Influence of chemical degradation on mechanical behavior of a petroleum cement paste

Cement paste used in the Oil Industry is generally subjected to chemical degradation due to flow of acid fluids in various situations. The present study focuses on the evolution of thermo-hydro-mechanical (THM) behavior with chemical degradation of petroleum cement paste. Triaxial compression tests with different confining pressures (0, 3, 10 and 20 MPa) are carried out on a standard oil cement paste in sound state and completely degraded state by ammonium nitrate solution under a temperature of 90 °C. The results obtained show that the material in its initial state exhibits a small elastic phase and a strong capacity of compaction. The mechanical behavior depends on the load induced pore water pressure. Because of the increase in porosity caused by chemical degradation, the mechanical strength (cohesion and friction angle) and Young's modulus decrease. The dependence of mechanical strength and Young's modulus on confining pressure is smaller in the chemically degraded cement paste than in the sound one. In fine, the mechanical behavior of the whole material becomes more ductile. As a result, such effects of chemical degradation should be taken into account when modeling such cement paste materials exposed to such chemical degradations.     

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.     

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.     

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.     

Porosity and specific surface area of Roman cement pastes

Mercury porosimetry, water vapour and nitrogen adsorption were used to follow the hydration of Roman cements — belite cements calcined at low temperature. Generally, unimodal distribution of pore sizes was observed, with the threshold pore width decreasing considerably with increasing curing time. An open porous structure with the threshold pore diameter between 0.2 and 0.8 μm and the specific surface area not exceeding 20 m²/g was produced at early ages when quick growth of the C–A–H phases is observed. The surface area reached up to 120 m²/g and the threshold pore width shifted to around 0.02 μm when the subsequent formation of C–S–H gel filled the larger pores. Both mercury porosimetry and water vapour adsorption were found to be capable of following the progress of hydration of the Roman cements with high reliability at least for a comparative evaluation of historic Roman cement mortars and repair materials used in restoration projects.     

Characterization of pore structure in cement-based materials using pressurization-depressurization cycling mercury intrusion porosimetry (PDC-MIP)

Numerous mercury intrusion porosimetry (MIP) studies have been carried out to investigate the pore structure in cement-based materials. However, the standard MIP often results in an underestimation of large pores and an overestimation of small pores because of its intrinsic limitation. In this paper, an innovative MIP method is developed in order to provide a more accurate estimation of pore size distribution. The new MIP measurements are conducted following a unique mercury intrusion procedure, in which the applied pressure is increased from the minimum to the maximum by repeating pressurization-depressurization cycles instead of a continuous pressurization followed by a continuous depressurization. Accordingly, this method is called pressurization-depressurization cycling MIP (PDC-MIP). By following the PDC-MIP testing sequence, the volumes of the throat pores and the corresponding ink-bottle pores can be determined at every pore size. These values are used to calculate pore size distribution by using the newly developed analysis method. This paper presents an application of PDC-MIP on the investigation of the pore size distribution in cement-based materials. The experimental results of PDC-MIP are compared with those measured by standard MIP. The PDC-MIP is further validated with the other experimental methods and numerical tool, including nitrogen sorption, backscanning electron (BSE) image analysis, Wood's metal intrusion porosimetry (WMIP) and the numerical simulation by the cement hydration model HYMOSTRUC3D.     

Alternative blended cement with ceramic residues: Corrosion resistance investigation on reinforced mortar

Blended cements are largely used for concrete: they are usually considered cements with a low environmental impact, as they require less clinker than ordinary Portland cement (OPC). Different constituents can be used as supplementary clinker component usually leading to cement with high resistance to outdoor environment. Polishing residue (PR), coming from porcelain stoneware tiles production, can be successfully used as new constituent for blended cement, however its action for enhancing the durability of cement matrix must be assessed. With this purpose, electrochemical tests (half cell potential, impressed voltage and linear polarization techniques) have been carried out on steel reinforced mortar samples, prepared using a 25% PR based cement and 100% OPC as binder and exposed to a 3.5% NaCl solution. The corrosion resistance results and microstructure analysis highlight better durability performances for PR based cement than those exhibited by OPC, mainly for curing time > 28 days.     

Identification of viscoelastic C-S-H behavior in mature cement paste by FFT-based homogenization method

A powerful and robust numerical homogenization method based on fast Fourier transform (FFT) is formulated to identify the viscoelastic behavior of calcium silicate hydrates (C-S-H) in hardened cement paste from its heterogeneous composition. The identification is contingent upon the linearity of the creep law. To characterize cement paste microstructure, the model developed by Bentz at the National Institute of Standards and Technology, which has the resolution of 1 μm, is adopted. Model B3 for concrete creep is adapted to characterize the creep of C-S-H in cement paste. It is found that the adaptation requires increasing the exponent of power law asymptote of creep compliance. This modification means that the rate of attenuation of creep with time is lower in C-S-H than in cement paste, and is explained by differences in stress redistribution. In cement paste, the stress is gradually transferred from the creeping C-S-H to the non-creeping components. The viscoelastic properties of C-S-H at the resolution of 1 μm were identified from creep experiments on cement pastes 2 and 30 years old, having the water-cement ratio of 0.5. The irreversible part of C-S-H creep, obtained from these old specimens at almost saturated state, is found to be negligible unless the specimens undergo drying and resaturation prior to the creep test.     

