Mechanical performance and microstructure of the calcium carbonate binders produced by carbonating steel slag paste under CO2 curing

Calcium carbonate binders were prepared via carbonating the paste specimens cast with steel slag alone or the steel slag blends incorporating 20% of Portland cement (PC) under CO₂ curing (0.1 MPa gas pressure) for up to 14 d. The carbonate products, mechanical strengths, and microstructures were quantitatively investigated. Results showed that, after accelerated carbonation, the compressive strengths of both steel slag pastes and slag-PC pastes were increased remarkably, being 44.1 and 72.0 MPa respectively after 14 d of CO₂ curing. The longer carbonation duration, the greater quantity of calcium carbonates formed and hence the higher compressive strength gained. The mechanical strength augments were mainly attributed to the formation of calcium carbonate, which caused microstructure densification associated with reducing pore size and pore volume in the carbonated pastes. In addition, the aggregated calcium carbonates exhibited good micromechanical properties with a mean nanoindentation modulus of 38.9 GPa and a mean hardness of 1.79 GPa.     

Thermodynamic modeling of hydrated white Portland cement–metakaolin–limestone blends utilizing hydration kinetics from 29Si MAS NMR spectroscopy

Hydration kinetics for the principal phases of Portland cement blends have been incorporated in thermodynamic modeling (GEMS package), utilizing degrees of hydration from ²⁹Si MAS NMR. An empirical relationship for the reaction of these phases is established which includes three variable parameters that all can be estimated from the degrees of hydration. This approach is compared with thermodynamic equilibrium modeling (full hydration) for white Portland cement–metakaolin (0–30 wt.%) blends and for ternary blends of white Portland cement (65 wt.%)–metakaolin–limestone. The predicted phase assemblages have been compared with the phases identified by XRD, ²⁷Al and ²⁹Si MAS NMR which reveals that the incorporation of hydration kinetics improves the agreement between modeling and experiments. The results show also that the formation of strätlingite depends critically on the quantity of charge-balancing anions in the AFm phases, especially carbonate and sulfate anions, and on the degree of hydration for metakaolin.     

Carbonation in the pore solution of metakaolin-based geopolymer

An experimental approach based on the study of the pore solution of metakaolin-based geopolymer has been established in this study to investigate the phenomenon of carbonation in these materials. The results obtained showed a very fast decrease in the pH, compared to Portland cement, and an almost total carbonation of the pore solution in natural condition after only 14 days. In natural CO₂ conditions, the formation of sodium carbonate did not lead to a decrease of pH below 10.5 at one year, thus limiting the risk of corrosion by depassivation of the reinforcement. Accelerated carbonation performed under 50% of CO₂ highlighted the formation of large amounts of sodium bicarbonate responsible for a lower pH of the pore solution, and a potential risk of corrosion by carbonation. That result also demonstrated that the accelerated carbonation tests made for Portland cement are not representative of the natural reaction in geopolymer cases.     

The effect of temperature on the rate of sulfate attack of Portland cement blended mortars in Na2SO4 solution

Sulfate attack on Portland cement and Portland blended cement concretes is a well-researched field. However, the effect of varying temperature on the rate of sulfate attack requires further attention. This laboratory experiment studied temperatures of 23 °C, 10 °C, 5 °C, and 1 °C. Both Portland and Portland limestone cements were studied in combination with several supplementary cementing materials. The mortar bars were submerged in 5% Na2SO4 (33,800 ppm SO₄^2 −) solution for 15–30 months. At higher temperatures the supplementary cementing materials, particularly the fly ashes, greatly improved the resistance to external sulfate attack. At lower temperatures the metakaolin improved the resistance to sulfate attack; the fly ashes had little to no effect on the low-temperature sulfate resistance. The alterations to sulfate resistance are attributed to: dilution of Portland cement in the presence of supplementary cementing materials; additional nucleation sites provided by finely ground SCMs; and the pozzolanic and hydraulic reactions of the SCMs.     

Cement substitution by a combination of metakaolin and limestone

This study investigates the coupled substitution of metakaolin and limestone in Portland cement (PC). The mechanical properties were studied in mortars and the microstructural development in pastes by X-ray diffraction, thermogravimetry analysis, mercury intrusion porosimetry and isothermal calorimetry. We show that 45% of substitution by 30% of metakaolin and 15% of limestone gives better mechanical properties at 7 and 28 days than the 100% PC reference. Our results show that calcium carbonate reacts with alumina from the metakaolin, forming supplementary AFm phases and stabilizing ettringite. Using simple mass balance calculations derived from thermogravimetry results, we also present the thermodynamic simulation for the system, which agrees fairly well with the experimental observations.It is shown that gypsum addition should be carefully balanced when using calcined clays because it considerably influences the early age strength by controlling the very rapid reaction of aluminates.     

