Modeling and simulation of cement hydration kinetics and microstructure development

Efforts to model and simulate the highly complex cement hydration process over the past 40 years are reviewed, covering different modeling approaches such as single particle models, mathematical nucleation and growth models, and vector and lattice-based approaches to simulating microstructure development. Particular attention is given to promising developments that have taken place in the past few years. Recent applications of molecular-scale simulation methods to understanding the structure and formation of calcium–silicate–hydrate phases, and to understanding the process of dissolution of cement minerals in water are also discussed, as these topics are highly relevant to the future development of more complete and fundamental hydration models.     

Modelling and simulations of the chemo-mechanical behaviour of leached cement-based materials: Interactions between damage and leaching

The assessment of the durability of cement-based materials, which could be employed in underground structures for nuclear waste disposal, requires accounting for deterioration factors, such as chemical attacks and damage, and for the interactions between these phenomena. The objective of the present paper consists in investigating the long-term behaviour of cementitious materials by simulating their response to chemical and mechanical solicitations. In a companion paper (Stora et al., submitted to Cem. Concr. Res. 2008), the implementation of a multi-scale homogenization model into an integration platform has allowed for evaluating the evolution of the mineral composition, diffusive and elastic properties inside a concrete material subjected to leaching. To complete this previous work, an orthotropic micromechanical damage model is presently developed and incorporated in this numerical platform to estimate the mechanical and diffusive properties of damaged cement-based materials. Simulations of the chemo-mechanical behaviour of leached cementitious materials are performed with the tool thus obtained and compared with available experiments. The numerical results are insightful about the interactions between damage and chemical deteriorations.     

Influence of aggregate size and volume fraction on shrinkage induced micro-cracking of concrete and mortar

In this paper, the influence of aggregate size and volume fraction on shrinkage induced micro-cracking and permeability of concrete and mortar was investigated. Nonlinear finite element analyses of model concrete and mortar specimens with regular and random aggregate arrangements were performed. The aggregate diameter was varied between 2 and 16 mm. Furthermore, a range of volume fractions between 0.1 and 0.5 was studied. The nonlinear analyses were based on a 2D lattice approach in which aggregates were simplified as monosized cylindrical inclusions. The analysis results were interpreted by means of crack length, crack width and change of permeability. The results show that increasing aggregate diameter (at equal volume fraction) and decreasing volume fraction (at equal aggregate diameter) increase crack width and consequently greatly increases permeability.     

Sustainable development and climate change initiatives

In the present paper we argue that the cement and concrete industry is contributing positively to the Climate Change Initiative by:

? Continuously reducing the CO₂ emission from cement production by increased use of bio-fuels and alternative raw materials as well as introducing modified low-energy clinker types and cements with reduced clinker content.

? Developing concrete compositions with the lowest possible environmental impact by selecting the cement type, the type and dosage of supplementary cementitious materials and the concrete quality to best suit the use in question.

? Exploiting the potential of concrete recycling to increase the rate of CO₂ uptake.

? Exploiting the thermal mass of concrete to create energy-optimized solutions for heating and cooling residential and office buildings.

     

Comprehensive modeling of chloride ion and water ingress into concrete considering thermal and carbonation state for real climate

This article presents a comprehensive modeling of temperature, carbonation, water and chloride ions transport in cover concrete using the transport model “TransChlor”. The TransChlor transport model employs weather data and chloride ion concentrations present on the concrete surface to predict the temporal and spatial evolution of the presence of chloride ion concentrations in the cover concrete pores. The main features of the TransChlor model are presented and validated.The TransChlor model has been calibrated using experimental data on liquid water movement in concrete of different permeabilities under realistic microclimatic conditions. Chloride ion transport is validated by means of experimental results obtained from a newly developed chloride ion optical fiber based sensor.     

