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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.
Knowledge of the durability and related properties of alkali-activated materials is a prerequisite for their application as building materials. However, to date only limited data exists in this regard. The present contribution focuses on durability-related transport properties of geopolymer-based materials. We present results of accelerated carbonation, rapid chloride migration (RCM) and air permeability measurements, together with strength and porosity data, for fly ash-based geoplymers, including formulations containing ground granulated blast furnace slag (GGBFS).
It was found that, 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. Thus, there exists no simple correlation between air permeability (of harshly dried mortars) and durability-related transport coefficients for the studied alkali-activated materials.
In addition, corrosion potential, polarization resistance data and current density-potential curves of carbon steel in two of the geopolymer mortars are presented. 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.
Alkali-activated materials such as geopolymers are currently receiving a lot of attention because of their potential to be used as binders for concrete with advantageous engineering properties and reduced manufacturing CO2 emissions. Knowledge of the durability of steel in these concretes and related properties of alkali-activated materials is a prerequisite for their application as building materials, if they are to be used for steel reinforced elements. However, to date only limited data exists on this topic. The present contribution focuses on durability-related transport properties of geopolymer-based mortars (as model systems for concrete). We report results of accelerated carbonation, rapid chloride migration (RCM) and air permeability measurements as well as porosity data 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. Thus, there exists no simple correlation between air permeability (of harshly dried mortars) and durability-related transport coefficients for the studied alkali-activated materials.
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; possible reasons for this behavior are discussed.
Mixing and curing of geopolymers and related alkali-activated materials without storage and handling of highly alkaline solutions possesses advantages regarding safety and economic viability; one possible approach is to produce these materials from solid silica feedstocks and solid sodium aluminate, and subsequent mixing with water. We present a comparison between geopolymers and geopolymer-zeolite composites synthesized by this route from different silica feedstocks (by-product silica from chlorosilane production, microsilica, rice husk ash) and with different SiO2/Al2O3 ratios, using results from XRD, NMR, SEM, thermal analysis, mechanical and acid resistance testing. The use of rice husk ash favors formation of a fully amorphous geopolymer with high strength. Utilization of the other silica feedstocks leads to formation of geopolymer-zeolite composites, the amount and kind of zeolites depending on the feedstock and the SiO2/Al2O3 ratio. These composites show beneficial dehydration behavior, viz. no distinct dehydration step of thermal strain, with the phase assemblage after heating to 1000 °C controlled by the starting composition. Mortars produced from both, the geopolymers as well as the compo¬sites, exhibit high resistance to sulfuric acid attack, making them promising materials for the construction and the repair of industrial and sewer structures.
One-part geopolymers (OPGs) are a sort of alkali-activated materials (AAMs) which production avoids the use of highly-alkaline activator-solutions and contributes to a better acceptance of alternative mineral binders in terms of safety-related and economic aspects. In the present contribution OPGs were synthesized by blending silica sources (two industrial silicas and two biogenic silicas) with sodium aluminate and only water must be added to initiate the hardening, i.e. mixing is performed in the same way as for conventional Portland cements. The OPGs were characterized by XRD, and SEM and the degrees of reaction of the silicas were determined by a chemical dissolution method.
The industrial silicas led to the formation of geopolymer-zeolite composites, that contained, besides geopolymeric gel, crystalline tectosilicates (e.g. zeolite A and hydrosodalite) and depending on the starting composition also unreacted silica. The biogenic silicas provided a higher reactivity and avoided the formation of crystallite by-products. The differences in the microstructures caused differences in the mechanical strength of the specimens.
The treatment of the OPG composites at moderate elevated temperatures revealed promising behavior on thermal dehydration in terms of shrinkage and residual strength up to 700 °C. Above 700 °C sintering and partial melting occurred, and new phase formation commenced. After exposure to 1000 °C the specimens appeared virtually amorphous or formed stuffed silica structures of nepheline- or carnegieite-type type.
The investigations of the OPG based mortars on their resistance against sulfuric acid in accordance with DIN 19573 (Appendix A) revealed very high residual strengths up to 78 % after treatment with H2SO4 (pH 1) for 70d. A mechanism of dissolution of the primary aluminosilicate reaction products of the pastes and the precipitation of a silica gel that protects the remaining aluminosilicates and decelerates further corrosion was found to be the main reason for the good performance under acidic conditions. The addition of CaO-containing feedstocks enhanced hardening, but at a certain content the resistance against sulfuric acid decreased, due to the formation of gypsum on exposure to sulfate.
In addition, the mortars exhibited excellent shrinkage behavior as well as good bond to concrete substrates with pull-off strength up to > 3 MPa. The workability of the fresh mortars provided very good manual applicability; automatic applications such as sprayed and spun mortars will require further optimization regarding rheological properties. In summary, the studied OPG are promising materials for the construction and the repair of concrete structures, such as sewers, that are affected by biogenic sulfuric acid corrosion.
Materials with a high acid resistance are required in different important infrastructures. Examples include repair systems for sewer structures, where biogenic sulfuric acid corrosion is the major degradation mechanism. Low-calcium alkali-activated materials (AAMs) have been repeatedly observed to exhibit high acid resistance. However, the reasons for the high acid resistance of these materials were not fully under¬stood until recently, and the use of highly alkaline activator solutions to produce AAMs appears to hamper their commercial uptake. These issues have been tackled by characterising one-part AAMs and studying their alteration when exposed to sulfuric acid.
