Abstract: Addition of a labile sulphur donor to light sensitive silver halide microcrystals results in the formation of a distribution of silver sulphide clusters on the crystal surface. These silver sulphide clusters enhance the efficiency of image formation during the photographic process. Their activity towards the capturing of light photons, however, is very critical to their size (aggregation number) and concentration. By incorporating gold ions into silver sulphide clusters it was possible to monitor the size distribution by measuring the amount of gold reacted. From these experiments, no evidence was found for aggregation of the reacted sulphur entities on the surface. The uptake of gold ions at different sulphur concentrations could well be fitted with a simulated size distribution when a catalyzed deposition of sulphur was assumed, with a reactivity of the surface equal to 1.0 % for the microcrystals studied. From a simulation of the silver sulphide cluster size distribution a correlation could also be found between increasing aggregation numbers and the absorption at increasing wavelengths in diffuse reflectance spectroscopy.

Abstract: Not much about the effect of thiocyanate addition on the sulphur ripening is known, although it is used for many applications in photographic practice. Via a combination of tracer analysis and diffuse reflectance spectroscopy the effect of thiocyanate addition on the sulphur and sulphur-plus-gold ripening could be unveiled. When thiocyanate is added prior to the sulphur addition, it appears to rearrange the silver halide surface in such way that the sulphur deposition rate is enhanced, but the supply of interstitials is limited. Addition of thiocyanate after the sulphur reaction results in the formation of thiocyanate complexes with silver, from which a silver ion is more easily deposited in a surface cell of the silver sulphide clusters thus enhancing the sensitization rate. For sulphur-plus-gold sensitized emulsions it was observed that part of the gold ions could be removed out of the Ag2-xAuxS clusters by addition of thiocyanate ions and subsequent washing. Hence, it was concluded that two different types of gold ions are present in the silver sulphide clusters; 1. gold ions which are substitutional for silver (bound between sulphur and bromide ions) 2. gold ions which bridge two or three sulphur atoms. Incorporation of gold ions into silver sulphide clusters suppresses their optical absorption in diffuse reflectance spectroscopy. Since the optical absorption at 505 nm can completely be restored by addition of thiocyanate, it is assumed that the entity absorbing at this wavelength is a monomer of silver sulphide.