Influence of carbonation and carbonation methods on leaching of metals from mortars

Mortars with varying water-to-cement (w/c) ratio were spiked with heavy metals. After hardening, some samples were carbonated in a CO₂ chamber, others were carbonated using supercritical CO₂ (SCC). Porosity and carbonation depth of treated and untreated samples were compared. Leaching was tested using the diffusion (NEN 7345) and extraction test (based on DIN 38414-S4). The results show that carbonation decreases the porosity of the samples. The decrease is more important with increasing w/c ratio. Carbonation runs deeper into the monolith with increasing w/c ratio. In the supercritical method, not all samples were carbonated to the same extent. The diffusion test shows that carbonation decreases leaching of Na, K, Ca, Ba, Cu, and Pb and increases leaching of Mg. Ni leaching depends on the pH induced by carbonation. Influence of pH and formation of metal carbonates is evaluated with the extraction test and enhances understanding of metal leaching in the diffusion test.     

Opal-A rich additives used in ancient lime mortars

Ancient stone and brick masonry mortars from three monuments in Konya, Central Anatolia dated to the Anatolian Selçuk Period (12th and 13th centuries AD) were examined for their raw material composition and durability characteristics to understand some characteristics of medieval mortar technology.Optical microscopy, XRD, SEM, EDX, FTIR and TGA analyses revealed that the mortars contained high percentage of lime binder totally carbonated into micritic calcite. Coarse and medium aggregates were mainly composed of sandstone and metamorphic rock fragments, quartz, feldspar and mica minerals. Opal-A was found in considerable amounts in the fine aggregates, likely not derived from the coarser ones but added separately. Pozzolanic activity of the fine aggregates was determined by conductometric measurements. Their ability to form C-S-H was observed by treating them with saturated Ca(OH)₂ solution.Bulk density and total porosity measurements showed that the mortars were highly porous due to the use of high amount of lime. On the other hand, they possessed sufficient mechanical strength. Mechanical properties were determined by point load tests and ultrasonic pulse velocity measurements. They were expressed as uniaxial compressive strength (UCS) and modulus of elasticity (E_mod) in MPa.The results were also discussed in terms of durability characteristics of the mortars. They were expressed with the use of uniaxial compressive strengths in dry and wet states, and total porosity values. The mortars were considered to have high durability to wetting and drying cycles but had poor durability to the crystallization of water-soluble salts.     

Study on the replacement of the hydrated lime by kaolinitic clay in mortars

ABSTRACT

Mortars are cement-based materials used mainly to coat and settle construction blocks. In addition to cement, their composition usually includes hydrated lime, sand, and water. The hydrated lime is important to improve the mortar workability. However, lime has a high commercial cost, and its production causes emission of CO₂, a major responsible for global warming. Therefore, the purpose of this work was to investigate the possibility of total or partial replacement of hydrated lime in mortars by a kaolinitic clay with ideal plasticity parameters. Clay amounts of 0, 25, 50, 75, and 100?wt-% were used as replacement of hydrated lime in mortars. The results showed that with up to 50?wt-% of hydrated lime replacement, it is perfectly feasible to fulfil with technological parameters of standards.     

Effect of pig slurry on two cement mortars: Changes in strength, porosity and crystalline phases

The present article addresses the variations observed in porosity and flexural and compressive strength in two types of cement mortar when submerged in pig slurry. The tests were conducted in a 100 m³ experimental lagoon. The mortars were exposed to three types of environments for 36 months: two submerged in the test lagoon, at two different depths, and one outside it. Bending and compression measurements were taken after 3, 12, 24, 36 and 48 months. In addition, 3, 24, 36 and 48 month specimens were tested for total porosity and pore-size distribution. Changes in the mineralogical characteristics of the mortars after 24, 36 and 48 months were also recorded. The strength studies showed that the load capacity attained by the two cements was similar after 48 months, the use of more expensive 42.5 sulphate-resistant cement is not justified. The XRD results showed no evidence in any of the cements of precipitation originating in the ions in the aggressive medium.     

Forced and natural carbonation of lime-based mortars with and without additives: Mineralogical and textural changes

We have studied the carbonation process in different types of mortars, with and without pozzolana or air-entraining additives, subject to a CO₂-rich atmosphere and compared the results with those of similar naturally carbonated mortars. We used X-ray diffraction technique to demonstrate that high CO₂ concentrations favour a faster, more complete carbonation process with 8 days being sufficient to convert portlandite into 90 wt.% calcite. Full carbonation, however, is not reached during the life-span of the tests, not even in forced carbonation experiments. This could be due to at least one of the following phenomena: a premature drying of samples during carbonation reaction, the temperature at which the carbonation process was carried out or the reduction of pore volume occupied by newly formed calcite crystals. This last option seems to be the least probable. We observed a more prolific development of calcite crystals in the pores and fissures through which the carbonic anhydride flows. Under natural conditions, carbonation is much slower and similar levels are not reached for 6 months. These differences suggest that the carbonation process is influenced by the amount of CO₂ used.

