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.     

Property improvement of Portland cement by incorporating with metakaolin and slag

The physical and mechanical properties of Portland cement (PC) containing metakaolin (MK) or combination of MK and slag and the compatibility between such materials and superplasticizers were investigated in present study. After MK was incorporated into PC, the compressive strength of the blended cement was enhanced. However, the fluidity of MK blended cement became poorer than that of PC at the same dosage of superplasticizer and the same water/binder ratio. When both MK (10%) and ultra-fine slag (20% or 30%) were incorporated into PC together, not only the compressive strength of the blended cement was increased, but also the fluidity of the blended cement paste was improved comparing to MK blended cement. This indicates that ultra-fine slag can improve the physical and mechanical properties of MK blended cement. The physical and chemical effects of two mineral admixtures were also discussed.     

The macro- and micro properties of cement pastes with silica-rich materials cured by wet-mixed steaming injection

This research used cement pastes with a low water/blaine ratio (W/b=0.27). Rice husk ashes (RHA) burned at 700 and 850 °C, silica fume, silica sand (Ottawa standard sand), etc., were the added ingredients. Wet-mixed steam injection (WMSI) was at five different temperatures: 65, 80, 120, 150 and 180 °C. We investigated cement pastes with added silica-rich materials. For different WMSI temperatures and times, we explored the relations between compressive strength, hydration products, and pozzolanic reaction mechanism. From scanning electron microscopy (SEM) and EDS, we know that hydration products become very complicated, depending on the WMSI temperatures and times. It is difficult to determine the direct effects on the strength based on changes in the products. Experimental results, however, clearly showed that the compressive strength was worst for 80 °C and best for 180 °C. High-temperature WMSI is best with 4-h presteaming period and 8-h retention time. Curing in saturated limewater for 28 days did not increase the strength. The three types of silica-rich materials used in this research all participated in the reaction during high-temperature WMSI; they helped to increase the strength. Addition of Ottawa standard sand resulted in the best strength, followed by addition of RHA, while addition of silica fume was worse than the others. Specimens treated with high-temperature WMSI would swell slightly if they were placed in air. This was different from normal-temperature curing.     

Study of the influence of superplasticizers on the hydration of cement paste using nuclear magnetic resonance and X-ray diffraction techniques

Melamine and naphthalene-based superplasticizers have been used, over the past few decades, in order to improve the workability of concrete. Recently, more efficient copolymer formulations have been introduced for the same purpose. However, the influence of these chemical admixtures on the microstructure of the hardened concrete and, consequently, on its properties still needs to be extensively evaluated. Accordingly, the present work analyzes the hydration characteristics of cement pastes with naphthalene, melamine and copolymer-based superplasticizers, using the techniques of X-ray diffraction (XRD) and nuclear magnetic resonance (NMR), up to the age of 28 days. The results indicate a significant influence of the superplasticizer on the growth rates of the hydrates and on the state of polymerization of the silicates.     

The influence of nano-silica and zircon additions on the sintering and mechanical properties of in situ formed forsterite

The influence of nano-silica and zircon additions on the sintering and mechanical properties of in situ formed forsterite fired at 1550 °C for 2 h was investigated. The results indicated that, nano-silica improved in situ formed forsterite at the firing temperature, while zircon additions enhanced the sintering of the investigated samples. XRD analysis and SEM examination observed a good crystallinity of in situ formed forsterite with nano-silica and/or zircon additions. Densification parameter (BD ∼3.22 g/cm³ and AP ∼5.82%), cold crushing strength (CCS ∼285 MPa) and micro-hardness (Hv ∼660) were enhanced with zircon additions.     

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.     

Porosity study on free mineral addition cement paste

A study of the hydration process and the porosity evolution in a cement paste is presented. The analysis of porosity was made in samples with water to cement ratios (w/c) of 0.24, 0.40 and 0.60 at age of 3, 7, 28 and 365 days, respectively. Information on the evolution of total porosity and on the strength of the paste were obtained using positron annihilation lifetime spectroscopy (PALS), scanning electron microscopy (SEM), X-ray diffraction (XRD), mechanical tests (compression and flexion) and water absorption techniques. Specifically, positron lifetime technique allowed us to analyze the evolution of gel and capillary porosity during the hydration process. Using a simple function proposed, reasonable fits to the experimental data of the porosity evolution as a function of the compression strength were obtained.     

