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Die Hauptfunktion von Verschlussbauwerken für End- und Zwischenlager von radioaktiven Abfällen besteht in der Erhaltung der geologischen Barriere. Vor allem soll ein potenzieller Stofftransport durch eine möglichst geringe Permeabilität des Bauwerks verhindert bzw. auf vernachlässigbare Werte herabgesetzt werden. Die in-situ-Permeabilität des Verschlussbauwerks steht dabei in direktem Zusammenhang mit dessen Poren- und Makrostruktur, welche bei Bauwerken auf Basis von Beton insbesondere durch Schwind-verformungen und durch thermisch induzierte Rissbildung infolge der Reaktionswärmeentwicklung des Bindemittels gestört werden kann. Die Betone müssen daher neben einer hohen chemischen Langzeitstabilität auch eine geringe bzw. langsame Wärmeentwicklung während der Erhärtungsreaktionen aufweisen. Als hybride Zemente werden Mischungen aus Portlandzement, Betonzusatzstoffen und einem alkalischen Aktivator bezeichnet. Dabei können u. a. Alkalisulfate, Alkalicarbonate, Alkalisilicate und Alkalihydroxide als Aktivatoren zum Einsatz kommen. Aufgrund ihrer hohen chemischen Stabilität im salinaren Milieu sind Betone aus solchen Zementen potenziell besonders gut als Verfüllmaterial für End- und Zwischenlager im Steinsalz geeignet. In der vorliegenden Studie wurden daher hybride Zemente hinsichtlich ihrer Wärmeentwicklung in einem isothermen Kalorimeter sowie hinsichtlich Phasenbestand und Festigkeiten untersucht. Hybride Zementleime wurden auf Basis von Portlandklinker, Hüttensandmehl, Flugasche und Natriumsulfat hergestellt und die Zusammensetzungen systematisch variiert, um den Einfluss der Komponenten auf Wärmeentwicklung, Phasenbestand und mechanische Eigenschaften der Leime zu untersuchen; zusätzlich wurden zu Vergleichszwecken ein Zementleim auf Basis der Betonrezeptur M2 sowie eine alkalisch aktivierte Flugasche untersucht.
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.
This contribution presents the results of structural and compressive strength investigations on cured andhigh-temperature treated silica-based one-part geopolymer-zeolite composites. The specimens weresynthesized from two different silica sources, sodium aluminate and water. The phase content as well asthe compressive strength of the cured composites varied depending on the starting mix-design and thesilica feedstock. Besides geopolymeric gel, A-type zeolites and hydrosodalites were the major reactionproducts. One of the silica feedstocks yielded significantly higher compressive strength (19 MPa), whilethe other one appears to cause less variation in phase content. Strength testing indicated an improvementon heating up to
200–400 °C (28 MPa) followed by a moderate decrease up to 700 °C. Above 700 °C the sys-tems underwent new phase formation and shrinkage (volume decrease) deformations. After exposureat 1000 °C the different mixes consisted of a mix of several stuffed silica phases, almost pure hexago-nal nepheline or amorphous phase. Depending on the mix-design, the onset temperature of the hightemperature phase transformations varied.
One-part geopolymers offer advantages over conventional geopolymers with regard to handling and storage of feedstocks. However, they often suffer from a low degree of reaction, a high amount of crystalline byproducts, and consequently low strength. In this study, one-part geopolymers were produced from rice husk ash (RHA) and sodium aluminate, and investigated by XRD, ATR-FTIR, SEM and compressive strength testing. The compressive strength of the material was 30 MPa, i.e. significantly higher than for comparable one-part geopolymers. This is attributed to an almost complete reaction of the RHA and the absence of crystalline byproducts (zeolites) in the hardened geopolymer.
One-part alkali-activated (geopolymer) mortars based on three different silica-rich starting materials and sodium aluminate, with and without ground granulated blast furnace slag (GGBFS) addition, were tested regarding sulfuric acid resistance according to DIN 19573:2016-03 (70 days at pH = 1). Corresponding pastes were characterized by XRD, SEM, chemical analysis, 29Si MAS NMR and 1H-29Si CPMAS NMR after water storage and after acid exposure. The mortars exhibited a high resistance against sulfuric acid attack, with the best ones conforming to the requirements of DIN 19573:2016-03. The analytical results showed that this was due to precipitation of silica gel at the acid-mortar interface, which formed a mechanically stable layer that protected the subjacent mortar and thus inhibited further degradation. The addition of GGBFS decreased the acid resistance via formation of expansive calcium sulfate phases.