Both the mineralogy and texture of mortars vary depending on the type of additive used but the speed of the portlandite–calcite transformation does not change significantly. Pozzolana produces hydraulic mortars although the quantity of calcium aluminosilicate crystals is low. The air-entraining agent significantly alters the texture of the mortars creating rounded pores and eliminating or reducing the drying cracks.     

A new approach for the characterization of the pore structure of dual porosity rocks

For the realistic representation of the pore space of dual porosity rocks, a new method of pore structure characterization is developed by combining experimental Hg intrusion/retraction curves with back-scattered scanning electron microscope (BSEM) images and inverse modeling algorithms. The pore space autocorrelation function measured by processing the digitized BSEM images is combined with the surface fractal dimension estimated from the high pressure Hg intrusion (MIP) data to derive a synthetic small-angle neutron scattering (SANS) intensity function, the inversion of which provides a volume-based pore body radius distribution (PBRD). The volume-based PBRD is fitted with a multimodal number-based PBRD consisting of two component distributions: one representing the macroporosity and another one representing the microporosity. Based on arguments of percolation theory, analytical mathematical models are developed to describe the Hg intrusion in and retraction from dual pore networks in terms of the complete PBRD, pore throat radius distribution (PTRD) of macroporosity, drainage accessibility functions (DAFs) of both porosities, and imbibition accessibility functions (IAFs) of both porosities. Inverse modeling of the Hg intrusion data set enables us to estimate the PTRD and DAFs. Inverse modeling of the Hg retraction datasets enables us to estimate a set of primary and secondary IAFs. The method is demonstrated by the pore structure characterization of four outcrop samples of carbonate and sandstone rocks. Analytic approximate equations developed from the critical path analysis (CPA) of percolation theory enable us to calculate explicitly the absolute permeability and the formation factor of the porous rocks using the estimated parameters (PBRD, PTRD, DAF) of the macroporosity. The measured permeability of cores is predicted satisfactorily and observed discrepancies may be attributed to large length-scale macro-heterogeneities which are not evident in BSEM images and Hg porosimetry data.     

Influence of superplasticizers on the hydration of cement and the pore structure of hardened cement

This paper describes the influence of various types of superplasticizers such as naphthalene type (β-NS), refined lignin sulfonate type (LS) and polycarboxylate types (P34, S34) on the hydration of cement and the pore structure of hardened cement. Other superplasticizers except β-NS delayed the initial hydration of cement. In any case, it hardly influences the hydration reaction at late stage of cement. The retardation by the addition of superplasticizers is not observed after 28 days of curing. Large pores of 0.1 μm or more for hardened cement with LS or β-NS are larger than those of hardened samples with P34 or S34 cured for 28, 56 and 91 days. This is related to the coagulated structures of fresh cement pastes with various types of superplasticizers. It was presumed that the size of the cluster of aggregated particles became small when S34 or P34 that has a high dispersing ability was added compared to LS or β-NS that has a lower dispersing ability.     

Pore structure in mortars applied on restoration: Effect on properties relevant to decay of granite buildings

Since mortars play a key role in buildings decay, their suitable choice is critical to the success of restoration projects. The focus of this paper is to characterise the pore structures of a set of mortars and correlate them with mechanical properties and vapour permeability, which are relevant to the decay of granite buildings. Water vapour transport was tested by means of a simple set-up developed in our laboratory. A good correlation was found between total porosity and the two parameters tested: strength and vapour diffusivity. Pore size distribution also showed a strong influence on diffusivity. A mix based on cement with a high sand proportion was considered as the most suitable for granite building restoration because it showed good mechanical properties and low free calcium content. A negative aspect was that this mix exhibited significantly lower vapour permeability than mortar containing lime; this could be explained by the smaller radius of its pores.     

Effects of metakaolin, water/binder ratio and interfacial transition zones on the microhardness of cement mortars

Variations in the microhardness of the hydrated cement matrix component of model mortars have been investigated as functions of the distance from the aggregate surfaces for specimens in which the binder was Portland cement or a blend of Portland cement and metakaolin.Microhardness measurements were made using a Knoop indenter at distances of up to 120 μm from the aggregate. The microhardnesses of the paste-aggregate interfacial transition zones (ITZs) were found to be between 14% and 22% lower than those of the corresponding bulk cement pastes at the lower water/binder ratios investigated, i.e. 0.4 and 0.5 for samples prepared with Portland cement and 0.4 for samples prepared with a binder comprising Portland cement and metakaolin.Metakaolin increased the mean microhardness of specimens prepared at the higher water/binder ratios of 0.5 and 0.6 by 13% and 54%, respectively.     

