Laboratory investigation of carbonated BOF slag used as partial replacement of natural aggregate in cement mortars

Direct mineral carbonation produces a material rich in carbonates and with reduced quantities of free oxides. The aim of this work was to show that such materials can be used in the construction domain. Basic Oxygen Furnace (BOF) slag from the steelmaking process has been traditionally seen as unfit for bounded applications due to its propensity to swelling, resulting from hydration of its high free lime content. Here, BOF slag was crushed to suitable particle sizes, carbonated in an aqueous solution of carbonic acid, and utilized to replace 50% of natural sand aggregate in cement mortars. The mechanical and chemical properties of these mortars were compared to mortars containing non-carbonated slags, and a standard cement mortar as a reference. Tests were conducted to determine mortar paste consistency and soundness, and cured mortar compressive strength and leaching tendencies. The results showed a satisfactory performance for all considered aspects (comparable with the reference) of the mortar sample containing 37.5 wt% (1.5 in 4 parts solids) carbonated BOF slag of <0.5 mm particle size.     

Sulfate resistance and carbonation of plain and blended cements

Results of an experimental investigation on the sulfate resistance and carbonation of plain and blended cement mortars are reported in this paper. In the sulfate resistance test all the specimens were immersed in a 5% Na₂SO₄ solution for 24 months. Two different types of lignite fly ashes and two natural pozzolans were used for the production of 13 blended cements. An ordinary portland cement and a commercially available blended cement were also used for reference. The effect of mineral admixtures on the carbonation depth of mortars was also investigated. Results show that the addition of pozzolanic admixtures in most cases had a positive effect on the sulfate resistance. The carbonation depth in all blended mortars was greater than that in portland cement mortar. However the rate of carbonation of blended mortars was reduced as hydration progressed.     

碳酸化钢渣和矿渣作硅酸盐水泥混合材水化性能研究

通过对钢渣碳酸化前后的硅酸盐相提取及水化放热性能和将碳酸化钢渣和矿渣作为混合材的硅酸盐水泥的胶砂强度和水化产物种类的测定,以及对它们微观形貌的观察,研究了碳酸化钢渣对胶凝体系水化性能的影响.结果表明,碳酸化使钢渣中硅酸盐相的含量由47.06％下降至14.38％;碳酸化促进了钢渣的早期水化,抑制其后期水化;在配比相同的条件下,碳酸化钢渣-矿渣-硅酸盐熟料体系试样的3、28d抗压强度较未碳酸化钢渣-矿渣-硅酸盐熟料体系试样的高;碳酸化生成的CaCO3促进了熟料的水化;碳酸化钢渣促进了胶凝体系中AFt的生成,且生成水合碳铝酸钙.     

Steady-state O<Subscript>2</Subscript> and CO<Subscript>2</Subscript> diffusion in carbonated mortars produced with blended cements

The diffusion coefficient \(D_{{{\text{O}}_{2} }}\), the porosity and the pore structure of mortars produced with a Portland cement and a range of blended cements containing limestone powder, microsilica, portlandite or slag were measured in the non-carbonated and the carbonated state. Additionally, the setup for measuring O₂ diffusion was adapted to measure also the CO₂ diffusion of the carbonated mortars. The diffusion coefficient \(D_{{{\text{O}}_{2} }}\) and the total porosity were increased in the mortars containing microsilica and slag, while they were decreased in the other mortars due to carbonation. Invariably, the pore structure became coarser in all samples. The relationship between diffusion coefficients \(D_{{{\text{O}}_{2} }}\) and \(D_{{{\text{CO}}_{2} }}\) in the carbonated mortars was always linear, with \(D_{{{\text{O}}_{2} }}\) systematically higher by factor of 1.37. As this factor broadly agrees with what was found in the scant literature about CO₂ diffusion, it could be used for estimating \(D_{{{\text{CO}}_{2} }}\) of carbonated mortar and concrete based on measurements of O₂ diffusion.     

