The development of microstructure during the hydration of Portland cement.

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Determination of the degree of reaction of fly ash in blended cement pastes

This paper gives a review over methods to determine the degree of reaction for supplementary cementitious materials (SCMs) with focus on Portland cement - fly ash blends only and summarizes and highlights the most important findings which are detailed in a parallel paper published in Materials and Structures. Determination of the extent of the reaction of SCMs in mixtures is complicated for several reasons: (1) the physical presence of SCMs affects the rate and extent of the reaction of the ground clinker component – the so called “filler effect”; (2) SCMs are usually amorphous with complex and varied mineralogy which make them difficult to quantify by many classical techniques such as X-ray diffraction; (3) the rate of reaction of SCMs in a cement blend may be quite different from its rate of reaction in systems containing simply alkali or lime. From this review it is clear that measuring the degree of reaction of SCMs remains challenging. Nevertheless progress has been made in recent years to offer alternatives to the traditional selective dissolution methods. Unfortunately some of these – image analysis and EDS mapping in the scanning electron microscope, and NMR - depend on access to expensive equipment and are time consuming. With regard to fly ashes, NMR seems to be reliable but limited to fly ash with low iron content. New methods with quantitative EDS mapping to segment fly ash particles from the hydrated matrix and to follow the reaction of glass groups of disparate composition separately look very promising, but time consuming. Sources with a high proportion of fine particles will have higher errors due to lower limit of resolution (1-2 μm). Whereas for SCMs which react relatively fast (e.g. slag, calcined clay) the methods based on calorimetry and chemical shrinkage seem promising on a comparative basis, the very low reaction degree of fly ashes before 28 days means that the calorimetry method is not practical. There is a lack of data to assess the usefulness of long term chemical shrinkage measurements. The possibility to quantify the amorphous phase by XRD is promising as this is a widely available and rapid technique which can at the same time give a wealth of additional information on the phases formed. However, the different reaction rates of different glasses in compositionally heterogeneous fly ashes will need to be accounted for and may strongly reduce the accuracy of the profile decomposition method. This paper is the work of working group 2 of the RILEM TC 238-SCM “Hydration and microstructure of concrete with supplementary cementitious materials”

Performance of Concrete Made with a Calcined Clay – Limestone-Portland Cement Exposed to Natural Conditions

This work presents the results of an investigation carried out to assess durability of concrete made with a calcined clay- limestone-Portland cement with 47% of clinker, hereafter named LC3, produced during an industrial trial in 2013. LC3 was used to cast concrete blocks and later expose them at a natural location at the northern coast of Cuba. Reference concrete was cast with Cuban Portland cement having 88% of clinker. Throughout three years (2015, 2016, 2017) concrete cores were systematically taken and the specimens were subjected to a testing program that included Formation factor, chloride profiling, surface resistivity, air permeability and carbonation depth. The studies proved that concrete made with the new binder presents a more refined capillary pore network, thus the movement of ions through the concrete matrix is slower than in normal PC concrete. Experimental measurement of the chloride profiles, Formation factor, surface resistivity and air permeability confirm an improvement of performance in the range of 2-3 compared to PC concrete. This is attributed to the presence of calcined clay in the new system and the synergy with limestone. For concrete exposed in coastal areas in hot & humid regions, carbonation is hindered by the high Relative Humidity, which saturates the pore system and reduces CO2 diffusion. The use of LC3 in concrete in very aggressive –chloride- conditions could yield a better performance against steel corrosion, as the tests on surface resistivity have proven

Deterioration of mortar bars immersed in magnesium containing sulfate solutions

Mortars prepared with a CEM I and a CEM III/B binder were investigated in different magnesium sulfate solutions. The main deterioration mechanism for the CEM I was expansion, while surface erosion was dominant for CEM III/B. The presence of sodium, potassium and calcium in a magnesium sulfate solution led to less expansion and less surface deterioration for both, CEM I and CEM III/B, than which was observed in solutions containing only sodium or magnesium sulfate. The presence of a mixture of different cations seems to lower both the surface deterioration and the expansion and might explain why sulfate attack damages are not as frequent in the field as in laboratory tests. Sulfate binding before cracking/expansion is similar in the presence of all different solutions investigated, indicating that the speed of sulfate ingress and the amount of bound sulphate depends during the first months mainly on the binde

Evolution of pore structure in blended systems

In this study, the effect of SCM in the cement paste was isolated by using ternary systems combining Portland cement, quartz and SCM. The results show clear differences in how the hydrates from the reaction of clinker, slag and fly ash fill space. The reaction of slag is more efficient than that of fly ash in modifying the porosity. Our results indicate that Portland cement (PC), slag and fly ash reactions are limited at later ages by the lack of water-filled capillary pores. The higher the space available, with increasing the water/solids ratio, the later the reaction is limited. This explains the lower degree of reaction of SCM in blended systems at high replacement level

