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Im Gegensatz zur Druckfestigkeit weisen zementgebundene Werkstoffe i. a. nur geringe Zugfestigkeiten auf. Ein Weg, Zugfestigkeiten zementgebundener Werkstoffe zu erhöhen und Rissbildung aufgrund von Zugspannungen zu verringern, besteht in der Einarbeitung von Fasern, die diese Spannungen aufnehmen. Häufig eingesetzt werden Stahlfasern, obwohl synthetische Polymerfasern leichter und meist beständiger gegenüber chemischen Angriffen und Korrosion sind. Die Polymerfasern zeigen allerdings meist einen deutlich schwächeren Haftverbund, was an der hydrophoben Faseroberfläche liegt. Um nun eine Anbindung der Fasern an die mineralische Matrix zu erreichen, müssen die Faseroberflächen modifiziert werden, ohne dass die mechanischen Eigenschaften negativ beeinflusst werden. Eine Herausforderung besteht somit in einer Oberflächenmodifikation durch eine schonende Behandlung der Fasern zur Erzeugung von anbindungsfähigen Gruppen.
Durch eine Behandlung von modifizierten Fasern mit geeigneten Polymerlösungen werden die Oberflächeneigenschaften verändert und erlauben eine Anbindung an die Zementsteinmatrix. Der Einsatz von Tensiden als grenzflächenaktive Verbindungen ermöglicht in diesem Zusammenhang eine Vermittlung zwischen Polymeroberflächen und mineralischen Werkstoffen.
Im Gegensatz zur Druckfestigkeit weisen zementgebundene Werkstoffe i. a. nur geringe Zugfestigkeiten auf. Ein Weg, Zugfestigkeiten zementgebundener Werkstoffe zu erhöhen und Rissbildung aufgrund von Zugspannungen zu verringern, besteht in der Einarbeitung von Fasern, die diese Spannungen aufnehmen. Häufig eingesetzt werden Stahlfasern, obwohl synthetische Polymerfasern leichter und meist beständiger gegenüber chemischen Angriffen und Korrosion sind. Die Polymerfasern zeigen allerdings meist einen deutlich schwächeren Haftverbund, was an der hydrophoben Faseroberfläche liegt. Um nun eine Anbindung der Fasern an die mineralische Matrix zu erreichen, müssen die Faseroberflächen modifiziert werden, ohne dass die mechanischen Eigenschaften negativ beeinflusst werden. Eine Herausforderung besteht somit in einer Oberflächenmodifikation durch eine schonende Behandlung der Fasern zur Erzeugung von anbindungsfähigen Gruppen. Durch eine Behandlung von modifizierten Fasern mit geeigneten Polymerlösungen werden die Oberflächeneigenschaften verändert und erlauben eine Anbindung an die Zementsteinmatrix. Der Einsatz von Tensiden als grenzflächenaktive Verbindungen ermöglicht in diesem Zusammenhang eine Vermittlung zwischen Polymeroberflächen und mineralischen Werkstoffen.
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.
Ultra high performance concrete (UHPC) is characterised by its high compressive strength of more than 150 MPa and its high durability. Due to thermal treatment at 90°C a strength comparable to the 28-days-strength can be achieved immediately after the treatment and in some cases can be even further increased up to 30 %. The explanations for the increase in strength are the accelerated hydration of the clinker minerals and the intensified pozzolanic reaction contributing to a denser microstructure and hence, a high performance in compressive strength.
Former research shows that thermal treatment can lead to inhomogeneities in form of a visible zonation within the cross-section. The width of the margin increases with shorter pre-storage time before the thermal treatment and with omitting protective measures against desiccation during the treatment. Specimens exhibiting a zonation typically show a lower compressive strength compared to the undisturbed reference whereas changes in chemistry, mineral content and microstructure were not reported in detail.
In this study the zonation of thermally treated UHPC is investigated with respect to its chemistry, mineral composition and microstructure to allow predictions on durability and strength development. Measurements show a change in pore sizes, minerals phase composition and element distribution leading to the visible zonation and weaker bending tensile strength compared to the reference.
The low tensile strength of cement-based materials can be improved by the addition of fibres. In a joint research project, an industrial partner designed special coatings for polymer and carbon fibres by integrating surfactants and hydrophilic compounds. Aim of the developed functionalization was to ensure an even coverage of the fibre surfaces and to anchor them chemically in the cement-based matrix. Task of the BAM was to quantify the effect of the improved bond. In a first step a workable mortar adjusted to the strength of the tested fibres was developed and the fibre distribution assessed by light microscopy and computed tomography. To test the new coating for its efficiency to prevent cracking during hardening and to improve the loadbearing behaviour new test setups were developed or existing methods were adjusted.