Geopolymers are promising alkali activated materials with a wide range of possible applications like heat-resistant coatings and adhesives or concretes with lower C02 emissions than conventional Portland cement-based systems. Conventional ("two-part") geopolymers are synthesized by an activation of aluminosilicate feedstocks like metakaolin or blast furnace slags with highly alkaline solutions like sodium hydroxide solutions and/or water glass solutions.
A more recent approach are so called one-part geopolymers, where the alkaline activator is provided in solid form, so that only water has to be added to initiate the geopolymerisation reaction. The handling of alkaline solutions is avoided, which possesses several advantages compared to conventional geopolymers, in particular regarding safety and health issues, and, thus, it improves economic and social acceptance of these binders. However, the new formulations are less exhaustively studied and the knowledge about conventional geopolymers cannot simply be transferred to this new class of binders.
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.
Within the project SealWasteSafe, we advance construction materials and monitoring concepts of sealing structures applied for underground disposal of nuclear or toxic waste. As these engineered barriers have high demands concerning integrity, an innovative alkali-activated material (AAM) is improved and tested on various laboratory scales. This AAM has low reaction kinetics related to a preferential slow release of the heat of reaction in comparison to alternative salt concretes based on Portland cement or magnesium oxychloride cements. Hence, crack formation due to thermally induced strain is reduced. After successful laboratory scale analysis (Sturm et al., 2021), the AAM is characterised on a larger scale by manufacturing test specimens (100–300 L).
Conventional salt concrete (DBE, 2004) and the newly developed AAM are compared using two specimen geometries, i.e. cylindrical and cuboid. A comprehensive multisensor monitoring scheme is developed to compare the setting process of AAM and salt concrete for these manufactured specimens. The analysed parameters include temperature and humidity of the material, acoustic emissions, and strain variations. Passive sensor systems based on radiofrequency identification technology (RFID) embedded in the concrete, enable wireless access to temperature and humidity measurements and are compared to conventional cabled systems. Additionally, fibre-optic sensors (FOS) are embedded to record strain, but also have potential to record temperature and moisture conditions. Part of this project aims at demonstrating the high reliability of sensors and also their resistance to highly alkaline environments and to water intrusion along cables or at sensor locations. Further technical improvements were implemented so that first results clearly show the scalability of the setting process from previous small-scale AAM experiments and particularly the high potential of the newly developed approaches.
Furthermore, ultrasonic methods are used for quality assurance to detect obstacles, potential cracks and delamination. On the one hand, both active and passive ultrasonic measurements complement the results obtained from the multisensor monitoring scheme for the produced specimens. On the other hand, the unique large aperture ultrasonic system (LAUS) provides great depth penetration (up to nearly 10 m) and can thus be applied at in situ sealing structures built as a test site in Morsleben by the Federal Company for Radioactive Waste Disposal (Bundesgesellschaft für Endlagerung, BGE) as shown by Effner et al. (2021). An optimised field lay-out identified from forward modelling studies and advanced imaging techniques applied to the measured data will further improve the obtained results. To characterise the inside of the test engineered barrier and achieve a proof-of-concept, an ultrasonic borehole probe is developed to enable phased arrays that can further improve the detection of potential cracks. Modelling results and first analysis of semispherical specimens confirmed the reliability of the directional response caused by the phased arrays of the newly constructed ultrasonic borehole probe.
Overall, the project SealWasteSafe improves the construction material, multisensor monitoring concepts and ultrasonics for quality assurance. This will help to develop safe sealing structures for nuclear waste disposal. The outcomes are particularly valuable for salt as a host rock but partly also transferrable to alternative conditions.
Properties of alkali-activated mortars with salt aggregate for sealing structures in evaporite rock
(2021)
Concrete structures for sealing of tunnels in the host rock are an essential part of systems for nuclear waste storage. However, concretes based on blended cements or magnesium oxychloride cements, which are commonly considered for this application, can deteriorate severely due to a significant heat of hydration and associated deformation and cracking. Alkali-activated materials (AAMs) offer a potential solution to this problem because of their low heat release during hardening. To explore their suitability for the construction of sealing structures in evaporite rock, various AAMs with salt aggregate were studied regarding fresh properties, heat release, mechanical properties and microstructure. The heat of reaction of the AAMs was up to 55% lower than that of a blended cement designed for sealing structures, indicating significant benefits for the intended application. Other relevant properties such as mechanical strength and permeability depended strongly on the mix-design of the AAMs and curing conditions.
