To improve temperature durability for autoclaving of SiOx diffusion barrier coatings on polypropylene, plasma polymerized hexamethyldisiloxane (pp-HMDSO) is applied by plasma enhanced chemical vapour deposition as interlayer material and compared with results obtained with amorphous hydrogenated carbon-nitrogen (a-C : N : H) and a-Si : C : O : N : H interlayers. The influence of the O2/HMDSO ratio on the chemical structure and related mechanical and oxygen barrier properties is investigated by fragmentation tests, dilatometry, oxygen transmission rate, internal stress and mass density measurements as well as Fourier transform infrared and x-ray photoelectron spectroscopy. Carbon-rich, polymer-like coatings with low density, low internal stress and excellent adhesive and cohesive properties are found for pp-HMDSO at the expense of barrier performance. In the SiO x/pp-HMDSO coating a broad transition in chemical composition was observed, explaining improved mechanical properties responsible for good barrier performance after thermal cycling or autoclaving.