The experiments showed that the functionalization leads to a reduction of the crack area measured after the exposure of the wet mortar to strong drying conditions in the wind channel. Regarding the Efficiency to mitigate shrinkage cracks the functionalisation turned out to be more efficient for fibres made from polyacrylonitrile (PAN) than for carbon fibres. An improvement of the tensile strength after cracking of the cementitious matrix could only be documented for the coated carbon fibres. It could be quantified, however, only in the three-point bending tests because the fibres turned out to be too brittle for the applied single fibre pull-through test.
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.
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 obermorite, a mineral which is known to be susceptible for disintegration at Long autoclaving duration. This explains why no significant strength loss appeared.
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.
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.
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.
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.
Ultra high performance concrete (UHPC) is characterised by its high compressive strength of more than 120 MPa and its high durability. With thermal treatment at 90°C, hydration is accelerated and a strength comparable to the 28-day strength can be achieved immediately after the treatment. In applying Optimum process conditions, the strength can be even further increased by up to 30%. Previous Research showed that thermal treatment can lead to inhomogeneities in form of a visible zonation within the cross-section, if the UHPC is not protected sufficiently from desiccation. This led to the question, to what extent the related changes in mechanical properties, microstructure and phase composition are of relevance for the performance of the UHPC. First investigations of small specimens thermally treated without protection exhibited a decrease of compressive strength, indicating that the zonation aspect requires further research.
In this study the zonation of UHPC treated thermally at 90°C is investigated after applying four different procedures of treatment and curing in comparison. The samples are characterized with respect to their chemistry, mineral composition and microstructure to allow an assessment on durability and strength development, with focus on potential depth dependent changes associated with the zonation.
The measurements reveal the formation of a visible zonation in case of unprotected treatment, if followed by immersion in water. The compressive strength is not significantly impaired, but a decrease in bending strength gives reason for concern. Further results allow clear correlation with changes in pore structure, whereas the interpretation of relationships with phase distribution, degree of hydration, microchemistry is more complex and therefore, provides only partial clarification.
Composite Facade Elements with Self-Cleaning Surface made of Ultra-High-Performance Concrete (UHPC)
(2020)
In the framework of the European project H-House various concrete façade elements were developed with the aim to ensure a long service life by combining a very durable material with self-cleaning properties. The façade elements presented are made of a shell of UHPC filled with blocks of aerated autoclaved concrete as insulating material. Self-cleaning properties were realized amongst others by imprinting a microstructure into the surface during casting. The paper focuses on selected technological aspects of the manufacturing process of prototypes which had to be performed in two concreting sections. Furthermore the challenges faced when upscaling the self-cleaning properties are addressed and the strategy to assess the self-cleaning properties by measuring the contact and the roll-off angel is presented. The results show that a successfull upscalaing process requires detailed planning and that the best results can often be achieved with a moderate work effort or material use.
Composite Facade Elements with Self-Cleaning Surface made of Ultra-High-Performance Concrete (UHPC)
(2020)
In the framework of the European project H-House various concrete façade elements were developed with the aim to ensure a long service life by combining a very durable material with self-cleaning properties. The façade elements presented are made of a shell of UHPC filled with blocks of aerated autoclaved concrete as insulating material. Self-cleaning properties were realized amongst others by imprinting a microstructure into the surface during casting. The paper focuses on selected technological aspects of the manufacturing process of prototypes which had to be performed in two concreting sections. Furthermore the challenges faced when upscaling the self-cleaning properties are addressed and the strategy to assess the self-cleaning properties by measuring the contact and the roll-off angel is presented. The results show that a successfull upscalaing process requires detailed planning and that the best results can often be achieved with a moderate work effort or material use.
Ultra high performance concrete (UHPC) is known for its high compressive strength of more than 150 MPa and its high durability. Thermal treatment at 90°C can accelerate the strength development so that the 28-days-strength can be achieved immediately after the treatment and an additional increase up to 30 % in some cases. The reason for the strength development is an accelerated hydration of the clinker minerals and an intensified pozzolanic reaction leading to a denser microstructure.
In previous research inhomogeneities in form of a zonation after unprotected thermal treatment were observed and analysed in respect to changes in the microstructure. This zonation is defined by a different microstructure in the core compared to the outer zone in the matter of porosity, mineral phase composition and a significant change in the potassium and sulphur concentration of the zones is measurable.
To isolate different transport mechanisms responsible for these element distributions UHPC samples were thermally treated at 90 °C and the microstructure was investigated under dry conditions and after immersion in water to investigate the influence of dehydration during and rehydration after the thermal treatment on the microstructure. Through durability testing via water absorption, water vapour diffusion, permeability testing and sulfuric acid resistance transport mechanisms like diffusion, migration, capillary suction are under investigation in correlation with the microstructure analysis. For the microstructure analysis measurements with µXRF, mercury intrusion porosity, XRD and SEM were conducted.
