Electro-chemical chloride extraction: Influence of C3A of the cement on treatment efficiency

The aim of this study was to clarify whether the C₃A content of cement had a significant effect on electrochemical chloride extraction (ECE) treatment efficiency. It is known that a higher C₃A content in a cement gives it superior chloride complexing ability resulting in the formation of an “insoluble” calcium chloro aluminate compound.ECE was applied using cylindrical specimens made from concrete containing two levels of C₃A (4.3% and 9.05%). Specimens were 5 cm in diameter and 10 cm in height. Steel was placed in the axial direction with an embedded length of 7 cm. These specimens were immersed in an NaCl solution and dried in a stream of air at 40 °C for 10 months. The corrosion was monitored by half-cell potential and polarization resistance measurements. After steel depassivation, ECE was applied for 20, 30, 40 and 50 days using a constant current density of 1 A/m² of steel. At the end of the treatment, the specimens were maintained at 20 °C and 70% RH in order to observe the evolution of the steel (electrochemical measurements).The results show that, after 30 days of treatment, the chloride content remained constant in the specimen. This was probably due to OH⁻ ion formation on the steel. The OH⁻ ions “contribute” to the current transport, decreasing the ECE efficiency. Concerning the C₃A content, ECE efficiency was slightly affected by C₃A because only a part of the bound chloride ions was released. From the point of view of corrosion, half-cell potential showed a shift in the positive direction, indicating little corrosion activity at 20 °C and 70% RH. However, polarization resistance measurements showed that 2 months post treatment corrosion rates were significant, although the corrosion rate decreased from 6 μA/cm² to 2.5 μA/cm².     

Effect of temperature and type of sand on the magnesium sulphate attack in sulphate resisting Portland cement mortars

External Sulphate Attack on sulphate-resisting Portland cement concretes is a well-researched field. However, the effect of temperature on the performance of sulphate attack requires further attention. For this purpose, cubic mortars were made with sulphate resisting Portland cement (low C₃A) and two types of sand, silica and limestone, which were then immersed in a 5% MgSO₄ solution at different temperatures: 5, 20 and 50 °C, for 24 months. The deterioration of mortars due to magnesium sulphate attack was evaluated by measuring changes in mass, compressive strength, porosity and sorptivity. The X-ray diffraction was also used to determine the different mineral phases, and the pH of the conservation solutions was monitored. No damage was observed on the samples exposed at 50 °C. However, serious damage was noted on mortars made with silica sand exposed at 5 °C. Results show that high temperature improved some physical and mechanical properties and do not necessarily accelerate the degradation due to magnesium sulphate attack. Sulphate-resisting Portland cements with limited C₃A content was found to be susceptible to Thaumasite Sulphate Attack. The type of sand has a remarkable effect on the performance of mortars at low temperature compared to high temperature. The samples with limestone sand showed better resistance against magnesium sulphate attacks.     

Examination of mortar bars containing varying percentages of coarsely crystalline gypsum as aggregate

Contamination of aggregate sources by coarsely crystalline gypsum occurs frequently in the Middle East. Mortar bars were made which contained up to 5% gypsum (by weight of aggregate) in the form of aggregate pieces. The bars were made using three different cements of varying C₃A content and were stored at 20°C and 38°C. The results show that significant expansions do not occur within mortar bars if their total sulphate content lies below the present British Standard limit of 4% SO₃ by weight of cement. Sulphate Resisting Portland Cement (SRPC) can tolerate a higher level of contaminant gypsum than Ordinary Portland Cement (OPC). Temperature also effects the degree of expansion, especially in the case of high C₃A cement.     

Binding of chloride and alkalis in Portland cement systems

A thermodynamic model for describing the binding of chloride and alkalis in hydrated Portland cement pastes has been developed. The model is based on the phase rule, which for cement pastes in aggressive marine environment predicts multivariant conditions, even at constant temperature and pressure. The effect of the chloride and alkalis has been quantified by experiments on cement pastes prepared from white Portland cements containing 4% and 12% C₃A, and a grey Portland cement containing 7% C₃A. One weight percent calcite was added to all cements. The pastes prepared at w/s ratio of 0.70 were stored in solutions of different Cl (CaCl₂) and Na (NaOH) concentrations. When equilibrium was reached, the mineralogy of the pastes was investigated by EDS analysis on the SEM. A well-defined distribution of chloride was found between the pore solution, the C-S-H phase, and an AFm solid solution phase consisting of Friedel's salt and monocarbonate. Partition coefficients varied as a function of iron and alkali contents. The lower content of alkalis in WPC results in higher chloride contents in the C-S-H phase. High alkali contents result in higher chloride concentrations in the pore solution.     