Application of the Rietveld method to the analysis of anhydrous cement

X-ray powder diffraction allows direct measurement of the phase content in cement. More recently, whole pattern approaches such as the Rietveld method show an improvement in both within (repeatability) and between laboratory (reproducibility) precision. The aim of this paper is to discuss the influence of the different parameters involved in the Rietveld method and review the most recent quantitative X-ray powder diffraction studies on anhydrous cement. Comparisons with Bogue calculations, scanning electron microscopy and nuclear magnetic resonance are also discussed.     

Measurement and simulation of dendritic growth of ice in cement paste

We re-examine experiments by Helmuth (1962) from which he concluded that ice grows in the pores of cement paste under heat-flow control, and that the internal temperature rises to the melting point given by the Gibbs-Thomson equation. We find that his conclusions are correct, but the growth rates he reports are misleading. Using experimental and computational methods, we show that the ice grows in the form of dendrites, which allows a constant growth rate under heat-flow control. A modification of the experimental procedure permits accurate measurement of the growth rate of ice in the pores.     

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.     

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.     

Micro-spectroscopic investigation of Al and S speciation in hardened cement paste

Synchrotron-based micro X-ray fluorescence (micro-XRF) and micro X-ray absorption near edge spectroscopy (micro-XANES) have been used to determine the spatial distribution of Al and S and to identify the Al- and S-bearing species in compact hardened cement paste hydrated at 50 °C. The contribution of the S-bearing cement phases to the composed S K-edge XANES spectra collected in ten S-rich regions was determined using least-squares fitting. Ettringite and calcium monosulfoaluminate were identified as the main S-bearing species in the selected regions. Factor analysis was employed to determine the contribution of the various Al-bearing cement minerals to the composed Al K-edge XANES collected in different Al-rich regions of the cement matrix. Principal component analysis revealed that all spectra could be fitted using three components. Target transformation further suggested that the two Al-bearing clinker phases (aluminate, ferrite) and secondary phases of the hydrate assemblage (ettringite, AFm phases, hydrotalcite) contributed to the set of components that made up the experimental spectra. Least-squares fitting allowed the relative contribution of each reference compound to be determined. Aluminate and/or ferrite were detected in all Al-rich regions. AFm phases were identified in six out of the ten regions studied, while ettringite was detected in only two regions. The study confirmed that AFm phases are important cement minerals in hardened cement paste hydrated at 50 °C.     

Association of macroscopic laboratory testing and micromechanics modelling for the evaluation of the poroelastic parameters of a hardened cement paste

The results of a macro-scale experimental study performed on a hardened class G cement paste [Ghabezloo et al. (2008) Cem. Con. Res. (38) 1424-1437] are used in association with the micromechanics modelling and homogenization technique for evaluation of the complete set of poroelastic parameters of the material. The experimental study consisted in drained, undrained and unjacketed isotropic compression tests. Analysis of the experimental results revealed that the active porosity of the studied cement paste is smaller than its total porosity. A multi-scale homogenization model, calibrated on the experimental results, is used to extrapolate the poroelastic parameters to cement pastes prepared with different water-to-cement ratio. The notion of cement paste active porosity is discussed and the poroelastic parameters of hardened cement paste for an ideal, perfectly drained condition are evaluated using the homogenization model.     

Micromechanics analysis of thermal expansion and thermal pressurization of a hardened cement paste

The results of a macro-scale experimental study of the effect of heating on a fluid-saturated hardened cement paste are analysed using a multi-scale homogenization model. The analysis of the experimental results revealed that the thermal expansion coefficient of the cement paste pore fluid is anomalously higher than the one of pure bulk water. The micromechanics model is calibrated using the results of drained and undrained heating tests and permits the extrapolation of the experimentally evaluated thermal expansion and thermal pressurization parameters to cement pastes with different water-to-cement ratios. It permits also to calculate the pore volume thermal expansion coefficient α_? which is difficult to evaluate experimentally. The anomalous pore fluid thermal expansion is also analysed using the micromechanics model.     

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.     

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.     

Role of disjoining pressure in cement based materials

During the hydration process of Portland cement a nanoporous gel is formed. The high internal surface of the hydration products, mainly calcium-silicate hydrates, and the numerous adsorbed cations interact with water. At an equilibrium moisture content below 50% adsorbed water molecules reduce the surface tension of the solid particles. Water adsorbed at higher relative humidity is at the origin of disjoining pressure acting in small gaps between particles. Both processes are major mechanisms of shrinkage and swelling of hardened cement paste. Results of investigations into the disjoining pressure are summarised. The relevance of disjoining pressure for the behaviour of cement-based materials will be discussed.     

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.     

Effect of the variations of clinker composition on the poroelastic properties of hardened class G cement paste

The effect of the variations of clinker composition on the poroelastic properties of class G oil-well cement pastes is studied using a multiscale homogenization model. The model has been calibrated in a previous work based on the results of a laboratory study. Various compositions of class G cements from literature are used in a hydration model to evaluate the volume fractions of the microstructure constituents of hardened cement paste. The poroelastic parameters such as drained bulk modulus, Biot coefficient, and Skempton coefficient are evaluated using the homogenization model. The results show that the variations in chemical composition of class G cements have no important effect on the variations of the poroelastic properties.