Reactive pozzolana from Indian clays—their use in cement mortars

Studies were undertaken to produce reactive pozzolana i.e. metakaolin from four kaolinitic clays collected from different sources in India. The metakaolin produced from these clays at 700-800 °C show lime reactivity in between 10.5 to 11.5 N/mm² which is equivalent to commercially available calcined clay Metacem-85. The microstructure of the metakaolin has been reported. The effect of addition of metakaolin up to 25% in the Portland cement mortars was investigated. An increase in compressive strength and decrease of porosity and pore diameter of cement mortars containing metakaolin (10%) was noted over the cement mortars without metakaolin. The hydration of metakaolin blended cement mortars was investigated by differential thermal analysis (DTA) and scanning electron microscopy (SEM). The major hydraulic products like C-S-H and C₄AH₁₃ have been identified. Durability of the cement mortars with and without metakaolin was examined in different sulphate solutions. Data show better strength achievement in cement mortars containing 10% MK than the OPC mortars alone.     

The effect of SCMs and curing time on resistance of mortars subjected to organic acids

Agricultural effluents such as liquid manure and ensilage effluents contain organic acids that constitute a severe chemical threat toward the concrete of agricultural structures. In contact with an acidic solution, the chemical equilibrium of the hydrates in cement paste is destabilized, causing negative effects on porosity, reinforcement corrosion, mechanical strength, and, in the long term, may result in the collapse of the structure. More durable concrete in this environment is needed. The purpose of this study is to examine the effect of the nature of the supplementary cementing materials (SCMs) as well as the curing time on the chemical and the physical modifications of cement pastes and on the compressive strength, mass loss, altered depth and microstructure of mortars immersed in acetic acid at a pH of 4.This study concentrated on three types of hardened cement pastes or mortars made with ordinary Portland cement (OPC), slag and metakaolin cements, cured for period varying from 28 days to 1 year. The results show the beneficial effect of the curing time before the acid immersion, the better durability of metakaolin cement and the good chemical resistance of the slag cement against acid attack. The latter develops low compressive strength and is more sensitive to the curing time but the drop of its resistance due to the acid immersion is minimal due to its strong chemical resistance.     

Impact of hydrated magnesium carbonate additives on the carbonation of reactive MgO cements

Reactive magnesia (MgO) cements have emerged as a potentially more sustainable and technically superior alternative to Portland cement due to their lower production temperature and ability to sequester significant quantities of CO₂. Porous blocks containing MgO were found to achieve higher strength values than PC blocks. A number of variables are investigated to achieve maximum carbonation and associated high strengths. This paper focuses on the impact of four different hydrated magnesium carbonates (HMCs) as cement replacements of either 20 or 50%. Accelerated carbonation (20 °C, 70–90% RH, 20% CO₂) is compared with natural curing (20 °C, 60–70% RH, ambient CO₂). SEM, TG/DTA, XRD, and HCl acid digestion are utilized to provide a thorough understanding of the performance of MgO-cement porous blocks. The presence of HMCs resulted in the formation of larger size carbonation products with a different morphology than those in the control mix, leading to significantly enhanced carbonation and strength.     

Lime enhanced gasification of solid fuels: Examination of a process for simultaneous hydrogen production and CO2 capture

The lime enhanced gasification (LEGS) process uses CaO as a CO₂ carrier and consists of two coupled reactors: a gasifier in which CO₂ absorption by CaO produces a hydrogen-rich product gas, and a regenerator in which the sorbent is calcined producing a high purity CO₂ gas stream suitable for storage. The LEGS process operates at a pressure of 2.0 MPa and temperatures less than 800 °C and therefore requires a reactive fuel such as brown coal. The brown coal ash and sulfur are purged from the regenerator together with CaO which is replaced by fresh limestone in order to maintain a steady-state CaO carbonation activity (a_ave). Equilibrium calculations show the influence of process conditions and coal sulfur content on the gasifier carbon capture (>95% is possible). Material balance calculations of the core process show that the required solid purge of the sorbent cycle is mainly attributed to the necessary removal of ash and CaSO₄ if the solid purge is used as a pre-calcined feedstock for cement production. The decay in the CaO capture capacity over many calcination–carbonation cycles demands a high sorbent circulation ratio but does not dictate the purge fraction. A thermodynamic analysis of a LEGS-based combined power and cement production process, where the LEGS purge is directly used in the cement industry, results in an electric efficiency of 42% using a state of the art combined cycle.     

