Corrosion resistance and chloride diffusivity of volcanic ash blended cement mortar

This article reports the results of an investigation on the chloride diffusivity and corrosion resistance of volcanic ash (VA) blended cement mortars with varying curing times of up to 1 year. The mortars had 20% and 40% VA as cement replacement and water/binder ratio of 0.55. The accelerated chloride ion diffusion (ACID) test was used to calculate the chloride ion (Cl⁻) diffusion coefficient (D_i) of the mortars using the Nernst-Plank equation for steady state condition. In addition, electrical resistivity, mercury intrusion porosimetry and differential scanning calorimetry (DSC) tests were conducted. Electrochemical measurement such as linear polarization resistance was used to monitor the corrosive behavior of the embedded steel bars. The chloride ingress into the mortars was also studied. Good correlations were found among D_i, total pore volume (TPV) and electrical resistivity of the mortars. It was also found that blending cement with VA significantly reduced the long-term D_i and hence increased the long-term corrosion resistance of mortars. This fact was also supported by the presence of lower quantity of Ca(OH)₂ and higher quantity of Friedel's salt in the VA blended mortars as observed from the DSC tests. Mortars with 40% VA showed better performance in terms of Cl⁻ diffusivity, chloride ingress and passivation period of embedded steel compared with the control mortar with 0% VA.     

The influences of siliceous waste on blended cement properties

The influences of siliceous waste on the properties of fly ash and blast furnace slag cement were studied, and its optimum mixing amount in blended cement was determined. The strength, setting time, resistance to chemical attack, dry shrinkage, and impermeability of blended cement mixed with siliceous waste were also investigated by different experiments. The measurement of pore size distribution for hardened cement pastes made by Poremaster-60 was recorded and analyzed in this article.     

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.     

Pore size and shape in mortar by thermoporometry

The pore structure of mortar (w/c = 0.55) was examined using thermoporometry (TPM), nitrogen adsorption/desorption (NAD), and mercury intrusion porosimetry (MIP). The TPM measurements were calibrated by comparison to NAD and MIP measurements on porous glass; similar comparisons were made on dried and resaturated mortars. For undried mortars, TPM provides the size of pore entries (from the freezing cycle) and interiors (from the melting cycle). In keeping with previous studies, we find that there is an unfrozen layer of water between the ice and the pore wall in porous glass that is about 0.8 nm thick; when lime-saturated water is used, the thickness of that layer increases by about 10%. In mortar, the unfrozen layer is about 1.0-1.2 nm thick, so no freezing occurs in pores with diameters ≤ 4.5 nm, at least down to − 40 °C (where the radius of the crystal/liquid interface is ∼ 1.5 nm). Based on the hysteresis in the freezing and melting curves, the larger mesopores in mortar were found to be rather spheroidal, while the smaller ones were more cylindrical.     

Corrosion process and structural performance of a 17 year old reinforced concrete beam stored in chloride environment

The long-term corrosion process of reinforced concrete beams is studied in this paper. The reinforced concrete elements were stored in a chloride environment for 17years under service loading in order to be representative of real structural conditions. At different stages, cracking maps were drawn, total chloride contents were measured and mechanical tests were performed. Results show that the bending cracks and their width do not influence significantly the service life of the structure. The chloride threshold at the reinforcement depth, used by standards as a single parameter to predict the end of the initiation period, is a necessary but not a sufficient parameter to define service life. The steel-concrete interface condition is also a determinant parameter. The bleeding of concrete is an important cause of interface de-bonding which leads to an early corrosion propagation of the reinforcements. The structural performance under service load (i.e.: stiffness in flexure) is mostly affected by the corrosion of the tension reinforcement (steel cross-section and the steel-concrete bond reduction). Limit-state service life design based on structural performance reduction in terms of serviceability shows that the propagation period of the corrosion process is an important part of the reinforced concrete service life.     

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.     