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.
Multi-sensory monitoring and ultrasound for quality assurance at underground sealing structures
(2023)
Within the safety concepts of underground disposal sites of nuclear waste, engineered barriers play an important role. As these sealing structures have high demands concerning integrity, we aim at advancing the available construction materials, monitoring, and inspection techniques within the project SealWasteSafe. A specifically developed alkali-activated material is compared to classical salt concrete. A comprehensive multi-sensory monitoring scheme is used at 150-340 l specimens to monitor setting and hardening of both materials. All sensors are demonstrated to resist the highly alkaline environments. Besides cabled and wireless temperature and humidity of the materials, strain variations using fibre optic sensors and acoustic emissions are recorded over periods of at least 28 days, partly for more than eight months. After hardening of the specimens, further nondestructive evaluations using ultrasonic echo and thermographic measurements are conducted.
Preliminary results proof the suitability of the tested sensors and clearly highlight differences between the tested materials. Particularly, the newly developed alkali-activated material shows lower acoustic emission activity indicating less cracking activity. Additionally, unique ultrasonic methods will enable better images of potential internal objects and cracks at in-situ sealing structures. A largescale ultrasonic system is optimised to reliably detect objects at a depth exceeding 9 m while still obtaining a good resolution. Modelling studies show the potential of further increasing the distance between individual transducer arrays. Additionally, a new ultrasonic borehole probe using phased arrays allowing for beam focussing is constructed and tested. Laboratory measurements at a halfcylindrical concrete specimen coincide well with the previous modelling. In total, the presented safe materials, detailed monitoring approaches and ultrasonic quality assurance methods will help to obtain safe sealing structures within salt as a host rock. The concepts can partly be transferred to sealing structures in alternative host rocks and will also be valuable for non-nuclear waste repositories.
The project "SealWasteSafe" of the Bundesanstalt für Materialforschung und -prüfung (BAM, Berlin) deals with sealing structures applied for underground disposal of nuclear waste from two perspectives: (1) material improvement for application in sealing constructions and (2) feasibility study regarding multi-sensor approaches to ensure quality assurance and long-term monitoring.
One specimen of 150 l made of alkali-activated material, which was found innovative and suitable for sealing constructions based on preliminary laboratory studies, and, for comparison purpose, another one made of salt concrete, are manufactured with an integrated multi-sensory setup for quality assurance and long-term-monitoring. The specimens were left in their cast form and additionally thermally insulated to simulate the situation in the repository. The multi-sensory concept comprises RFID technology embedded in the specimens suppling material temperature and moisture measurements, integrated fibre optic sensing allowing strain measurement and acoustic emission testing for monitoring possible crack formation. Overall, the suitability and the functionality of the sensors embedded into and attached to strongly alkaline (pH > 13 for the AAM) and salt corrosive (NaCl) environment was proven for the first 672 h.
First temperature measurement based on RFID succeeded after 626 h for the alkali-activated material and after 192 h for the conventional salt concrete. Strain measurement based on distributed fibre optic sensing turned out the alkali-activated material with > 1 mm m-1 undergoing approximately twice the compression strain as the salt concrete with strains < 0.5 mm m-1. In contrast, the acoustic emission first and single hits representing crack formation in numbers, was found for alkali-activated material half of that detected at the salt concrete.
One-part geopolymers, synthesized from three different silica sources and sodium aluminate, were investigated regarding their microstructure and the evolution of their compressive strength on curing at slightly elevated temperatures. The effect of thermal treatment was studied up to 1000 °C and for the investigation of the chemical durability specific samples were treated with sulfuric acid (H2SO4, pH = 1).
Depending on the silica feedstock, different degrees of reaction were observed. One of the silicas had a significantly higher reactivity. For two of the silicas, significant amounts of zeolites occurred as reaction products besides geopolymeric gel, whereas the more reactive silica source lead to the formation of a rather fully condensed geopolymeric network.
