Delayed ettringite formation (DEF) in mortars of white cement

In this study white cement CEM I-52.5 and white limestone cement CEM II-LL, A and B, with 15% and 25% limestone substitution, were studied. The way delayed ettringite forms, due to exposure to high temperatures (50 °C) and external sulphate attacks, was examined in the mortar samples.The mortars were immersed at 50 °C for 180 days in: (a) a saturated Ca(OH)₂ solution and (b) a 5% Na₂SO₄ solution. During the experiment’s duration, the mortar samples were being observed visually on a regular basis while their expansion was estimated on a weekly basis by measuring the change of length with a micrometer. At the end of the experiment, the mortar samples’ compressive strength was determined and the deterioration products were identified through means of X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM-EDAX), Thermogravimetry (TG) and Infra-Red Spectroscopy (FT-IR).Concluding it is evident that the amount of ettringite is proportional to the C₃A content of cement. Sulphates amount in cement is the controlling factor for heat induced ettringite formation since when they are consumed the reaction stops. On the other hand in the case of external sulphate attack another important controlling factor is the compressive strength of the cement; the higher compressive strength the lower the risk of expansion. Finally, in the case of external sulphate attack, limestone, when added to cement, was proved to enhance the durability against sulphates attack when compared to a cement of the same class.     

Microstructure changes in mortars attacked by sulphates at 5 °C

In this study mortars have been produced using ordinary Portland cement (CEM I – 32.5) and limestone cement with 15% limestone addition (CEM II/A-LL – 32.5). The mortars were immersed in a solution of 5% Na₂SO₄ at 5 °C for 6 months and the caused deterioration was observed visually at a regular basis. The deterioration product of the surface of both mortars has been identified as thaumasite by the means of XRD, FT-IR, DTA and SEM/EDAX analysis. The damage caused due to formation of thaumasite in both mortars was approximately the same and not influenced by the addition of limestone. Furthermore, expansion and compressive strength of the mortars were studied as a function of time and it was proved they were not influenced by thaumasite formation at the age of 6 months.     

Performance of limestone cement mortars in a high sulfates environment

With the aim of studying the influence of cement composition on resistance in high sulfates environment, standard mortars have been produced using ordinary Portland cement (CEM I – 32.5) and limestone cement with 35% limestone (CEM II/B-LL – 32.5). The pore size distribution of the cement pastes was measured. The mortars were immersed in a 5% Na₂SO₄ solution at 20 °C for 1.5 years and the caused deterioration was been visually observed at a regular basis. Furthermore, the mortars expansion was being estimated by measuring the change of length. At the end of the experiment the compressive strength of the mortars was measured. The deterioration products of the mortars have been identified by means of X-ray diffraction, optical microscopy and environmental scanning electron microscopy. The limestone cement based mortar presented cracking that started at the age of 6 months and continued throughout the experiment. It also displayed high expansion after 250 days of immersion in a 5% Na₂SO₄ caused, as proved using the analytical techniques, by the formation of gypsum and ettringite. Concluding, the cement with 35% limestone did not perform as well as ordinary Portland cement under the most aggressive laboratory conditions. Hence, it is obvious that the addition of limestone in the cement leads to a totally different behaviour than Portland cement with respect to the resistance in high sulfates environment.     

Effects of limestone replacement ratio on the sulfate resistance of Portland limestone cement mortars exposed to extraordinary high sulfate concentrations

A comparative study has been performed on the sulfate resistance of Portland limestone cement (PLC) mortars exposed to extraordinary high sulfate concentrations (200 g/l). PLCs have been prepared by using two types of clinkers having different C₃S/C₂S ratios and interstitial phase morphologies. Blended cements have been prepared by replacing 5%, 10%, 20% and 40% of clinker with limestone. Cubic (50 × 50 × 50 mm) and prismatic (25 × 25 × 285 mm) cement mortars were prepared. After two months initial water curing, these samples were exposed to three different sulfate solutions (Na₂SO₄ at 20 °C and 5 °C, MgSO₄ at 5 °C). Solutions were not refreshed and pH values of solutions were monitored during the testing stage. The compressive strength and length changes of samples have been monitored for a period of 1 year. Additional microstructural analyses have been conducted by XRD and SEM/EDS studies. Results indicated that in general, limestone replacement ratio and low temperature negatively affect the sulfate resistance of cement mortars. Additionally, clinkers of high C₃S/C₂S ratios with dendritic interstitial phase structure were found to be more prone to sulfate attack in the presence of high amounts of limestone.From the results, it is postulated that in the absence of solution change, extraordinary high sulfate content modified the mechanism of sulfate reactions and formation of related products. At high limestone replacement ratios, XRD and SEM/EDS studies revealed that while ettringite is the main deterioration product for the samples exposed to Na₂SO₄, gypsum and thaumasite formation were dominant products of deterioration in the case of MgSO₄ attack. It can be concluded that, the difference between reaction mechanisms of Na₂SO₄ and MgSO₄ attack to limestone cement mortars strongly depends on the pH change of sulfate solutions.     