Impact of accelerated carbonation on OPC cement paste blended with fly ash

Cement is a huge carbon dioxide producer. Supplementary cementitious materials can help reduce this outcome. However, carbonation of these blended cements remains an active subject of research. Accelerated carbonation tests (10% CO₂, 25 °C and 62% RH) are performed on fly ash blended cement pastes. Experiments are performed at varying ages of carbonation (1 to 16 weeks) to measure the evolution of the carbonation depth over time and to quantify key parameters: thermogravimetric analysis (TGA), mercury intrusion porosimetry (MIP) and gamma ray attenuation method (GRAM). The total porosity decreases with a rearrangement of the microstructure due to carbonation and the creation of big capillary pores for the paste with the highest contents of fly ash (60 vol.%). The C-S-H molar volume evolution during fly ash-blended cement carbonation is calculated using a method combining MIP, TGA and GRAM formerly successfully applied to OPC paste in a paper published in the same journal.     

13C chemical shift anisotropies for carbonate ions in cement minerals and the use of 13C, 27Al and 29Si MAS NMR in studies of Portland cement including limestone additions

¹³C isotropic chemical shifts and chemical shift anisotropy parameters have been determined for a number of inorganic carbonates relevant in cement chemistry from slow-speed ¹³C MAS or ¹³C{¹H} CP/MAS NMR spectra (9.4 T or 14.1 T) for ¹³C in natural abundance. The variation in the ¹³C chemical shift parameters is relatively small, raising some doubts that different carbonate species in Portland cement-based materials may not be sufficiently resolved in ¹³C MAS NMR spectra. However, it is shown that by combining ¹³C MAS and ¹³C{¹H} CP/MAS NMR carbonate anions in anhydrous and hydrated phases can be distinguished, thereby providing valuable information about the reactivity of limestone in cement blends. This is illustrated for three cement pastes prepared from an ordinary Portland cement, including 0, 16, and 25 wt.% limestone, and following the hydration for up to one year. For these blends ²⁹Si MAS NMR reveals that the limestone filler accelerates the hydration for alite and also results in a smaller fraction of tetrahedrally coordinated Al incorporated in the C-S-H phase. The latter result is more clearly observed in ²⁷Al MAS NMR spectra of the cement–limestone blends and suggests that dissolved aluminate species in the cement–limestone blends readily react with carbonate ions from the limestone filler, forming calcium monocarboaluminate hydrate.     

The CO2 uptake of concrete in a 100 year perspective

More than 50% of the CO₂ emitted during cement production originates from the calcination of limestone. This CO₂ is reabsorbed during the life cycle of cement based product such as concrete and mortars in a process called carbonation.The impact that concrete carbonation has in the assessment of CO₂ emissions from cement production has not been fully documented. Specifically, there is a lack of knowledge about the carbonation of demolished and crushed concrete. The existing models for calculating carbonation do not take into account what takes place after the concrete has been demolished. Consequently, the contribution of the cement and concrete industry to net CO₂ emissions may be significantly overestimated.This paper encompasses theoretical work, laboratory studies, surveys and calculations based on the concrete production in the Nordic countries of Denmark, Iceland, Norway and Sweden. The estimated CO₂-uptake through carbonation of the concrete produced in the year 2003 seems during a 100 year period to amount to a significant proportion of the CO₂ emitted by calcination of the raw mix used to produce the Portland cement used in the concrete.     

Investigation of the carbonation mechanism of CH and C-S-H in terms of kinetics,microstructure changes and moisture properties

The purpose of this article is to investigate the carbonation mechanism of CH and C-S-H within type-I cement-based materials in terms of kinetics, microstructure changes and water released from hydrates during carbonation. Carbonation tests were performed under accelerated conditions (10% CO₂, 25 °C and 65 ± 5% RH). Carbonation profiles were assessed by destructive and non-destructive methods such as phenolphthalein spray test, thermogravimetric analysis, and mercury intrusion porosimetry (destructive), as well as gamma-ray attenuation (non-destructive). Carbonation penetration was carried out at different ages from 1 to 16 weeks of CO₂ exposure on cement pastes of 0.45 and 0.6 w/c, as well as on mortar specimens (w/c = 0.50 and s/c = 2). Combining experimental results allowed us to improve the understanding of C-S-H and CH carbonation mechanism. The variation of molar volume of C-S-H during carbonation was identified and a quantification of the amount of water released during CH and C-S-H carbonation was performed.     