Occurrence of thaumasite in gypsum lime mortars for restoration

For restoration purposes, it is essential to have compatible mortars for historic masonry built originally with gypsum mortars. For that reason, gypsum lime mortars with high weathering resistance were developed. Due to the added hydraulic components and carbonate components of the used limes of these mortars, the occurrence of thaumasite can take place. Different mortar mixtures with variable binder contents, using lime with differing amounts of hydraulic components, were prepared and stored under two contrasting curing conditions. Over 90 days of curing, these mortars were investigated using physical-mechanical and chemical-mineralogical techniques. The results have shown that the potential for the growth of thaumasite depends on the composition of the raw materials, especially of the lime. In gypsum lime mortars which were used for restoration purposes, small amounts of thaumasite were also detected, but these small amounts of thaumasite do not reduce mechanical properties. This assumption was confirmed by investigations of gypsum lime mortars, which were exposed outdoors for 13 years.     

Hydraulic lime mortars for the restoration of historic masonry in Crete

This study presents the results of the physico-chemical characterization of original mortars and plasters and the evaluation of the repair ones prepared with natural hydraulic lime (NHL) as binding material and siliceous sand and crushed brick as aggregates. The repair mortars were applied in restoration works of a historic masonry in Crete, Greece. The proportions of binder, aggregates and water were selected in order to achieve optimum workability. Original mortars, containing magnesian lime, had to be replaced since previous interventions with cement-based mortars have provoked damage acceleration. Water absorption by capillarity, compressive strength, modulus of elasticity, porosity and pore size distribution were determined at early stages and after 1 year of curing time; these properties prove the suitability of the proposed mortars for such an application. After 3 years of intervention with NHL-based mortars and plasters, macroscopic survey and analyses of the applied materials reveal that no cracks or release of soluble salts occur.     

Depth profiles of carbonates formed during natural carbonation

The depth profiling of carbonates formed during a natural carbonation of mortars with one face exposed directly to rain and the opposite face sheltered have been measured. The amount of carbonates formed on mortars sheltered from rain is generally higher. The depth of carbonation evaluated by the phenolphthalein test cannot be directly correlated with the carbonate profile. The CO₂ diffusion coefficients calculated on the basis of the distribution of carbonates are of the same order of magnitude as those measured by a direct method. A threshold value of diffusivity appears when the sand concentration increases. This point is discussed and compared with other characteristics of mortars and concretes that exhibit similar behavior.     

Mechanical properties of masonry repair dolomitic lime-based mortars

180 different mortars made with a dolomitic lime and different aggregates were prepared in order to be used in restoration works. This paper focuses on the effect of technological variables on pore structure and mechanical properties of magnesian lime-based mortars. Compressive and flexural strengths of the specimens were discussed according to curing time, binder : aggregate ratios, attributes of the aggregates and porosity, at long-term tests.A strong increase in the strength of mortars has been found after 365 curing days as compared to 28 curing days. The strength has been mainly attributed to the portlandite carbonation, because no significant changes have been observed in the brucite. However, higher strengths than similar aerial lime-based mortars led us to think of other mechanism which increases the strength: the calcite formation through a reaction of dedolomitization (alkali carbonate reaction, ACR) and the brucite crystallization were discussed.The pore structure has presented a significant influence on the strength. More binder amounts mean more strength due to the higher values of open porosity, which allows the carbonation process. The aggregate characteristics have been correlated with the strength and porosity. Limestone and angle-shaped aggregates, reducing large pores, cause a strength increment.     

Influence of polymers on microstructure and adhesive strength of cementitious tile adhesive mortars

The impact of polymer modification on the physical properties of cementitious mortars is investigated using a multimethod approach. Special emphasis is put on the identification and quantification of different polymer components within the cementitious matrix. With respect to thin-bed applications, particularly tile adhesives, the spatial distributions of latex, cellulose ether (CE), polyvinyl alcohol (PVA), and cement hydration products can be quantified. It is shown that capillary forces and evaporation induce water fluxes in the interconnected part of the pore system, which transport CE, PVA, and cement ions to the mortar interfaces. In contrast, the distribution of latex remains homogeneous. In combination with results from qualitative experiments, the quantitative findings allow reconstruction of the evolution from fresh to hardened mortar, including polymer film formation, cement hydration, and water migration. The resulting microstructure and the failure modes can be correlated with the final adhesive strength of the tile adhesive. The results demonstrate that skinning prior to tile inlaying can strongly reduce wetting properties of the fresh mortar and lower final adhesive strength.     