Probing the microstructure and water phases in composite cement blends

¹H nuclear magnetic resonance relaxometry has been used in combination with the more conventional techniques of mercury intrusion porosimetry, freeze-drying and thermogravimetric analysis to investigate the evolution of the microstructure and the distribution of water phases in two composite cement blends hydrating over a one year period. These two blends are composed of high substitution of Ordinary Portland Cement (OPC) with Blast Furnace Slag (BFS) at level of 75 wt.% (3:1 blend) and 90 wt.% (9:1 blend).After one year, the 3:1 blend microstructure is characterised by poorly interconnected gel pores filled with about 35 vol.% of water while less than 4 vol.% of water is trapped in remaining capillary pores. The 9:1 blend microstructure is characterised by a network of larger gel and capillary pores filled with about 21 and 22 vol.% of water respectively. Further hydration is ruled out for this blend.     

A gap-graded particle size distribution for blended cements: Analytical approach and experimental validation

To increase the packing density of blended cement paste, a gap-graded particle size distribution (PSD) was theoretically deduced and modified according to the wet density of actual paste. Then experiments were conducted to validate the hypothesis of improvement of the properties of blended cements by the gap-graded PSDs proposed. The experimental results show that the gap-graded PSD resulted in a decreased water requirement and an increased packing density of blended cement paste, and modified gap-graded PSDs gave further effects. The heat of hydration of gap-graded blended cement pastes released slowly in the first 24 h and increased rapidly afterward. The microstructure of gap-graded blended cements was much more homogeneous and denser than that of reference blended cement, therefore both early and late mechanical properties of low clinker gap-graded blended cements were improved significantly and even higher than those of Portland cement.     

Corrosion of steel bars in OPC mortar exposed to NaCl, MgCl2 and CaCl2: Macro- and micro-cell corrosion perspective

In North America, corrosion of the steel rebar commonly occurs due to chloride attack from deicing salts. In Canada, based on the severity and temperature of the ambient environment, three different deicing salts, or combination of them, are used: NaCl, MgCl₂ and CaCl₂. In this paper, the effect of each of these salts on the corrosion of steel rebar and their impact on the durability of the mortar have been investigated. The results show that CaCl₂ has the most negative effect on the steel and, in high concentrations, on the integrity of the mortar. MgCl₂ also deteriorates the mortar if used in high concentration, while NaCl has no apparent effect on mortar durability even in high concentration.     

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.     

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.     

Cover cracking of reinforced concrete due to rebar corrosion induced by chloride penetration

Cracking of concrete cover due to corrosion induced expansion of steel rebar is one of the major causes of the deterioration of reinforced concrete (RC) structures exposed to marine environments and de-icing salts.This paper presents two models that deal with the chloride-induced corrosion and subsequent cracking of concrete cover in RC structures. The former analyses the chloride diffusion within partially saturated concrete. A comprehensive model is developed through the governing equations of moisture, heat and chloride-ion flow. Nonlinearity of diffusion coefficients, chloride binding isotherms and convection phenomena are also highlighted. The latter describes the internal cracking around the bar due to expansive pressures as corrosion of the reinforcing bar progresses. Once a certain chloride concentration threshold is reached in the area surrounding the bar, oxidation of steel begins and oxide products are generated, which occupy much greater volume than the original steel consumed by corrosion. An embedded cohesive crack model is applied for cracking simulation.Both models are incorporated in the same finite element program. The models are chained, though not explicitly coupled, at first instance. Comparisons with experimental results are carried out, with reasonably good agreements being obtained. The work is a step forward for the integration of the two traditional phases (initiation and propagation) widely used in the literature and usually analysed separately. The estimation of the service life of the structure needs to evaluate the associated time for each one.     

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.     

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.     

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.     

Encapsulation of caesium-loaded Ionsiv in cement

The microporous material Ionsiv is used for ¹³⁷Cs removal from aqueous nuclear waste streams. In the UK, Cs-loaded Ionsiv is classed as an intermediate-level waste; no sentencing and disposal route is yet defined for this material and it is currently held in safe interim storage on several nuclear sites. In this study, the suitability of fly ash and blast furnace slag blended cements for encapsulation of Cs-Ionsiv in a monolithic wasteform was investigated. No evidence of reaction or dissolution of the Cs-Ionsiv in the cementitious environment was found by scanning electron microscopy and X-ray diffraction. However, a small fraction (≤ 1.6 wt.%) of the Cs inventory was released from the encapsulated Ionsiv during leaching experiments carried out on hydrated samples. Furthermore, it was evident that K and Na present in the cementitious pore water exchanged with Cs and H in the Ionsiv. Therefore, cement systems lower in K and Na, such as slag based cements, showed lower Cs release than the fly ash based cements.     

