The effect of dry milling in a vibratory mill on the structural changes and microstructural characteristics of hematite using different methods was investigated. We have described the line profile analysis (LPA) to extract the size of coherently diffracting domains and the lattice strain of activated hematite in a vibratory mill. The Warren-Averbach and Williamson-Hall methods were used as the main tools for characterization. The changes in the particle size, surface area and new phase formation of hematite concentrate were also investigated. It was concluded that the breakage and agglomeration of particles take place mainly at lower and higher levels of specific energy input, respectively. The pores in agglomerates remain accessible for the nitrogen gas. Milling of hematite increased specific surface area up to 18.4 m(2)/g. The hematite milled under various levels of specific energy input did not undergo a significant reaction or phase transformation during milling. The Williamson-Hall method confirms its merit for a rapid overview of the line broadening effects and possible understanding of the main causes. The anisotropic character of line broadening for deformed hematite as a function of specific energy input was revealed. Higher level of specific energy input favors the generation of small crystallite size, higher microstrain, BET surface area, amorphization and line breadth. The Warren-Averbach method suggested that the nanocrystalline hematite with grain sizes of 73.5-12.2 nm was formed by mechanical treatment using different milling intensities in the vibratory mill. The root mean square strain (RMSS) at L = 10 nm varies between 1.7 x 10(-3) and 4.0 x 10(-3) depending on the level of energy input. Limits in the applicability of Williamson-Hall method and reliability of the results are discussed in detail. (c) 2006 Elsevier B.V. All rights reserved.