of amorphous PET is estimated to be 1.33 g/cm as determined experimentally using rapidly quenched polymer. Assuming the fiber is composed of only perfect crystals or amorphous material, the percent crystallinity can be estimated and correlated to other properties. 

A crystalline solid is never perfect in that all of tire lattice sites are occupied in a regular manner, except, possibly, at the absolute zero of temperature in a perfect crystal. Point defects occur at temperatures above zero, of which the principal two forms are a vacant lattice site, and an interstitial atom which... 

In Chapter 5 we said that many important engineering materials (e.g. metals) were normally made up of crystals, and explained that a perfect crystal was an assembly of atoms packed together in a regularly repeating pattern. 

In the concepts developed above, we have used the kinematic approximation, which is valid for weak diffraction intensities arising from imperfect crystals. For perfect crystals (available thanks to the semiconductor industry), the diffraction intensities are large, and this approximation becomes inadequate. Thus, the dynamical theory must be used. In perfect crystals the incident X rays undergo multiple reflections from atomic planes and the dynamical theory accounts for the interference between these reflections. The attenuation in the crystal is no longer given by absorption (e.g., p) but is determined by the way in which the multiple reflections interfere. When the diffraction conditions are satisfied, the diffracted intensity ft-om perfect crystals is essentially the same as the incident intensity. The diffraction peak widths depend on 26 m and Fjjj and are extremely small (less than... 

Shockley, W., Hollomon, J.H., Maurer, R. and Seitz, F. (editors) (1952) Imperfections in Nearly Perfect Crystals (Wiley, New York). 

The early understanding of the geometry and dynamics of dislocations, as well as a detailed discussion of the role of vacancies in diffusion, is to be found in one of the early classics on crystal defects, a hard-to-find book entitled Imperfections in Nearly Perfect Crystals, based on a symposium held in the USA in 1950 (Shockley et al. 1952). Since in 1950, experimental evidence of dislocations was as yet very sparse, more emphasis was placed on a close study of slip lines (W.T. Read, Jr.,... 

The shock-compression pulse carries a solid into a state of homogeneous, isotropic compression whose properties can be described in terms of perfect-crystal lattices in thermodynamic equilibrium. Influences of anisotropic stress on solid materials behaviors can be treated as a perturbation to the isotropic equilibrium state. ... 

At low temperatures, in a sample of very small dimensions, it may happen that the phase-coherence length in Eq.(3) becomes larger than the dimensions of the sample. In a perfect crystal, the electrons will propagate ballistically from one end of the sample and we are in a ballistic regime where the laws of conductivity discussed above no more apply. The propagation of an electron is then directly related to the quantum probability of transmission across the global potential of the sample. 

So far we have discussed the surface of a perfect crystal. But for an imperfect crystal there is another possibility to provide a step source. This is due to the screw dislocation. Assume that one cuts a crystal half-way from one side into the center, and slides the freshly created two faces against each other in... 

An alternative choice of origin would be midway between A and B planes. Let us say that the first plane at x>0 is then a B plane. It must be weighted with 3/4. The following A plane has the weight 1/4. That completes the termination, which this time is truly tapered. The excess energy of a stoichimetric unit in the perfect crystal is zero. Thus the excess energy of 3B/4+A/4 is equal to the excess energy of B/2, which was our first choice of termination. 

ZnO contauns excess metal which is accommodated interstitially, i.e. at positions in the lattice which are unoccupied in the perfect crystal. The process by which ZnO in oxygen gas acquires excess metal may be pictured as follows. The outer layers of the crystal are removed, oxygen is evolved, and zinc atoms go into interstitial positions in the oxide. We represent interstitial zinc by (ZnO). However, the interstitial zinc atoms may ionise to give (Zn O) or even (Zn O). The extra electrons produced in this way must occupy electron levels which would be vacant in the perfect crystal. We represent them by the symbol (eo), and refer to them as free electrons. They can be pictured as Zn ions at normal cation sites. We see therefore that three reactions can be written, each giving non-stoichiometric ZnO ... 

The reason for this can be seen as follows. In a perfect crystal with the ions held fixed, a positive hole would move about like a free particle with a mass m depending on the nature of the crystal. In an applied electric field, the hole would be uniformly accelerated, and a mobility could not be defined. The existence of a mobility in a real crystal derives from the fact that the uniform acceleration is continually disturbed by deviations from a perfect lattice structure. Among such deviations, the thermal motions of the ions, and in particular, the longitudinal polarisation vibrations, are most important in obstructing the uniform acceleration of the hole. Since the amplitude of the lattice vibrations increases with temperature, we see how the mobility of a... 

Thermodynamics is concerned with the relationship between heat energy and work and is based on two general laws, the 1st and 2nd laws of thermodynamics, which both deal with the interconversion of the different forms of energy. The 3rd law states that at the absolute zero of temperature the entropy of a perfect crystal is zero, and thus provides a method of determining absolute entropies. 

We say then that a crystal is satisfactory for purposes of chemical analysis if the beam it reflects is monochromatic within the limits established by the collimating system. As theory shows,15 some broadening is to be expected on Bragg reflection even from perfect crystals, but this broadening is so small (not over 0.001°) that we need not consider it. Relatively few crystals, notably some diamonds and calcites, approach perfection. Sodium chloride, more useful in x-ray spectrog-raphy, broadens monochromatic x-rays appreciably, but the. total broadening can be smaller than 0.30°,16 the collimator a perture. See Figure 4-9. 

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