Effect of temperature on the pore solution, microstructure and hydration products of Portland cement pastes

The effect of temperature on the hydration products and the composition of the pore solution are investigated for two Portland cements from 5 to 50 °C. Increased temperature leads to an initially fast hydration and a high early compressive strength. At 40 and 50 °C, the formation of denser C-S-H, a more heterogeneous distribution of the hydration products, a coarser porosity, a decrease of the amount of ettringite as well as the formation of very short ettringite needles has been observed. At 50 °C, calcium monosulphoaluminate has formed at the expenses of ettringite. In addition, the amount of calcium monocarboaluminate present seems to decrease. The composition of the pore solution mirrors the faster progress of hydration at higher temperatures. After 150 days, however, the composition of the pore solution is similar for most elements at 5, 20 and 50 °C. Exceptions are the increased sulphate concentrations and the slightly lower Al and Fe concentrations at 50 °C.     

Alkali binding in hydrated Portland cement paste

The alkali-binding capacity of C-S-H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C-S-H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data reported in literatures concerning thirteen different recipes are analyzed and used as references. A three-dimensional computer-based cement hydration model (CEMHYD3D) is used to simulate the hydration of Portland cement pastes. These model predictions are used as inputs for deriving the alkali-binding capacity of the hydration product C-S-H in hydrated Portland cement pastes. It is found that the relation of Na⁺ between the moles bound in C-S-H and its concentration in the pore solution is linear, while the binding of K⁺ in C-S-H complies with the Freundlich isotherm. New models are proposed for determining the alkali-binding capacities of C-S-H in hydrated Portland cement paste. An updated method for predicting the alkali concentrations in the pore solution of hydrated Portland cement pastes is developed. It is also used to investigate the effects of various factors (such as the water to cement ratio, clinker composition and alkali types) on the alkali concentrations.     

The origin of early age expansions induced in cementitious materials containing shrinkage reducing admixtures

Studies on the early-age shrinkage behavior of cement pastes, mortars, and concretes containing shrinkage reducing admixtures (SRAs) have indicated these mixtures frequently exhibit an expansion shortly after setting. While the magnitude of the expansion has been noted to be a function of the chemistry of the cement and the admixture dosage; the cause of the expansion is not clearly understood. This investigation uses measurements of autogenous deformation, X-ray diffraction, pore solution analysis, thermogravimetry, and scanning electron microscopy to study the early-age properties and describe the mechanism of the expansion in OPC pastes made with and without SRA. The composition of the pore solution indicates that the presence of the SRA increases the portlandite oversaturation level in solution which can result in higher crystallization stresses which could lead to an expansion. This observation is supported by deformation calculations for the systems examined.     

An ESEM investigation of latex film formation in cement pore solution

Environmental scanning electron microscopy (ESEM) and complementary methods were employed to study the time dependent film formation of a latex dispersion in water and cement pore solution. First, a model carboxylated styrene/n-butyl acrylate latex dispersion possessing a minimum film forming temperature (MFFT) of 18 °C was synthesized in aqueous media via emulsion polymerization. Its film forming property was at a temperature of 40 °C, studied under an ESEM. The analysis revealed that upon removal of water, film formation occurs as a result of particle packing, particle deformation and finally particle coalescence. Film formation is significantly retarded when the latex dispersion is present in cement pore solution. This effect can be ascribed to adsorption of Ca²⁺ ions onto the surface of the anionic latex particles and to interfacial secondary phases. This layer of adsorbed Ca²⁺ ions hinders interdiffusion of the macromolecules and subsequent film formation of the latex polymer.     

Experimental determination of the effective anionic charge density of polycarboxylate superplasticizers in cement pore solution

