Filtern
Dokumenttyp
- Zeitschriftenartikel (18) (entfernen)
Sprache
- Englisch (18)
Schlagworte
- Alkali-activated materials (18) (entfernen)
Organisationseinheit der BAM
Paper des Monats
- ja (2)
Alkali-activated fly ashes have been proposed for various applications where resistance against high temperatures is required, yet several details regarding the response of these materials to heat-exposure need to be clarified. In the present study, heat-induced cracking in fly ash-based alkali-activated pastes and lightweight mortars was analyzed by in-situ acoustic emission (AE) detection during complete heating-cooling cycles (up to ∼1100 °C), augmented by thermogravimetry and ex-situ SEM and XRD analyses. The applicability of the lightweight mortars as passive fire protection coatings was assessed by recording temperature-time curves of mortar-coated steel plates. Cracking during heating was limited and associated exclusively with the dehydration of the materials in the temperature range ∼90–360 °C. However, samples heated to temperatures above ∼600 °C exhibited intense cracking on cooling. This was attributed to differential deformations caused by local sintering and partial melting at the glass transition temperature, and subsequent quenching on cooling.
Many standardised durability testing methods have been developed for Portland cement-based concretes, but require validation to determine whether they are also applicable to alkali-activated materials. To address this question, RILEM TC 247-DTA ‘Durability Testing of Alkali-Activated Materials’ carried out round robin testing of carbonation and chloride penetration test methods, applied to five different alkali-activated concretes based on fly ash, blast furnace slag or metakaolin. The methods appeared overall to demonstrate an intrinsic precision comparable to their precision when applied to conventional concretes. The ranking of test outcomes for pairs of concretes of similar binder chemistry was satisfactory, but rankings were not always reliable when comparing alkali-activated concretes based on different precursors. Accelerated carbonation testing gave similar results for fly ash-based and blast furnace slag-based alkali-activated concretes, whereas natural carbonation testing did not. Carbonation of concrete specimens was observed to have occurred already during curing, which has implications for extrapolation of carbonation testing results to longer service life periods. Accelerated chloride penetration testing according to NT BUILD 443 ranked the tested concretes consistently, while this was not the case for the rapid chloride migration test. Both of these chloride penetration testing methods exhibited comparatively low precision when applied to blast furnace slag-based concretes which are more resistant to chloride ingress than the other materials tested.
Chloride contents at the steel–mortar interface that initiate steel corrosion were determined for carbon steel in alkali‐activated fly ash mortar for three different exposure conditions: exposure to 1 M NaCl solution; leaching in deionized water and then exposure to 1 M NaCl solution; and leaching in deionized water, aging in air at 20°C and natural CO2 concentration, and then exposure to 1 M NaCl solution. For comparison, a Portland cement mortar, exposed to 1 M NaCl solution, was studied. The median values of the corrosion‐initiating chloride contents (average over the full length of the rebar) in the alkali‐activated fly ash mortar varied between 0.35 and 1.05 wt% Cl with respect to binder, consistently lower than what was obtained for the Portland cement mortar, but with no clear trend regarding the exposure conditions. For most of the alkali‐activated fly ash mortar specimens, preferential corrosion at the connection between the working electrode and the external measurement setup was observed, while preferential corrosion did not occur for the Portland cement mortar. Scanning electron microscopy and auxiliary experiments in synthetic solutions indicated that this behavior was caused by inhomogeneities at the steel–mortar interface in the alkali‐activated mortar, likely due to its peculiar rheological properties in the fresh state.
