Properties and hydration of blended cements with steelmaking slag

The present research study investigates the properties and hydration of blended cements with steelmaking slag, a by-product of the conversion process of iron to steel. For this purpose, a reference sample and three cements containing up to 45% w/w steel slag were tested. The steel slag fraction used was the “0-5 mm”, due to its high content in calcium silicate phases. Initial and final setting time, standard consistency, flow of normal mortar, autoclave expansion and compressive strength at 2, 7, 28 and 90 days were measured. The hydrated products were identified by X-ray diffraction while the non-evaporable water was determined by TGA. The microstructure of the hardened cement pastes and their morphological characteristics were examined by scanning electron microscopy. It is concluded that slag can be used in the production of composite cements of the strength classes 42.5 and 32.5 of EN 197-1. In addition, the slag cements present satisfactory physical properties. The steel slag slows down the hydration of the blended cements, due to the morphology of contained C₂S and its low content in calcium silicates.     

Hydration in high-performance cementitious systems containing vitreous calcium aluminosilicate or silica fume

The influence of a relatively new high-performance cement replacement material—vitreous calcium aluminosilicate (VCAS)—on the hydration behavior in cementitious systems, and its comparison to silica fume (SF) are presented in this paper. VCAS is shown to have no cementitious qualities, but exhibits significant pozzolanicity, which has been quantified using strength activity index and electrical conductivity change. VCAS modified pastes are found to consume more water during hydration than the corresponding SF modified pastes. Based on a normalized calcium hydroxide content defined in this paper, it is seen that the pozzolanic reaction of VCAS does not happen until 7 days while that of SF occurs as early as the first day. The degrees of hydration of the modified pastes are predicted using a model that employs the change in non-evaporable water resulting from the use of these replacement materials. VCAS modified pastes show lower later age porosities as compared to the plain and SF modified pastes. However, at equal degrees of hydration, SF modified pastes show the lowest porosity.     

Cement hydration and microstructure formation in the presence of water-soluble polymers

Hardening of cement mortars modified with small amounts of water-soluble polymers implies both cement hydration and polymer film formation. In this paper, the effect of the presence of water-soluble polymers on the cement hydration reactions is investigated by means of isothermal calorimetry, thermal analysis, FT-IR spectroscopy and SEM investigation. In spite of an initial retardation of the hydration reactions, a higher degree of hydration is found after 90 days for 1% PVAA, MC and HEC modified mortars, due to a better dispersion of the cement particles in the mixing water. MC also affects the morphology of the Ca(OH)₂ crystals. Polymer bridges are detected between the layered crystals, gluing the layers together and strengthening the microstructure. Additionally, the internal cohesion of all bulk polymer modified cement pastes is improved. In the presence of the polymers, a more cohesive microstructure with a smaller amount of microcracks is created.     

In situ synchrotron X-ray powder diffraction study of the early age hydration of cements blended with zeolitite and quartzite fines and water-reducing agent

A comparison was made between the early-age hydration of cements blended with micronized zeolitite and quartzite powders. The Portland cement replacement in the mixes was 30%, and the effect of introducing a superplasticiser to lower the required water to solid ratio was assessed. The cement pastes were hydrated at 40 °C and monitored in situ by time-resolved synchrotron X-ray powder diffraction combined with Rietveld quantitative phase analysis.The quantitative evolution of phase weight fractions showed that the addition of the zeolite tuff accelerated the hydration rate of the main C₃S cement component. Blending with the quartzite powder of similar fineness did not affect the C₃S hydration rate. Reduction of the water to solid ratio by introduction of the superplasticiser had a retarding effect on the hydration of the zeolitite-blended cement over the early hydration period up to 3 days.The AFt or ettringite reaction products, formed promptly after the addition of water to the mixtures, underwent a crystal structural modification over the induction period up to 4 to 6 hours of reaction. The continuous contraction of the c-cell parameter and expansion of the a-cell parameter towards the ideal values for AFt or ettringite reflects the structural adaptation of the AFt to the changing availability of sulphate over the course of the first hours of hydration. The observed structural changes were less pronounced in the zeolitite blended cement. This is related to the dilution of the overall sulphate content in the blended cement and highlights the need to control and optimise sulphate additions in blended cements.     

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%.     

