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Application of electrochemical methods for studying steel corrosion in alkali-activated materials
(2023)
Alkali-activated materials (AAMs) are binders that can complement and partially substitute the current use of conventional cement. However, the present knowledge about how AAMs protect steel reinforcement in concrete elements is incomplete, and uncertainties exist regarding the application of electrochemical methods to investigate this issue. The present review by EFC WP11-Task Force ‘Corrosion of steel in alkali-activated materials’ demonstrates that important differences exist between AAMs and Portland cement, and between different classes of AAMs, which are mainly caused by differing pore solution compositions, and which affect the outcomes of electrochemical measurements. The high sulfide concentrations in blast furnace slag-based AAMs lead to distinct anodic polarisation curves, unusually low open circuit potentials, and low polarisation resistances, which might be incorrectly interpreted as indicating active corrosion of steel reinforcement. No systematic study of the influence of the steel–concrete interface on the susceptibility of steel to corrosion in AAMs is available. Less common electrochemical methods present an opportunity for future progress in the field.
The oxidation of sulfur in aqueous solutions is an important process in several geochemical and industrial contexts. In concrete technology, it is particularly relevant for the protection of steel reinforcement in slag cement-based concretes, as the presence of sulfides affects the passivation of the steel and corrosion initiation in the presence of chlorides. However, the knowledge about the kinetics of sulfide oxidation in alkaline solutions, such as concrete pore solutions, is incomplete. To address this issue, we prepared solutions with 0.80 M NaOH, and nominally 10, 100 and 350 mM HS−, respectively, and followed the evolution of the sulfur species during bubbling with oxygen-containing gas (concentration 100% or 22%) using X-ray absorption near-edge structure (XANES) spectroscopy at the sulfur K-edge. Polysulfide, thiosulfate, sulfite and sulfate were identified and quantified via linear combination fitting of the spectra, using previously measured standards. A preliminary analysis of the results shows that the initial rate constant of sulfide oxidation depends strongly on the HS− concentration, while it less strongly depending on the oxygen concentration, in line with previous results for lower pH values. Approaches to fit the data to obtain the rate constants of all relevant reactions will be discussed.
The development of alkali‐activated materials (AAMs) as an alternative to Portland cement (PC) has seen significant progress in the past decades. However, there still remains significant uncertainty regarding their long term performance when used in steel‐reinforced structures. The durability of AAMs in such applications depends strongly on the corrosion behaviour of the embedded steel reinforcement, and the experimental data in the literature are limited and in some cases inconsistent. This letter elucidates the role of the chemistry of AAMs on the mechanisms governing passivation and chloride‐induced corrosion of the steel reinforcement, to bring a better understanding of the durability of AAM structures exposed to chloride. The corrosion of the steel reinforcement in AAMs differs significantly from observations in PC; the onset of pitting (or the chloride ‘threshold’ value) depends strongly on the alkalinity, and the redox environment, of these binders. Classifications or standards used to assess the severity of steel corrosion in PC appear not to be directly applicable to AAMs due to important differences in pore solution chemistry and phase assemblage.