The specific anionic charge density of polycarboxylate superplasticizers can be determined experimentally by titration with a cationic polyelectrolyte. In this study, the anionic charge densities of several polycarboxylates based on methacrylate ester chemistry were measured in aqueous solution at pH 7 and 12.6, resp., and in cement pore solution. The anionic charge of the polycarboxylates increases with increasing pH value as a result of deprotonation of the carboxylate groups in the polymer backbone. Addition of Ca²⁺ ions generally causes a decrease of the anionic charge density. The reduction in anionic charge varies and depends on the architecture of the polycarboxylate. The effect results from the binding of calcium ions by the carboxylate groups, both through complexation and counter-ion condensation. Consequently, the effective anionic charge density of polycarboxylates in cement pore solution can differ significantly from the charge density which is calculated based on the chemical composition. Generally the -COO⁻ functionality may coordinate Ca²⁺ as a monodentate or bidentate ligand. The type of coordination depends on the steric accessibility of the carboxyl group. In PC molecules possessing high side chain density, the -COO⁻ group is shielded by the side chains and coordinates as bidentate ligand, producing a neutral Ca²⁺-PC complex. Accordingly, this type of PC shows almost no anionic charge anymore in cement pore solution. In PCs possessing high amount of -COO⁻, Ca²⁺ is coordinated monodentate, resulting in an anionic complex. Consequently, this type of PC shows significant anionic character in pore solution. Its adsorption behaviour is determined by a gain in enthalpy which derives from the electrostatic attraction between the PC and the surface of cement. This way, by utilizing the relatively simple method of charge titration, it is possible to assess the electrostatic attraction which, besides entropy gains, is the driving force behind the adsorption of polycarboxylates on the cement surface and thus determines their effectiveness as dispersing agent. The findings are generally applicable to other anionic admixtures used in cement.     

Impact of admixtures on the hydration kinetics of Portland cement

Most concrete produced today includes either chemical additions to the cement, chemical admixtures in the concrete, or both. These chemicals alter a number of properties of cementitious systems, including hydration behavior, and it has been long understood by practitioners that these systems can differ widely in response to such chemicals.In this paper the impact on hydration of several classes of chemicals is reviewed with an emphasis on the current understanding of interactions with cement chemistry. These include setting retarders, accelerators, and water reducing dispersants. The ability of the chemicals to alter the aluminate–sulfate balance of cementitious systems is discussed with a focus on the impact on silicate hydration. As a key example of this complex interaction, unusual behavior sometimes observed in systems containing high calcium fly ash is highlighted.     

Effects of mixing energy on technological properties and hydration kinetics of grouting mortars

During slurry preparation, effects of certain phenomena on fluidity and hardening characteristics of cement-based grouts have been reported. Deterioration of fluidity and hardening will affect the slurry performance, quality of workmanship and result in subsequent structural defects. There has been little research conducted on the effects of mixing energy during slurry preparation which has focused on the reasons or mechanisms for changes in characteristic properties. This work describes and measures the effects of several mixing parameters on properties of grouting materials, such as fluidity, hardening characteristics, shrinkage, heat of hydration, ion elution and crystallographic structure using X-ray diffraction and SEM. The results indicate that long mixing processes cause deterioration in fluidity and setting properties. These observations can be explained by acceleration in hydration kinetics and changes in microstructures and subsequent changes in dispersion states due to different mixing durations.     

Influence of bleed water reabsorption on cement paste autogenous deformation

The effects of bleed water reabsorption and subsequent early age expansion on observed autogenous deformation are investigated in this research. Bleeding was induced by varying superplasticizer and shrinkage-reducing admixture dosages and by increasing the water-to-cement ratio. This research revealed that significant early age expansion occurs with increasing chemical admixture dosages and higher water-to-cement ratios, as expected, due to increasing bleeding of those samples. When samples were rotated, negligible early age expansion was observed. Thus, bleed water reabsorption is shown to be the primary mechanism causing initial expansion in sealed autogenous deformation samples. Thermal dilation and ettringite growth appear to have a minimal influence on the observed expansion. Rotating the samples during setting eliminates the potential for bleed water reabsorption and is recommended for all autogenous deformation testing.     

Pore solution composition and alkali diffusion in inorganic polymer cement

Extraction of pore solutions from hardened inorganic polymer cement (“geopolymer”) paste samples shows that the pore network of these materials is rich in alkali cations and has pH > 13, with a relatively low dissolved Si concentration. However, there is little soluble Ca available in these materials to play a buffering role similar to Ca(OH)₂ or high-Ca C-S-H in hydrated Portland cements, meaning that preventing alkali loss is essential in ensuring the protection of reinforcing steel. It has been seen previously that calcium in an inorganic polymer cement binder is important in the formation of a low-permeability pore system; alkali diffusion measurements confirm these observations and highlight the role of Ca in reducing effective alkali diffusion coefficients by up to an order of magnitude. This is crucial for the durability of inorganic polymer concretes containing steel reinforcement, as it appears that the use of calcium-containing raw materials will be highly preferable.     

