A remarkable observation that detonation of oxygen-deficient explosives in an inert medium produces ultra-fine diamond particles having diameters of 4–5 nm was made four decades ago, but this novel form of diamond has never been isolated in pure form thereafter. The reason for the difficulty was that the core aggregates having a diameter range of 100–200 nm are extremely tight and could not be broken up by any known method of de-aggregation. After a number of futile attempts, we were able to obtain primary particles by using the recently emerging technique of stirred-media milling with micron-sized ceramic beads. The milled aqueous slurry of nanodiamond gave a stable, thick and dark-coloured colloidal solution. After light sonication, dynamic light scattering measurements gave a sharp distribution in the single-digit nano-range, and HRTEM indicated separate particles having diameters of 4–5 nm, which agreed with the X-ray value of 4.4 nm for the primary particles. A model is presented for the core aggregates, which resembles the well-known grape-shaped 'aggregate structure' of the hardest type of carbon black.