How sulfates and increased temperature affect delayed ettringite formation (DEF) in white cement mortars

In this study,white cement CEM I and white limestone cement CEM II-LL A and Β with 15%, 25% and 35% limestone substitution were studied. The way delayed ettringite is forming due to exposure to increased temperature (50 °C) and external sulfate attack was examined in mortar samples which were immersed for 90 days in three different solutions: (a) saturated solution Ca(OH)₂ at 50 °C, (b) saturated solution of Ca(OH)₂ at 20 °C and (c) 5% w/w Na₂SO₄ solution at 50 °C. During this period mortar samples were visually observed regularly while their expansion was estimated on a weekly basis by measuring the change of length with a micrometer. At the end of the 90-days period the compressive strength of the mortars was determined and the deterioration products were identified through means of X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and thermogravimetric analysis (DTG). The results of this study show that DEF occurred in two forms. Samples cured at increased temperature contained DEF type I, which caused mediocre expansion and damage. Samples cured at increased temperature in the presence of sulfates produced DEF type II, which caused significant damage on the surface and exhibited high expansion.     

Properties of cement mortars containing clinoptilolite as a supplementary cementitious material

This paper presents a study of the properties and behavior of cement mortar with clinoptilolite which is one of the most common zeolite minerals found in nature. Six mortar mixtures were prepared by replacing the Portland cement with 0%, 5%, 10%, 15%, 20% and 30% clinoptilolite by weight. Test results showed that water demand, soundness and setting times of the cement pastes increased with the increase of clinoptilolite content. Compressive and flexural strength of the mortars containing clinoptilolite were higher than the control mixture. Dry unit weight of the mortars with clinoptilolite was lower than the control mortar. Clinoptilolite replacement decreased water absorption and porosity of the mortars. The control mortar showed less durability to carbonation compared to the mortars made with clinoptilolite at the end of carbonation tests. Freeze–thaw resistance of the mortars containing 5% clinoptilolite was higher than control mortar. The effect of clinoptilolite incorporation on high-temperature resistance seemed to be dependent on amount of clinoptilolite, temperature level, and the cooling method.     

Thaumasite formation in sugary solutions: Effect of temperature and sucrose concentration

Thaumasite formation in cementitious environments is attributed to sulphate attack (internal or external). Thaumasite is characterized by the presence of octahedrally coordinated silicon, but is formed from the silicate phases of cement, (mainly C–S–H gel), whose silicon atoms are tetrahedrally coordinated. Thaumasite formation is favoured at low temperatures and from recent studies sugar solutions increases calcium solubility and also increases the velocity of formation of thaumasite. The aim of the present study is to explore the effect of temperature (5 °C and 25 °C) and sucrose concentration (5%; 10% and 20% wt) on thaumasite formation from lime and sodium carbonate, sulphate, silicate sugary solutions. Precipitates formed different ages were characterized by XRD and FTIR. At 5 °C larger proportions of thaumasite were formed in 10% sucrose however at 25 °C, the 20% sugary solution generates more thaumasite at shorter times.     

