Interaction processes in Al/Ni/.../Al/Ni multilayer systems with an excess of one of the components are studied by of DSC, XRD and TEM methods. It is shown that the compounds formation sequence differs depending on which component is excessive. There is proposed a rule for compounds formation sequence in systems with an excess of one of the initial phases. It is based on the assumption that behaviour of two contacting solid phases system is analogical to that of a gas system: energy density change in a solid-state system is analogical to pressure change in gas system. The prediction is built on the calculation of parameter Δ
H
0
/ν
V
, where Δ
H
0
and ν
V
are enthalpy change and volume of new phase forming as a result of the reaction.
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