Effect of some superplasticizers on the mechanical and physicochemical properties of blended cement pastes

Blended cement pastes made of Portland cement and fine sand (known in Egypt as El-Karnak cement) were made using a water–cement ratio of 0.25 by weight. Three pastes containing admixture (water-soluble condensates) were also prepared using a water–cement ratio of 0.25 and condensate (superplasticizer) content of 0.25% by the weight of cement; the superplasticizers used are Na-phenol sulfonate formaldehyde, Na-polystyrene sulfonate, and Na-ß-naphthol sulfonate formaldehyde condensates. All pastes were cured for various time intervals within the range of 0.02–90 days. Compressive strength tests, hydration kinetics, X-ray diffraction analysis, thermal analysis, and surface properties were studied and related as much as possible to the pore structure of the hardened pastes. © 1995 John Wiley & Sons, Inc.     

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.     

Hydration of cement and pore structure of concrete cured in tropical environment

This paper presents the results of an experimental study on the effect of curing on the degree of cement hydration and capillary porosity of concrete in a tropical environment. It provides basic information for the estimation of w/c of hardened concrete using petrographic methods. Concrete with w/c ratios of 0.30 to 0.70 with an increment of 0.05 was investigated. The concrete was cured at 20 and 35 °C and exposed to various durations of moist curing. The results indicated that the concrete cured at 20 °C water for 28 days had a higher degree of cement hydration and lower capillary porosity than did the concrete cured in water of the same temperature for 7 days followed by exposure to outdoor air for 21 days, but had an opposite trend compared to the concrete cured in 35 °C water for 7 days followed by exposure to outdoor air. However, the differences on the degree of cement hydration and capillary porosity for the concrete cured in these different conditions were not significant.     

Adsorption characteristics of superplasticizers on cement component minerals

Adsorption characteristics of various superplasticizers on portland cement component minerals were investigated. Adsorption isotherms of various types of superplasticizers and ζ-potentials of cement component minerals at the maximum adsorption of the superplasticizers were measured. The value of the adsorption isotherm was calculated from the amount of the superplasticizer adsorbed on a cement component mineral in an equilibrated solution. The maximum amounts of adsorption and the adsorption isotherms varied with types of component mineral and superplasticizer. For all types of superplasticizers, a larger amount of superplasticizer was adsorbed on C₃A and C₄AF than C₃S and C₂S. However, the equilibrated concentration of each superplasticizer at the maximum adsorption was not influenced by types of superplasticizer. Without superplasticizer, C₃S and C₂S had negative ζ-potential. On the contrary, C₃A and C₄AF had positive ζ-potential. Therefore, accelerated coagulation of cement particles might occur due to their electrostatic potentials that are opposite each other. However, all component minerals of cement had negative ζ-potential when they were mixed with any superplasticizer. Fluidity of fresh cement paste is improved due to electrostatic repulsion acting between particles.     

Pore size distribution in epoxy impregnated hardened cement pastes

Specimens of hardened portland cement paste (Type 1), hydrated for various periods of time, were ovendried and subsequently filled with an epoxy resin system via a vacuum-pressure technique. Data obtained from mercury intrusion porosimetry indicate that a significant amount of porosity is left unfilled by polymer in the more mature (28 days hydration) specimens. Calculations indicate that the smallest micropores (< 0.0044 μm) are essentially inaccessible to the monomer system used in this study.     

Phase changes during the early hydration of Portland cement with Ca-lignosulfonates

The influence of two Ca-lignosulfonates (LS), one softwood (LSs) and one hardwood (LSh) based, on the phase changes during the early hydration of ordinary Portland cements was investigated using isothermal calorimetry, in-situ XRD, and thermal analysis. In the presence of LS the hydration of C₃S and C₃A was retarded. LS was found to influence the solubility of the sulphate phase; in case of bassanite/gypsum the initial dissolution was accelerated. An acceleration of the initial ettringite formation was observed in the presence of LS. However, the second ettringite formation was retarded. The amounts of bound water (H) and calcium hydroxide (CH) formed were measured using TG/DTG on cement pastes hydrated for 90 min, 5, 12 and 24 h. At 90 min the amount of H was increased the higher the concentration of LS. The amount of CH formed between 5–24 h was decreased the higher the concentration of LS.     