Interactions between shrinkage reducing admixtures (SRA) and cement paste's pore solution

Shrinkage reducing admixtures (SRA) have been developed to combat shrinkage cracking in concrete elements. While SRA has been shown to have significant benefits in reducing the magnitude of drying and autogenous shrinkage, it has been reported that SRA may cause a negative side effect as it reduces the rate of cement hydration and strength development in concrete. To examine the influence of SRA on cement hydration, this study explores the interactions between SRA and cement paste's pore solution. It is described that SRA is mainly composed of amphiphilic (i.e., surfactant) molecules that when added to an aqueous solution, accumulate at the solution-air interface and can significantly reduce the interfacial tension. However, these surfactants can also self-aggregate in the bulk solution (i.e., micellation) and this may limit the surface tension reduction capacity of SRA. In synthetic pore solutions, SRA is observed to form an oil-water-surfactant emulsion that may or may not be stable. Specifically, at concentrations above a critical threshold, the mixture of SRA and pore fluid is unstable and can separate into two distinct phases (an SRA-rich phase and an SRA-dilute phase). Further, chemical analysis of extracted pore solutions shows that addition of SRA to the mixing water depresses the dissolution of alkalis in the pore fluid. This results in a pore fluid with lower alkalinity which causes a reduction in the rate of cement hydration. This may explain why concrete containing SRA shows a delayed setting and a slower strength development.     

Green preparation of in situ Cr3C2 nano-coatings on graphite surface and their water-wettability and rheological properties

Cr₃C₂ coatings were successfully prepared on the surface of graphite flakes via a molten salt route by mixing Cr powders with natural graphite flakes in a binary LiCl-KCl salt at 450–950?°C for 4–12?h. The phases and microstructures of the coatings were verified by its XRD/XPS spectra and SEM/AFM observations, respectively. Together with the dissolution/dispersion evidence of chromium powders after interaction with the salt, and the slightly increased particle sizes due to the formation of Cr₃C₂ coatings on graphite flakes, a ‘template-growth’ kinetic process was therefore proposed on the formation of such coatings in the molten salt. The resultant coatings decreased the contact angle between water and graphite from 101° to ~ 75° and lowered the apparent viscosities of graphite water slurry by two orders of magnitude accordingly, suggesting that the coatings will afford graphite with good processing abilities for carbon-water based materials.     

Yield stress and viscosity equations for mortars and self-consolidating concrete

The rheological behavior of flowable concrete, such as self consolidating concrete is closely influenced by concreting temperature and the elapsed time. The variation of the plastic viscosity and the yield stress with the elapsed time and temperature must be accurately quantified in order to forecast the variation of workability of cement-based materials. A convenient method to study the variation of these rheological parameters is proposed, using the mortar of the concrete. This latter is designed from the concrete mixture, taking in account the liquid and solid phases with a maximum granulometry of 315 μm. Different SCC and mortars proportioned with two types of high range water reducing admixtures (HRWRA) were prepared at temperatures ranging from 10 to 33 °C. Test results indicates that the yield stress and the plastic viscosity of the mortar mixtures vary in a linear way with the elapsed time while an exponential variation of these rheological parameter is seen on SCC. In order to enhance robotization of concrete, general equations to predict the variations of the yield stress and plastic viscosity with time are proposed, using the corresponding mortar initial yield stress and plastic viscosity. Such equations, derived from existing models, can easily be employed to develop concrete design software. Experimental constants which are related to the paste fluidity or the aggregates proportioning can be extracted from a database created with either mortar or aggregates test results.     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Effect of natural and synthetic tackifiers on viscosities,adhesion properties and thermal stability of SNR and DPNR solution adhesives

Styrene-grafted natural rubber (SNR) and deproteinized natural rubber (DPNR) latexes were formulated with coumarone-indene (CI), gum rosin and petro resin (PR) tackifiers into solution adhesives with toluene as a solvent. The solution viscosities were evaluated by a Brookfield viscometer DV-II Plus with spindle No. 3. Pressure sensitive adhesives (PSAs) films were made and the adhesion properties were evaluated with loop tack, peel strength and shear strength tests. Thermal stability of the film was evaluated via Perkin-Elmer Pyris 6^TM thermogravimetric analysis at temperatures ranging from 30 to 600?°C at a heating rate of 10?°C per minute in nitrogen environment. Results indicate that as the tackifiers content increased, the solution viscosities increased with SNR/PR and DPNR/PR formulations showing the highest viscosities. Adhesion test also indicates that loop tack and peel strength of the adhesive solution increased but their shear strength decreased; increase of CI tackifier loadings conferred the highest peel strength for both SNR- and DPNR-based PSAs. Thermal analyses show that the addition of 40 phr CI tackifiers improved thermal stability of SNR adhesives based on their higher T_max and integral procedural decomposition temperature properties.     

Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C₃S, β-C₂S, C₃A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, ²⁹Si and ²⁷Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.     

Design and function of novel superplasticizers for more durable high performance concrete (superplast project)

In this article we shall describe our quest and ultimate success in furthering our understanding of the action of superplasticizers on the rheology of cement and concrete. By specifically producing superplasticizers with varied architectures, we have been able to show the important structural features of the macromolecules that lead to a successful superplasticizer or water reducing agent. Both polycarboxylate and lignosulfonate polymers have been investigated. Using both non-reactive model MgO powders, three different types of cement blends, the adsorption behaviour and the effect on the rheological properties of these two important superplasticizer families have been used to further develop a conceptual model for superplasticizer — cement behaviour. This paper will deal mainly with the conceptual model, the materials and methods used to asses the polymer adsorption behaviour and rheological properties of the systems studied. We shall briefly describe the adsorption of the polymers onto the different surfaces and their influence on surface charge and rheology and the influence of the various ionic species found in cement pore solutions that may influence polymer-cement affinity. The key factors are shown to be the effective adsorbed polymer thickness and the induced surface charge which can be influenced by the polymer architecture, the pore solution composition and the initial particle surface charge.     

Linear and non-linear analysis of desorption processes in cement mortar

Based on the gathered experimental data concerning adsorption/desorption processes in cement mortar, it has been stated that the rate of these processes changes in time even if they proceed in stable conditions. In this paper an attempt is made to describe such processes by applying linear and non-linear diffusion theories for comparison. The main aim of these studies is to determine the diffusion coefficient by correlating the theoretically determined desorption isotherms with the experimental ones. The validation of the diffusion coefficient was accomplished through comparison of the theoretical desorption curves with the experimental data for narrow and broad ranges of the air humidity changes. The final conclusion is that the moisture transfer in hygroscopic porous materials for broad ranges of the air humidity changes should be modeled by the non-linear diffusion theory, in which the diffusion coefficient is a function of moisture content. The new material in this paper concerns very long time measurements in desiccators, and evaluation of the diffusion coefficient by an advanced optimization algorithm.     

Wavelet-based analysis of ultrasonic longitudinal and transverse pulses in cement-based materials

Ultrasonic pulse velocity has been used for decades to detect localized damage and to estimate concrete properties. More recent applications aim at diffuse damage characterization, such as environmental and mechanical damage. In most applications the methodology to calculate pulse speed is a very important issue. This work, applying continuous wavelet transform (CWT) to construct time-frequency signal representations, calculates frequency-dependent velocity of longitudinal and transverse ultrasonic pulses using wavelet scales. The method is applied to a total of 14 specimens of 5 different mixes and frequency-dependent velocities are calculated using four wavelet families. The CWT capability to decompose the inquiring pulse spectrum and analyze phase velocities is discussed with regard to wavelet, pulse type, and mixture. Frequency-dependent velocity of longitudinal pulses at lower frequencies (from 100 kHz up to 250 kHz) was proven to be much more sensitive to mix proportions than transverse pulses.     

Surface and internal deterioration of concrete due to saline and non-saline freeze-thaw loads

Concrete deterioration due to frost action in non-saline and saline environments was studied statistically. The most significant variables affecting the freeze-thaw durability of concrete were calculated statistically and contours of estimated response surface were produced. Water-cement ratio and air content of the concretes were the most dominant variables affecting the internal and surface damage caused by the freezing and thawing loads. In the non-saline environment, water curing improved the R² values of the developed deterioration models in the surface scaling part of the tests. In the internal damage tests, the curing measures did not improve the statistical relevancy of the estimated response surfaces. In the saline freeze-thaw tests, high-strength concretes were studied. When water-binder ratio was below 0.42 internal deterioration was the governing freeze-thaw damage mechanism which needed larger air content compared to surface scaling.     