Ultrasound monitoring of the influence of different accelerating admixtures and cement types for shotcrete on setting and hardening behaviour

The possible use of ultrasound measurements for monitoring setting and hardening of mortar containing different accelerating admixtures for shotcrete was investigated. The sensitivity to accelerator type (alkaline aluminate or alkali-free) and dosage, and accelerator-cement compatibility were evaluated. Furthermore, a new automatic onset picking algorithm for ultrasound signals was tested. A stepwise increase of the accelerator dosage resulted in increasing values for the ultrasound pulse velocity at early ages. In the accelerated mortar no dormant period could be noticed before the pulse velocity started to increase sharply, indicating a quick change in solid phase connectivity. The alkaline accelerator had a larger effect than the alkali-free accelerator, especially at ages below 90 min. The effect of the alkali-free accelerator was at very early age more pronounced on mortar containing CEM I in comparison with CEM II, while the alkaline accelerator had a larger influence on mortar containing CEM II. The increase of ultrasound energy could be related to the setting phenomenon and the maximum energy was reached when the end of workability was approached. Only the alkaline accelerator caused a significant reduction in compressive strength and this for all the dosages tested.     

Early hydration and setting of oil well cement

A broad experimental study has been performed to characterize the early hydration and setting of cement pastes prepared with Class H oil well cement at water-to-cement ratios (w/c) from 0.25 to 0.40, cured at temperatures from 10 to 60 °C, and mixed with chemical additives. Chemical shrinkage during hydration was measured by a newly developed system, degree of hydration was determined by thermogravimetric analysis, and setting time was tested by Vicat and ultrasonic velocity measurements. A Boundary Nucleation and Growth model provides a good fit to the chemical shrinkage data.Temperature increase and accelerator additions expedite the rate of cement hydration by causing more rapid nucleation of hydration products, leading to earlier setting; conversely, retarder and viscosity modifying agents delay cement nucleation, causing later setting times. Lower w/c paste needs less hydration product to form a percolating solid network (i.e., to reach the initial setting point). However, for the systems evaluated, at a given w/c, the degree of hydration at setting is a constant, regardless of the effects of ambient temperature or the presence of additives.     

The role of alkali content of Portland cement on the expansion of concrete prisms containing reactive aggregates and supplementary cementing materials

This paper presents results covering the effects of alkali content of Portland cement (PC) on expansion of concrete containing reactive aggregates and supplementary cementing materials (SCM). The results showed that the alkali content of PC has a significant effect on expansion of concrete prisms with no SCM. When SCM is used, the expansion was found to be related to both the chemical composition of the SCM and, to a lesser extent, the alkali content of the PC. The concrete expansions were explained, at least partly, on the basis of the alkalinity of a pore solution extracted from hardened cement paste samples containing the same cementing blends. An empirical relation was developed correlating the chemical composition (Ca, Si and total Na₂O_e) of the cementing blend (PC + SCM) and the alkalinity of the pore solution. Results from accelerated mortar bar test (ASTM C 1260) and a modified version thereof are also presented.     

Study on effects of solar radiation and rain on shrinkage, shrinkage cracking and creep of concrete

In this paper, the effects of actual environmental actions on shrinkage, creep and shrinkage cracking of concrete are studied comprehensively. Prismatic specimens of plain concrete were exposed to three sets of artificial outdoor conditions with or without solar radiation and rain to examine the shrinkage. For the purpose of studying shrinkage cracking behavior, prismatic concrete specimens with reinforcing steel were also subjected to the above conditions at the same time. The shrinkage behavior is described focusing on the effects of solar radiation and rain based on the moisture loss. The significant environment actions to induce shrinkage cracks are investigated from viewpoints of the amount of the shrinkage and the tensile strength. Finally, specific compressive creep behavior according to solar radiation and rainfall is discussed. It is found that rain can greatly inhibit the progresses of concrete shrinkage and creep while solar radiation is likely to promote shrinkage cracking and creep.     