Several studies show that thermal and hydrothermal treatment can further improve the excellent properties of UHPC in terms of mechanical strength and durability. While for the thermal treatment the increase in strength is attributed to an intensified pozzolanic and hydraulic reaction, for the hydrothermal treatment previous studies accredited it mostly to the formation of tobermorite. In the presented study thermal and hydrothermal treatment of UHPC samples was systematically varied and the phase formation analysed related to the strength development of a reference sample cured for 28 days in water. For the thermal treatment the results show that the strength increase depends on the protection against desiccation and can be ascribed to an improved pozzolanic reaction of the siliceous fillers. To achieve a significant enhancement of strength, a pre-storage time of few days and a long dwell time at elevated temperature/pressure are required. For the hydrothermal treatment already heating the specimens up to 185 °C in saturated steam followed by an immediate cooling leads to a substantial increase in compressive strength. Pre-storage time did not affect the result as far as a minimum of several hours is guaranteed. The improved performance is due to an increase in the pozzolanic and hydraulic reaction. Surprisingly, tobermorite was only found within a very thin layer at the surface of the sample, but not in the bulk. Sulphate and aluminium stemming from the decomposition of the ettringite are bound in the newly formed phases hydroxylellestadite and hydrogarnet.
Composite UHPC facade elements with self-cleaning surface: Aspects of technological manufacturing
(2020)
In the framework of the European collaborative project H-House, which was finished in 2017, large façade elements were developed consisting of a box shaped external shell of ultra-high-performance concrete (UHPC) with a functionalized surface and an insulation of autoclaved aerated concrete (AAC). The exposed concrete of the elements was further refined by adding self-cleaning properties to the surface through imprinting a microstructure in combination with chemical agents directly in the casting process. The paper focuses on selected technological aspects of the manufacturing process of large-scale prototypes. Presented are results of the upscaling process of functionalized surfaces from small specimen up to large UHPC composite facade elements produced for the construction of a demonstrator.
Composite UHPC facade elements with self-cleaning surface: Aspects of technological manufacturing
(2020)
In the framework of the European collaborative project H-House, which was finished in 2017, large façade elements were developed consisting of a box shaped external shell of ultra-high-performance concrete (UHPC) with a functionalized surface and an insulation of autoclaved aerated concrete (AAC). The exposed concrete of the elements was further refined by adding self-cleaning properties to the surface through imprinting a microstructure in combination with chemical agents directly in the casting process. The paper focuses on selected technological aspects of the manufacturing process of large-scale prototypes. Presented are results of the upscaling process of functionalized surfaces from small specimen up to large UHPC composite facade elements produced for the construction of a demonstrator.
Die geringe Zugfestigkeit von zementgebundenen Materialien kann durch die Zugabe von Fasern maßgeblich verbessert werden. Ziel eines gemeinsamen Verbundprojekts mit einem Industriepartner war die Erhöhung der Leistungsfähigkeit von kurzen Polymer- und Carbonfasern durch eine Verbesserung des Verbundes zwischen Faseroberfläche und Zementsteinmatrix.
Von der IONYS AG wurde dazu eine spezielle Funktionalisierung entwickelt, die über eine Hydrophilisierung der Faseroberfläche eine chemische Anbindung an die Zementsteinmatrix gewährleistet. Aufgabe der BAM war es, die Effizienz der neuen Beschichtung bezüglich der Erhöhung der Nachrissbiegezugfestigkeit und der Reduzierung der Schwindrissbildung während der Erhärtungsphase zu quantifizieren. Die Ergebnisse zeigen, dass die Funktionalisierung die Neigung zur Schwindrissbildung für die Carbonfasern und in noch stärkerem Maße für die Polymerfasern reduziert.
Eine Erhöhung der Nachrissbiegezugfestigkeit konnte dagegen nur für die deutlich steiferen Carbonfasern nachgewiesen werden.
Die geringe Zugfestigkeit von zementgebundenen Materialien kann durch die Zugabe von Fasern maßgeblich verbessert werden. Ziel eines gemeinsamen Verbundprojekts mit einem Industriepartner war die Erhöhung der Leistungsfähigkeit von kurzen Polymer- und Carbonfasern durch eine Verbesserung des Verbundes zwischen Faseroberfläche und Zementsteinmatrix.
Von der IONYS AG wurde dazu eine spezielle Funktionalisierung entwickelt, die über eine Hydrophilisierung der Faseroberfläche eine chemische Anbindung an die Zementsteinmatrix gewährleistet. Aufgabe der BAM war es, die Effizienz der neuen Beschichtung bezüglich der Erhöhung der Nachrissbiegezugfestigkeit und der Reduzierung der Schwindrissbildung während der Erhärtungsphase zu quantifizieren. Die Ergebnisse zeigen, dass die Funktionalisierung die Neigung zur Schwindrissbildung für die Carbonfasern und in noch stärkerem Maße für die Polymerfasern reduziert.
Eine Erhöhung der Nachrissbiegezugfestigkeit konnte dagegen nur für die deutlich steiferen Carbonfasern nachgewiesen werden.