Effects of sintering temperature on structural and electromagnetic properties of MgCuZn ferrite prepared by microwave sintering

Nanocrystalline magnesium–copper–zinc (Mg_0.30Cu_0.20Zn_0.50Fe₂O₄) ferrites were prepared by microwave sintering technique. The effects of the sintering temperature on particle size and magnetic properties were investigated. In this article, optimum sintering temperature required for MgCuZn ferrite system for obtaining good electromagnetic properties, suitable for applications in low temperature co-fired ceramics (LTCC) chip components was studied. The grain size, initial permeability, dielectric constant and saturation magnetisations were found to increase, and dielectric loss was found to decrease with the increasing sintering temperature. Mg–Cu–Zn ferrites with a permeability of μ?=?1110 (at 1?MHz) were fully densified at the standard LTCC sintering temperature of 950°C.     

Influence of citric acid on the hydration of Portland cement

Citric acid can be used to retard the hydration of cement. Experiments were carried out to investigate the influence of citric acid on the composition of solid and liquid phases during cement hydration. Analyses of the solid phases showed that dissolution of alite and aluminate slowed down while analyses of the pore solution showed that citric acid was removed almost completely from the pore solution within the first hours of hydration. The complexation of the ions by citrate was weak, which could also be confirmed by thermodynamic calculations. Only 2% of the dissolved Ca and 0.001% of the dissolved K formed complexes with citrate during the first hours. Thus, citric acid retards cement hydration not by complex formation, but by slowing down the dissolution of the clinker grains. Thermodynamic calculations did not indicate precipitation of a crystalline citrate species. Thus, it is suggested that citrate sorbed onto the clinker surface and formed a protective layer around the clinker grains retarding their dissolution.     

Effects of ZnO nanoparticulate addition on the properties of PMNT ceramics

This research was conducted in order to study the effect of ZnO nanoparticulate addition on the properties of 0.9 Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ [PMNT] ceramics. The PMNT ceramics were prepared by a solid-state reaction. The ZnO nanoparticles were added into PMNT ceramics to form PMNT/xZnO (x = 0, 0.05, 0.1, 0.5, and 1.0 wt.%). The PMNT/xZnO ceramics were investigated in terms of phase, microstructure, and mechanical and electrical properties. It was found that the density and grain size of PMNT ceramics tended to increase with an increasing amount of ZnO content. Moreover, a transgranular fracture was observed for the samples containing ZnO, while pure PMNT ceramics showed only a intergranular fracture. An addition of only 0.05 wt.% of ZnO was also found to enhance the hardness and dielectric and ferroelectric properties of the PMNT ceramics.     

An investigation on microstructure of cement paste containing fly ash and silica fume

In this study, high-calcium fly ash (HCFA) and silica fume (SF) were used as mineral admixtures. The effect of these admixtures on the microstructure of cement paste was investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The reaction of HCFA and SF with portlandite, which occurs in Portland cement (PC), forms a new calcium-silicate-hydrate (C-S-H) gel.     

Effect of various superplasticizers on the rheological properties of Portland cement pastes

In the present work, the influence of the addition of some superplasticizers employed for maximising the solid loading of Portland cement pastes has been investigated. Cement pastes were prepared from deionized water and a commercial manufactured ordinary Portland cement 32.5 R (produced by Buzzi Unicem). Cement and water were mixed with a vane stirrer according to ASTM Standard C305. The water/cement ratio was kept fixed at 0.32. Three commercial superplasticizing agents produced by Ruredil were used: they are based on a melamine resin (Fluiment 33 M), on a modified lignosulphonate (Concretan 200 L), and on a modified polyacrylate (Ergomix 1000). Rheological tests were carried out at 25 °C by using the rate controlled coaxial cylinder viscometer Rotovisko-Haake 20, system M5-Osc., measuring device MV2P with serrated surfaces. The tests were performed under both continuous and oscillatory flow conditions. Ergomix 1000 presents a different behaviour as that of the other two superplasticizers studied, because it shows a marked shear-thickening behaviour above a critical deflocculant concentration and slight elastic effects particularly at high dosages as well.     