Effect of crosslinked polycarboxylate superplasticizers with varied structures on cement dispersion performance

In order to investigate the effect of double bond content in the crosslinkers on the performance of superplasticizers, three different crosslinked polycarboxylate superplasticizers were synthesized herein with various respective crosslinkers. Their impacts on the fluidity, absorption, and hydration behavior of cement systems were studied. The results showed that the polymer, which was synthesized using a crosslinker with four double bonds and five/six double bonds, had higher fluidity and the highest fluidity reached up to 395 mm at W/C of 0.35. Additionally, thermogravimetric analysis and hydration heat tests showed that the crosslinked polycarboxylate superplasticizers could prolong the hydration process of cement slurries. Among these three kinds of crosslinked polycarboxylate superplasticizers, the induction period of cement slurry containing the polymer with crosslinker of four double bonds was significantly extended to facilitate the processing of the concrete. The purpose of this study is to provide strategies for studying high-performance polycarboxylate superplasticizers with novel topological structure.     

Microstructure and mechanical properties of carbon nanotube reinforced cementitious composites developed using a novel dispersion technique

The present paper reports the first attempt of developing carbon nanotube (CNT) reinforced cement composites through a short dispersion route using Pluronic F-127 as a novel dispersing agent. Optimum concentrations of Pluronic for various types of CNT were determined, and the influences of Pluronic and CNT on the microstructure and mechanical properties of cementitious composites were thoroughly investigated. Pluronic with optimized defoamer concentration significantly improved the bulk density and mechanical properties of cement mortar. Further, dispersion of 0.1% single walled nanotube (SWNT) improved flexural modulus of mortar by 72% and flexural and compressive strengths by 7% and 19%, respectively after 28 days of hydration. Flexural and compressive strengths with functionalized SWNT increased with the hydration period up to 17% and 23% after 56 days, respectively. All CNT reinforced samples exhibited significantly higher stiffness, fracture energy and ductility as compared to plain mortar and composite samples prepared using a common surfactant.     

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.     

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.     

Hydration of Portland cement with high replacement by siliceous fly ash

The effects of two different low calcium fly ashes on the hydration of ordinary Portland cement (OPC) pastes containing 50 wt.% of fly ash were investigated over a hydration time of 550 days. The results were compared with a reference blend of OPC containing 50 wt.% of inert quartz powder allowing the distinction between "filler effect" and pozzolanic reaction.Until 2 days, no evidence of fly ash reaction was measured and its influence on the hydration is mainly related to the “filler effect”. From 7 days on, the effects of the pozzolanic reaction were observed by the consumption of portlandite, the change of the pore solution chemistry, the formation of a presumably water-rich inner hydration product and the change of the C–S–H composition towards higher Al/Si ratio compared to the C–S–H of neat OPC. Additional strength due to the pozzolanic reaction developed after 28 days of hydration.     

Understanding the effect of MPEG-PCE's microstructure on the adsorption and hydration of OPC

Polycarboxylic ethers or polycarboxylate (PCEs) are one of the most employed superplasticizers in construction. However, the understanding of their microstructure–property relationship is still incomplete. Recently, a theoretical model was proposed that relates the microstructure–conformation of the PCE to its effect on the adsorption onto cement particles and cement hydration time. In this work, the effects of a wide range of PCEs with different side chain lengths (P = 5, Group 1; P = 20, Group 2; and P = 45 and 113, Group 3) having flexible backbone worm conformation except one which has stretch backbone worm conformation (P = 113) were experimentally investigated for their effect on adsorption and cement hydration. It is found that PCEs from Group 1 show electrostatic repulsion as dispersing mechanism, unlike PCEs from Groups 2 and 3. Furthermore, the prediction of the theoretical model is also assessed for all the studied PCEs. Only Group 1 PCEs (shortest side chains) showed deviation from the theoretical predictions, and it was attributed to their different behaviors from the standard PCEs for which the theoretical model was developed.     

磺化淀粉开发用作新型水泥减水剂的研究

以氯磺酸为磺化试剂,半干法制备了磺化淀粉,并对其用作水泥减水剂的性能进行了系统的研究。结果表明:磺化淀粉减水率随磺酸基取代度增加而增加,当其取代度达到0.060 4,质量分数为0.3%时测得的水泥净浆减水率、净浆标准凝结时间和3 d、28 d砂浆强度等各项指标均达到高效减水剂的国标要求,磺化淀粉对水泥还具有一定的缓凝作用。通过XRD和SEM,对掺加了磺化淀粉的水泥材料进行了微观结构表征,结果表明:磺化淀粉掺入水泥浆后,由于缓凝作用导致初期水化反应发展缓慢;而经较长时间(如28 d)后硬化水泥结构比基准样密实、强度更高。而且磺化淀粉掺量0.3%(质量分数)即可达到高效减水剂的要求,比现有的高效减水剂掺量都低。     

Influence of silica fume on the microstructure of cement pastes: New insights from 1H NMR relaxometry

¹H NMR has been used to characterise white Portland cement paste incorporating 10 wt.% of silica fume. Samples were measured sealed throughout the hydration without sample drying. Paste compositions and C–S–H characteristics are calculated based on ¹H NMR signal intensities and relaxation analysis. The results are compared with a similar study of plain white cement paste. While the presence of silica fume has little influence on C–S–H densities, the chemical composition is impacted. After 28 days of sealed hydration, the Ca/(Si + Al) ratio of the C–S–H is 1.33 and the H₂O/(Si + Al) ratio is 1.10 when 10% of silica fume is added to the white cement. A densification of the C–S–H with time is observed. There are no major changes in capillary, C–S–H gel and interlayer pore sizes for the paste containing silica fume compared to the plain white cement paste. However, the gel/interlayer water ratio increases in the silica fume blend.     

