Accelerated tests of hardened cement pastes alteration by organic acids: analysis of the pH effect

Effluents, such as liquid manure and silage effluents, stored in silos often made of concrete, contain organic acids that are chemically very aggressive for the cement-based matrix. The pH of liquid manure is comprised between 6 and 8, and the pH of silage effluent is about 4. There has already been much research done on manure's effect on concrete using aggressive solutions with a pH of or inferior to 4, in order to accelerate alteration kinetics. These studies aimed at simulating liquid manure and silage effluent, equally. The goal of this article is to validate the use of solutions with a pH of 4 to implement accelerated studies on alterations occurring to structures exposed to the acidic part of liquid manure. In this study, the alteration mechanisms of the cement-based matrix produced by two solutions of organic acids with pH of 4 and 6 were compared. At the end of the experiment, carried out on ordinary Portland cement and slag cement pastes, the kinetics of alteration of the cement pastes immersed in the solution with a pH of 4 was ninefold higher than in the solution with a pH of 6. The chemical and mineralogical modifications of the paste were analyzed by electron microprobe, XRD and BSE mode observations. It was shown that the alteration mechanisms of the paste are sensibly identical for both solutions: almost complete decalcification, the disappearance of the crystallized or amorphous hydrated phases and the probable formation of a silica gel containing aluminum and iron, mainly. The differences in alteration mechanisms between the two solutions are minor and mainly concern the stability of the anhydrous phases: C4AF and slag grains