Sulphation and carbonation properties of hydrated sorbents from a fluidized bed CO2 looping cycle reactor

Sulphation and carbonation have been performed on hydrated spent residues from a 75 kW_th dual fluidized bed combustion (FBC) pilot plant operating as a CO₂ looping cycle unit. The sulphation and carbonation tests were done in an atmospheric pressure thermogravimetric analyzer (TGA), with the sulphation performed using synthetic flue gas (0.45% SO₂, 3% O₂, 15% CO₂ and N₂ balance). Additional tests were carried out in a tube furnace (TF) with a higher SO₂ concentration (1%) and conversions were determined by quantitative X-ray diffraction (QXRD) analyses. The morphology of the sulphated samples from the TF was examined by scanning electron microscopy (SEM). Sulphation tests were performed at 850 °C for 150 min and carbonation tests at 750 °C, 10 cycles for 15 min (7.5 min calcination + 7.5 min carbonation). Sulphation conversions obtained for the hydrated samples depended on sample type: in the TGA, they were ～75–85% (higher values were obtained for samples from the carbonator); and in the TF, values around 90% and 70% for sample from carbonator and calciner, respectively, were achieved, in comparison to the 40% conversion seen with the original sample. The SEM analyses showed significant residual porosity that can increase total conversion with longer sulphation time. The carbonation tests showed a smaller influence of the sample type and typical conversions after 10 cycles were 50% – about 10% higher than that for the original sample. The influence of hydration duration, in the range of 15–60 min, is not apparent, indicating that samples are ready for use for either SO₂ retention, or further CO₂ capture after at most 15 min using saturated steam. The present results show that, upon hydration, spent residues from FBC CO₂ capture cycles are good sorbents for both SO₂ retention and additional CO₂ capture.     

Eco-friendly concretes with reduced water and cement contents — Mix design principles and laboratory tests

The major environmental impact of concrete is caused by CO₂-emissions during cement production. Great potential for reducing the impact is seen especially for concretes with normal strength. The use of superplasticizers and highly reactive cements as well as optimization of particle-size distribution and reduction in water content allows a significant reduction in Portland cement clinker in the concrete. Essential is the addition of mineral fillers (e.g. limestone powder) to provide an optimal paste volume. In addition, the already practicable substitution of secondary raw materials like fly-ash or furnace-slag for cement clinker is an appropriate option which is however limited by the availability of these resources.In several test series the fresh and hardened concrete properties of concretes with reduced water and cement contents were investigated, especially their workability, strength development, design-relevant mechanical properties as well as durability aspects such as carbonation. It was shown that concretes with cement clinker and slag contents as low as 150 kg/m³ were able to meet the usual requirements of workability, compressive strength (approx. 40 N/mm²) and mechanical properties. The carbonation depth of concretes with 150-175 kg/m³ clinker and slag was equal or lower than the depth of conventional reference concretes for exterior structures. The ecological advantages were identified, using environmental performance evaluation. A reduction of up to 35% in environmental impact was calculated compared with conventional concrete and of more than 60% with granulated blast-furnace slag. Practical application was verified by means of full-scale tests in a precast and ready-mix concrete plant.     

Microstructural characterization of ITZ in blended cement concretes and its relation to transport properties

The improvements in the overall performances of concrete with blended materials were often ascribed to the modification of its hardened paste in general. In this paper, the effects of limestone filler (LF) and slag (GGBS) on chloride migration and water absorption of concretes with systematically varied aggregate properties were evaluated from the view point of ITZ by using BSE image, EDS, and MIP analysis. It was found that the incorporation of moderate amount of LF and GGBS would compact the microstructure of both ITZ and bulk cement matrix. The reduction in the pore volume (> 100 nm) contributes to the largest decrease in total porosity. Additionally, incorporating GGBS avoids the build-up of Ca(OH)₂ within ITZ and provides a more uniform microstructure. The mechanism for the improvement in limiting water and ions penetration was found to be mainly related to the densification of bulk cement matrix rather than the modification of ITZ.     