Effect of cement C3A content, temperature and storage medium on thaumasite formation in carbonated mortars

The purpose of this study is to determine the effect of cement C₃A content, temperature and composition of the immersion medium (water, gypsum and magnesium sulphate solution) on the rate of thaumasite formation in cement mortars. It also aims to ascertain how the C₃A content influences the composition of the salt formed.The mortar prisms for this study were made with two different cements, one with low and the other with high Al₂O₃ content, with or without gypsum and/or calcium carbonate. After hydration, curing and carbonation, the prisms were partially immersed in distilled water and stored at temperatures ranging from 0 to 5 °C for up to 5 years. Some of the prisms were immersed in a 2% (w/w) gypsum solution or in 1.4% (w/w) magnesium sulphate solution at ambient temperature. Samples were taken at different ages and mineralogical and micro-structurally characterised.Some of the specimens tested were observed to expand, in a process concurring with the formation of thaumasite or a solid solution of thaumasite and ettringite, at both ambient and cooler temperatures. A correlation was found between cement C₃A content and the composition of the deterioration product involved in the expansive process: thaumasite forms in mortars made with low C₃A cement, whereas mixed crystals or solid solutions of thaumasite and ettringite form in mortars made with high C₃A content cement.     

Pore solution composition and reinforcement corrosion characteristics of microsilica blended cement concrete

Plain and microsilica blended cement pastes with water-cement ratio of 0.6 were prepared using a 14% C₃A cement. Two levels of chloride from NaCl corresponding to 0.6% and 1.2% by weight of cement were added through mix water. The pastes were allowed to hydrate in sealed containers for 180 days and then subjected to pore solution expression. The expressed pore fluids were analyzed for chloride and hydroxyl ion concentrations. The results show that the OH⁻ ion concentration in the pore solutions of both chloride-free and chloride-bearing pastes drop steeply with increasing cement replacement by microsilica. For 10% microsilica cement pastes the pH for both 0.6% and 1.2% chloride addition was found to be around 13.30. However, the pH drops to a level below that of saturated Ca(OH)₂ solution when cement replacement by microsilica is increased from 10% to 20%. This is ascribable to the consumption of Ca(OH)₂ by microsilica as shown by the DTA/TGA results. 10% and 20% microsilica blending more than doubles the free chloride ion concentration in the pore solutions of the chloride-bearing pastes. 10% microsilica replacement raises the Cl⁻/OH⁻ ratio 4 to 5 fold, whereas for 20% microsilica replacement, the Cl⁻/OH⁻ ratio is increased to 77 and 39 folds over the corresponding values for the plain cement pastes for 0.6% and 1.2% chloride additions respectively. Accelerated corrosion monitoring tests carried out on steel bars embedded in plain and microsilica blended cement concretes exposed to 5% NaCl solution show a 3 fold superior performance of microsilica blended cement concretes in terms of corrosion initiation time. This corrosion behaviour is contrary to the prediction from the increased aggressivity of pore solution composition in terms of highly elevated Cl⁻/OH⁻ ratios. This is attributable to the densification of cement matrix by the pozzolanic reaction between microsilica and calcium hydroxide. No discernable advantage in terms of corrosion initiation time is evident by increasing microsilica blending from 10% to 20%.     

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.     

Corrosion behaviour of hafnium diboride in aqueous solutions

A dense HfB₂ ceramic material was prepared by hot pressing in the presence of 2.5 wt.% Si₃N₄, as a sintering aid. The microstructure consisted of a fine HfB₂ matrix with refractory secondary phases (BN, HfO₂, Hf(C,N,O)) and Si, mainly located at the triple points. The material corrosion behaviour in acid and alkaline solutions of chlorides and sulphates was investigated by means of several experimental techniques, that is potentiodynamic polarization curve recording and potentiostatic tests coupled to solution chemical analysis, scanning electron microscope (SEM) observations and X-ray photoelectron spectroscopy (XPS) surface chemical characterization. Sintered HfB₂ undergoes an electrochemical corrosion attack of the HfB₂ phase and a chemical corrosion attack, mainly localized on the secondary phases. In acid sulphate solution a strong corrosion attack on the diboride phase occurs which leaves a secondary phase skeleton. In acid chloride solution and in alkaline chloride and sulphate solutions, the rate of secondary phase dissolution is quicker than the dissolution rate of the primary diboride phase and an intergranular corrosion attack morphology occurs. The Si phase dissolves relatively fast only in alkaline solutions. In analogy with the corrosion behaviour of ZrB₂, corrosion of HfB₂ phase is thought to produce both soluble and insoluble (hafnium and boron oxides) corrosion products. In acid sulphate solution the soluble corrosion products are mainly boric acid and a sulphate complex of Hf(IV). In the other solutions they are mainly constituted by boric acid (or borates, depending on the solution pH). The high corrosion rates detected in acid sulphate solution are due to the marked stability of the soluble sulphate complex of Hf(IV).     

