Investigations on lightweight concrete by in situ compression tests using high-resolution computed tomography (µ-CT).

The fracture behaviour of concrete is studied in various micro- and macro-damage models. This is important for estimating serviceability and stability of concrete structures. However, a detailed understanding of the material behaviour under load is often not available. In order to better interpret the fracture behaviour and pattern, images of lightweight concrete were taken using a high-resolution computed tomography (µ-CT) scanner. The samples were loaded between the taken images and the load was kept constant during the measurement. This study describes the method used and how the data set was analysed to investigate displacements and cracks. It has been shown that displacements and damage to the concrete structure can be detected prior to failure, allowing conclusions to be drawn about the structural behaviour. In principle, the µ-CT measurement can be used to examine different kinds of concrete as well as other systems with inorganic binders and to compare the fracture behaviour of different systems.

Prediction Model Based on DoE and FTIR Data to Control Fast Setting and Early Shrinkage of Alkaline-Activated Slag/Silica Fume Blended Cementitious Material.

This study aims to develop a material-saving performance prediction model for fast-hardening alkali-activated slag/silica fume blended pastes. The hydration process in the early stage and the microstructural properties after 24 h were analyzed using design of experiments (DoE). The experimental results show that the curing time and the FTIR wavenumber of the Si-O-T (T = Al, Si) bond in the band range of 900-1000 cm-1 after 24 h can be predicted accurately. In detailed investigations, low wavenumbers from FTIR analysis were found to correlate with reduced shrinkage. The activator exerts a quadratic and not a silica modulus-related conditioned linear influence on the performance properties. Consequently, the prediction model based on FTIR measurements proved to be suitable in evaluation tests for predicting the material properties of those binders in the building chemistry sector.

Potential of Fe-Mn-Al-Ni Shape Memory Alloys for Internal Prestressing of Ultra-High Performance Concrete.

Prestressing of concrete is a commonly used technique in civil engineering to achieve long spans, reduced structural thicknesses, and resource savings. However, in terms of application, complex tensioning devices are necessary, and prestress losses due to shrinkage and creep of the concrete are unfavourable in terms of sustainability. In this work, a prestressing method using novel Fe-Mn-Al-Ni shape memory alloy rebars as a tensioning system in UHPC is investigated. A generated stress of about 130 MPa was measured for the shape memory alloy rebars. For the application in UHPC, the rebars are prestrained prior to the manufacturing process of the concrete samples. After sufficient hardening of the concrete, the specimens are heated inside an oven to activate the shape memory effect and, thus, to introduce the prestress into the surrounding UHPC. It is clearly shown that an improvement in maximum flexural strength and rigidity is achieved due to the thermal activation of the shape memory alloy rebars compared to non-activated rebars. Future research will have to focus on the design of the shape memory alloy rebars in relation to construction applications and the investigation of the long-term performance of the prestressing system.

Comparative Study of 2D Petrographic and 3D X-ray Tomography Investigations of Air Voids in Asphalt.

Knowledge of the exact composition of building materials (aggregate, binder, air voids, etc.) is essential for the further development of more resistant and sustainable building materials. In numerous scientific studies, the material behavior of asphalt is tested using mechanical methods. Here, the overall material behavior is determined (bitumen, air voids, aggregate). With the advent of imaging techniques, it is becoming possible to determine the individual constituents separately and perform a more detailed analysis of their location, shape and composition. Three-dimensional and two-dimensional methods are available for this purpose. For this study, two different types of asphalt (porous asphalt and asphalt concrete) were analyzed using 3D X-ray computed tomography and asphalt petrology as 2D methods; the results of both investigations are compared. The objective of this study is to determine whether the 2D method provides suitable results for the microstructural analysis of asphalt samples and how the results differ from those studied by the 3D method. The comparison shows that both methods can be used to analyze voids in asphalt samples. The 2D method provides valuable insight into the distribution of voids in a sample. In addition to the distribution of voids within a 2D section, the 2D method can also be used to make some structural statements about the location and structure of the voids in the 2D plane. The X-ray computed tomography method allows more complex analyses of the pore structure because of the third direction (3D). In addition, the 3D method provides more data, so that the pore structure can be described even more precisely, and the pore size (length, width, height) can be mapped and analyzed with a high degree of accuracy.

Dissolution of ß-C2S Cement Clinker: Part 2 Atomistic Kinetic Monte Carlo (KMC) Upscaling Approach.