A study of the permeability and acid attack of corn cob ash blended cements

The durability of concrete made with corn cob ash (CCA) blended cement was investigated in this study. Permeability and chemical attack involving H₂SO₄ and HCl were the key parameters considered. Nine classes of CCA blended cements were employed with the CCA content ranging from 0% to 25%. The 0% CCA replacement involved the use of normal ordinary Portland cement and it served as the control. The water absorption of blended cement concrete was performed using 100 mm cube specimens of mix proportions 1:1½:3, 1:2:4 and 1:3:6 with 0.5, 0.6 and 0.7 water-to-binder ratios, respectively. The chemical attack test was carried out using 50 × 50 × 15 mm mortar specimens of mix proportions 1:1, 1:2 and 1:3 with water-to-binder ratio ranging between 0.26 and 0.29. The results indicated that the use of CCA blended cement reduces the water absorption of concrete specimens. Optimal reduction occurred at 10% CCA replacement for 1:1½:3 and 1:2:4 mix proportions and at 15% CCA replacement for 1:3:6 mix proportion. The resistance to chemical attack was improved as the addition of CCA up to 15% replacement level, caused a decrease in permeability and reduction in weight loss due to reaction of the specimens with HCl and H₂SO₄ acid water.     

Freeze–thaw resistance of blended cements containing calcined paper sludge

This work deals with the frost resistance of blended cements containing calcined paper sludge (source for metakaolin) as partial Portland cement replacements. Freeze–thaw tests were performed on blended cement mortars containing 0%, 10% and 20% waste paper sludge calcined at 650 °C for 2 h. Cement mortar specimens were exposed to freezing and thawing cycles until the relative dynamic modulus of elasticity fell below 60%. The performance of the cement mortars was assessed from measurements of weight, ultrasonic pulse velocity, compressive strength, mercury intrusion porosimetry and SEM. Failure of the control cement mortar occurred before 40 freeze/thaw cycles, while cement mortar containing 20% calcined paper sludge failed after 100 cycles. After 28 and 62 freezing and thawing cycles, cement blended with 10% and 20% calcined paper sludge exhibited a smaller reduction in compressive strength than the control cement.     

Study on microstructure and mechanical property of interfacial transition zone between limestone aggregate and Sialite paste

The hydrating products as well as the microstructure at the interfacial transition zone (ITZ) between limestone aggregate and Sialite paste have been studied using XRD, SEM and EDAX methods. The inductive coupled plasma emission spectrometer (ICP) has been employed to investigate the solution phenomena of limestone by three kinds of different liquids. This paper reports the bonding strength of ITZ and the durability of Sialite concrete including water penetrability, chloride penetration, carbonated depth and freeze–thaw durability. It was found that Ca(OH)₂ crystals were not observed in the Sialite hydrating products at 28 days and at the ITZ. The interfacial bonding strength of Sialite was significantly stronger than that of ordinary Portland cement (OPC). The presence of rock-forming liquid comprising a variety of minerals was also effective in improving the interfacial bonding strengths between limestone aggregates and Sialite paste.     

Evaluation of sulfate resistance of Portland and high alumina cement mortars using hardness test

Portland cement and high alumina cement mortar specimens were exposed to cycles of drying at 40 °C, cooling at 20 °C and immersion in Na₂SO₄ and MgSO₄ solutions at 20 °C. The resistance of mortars was evaluated by visual inspection and by measuring the change in surface hardness and weight of the specimens. The decrease and increase in surface hardness were observed in both mortars by treating with Na₂SO₄ and MgSO₄ solutions, respectively. The combined effect of the chemical and physical attack by Na₂SO₄ was attributed to the complete failure of Portland cement mortar, whereas only marginal damage of high alumina cement mortar was believed owing to physical salt crystallization. No damage was observed in both mortars treated with MgSO₄ solution.     

Durability of gamma irradiated polymer-impregnated blended cement pastes

This study is focusing on durability of the neat blended cement paste as well as those of the polymer-impregnated paste towards seawater and various concentrations of magnesium sulfate solutions up to 6 months of curing. The neat blended cement paste was prepared by a partial substitution of ordinary Portland cement with 5% of active rice husk ash (RHA). These samples were cured under tap water for 7 days. A similar paste was impregnated with unsaturated polyester resin (UPE) followed by gamma rays ranging from 10 to 50 kGy. The obtained data indicated that the polymer-impregnated specimens higher values of compressive strength than those of the neat blended cement paste. In addition, the polymer-impregnated blended cement specimens irradiated at a dose of 30 kGy and neat blended cement specimens were immersed in seawater and different concentrations of magnesium sulfate solutions namely, 1%, 3% and 5% up to 6 months. The results showed that the polymer-impregnated blended cement (OPC–RHA–UPE) paste irradiated at a dose of 30 kGy has a good resistance towards sulfate and seawater attack as compared to the neat blended cement (OPC–RHA) paste. These results were confirmed by scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) studies.     