基于不同胶凝材料钢筋混凝土耐腐蚀性试验研究

针对混凝土结构中钢筋的锈蚀问题,以普通硅酸盐水泥和镁水泥作为胶凝材料,制作了钢筋裸露和涂有环氧树脂涂层的4种钢筋混凝土试件,将其浸泡在氯盐、硫酸盐及镁盐的耦合溶液中,利用电化学方法得到极化曲线和交流阻抗谱,通过塔菲尔外推法进行非线性最小二乘法拟合计算得到腐蚀电流密度、腐蚀电位、腐蚀速率等相关评价指标来衡量混凝土中钢筋锈蚀情况.结果表明:长期浸泡在耦合盐溶液中,普通硅酸盐水泥和镁水泥钢筋混凝土试件都发生了较严重的腐蚀,普通硅酸盐水泥的抗腐蚀性优于镁水泥;在钢筋表面涂有GHT涂层可极大地降低钢筋的腐蚀速率;镁水泥GHT涂层混凝土试件的抗腐蚀性能劣于硅酸盐GHT涂层混凝土试件但优于硅酸盐裸露钢筋混凝土.     

Corrosion rates of steel embedded in cement pastes

Dynamic polarization techniques were used to estimate the corrosion rates of steel embedded in cement paste made with different binder systems. A corrosion model is proposed. The corrosion rates were determined by employing the Evans diagrams constructed from cathodic polarization curve of steel embedded in chloride free cement paste and anodic polarization curve of steel embedded in cement pastes containing chloride. Within the limitations of the adopted experimental conditions and sample configuration, the preliminary results indicate that corrosion rates of steel embedded in blended cement pastes generally fall within the range shown by steel embedded in portland cement pastes.     

Sulfate attack on cementitious materials containing limestone filler — A review

This review summarizes the results of sulfate performance in laboratory and field tests where limestone is used as a constituent of cement (PLC) or as a sand replacement where it is particularly beneficial to the properties of self compacting concretes (SCC).Laboratory studies on paste, mortar or concrete specimens exposed to Na₂SO₄ and MgSO₄ solutions in a wide range of concentrations at different temperatures as well as mixtures with different compositions, cement compositions and limestone proportions are considered in a conceptual analysis as for the resistance to external sulfate attack and, especially, thaumasite sulfate attack.A detailed analysis of environmental aggressiveness (concentration, temperature and pH), mixture composition and cement composition used in each study are presented for PLC and SCC. Reported field studies are also shown, only a few cases have used limestone filler in their composition. A conceptual graphical analysis is then proposed to relate the degree of surface deterioration and mineralogical composition of attacked surface to the main variables of external sulfate attack: water/cementitious material ratio, limestone content and C₃A content of the cement. Observation of graphical analysis clearly shows that deterioration by ESA is mainly governed by effective w/c ratio and C₃A content of the cement. Surface damage is controlled when low effective w/c ratio and low C₃A are used. In MgSO₄ solution, low temperatures increase the degree of deterioration. Thaumasite is the last attack stage in the different sulfate environments.     

Laboratory investigation of reinforcement corrosion initiation and chloride threshold content for self-compacting concrete

Time-to-corrosion (T_i) of reinforcement in concrete and chloride threshold content (C_th) are important service life determinants for reinforced concrete structures in chloride-laden environments. In this study, the two determinants of a series of self-compacting concretes (SCC) and regular concretes were experimentally investigated. A new sampling approach for C_th determination (milling powder from corrosion active site at the rebar/concrete interface) was adopted to accurately express chloride content resulting in corrosion occurrence. It is found that the T_i and C_th follow the 3-parameter Weibull distribution. The results indicate that the corrosion initiation of rebar in concrete slabs depends upon both cement alkalinity and superplasticizer. Rebar, embedded in high alkalinity cement SCC, exhibits better corrosion resistance as indicated by the longer T_i, higher C_th and larger Weibull modulus, m. A larger Weibull modulus indicates that anti-corrosion performance of rebar in slabs is more stable and less scattered. The effects of specific superplasticizer on rebar corrosion resistance are discussed from the viewpoint of air void amount and size distribution at the rebar/concrete interface.     