One-part AAMs were synthesized by mixing blends of solid silica and sodium aluminate with water, and subsequent curing at 60–80 °C. Acid resistance testing was performed according to DIN 19573, i.e. exposure to sulfuric acid at pH = 1 for 70 days. Characterisation of the cured and the acid-exposed materials was done by XRD, ATR-FTIR, SEM as well as 29Si, 27Al and 1H MAS NMR spectroscopy, including cross-polarisation and double-resonance methods.
Materials synthesized from industrial silicas were gel-zeolite composites, containing a substantial amount of unreacted ‘excess’ silica, while materials synthesized from rice husk ash were fully amorphous, containing ‘excess’ hydrous alumina. The sulfuric acid resistance of mortars based on these binders conformed to the requirements of DIN 19573 for sewer repair applications. The high acid resistance was caused by precipitation of silica gel at the mortar–solution interface, inhibiting further degradation. The presence of alumina gel may inhibit bacterial activity, potentially further improving performance in sewer environments.
The phase assemblage of silica/sodium aluminate-based one-part AAMs can be adjusted via choice of the silica starting material. Properly designed materials exhibit excellent acid resistance, caused by precipi¬tation of silica gel which protects subjacent regions, and they may also inhibit bacterial activity.
Alkali-activated materials are ideal for the repair of concrete structures in harsh environmental conditions due to their high durability in chemically aggressive environments. However, slag-based mortars, in particular, are prone to shrinkage and associated cracks. In this respect, the application of steel fibres is one solution to reduce the formation of shrinkage induced cracks and to improve post cracking behaviour of these mortars. This study investigated the influence of two different types of steel fibres on the tensile properties of two alkali-activated mortars. Direct tensile tests and single fibre pull-outs were performed to analyse the determining failure modes both on macro and micro scale. Mechanical testing was accompanied by non-destructive testing methods such as digital image correlation and acoustic emission for a detailed analysis of the fracture process.
Mortars for application on concrete, e.g. repair mortars or protective coatings, need to have a durable bond to the substrate. This bond is determined by the adhesion between the two materials and by the differential deformations of the mortar and the substrate. In the present contribution, the hygric deformations (shrinkage/expansion) of novel one-part alkali-activated mortars and their bond to concrete substrates are studied. Shrinkage of the mortars was studied at 50 % r.H., while expansion was studied on mortars stored over an open water surface (> 99% r.H.). The bond behaviour was studied by pull-off tests according to DIN EN 1542 and by optical microscopy.
The alkali-activated mortars exhibit hygric deformations much lower than the deformations of an established, commercial mortar for sewer maintenance that was tested as reference in parallel with the alkali-activated mortars. The bond behaviour of the alkali-activated mortars depends strongly on their mix-design and curing. Optical microscopy showed that in the mortars with lower bond strength, cracks developed in the mortar during curing. Mortars with appropriate mix-design and curing did not exhibit cracking, and their pull-off strength (up to > 3 MPa) conformed to the requirements of relevant standards.
Corrosion of steel reinforcement in concrete is one of the major deterioration mechanisms limiting the service life of reinforced concrete structures. While for conventional (Portland cement-based) concretes a great amount of experience exists in this regard, the factors that determine the onset of reinforcement corrosion in alkali-activated materials are incompletely understood yet.
One aspect of corrosion protection is leaching and the accompanying changes of the concrete pore solution. In the present study, alkali-activated fly ash mortars with embedded carbon steel rebars were exposed to de-ionised water for periods up to 330 days, and the electrochemical response of the steel (free corrosion potential, polarisation resistance), the alteration of the mortar (ohmic resistance, mechanical strength, pore size distribution) as well as the pore solu¬tion composition were monitored.
Although substantial alkali leaching was observed, the pH of the pore solution remained at values sufficient to protect the embedded steel from depassivation. The mortar did not exhibit indications of significant deterioration. Thus, the present results suggest that leaching is not critical for pro¬tec¬tion of steel reinforcement in alkali-activated fly ash mortars and concretes.
Alkali-activated materials have been repeatedly reported to exhibit high acid resistance, but no generally accepted hypothesis regarding the underlying mechanisms has emerged yet. To contribute to this issue, K-waterglass-activated metakaolin specimens, with and without the addition of CuSO4·5H2O in the starting mix, were exposed to either a chemically aggressive sewer environment (mortars) or sulfuric acid (pastes). The mode of copper incorporation in the materials and the formation of copper phases in the corroded layers were studied by XANES at the Cu K-edge, and 29Si, 27Al and 1H MAS NMR was employed to understand the processes during acid attack. Copper was found as a spertiniite-like phase in the as-cured materials, while in the deterioration layers of the pastes it was present as copper sulfate. In the corroded regions of the mortars, unequivocal identification of Cu phases was not possible, but the results were reconcilable with the presence of copper carbonate hydroxide. The solid-state NMR results revealed virtually complete dissolution of the K-A-S-H gel and the formation of silica gel, interpreted to be a central mechanism determining the acid resistance. No significant differences between the microstructural alterations of the pastes with and without Cu addition on (chemical) sulfuric acid attack were observed.