With the recent improvements in severe plastic deformation (SPD) and cold-rolling (CR), deformation processing has become an alternative to rapid-solidification for the processing of bulk-metastable structures. Further progress is linked to the prediction of glass-forming systems as well as to the understanding of the deformation-induced transformation reactions. Cold-rolling experiments on systems with different mixing enthalpy values, including Al-Pt, Al-Pd, Al-Ni and Al-Cu, indicate that the heat of mixing is fundamental to the reactions that occur during the processing. However, cold-rolling of Al-Hf demonstrates that a large negative heat of mixing alone is not sufficient for rolling-induced amorphization reactions. SEM cross sectional images of Al-Hf and Al-Pt systems reflect a connection between the layer refinement and the amorphization reaction. Complete amorphization is only possible with a layer refinement to a nm-thickness level. In addition to a large negative heat of mixing, a rapid structural refinement is therefore necessary for rolling-induced amorphization reactions. Measurements of the interfacial area per unit volume highlight the difference between the layer-refinement of cold-rolled Al-Pt and Al-Hf samples.