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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. A particularly important role in this context is played by layered double hydroxides (LDHs), including AFm phases. Chloride binding isotherms of individual LDH/AFm phases would be required as input for computational models of chloride ingress, but such isotherms are only available for a few AFm phases, and in addition the available data are partly conflicting.
The present study, conducted in the context of RILEM TC 283-CAM ‘Chloride transport in alkali-activated materials’, significantly extends the available database by determining the chloride binding isotherms of LDH/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 chloride binding isotherms of LDH/AFm phases depended strongly on the liquid/solid ratio during the experiments, resolving apparent contradictions of the previously available data. The dependency on liquid/solid ratio must be attributed to kinetic restrictions, which are, however, currently poorly understood. Chloride binding by AAS pastes was generally higher than for Portland cement pastes and was only moderately influenced by the employed activator. A steep increase of the chloride binding by AAS occurred 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.
Portland cement is one of the principal sources of anthropomorphic CO2 emissions. It is estimated that cement production contributes up to 10% of greenhouse gas emissions and annual cement production over 4 billion tons. This has led to the development of a range of alkali activated materials (AAM), the most common precursor materials being class F fly ash and blast furnace slag. At present Class C Fly Ash is not widely utilized as an AAM due to the chemical composition and activation requirements. However, initial research on high Calcium German Class C Fly Ash suggests that the material may have potential for application as an AAM. This paper reports the development of ambient cured alkali activated mortar optimised by varying the alkali modulus and w/b ratio. The evolution of the mechanical and microstructural properties is reported over the initial 28 day period. Compressive strength in excess of 10 MPa at 7 days and 15 MPa at 28 days was achieved at ambient temperature. Similar strengths were observed for both 10% and 15% dosage but as dosage increases the optimal Alkali Modulus reduces.
Alkali-aktivierte Hüttensandbetone – CO2-reduzierte Bindemittel mit hohem Korrosionsschutzpotential
(2023)
Durch den Ersatz von Portlandzement können alkali-aktivierte Bindemittel einen bedeutenden Beitrag zur Verringerung der durch die Zementklinkerherstellung verursachten CO2-Emissionen leisten. Für die Verwendung von alkali-aktivierten Bindemitteln in Stahlbetonkonstruktionen, die Chloriden oder Carbonatisierung ausgesetzt sind, ist die Fähigkeit des Stahls, den passiven Zustand zu erreichen und aufrechtzuerhalten, von großer Bedeutung. Die Prozesse der Deckschichtbildung von Stahl in alkali-aktivierten Materialien unterscheiden sich jedoch zum Teil grundlegend von denen in Portlandzementen. Alkali-aktivierte Hüttensandbetone weisen gute technische Eigenschaften auf, bisher fehlen jedoch grundlegende Kenntnisse bzgl. ihrer schützenden Wirkung bei korrosiven Angriffen. Dies ist vor allem auf ihre sulfidhaltige Porenlösung zurückzuführen, welche die elektrochemischen Eigenschaften der Stahloberfläche beeinflusst und die Verwendung herkömmlicher Bewertungsmaßstäbe erschwert. Es werden erste Ergebnisse eines DFG-Forschungsprojektes vorgestellt, in dem das Passivierungsverhalten von Stahl in alkali-aktivierten Hüttensandmörteln unterschiedlicher Zusammensetzungen sowie in Mörteln auf Basis hüttensandhaltiger Normzemente untersucht wird. Über einen Zeitraum von mindestens 28 Tagen werden an Zylinderprüfkörpern im 3-Elektroden-Aufbau das Ruhepotential sowie die Polarisationswiderstände der Stahlelektroden ermittelt.
The RILEM TC 281–CCC "Carbonation of concrete with supplementary cementitious materials" is studying the effect of supplementary cementitious materials (SCMs) on natural and accelerated carbonation of blended cements. In this context a large database with carbonation depths over time has been set-up with currently 910 concrete and mortar mixes, which have been tested at different curing conditions. The collected data includes information on chemical composition and physical properties of the raw materials, on mix-design, compressive strength, curing and carbonation testing conditions. Data for a large variety of binders (with up to 94 % SCMs) and mix designs (with w/b ratios ranging from 0.26 to 0.75) were collected from the literature and unpublished material testing projects. Natural carbonation was recorded for several years in many cases, and indoor as well as outdoor results are included. However, in this contribution only lab conditions are considered. Carbonation kinetics are investigated considering the binder composition and mix design. Furthermore, the accuracy of accelerated carbonation testing is evaluated. As described in literature, the w/CaOreactive-ratio is a decisive factor for carbonation resistance but curing and exposure conditions influence the results as well. Even with identical test conditions, the scatter is very large.
