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Paper des Monats
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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.
Future lunar exploration will be based on in-situ resource utilization (ISRU) techniques. The most abundant raw material on the Moon is lunar regolith, which, however, is very scarce on Earth, making the study of simulants a necessity. The objective of this study is to characterize and investigate the sintering behavior of EAC-1A lunar regolith simulant. The characterization of the simulant included the determination of the phase assemblage, characteristic temperatures determination and water content analysis. The results are discussed in the context of sintering experiments of EAC-1A simulant, which showed that the material can be sintered to a relative density close to 90%, but only within a very narrow range of temperatures (20–30 °C). Sintering experiments were performed for sieved and unsieved, as well as for dried and non-dried specimens of EAC-1A. In addition, an analysis of the densification and mechanical properties of the sintered specimens was done. The sintering experiments at different temperatures showed that the finest fraction of sieved simulant can reach a higher maximum sintering temperature, and consequently a higher densification and biaxial strength. The non-dried powder exhibited higher densification and biaxial strength after sintering compared to the dried specimen. This difference was explained with a higher green density of the non-dried powder during pressing, rather than due to an actual influence on the sintering mechanism. Nevertheless, drying the powder prior to sintering is important to avoid the overestimation of the strength of specimens to be fabricated on the Moon.
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.
The conversion of hydrated calcium aluminate cement (CAC) leads to an increase of its porosity which results in lower strength and higher permeability. Due to particular failures in the past, caused by conversion of CAC concretes, their use is sometimes considered to be not reliable. To evaluate the durability of converted CAC, pastes of two CACs were prepared at low w/c ratios (0.25 and 0.35), heated to 105 °C for 15 days and investigated by means of helium pycnometry, mercury porosimetry and nitrogen adsorption as well as by air permeability measurements. The results were compared to the pore structure properties and permeabilities of hardened Portland cement (OPC) pastes. At identical w/c, CAC pastes and OPC pastes exhibited similar open and total porosities. The threshold radii of the CAC pastes were about one order of magnitude greater while the hydraulic radii of their open pore system were smaller. The CAC pastes possessed somewhat smaller permeabilities than the OPC pastes and can thus be regarded as being as durable as the latter in this respect. From comparison of pore structure parameters and permeabilities it was furthermore concluded that significant pore structure damage occurs in the CAC pastes during mercury porosimetry measurements and therefore the measured threshold radii have to be considered as unreliable.
Alkali-activated fly ash mortars were studied with regard to durability-relevant transport coefficients and the electrochemical behaviour of embedded carbon steel bars on exposure of the mortars to leaching, carbonation and chloride penetration environments. The transport coefficients differed considerably between different formulations, being lowest for a mortar with BFS addition, but still acceptable for one of the purely fly ash-based mortars. Leaching over a period of ~300 days in de-ionized water did not lead to observable corrosion of the embedded steel, as shown by the electrochemical data and visual inspection of the steel. Exposure to 100 % CO2 atmosphere caused steel depassivation within approx. two weeks; in addition, indications of a deterioration of the mortar were observed. The results are discussed in the context of the different reaction products expected in high- and low-Ca alkali-activated binders, and the alterations caused by leaching and carbonation.
The current understanding of the carbonation of alkali-activated concretes is ham-pered inter alia by the wide range of binder chemistries used. To overcome some of the limitations of individual studies and to identify general correlations between their mix design parameters and carbonation resistance, the RILEM TC 281-CCC working group 6 compiled 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. A preliminary analysis of the database indicates that w/CaO ratio and w/b ratio exert an influence on the carbonation resistance of alkali-activated concretes but, contrary to what has been reported for concretes based on (blended) Portland cements, these are not good indicators of their carbonation resistance when considered individually. A better indicator of the carbonation resistance of alkali-activated concretes under conditions approxi-mating natural carbonation appears to be their w/(CaO + Na2O + K2O) ratio. Furthermore, the analysis points to significant shortcomings of tests at elevated CO2 concentrations for low-Ca alkali-activated concretes, indicating that even at a concentration of 1 % CO2, the outcomes may lead to inaccurate predictions of the carbonation coefficient under natural exposure conditions.
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.
A silica residue from waste treatment of chlorosilane production was used together with solid sodium aluminate to test its applicability for the production of one-part geopolymers. The blend was activated with water and cured at 70 °C. The degree of reaction and strength were determined after 1, 3, and 7 days. The reaction products were analyzed by XRD and SEM/EDX. Until the third day of curing the degree of reaction of the residue reached 51 % and the strength was 8.9 MPa. The reaction product was identified as geopolymer containing zeolite A. Thus, the results confirmed that the residue may be used in the production of geopolymers. However, after 3 days of curing no further progress of reaction was observed and the strength slightly decreased, which was attributed to changes in the structure of the geopolymeric gel. It was further observed that even harsh vacuum drying left some water (presumably zeolitic water and surface hydroxyl groups) in the geopolymer.