Effect of curing time on the physicomechanical characteristics of the hardened cement pastes containing limestone

The effect of curing time on the physico-mechanical properties of the hardened Portland cement pastes containing limestone was studied. Five cement-limestone blends were prepared using 0%, 5%, 10%, 15%, and 20% of limestone as a partial substituent of Portland cement. The cement pastes were prepared using the standard water of consistency of 0.255, 0.255, 0.258, 0.261, and 0.263, respectively. The fresh pastes, thus produced, were moulded into 2×2×2-cm cubes. The pastes were first cured within the moulds at 100% relative humidity for 24 h, then the specimens were demoulded and cured under tap water for 3, 7, 14, and 28 days. At each hydration age, the hardened pastes were tested for bulk density, compressive strength, differential scanning calorimetery (DSC), and X-ray diffraction analysis (XRD). The results obtained were related as much as possible to the mechanical properties of the hardened cement pastes. The inclusion of limestone results in a notable improvement of the mechanical properties of the cement pastes containing limestone.     

减水剂的加入时间对新拌水泥浆体流变性能的影响

研究了三聚氰胺甲醛磺酸盐(MFS)减水剂的掺加时间对普通硅酸盐水泥浆体在初始120 min的水化时间内流变性能的影响,研究中MFS的后掺时间为0 min、5 min、10 min、15 min、20 min和25 min。检测了在不同减切速率(3～147 s-1)下水泥浆体水化30 min和120 min时的剪切应力和表观粘度。测定了水化120 min后的水泥浆体的Ca2+浓度和化学结合水。结果表明:推迟减水剂的后掺时间降低了水泥浆体在120 min内的屈服应力和表观粘度,减水剂MFS的最佳后掺时间为10～15 min。     

Effect of treatment temperature on the early hydration characteristics of superplasticized silica fume blended cement pastes

In this investigation, two mixes were used: ordinary Portland cement (OPC) and a blended cement prepared with the partial substitution of OPC by 10 mass% silica fume (SF). The setting and hardening characteristics were monitored by the aid of electrical conductivity as a function of curing time. The shear stress and electrical conductivity were studied at different temperatures, namely, 20, 35, 45 and 55 °C. As the temperature increases, the shear stresses decrease with the increase of shear rate. The height of electrical conductivity peaks of superplasticized cement pastes increases due to the increase of the paste fluidity. In the presence of 1.0% polycarboxylate (PC), the electrical conductivity of cement pastes decreases from 1 to 28 days. PC retards the hydration of cement pastes. The presence of PC extended the setting times of cement pastes at 35 °C than at 20 °C due to the increase in the adsorption capacity at this temperature. PC extends the dormant stage of the hydration process and delays the onset of the accelerating stage, without affecting its rate.     

Formation of magnesium silicate hydrate (M-S-H) cement pastes using sodium hexametaphosphate

Magnesium silicate hydrate (M-S-H) gel is formed by the reaction of brucite with amorphous silica during sulphate attack in concrete and M-S-H is therefore regarded as having limited cementing properties. The aim of this work was to form M-S-H pastes, characterise the hydration reactions and assess the resulting properties. It is shown that M-S-H pastes can be prepared by reacting magnesium oxide (MgO) and silica fume (SF) at low water to solid ratio using sodium hexametaphosphate (NaHMP) as a dispersant. Characterisation of the hydration reactions by x-ray diffraction and thermogravimetric analysis shows that brucite and M-S-H gel are formed and that for samples containing 60 wt.% SF and 40 wt.% MgO all of the brucites react with SF to form M-S-H gel. These M-S-H cement pastes were found to have compressive strengths in excess of 70 MPa.     

Development of low-pH cementitious materials for HLRW repositories: Resistance against ground waters aggression

One of the most accepted engineering construction concepts of underground repositories for high radioactive waste considers the use of low-pH cementitious materials. This paper deals with the design of those based on Ordinary Portland Cements with high contents of silica fume and/or fly ashes that modify most of the concrete “standard” properties, the pore fluid composition and the microstructure of the hydrated products. Their resistance to long-term groundwater aggression is also evaluated. The results show that the use of OPC cement binders with high silica content produces low-pH pore waters and the microstructure of these cement pastes is different from the conventional OPC ones, generating C-S-H gels with lower CaO/SiO₂ ratios that possibly bind alkali ions. Leaching tests show a good resistance of low-pH concretes against groundwater aggression although an altered front can be observed.     

Effect of calcium formate as an accelerator on the physicochemical and mechanical properties of pozzolanic cement pastes

The aim of the present work is to study the effect of calcium formate (CF) as an accelerator on the properties of pozzolanic cement pastes. Three types of cements were used in this investigation. These cements were OPC and pozzolanic cements containing 80 mass% OPC and 20 mass% silica fume (SF) or 20 mass% ground clay bricks (GCB). The dosages of CF were 0.00, 0.25, 0.50, and 0.75 mass% of cement. The compressive strength, total porosity, and hydration kinetics such as free lime and combined water contents were investigated. The results obtained in this study showed that the addition of CF shortens the initial and final setting times and increases the compressive strength and combined water content as well as gel/space ratio at all ages of hydration. On the other hand, it decreases the total porosity. CF activates the liberation of Ca(OH)₂ of OPC pastes. The free lime content of pozzolanic cement in the presence of CF increases up to 7 days, then decreases at the later ages of hydration.     

