Mechanical spectroscopy and neutron diffraction studies were performed on several samples with compositions Fe - 25 at. % (Al + Si) and Fe - 15 at. % (Al + Si). It was found that the solute grain boundary relaxation is strongly dependent on the degree of order in the sample. A decrease in the orderdegree allows the development of a relaxation peak at around 1000 K during cooling from 1200 K. In contrast, if the order degree is not decreased, the grain boundaries remain locked and consequently the relaxation peak does not appear. The magnetic response both in the asquenched and after thermal treatment states was also explored and correlated to the microstructural state.