By introducing a high fraction of interstitial carbon through low temperature carburization, the pitting corrosion resistance of austenitic stainless steel can be signi cantly improved. Previous work attributed this enhancement to the improvement of passive lm properties. However, we show here that interstitial carbon actually weakens the passive lm on stainless steel. In fact, the enhancement in pitting resistance is a result of carbon reducing the metal dissolution rate in a local pit environment by many orders of magnitude, which extremely decreases the growth stability of a pit and prevents it from transitioning into stable growth. Electronic structure calculations show that carbon bonds to the metal atoms and that the metal-carbon bonds are 1.6 to 2.0 times stronger than the metal-metal bonds. Different from prior theories, we show that the signi cant increase of pitting resistance originates from the formation of covalent bonds between interstitial carbon and its neighboring metal atoms, resulting in a signi cantly reduced dissolution rate. This study indicates a new strategy for the design of corrosion resistant alloys, namely alloying with concentrated interstitials that form strong bonds with the matrix atoms.
Main TextTo meet the fast-growing demand of alloys serving in harsh environments, great efforts have been made to design alloys combining enhanced mechanical properties and improved corrosion resistance. 1, 2 One strategy to achieve this goal is to modify the alloy surface using surface engineering techniques, such as carburization. The deleterious precipitation of intergranular Cr carbides during carburization of stainless steels by standard methods can be prevented by low temperature carburization (LTC), 3, 4, 5 which allows the diffusion of carbon atoms into the alloy matrix resulting in a high concentration, without precipitation of carbides. Generally, carbon atoms are incorporated in the octahedral sites of face-centered cubic (FCC) structures, forming a subsurface zone of concentrated interstitial carbon, with carbon fraction up to 0.15 and the mean depth on the order of 10 mm. 6 Even low concentrations of interstitial carbon can improve the corrosion properties of iron, 7, 8 but the bene ts are small relative to those imparted by higher concentrations.
Concentrated interstitial carbon was widely reported to improve the corrosion resistance of stainless