The self-diffusion coefficients of water and casein aggregates in aqueous Na-caseinate dispersions were measured using a pulsed gradient stimulated echo nuclear magnetic resonance technique (PGSTE-NMR). The results for water self-diffusion are discussed in terms of the cell model. The influence of Na-caseinate concentration on water self-diffusion can be explained by obstruction and tortuosity effects arising due to the presence of casein aggregates. Unrestricted diffusion of casein aggregates was measured for all concentrations at short observation times (similar to 20 ms). Despite a near uniform size distribution on increasing Na-caseinate concentration the measured unrestricted diffusion coefficient was a decreasing function of Na-caseinate concentration. Enhanced packing interaction between the aggregates and the slight augmentation of the large tail in the size distribution is the main reason for this observed decrease. On increasing the experimental observation times restricted diffusion of the aggregates is measured. The rheological response of the dispersions was investigated. The stress evolution of the sample with time exhibits three distinct behaviours, irrespective of Na-caseinate concentration and applied shear rate: a spontaneous increase of stress at very short times (<1 s), followed by a plateau with fine Structure superposed and lastly a sharp increase in stress attributed to irreversible gelation. The latter occurs at significantly reduced times on increasing Na-caseinate concentration. Linear rheology measurements indicate that the dispersions are predominantly locally liquid-like while being macroscopically in a gelled state. (C) 2009 Elsevier Inc. All rights reserved.