Cement clinkers containing mainly belite (ß-C2S as a model crystal), replacing alite, offer a promising solution for the development of environmentally friendly solutions to reduce the high level of CO2 emissions in the production of Portland cement. However, the much lower reactivity of belite compared to alite limits the widespread use of belite cements. Therefore, this work presents a fundamental atomistic computational approach for comprehending and quantifying the mesoscopic forward dissolution rate of ß-C2S, applied to two reactive crystal facets of (100) and (1¯00). For this, an atomistic kinetic Monte Carlo (KMC) upscaling approach for cement clinker was developed. It was based on the calculated activation energies (ΔG*) under far-from-equilibrium conditions obtained by a molecular dynamic simulation using the combined approach of ReaxFF and metadynamics, as described in the Part 1 paper in this Special Issue. Thus, the individual atomistic dissolution rates were used as input parameters for implementing the KMC upscaling approach coded in MATLAB to study the dissolution time and morphology changes at the mesoscopic scale. Four different cases and 21 event scenarios were considered for the dissolution of calcium atoms (Ca) and silicate monomers. For this purpose, the (100) and (1¯00) facets of a ß-C2S crystal were considered using periodic boundary conditions (PBCs). In order to demonstrate the statistical nature of the KMC approach, 40 numerical realizations were presented. The major findings showed a striking layer-by-layer dissolution mechanism in the case of an ideal crystal, where the total dissolution rate was limited by the much slower dissolution of the silicate monomer compared to Ca. The introduction of crystal defects, namely cutting the edges at two crystal boundaries, increased the overall average dissolution rate by a factor of 519.

Dissolution of ß-C2S Cement Clinker: Part 1 Molecular Dynamics (MD) Approach for Different Crystal Facets.

A major concern in the modern cement industry is considering how to minimize the CO2 footprint. Thus, cements based on belite, an impure clinker mineral (CaO)2SiO2 (C2S in cement chemistry notation), which forms at lower temperatures, is a promising solution to develop eco-efficient and sustainable cement-based materials, used in enormous quantities. The slow reactivity of belite plays a critical role, but the dissolution mechanisms and kinetic rates at the atomistic scale are not known completely yet. This work aims to understand the dissolution behavior of different facets of ß-C2S providing missing input data and an upscaling modeling approach to connect the atomistic scale to the sub-micro scale. First, a combined ReaxFF and metadynamics-based molecular dynamic approach are applied to compute the atomistic forward reaction rates (RD) of calcium (Ca) and silicate species of (100) facet of ß-C2S considering the influence of crystal facets and crystal defects. To minimize the huge number of atomistic events possibilities, a generalized approach is proposed, based on the systematic removal of nearest neighbors' crystal sites. This enables us to tabulate data on the forward reaction rates of most important atomistic scenarios, which are needed as input parameters to implement the Kinetic Monte Carlo (KMC) computational upscaling approach. The reason for the higher reactivity of the (100) facet compared to the (010) is explained.

Bonding Behaviour of Steel Fibres in UHPFRC Based on Alkali-Activated Slag.

The mechanical performance of fibre-reinforced ultra-high-performance concrete based on alkali-activated slag was investigated, concentrating on the use of steel fibres. The flexural strength is slightly higher compared to the UHPC based on Ordinary Portland Cement (OPC) as the binder. Correlating the flexural strength test with multiple fibre-pullout tests, an increase in the bonding behaviour at the interfacial-transition zone of the AAM-UHPC was found compared to the OPC-UHPC. Microstructural investigations on the fibres after storage in an artificial pore solution and a potassium waterglass indicated a dissolution of the metallic surface. This occurred more strongly with the potassium waterglass, which was used as an activator solution in the case of the AAM-UHPC. From this, it can be assumed that the stronger bond results from this initial etching for steel fibres in the AAM-UHPC compared to the OPC-UHPC. The difference in the bond strength of both fibre types, the brass-coated steel fibres and the stainless-steel fibres, was rather low for the AAM-UHPC compared to the OPC-UHPC.

Dissolution of Portlandite in Pure Water: Part 1 Molecular Dynamics (MD) Approach.

The current contribution proposes a multi-scale bridging modeling approach for the dissolution of crystals to connect the atomistic scale to the (sub-) micro-scale. This is demonstrated in the example of dissolution of portlandite, as a relatively simple benchmarking example for cementitious materials. Moreover, dissolution kinetics is also important for other industrial processes, e.g., acid gas absorption and pH control. In this work, the biased molecular dynamics (metadynamics) coupled with reactive force field is employed to calculate the reaction path as a free energy surface of calcium dissolution at 298 K in water from the different crystal facets of portlandite. It is also explained why the reactivity of the (010), (100), and (11¯0) crystal facet is higher compared to the (001) facet. In addition, the influence of neighboring Ca crystal sites arrangements on the atomistic dissolution rates is explained as necessary scenarios for the upscaling. The calculated rate constants of all atomistic reaction scenarios provided an input catalog ready to be used in an upscaling kinetic Monte Carlo (KMC) approach.

