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Alkali-silica reaction (ASR) is a chemical reaction within concrete which can lead over time to cracking and spalling. Due to the complexity of the problem, it still causes damage to concrete constructions worldwide.
The publication aims to illustrate the interdisciplinary research of the German Federal Institute for Materials Research and Testing (BAM) within the last 20 years, considering all aspects of ASR topics from the macro to the micro level. First, methods for characterization and assessment of ASR risks and reaction products used at BAM are explained and classified in the international context. Subsequently the added value of the research approach by combining different, preferably nondestructive, methods across all scales is explained using specific examples from a variety of research projects. Aspects covered range from the development of new test-setups to assess aggregate reactivity, to analysis of microstructure and reaction products using microscopical, spectroscopical and X-ray methods, to the development of a testing methodology for existing concrete pavements including in-depth analysis of the visual damage indicator and the de-icing salt input using innovative testing techniques. Finally, research regarding a novel avoidance strategy that makes use of internal hydrophobization of the concrete mix is presented.
By the combination of an optimized granulometry, a reduced water cement ratio and the use of superplasticizers ultra-high performance concrete achieves a compressive strength of over 150 N/mm2 and a high resistance regarding acids and water-soluble salts. In different Research projects the effect of an autoclavation on the mechanical strength and the phase composition was analyzed. In systematic studies, the concrete mix and the process parameters were varied.
The results show that autoclavation leads to an improved pozzolanic and hydraulic reaction and significantly improves the mechanical strength compared to a conventional thermal treatment. If a minimum time-span for hydration is ensured, the achievable strength level is not dependent on the prestorage time. However, the duration of the autoclaving is significant. After the Maximum strength is reached there is only a very slight decrease, even if unrealistically long autoclaving times are applied.
Alkali silica reaction (ASR) is a major concrete durability problem resulting in significant maintenance and reconstruction costs for concrete infrastructures all over the world. To determine whether an aggregate is potentially reactive, accelerated concrete tests are used. Aim of this study is the chemical and microstructural characterization of ASR-products formed under the performance conditions of motorway pavements and during subsequent tests on the remaining ASR susceptibility. Samples were taken from concrete motorway pavements. Some of the samples already showed first indications for beginning damages whereas others showed deteriorations only after applying a performance testing procedure for the estimation of future risk of ASR damage. In a first step ASR-products were identified by polarized light microscopy in thin sections. The reaction products where then analyzed by Raman Spectroscopy and finally the chemical composition of the ASR-products was identified by SEM with EDX.
The results indicate that most reaction products show an increasing Ca/Si-ratio with progressive crack length. If an ASR-product develops inside an aggregate and moves through the cement paste, it has a high (Na+K)/Si-ratio at the beginning which decreases with increasing distance from its place of origin. The Raman spectra of the ASR-products are characterized by two broad bands indicating specific Q-species of different amorphous gel networks. Within the scope of the analysis distinctions in the microstructure and the chemical composition of the ASR-gels were detected relating to various conditions of accelerated testing.
There is an ongoing debate on European scale concerning the criticality of phosphorus. In Switzerland and Germany, phosphorus recovery from phosphorus-rich waste streams will become obligatory. Sewage sludge ash is rich in phosphorus and may become an important secondary feedstock. Thermochemical treatment of sewage sludge ash with sodium sulphate under reducing conditions was shown to remove heavy metals from the solid product and produce the fully plant available crystalline phase CaNaPO4. Pilot-scale experiments in a rotary kiln were carried out at temperatures between 750 and 1000 °C and were compared to laboratory-scale experiments with crucibles. Process upscaling was successfully demonstrated but a series of differences were noticed: In comparison to laboratory-scale, solubility of phosphorus in samples from pilot-scale experiments was lower at all chosen treatment temperatures because of shorter retention time and incomplete decomposition of sodium sulphate. X-ray diffraction analysis revealed remaining phase fractions of whitlockite (Ca3-x(Mg,Fe)x(PO4)2) and sodium sulphate from the starting materials in products and thus indicated incomplete reaction. In contrast to the results of laboratory-scale experiments, the crystalline phase CaNaPO4 was clearly absent in the products from the rotary kiln but instead a Mg-bearing phase (Ca,Mg)NaPO4 was formed. Laboratory-scale experiments confirmed (Ca,Mg)NaPO4 is an intermediate phase between whitlockite and CaNaPO4. However, both crystalline phases are characterized by high plant availability. It was shown that heavy metal removal increased at higher temperatures whereas solubility and thus plant availability of phosphorus already reached its maxima at temperatures of 950 °C in pilot-scale and 875 °C in laboratory-scale experiments.