Thermal analysis of borogypsum and its effects on the physical properties of Portland cement

Borogypsum, which consists mainly of gypsum crystals, B₂O₃ and some impurities, is formed during the production of boric acid from colemanite, which is an important borate ore. In this study, the effect of borogypsum and calcined borogypsum on the physical properties of ordinary Portland cement (OPC) has been investigated. The calcination temperature and transformations in the structures of borogypsum and natural gypsum were determined by differential thermal analysis (DTA), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) techniques. Thermal experiments were carried out between ambient temperature and 500 °C in an air atmosphere at a heating rate of 10 °C min⁻¹. After calculation of enthalpy and determination of conversion temperatures, borogypsum (5% and 7%), hemihydrate borogypsum (5%) and natural gypsum (5%) were added separately to Portland cement clinker and cements were ground in the laboratory. The final products were tested for chemical analysis, compressive strength, setting time, Le Chatelier expansion and fineness properties according to the European Standard (EN 196). The results show that increasing the borogypsum level in Portland cement from 5% to 7% caused an increase in setting time and a decrease in soundness expansion and compressive strength. The cement prepared with borogypsum (5%) was found to have similar strength properties to those obtained with natural gypsum, whereas a mixture containing 5% of hemihydrate borogypsum was found to develop 25% higher compressive strength than the OPC control mixtures at 28 days. For this reason, utilization of calcined borogypsum in cement applications is expected to give better results than untreated borogypsum. It is concluded that hemihydrate borogypsum could be used as a retarder for Portland cement as an industrial side. This would play an important role in reducing environmental pollution.     

Effects of emulsifiers on properties of poly(styrene-butyl acrylate) latex-modified mortars

Two styrene-butyl acrylate copolymer latices having the same chemical components but different emulsifiers were synthesized under the same reaction conditions, and their effects on such properties as workability, air content, compressive strength, flexural strength and water absorption of fresh and hardened polymer-modified mortars were assessed and discussed. From the tested properties of the polymer-modified mortars, it is concluded that a polymeric emulsifier provides a much more positive effect on the properties of the polymer-modified mortars than a low-molecular emulsifier.     

Characterisation of the microstructure and deformation of high modulus cellulose fibres

This paper reports on the microstructure and deformation of one type of high modulus cellulose fibre characterised using the techniques of Raman spectroscopy and synchrotron X-ray diffraction and it compares this fibre to a lower modulus conventional viscose fibre. The crystallinity of the fibres has been determined using X-ray diffraction. The orientation parameter has been determined by measuring the width of the (200) equatorial reflections for each fibre using microfocus synchrotron radiation and it has also been shown that the crystal orientation parameter varies from the skin to core of the fibres and is different for each type. Mechanical properties of the fibres are reported and it is shown that the high modulus cellulose fibres have very different stress-strain behaviour to the viscose fibres. Finally, it is shown for the high modulus fibre that the 1414, 1260, 1095 and 895 cm⁻¹ Raman bands shift under the application of tensile deformation towards a lower wavenumber with the 1095 cm⁻¹ band giving information about the backbone chain stretching of the cellulose. The viscose fibres show less significant shifts in this peak. The crystal modulus of the high modulus cellulose fibre has also been determined by calculating the change in the c-spacing upon the application of tensile deformation to individual cellulose monofilaments. This change in the c-spacing is determined from the change in position of the (002) meridional reflection giving a crystal modulus of 77 GPa. This value is a little low compared to other published data, and reasons for this are discussed. The shear modulus between crystallites is also calculated and compared to previously published data.     