Dissolution of Portlandite in Pure Water: Part 2 Atomistic Kinetic Monte Carlo (KMC) Approach.

Portlandite, as a most soluble cement hydration reaction product, affects mechanical and durability properties of cementitious materials. In the present work, an atomistic kinetic Monte Carlo (KMC) upscaling approach is implemented in MATLAB code in order to investigate the dissolution time and morphology changes of a hexagonal platelet portlandite crystal. First, the atomistic rate constants of individual Ca dissolution events are computed by a transition state theory equation based on inputs of the computed activation energies (ΔG*) obtained through the metadynamics computational method (Part 1 of paper). Four different facets (100 or 1¯00, 010 or 01¯0, 1¯10 or 11¯0, and 001 or 001¯) are considered, resulting in a total of 16 different atomistic event scenarios. Results of the upscaled KMC simulations demonstrate that dissolution process initially takes place from edges, sides, and facets of 010 or 01¯0 of the crystal morphology. The steady-state dissolution rate for the most reactive facets (010 or 01¯0) was computed to be 1.0443 mol/(s cm2); however, 0.0032 mol/(s cm2) for 1¯10 or 11¯0, 2.672 × 10-7 mol/(s cm2) for 001 or 001¯, and 0.31 × 10-16 mol/(s cm2) for 100 or 1¯00 were represented in a decreasing order for less reactive facets. Obtained upscaled dissolution rates between each facet resulted in a huge (16 orders of magnitude) difference, reflecting the importance of crystallographic orientation of the exposed facets.

Growth of C-S-H phases on different metallic surfaces.

The influence of reinforcement, especially fibre reinforcement in ultra-high performance concrete is strongly dependent on the bonding (adhesive, shear and friction bond) between metallic surface and cementitious matrix. As usually straight fibres are used for fibre reinforcement and, thus, no significant mechanical bonding is existent, the adhesive bond is particularly important. Previous studies stated that the adhesive bonding behaviour between metallic materials and cementitious matrix strongly depends on the chemical composition of metallic alloys. Therefore, in order to address this topic, the present study investigates the growth of C-S-H phases on stainless steel and on cold drawn steel. This growth process was realised by a surface treatment of the metallic alloys using a synthetically manufactured Tricalciumsilicate (C3 S) powder diluted in water. After defined times of the C3 S treatment the process is stopped to get a time dependent growing behaviour of the cementitious phases. Light microscopy as well as scanning electron microscopy was used in order to investigate the surfaces following the application of the C3 S. The results reveal that the growth of C-S-H phases is more dependent on the metallic surface and its topography than on the alloy composition.

Adsorption of PCE in alkali-activated materials analysed by fluorescence microscopy.

The realisation of high-performance concrete mixtures requires the use of superplasticizers to achieve a low water/binder ratio and thus high strengths. Polycarboxylate ethers (PCE) are mostly used as superplasticizers. The effectiveness of these superplasticizers depends on their chemical structure, the binders' alkaline environment and the ions present in the pore solution of the binder. In high alkaline systems like some alkali-activated materials no effective superplasticizer have been found yet. To unravel the compatibility of certain PCE to such a highly alkaline system a fluorescence microscopy approach was used. In first experiments, the adsorption of APEG (allyl ether) and MPEG (methacrylate) PCE on ground granulated blast furnace slag and fly ash was investigated varying the concentration of the activators. At a certain concentration, a complexation of the PCE can be recognised in fluorescence microscope. APEG shows a better stability compared to MPEG; this correlates with rheological investigations.

Determination of Suitable Imaging Techniques for the Investigation of the Bonding Zones of Asphalt Layers.

