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.

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 $\overline{1}00$, 010 or 0$\overline{1}$0, $\overline{1}10$ or $1\overline{1}0$, and 001 or 00$\overline{1}$) 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 0$\overline{1}$0 of the crystal morphology. The steady-state dissolution rate for the most reactive facets (010 or 0$\overline{1}0$) was computed to be 1.0443 mol/(s cm²); however, 0.0032 mol/(s cm²) for $\overline{1}10$ or $1\overline{1}0$, 2.672 × 10⁻⁷ mol/(s cm²) for 001 or 00$\overline{1}$, and 0.31 × 10⁻¹⁶ mol/(s cm²) for 100 or $\overline{1}00$ 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.

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.

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 (1$\overline{1}$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.

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 ( $0\overline{1}\overline{1}$ ), (011), (100), and $\left(\overline{1}00\right)$ surfaces of C₃S due to the strong interaction with the water, whereas, the dissolution profile explains the lower reactivity of ( $\overline{1}\overline{1}0$ ), (110), ( $0\overline{1}0$ ) and the effect of water tessellation on the (001), (010) planes.

Cement clinkers containing mainly belite (β-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 β-C₂S, applied to two reactive crystal facets of (100) and ($\overline{1}00$). 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 ($\overline{1}00$) facets of a β-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.