Nanocrystalline Ni3Fe powders were obtained via wet mechanical alloying using benzene as surfactant. The differential scanning calorimetry (DSC) measurements showed the presence of an exothermic peak which does not correspond to any phase transformation or phase formation as was proved by X-ray diffraction measurements. The exothermic peak was observed neither for the dry milled samples nor for the wet milled and subsequently annealed powders at 350 degrees C for 4 h. The infra-red (IR) spectra registered for the wet milled samples showed a series of vibration bands corresponding to C6H6 and also to a series of fragments resulting from benzene decomposition. The results obtained by IR investigation were confirmed by thermogravimetry and mass spectrometry (TG + MS) investigations. The main fragments resulting from the benzene decomposition on the surface of the nanocrystalline Ni3Fe powders are: CO2, CO and C. The evolution of the particle size distribution versus the milling time has been determined for the wet mechanical milling process of nanocrystalline Ni3Fe powders. The DSC analysis reveals a displacement of the exothermic peak onset towards lower temperatures and an increase of the surface of this peak attributed to the changes in the particles specific surface and to the quantity of benzene added in the milling experiments. (C) 2010 Elsevier B.V. All rights reserved.