The material behavior of asphalt depends on its composition of aggregate, bitumen, and air voids. Asphalt pavements consist of multiple layers, making the interaction of the materials at the layer boundary important so that any stresses that occur can be relieved. The material behavior at the layer boundary is not yet understood in detail, as further methods of analysis are lacking in addition to mechanical methods. For this reason, the layer boundary of asphalt structures was analyzed using imaging methods. The aim of this research was to find an imaging method that allows a detailed analysis of the bonding zone of asphalt layers. Two different imaging techniques were used for this purpose. One is a 2-D imaging technique (asphalt petrology) and the other is a 3-D imaging technique (high-resolution computed tomography). Image analysis is a widely used technique in materials science that allows to analyze the material behavior and their composition. In this research, attention was paid to the analysis of the position of the bitumen emulsion, because the contained bitumen is supposed to bond the layers together. It was found that the application of 2-D imaging (asphalt petrology) lacked the precision for a detailed analysis of the individual materials at the layer boundary. With high-resolution computed tomography, a detailed view is possible to visualize the individual materials at the layer boundary in 3D. However, it is difficult to differentiate the materials because there are no gradations in the gray values due to the identical densities. However, it is possible to differentiate between the bitumen from the asphalt and from the emulsion if a high-density tracer is added to the bitumen emulsion for the CT studies. The results of the investigations are presented in this article.

Use of Design of Experiments (DoE) to Model the Sulphate Agent Amount of (Ultra)Finely Ground and Fast Hardening Portland Cement Clinker.

This paper presents a model to calculate the sulphate agent amount and sulphate agent ratio for fine grounded and fast hardening Portland cement clinker. Despite sufficient knowledge about the influence of calcium sulphate on the hydration process of cement, the sulphate agent amount is mostly adjusted empirically. As a result, often a wide and unfeasible experimental matrix has to be tested. In this work, Design of Experiments (DoE) was used in combination with in-situ X-ray diffraction (XRD) tests to accurately adjust the sulphate agent of different finely ground cement by calculation. With only 42 tests, it was possible to analyse in total the influence of the sulphate agent, the grinding fineness and the use of C-S-H-seeds for the use in fast-hardening Portland cement-based systems. In addition, it was found that a hemihydrate to anhydrite content of 25/75 leads to a stabilisation of the hydrated system in the first 24 h of hydration. A model for the optimisation of the sulphate agent composition in dependency of the cement fineness could be determined. Furthermore, it was shown that the DoE also provides optimal results in material sciences in a resource-saving way.

Durability Properties of Ultra-High Performance Lightweight Concrete (UHPLC) with Expanded Glass.

It is important to ensure the durability and safety of structures. In the case of newly developed materials that are outside the current rules, it is important to investigate all aspects of structural safety. The material studied in the following is a structural lightweight concrete with an ultra-high-performance matrix and expanded glass as a lightweight aggregate. The material, with a compressive strength of 60-100 MPa and a bulk density of 1.5-1.9 kg/dm3, showed high capillary porosities of 12 vol% (ultra-high-performance concretes (UHPC) < 5 vol%). Since the capillary porosity basically enables transport processes into the concrete, the material had to be examined more closely from the aspect of durability. Freeze-thaw resistance (68 g/m2) and chemical attack with sulfate at pH 3.5 for 12 weeks (16 g/m2) showed no increase in concrete corrosion. Targeted carbonation (0.53 mm/year0.5) and chloride penetration resistance (6.0 × 10-13 to 12.6 × 10-13 m2/s) also showed good results against reinforcement corrosion. The results show that most of the measured capillary pores resulted from the lightweight aggregate and were not all present as a pore system. Thus, the durability was only slightly affected and the concrete can be compared to an UHPC. Only the abrasion resistance showed an increased value (22,000 mm3/5000 mm2), which, however, only matters if the material is used as a screed.

Fluorescence Microscopy of Superplasticizers in Cementitious Systems: Applications and Challenges.

In addition to the desired plasticizing effect, superplasticizers used in high and ultra-high performance concretes (UHPC) influence the chemical system of the pastes and for example retardation of the cement hydration occurs. Thus, superplasticizers have to be chosen wisely for every material composition and application. To investigate the essential adsorption of these polymers to particle surfaces in-situ to overcome several practical challenges of superplasticizer research, fluorescence microscopy is useful. In order to make the superplasticizer polymers visible for this microscopic approach, they are stained with fluorescence dyes prior the experiment. In this work, the application of this method in terms of retardation and rheological properties of sample systems is presented. The hydration of tricalcium oxy silicate (C3S) in combination with different polycarboxylate ether superplasticizers is observed by fluorescence microscopy and calorimetry. Both methods can identify the retarding effect, depending on the superplasticizer's chemical composition. On the other hand, the influence of the superplasticizers on the slump of a ground granulated blast furnace slag/cement paste is correlated to fluorescence microscopic adsorption results. The prediction of the efficiency by microscopic adsorption analysis succeeds roughly. At last, the possibility of high-resolution imaging via confocal laser scanning microscopy is presented, which enables the detection of early hydrates and their interaction with the superplasticizers.