Physical and mechanical properties of styrene-butadiene rubber emulsion modified cement mortars

Polymer-modified cement mortars were prepared by varying polymer/cement mass ratio (P/C) with a constant water/cement mass ratio of 0.4. The effect of styrene-butadiene rubber (SBR) emulsion on the physical and mechanical properties of cement mortars is studied. With P/C below 10%, the toughness of the modified mortars enhances with the increase of P/C. A relationship between the physical and mechanical properties of the modified cement mortars at P/C below 10% is found; that is, the compressive strength and flexural strength of the modified mortars are directly proportional to the apparent bulk density. But when P/C is above 10%, the mechanical properties are not highly dependent on the apparent bulk density, and the flexural and compressive strength of the mortars are not improved further with more polymer. Two curing methods [wet cure: 2, 6 or 27 days immersed in 20 °C water; mixed cure: 6 days immersed in 20 °C water followed by 21 days at 20 °C and 70% relative humidity (RH)] were also evaluated in this paper. The results have shown that the mixed cure is more beneficial to the improvement of the mortar properties. A possible mechanism for polymer modification and the relationship between the physical and mechanical properties is proposed based on SEM and IR analyses. The interpenetrating structure between the polymeric phase and cement hydrates forms at a P/C of 8%, and fully develops at a P/C of 10%. The properties of the polymer-modified mortars are influenced by the polymer film, cement hydrates and the combined structure between the organic and inorganic phases.     

Effects of hydroxypropyl cellulose and hydroxyethyl cellulose adsorption on the wetting of low energy solid surfaces

Advancing and receding contact angles on paraffin (PF) and poly(methyl methacrylate) (PMMA) have been measured for solutions of hydroxypropyl cellulose (HPC) and hydroxycthyl cellulose (HEC), two hydrophohic polymers differing considerably in their surface activity at the air-water interface. Consistent with observations made previously with hydrocarbon-chain surfactant solutions, advancing contact angles with PF are the same as those observed with pure liquids having the same surface tension, while those with PMMA are considerably greater. Receding contact angles for these polymer solutions appear to he the same as those observed with pure liquids. Consequently, this leads to less wettability in an advancing mode and greater apparent contact angle hysteresis than might be expected. Concurrent studies of HPC and HEC adsorption with the same PMMA samples used in the wetting studies and estimates of adsorption of HPC and HEC at the air-water interface indicate that these effects on wetting are due primarily to greater nonspecific polymer adsorption to the air-water interface than to the more polar PMMA-water interface.     

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.     

Hydration and properties of novel blended cements based on cement kiln dust and blast furnace slag

The aim of the present paper is to address the key technical issues pertaining to the utilization of cement kiln dust (CKD) as an activator for ground granulated blast furnace slag (GGBFS) to create nonconventional cementitious binders for concrete. The relatively high alkaline content of CKD is the predominant factor preventing its recycling in cement manufacture. However, it was observed that depending on the water-soluble alkali and sulfate compounds, CKD could provide the environment necessary to activate latent hydraulic materials such as GGBFS. Binary blends containing slag and CKDs from different sources were characterized and compared in terms of the rates of heat evolution and strength development, hydration products, and time of initial setting. A study of the effects of the influencing factors in terms of soluble alkali content, particle size, and free lime content was undertaken. The results confirm the dependence of the dissolution rate of slag on the alkalinity of the reacting system, and the importance of the optimum lime content on the rate of strength gain.     

Influence of time addition of superplasticizers on the rheological properties of fresh cement pastes

It is well known that the fluidity and the fluidity loss of fresh cement pastes are affected by the kind and the time of addition of organic admixtures. The influence of the time addition of two chemical admixtures, namely, melamine formaldehyde sulfonate (MFS) and naphthalene formaldehyde sulfonate (NFS), on the rheological properties of ordinary Portland and sulfate-resisting cement pastes through the first 120 min of hydration was investigated. The admixture addition was delayed by 0, 5, 10, 15, 20, and 25 min. Shear stress and apparent viscosity of the cement pastes were determined at different shear rates (3-146 s⁻¹) and hydration times of 30, 60, 90, and 120 min. The concentration of Ca²⁺ and the combined water content of the cement pastes were determined after 120 min. Yield stress and plastic viscosity values were also determined by using the Bingham model. The results show that an increase in the addition time of the admixture reduces the shear stress, the yield stress, and the plastic viscosity of the cement pastes at the early ages (15 min) as well as at later early ages (120 min). The optimum delaying time of admixture addition is found to be 10-15 min. This time does not depend on the cement and superplasticizer type.