Effectiveness of using CO2 pressure to enhance the carbonation of Portland cement-fly ash-MgO mortars

Acceleration on the carbonation of reactive MgO cement is essential for its widespread application. There is currently a dearth of published reports on the effect and sensitivity of using pressurized CO₂ on the properties and performance of reactive MgO cement blends. This study is motivated by improving the understanding of the effectiveness of accelerating the carbonation process. Pressurized CO₂ (up to 1.0 MPa) was employed to enhance the carbonation of mortar blends consisting of Portland cement, fly ash and reactive MgO. Results revealed that the carbonation front and mechanical properties of the mortars were developed quickly owing to the effectively accelerated carbonation under pressurized CO₂. In comparison to the 0.1 MPa pressure, the relatively higher pressure (0.55 and 1.0 MPa) were much more effective in achieving stronger mechanical properties within 1 day. However, an increasing curing duration from 1d to 14d under the lower CO₂ pressure of 0.1 MPa caused a 1.8–2.9 times increase in compressive strength. This indicates that either increases in pressure or curing duration under pressurized CO₂ enhances the carbonation and mechanical properties of the mortars.     

Properties of binary and ternary reactive MgO mortar blends subjected to CO2 curing

Research and development of low CO₂ binders for building material applications is warranted in efforts to reduce the negative environmental impacts associated with the cement and concrete industry. The purpose of this study is to investigate the effect of carbonation curing on the mineralogy, morphology, microstructure and evolution of compressive strength of mortars comprised of general use (GU) cement, ground granulated blast furnace slag (GGBFS), and reactive MgO used as cement replacement. This study investigates binary (GU–MgO) and ternary (GU–GGBFS–MgO) blends exposed to atmosphere curing (0.0038%CO₂) and carbonation curing (99.9%CO₂). Carbonation-cured mortars exhibited greater compressive strengths than atmosphere mortars at all ages (7 d, 28 d, and 56 d). Increasing percentages of reactive MgO decreased the compressive strength markedly less for carbonation-cured mortars than atmosphere-cured mortars particularly due to magnesium calcite formations. Magnesium calcite influenced the morphology of carbonates and promoted the carbonate agglomeration resulting in a dense and interconnected microstructure.     

Mechano-chemical modification of cement with high volumes of blast furnace slag

The application of chemical admixtures significantly improves the performance of cement-based materials. Some admixtures can also be used to modify the cement grinding process and induce changes in the structure of cement minerals due to mechano-chemical activation. A reactive silica-based complex admixture was developed for the modification of cement grinding. This paper examines the effect of grinding on the strength of a modified cement containing granulated blast furnace slag in high volumes. According to the test results, mortars based on the modified cement possess a compressive strength of up to 91.7 MPa, a 62% increase over the reference.     

Influence of KOH solution on the hydration and carbonation of high alumina cement mortars

The influence of KOH presence on the evolution of hydration and carbonation of high alumina cement mortars at two different curing temperatures (4 and 40 °C) has been studied. It has been confirmed that hydration reactions at both temperatures are accelerated with KOH presence and it has a great influence on hydrated and carbonated species. The massive deposition of carbonation products leads, in all cases to a decrease in mortar porosity which leads to an increase of mechanical strengths.     

Performance of blended metakaolin/blastfurnace slag alkali-activated mortars

This paper studies the effect of silicate content on the mechanical and durability-related properties of metakaolin (MK) and metakaolin/blastfurnace slag (BFS) alkaline activated mortars. A reference mortar based on the alkaline activated MK was compared to 60/40 MK/BFS mortars containing different SiO₂/Na₂O molar ratios in the activator. The properties assessed were compressive strength, porosity (water saturation), porosity and pore size distribution by Mercury Intrusion Porosimetry (MIP) and water capillary sorption. The microstructure was assessed using SEM and x-ray computerized micro-tomography (μ-CT). Results show that the addition of BFS significantly alters the microstructure of alkali-activated mortars, promoting a reduction of porosity and capillary sorption. In addition, an optimum SiO₂/Na₂O molar ratio in the activator is required to produce better durability mortars, which however do not necessarily present the highest mechanical strength.     

