The evolution of the chemical composition of grain boundaries during layering of metal microvolumes on the friction surfaces is studied using Auger electron spectroscopy. Metal layering on the friction surfaces leads to its saturation with oxygen from the working medium and dissolution of the carbide phase. Most of both the oxygen atoms and the carbon atoms of dissolved carbides are in friction layers in the form of a solid solution in structurally disorganized near-boundary regions of grains. The individual nearest atomic surrounding of impurity atoms in the near-boundary regions of grains is determined by analysing the extended fine structure of the scattered electron energy loss spectra (EELS). The carbon atoms at the grain boundaries of the deformed original metal are located in the octahedral pores of the b.c.c.-iron–chromium alloy and form a dispersed carbide phase (Cr, Fe)$_{7}$C$_{3}$. The finely dispersed carbide phase (Cr, Fe)$_{7}$C$_{3}$ disappears in the near-boundary regions of the grains of the friction surface layers. In this case, a significant number of carbon atoms are transferred to new crystal structure positions. Together with oxygen atoms and metal atoms, they form metastable Fe–O–C (Fe–Cr–O–C) atomic clusters. The effect of impurity atoms on the electronic structure and character of interatomic bonds in the near-boundary regions of grains is studied using zone calculations within the LAPW approximation using the full potential and the generalized gradient correction of electron density (GGA). As shown, the carbon atoms in the octahedral pores of the b.c.c.-iron–chromium alloy form strong covalent bonds with the surrounding metal atoms. They reduce the mobility of atoms and increase the work hardening of the metal. Metastable Fe–O–C (Fe–Cr–O–C) atomic clusters and the metal atoms around them separate regions with low electron density. The consequence of this is the limited participation of valence electrons in the formation of bonds between the metal atoms and the clusters’ atoms. These bonds are easily destroyed during local deformation of the metal. This increases the plasticity of the metal in places of accumulation of metastable atomic clusters. The instability of the interatomic bonds formed by 3$d$ electrons of clusters’ metal atoms with the shift of the atoms also contributes to this effect. As shown, metal layering on the friction surfaces causes the accumulation of metastable atomic clusters Fe–O–C (Fe–Cr–O–C) and ultrafine oxide phase $\alpha$-Fe$_2$О$_3$ at the grain boundaries of friction layers. This one contributes to the formation of dynamic systems in the friction layers. The mechanism of deformation of these systems is connected with the collective forms of motion of defects in the crystal lattice. Therefore, a high-energy impulse impact on the ultrafine systems saturated with oxygen and carbon can transfer them into a structurally unstable state. In this case, a crystal-amorphous nanostructured material is formed.