造纸白泥的分解和碳酸盐化特性

造纸白泥作为一种碱性工业废弃物占据了大量的土地资源,其资源化利用是一个有待解决的问题。白泥用于工业烟气中CO2的回收是一种有效的资源化利用方式,然而其中还存在一些机理问题有待研究。本文利用热重分析（TGA）技术对造纸白泥和天然石灰石的煅烧分解特性和碳酸盐化特性进行了对比研究。结果表明,在相同煅烧条件下,白泥的分解速率较石灰石快得多,因此完全煅烧所需时间更短。经过相同的煅烧过程后（850℃,纯N2,15min）,白泥煅烧产物的碳酸盐化转化率低于石灰石煅烧产物,可能原因在于白泥煅烧产物较石灰石煅烧产物具有更低的比表面积。碳酸盐化温度（600～700℃）对白泥和石灰石煅烧产物碳酸盐化的影响规律相似,升高温度对快速碳酸盐化阶段的反应速率没有明显影响,但是延长了快速反应阶段的持续时间,提高了碳酸盐化转化率。     

Damage evolution analysis in mortar, during compressive loading using acoustic emission and X-ray tomography: Effects of the sand/cement ratio

This paper explores the use of acoustic emission (AE) and X-ray tomography to identify the mechanisms of damage and the fracture process during compressive loading on concrete specimens. Three-dimensional (3D) X-ray tomography image analysis was used to observe defects of virgin mortar specimen under different compressive loads. Cumulative AE events were used to evaluate damage process in real time according to the sand/cement ratio. This work shows that AE and X-ray tomography are complementary nondestructive methods to measure, characterise and locate damage sites in mortar. The effect of the sand proportion on damage and fracture behaviour is studied, in relation with the microstructure of the material.     

Investigations on the performance of silica fume-incorporated cement pastes and mortars

Studies on the performance of cementitious products with silica fume (SF) are very important, as it is one of the inevitable additives to produce high-performance concrete (HPC). In this study, some experimental investigations on the influence of SF on various preliminary properties of cement pastes and mortars are reported. The properties included specific gravity and normal consistency (NC) of cement and air content and workability of mortar with different SF contents. Pozzolanic and chemical reactions of SF have been studied on setting times, soundness and shrinkage of cement pastes. Further, strength developments in compression and tension in cement mortars have also been studied at various SF contents. SF was varied from 0% to 30% at a constant increment 2.5/5% by weight of cement. Test results show that the SF changes the behavior of cement pastes and mortars significantly. It has been observed that the water-binder (w/b) (cement+SF) ratio seemed to play an important role for the performance of the products with higher SF contents. NC, soundness and drying shrinkage of cement pastes and the strength of mortar increase as the SF content increases, while the initial setting times of cement pastes and the air content and workability of mortar decrease as the SF content increases. However, hardly any influence has been observed on the final setting times of cement pastes. The early age hydration reactions of C₃A and C₃S increase with the addition of SF. The optimum SF content ranges between 15% and 22%.     

On the relationship between pore structure and chloride diffusivity from accelerated chloride migration test in cement-based materials

In this study the electrochemical technique is applied to accelerate chloride ion migration in concrete to determine the chloride ions in anode cell, and the pore characteristic of the same mortars in concrete was obtained from the mercury intrusion porosimetry (MIP). The plain ordinary Portland cement and the constant aggregate with eight w/c ratios ranging from 0.3 to 0.65 were used. A good linear relationship between the steady-state migration coefficient and non-steady-state migration coefficient based on the same experimental setup and specimens was obtained. Both of the steady-state migration coefficient and non-steady-state migration coefficient were linearly related to the capillary pore volume and the critical pore diameter.     

Enhancement of SO2 sorption on lime by structure modifiers

The presence of certain inert compounds in lime can improve the rate and the final limiting conversion significantly during the lime SO₂ reaction. This physical effect is primarily due to modification of porosity. In particular, the enhancement appears to he due to increase in macro-porosity and macro-pore diffusivity; this in turn increases the sulfation rate and decreases pore plugging. In certain lime application processes, these compounds (structure modifiers) can be added to lime as beneficial additives to promote the reaction. Experimental data on the effect of kaolin, silica and bauxite as structure modifiers are presented. A theoretical model is developed which explains the observed effects both qualitatively and quantitatively.     

Calcium silicate structure and carbonation shrinkage of a tobermorite-based material

Carbonated autoclaved aerated concretes (AACs) show no shrinkage at a degree of carbonation approximately less than 20%. The ²⁹Si MAS NMR spectrum showed that at a degree of carbonation less than 25%, the typical double-chain silicate anion structure of tobermorite-11Å was well maintained and interlayer Ca ions were exchanged with protons. This corresponded to the absence of carbonation shrinkage at a degree of carbonation less than 20%. When the degree of carbonation increased from 25% to 50% up to 60%, the double-chain silicate anion structure of tobermorite-11Å was decomposed and Ca ions in the Ca-O layers were dissolved, showing a possible mechanism of carbonation shrinkage.