Tricalcium aluminate (C3A) is found with less than 10% wt. of the total composition; however, during hydration, C3A plays an important role in the early hydration of cement in the presence of gypsum as a set retarder.
The aim of this investigation is to assess the suitability of optical spectroscopy and a dye-based optical probe to monitor early hydration of C3A in the presence of gypsum and hemihydrate. Optical evaluation was performed using steady-state fluorescence and diffuses reflectance spectroscopy (UV-VisDR). Phase characterization during hydration was done with in-situ X-ray diffraction. UV-VisDR with a cyanine dye probe was used to monitor the formation of metastable phases and was employed together with fluorescence spectroscopy, to follow the Aggregation and disaggregation of the dye during hydration. In conclusion, for the first time, a cyanine dye was identified as a feasible and stable probe to monitor C3A hydration changes in the presence of calcium sulfate.
Fused cement clinker can be produced from molten basic oxygen furnace slag (BOFS) by way of a reductive thermochemical treatment. During the thermochemical treatment, oxidic iron is reduced to metallic iron and separated. The resulting low-iron slag has a chemical and mineralogical composition similar to ordinary Portland cement (OPC) clinker. In this study, the hydraulic reactivity of the fused clinker from BOFS with and without gypsum was investigated using isothermal calorimetry, differential scanning calorimetry, in situ X-ray diffraction and powder X-ray diffraction. Furthermore, a synthetic fused clinker without foreign ions and fused clinker produced by a mixture of both materials was studied. The hydraulic reaction of the fused clinker from BOFS was considerably slower than that of OPC. However, the reaction can be accelerated by adding gypsum as a sulfate carrier. Furthermore, the results showed an increased reaction rate with decreasing content of foreign ions such as Fe, P or Mn.
UHPC (engl. ultra-high-performance concrete) bietet außergewöhnliche Eigenschaften, die sich durch eine optimierte Wärmebehandlung weiter verbessern lassen. Wie bei normalen Beton beschleunigt eine Wärmebehandlung den Aushärteprozess und reduziert das Schrumpfen. Durch Ausbildung eines dichteren Gefüges wird weiterhin die Druckfestigkeit und die Resistenz gegenüber Umwelteinflüssen erhöht.
Die Art der Wärmebehandlung wird durch die Parameter: Temperatur, Druck, Wasserdampfsättigung und Dauer definiert und hat einen entscheiden Einfluss auf die Phasenentwicklung und damit auf die makro- und mikroskopischen Eigenschaften des UHPCs. Auch die Dauer und Art der Vorlagerung des UHPCs vor der thermischen Behandlung sind von Bedeutung.
Ziel der vorgestellten Untersuchung war der Vergleich und die Optimierung verschiedener Wärmebehandlungsarten mit Blick auf die Druckfestigkeits- und Phasenentwicklung. Dafür wurden UHPC-Zylinder und Prismen hergestellt und ungeschützt bzw. in Folie eingeschweißt bei 90 °C im Ofen, im Heißwasserbad, sowie alternativ bei 185 °C und 1.1 MPa im Autoklaven wärmebehandelt. Zusätzlich wurde die Vorlagerungs- und die Behandlungszeit systematisch variiert.
Die Ergebnisse zeigen, dass eine praxisnahe Wärmebehandlung im Ofen (kurze Vorlagerungs- und Behandlungszeit, Verdunstungsschutz durch Einschweißen in Folie) zwar zu einer stark erhöhten Frühfestigkeit führt, aber die Langzeitfestigkeit wird nicht signifikant erhöht. Erst längere Behandlungszeiten verbunden mit intensiviertem Schutz gegen das Austrocknen führen darüber hinaus zu deutlich erhöhten Langzeitfestigkeiten. Nach der Autoklavierung dagegen wurden Festigkeitszuwächse von bis zu 30 % gemessen.