Superior carbon-based CO2 adsorbents prepared from poplar anthers

A series of renewable nitrogen-containing granular porous carbons with developed porosities and controlled surface chemical properties were prepared from poplar anthers. The preparation conditions such as pre-carbonization and activation temperatures and KOH amount significantly influence the structures and chemical compositions of the porous carbons, the CO₂ adsorption capacities of which are highly dependent on their pore structures, surface areas, nitrogen contents and adsorption conditions. The sample with developed microporosity, especially with the pores between 0.43 and 1 nm and high nitrogen content shows high CO₂ adsorption capacity at 1 bar and 25 °C. In contrast, when the adsorption pressure is higher than 5 bar, its CO₂ adsorption capacity is dominated by its surface area, and more accurately by its pore volume. Irrespective of this, if the pressure was decreased to 0.1 bar, its CO₂ capture ability is closely correlated to its nitrogen content but not to its porosity. By optimizing the preparation conditions, a porous carbon with a surface area of 3322 m² g⁻¹ and a CO₂ adsorption capacity as high as 51.3 mmol g⁻¹ at 50 bar and 25 °C was prepared.     

Enhancing the carbonation of MgO cement porous blocks through improved curing conditions

The use of reactive magnesia (MgO) as the binder in porous blocks demonstrated significant advantages due to its low production temperatures and ability to carbonate, leading to significant strengths. This paper investigates the enhancement of the carbonation process through different curing conditions: water to cement ratio (0.6–0.9), CO₂ concentration (5–20%), curing duration (1–7 days), relative humidity (55–98%), and wet/dry cycling frequency (every 0–3 days), improving the carbonation potential through increased amounts of CO₂ absorbed and enhanced mechanical performance. UCS results were supported with SEM, XRD, and HCl acid digestion analyses. The results show that CO₂ concentrations as low as 5% can produce the required strengths after only 1 day. Drier mixes perform better in shorter curing durations, whereas larger w/c ratios are needed for continuous carbonation. Mixes subjected to 78% RH outperformed all the others, also highlighting the benefits of incorporating wet/dry cycling to induce carbonation.     

Production of nepheline/quartz ceramics from geopolymer mortars

This research has investigated the mechanical properties and microstructure of metakaolin derived geopolymer mortars containing 50% by weight of silica sand, after exposure to temperatures up to 1200 °C. The compressive strength, porosity and microstructure of the geopolymer mortar samples were not significantly affected by temperatures up to 800 °C. Nepheline (NaAlSiO₄) and carnegieite (NaAlSiO₄) form at 900 °C in the geopolymer phase and after exposure to 1000 °C the mortar samples were transformed into polycrystalline nepheline/quartz ceramics with relatively high compressive strength (～275 MPa) and high Vickers hardness (～350 HV). Between 1000 and 1200 °C the samples soften with gas evolution causing the formation of closed porosity that reduced sample density and limited the mechanical properties.     

Sequential SO2/CO2 capture enhanced by steam reactivation of a CaO-based sorbent

The steam hydration reactivation characteristics of three limestone samples after multiple CO₂ looping cycles are presented here. The CO₂ cycles were performed in a tube furnace (TF) and the resulting samples were hydrated by steam in a pressure reactor (PR). The reactivation was performed with spent samples after carbonation and calcination stages. The reactivation tests were done with a saturated steam pressure at 200 °C and also at atmospheric pressure and 100 °C. The characteristics of the reactivation samples were examined using BET and BJH pore characterization (for the original and spent samples, and samples reactivated under different conditions) and also by means of a thermogravimetric analyzer (TGA). The levels of hydration achieved by the reactivated samples were determined as well as the conversions during sulphation and multiple carbonation cycles. It was found that the presence of a CaCO₃ layer strongly hinders sorbent hydration and adversely affects the properties of the reactivated sorbent with regard to its behavior in sulphation and multiple carbonation cycles. Here, hydration of calcined samples under pressure is the most effective method to produce superior sulphur sorbents. However, reactivation of calcined samples under atmospheric conditions also produces sorbents with significantly better properties in comparison to those of the original sorbents. These results show that separate CO₂ capture and SO₂ retention in fluidized bed systems enhanced by steam reactivation is promising even for atmospheric conditions if the material for hydration is taken from the calciner.