Composition of C-S-H in pastes with increasing levels of silica fume addition

New results show that the microstructure development of cement–silica fume blends is very different from plain cement. Portlandite (CH) tends to precipitate as platelets and even around clinker grains as “CH rims” and is consumed by pozzolanic reaction with silica fume. The Ca/Si ratio in the inner product (IP) C–S–H decreases as CH is consumed to reach Ca/Si ≈ 1.40–1.50 at the point when CH has disappeared, and then drops down to 1.00 in absence of CH. At later ages, the IP C–S–H is often composed of two distinct regions. The outermost (formed first) consists of originally high Ca/Si C–S–H, which Ca/Si slowly decreases. The second (formed later) forms only once CH is no longer present and has a lower Ca/Si. Between 10 and 38 °C, the main effect of increasing the temperature is to accelerate the reaction of cement and increase the reactivity of silica fume. The changes in Ca and Si in the pore solution of similar systems suggest that the composition of the solution and the solids reciprocally influence each other

TC 238-SCM: hydration and microstructure of concrete with SCMs State of the art on methods to determine degree of reaction of SCMs

This paper is the work of working group 2 of the RILEM TC 238-SCM. Its purpose is to review methods to estimate the degree of reaction of supplementary cementitious materials in blended (or composite) cement pastes. We do not consider explicitly the wider issues of the influence of SCMs on hydration kinetics, nor the measurement of degree of reaction in alkali activated materials. The paper categorises the techniques into direct methods and indirect methods. Direct methods attempt to measure directly the amount of SCM remaining at a certain time, such as selective dissolution, microscopy combined with image analysis, and NMR. Indirect methods infer the amount of SCM reacted by back calculation from some other measured quantity, such as calcium hydroxide consumption. The paper first discusses the different techniques, how they operate and the advantages and limitations along with more details of case studies on different SCMs. In the second part we summarise the most suitable approaches for each SCM, and the paper finishes with conclusions and perspectives for future work

pyCSH: Automated atomic-level structure generation of bulk C-S-H and investigation of their intrinsic properties

A new Python code for the automated generation of realistic bulk calcium silicate hydrate (C-S-H) structures is introduced. The code was used to generate 400 structures with Ca/Si of 1.3, 1.5, 1.7, and 1.9. The generated structures are in excellent agreement with experimentally measured C-S-H properties (Ca/Si, 2H/Si, MCL, Si-OH/Si, and Ca-OH/Ca). Molecular dynamics was used to simulate the structures, which were then investigated for their structural features and energetic stability. The results indicate very similar short-range ordering and energetic stability between all 400 structures. Finally, it is shown how computational C-S-H models can be used to understand the experimentally measured pair distribution functions. The code, named pyCSH, is available as open source under GPL-2 license at GitHub https://github.com/hegoimanzano/pyCSH.git and https://github.com/akmiitm/pyCSH.git

On-Chip Super-Resolution Imaging with Fluorescent Polymer Films

Wide field of view (FOV), label-free super-resolution imaging is demonstrated using a specially designed waveguide chip that can illuminate a sample with multi-colour evanescent waves travelling along different directions. The method is enabled by a polymer fluorescent film which emits over a broad wavelength range. Its polygonal geometry ensures coverage over all illumination directions, enabling high fidelity image reconstruction whilst minimizing distortion and image blurring. By frequency shifting and iterative stitching of different spatial frequencies in Fourier space, the reconstruction of two dimensional samples is achieved without distortion over wide FOVs. The fabrication process is facile and compatible with conventional semiconductor-fabrication methods. The super-resolution chip (SRC) can thus be produced with high yield, offer opportunities for potential conjunction of super-resolution techniques integrated optical circuits or for the development of single-use diagnostic kits

The Atomic-Level Structure of Cementitious Calcium Silicate Hydrate

Efforts to tune the bulk physical properties of concrete are hindered by a lack of knowledge related to the atomic-level structure and growth of calcium silicate hydrate phases, which form about 50-60% by volume of cement paste. Here we describe the first synthesis of compositionally uniform calcium silicate hydrate phases with Ca:Si ratios tunable between 1.0 and 2.0. The calcium silicate hydrate synthesized here does not contain a secondary Ca(OH)(2) phase, even in samples with Ca:Si ratios above 1.6, which is unprecedented for synthetic calcium silicate hydrate systems. We then solve the atomic-level three-dimensional structure of these materials using dynamic nuclear polarization enhanced H-1 and Si-29 nuclear magnetic resonance experiments in combination with atomistic simulations and density functional theory chemical shift calculations. We discover that bridging interlayer calcium ions are the defining structural characteristic of single-phase cementitious calcium silicate hydrate, inducing the strong hydrogen bonding that is responsible for stabilizing the structure at high Ca:Si ratios