Si was coated on the surface of Ti-49Ni (at%) alloy powders by ball milling in order to improve the electrochemical properties of the Si electrodes of secondary Li ion batteries and then the microstructure and martensitic transformation behavior were investigated by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and differential scanning calorimetly (DSC). Ti-Ni powders coated with Si were fabricated, successfully by ball milling. As-milled powders consisted of highly deformed Ti-Ni powders with the B2 phase and amorphous Si layers. The thickness of the Si layer coated on the surface of the Ti-Ni powders increased from 3-5 pm to 1015 pm by extending the milling time from 3 h to 48 h. However, severe contamination from the grinding media, ZrO2 occurred when the ball milling time was as long as 48 h. By heating as-milled powders to various temperatures in the range of 673-873 K, the highly deformed Ti-Ni powders were recovered and Ti4Ni4Si7 was formed. Two-stage B2-R-B19' transformation occurred when as-milled Si-coated Ti-49Ni alloy powders were heated to temperatures below 873 K, above this temperature one-stage B2-B19' transformation occurred. (C) 2013 Elsevier Ltd. All rights reserved.