The influence of mineral admixtures on sulfate resistance of limestone cement pastes aged in cold MgSO4 solution

The influence of slag (S), fly ash (FA) and silica fume (SF) on the sulfate resistance of limestone cements was evaluated. Hardened pastes were exposed to MgSO₄ solution at 5 °C. Visible changes of the samples during the exposure were followed. Absorption of sulfate was measured and changes in mineralogical composition were evaluated by thermogravimetric analysis and X-ray diffraction (XRD). It was found that among admixtures used, only the addition of silica fume to limestone cement significantly improved its sulfate resistance. Cement with lower contents of C₃A and C₃S also showed favorable performance compared to cement having higher contents of these minerals.     

Effect of temperature on pore solution composition in plain cements

Cement pastes with a water-cement ratio of 0.6 were prepared using three ordinary portland cements with C₃A contents of 2.43, 7.59 and 14%. Three levels of chlorides 0.3, 0.6 and 1.2% by weight of cement, derived from sodium chloride, were added through mix water. The pastes were allowed to cure in sealed containers at 20 and 70°C for 180 days and then subjected to pore solution extraction. The expressed pore solutions were analyzed for chloride and hydroxyl ion concentrations. Results show that increase in temperature from 20 to 70°C increased unbound chlorides and decreased hydroxyl ion concentration of pore solutions for all the three cements. The simultaneous increase in unbound chlorides and decrease in hydroxyl ion concentration drastically increased Cl⁻/OH⁻ ratio of the pore solution, thereby indicating an increase in corrosion risk. This adverse effect of increase in the Cl⁻/OH⁻ ratio of the pore solution with increase in temperature is higher in the high 14% C₃A cement than in the low C₃A cements, and is also higher for the low 0.3% chloride treatment level than the higher chloride inductions. Increase in temperature is also expected to cause an increase in ionic diffusion to steel embedded in concrete as well as in the rate of corrosion reaction. All these factors tend to increase corrosion risk of steel reinforcement in concrete with an increase in temperature.     

Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3-Ni nano composite coatings

In this paper, the results on the electrochemical impedance spectroscopy and corrosion properties of electrodeposited nanostructured Al₂O₃-Ni composite coatings are presented. The nanocomposite coatings were obtained by codeposition of alumina nanoparticles (13 nm) with nickel during plating process. The coating thickness was 50 μm on steel support and an average of nano Al₂O₃ particles inside of coatings at 15 vol.% was present. The structure of the coatings was investigated by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure. The electrochemical behavior of the coatings in the corrosive solutions was investigated by polarization potentiodynamic and electrochemical impedance spectroscopy methods. As electrochemical test solutions 0.5 M sodium chloride and 0.5 M potassium sulphate were used in a three electrode open cell. The corrosion potential is shifted to more negative values for nanostructured coatings in 0.5 M sodium chloride. The polarization resistance in 0.5 M sodium chloride decreases in 24 h, but after that increases slowly. In 0.5 M potassium sulphate solution the polarization resistance decreases after 2 h and after 30 h of immersion the polarization resistance is higher than that of the beginning value. The corrosion rate calculated by polarization potentiodynamic curves obtained after 30 min from immersion in solution is smaller for nanostructured coatings in 0.5 M potassium sulphate (4.74 μm/year) and a little bit bigger in 0.5 M sodium chloride (5.03 μm/year).     

Voltammetric behaviour of iron in cement. I. Development of a standard procedure for measuring voltammograms

A reproducible procedure has been developed to study the cyclic voltammetry of iron electrodes embedded in cured Portland cement: It is recommended that suchin situ measurements be used in preference to those in simulated pore solutions. This method, which should prove useful as a means of studying the corrosion of reinforced concrete, is described in detail. The usefulness of the method has been demonstrated by means of a series of brief preliminary studies. Specifically, studies on the effects of sweep rate, chloride additions, and the role of Ca(OH)₂ in the passivation of iron in alkaline solutions, were performed. The sweep rate behavior of the passivation peak in cement was consistent with that predicted by a pore diffusion model. As expected, the chloride additions were found to disrupt the passivity, as evidenced by a general increase in the voltammetric currents and the electrode resistance, as well as by the appearance of a new anodic peak in the normally passive potential regime. The results indicated that, although the reaction mechanism is similar in cement to that in aqueous alkaline solution, the passivity of iron is enhanced in cement, relative to that observed in aqueous KOH or NaOH solutions. This is shown to be related to the presence of Ca(OH)₂ in the cement pore solution.     

Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques

In situ Raman spectroscopy, electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the corrosion behavior of reinforcing steel in simulated concrete pore (SCP) solutions (saturated Ca(OH)₂ solutions). Results indicated that the reinforcing steel remained passive in chloride-free SCP solutions. However, the anodic polarization curve of the steel did not exhibit a stable passive region in the SCP solution with 0.5 M NaCl, the corrosion current density exceeded 0.1 μA cm⁻², the steel surface was unstable with chloride attack and localized corrosion appeared on it with FeCO₃ and Fe₂O₃ as the main corrosion products.     

Performance of volcanic ash and pumice based blended cement concrete in mixed sulfate environment

The deterioration of concrete structures due to the presence of mixed sulfate in soils, groundwater and marine environments is a well-known phenomenon. The use of blended cements incorporating supplementary cementing materials and cements with low C₃A content is becoming common in such aggressive environments. This paper presents the results of an investigation on the performance of 12 volcanic ash (VA) and finely ground volcanic pumice (VP) based ASTM Type I and Type V (low C₃A) blended cement concrete mixtures with varying immersion period of up to 48 months in environments characterized by the presence of mixed magnesium-sodium sulfates. The concrete mixtures comprise a combination of two Portland cements (Type I and Type V) and four VA/VP based blended cements with two water-to-binder ratio of 0.35 and 0.45. Background experiments (in addition to strength and fresh properties) including X-ray diffraction (XRD), Differential scanning calorimetry (DSC), mercury intrusion porosimetry (MIP) and rapid chloride permeability (RCP) were conducted on all concrete mixtures to determine phase composition, pozzolanic activity, porosity and chloride ion resistance. Deterioration of concrete due to mixed sulfate attack and corrosion of reinforcing steel were evaluated by assessing concrete weight loss and measuring corrosion potentials and polarization resistance at periodic intervals throughout the immersion period of 48 months. Plain (Type I/V) cement concretes, irrespective of their C₃A content performed better in terms of deterioration and corrosion resistance compared to Type I/V VA/VP based blended cement concrete mixtures in mixed sulfate environment.     

Acidic and basic binders for magnesite based aggregate in plaster of tundish

Binders are generally inorganic, organic or organomineral and have an important influence on the performance and corrosion resistance of slag line and deskulling. Since silicate and phosphate binders have some side effects, in this work sulphate binders such as sulphamic acid, H₂NSO₃H; aluminum sulphate, Al₂(SO₄)₃; ammonium sulphate, (NH₄)₂SO₄; magnesium sulphate, MgSO₄; calcium sulphate, CaSO₄; sodium sulphate, Na₂SO₄; and potassium sulphate, K₂SO₄, are investigated. Cold crushing strength at different heat treatments of room temperature, 110 °C, 1100 °C, 1400 °C is measured. Apparent porosity of samples without pulp and bulk density together with pH of the binder solution is evaluated and XRD and SEM studies are performed. Among these sulphate binders MgSO₄ was found to be the best. It is acidic in nature and develops strong bonds to the basic aggregate, MgO, at low temperatures. At high temperatures it dissociates from MgO(s) and SO₃(g) and the remained portion of MgO is the same as host oxide, with no corrosion and easy deskulling. Basic binders such as calcium sulphate, sodium sulphate and potassium sulphate could not strongly bond the MgO aggregates.     

水泥基材料中氯离子结合机理及其影响因素研究进展

氯离子侵蚀是造成钢筋混凝土中钢筋锈蚀的主要原因,水泥基材料中氯离子的结合可以有效延缓钢筋的锈蚀.本文主要从三个方面进行了综述:(1)氯离子结合机理;(2)氯离子结合的测试方法及表征;(3)氯离子结合影响因素.具体研究了水泥组分及水化产物对氯离子的结合情况,以及不同测试方法及表征的应用范围、优缺点等,分析了辅助胶凝材料、...