Reduced titanium chlorides dissolved in fused alkali and alkaline earth chlorides may be electrolyzed in diaphragmed cells under an inert gas atmosphere to yield ductile titanium as adherent, crystalline deposits. The reduced titanium chlorides are prepared in situ by adding TiCl4 through a hollow cathode at a controlled feed to current ratio.

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unsuccessful. Only single inflections were observed. This indicates the differences in the magnitude of maximum AE/AV probably represent minor differences in actual base strength. DISCUSSIONSulfides and sulfones, possible impurities in sulfoxides, in general exhibit no measurable basicity in acetic anhydride when titrated with perchloric acid.Trimethylphosphine oxide, though not a sulfoxide, has been included for comparison as amine oxides have been found to exhibit very sharp inflections in acetic anhydride. Diethoxy sulfoxide (diethyl sulfite) could not be titrated as a base in acetic anhydride.The direct titration of sulfoxides in acetic anhydride offers a rapid and reproducible approach to purity determination. The method appears to be limited only by the solubility of the particular sulfoxide in acetic anhydride.

Baked alkyd urea-formaldehyde coatings pigmented with titanium dioxide can b e varied from high to low gloss. Contraction of the film on cooling produces surface irregularities above flocculated particles, with a resulting loss of gloss. In the test system gloss is increased by the formation of surface active salts from the acids of the alkyd. It is suggested that the cation of this salt is adsorbed within the water layer present as an adsorbed film on the pigment surface. This cation confers a positive electrical charge on the pigment, while the high molecular weight anion serves as counterion. This explains the gloss increase obtained b y treatment with appropriate basic agents, particularly alumina hydrate, or by increase in relative humidity, and also the gloss decrease caused by low molecular weight acids having a strength equal to or greater than that of the alkyd acids.LKYD urea-formaldehyde enamels pigmented with titanium A dioxide can be prepared to yield baked coatings varying in appearance from essentially a matte to a high-gloss finish without change in pigment-volume concentration. The desire to understand the phenomena involved prompted this study of both the mechanical and the colloid chemical aspects of gloss development.After standard procedures for preparing, applying, and baking the finishes had been developed, consideration was given to the influence of the alkyd and urea-formaldehyde vehicles, and of the titanium dioxide pigment. Through electron microscope, hiding power, and electrophoresis studies it has been possible to develop a hypothesis relating the gloss results to vehicle interaction with the pigment causing it to cluster. This in turn is related to the nature of the ionic double layer a t the pigment surface. This hypothesis has suggested an experimental approach emphasizing the nature and strength of the acids of the alkyd vehicle and their interaction with the pigment to yield ions that form the ionic double layer. Modified potentiometric procedures have been developed for these studies. Experimental ProcedureThe conditions chosen for the preparation of the films, in particular the alkyd selected from a number of commercial vehicles and also the details of dipping and baking the panels, were designed to yield large differences in gloss between films, thereby simplifying the interpretation of the results.