Die röntgenographisch nachgewiesene Phasenentwicklung wird in beiden Behandlungsarten durch die Limitierung des zur Verfügung stehenden Wassers bestimmt. Bei der Wärmebehandlung im Ofen wird das durch den Ettringitzerfall freigesetzte Wasser für die puzzolanische Reaktion der Mikrosilika verbraucht, reicht aber für eine weitere Reaktion der Klinkerphasen nicht aus. Bei der hydrothermalen Behandlung dagegen zeigen die Veränderungen im Phasenbestand sowohl eine Intensivierung der puzzolanischen als auch der hydraulischen Reaktion. Der für autoklavierte Baustoffe charakteristische Tobermorit konnte jedoch nicht im Probeninneren, sondern nur als Belag auf der Probenoberfläche nachgewiesen werden. Ursächlich hierfür ist vermutlich wiederum das zu geringe Wasserangebot im Gefüge des UHPC.
UHPC (engl. ultra-high-performance concrete) bietet außergewöhnliche Eigenschaften, die sich durch eine optimierte Wärmebehandlung weiter verbessern lassen. Wie bei normalen Beton beschleunigt eine Wärmebehandlung den Aushärteprozess und reduziert das Schrumpfen. Durch Ausbildung eines dichteren Gefüges wird weiterhin die Druckfestigkeit und die Resistenz gegenüber Umwelteinflüssen erhöht.
Die Art der Wärmebehandlung wird durch die Parameter: Temperatur, Druck, Wasserdampfsättigung und Dauer definiert und hat einen entscheiden Einfluss auf die Phasenentwicklung und damit auf die makro- und mikroskopischen Eigenschaften des UHPCs. Auch die Dauer und Art der Vorlagerung des UHPCs vor der thermischen Behandlung sind von Bedeutung.
Ziel der vorgestellten Untersuchung war der Vergleich und die Optimierung verschiedener Wärmebehandlungsarten mit Blick auf die Druckfestigkeits- und Phasenentwicklung. Dafür wurden UHPC-Zylinder und Prismen hergestellt und ungeschützt bzw. in Folie eingeschweißt bei 90 °C im Ofen, im Heißwasserbad, sowie alternativ bei 185 °C und 1.1 MPa im Autoklaven wärmebehandelt. Zusätzlich wurde die Vorlagerungs- und die Behandlungszeit systematisch variiert.
Die Ergebnisse zeigen, dass eine praxisnahe Wärmebehandlung im Ofen (kurze Vorlagerungs- und Behandlungszeit, Verdunstungsschutz durch Einschweißen in Folie) zwar zu einer stark erhöhten Frühfestigkeit führt, aber die Langzeitfestigkeit wird nicht signifikant erhöht. Erst längere Behandlungszeiten verbunden mit intensiviertem Schutz gegen das Austrocknen führen darüber hinaus zu deutlich erhöhten Langzeitfestigkeiten. Nach der Autoklavierung dagegen wurden Festigkeitszuwächse von bis zu 30 % gemessen.
Die röntgenographisch nachgewiesene Phasenentwicklung wird in beiden Behandlungsarten durch die Limitierung des zur Verfügung stehenden Wassers bestimmt. Bei der Wärmebehandlung im Ofen wird das durch den Ettringitzerfall freigesetzte Wasser für die puzzolanische Reaktion der Mikrosilika verbraucht, reicht aber für eine weitere Reaktion der Klinkerphasen nicht aus. Bei der hydrothermalen Behandlung dagegen zeigen die Veränderungen im Phasenbestand sowohl eine Intensivierung der puzzolanischen als auch der hydraulischen Reaktion. Der für autoklavierte Baustoffe charakteristische Tobermorit konnte jedoch nicht im Probeninneren, sondern nur als Belag auf der Probenoberfläche nachgewiesen werden. Ursächlich hierfür ist vermutlich wiederum das zu geringe Wasserangebot im Gefüge des UHPC.
Tricalcium-silicate (C3S) or Alite is the most important mineral in Portland cement. Since pure tricalcium-silicate is only stable above temperatures of 1250 °C, its decomposition has to be prevented technically by fast cooling after the sintering process. At room temperature, the decomposition velocity is very slow so that metastable tricalcium-silicate is obtained.
Although the mechanisms of clinker phase formation during burning process of Portland cement in a rotary kiln were solved and improved over the years, in view of possible economic and ecological benefits current projects aim to produce clinker phases from metallurgical slags. Recent studies discovered that the mineral phase which remained after a reducing treatment and separation of formed metallic iron from molten Linz-Donawitz (LD-) slags contained about 60 wt.% Alite despite it was cooled slowly. Because the results could be verified using slags from different origins and varying cooling velocities a chemical stabilisation of the Alite can be assumed. First tests in mortars indicate that workability, hardening and solid state properties are comparable with an ordinary Portland cement. An application of the observed phenomenon in cement production requires enhanced knowledge about formation and stabilisation conditions of Alite during crystallisation from melts in contrast to the sintering reactions in conventional Portland cement production. Therefore, this study focuses on the stabilisation mechanisms of Alite in consolidating melts. Samples from different melting experiments are analysed to determine stabilising factors.
