Kinetics of release of a model disperse dye from supersaturated cellulose acetate matrices.

A study has been made of the kinetics of release into water of a model disperse dye (4-aminoazobenzene) from supersaturated solvent-cast cellulose acetate films at room temperature. Excess dye was introduced into the polymer matrix by: (i) sorption from aqueous solution at 100 degrees C; (ii) sorption from the vapour phase at 110 degrees C; or (iii) prior dissolution in the casting solvent. The effect of the method of introduction of the dye, the degree of supersaturation and the rate of agitation of the bath were investigated. Under conditions of strong agitation, the release kinetics from films dyed by method (i) or (iii) were in general accord with the theoretical model which assumes solute in the film in excess of the saturation limit to be in the form of immobile aggregates at equilibrium with mobile dye; although the value of the diffusion coefficient of the solute in the film was found to be substantially higher than that in the unsaturated film. On the other hand, when dyeing had been effected from the vapour phase, Fickian kinetics was followed and the diffusion coefficient was found to be equal to that observed in unsaturated film. It was concluded that under these conditions, the excess dye in the film tends to remain molecularly dispersed. Under conditions of slow agitation, the square root of t kinetics was not attained in many instances. General and early-time approximate expressions based on the Roseman-Higuchi model proved useful for the interpretation of the results in such cases; while the said model was extended to include the effect of significant variation of the partition coefficient of the solute with concentration.