Nucleation, halides

Various appHcations such as lubricant additives, dyes, pigments, and catalysts are under investigation. Tungsten can be deposited from tungsten hexacarbonyl, but carbide formation and gas-phase nucleation present serious problems (1,2). As a result, tungsten halides are the preferred starting material. 

The capacitance determined from the initial slopes of the charging curve is about 10/a F/cm2. Taking the dielectric permittivity as 9.0, one could calculate that initially (at the OCP) an oxide layer of the barrier type existed, which was about 0.6 nm thick. A Tafelian dependence of the extrapolated initial potential on current density, with slopes of the order of 700-1000 mV/decade, indicates transport control in the oxide film. The subsequent rise of potential resembles that of barrier-layer formation. Indeed, the inverse field, calculated as the ratio between the change of oxide film thickness (calculated from Faraday s law) and the change of potential, was found to be about 1.3 nm/V, which is in the usual range. The maximum and the subsequent decay to a steady state resemble the behavior associated with pore nucleation and growth. Hence, one could conclude that the same inhomogeneity which leads to pore formation results in the localized attack in halide solutions. 

Hasse et al. [366] have used in situ AFM for the detection of silver nucleation at the three-phase junction of the type metal-silver halide-electrolyte solution. At this phase boundary, electrochemical reduction of submicrometer size silver halide crystals immobilized on the surface of gold and platinum electrodes took place. Following nucleation, the reaction advanced until the entire surface of the silver hahde crystals was covered with 20 atomic layers of silver. Then, reduction was terminated. The obtained silver layer could be oxidized and the next layer of silver halide crystals became accessible for further reduction. 

Periodical boundary conditions that have widely been examined by MD simulations of liquids and solutions have been employed for simulating the nucleation process of some alkali halides. 

The work of Yamamoto (43) with growth-active impurities such as Pb+2, Sn+2, and Mn+2 ions reveals that their presence in very small quantities decreases the probability of nucleation, thus extending the metastable region of aqueous solutions of the alkali halides. These ions of the transition elements because of their screening demands withdraw Cl- ions from solution and form complexes such as (PbCl6) 4 and (MnCl6)-4. Without changing the over-all composition of the solution, these ions lower the effective concentration of the Cl ions and thus decrease the nucleation rate of NaCl. 

In the 1940 s a CVD process using a flame to produce homogeneously nucleated (powder) oxides of titanium, zirconium, iron, aluminum, and silicon was reported. A mixture of metal halide vapor and oxygen is injected through the central nozzle of a burner, with fuel gas and supplemental oxygen provided through two concentric outer rings. At 950°C to 1100 C flame temperature, the metal halide vapor decomposes to form very fine oxide powders. 

In the present study, we have made X-ray diffraction, neutron diffraction with isotopic substitution, and quasi-elastic neutron scattering measurements on highly concentrated aqueous solutions of lithium halides in a wide temperature range from room temperature to below glass transition temperature, from which the microscopic behaviors of the static structure and dynamic properties of the solutions are revealed with lowering temperature. The results obtained are discussed in connection with ice nucleation, anisotropic motion of water, crystallization, and the partial recovery of hydrogen bonds. 

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