Microstructure and durability of mortars modified with medium active blast furnace slag

Mechanical characteristics and durability properties of blast furnace slag cement composites largely depend on the hydraulic activity of the slag. In this paper, a Granulated Blast Furnace Slag with a low reactivity index is used in modifying mortar composition. Microstructure and durability of mixes containing 0%, 30% and 50% of slag as substitution to OPC are respectively compared and analyzed. Water porosity, Mercury Intrusion Porosity and pore size distribution are studied after 28, 90 and 360 days of wet curing. A qualitative microstructure analysis of mortars is proposed with Scanning Electron Microscope (SEM). The durability of mortar is evaluated through capillary water absorption and chloride diffusion tests. The results indicate a finer porosity and lower water absorption for slag mortars at old ages (90 and 360 days). Moreover, lower chloride diffusion for 50% blast furnace slag substitution is observed.     

The assessment of porosity and pore size distribution of limestone Portland cement pastes

The cement production industry is one of the most energy and raw materials consuming one. Over the last years a great effort is performed in order to substitute clinker for less energy demanding materials. Nevertheless, construction industry needs durable materials with improved properties. Limestone is being used in blended cements widely. The most important parameter that affects all the properties of cement paste is its pore structure. In this study, four different limestone cements were produced and their pore structure was determined by means of mercury intrusion porosimetry (MIP) and nuclear magnetic resonance (NMR) cryoporometry. The conclusion of the study was that limestone addition affects the pore structure of the cement paste by increasing linearly the size of capillary pores from 20 nm to 40 nm when the maximum amount (35%) of limestone that is allowed by EN 197-1 is used. On the other hand the threshold diameter decreases exponentially and it is evident that limestone hardened cement pastes have many pores of the same size due to the filling effect that minerals additives have. Furthermore, limestone decreases the size of gel pores which is related to higher hydration rates. Hence, the use of limestone in cement produces a material that is structurally adequate to be used in construction.     

Use of natural and thermally activated porphyrite in cement production

The aim of the present study was to investigate the use of porphyrite in the production of Portland cement. Natural and thermally activated porphyrites were used as a clay raw material and an activator, respectively, at 0, 10, 20, 30, 40 and 50 wt% in order to assess their effects on the cement properties. According to the test results, the compressive strength of the specimens decreased with increasing natural porphyrite content in various curing periods. However, the compressive strength of cement produced with 10 wt% porphyrite (activator) activated at 650 °C for 30 min showed a higher value (56 MPa in TPC-6) than cement without activator (51 MPa in RPC-2). Due to thermal activation, porphyrite activator containing a glass phase possesses an enhanced reactivity during clinker hydration that intensifies the synthesis of hydrosilicates and improves compressive strength accordingly. The X-ray diffraction analysis confirmed an intensive formation of Portland cement minerals such as C₃S, β-C₂S, C₃A and C₄AF. The addition of thermally activated porphyrite has also led to an improvement of the rheological behavior, stability to expansion, increase in setting time and decrease in specific surface area of cement. As prepared cement composites and concretes with improved properties meet the requirements of State Standards 310-86 and 10181-81 for Portland cement and concrete, respectively. The findings in this report indicate that porphyrite can be utilized both as a raw material and an activator in the production of cement.     

Compressive strength and shrinkage of mortar containing various amounts of mineral additions

Three mineral additions largely used in cementitious materials were tested in order to follow the shrinkage behaviour for 1 year of observation when they substitute a part of cement. The tests were carried out on standardized mortars specimen where cement was replaced by 5%, 15% and 25% of limestone, 10%, 20%, 30% of natural pozzolan and 10%, 30% and 50% of slag. The substitution of cement by 10%, 20% and 30% of limestone powder, natural pozzolan and slag respectively involves an optimal improvement of compressive strength of mortar. The separate quantification of the autogeneous and drying shrinkage development shows the effective contribution of each addition on microstructure modification and of the additional hydrates production. The microstructure was improved in the presence of limestone and of a moderate rate of slag, whereas it remains normal with natural pozzolan. The replacement rate of an active addition lower than 10% led to an additional hydrates production. This overproduction which accompanies the autogeneous shrinkage is more pronounced when cement is largely replaced by limestone. The evolutions of strength and shrinkage of mortars follow the same tendency from where it is easier to find a linear relationship giving the shrinkage deformation according to the compressive strength.     