Influence of polymer on cement hydration in SBR-modified cement pastes

The influence of styrene-butadiene rubber (SBR) latex on cement hydrates Ca(OH)₂, ettringite, C₄AH₁₃ and C-S-H gel and the degree of cement hydration is studied by means of several measure methods. The results of DSC and XRD show that the Ca(OH)₂ content in wet-cured SBR-modified cement pastes increases with polymer-cement ratio (P/C) and reaches a maximum when P/C is 5%, 10% and 10% for the pastes hydrated for 3 d, 7 d and 28 d, respectively. With wet cure, appropriate addition of SBR promotes the hydration of cement, while the effect of SBR on the content of Ca(OH)₂ and the degree of cement hydration is not remarkable in mixed-cured SBR-modified cement pastes. XRD results illustrate that SBR accelerates the reaction of calcium aluminate with gypsum, and thus enhances the formation and stability of the ettringite and inhibits the formation of C₄AH₁₃. The structure of aluminum-oxide and silicon-oxide polyhedron is characterized by ²⁷Al and ²⁹Si solid state NMR spectrum method, which shows that tetrahedron and octahedron are the main forms of aluminum-oxide polyhedrons in SBR-modified cement pastes. There are only [SiO₄]⁴⁻ tetrahedron monomer and dimer in the modified pastes hydrated for 3 d, but there appears three-tetrahedron polymer in the modified pastes hydrated for 28 d. The effect of low SBR dosage on the structure of aluminum-oxide and silicon-oxide polyhedron is slight. However, the combination of Al³⁺ with [SiO₄]⁴⁻ is restrained when P/C is above 15%, and the structure of Al³⁺ is changed obviously. Meantime, the polymerization of the [SiO₄]⁴⁻ tetrahedron in C-S-H gel is controlled.     

Determining the water–cement ratio, cement content, water content and degree of hydration of hardened cement paste: Method development and validation on paste samples

We propose a new method to estimate the initial cement content, water content and free water/cement ratio (w/c) of hardened cement-based materials made with Portland cements that have unknown mixture proportions and degree of hydration. This method first quantifies the composition of the hardened cement paste, i.e. the volumetric fractions of capillary pores, hydration products and unreacted cement, using high-resolution field emission scanning electron microscopy (FE-SEM) in the backscattered electron (BSE) mode and image analysis. From the obtained data and the volumetric increase of solids during cement hydration, we compute the initial free water content and cement content, hence the free w/c ratio. The same method can also be used to calculate the degree of hydration. The proposed method has the advantage that it is quantitative and does not require comparison with calibration graphs or reference samples made with the same materials and cured to the same degree of hydration as the tested sample. This paper reports the development, assumptions and limitations of the proposed method, and preliminary results from Portland cement pastes with a range of w/c ratios (0.25–0.50) and curing ages (3–90 days). We also discuss the extension of the technique to mortars and concretes, and samples made with blended cements.     

Fire resistance of fired clay bricks-fly ash composite cement pastes

This work aims to study the effect of substitution of fly ash for homra on the hydration properties of composite cement pastes. The composite cements are composed of constant proportion of OPC (80%) with variable amounts of fly ash and homra. The addition of fly ash accelerates the initial and final sitting time, whereas the free lime and combined water contents decrease with fly ash content. The fly ash acts as nucleation sites which may accelerate the rate of formation of hydration products which fill some of the pores of the cement pastes. The fire resistance of composite cement pastes was evaluated after firing at 250, 450, 600, 800 °C with rate of firing 5 °C/min with soaking time for 2 h. The physico-mechanical properties such as bulk density and compressive strength were determined at each firing temperature. Moreover, the phase composition, free lime and microstructure for some selected samples were investigated. It can be concluded that the pozzolanic cement with 20 wt% fly ash can be used as fire resisting cement.     

Influence of a fine glass powder on cement hydration: Comparison to fly ash and modeling the degree of hydration

This paper reports the results of an investigation carried out to understand the influence of a fine glass powder on cement hydration. The pozzolanicity of the glass powder and a Class F fly ash for comparison was evaluated using strength activity index over a period of time, and a rapid electrical conductivity based method. Flame emission spectroscopy and electrical conductivity tests were used to quantify the alkali release from glass powder, and gain information on the rate of alkali release. It was found that the glass powder releases only a very small fraction of sodium ions into the solution. It was observed that the glass powder modified pastes show higher non-evaporable water contents than the plain paste and fly ash modified pastes, indicating that glass powder facilitates enhancement in cement hydration. An expression has been developed for the change in non-evaporable water content as a result of enhancement in cement hydration and the hydration of the cement replacement material. The efficiency of any cement replacement material with age in the paste system can be quantified using this parameter. Based on this parameter, a 5% cement replacement with glass powder was found to be effective at the chosen water-to-cementing materials ratio (w/cm), whereas at higher replacement levels, the dilution effect dominates. A model to predict the combined degree of hydration of cement pastes incorporating more than one cementing material is outlined. The measured and predicted combined degrees of hydration agree well.     

