Structural Changes and Reactivity of Hematite Subjected to Extended Milling

Several structural characteristics change during intensive milling such as chemical composition, phase transformation, crystallite size, lattice strain, lattice parameter (s) and solid reactivity etc. The creation of defects enhances the stored energy (enthalpy) in the solids and consequently causes a decrease of activation barrier for the process and/or subsequent processes. In this paper, the effects of milling on the structural changes of hematite have been investigated using dry millings. The structural changes have been characterized using a combination analysis of BET surface area measurements and X-ray diffraction (XRD) analysis. Besides, the hydrogen reduction behaviors and kinetics of mechanically activated samples and initial sample were studied using simultaneous thermal analysis (STA). The methods of Williamson-Hall and Warren-Averbach were used for analyzing of XRD patterns to resolve and extract the microstructural characteristics of hematite phases. It was concluded that the breakage and aggregation of particles take place mainly in the starting and prolonged stages of dry grinding, respectively. The BET surface area enlarged steadily over the grinding processes whatever milling methods were utilized. The characterization of structural changes revealed that the hematite milled under various conditions did not undergo any significant reaction or phase transformation during milling processes. In addition, X-ray amorphous phase con-tent increased gradually with extending the grinding intensity. The maximum X-ray amorphous phase exceeds about 81% after 9 hours of milling in both tumbling mill and vibratory mill. The Williamson-Hall plots revealed the anisotropic character of line broadening for deformed hematite and changes in the trend of microstructural characteristics as a function of milling time. It was found that the surface weighted crystallite size decreases and lattice strain increases over the grinding periods. The minimum surface weighted crystallites were calculated about 17.3 nm, 12.2 nm for the products of tumbling and vibratory mills respectively. The maximum lattice strain,, in the grinding with tumbling and vibratory mills was calculated about 4.44×10-3 and 3.95×10-3respectively. 21/210nmLe=<> The non-isothermal kinetic analysis of the products revealed that Fe 2O3 reduced to Fe in a two-step process via Fe3O4. Intensive grinding resulted in improved resolution of overlapping reduction events. It was also established that the mechanical activation had a positive effect on the first step of reduction. The prereduction step in the activated samples initiated and completed at lower temperatures than that in non-activated samples. The activation energy of reduction decreased at the first step of reaction with increasing the grinding intensity. Intensive milling increased slightly the average activation energy of the second step of reduction due to the present of finely agglomerated particles and intensive sintering of the particles in higher temperature ranges.