Cementitious materials are frequently applied in environments in which they are exposed to acid attack, e.g., in sewer systems, biogas plants, and agricultural/food-related industries. Alkali-activated materials (AAMs) have repeatedly been shown to exhibit a remarkably high resistance against attack by organic and inorganic acids and, thus, are promising candidates for the construction and the repair of acid-exposed structures. However, the reaction mechanisms and processes affecting the acid resistance of AAMs have just recently begun to be understood in more detail. The present contribution synthesises these advances and outlines potentially fruitful avenues of research. The interaction between AAMs and acids proceeds in a multistep process wherein different aspects of deterioration extend to different depths, complicating the overall determination of acid resistance. Partly due to this indistinct definition of the ‘depth of corrosion’, the effects of the composition of AAMs on their acid resistance cannot be unambiguously identified to date. Important parallels exist between the deterioration of low-Ca AAMs and the weathering/corrosion of minerals and glasses (dissolution-reprecipitation mechanism). Additional research requirements relate to the deterioration mechanism of high-Ca AAMs; how the character of the corroded layer influences the rate of deterioration; the effects of shrinkage and the bond between AAMs and substrates.
The current understanding of the carbonation and the prediction of the carbonation rate of alkali-activated concretes is complicated inter alia by the wide range of binder chemistries used and testing conditions adopted. To overcome some of the limitations of individual studies and to identify general correlations between mix design parameters and carbonation resistance, the RILEM TC 281-CCC ‘Carbonation of Concrete with Supplementary Cementitious Materials’ Working Group 6 compiled and analysed carbonation data for alkali-activated concretes and mortars from the literature. For comparison purposes, data for blended Portland cement-based concretes with a high percentage of SCMs (≥ 66% of the binder) were also included in the database. The analysis indicates that water/CaO ratio and water/binder ratio exert an influence on the carbonation resistance of alkali-activated concretes; however, these parameters are not good indicators of the carbonation resistance when considered individually. A better indicator of the carbonation resistance of alkali-activated concretes under conditions approximating natural carbonation appears to be their water/(CaO + MgOeq + Na2Oeq + K2Oeq) ratio, where the subscript ‘eq’ indicates an equivalent amount based on molar masses. Nevertheless, this ratio can serve as approximate indicator at best, as other parameters also affect the carbonation resistance of alkali-activated concretes. In addition, the analysis of the database points to peculiarities of accelerated tests using elevated CO2 concentrations for low-Ca alkali-activated concretes, indicating that even at the relatively modest concentration of 1% CO2, accelerated testing may lead to inaccurate predictions of the carbonation resistance under natural exposure conditions.
Chloride binding by the hydrate phases of cementitious materials influences the rate of chloride ingress into these materials and, thus, the time at which chloride reaches the steel reinforcement in concrete structures. Chloride binding isotherms of individual hydrate phases would be required to model chloride ingress but are only scarcely available and partly conflicting. The present study by RILEM TC 283-CAM ‘Chloride transport in alkali-activated materials’ significantly extends the available database and resolves some of the apparent contradictions by determining the chloride binding isotherms of layered double hydroxides (LDH), including AFm phases (monosulfate, strätlingite, hydrotalcite, and meixnerite), and of alkali-activated slags (AAS) produced with four different activators (Na2SiO3, Na2O·1.87SiO2, Na2CO3, and Na2SO4), in NaOH/NaCl solutions at various liquid/solid ratios. Selected solids after chloride binding were analysed by X-ray diffraction, and thermodynamic modelling was applied to simulate the phase changes occurring during chloride binding by the AFm phases. The results of the present study show that the chloride binding isotherms of LDH/AFm phases depend strongly on the liquid/solid ratio during the experiments. This is attributed to kinetic restrictions, which are, however, currently poorly understood. Chloride binding by AAS pastes is only moderately influenced by the employed activator. A steep increase of the chloride binding by AAS occurs at free chloride concentrations above approx. 1.0 M, which is possibly related to chloride binding by the C–(N–)A–S–H gel in the AAS.