Relation between carbonation resistance,mix design and exposure of mortar and concrete

When cement with mineral additions is employed, the carbonation resistance of mortar and concrete may be decreased. In this study, mortars containing mineral additions are exposed both to accelerated carbonation (1% and 4% CO₂) and to natural carbonation. Additionally, concrete mixtures produced with different cements, water-to-cement ratios and paste volumes are exposed to natural carbonation. The comparison of the carbonation coefficients determined in the different exposure conditions indicates that mortar and concrete containing slag and microsilica underperform in the accelerated carbonation test compared to field conditions. The carbonation resistance in mortar and concrete is mainly governed by the CO₂ buffer capacity per volume of cement paste. It can be expressed by the ratio between water added during production and the amount of reactive CaO present in the binder (w/CaO_reactive) resulting in a novel parameter to assess carbonation resistance of mortar and concrete containing mineral additions.     

Enhancement of recycled aggregate properties by accelerated CO2 curing coupled with limewater soaking process

Strengthening the attached old cement mortar of recycled concrete aggregate (RCA) is a common approach to enhance the RCA properties. Accelerated CO₂ curing has been regarded as an alternative way to enhance the properties of RA. However, the improvement of the properties of RCA was limited by the shortage of reactive components in the old cement mortar available for the carbonation reactions. In this study, a CO₂ curing process associated with a limewater saturation method was performed cyclically on cement mortar samples, aiming to enhance the properties of cement mortars via artificially introducing additional calcium into the pores of the cement mortars. The results indicated that the adopted treatment method promoted the level of carbonation which was demonstrated by higher CO₂ uptake by the limewater saturated cement mortar when compared to that without limewater treatment. After 3-cycles of limewater-CO₂ treatment, the density of the cement mortar slightly increased by 5.7%, while the water absorption decreased by over a half. For mechanical properties, the compressive and flexural strength were increased by 22.8% and 42.4%, respectively. Compared to the untreated cement mortar samples, the total porosity of cement mortar was reduced by approximately 33% and the densified microstructure therefore resulted in a higher microhardness.     

Effect of carbonation of modeled recycled coarse aggregate on the mechanical properties of modeled recycled aggregate concrete

The modeled recycled aggregate concrete (MRAC) which is an idealized model for the real recycled aggregate concrete (RAC) was used in this study. The MRCAs prepared with two types of old mortars were modified by an accelerated carbonation process. The effects of carbonation of MRCA on the micro-hardness of MRCA and the mechanical properties of MRAC were investigated. The results indicated that the micro-hardness of the old interfacial transition zone (ITZ) and the old mortar in the carbonated MRCAs was higher than that in the uncarbonated MRCAs, and the enhancement of the old ITZ was more significant than that of the old mortar. The compressive strength and modulus of MRACs increased when the carbonated MRCAs were utilized, and the improvement was more significant for MRAC prepared with a higher w/c. In addition, a numerical study was carried out and it showed that the improvement in strength by carbonation treatment was less obvious when the difference between the new and old mortar was larger.     

Alkali-aggregate behaviour of alkali-activated slag mortars: Effect of aggregate type