The advantages of treating prefabricated components made of Ultra-High-Performance Concrete (UCPC) at 90 °C are largely recognized, while hydrothermal treatment at 185 °C and the corresponding saturation pressure of 1.1 MPa, in contrast, is not applied in building practice so far and was studied only by a few researchers.
In the research presented, the parameters pre-storage-time before treatment and dwell time in the autoclave were systematically varied. The results illustrate in which way compressive strength increases with the duration of treatment. Already samples which were only heated up and immediately cooled down show an increase in strength compared to the 28-day reference of about 10 %. After 20 h the maximum increase of about 25 % is reached. Interestingly the compressive strength of samples treated very long hardly decreases. It can be therefore concluded that for the composition investigated the achievable mechanical strength is not severely sensitive regarding the duration of the treatment.
Also, pre-storage times before autoclaving longer than 0.5 days showed no significant impact on strength development.
The phase composition measured by XRD exhibits significant changes compared to the reference. The amount of ettringite and portlandite have vanished, the cement clinker phases are substantially decreased and hydroxylellestadite and hydrogarnet are formed as new phases. The increase in strength can be assigned to an improved pozzolanic and hydraulic reaction. Contradictory to literature, there was found no tobermorite, a mineral which is known to be susceptible for disintegration at Long autoclaving duration. This explains why no significant strength loss appeared.
Aim of this study is to provide information about moisture dependent material behaviour of unstabilised loadbearing earth blocks and mortars. Compressive strength and Young’s modulus were investigated after conditioning in varying relative humidity reaching from 40 % up to 95 %. The material composition and physical properties were investigated to understand the influence of relative humidity onto the mechanical properties. A normalisation of strength and stiffness by the values obtained at 23 ◦C and 50 % relative humidity reveals a linear dependence of compressive strength and Young’s modulus that is regardless of the material composition.
Thus, it is possible to describe the influence of relative humidity onto the load-bearing behaviour of unstabilised earth masonry materials in a generally valid formulation.
If the amount of sulfate within the mix design for concrete is not balanced, ettringite formation which first controls solidification continues while the concrete is hardening. Ettringite forms by reaction of sulfate contained in the cement or in some admixture with calcium aluminate (C3A) as cement component. The “late primary ettringite formation” promotes an increase in volume within the hardened concrete leading to cracks. To analyze the effect of substituting part of ordinary Portland cement (OPC) by a treated brown coal fly ash mortar bars were tested according to ASTM C452. This test method was originally developed to extrapolate from the internal to external sulfate attack and is based on the idea that by testing a concrete mixture containing sulfate the process of deterioration is accelerated because it does not have to diffuse into the concrete before reaction first. In addition to the samples prescribed in ASTM C452 further samples in the size of the German SVA procedure were tested also designed for accessing the external sulfate resistance. The results show that while the replacement of 25 % of cement by brown coal fly ash leads to length changes around the limit defined by ASTM, the substitution of 50 % cement exceeded the limit by a multiple. The progress of expansion is the very similar for the two geometries tested. In-situ XRD measurements confirmed that while for pastes made of OPC the formation of ettringite is completed after 20 hours, this is not true for the mixtures containing the brown coal fly ash.
In a different study the effect of hydrothermal treatment on the phase composition of ultra-high-performance concrete was analyzed. The results show that the sulfate and aluminate resulting from the decomposition of ettringite are bound into new phases.
If this binding is permanent this might allow the larger use of sulfate bearing raw materials.
The production of Portland cement causes a substantial environmental impact, since the calcination of limestone results in high emissions of carbon dioxide. The use of supplementary cementitious materials such as calcined clays as partial replacement for Portland cement offers a solution to limit this environmental impact. This paper investigates four clays from deposits in central Germany with the aim of obtaining pozzolans for the production of Portland-pozzolana cement. The results obtained show that the calcined clays possess pozzolanic properties, which differ depending on calcination temperature and the relative amounts of Kaolinite and 2:1 clay minerals.
