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Design of a cementitious coating system for corrosion protection: Phase 1 binder materials selection
(2014)
This paper presents the first results of an ongoing research project on the development of a cementitious thin layer coating system with high resistance against chloride penetration and carbonation. It is intended to display the decision process used for selecting raw materials as well as the conclusions based on test results and theoretical deliberations. In this phase, only the influence of the binder materials was analyzed concerning mechanical properties. The system should enhance the durability of new and old concrete structures exposed to aggressive environments, be based on market available materials and fulfill the requirements of the German guideline for concrete repair (Rili-SIB).
The contribution reports on durability-related transport properties of geopolymer-based mortars. We show results of accelerated carbonation, rapid chloride migration (RCM), accelerated chloride diffusion, and air permeability measurements for fly ash-based geopolymer mortars, including mixes containing ground granulated blast furnace slag (GGBFS). In addition, we report polarization resistance data and corrosion potential vs. time curves for carbon steel bars embedded in two of the fly ash-based geopolymer mortars and a CEM I-based mortar (as reference).
Despite comparable total porosities, the carbonation depths, the chloride migration coefficients and the air permeabilities of the mortars differed significantly. In general, the addition of GGBFS to the binders improved the performance (decreased transport coefficients); however, this was not found to be true for the air permeability in all cases. This latter effect can be explained by drying damage of the C-(A-)S-H gel in GGBFS-containing binders. On the other hand, low transport coefficients can also be achieved by optimization of the binder formulation without the addition of GGBFS, which is also reflected in the material’s air permeability.
The corrosion potential vs. time curves in combination with polarization resistance values reveal that the steel reinforcement in geopolymer mortars assumed a passive state. However, this happened considerably later than for steel in CEM I-based mortars. The free corrosion potential of carbon steel reinforcement in the geopolymer mortars had different values than the free corrosion potential values for the CEM I-based mortar for both the active and the passive state.
The majority of the built infrastructure is made of concrete, which is a multiphase system made of cement, aggregates, water and pores (every year nearly 4 billion tons of cement are produced which is largest mass flow generated by mankind). Concrete is often used in combination with steel as reinforced concrete. Environmental influences, especially the ingress of harmful ions in combination with the ingress of water, trigger different damage processes which reduce the designed lifetime of a structure. The ingress of chlorides from de-icing salt or sea water leads to corrosion of the reinforcement. Also the carbonation of the concrete may trigger the corrosion of the reinforcement. The ingress of alkalis from de-icing salts may cause the expansion of the amorphous silica aggregates (alkali-silica reaction) through formation of a swelling gel of calcium silicate hydrate if water is present. The ingress of sulfates may cause spalling of the concrete surface due to ett-ringite formation. For the standard procedure in civil engineering cores are taken, cut in slices, grinded and the obtained homogenized powder is solved in acid and investigated by standard procedures. BAM has developed the LIBS technique for the 2D evaluation of the chemical composition of concrete [1-5]. The technique is established for automated laborato-ry use with high numbers of samples to investigate transport processes of harmful species (Cl-, CO2, SO42- and alkalis) in concrete. Information about ingress depth and the quantitative values are important to estimate the remaining lifetime of the infrastructure. LIBS is a surface technique. To get information about the ingress depth, a core has to be taken and cut in the middle. The measurements are carried out at the cross section. The main advantages of LIBS are the direct measure-ment on the surface of the concrete, fast analysis (sample rate 100 Hz) with a spatial resolution of up to 100 μm, the consideration of the heterogeneity of the concrete and the possibility of automated measurements which save a lot of man-power and time. As an example the investigation of ingress profiles for standard diffusion and migration tests in civil engi-neering takes hours in comparison to just a few minutes using LIBS. At the same time a 2D-evaluation provides information about hot spots of elemental concentration which may not be found by standard methods.
The state of the art of LIBS technique for applications in civil engineering will be presented, including typical results of 2D investigation of concrete in laboratory. The performance is also demonstrated by examples for on-site applications using a mobile LIBS system. The road map to standardization is presented as well.
Corrosion of steel rebars in concrete presents one of the main deterioration mechanisms limiting service life of the reinforced structures. The corrosion is accompanied by an expansion of the corrosion products causing high pressures, concrete cracking and finally spalling of a cover layer. Critical chloride concentration, loss of alkalinity and modeling of the steel corrosion are in researchers' spotlight for decades, however reinforcement corrosion in alkali activated materials is insufficiently described and understood yet.
In this work, the steel reinforcement corrosion in alkali-activated fly ash mortars is investigated in terms of electrochemical behaviour of the reinforced mortars exposed to aggressive environments such as leaching, carbonation and chloride ingress. A selected geopolymer mixture based on hard coal fly ash activated with sodium hydroxide and sodium silicate solutions is used for the steel reinforcement-corrosion experiments. The formation of passive layer on the steel rebars is observed after approx. two weeks of hardening at laboratory temperature. However, alternative heat-treatment at 80°C for several hours leads to immediate formation of the passive layer as well as to a faster strength gain (80 MPa after 24h at 80°C). Chloride-induced corrosion, leaching and carbonation resistance of the alkali activated fly ash-based concrete is studied, where leaching in deionized water or carbonation under natural conditions (~0.04 % CO2) for 300 days did not lead to corrosion of the embedded steel. On the other hand, accelerated carbonation under 100 % CO2 atmosphere lead to depassivation within two weeks.
While alkali-activated binders offer certain advantages over traditional Portland cement binders, particu¬larly in terms of resistance against chemical attacks and potentially environmental footprint, their degra¬dation mechanisms remain incompletely understood at present, specifically carbonation. Thus, this study investigates the impact of natural and accelerated carbonation (1% and 4% CO2) on three different compositions of alkali-activated concretes: 100% calcined clay (C100) binder, 100% ground blast furnace slag (S100) binder, and a 40% calcined clay and 60% blast furnace slag blend (C40S60). C100 concretes exhibit faster carbonation kinetics, with five times greater natural carbonation depths than S100. This difference diminishes under accelerated carbonation, showing a 1.5 times difference for 1% CO2 and complete carbonation for 4% CO2 at 90 days. The results thus confirm that accelerated carbonation testing of low-Ca alkali-activated concretes yields results that are not representative of natural carbonation. The C40S60 sample demonstrates a carbonation profile similar to a CEM I concrete, i.e., a high carbonation resistance. Microstructure analysis indicates the formation of three polymorphs of calcium carbonate for S100 (calcite, vaterite, and aragonite), with a higher CO2 concentration favouring aragonite over vaterite. C100 exhibits no calcium carbonates; instead, sodium carbonates form, including trona for 4% CO2 and natrite for both accelerated tests. C40S60 shows calcium and sodium carbonates, although to a lesser extent, containing predominantly calcite and minor signals of natrite. Suitable compositions, like C40S60, prove as effective during natural or accelerated carbonation tests as conventional Portland cement concrete.