The alkali–silica reaction in waterglass-alkali-activated slag (waterglass-AAS) and ordinary Portland cement (OPC) mortars was evaluated using three types of (siliceous and calcareous) aggregates. The tests were conducted to the ASTM C1260-94 standard test method. The mortars were studied by volume stability, mechanical strength and Hg intrusion porosity. The ASR products were studied with XRD, FTIR and SEM/EDX techniques.According to the results obtained, under the test conditions applied in this study, waterglass-AAS mortars are stronger and more resistant to alkali-aggregate reactions than OPC mortars. When the mortars were made with a reactive siliceous aggregate, expansion was four times greater in the OPC than in the AAS material. When a reactive calcareous (dolomite) aggregate was used, no expansion was detected in any of the mortars after 14 days, although the characterization results showed that the dolomite had reacted and calcareous-alkali products (brucite) had in fact formed in both mortars. These reactive processes were more intense in OPC than in AAS mortars, probably due to the absence of portlandite in the latter. When the calcareous aggregate was non-reactive, no expansions were observed in any of the mortars, although a substantial rise was recorded in the mechanical strength of AAS mortars exposed to the most aggressive conditions (1 M NaOH and 80 °C).     

Effect of composition,environmental factors and cement-lime mortar coating on concrete carbonation

The paper describes the physicochemical processes of concrete carbonation and presents a simple mathematical model for the evolution of carbonation in time, applicable under constant relative humidity higher than 50%. The model is based on fundamental principles of chemical reaction engineering, and uses as parameters the ambient concentration of CO₂, the molar concentratrations of the carbonatable constituents, Ca(OH)₂ and CSH, in the concrete volume, and the effective diffusivity of CO₂ in carbonated concrete. The latter is given by an empirical function of the porosity of hardened cement paste and of relative humidity, derived from laboratory diffusion tests. The validity of the model for OPC or pozzolanic cement concretes and mortars is demonstrated by comparison of its predictions with accelerated carbonation test results obtained in an environment of controlled CO₂ concentration, humidity and temperature. The mathematical model is extended to cover the case of carbonation of the coating-concrete system, for concrete coated with a cement-lime mortar finish, applied either almost immediately after the end of concrete curing or with a delay of a certain time. Parametric studies are performed to show how the evolution of carbonation depth with time is affected by cement and concrete composition (water/cement or aggregate/cement ratio, percentage OPC or aggregate replacement by a pozzolan), environmental factors (relative humidity, ambient concentration of CO₂), the presence and the time of application of a lime-cement mortar coating and its composition (water/cement, aggregate/cement and lime/cement ratios of the mortar, percentage OPC or aggregate replacement by a pozzolan).     

Carbonation of calcium sulfoaluminate mortars

This study investigated potential physical and chemical parameters that could govern the carbonation rate of calcium sulfoaluminate (CSA) mortars and endeavored to elucidate the microstructural and chemical factors that govern CSA cement's carbonation rate. Experiments included: water absorption, oxygen diffusion, mercury intrusion porosimetry, quantitative X-ray diffraction, thermogravimetric analysis, accelerated carbonation, compression and flexure tests. Additionally, the carbonation process was investigated using thermodynamic modeling. The results show that CSA mortars carbonate much faster than Portland cement mortars and at approximately the same rate as calcium aluminate cement mortars. Additionally, CSA mortars carbonate slower with decreasing w/c, and the anhydrite content of the CSA mortars strongly affects the ye'elimite reaction kinetics which plays an important role in imparting carbonation resistance in CSA mortars. Finally, calcium sulfate additions to CSA clinker to produce CSA cement dilutes the clinker content and reduces the amount of CO₂ that the CSA cement can ultimately bind.     

Supercritical carbonation treatment on extruded fibre–cement reinforced with vegetable fibres

The objective of this research was to evaluate the effects of supercritical carbonation treatment for 2 h on the main hydrated phases of the cement matrix (calcium hydroxide and calcium silicate hydrate) and durability of extruded fibre–cement reinforced with bleached eucalyptus pulp and residual sisal chopped fibres. The thermal analysis, bulk density, porosity, physical characteristics and mechanical performance were evaluated before and after 200 soaking and drying cycles for following the degradation of the material under accelerated ageing conditions. The higher carbonation rate during the early stage of curing period decreased the porosity by sealing the opened pores around vegetable fibres and, consequently, led to lower water absorption and higher bulk density in the composites. The average MOR-values showed a significant increase in the case of the supercritical carbonated extruded fibre–cement in the initial age and after accelerated ageing. Besides, after 200 soaking and drying ageing cycles, the average values of energy of fracture (γ_WoF) of the carbonated composites decrease only 28%, showing evidences of the preservation of microstructural stability and toughness of the fibre–cement composites after supercritical CO₂ treatment.     