Effect of Fibre Material and Fibre Roughness on the Pullout Behaviour of Metallic Micro Fibres Embedded in UHPC.

The use of micro fibres in Ultra-High-Performance Concrete (UHPC) as reinforcement increases tensile strength and especially improves the post-cracking behaviour. Without using fibres, the dense structure of the concrete matrix results in a brittle failure upon loading. To counteract this behaviour by fibre reinforcement, an optimal bond between fibre and cementitious matrix is essential. For the composite properties not only the initial surfaces of the materials are important, but also the bonding characteristics at the interfacial transition zone (ITZ), which changes upon the joining of both materials. These changes are mainly induced by the bond of cementitious phases on the fibre. In the present work, three fibre types were used: steel fibres with brass coating, stainless-steel fibres as well as nickel-titanium shape memory alloys (SMA). SMA fibres have the ability of "remembering" an imprinted shape (referred to as shape memory effect), triggered by thermal activation or stress, principally providing for superior performance of the fibre-reinforced UHPC. However, previous studies have shown that NiTi-fibres have a much lower bond strength to the concrete matrix than steel fibres, eventually leading to a deterioration of the mechanical properties of the composite. Accordingly, the bond between both materials has to be improved. A possible strategy is to roughen the fibre surfaces to varying degrees by laser treatment. As a result, it can be shown that laser treated fibres are characterised by improved bonding behaviour. In order to determine the bond strength of straight, smooth fibres of different metal alloy compositions, the present study characterized multiple fibres in series with a Compact-Tension-Shear (CTS) device. For critical evaluation, results obtained by these tests are compared with the results of conventional testing procedures, i.e., bending tests employing concrete prisms with fibre reinforcements. The bond behaviour is compared with the results of the flexural strength of prisms (4 × 4 × 16 cm3) with fibre reinforcements.

Fluorescence Microscopic Investigations of the Retarding Effect of Superplasticizers in Cementitious Systems of UHPC.

The adsorption of superplasticizer molecules to particle surfaces in cementitious systems is a very important aspect for the desired liquefaction of pastes and concretes. This way, the comb shaped polymers shield attractive forces between the particles and induce a well-dispersed, homogeneous suspension. These admixtures allow the usage of fine fillers even in combination with low amounts of mixing water, and thus, are the basis for modern high performance concretes. However, the adsorption does not cause beneficial effects only: The polymer covered particle surfaces, especially clinker, are hindered to interact with water, thus hydration is retarded. This is the reason for lower early strength and is very disadvantageous for certain applications. Today it is known that the molecular structure of the polymers, for instance the chain length and charge density, affects the retardation strongly. The complexity and diversity of cementitious systems is the main reason why research in this field is quite empiric and time as well as cost intensive. To investigate the adsorption of superplasticizers in various systems in-situ, a fluorescence microscopic approach was applied: By staining the polymers with fluorescent dye they become localizable and the adsorption quantifiable. This work shows the influence of molecular structure to adsorption characteristic of different polymers and the correlation to the retarding effect of superplasticizers, especially concerning the presence of silica fume, which is indispensable for ultra-high performance concrete (UHPC).

Reactivity of Different Crystalline Surfaces of C3S During Early Hydration by the Atomistic Approach.

Early hydration of tricalcium silicate (C3S) has received great attention over the years due to the increased use of composite cement with a reduced number of clinker phases, especially the addition of what should be very reactive C3S to guarantee early strength. Although many mechanisms have been proposed, the dissolution of polygonal C3S at the material interface is not yet fully understood. Over the last decade, computational methods have been developed to describe the reaction in the cementitious system. This paper proposes an atomistic insight into the early hydration and the dissolution mechanism of calcium from different crystalline planes of C3S using reactive force field (ReaxFF) combined with metadynamics (metaD). The reactivity and thermodynamic stability of different crystal planes were calculated from the dissolution profile of calcium during hydration at 298 K. The simulation results, clearly describe the higher reactivity of ( 0 1 ¯ 1 ¯ ), (011), (100), and ( 1 ¯ 00 ) surfaces of C3S due to the strong interaction with the water, whereas, the dissolution profile explains the lower reactivity of ( 1 ¯ 1 ¯ 0 ), (110), ( 0 1 ¯ 0 ) and the effect of water tessellation on the (001), (010) planes.