Reaction products and strength development of wastepaper sludge ash and the influence of alkalis
(2014)
Wastepaper sludge ash (WSA) from a newsprint paper mill was investigated for its mineralogical composition and its reaction products and strength development after activation with water and sodium and potassium hydroxide solutions. The results showed the WSA to consist of calcite, free lime, gehlenite, tricalcium aluminate, belite, talc, quartz and probably a glassy phase. The principle reaction product was monocarboaluminate (CO3–AFm) for the water- as well as for the alkali-activated WSA. Formation of monocarboaluminate and strength gain was more rapid for the alkali-activated WSA until 1 day of curing. However, afterwards reactions proceeded much slower when alkali solutions were used, leading to an about twice as high compressive strength for water-activated WSA mortars after 28 days of curing. The observed behavior is tentatively ascribed to a less uniform microstructure of the alkali-activated WSA. Significant differences between NaOH- and the KOH-activated WSA were not observed.
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.
Two fly ash-based geopolymer concretes with quartz aggregates or with expanded clay (lightweight) aggregates were exposed to the ISO 834-1 standard fire curve in a small-scale fire test set-up. Acoustic emission measurements during fire exposure and subsequent cooling were employed to study spalling events and cracking during the tests. Optical microscopy and additional acoustic measurements were conducted after the testing to better understand the crack propagation in the samples. The testing revealed that neither of the concretes were susceptible to spalling, which is particularly notable for the concrete with quartz aggregates, as it is a high-strength concrete. This behavior is attributed to the relatively high permeability of the concretes and their low amount of chemically bound water. Significant crack formation was detected only around the temperature of the alpha–beta quartz transition (573 °C) and on cooling. Because of aggregate deformations at the quartz transition temperature, deterioration after heating was more significant in the geopolymer concrete with quartz aggregates. Crack formation also occurred in the concrete with expanded clay aggregates, caused by shrinkage of the geopolymer paste on cooling. Acoustic emission measurements proved to be a valuable tool to investigate processes during high temperature exposure.
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 aluminosilicate gel-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 aluminosilicate gel-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 composites, exhibit high resistance to sulfuric acid attack, making them promising materials for the construction and the repair of industrial and sewer structures.
Diffusional gas transport of a H2/CO2 mixture versus N2 in the pore system of hardened cement pastes was studied at four temperatures up to 350 °C in a Wicke-Kallenbach cell. The pastes possessed separation factors αH2,CO2 from 1.42 to 3.43, i.e. the diffusion of hydrogen took place considerably faster than the diffusion of carbon dioxide. The separation factors depended on the threshold radii of the pastes, smaller threshold radii leading to higher separation factors. The Knudsen numbers of the controlling constrictions of the pore system and the temperature dependence of the effective diffusion coefficients of the gases show that gas transport in these constrictions takes place in the transient regime between Knudsen diffusion and bulk diffusion, smaller constriction widths leading to predominating Knudsen diffusion. It is therefore possible to use cement paste membranes to separate gas components of low molecular weight from higher weight components.
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.
Geopolymer-zeolite composites were synthesized using a silica-rich industrial byproduct from chlorosilane production and sodium aluminate. Pastes were cured at 80 °C and 80% RH, and subsequently dried in two different climates: at 23 °C and 50% RH, and under vacuum. 1H MAS, 23Na MAS and 29Si MAS NMR and XRD measurements were performed after the drying procedures as well as after subsequent aging. Zeolite Na-A was found beside traces of faujasite-type zeolite and zeolite EMT as major crystalline phases in the cured composites; the fraction of geopolymeric gel in the reaction products was determined to be ~18% on a molar basis. Various water species could be distinguished using 1H MAS and 1H-29Si CP MAS NMR, applying rotorsynchronized echo experiments. The largest fraction of the pore water resides in the α-cages of the zeolite Na-A and in the geopolymeric gel; in addition, water exists in the β-cages of the zeolites and adsorbed at sodium ions. The water species in α-cages and in the pores of the geopolymeric gel exhibit slightly different chemical shifts of 4.7 ppm and 4.9 ppm, respectively, in the 1H MAS NMR spectra. Changes of the water content in the geopolymer pores of differently dried samples were observed and led to slightly varied chemical shifts in the 29Si MAS NMR spectra too. Measurements after more than 500 days revealed no significant aging effects of the composites, which confirm their chemical stability.
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.
Hybrid cements are composites made of Portland cement or Portland clinker and one or more supplementary cementitious materials like slag, fly ash or metakaolin, activated with an alkali salt. To date, their hydration mechanism and the phase formation at various temperatures is insufficiently understood, partly due to the large variability of the raw materials used. In the present study, three hybrid cements based on ground granulated blast furnace slag, fly ash, Portland clinker and sodium sulfate, and an alkali-activated slag/fly ash blend were cured at 10 and 21.5°C, and subsequently analyzed by XRD, 27Al MAS NMR, and TGA. The compressive strength of the hybrid cements was higher by up to 27% after 91-day curing at 10°C, compared to curing at 21.5°C. The experimental results as well as thermodynamic modeling indicate that the differences in compressive strength were related to a different phase assemblage, mainly differing amounts of strätlingite and C-N-A-S-H, and the associated differences of the volume of hydration products. While the strätlingite was amorphous to X-rays, it could be identified by 27Al MAS NMR spectroscopy, TGA and thermodynamic modeling. The microstructural properties of the hybrid cements and the alkali-activated slag/fly ash blend as well as the compatibility between thermodynamic modeling results and experimental data as a function of curing temperature and time are discussed.
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.