Early-age behavior of materials with a cement matrix

Materials with a cement matrix classically present early-age volume variations (shrinkage and/or swelling). This intrinsic early-age behavior strongly influences the length of time the buildings and structures will last because of the micro-cracking and cracking that results from it. One explanation for the macroscopic shrinkage is the presence of pore pressure in the porous medium. In this study, fine modeling of the coupling mechanism behind these internal strains is proposed. The chemical reaction associated with hydration is considered as the main force behind the hydric and mechanical evolutions in an endogenous configuration. Thus, the influence of chemical contraction, porosity, pore-size distribution and pore pressure are central to the study in the light of the numerical and experimental results obtained. A self-leveling layer of mortar of sulfo-aluminous concrete base was used.     

A volumetric technique for measuring the coefficient of thermal expansion of hardening cement paste and mortar

Knowledge of the coefficient of thermal expansion (CTE) is of paramount importance for the determination of the cracking risk of concrete structures at early ages. This paper presents a novel technique which is suitable to measure the CTE of hardening materials with high accuracy starting from casting time.The technique consists of casting a small amount of cement paste or mortar into flexible membranes. The specimens are immersed in an oil bath, whose temperature is rapidly changed and then kept constant in repeating cycles. By suspending the sample from a high-precision balance and reading the change of mass after each temperature step, the CTE is calculated with high accuracy from the measured temperature and strain.Results on cement pastes and mortars (water/cement 0.3) showed a good repeatability. In particular, a sudden decrease in the CTE at setting time, followed by a gradual increase as the cement paste self-desiccates, was measured.     

A microstructural approach to adherence mechanism of poly(vinyl alcohol) modified cement systems to ceramic tiles

PVA is a water soluble polymer used as cement modifier. An important modification observed by addition of PVA is the increase of the bond strength between cement paste and aggregate. The purpose of this work was to investigate the effect of PVA on the mechanism of adherence of cement pastes to ceramic tiles. Pastes with and without PVA were applied on the back side of porcelain tiles and after 56 days the microstructures of the interfaces were evaluated by SEM. The mode of rupture changed from mostly interfacial failure to a mixed-mode interfacial-cohesive failure for the paste with polymer addition in which was observed the reduction of the thickness of the porous transition zone between tile and paste bulk. Also, in plain paste the formation of a duplex film (CH plus C-S-H) in contact with tile surface was observed while in modified paste a single layer of C-S-H was identified.     

Characterization of multi-scale porosity in cement paste by advanced ultrasonic techniques

The effectiveness of advanced ultrasonic techniques to quantitatively characterize the capillary porosity and entrained air content in hardened cement paste is examined. Direct measurements of ultrasonic attenuation are used to measure the volume fraction and average size of entrained air voids and to assess variations in intrinsic porosity - as influenced by water-to-cement ratio (w/c) - in hardened cement paste samples. For the air entrained specimens, an inversion procedure based on a theoretical attenuation model is used to predict the average size and volume fraction of entrained air voids in each specimen, producing results in very good agreement with results obtained by standard petrographic methods and by gravimetric analysis. In addition, ultrasonic attenuation measurements are related to w/c to quantify the relationship between increasing porosity (with increasing w/c) and ultrasonic wave characteristics.     

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.     

Development of low pH cement systems forming magnesium silicate hydrate (M-S-H)

This work aimed to develop novel cement systems for waste encapsulation that would form with a pH of around 10. The approach taken was to investigate the formation of brucite by hydration of a light burned periclase (MgO). Commercially available MgO powders often contain some CaO, and therefore silica fume was added to form C-S-H gel. Identification of the hydrated phases in MgO/silica fume samples showed that brucite formed in substantial quantities as expected. However, brucite reacted with the silica fume to produce a magnesium silicate hydrate (M-S-H) gel phase. After 28 days, the pH of systems rich in MgO tended towards the pH controlled by residual brucite (~ 10.5), whereas when all brucite reacts with silica fume a cement with an equilibrium pH just below 10 was achieved.     

Analysis of C-S-H gel and cement paste by small-angle neutron scattering

The role of small-angle X-ray and neutron scattering (SAXS and SANS) in the characterization of cement is briefly reviewed. The unique information obtainable from SANS analysis of C-S-H gel in hydrating cement is compared with that obtainable by other neutron methods. Implications for the nature of C-S-H gel, as detected by SANS, are considered in relation to current models. Finally, the application of the SANS method to cement paste is demonstrated by analyzing the effects of calcium chloride acceleration and sucrose retardation on the resulting hydrated microstructure.