Corrosion behaviour of steel in high alumina cement mortar cured at 5,25 and 55 °C: chemical and physical factors

The corrosion behaviour of embedded steel was related to the composition of the pore phase in equilibrium with the hydrated phases and the porosity of the high alumina cement mortars subsequent to curing at 5,25 and 55 °C. The corrosion of reinforcements was evaluated by electrochemical techniques. The effect on corrosion of 3% by weight of cement of NaCl, added during the mixing process, and of the accelerated carbonation of mortars in CO₂ atmosphere were also determined. The pH value and the chemical composition of pore fluid of plain high alumina cement (HAC) mortar cured at all three temperatures suggested that the embedded steel was in a passivated state. The resistance of HAC to carbonation and its greater potential for chloride binding by chloroaluminate formation are believed to make HAC inherently more protective to steel, relative to normal Portland cement, during ingress of chloride from external sources. High corrosion rates reported in literature for steel embedded in HAC may be attributable to bad practice, not to lack of passivity.     

Influence of admixtures on strength development of Portland cement and on the microstructure of tricalcium silicate

The influence of various inorganic salts, used as additives to Portland cement paste, on strength development was studied. The salts used were: CaCl₂, CrCl₃, Cdl₂. It was found that CaCl₂ and CrCl₃ accelerate the rate of strength development, while Cdl₂ retards it compared to Portland cement without admixtures. No influence by CdCl₂ was observed. The effect of the same admixtures on the microstructure of hydrated tricalcium silicate was examined by a scanning electron microscope, and correlation between the morphology of the simple system and the mechanical behaviour of the complex cement system is discussed.     

Effects of thermal and mechanical activation methods on compressive strength of ordinary Portland cement–slag mortar

Activation methods and curing regimes have crucial effects on the strength of mortars and concretes. The objective of this investigation is to examine the early and later compressive strength of activated ordinary Portland cement (OPC)–ground granulated blast-furnace slag (GGBFS) mortars and identify the most effective activation technique. The methods of activation used were thermal, mechanical and thermal–mechanical combined. Two curing regimes were adopted and five groups of mortars were prepared. It was observed that OPC–GGBFS mortars have greater sensitivity to OPC mortars against the curing regimes. However, the study revealed that there was no particular activation method which when used gave the best results for both early and later strengths and did not cause strength loss. It also proved that the most effective activation method for early strength is a combination of both the thermal and mechanical, while for later strengths, none of the activation methods was recommended.     

Effect of curing time on granulated blast-furnace slag cement mortars carbonation

Currently, ground granulated blast-furnace slag cements use in cement-based materials is being increasing because perform well in marine and other aggressive environments. However, mortars and concretes made of this type of cement exhibit high carbonation rates, particularly in badly cured cement-based materials and when high blast-furnace slag contents are used. Concrete reinforcement remains passive but can be corroded if the pore solution pH drops as a result of the carbonation process promoting the reinforced concrete structure failure during its service life. Results show the very sensitive response to wet-curing time of slag mortars with regard to the natural carbonation resistance. Then, a minimum period of 3–7 days of wet curing is required in order to guarantee the usual projected service life in reinforced concrete structures. In this work, estimation models of carbonation depth and carbon dioxide diffusion coefficient in ground granulated blast-furnace slag mortars as a function of the curing period and the amount of ground granulated blast-furnace slag are proposed. This information will be useful to material and civil engineers in designing cement-based materials and planning the required curing time depending on their ground granulated blast-furnace slag content.