Pyrophosphate ions inhibit calcium phosphate cement reaction and enable storage of premixed pastes with a controlled activation by orthophosphate addition

The standard preparation routine of a calcium phosphate cement includes mixing a solid and a liquid component (reactive cement powder and mixing liquid) in an open bowl at the operating theatre. This poses the risk of preparation-related deviations of the resulting properties when the cements are mixed by different persons. Hence, facilitating this mixing procedure is highly desirable. It can be achieved by application of premixed cement pastes: The mixing liquid and a stable suspension of the cement powder are assembled and mixed in a special syringe, minimizing the impact of these preparation-related effects.In this study, a suspension of reactive α-tricalcium phosphate powder in water was stabilized by sodium pyrophosphate decahydrate (PP). Controlled activation of these premixed pastes was then accomplished by adding a concentrated Na₂HPO₄/NaH₂PO₄ (Na₂/Na) solution. Systematic assessment of the activation mechanism, including the effect of the PP concentration and the amount of Na₂/Na added, was performed by isothermal calorimetry, quantitative in-situ X-ray diffraction, rheological characterization and automated Gillmore needle measurements at 37 °C.Premixed pastes with addition of at least 0.05 wt% PP were successfully stabilized for up to 2 weeks at 25 °C, and even 4 weeks at 4 °C. This pre-storage had no significant impact on the setting performance of the pastes. Increasing the PP concentration at constant Na₂/Na amount systematically retarded the setting reaction, while an elevated quantity of Na₂/Na addition at constant PP concentration resulted in an acceleration.Based on these results, a composition stabilized with 0.05 wt% PP and activated with 20.8 vol% Na₂/Na related to the amount of liquid in the premixed pastes appears ideal with respect to the desired setting performance.     

Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C₃S, β-C₂S, C₃A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, ²⁹Si and ²⁷Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.     

Investigation of blended cement hydration by isothermal calorimetry and thermal analysis

Hydration of portland cement pastes containing three types of mineral additive; fly ash, ground-granulated slag, and silica fume was investigated using differential thermal analysis, thermogravimetric analysis (DTA/TGA) and isothermal calorimetry. It was shown that the chemically bound water obtained using DTA/TGA was proportional to heat of hydration and could be used as a measure of hydration. The weight loss due to Ca(OH)₂ decomposition of hydration products by DTA/TGA could be used to quantify the pozzolan reaction. A new method based on the composition of a hydrating cement was proposed and used to determine the degree of hydration of blended cements and the degree of pozzolan reaction. The results obtained suggested that the reactions of blended cements were slower than portland cement, and that silica fume reacted earlier than fly ash and slag.     

The pozzolanic reactivity of monodispersed nanosilica hydrosols and their influence on the hydration characteristics of Portland cement

This study reveals that the nanosilica hydrosols with higher specific surface areas had faster pozzolanic reactivity, especially at early ages; moreover, the results are indicative of the accelerating influence of nanosilicas and silica fume on the hydration of cement. Faster initial and final setting times observed for cement pastes containing nanosilicas are consequence of these mechanisms. However, less hydration degree of cement compared to the plain paste was observed at age of 7 days and after. This can be attributed to the entrapment of some of mix water in the aggregates of nanosilicas formed in cement paste environment, making less water available for the progress of cement hydration. The same mechanism is believed to be responsible for the reduction of flowability of cement pastes.     

Detection of Failures around Main Cracks and Their Relation to the Fracture Toughness of Cement Pastes

Fluorescence microscopy examinations revealed the characteristics of crack path and the presence of local failures around the main cracks in hardened cement pastes. Reduction in the water: cement ratio and the addition of silica fume led to a decrease in locally damaged regions around the main cracks. However, the R - curve of the silica fume-free cement paste with the water: cement ratio of 0.55 was much different from that of the silica fume-bearing paste. The silica fume-bearing cement paste exhibited a relatively flat R -curve, whereas reduction in the water: cement ratio in the silica fume-free paste led to a rising R-curve. These results were related to the toughening mechanisms of cement pastes derived from the characteristics of the crack path and the areas of local failures around main cracks that were revealed by fluoresence microscopy. Presumably, these differences in fracture toughness resulted from the nature of hydration products and/or their inherent microstructure.