The composites indicated promising behavior on heating in so far as no distinct shrinkage step occurred in the temperature range of dehydration. Up to 400 °C the residual strength of those mixes increased. Above 800 °C the samples underwent new phase formation. After exposure to sulfuric acid (pH 1; 70 d) specimens showed a residual compressive strength of about 77 % of the reference, indicating high acid resistance.
The passive fire protection of steel structures and other load-bearing components will continue to gain importance in future years. In the present contribution, novel intumescent aluminosilicate (geopolymer-bound) composites are proposed as fire-protective coatings on steel. Steel plates coated with these materials were exposed to the standard temperature-time curve as defined in ISO 834 – 1:1999. The coatings partially foamed during curing and expanded further during thermal exposure, demonstrating their intumescent characteristic.Thermogravimetryandoscillatory rheometry determined that the intumescent behavior is attributed to a transition to a viscous state (loss factor > 1) in the temperature range of major water release, differing from conventional geopolymers. XRD and SEM images showed that the coatings had characteristics of ceramic or glass-ceramic foams after fire resistance testing, suggesting superior performance under challenging conditions. The thickness of the coatings influenced their foaming and intumescent behavior and thus the time for the coated steel plates to reach 500 °C. A number of additives were also studied with the best performance obtained from samples containing sodium tetraborate.Acoating of just 6mmwas able to delay the time it takes for a steel substrate to reach 500 °C to more than 30 minutes.
Concretes produced from salt aggregate and hybrid alkaline cements, an alkali-activated slag/fly ash blend, or a Portland cement were exposed to a magnesium chloride-rich saline solution ([Mg2+] = 3.6 m, [Cl−] = 8.3 m), representing a solution formed after contact of surface water with evaporite rock (rock salt) in a nuclear waste repository. The hydration and deterioration of the concretes were studied with X-ray diffraction, thermogravimetric analysis, pH mapping and permeability measurements. The results show that calcium silicate hydrate (C-S-H) or sodium-substituted calcium aluminium silicate hydrate (C-N-A-S-H) and Friedel's salt were the major reaction products in the concretes prior to exposure to the saline solution. During exposure to the saline solution, increasing amounts of C-S-H/C-N-A-S-H dissolved, and gypsum and a secondary AFm phase formed. The durability of the concretes improved with increasing amounts of Portland clinker in the cements, due to the associated differences in permeability and chemical resistance. Nevertheless, a massive increase of permeability occurred for all concretes, likely caused by crack formation due to the formation of gypsum from anhydrite in the salt aggregate. Thus, the behavior of the concretes differed from, and was more complex than, the behavior of plain cement pastes.
Monitoring of repositories for radioactive waste requires techniques which can be applied long-term under harsh conditions. In this work, the reliability and suitability of materials and a capacitive sensor for measuring relative humidity are investigated, which are to be embedded in the special concrete components for the closure structures of underground repository. Preliminary tests with accelerated aging of the materials used, validation of the sensors under difficult conditions, investigations of the surfaces after aging by pH 14 solution, defined exposure of the sensors in a climatic chamber and the microscope images are discussed. The results will be used for further development and optimization of the RFID based sensor systems which can be applied to monitor the condition of different building structures without cabling.
In this work, one-part geopolymers were synthesized by mixing solid silica and sodium aluminate with water. Pastes were cured at elevated temperatures (60–90 °C) and relative humidity (r.H.) of 80–98 %. After curing the pastes at 80 °C and 80% r.H for one day, the reaction virtually ceased. Depending on the silica source either geopolymer- zeolite composites or zeolite-free geopolymeric gel forms. The compressive strength of the geopolymer-zeolite composites was lower as the compressive strength of a pure geopolymer, mainly due to a significantly denser and glassy microstructure with less interfaces of the latter one. The major part of the thermal dehydration occurred between 60 °C and 200 °C. Up to 700–800 °C only minor changes of the phase assemblage have been observed for the composites. Depending on the paste composition either ceramic or amorphous phases form during exposure to 1000 °C. Compared to other AAM, very low ambient drying/wetting shrinkage/expansion was observed for the mortars The mortars furthermore provide very high resistance against sulfuric acid (pH 1). Huge parts of the corroded layer are not dissolved from the specimen and can still provide protection for a potential substrate. In terms of sulfuric acid resistance, above a critical CaO content, the formation of gypsum is introduced. This causes expansion, cracking and the decrease of the sulfuric acid resistance.