The influence of starting materials and synthesis route on the properties and the structure of cementitious sodium aluminosilicate gels is not fully understood, partly due their amorphous nature and the fact that they often contain residual reactants, which can make the results of single-pulse NMR spectroscopy applied to these materials difficult to interpret or ambiguous. To overcome some of these limitations, 29Si{27Al} TRAPDOR NMR as well as 27Al{29Si} and 27Al{1H} REDOR NMR spectroscopy were applied to materials synthesized by the one-part alkali-activation route from three different amorphous silica starting materials, including rice husk ash. The latter led to formation of a fully amorphous sodium aluminosilicate gel (geopolymer), while the materials produced from the other silicas contained amorphous phase and crystalline zeolites. Application of the double-resonance NMR methods allowed to identify hydrous alumina gel domains in the rice husk ash-based material as well as significantly differing amounts of residual silica in the three cured materials. Four-coordinated Al existed not only in the aluminosilicate gel framework but also in a water-rich chemical environment with only a small amount of Si in proximity, likely in the alumina gel or possibly present as extra-framework Al in the aluminosilicate gel. The results demonstrate how the employment of different silica starting materials determines the phase assemblage of one-part alkali-activated materials, which in turn influences their engineering properties such as the resistance against chemically/biologically aggressive media.
In this study, a multi-proxy approach combining 29Si, 27Al and 1H MAS-NMR, FEG-EPMA, XANES at the Cu K-edge and XRD analytics with hydrochemical tools such as ICP-OES analyses, oxygen-isotope signatures, and thermodynamic modelling was applied to K-silicate-activated metakaolin specimens - with and without CuSO4·5H2O addition - exposed to sulfuric acid at pH = 2 for 35 days. The results revealed a multistage deterioration mechanism governed by (i) acid diffusion, (ii) leaching of K-A-S-H, (iii) microstructural damage related to precipitation of expansive (K,Ca,Al)-sulfate-hydrate phases (iv) complete dissolution of the K-A-S-H framework, (v) and formation of silica gel in the outermost corroded regions. Copper ions were mainly located in layered spertiniite-chrysocolla-like phases in the as-cured materials. The results demonstrate an overall negative effect of Cu addition on chemical material durability, implying that the reported higher durability of Cu-doped AAM in biocorrosion environments can be best explained by bacteriostatic effects.
Metakaolin-based alkali activated mortars (AAM) - with and without CuSO4·5H2O and ZnO addition (mass ratio Mn+/solid binder 0.08% to 1.7%) - were casted and exposed within an extensive long-term field campaign over the period of 20 months to a sewer basin, strongly affected by biogenic acid corrosion. (Un-)exposed AAM were tested regarding their physicochemical and microstructural properties, bioreceptivity and overall durability. Metal addition led to a retarding effect during alkali-activation reaction, as well as to an increase in open porosity of up to 3.0% and corresponding lower compressive strength of up to 10.9%. Reduced microbial colonization and diversity were observed on AAM with Cu, while Zn addition led to increased biodiversity. We propose that the observed higher durability of Cu-doped AAM is due to antibacterial effects and associated reduction of biogenic acid production, superseding overall negative effects of metal-dosage on physical material properties. Observed lower durability of Zn-doped AAM was related to combined negative physicochemical and microbial effects.
Two hybrid alkaline cements (HAC) based on Portland clinker, ground granulated blast furnace slag (GGBFS), fly ash and sodium sulfate, as well as an alkali-activated GGBFS/fly ash blend and a Portland cement paste were exposed to a saturated saline solution for 70 days. The combined chemical attack of chloride, magnesium and sulfate ions and the associated changes of the phase assemblage of the materials were studied by X-ray diffraction, thermal analysis and spatially resolved X-ray fluorescence spectroscopy. The experimental results revealed dissolution of ettringite, C-N-A-S-H and calcite, and the formation of gypsum, Kuzel's salt and Friedel's salt; thermodynamic modeling indicated the formation of M-S-H. The resistance of the HAC against attack by the saline solution increased with Portland clinker fraction. The capacity of portlandite to maintain pH at values above 10 is found to be a major factor controlling the resistance of HAC against corrosion in the saline solution.