Alkali halides surfaces

We have performed ionic mobility studies on mica and in alkali halide surfaces. Here we shall describe some results obtained on mica with different surface ions. Alkali halides will be discussed in detail in the next section. 

Large domains of oriented single crystals of poly(TCDU) and poly(DMDA) were produced on the alkali halide surface. Figures 1 and 2 show the typical elongated platelet morphology. Selected... 

Another method used involved the casting of a thin film of N P Cl from decane on a freshly cleaved alkali halide surface at room temperature, followed by heating to 130 C. The molten trimer film was then slow cooled to 110 C (4 C below the bulk melting temperature) and held at that temperature for 1 hour. 

The photon-induced dissociation and desorption of methyl bromide from a LiF surface was monitored [113]. Discuss the evidence that the photon energy was absorbed directly by the molecule adsorbed on the alkali halide surface. Would you expect the same photon-induced dissociation behavior if methyl bromide was chemisorbed on a transition metal surface ... 

Rickert, S., Baer, E., 1978. Epitaxial crystallization of iso tactic polypropylene on alkali halide surfaces. 

M., Loppacher, C., Gerber, C., and Giintherodt, H.J. (1998) Dynamic SFM with tme atomic resolution on alkali halide surfaces. Appl. Phys. A, 66, S293-S294. 

It is also noteworthy that urea interacts with the alkali halide surfaces in aqueous solution hence, the surrounding medium effect seems to be important. To examine the effect of the solvent, we performed calculations with the continuum solvation model (COSMO). The dielectrics ( = 78.4 for water) was used in these cases. The optimized gas-phase slabs for KCI 100, 110, and 111 with urea were computed with the COSMO model. The calculated interaction energies are shown in Table 8.2. Interaction energies were found to be lower in water compared to the gas-phase results. Importantly, the interaction energies for urea with all three surfaces were found to be comparable. Based on these calculated results, one could predict that the additional stabilization cannot be achieved for the unstable surfaces such as 111 ... 

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... 

Slides Plastic cavitation around inclusions in metals (e.g. metallographic section through neck in tensile specimen) SEM pictures of fracture surfaces in ductile metals, glass, alkali halide crystals. 

Many inorganic solids lend themselves to study by PL, to probe their intrinsic properties and to look at impurities and defects. Such materials include alkali-halides, semiconductors, crystalline ceramics, and glasses. In opaque materials PL is particularly surface sensitive, being restricted by the optical penetration depth and carrier diffusion length to a region of 0.05 to several pm beneath the surface. 

At a given ideal composition, two or more types of defects are always present in every compound. The dominant combinations of defects depend on the type of material. The most prominent examples are named after Frenkel and Schottky. Ions or atoms leave their regular lattice sites and are displaced to an interstitial site or move to the surface simultaneously with other ions or atoms, respectively, in order to balance the charge and local composition. Silver halides show dominant Frenkel disorder, whereas alkali halides show mostly Schottky defects. 

Developments in electron microscopy also promise to revolutionize other studies of the surfaces of solids in general and/of catalysts in particular. Previously, monatomic steps and other topographical features at the exterior surfaces of solids were best investigated by the powerful but cumbersome, and destructive technique of gold-decoration - see refs 69 and 70 for studies of alkali halide and layered sulphides, respectively. 

Epitaxial crystallization was accomplished by the immersion of a preheated substrate (the substrates for epitaxial crystallization were single crystals of alkali halides from Harshaw Chemical Co.) into the monomer solution followed by its in-situ cleavage to expose two fresh (100) surfaces. 

The sorption of water vapor onto nonhydrating crystalline solids below RHq will depend on the polarity of the surface(s) and will be proportional to surface area. For example, water exhibits little tendency to sorb to nonpolar solids like carbon or polytetrafluorethylene (Teflon) [21], but it sorbs to a greater extent to more polar materials such as alkali halides [34-37] and organic salts like sodium salicylate [37]. Since water is only sorbed to the external surface of these substances, relatively small amounts (i.e., typically less than 1 mg/g) of water are sorbed compared with hydrates and amorphous materials that absorb water into their internal structures. 

Unfortunately, the literature is relatively sparse with examples showing the water uptake profile onto crystalline, nonhydrating substances below RHq. This is most likely due to the difficulty in accurately measuring the small amounts of water that are sorbed. Alkali halides are an exception, however, likely due to their well-characterized particle morphologies [34—37]. Figure 2 shows a water uptake isotherm onto recrystallized sodium chloride [37]. Note that the amount of water sorbed as a function of relative humidity is normalized to the specific surface area of the sample. Since water is sorbed only to the external surface of... 

TABLE II. Corresponding-States Vapor Pressures and Surface Tensions for Molten Alkali Halides... 

An alkali halide (NaCl, KCl, KBr, etc.) which has a freshly cleaved (001) face is introduced into a polymer solution and then the pol5nner is to be crystallized epitaxially onto the face of the alkali halide. In general, flexible-chain polymers are apt to be crystallized as rod-like crystals on such an alkali halide these rod-like crystals are edge-on lamellae with their lateral surface being mostly in contact with the (001) face of the alkali halide. A given polymer deposited on an alkali halide can be melted and subsequently crystallized there in an epitaxial fashion. 

With ionic crystals, there are some rather interesting possibilities. A large part of the perturbation which a free surface introduces is associated with the change in the electrostatic environment of an ion in going from the interior to the surface. If the normally filled valence band is associated with the anions (as is the case with the alkali halides and with certain n-type semiconducting oxides), the surface perturbation acts in the direction of producing a band of surface states with its center lying above the center of the normal anion band. This anion surface band will normally be completely filled. Conversely, for the normally empty cation band (the... 

F centers may act as adsorption centers not only in the alkali halides, but in any other crystals as well. Take, for example, a crystal of ZnO, in which the F center is an oxygen valency with two (not one ) electrons localized near it, as depicted in Fig. 30. From the chemical point of view such a center represents two adjacent localized free valencies of like sign which on an ideal surface could never meet because of Coulomb repulsion between them. (This should be especially stressed.) As a result of this property, such an F center may play a specific role in catalysis acting as an active center for a number of reactions. 

Theoretical calculations of the surface free energy of solids date back to 1928 with the work of Lennard-Jones and Dent 10). Displacements of the positive and negative ions when a given interior layer becomes a surface layer were allowed for by Verwey 11). Calculations by Shuttleworth 12) showed that van der Waals terms make a significant contribution to surface energy. Benson and his co-workers have made an extensive study of alkali-halides 13-16) and of magnesium oxide 17). 

Yapp. C.J. (2000) Climatic implications of surface domains in arrays of 5D and 5180 from hydroxyl minerals Goethite as an example. Geochim. Cosmochim. Acta 64 2009-2025 Yariv, S. Mendelovid, E. Villalba, R. (1980) Thermal transformation of goethite into hematite in alkali halide discs. J. Chem. Soc. Faraday Trans. I. 76 1442-1454 Yariv, S. Mendelovid, E. Villalba, R. Cohen, M. (1979) Transformation of goethite to maghemite in Csl discs. Nature 279 519-520... 

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