Recycling of municipal incinerator fly-ash slag and semiconductor waste sludge as admixtures in cement mortar

We proposed to tackle the problem of fly-ash pollution from municipal solid waste incineration as well as sludge from chemical–mechanical polishing, by partial substitution of cement in mortar. The optimal modified cement mortar determined by the Taguchi method showed unexpected strengthening effects starting after 4 days of curing and gradually reached a maximum strengthening at 90 days of curing up to 139% of that of ordinary cement mortar. The polluting leachants from the modified cement mortar were barely detectable in toxicity characteristic leaching process tests. The mechanism of the precipitous strengthening effect is preliminarily attributed to nanoparticle activation and enriched hydration.     

Effects of curing regimes and cement fineness on the compressive strength of ordinary Portland cement mortars

Curing techniques and curing duration have crucial effects on the strength and other mechanical properties of mortars. Proper curing can protect against moisture loss from fresh mixes. The objective of this experimental work is to examine the compressive strength of ordinary Portland cement mortars (OMs) under various curing regimes and cement fineness. Six different curing methods including water, air, water heated, oven heated, air–water, and water–air were applied to the specimens and also six groups of mortars were used. The results showed that the highest and lowest compressive strengths are attributed to the specimens of OPC mortar water cured using grounded OPC for duration of 6 h (OM–G6–wc) and OPC mortar air cured under room temperature with oven heated after demoulding of the specimens at 60 °C for duration of 20 h (OM–OH–ac), respectively. The maximum levels obtained of compressive strengths at 7, 28, and 90 days are 57.5, 70.3, and 76.0 MPa, respectively.     

Hybrid effect of carbon nanotube and nano-clay on physico-mechanical properties of cement mortar

In this work, several nanomaterials have been used in cementitious matrices: multi wall carbon nanotubes (MWCNTs) and nano-clays. The physico-mechanical behavior of these nanomaterials and ordinary Portland cement (OPC) was studied. The nano-clay used in this investigation was nano-kaolin. The metakaolin was prepared by thermal activation of nano-kaolin clay at 750 °C for 2 h. The organic ammonium chloride was used to aid in the exfoliation of the clay platelets. The blended cement used in this investigation consists of ordinary Portland cement, carbon nanotubes and exfoliated nano metakaolin. The OPC was substituted by 6 wt.% of cement by nano metakaolin (NMK) and the carbon nanotube was added by ratios of 0.005, 0.02, 0.05 and 0.1 wt.% of cement. The blended cement: sand ratio used in this investigation was 1:2 wt.%. The blended cement mortar was prepared using water/binder ratio of 0.5 wt.% of cement. The fresh mortar pastes were first cured at 100% relative humidity for 24 h and then cured in water for 28 days. Compressive strength, phase composition and microstructure of blended cement were investigated. The results showed that, the replacement of OPC by 6 wt.% NMK increases the compressive strength of blended mortar by 18% compared to control mix and the combination of 6 wt.% NMK and 0.02 wt.% CNTs increased the compressive strength by 29% than control.     

Effects of crushed glass cullet sizes,casting methods and pozzolanic materials on ASR of concrete blocks

The aim of this study is to investigate the influence of using different particle sizes of recycled glass, casting methods and pozzolanic materials in reducing the expansion due to alkali-silica reaction (ASR) of concrete blocks prepared with the use of crushed glass as fine aggregate. In this work, 25 × 25 × 285 mm mortar bar specimens were prepared using conventional wet-mixed and dry-mixed methods. Except for the control mortar bar, all the specimens were prepared by completely replacing river sand with different particle sizes of recycled glass. In addition, the influence of fly ash (PFA) and metakaolin (MK) content on the reduction of ASR expansion was also investigated. The flexural strength of the mortar bar specimens before and after they had been exposed to 1N NaOH solution was determined to complement the results of ASR expansion test. SEM was performed to examine the microstructure as well as nature of the cement binder-glass interfacial zone. The results reveal that ASR expansion reduced with reducing particle size of glass used. For the same given mix proportion, the dry-mixed method resulted in 44% less expansion when compared with the wet-mixed method. Both PFA and MK were demonstrated to be able to significantly reduce ASR expansion of the concrete glass blocks.