Ageing effect in nanocrystalline TiCx/C studied by EPR

TiC/C nanocrystalline material: titanium carbide TiC dispersed in a carbon matrix has been prepared by a nonhydrolytic sol–gel process. Temperature dependence of the electron paramagnetic resonance (EPR) spectra of this material has been studied in the 3.5–120 K range. Two very different EPR lines have been recorded in fresh sample at temperatures below 120 K arising from the Ti(III) complex (broad and asymmetric line) and conduction electrons (very narrow line). In the same aged sample (1 year old) the magnetic anisotropy of Ti(III) line has increased while a narrow line attributed to conduction electrons has vanished. The existence of the paramagnetic centers connected with trivalent titanium ions could the result of disordering processes. The increase of anisotropy in Ti(III) line could be connected with the oxidation processes. The temperature dependence of the integrated intensity of the broad line revealed the presence of titanium antiferromagnetic dimers. The disappearance of a narrow EPR line suggests that the oxidation process (ageing effect) could influence also the electrical properties of titanium carbide.