Al-4mass%Fe and Al-7mass%Fe alloys were rapidly solidified into a ribbon shape at cooling rates about 10
5 and 10
6K/s by a single roller technique. The solid solubility of iron in aluminum extends up to 7.3mass% at a cooling rate about 10
6K/s. Angular-shaped and disc-shaped metastable phases are found in the alloys solidified at slightly lower cooling rates. Cell structure is observed in the alloys solidified at a rate about 10
5K/s. Dark field micrographs and diffraction rings show the cell boundary consisting of microcrystalline. In the decomposition process of supersaturated solid solution, three metastable phases form. Decomposition at temperatures up to 673K starts with the formation of angular-shaped metastable phase (diamond cubic, a=0.585±0.001nm). A disc-shaped metastable phase (f.c.c., a=2.406±0.001nm) precipitates on the {100} planes of the matrix coexisting with the angular-shaped one. Further annealing results in the formation of rod-shaped metastable phase (f.c.c., a=1.604±0.001nm) along the [100] direction of the matrix. A metastable phase Al
6Fe forms at grain boundaries and transforms to stable Al
3Fe at higher annealing temperatures.
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