A multi-technique investigation of the nanoporosity of cement paste

The nanometer-scale structure of cement paste, which is dominated by the colloidal-scale porosity within the C-S-H gel phase, has a controlling effect on concrete properties but is difficult to study due to its delicate structure and lack of long-range order. Here we present results from three experimental techniques that are particularly suited to analyzing disordered nanoporous materials: small-angle neutron scattering (SANS), weight and length changes during equilibrium drying, and nanoindentation. Particular attention is paid to differences between pastes of different ages and cured at different temperatures. The SANS and equilibrium drying results indicate that hydration of cement paste at 20 °C forms a low-density (LD) C-S-H gel structure with a range of gel pore sizes and a relatively low packing fraction of solid particles. This fine structure may persist indefinitely under saturated conditions. However, if the paste is dried or is cured at elevated temperatures (60 °C or greater) the structure collapses toward a denser (less porous) and more stable configuration with fewer large gel pores, resulting in a greater amount of capillary porosity. Nanoindentation measurements of pastes cured at different temperatures demonstrate in all cases the existence of two C-S-H structures with different characteristic values of the indentation modulus. The average value of the modulus of the LD C-S-H is the same for all pastes tested to date, and a micromechanical analysis indicates that this value corresponds to the denser and more stable configuration of LD C-S-H. The experimental results presented here are interpreted in terms of a previously proposed quantitative “colloid” model of C-S-H gel, resulting in an improved understanding of the microstructural changes associated with drying and heat curing.     

Properties and hydration of blended cements with calcareous diatomite

In this paper the effect of diatomite addition on blended cement properties and hydration was studied. Calcareous diatomaceous rocks of Zakynthos Island, Ionian Sea, containing mainly CaCO₃ and amorphous silica of biogenic origin with the form of opal-A were used. Cement mortars and pastes, with 0%, 10%, 20% and 35% replacement of cement with the specific diatomite, were examined. Strength development, water demand and setting time were determined in all samples. In addition, XRD, SEM and weight loss at 350 °C were applied in order to study the hydration products and the hydration rate in the cement-diatomite pastes. Blended cements, having up to 10% diatomite content, develop the same compressive strength, as the corresponding Portland cement, while the presence of diatomite leads to an increase of the paste water demand. Diatomite is characterized as natural pozzolana, as it satisfies the requirements of EN 197 1 concerning the active silica content. The pozzolanic nature of the diatomite results to the formation of higher amounts of hydrated products, specifically at the age of 28 days.     

Properties and hydration of blended cements with steelmaking slag

The present research study investigates the properties and hydration of blended cements with steelmaking slag, a by-product of the conversion process of iron to steel. For this purpose, a reference sample and three cements containing up to 45% w/w steel slag were tested. The steel slag fraction used was the “0-5 mm”, due to its high content in calcium silicate phases. Initial and final setting time, standard consistency, flow of normal mortar, autoclave expansion and compressive strength at 2, 7, 28 and 90 days were measured. The hydrated products were identified by X-ray diffraction while the non-evaporable water was determined by TGA. The microstructure of the hardened cement pastes and their morphological characteristics were examined by scanning electron microscopy. It is concluded that slag can be used in the production of composite cements of the strength classes 42.5 and 32.5 of EN 197-1. In addition, the slag cements present satisfactory physical properties. The steel slag slows down the hydration of the blended cements, due to the morphology of contained C₂S and its low content in calcium silicates.     

Studies on blended cement with a large amount of fly ash

The influence of the contents of the clinker, activators and fly ash on the properties of blended cement with high fly ash content was studied. Experimental data from X-ray diffraction and pore size distribution indicated that the main hydration product of the fly ash blended cement was C-S-H gel, ettringite and a small amount of Ca(OH)₂. The volume porosity of the pores with diameter bigger than 0.1 μm was lower than that of the micro pores and gel pores with diameter lower than 0.05 μm. The amount of chemical combined water has increased with the curing age duration, while the content of Ca(OH)₂ has reduced after 7 days.