Chemistry and engineering of the clinkerization process — Incremental advances and lack of breakthroughs

“Chemistry” and “process engineering” constitute the foundation of the clinkerization process but over the decades the engineering advances have been phenomenal to convert the chemical concepts into very large, fast reacting, energy-efficient and pollution-abated pyroprocessing systems.Excepting the cooler design that still lags behind in attaining the desired cooling rate for clinker phases, notwithstanding several innovations for thermal efficiency, the rest of the engineering for the pyroprocessing system seems to be touching a plateau of efficiency parameters. However, the occurrence of volatile cycles and controls of process and quality are governed more by the systemic parameters than simple chemical behavior of the feed materials. The emission norms and the engineering control features are mostly in sync with each other, except the organic emissions of dioxins, furans, PCBs and PAHs, where more precise determination of their precursors is called for.In respect of breakthroughs in new pyroprocessing technologies other than the conventional rotary kilns, the initiation of research dates back to eighties but the researches remain stalled perhaps in apprehension of non-viability. They need to be revived for efficiency and sustainability. The nano-cement technology should also be evaluated more intensely for its application potential.The present keynote paper attempts to portray the present status of pyroprocessing and to define the areas of challenges lying ahead.     

Cement hydration and microstructure formation in the presence of water-soluble polymers

Hardening of cement mortars modified with small amounts of water-soluble polymers implies both cement hydration and polymer film formation. In this paper, the effect of the presence of water-soluble polymers on the cement hydration reactions is investigated by means of isothermal calorimetry, thermal analysis, FT-IR spectroscopy and SEM investigation. In spite of an initial retardation of the hydration reactions, a higher degree of hydration is found after 90 days for 1% PVAA, MC and HEC modified mortars, due to a better dispersion of the cement particles in the mixing water. MC also affects the morphology of the Ca(OH)₂ crystals. Polymer bridges are detected between the layered crystals, gluing the layers together and strengthening the microstructure. Additionally, the internal cohesion of all bulk polymer modified cement pastes is improved. In the presence of the polymers, a more cohesive microstructure with a smaller amount of microcracks is created.     

2-(2'-咪唑偶氮)萘酚-4-磺酸的合成及其分析性质的研究

合成了新显色剂咪唑偶氮－２－萘酚－４－磺酸（ＩＡＮ－４Ｓ）,研究了试剂的离解常数及其与金属离子的显色反应。     

Comparison between surface and bulk hydrophobic treatment against corrosion of galvanized reinforcing steel in concrete

The effectiveness of bulk hydrophobic treatment against corrosion of galvanized steel reinforcement in concrete specimens with w/c = 0.45 and w/c = 0.75 was compared with that of surface treatment, even in the presence of cracks 0.5 and 1 mm wide in the concrete cover. In this case surface hydrophobic treatments were applied both before and after cracking as a preventive and a restorative method against reinforced concrete deterioration, respectively. The obtained results in terms of water absorption, electrochemical measurements, chlorides penetration, and visual observations carried out on reinforced concrete specimens during the exposure to wet–dry cycles in 10% NaCl solution showed that bulk hydrophobization is the most effective treatment in improving the corrosion resistance of galvanized steel reinforcements in concrete also in the presence of cracks. Surface hydrophobization is very effective just in the first few exposure cycles to the aggressive environment and when used as a restorative method which is able to cancel the deleterious effect of cracks only 0.5 mm wide.     

The mini-conical slump flow test: Analysis and numerical study

This paper provides a general study on cement paste flow. Both mini-slump and Marsh cone tests are used to evaluate the workability of fresh paste mixtures derived from self compacting concretes. A numerical approach is used to reproduce global flow behavior and to check the accuracy of the obtained viscosity as well as the validity of expressions available in the literature giving yield stress from the final diameter of slumped paste. The computational modeling allows access to local information in order to analyze different regions and corresponding flow types, i.e. falling solid and flowing fresh cementing material mixtures.The limitation of some empirical models allowing the prediction of yield stress τ₀ and plastic viscosity μ from mini-slump tests is underlined, conditions of validity are expressed and a new expression is proposed.