Alkalisch aktivierte Bindemittel (AAB) und Betone können herkömmliche Zemente beziehungsweise Betone potentiell in vielen Anwendungen ersetzen und dadurch den CO2-Fußabdruck der Bauindustrie wesentlich verkleinern. Zur Untersuchung der Stahlkorrosion in bewehrten („armierten“) Betonbauteilen werden elektrochemische Methoden wie Messungen des Freien Korrosionspotentials, des Polarisationswiderstands oder von Stromdichte-Potential-Kurven eingesetzt. Diese Methoden und die etablierten Grenzwerte zur Detektion von Korrosion sind für die Anwendung bei herkömmlichen Zementen beziehungsweise Betonen entwickelt und erprobt worden. Neue Forschungsergebnisse demonstrieren, dass Unterschiede zwischen den Porenlösungszusammensetzungen von herkömmlichen Zementen und bestimmten AAB sowie anderen schlackehaltigen Zementen erhebliche Unterschiede bei den Ergebnissen der elektrochemischen Messungen bewirken und damit zur fehlerhaften Detektion von Stahlkorrosion führen können. Ursache hierfür sind vor allem reduzierte Schwefelspezies in den Porenlösungen von AAB und anderen schlackehaltigen Zementen.
The impact of high additions of vegetable oil (12 vol%) on the mechanical and microstructural properties of metakaolin-slag-based alkali-activated materials (AAMs) was studied. The addition of oil resulted in a slight decrease in initial polymerization kinetics but did not affect the final degree of reaction. AAM-oil-composite-mortars exhibited approximately ∼30% lower compressive strength primarily due to the entrainment of air voids. Newly formed soap phases significantly reduced the volume of small capillary and gel pores (pore radii <15 nm), leading to a decrease in specific inner surface area by a factor of up to 15. The porosity modification induced by the oil addition greatly enhanced the resistance of AAMs against sulfuric acid attack, shifting the dominant processes from diffusion and cracks to framework-dissolution controlled by the inherent phase stabilities. Following the immersion in sulfuric acid (pHstat = 2) for 8 weeks, the depth of corroded layer decreased by 70% and no cracks due to expansive phases were observed. These promising findings suggest that the incorporation of vegetable oil in AAMs has the potential to address durability concerns associated with diffusion-based corrosion processes, thereby expanding the range of future applications.
Ein zentrales Fundament moderner Gesellschaften ist eine intakte Abwasserinfrastruktur. Schäden infolge biogener Schwefelsäurekorrosion von konventionellen Betonen haben jedoch zu einem erheblichen Sanierungsbedarf geführt. Alkaliaktivierte Mörtel besitzen aufgrund eines hohen Säurewiderstands das Potential, einen Beitrag zur langfristigen Lösung dieses Problems zu leisten. Dazu müssen jedoch zunächst die Faktoren, die den Haftverbund zwischen diesen Mörteln und dem Betonsubstrat bestimmen, besser verstanden werden, um die Eigenschaften der Beschichtungssysteme gezielt anpassen und verbessern zu können. Die vorliegende Arbeit liefert hierzu einen Beitrag und zeigt dadurch Wege zu einer technisch machbaren und nachhaltigen Sanierung von Abwasserbauwerken auf.
The current ability to predict the carbonation resistance of alkali-activated materials (AAMs) is incomplete, partly because of widely varying AAM chemistries and variable testing conditions. To identify general correlations between mix design parameters and the carbonation rate of AAMs, RILEM TC 281-CCC 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 results show that the water/CaO ratio is not a reliable indicator of the carbonation rate of AAMs. A better indicator of the carbonation rate of AAMs under conditions approximating natural carbonation is their water/(CaO + MgOeq + Na2Oeq + K2Oeq) ratio, where the index ‘eq’ indicates an equivalent amount based on molar masses. This finding can be explained by the CO2 binding capacity of alkaline-earth and alkali metal ions; the obtained correlation also indicates an influence of the space-filling capability of the binding phases of AAMs, as for conventional cements. However, this ratio can serve only as an approximate indicator of carbonation resistance, as other parameters also affect the carbonation resistance of alkali-activated concretes. In addition, the analysis of the dataset revealed peculiarities of accelerated tests using elevated CO2 concentrations for low-Ca AAMs, indicating that even at the relatively modest concentration of 1% CO2, accelerated testing may lead to inaccurate predictions of their carbonation resistance under natural exposure conditions.
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.
This chapter aims to give a brief introduction into the field of alkali activated materials (AAM) and their physicochemical material behavior when exposed to sulfuric acid and in biochemically aggressive sewer environments. Additionally, the differences in material behavior within chemical (abiotic) and microbially induced acid environments are highlighted. Finally, existing data on overall performance of AAM, compared to conventional concrete-based building materials in sewer systems will be discussed.