The oxidation of sulfur in aqueous solutions is an important process in several geochemical and industrial contexts. In concrete technology, it is particularly relevant for the protection of steel reinforcement in slag cement-based concretes, as the presence of sulfides affects the passivation of the steel and corrosion initiation in the presence of chlorides. However, the knowledge about the kinetics of sulfide oxidation in alkaline solutions, such as concrete pore solutions, is incomplete. To address this issue, we prepared solutions with 0.80 M NaOH, and nominally 10, 100 and 350 mM HS−, respectively, and followed the evolution of the sulfur species during bubbling with oxygen-containing gas (concentration 100% or 22%) using X-ray absorption near-edge structure (XANES) spectroscopy at the sulfur K-edge. Polysulfide, thiosulfate, sulfite and sulfate were identified and quantified via linear combination fitting of the spectra, using previously measured standards. A preliminary analysis of the results shows that the initial rate constant of sulfide oxidation depends strongly on the HS− concentration, while it less strongly depending on the oxygen concentration, in line with previous results for lower pH values. Approaches to fit the data to obtain the rate constants of all relevant reactions will be discussed.
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.
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.
Powder X-ray diffraction is a time-consuming and challenging task, especially for preparation of sensitive phases like ettringite and calcium-silicate-hydrate (C-S-H) phases. Fine-grained ultrahigh-performance concrete (UHPC) with an average grain size <100 μm could be investigated directly without time-consuming milling. As a proof of concept, small UHPC cylinders with plain surfaces were investigated with a newly designed sample holder. The comparison with conventionally prepared powder shows the feasibility of fast qualitative phase analysis using this approach. As a great benefit, a depth-dependent analysis, as well as a comparison of surface layers and core material, was carried out.
Hydrous lithium aluminosilicate (L–A–S–H) and lithium aluminate (L–A–H) gels are candidate precursors for glass-ceramics and ceramics with potential advantages over conventional processing routes. However, their structure before calcination remained largely unknown, despite the importance of precursor structure on the properties of the resulting materials. In the present study, it is demonstrated that L–A–S–H and L–A–H gels with Li/Al ≤ 1 can be produced via an organic steric entrapment route, while higher Li/Al ratios lead to crystallization of gibbsite or nordstrandite. The composition and the structure of the gels was studied by thermogravimetric analysis, X-ray diffraction, 27Al and 29Si magic-angle spinning nuclear magnetic resonance, and Raman spectroscopy. Aluminium was found to be almost exclusively in six-fold coordination in both the L–A–H and the L–A–S–H gels. Silicon in the L–A–S–H gels was mainly in Q4 sites and to a lesser extent in Q3 sites (four-fold coordination with no Si–O–Al bonds). The results thus indicate that silica-rich and aluminium-rich domains formed in these gels.
Basic oxygen furnace slags (BOFS) are by-products of the steelmaking process. Several researchers have studied the production of Portland cement clinker and metallic iron from BOFS via a reductive treatment.
In this study, we applied a carbothermal reduction of BOFS in a technical-scale electric arc furnace and characterised the clinker-like products. Those clinker-like non-metallic products (NMPs) had a chemical and mineralogical composition comparable to clinker for ordinary Portland cement (OPC) and contained large elongated alite crystals as major component. The pure NMPs reacted more slowly and achieved a lower degree of hydration compared with commercial OPC.
If the reactivity of the products can be further increased by employing specific adaptations, it can be used as a full clinker substitute for OPC. Nevertheless, it is also an option to use the material without further modifications as a cement component or concrete addition, which contributes to the strength development in both cases.
Slags from the nonferrous metals industry have great potential to be used as feedstocks for the production of alkali-activated materials. Until now, however, only very limited information has been available about the structural characteristics of these materials. In the work presented herein, synthetic slags in the CaO–FeOx–SiO2 system, representing typical compositions of Fe-rich slags, and inorganic polymers (IPs) produced from the synthetic slags by activation with alkali Silicate solutions have been studied by means of X-ray absorption near-edge structure (XANES) spectroscopy at the Fe K-edge. The iron in the slags was largely Fe2+, with an average coordination number of approximately 5 for the iron in the amorphous fraction. The increase in average oxidation number after alkali-activation was conceptualized as the consequence of slag dissolution and IP precipitation, and employed to calculate the degrees of reaction of the slags. The degree of reaction of the slags increased with increasing amorphous fraction. The iron in the IPs had an average coordination number of approximately 5; thus, IPs produced from the Fe-rich slags studied here are not Fe-analogs of aluminosilicate geopolymers, but differ significantly in terms of structure from the latter.