Time-dependent behaviour of hardened cement paste under isotropic loading

The experimental results of isotropic compression tests performed at 20 °C and 90 °C on a class G hardened cement paste hydrated at 90 °C (Ghabezloo et al., 2008, Cem. Conc. Res. 38, 1424–1437) have been revisited considering time-dependent response. Within the frame of a viscoplastic model, the non-linear responses of the volumetric strains as observed in drained and undrained tests and of the pore pressure in undrained tests are analysed. The calibration of model parameters based on experimental data allows to study the effect of the test temperature on the viscous response of hardened cement paste showing that the creep is more pronounced for a higher test temperature. The effect of the hydration temperature on the time dependent behaviour is also studied by evaluating the model parameters for a cement paste hydrated at 60 °C. The time-dependent deformations are more pronounced for hydration at a higher temperature.     

复合使用高效减水剂与缓凝剂对水泥水化历程的影响

用直接测温法及X射线衍射技术,系统研究了萘系、氨基磺酸盐系及聚羧酸盐系3种高效减水剂,三聚磷酸钠及糖钙2种缓凝剂及复合使用高效减水剂与缓凝剂对水泥水化热、水化温峰、温峰出现时间及不同水化龄期Ca(OH)2和钙矾石(ettringaite,AFt)生成量等方面的影响.结果表明:单掺高效减水剂使水化温峰升高,温峰出现时间延迟,水化热及温峰时的Ca(OH)2生成量增加.单掺缓凝剂使水化温峰降低,温峰出现时间大幅度延迟,水化热及温峰时的Ca(OH)2生成量明显减少.复合使用高效减水剂与缓凝剂时,由于协同效应,使高效减水剂的分散作用及缓凝剂的缓凝作用同时得到加强.与单掺缓凝剂相比,复掺后水泥水化温峰出现的时间进一步延迟,水化温峰进一步降低,水化热及水化温峰时Ca(OH)2生成量进一步减少;但是,外加剂对AFt生成量影响不大.     

Influence of superplasticizer type and dosage on the slump loss of Portland cement mortars—Part II

Fluidity and slump loss are cardinal features responsible for the quality of concrete. These are related to the dispersion of cement particles and the hydration process, which are greatly influenced by superplasticizers (SPs). A variety of SPs are commercially available. Their influence on the fluidity and slump loss differs considerably. In this work, SPs based on lignosulfonic acid (LS), melamine formaldehyde sulfonic acid (SMF), naphthalene formaldehyde sulfonic acid (SNF), and polyacrylic acid polymer (CE) are tested with ordinary Portland cement (OPC) at different water-to-cement ratio. The results reveal that not only SPs of different base groups behave differently but even the SP of the same base group SMF behave differently. Fluidity increased with increase in the dosage of SP. CE was most effective followed by LS, SNF, and SMF SP.     

Mechanism for performance of energetically modified cement versus corresponding blended cement

The microstructure of cement paste of 50/50 mixes of cement/quartz and cement/fly ash, both ground in a special mill [energetically modified cement (EMC) process] and simply blended, have been studied under sealed curing conditions. The grinding process reduced the size of both cement grains and quartz/fly ash markedly and created flaky agglomerates of high inner surface for the finer particles. EMCs had much higher degree of hydration at 1 day, but similar as blends at 28 days. The pores were much finer for EMC paste due to smaller particles as also reflected in the strength. The morphology of calcium hydroxide in EMC paste appeared more mass like. Pozzolanic reaction was insignificant for quartz in EMC, but increased for fly ash. Thus, improved performance of EMC versus OPC can be explained by increased early hydration and extensive pore size refinement of the hardened binder resulting in reduced permeability and diffusivity for concrete.     

Influence of solution chemistry on the hydration of polished clinker surfaces—a study of different types of polycarboxylic acid-based admixtures

The influence of two different types of polycarboxylic acid-based superplasticizers (homo- [HP] and copolymer [CP]) on the early hydration of Portland cement clinker is investigated. Polished clinker surfaces are hydrated in aqueous phase extracted from cement paste with and without superplasticizers as well as in saturated Ca(OH)₂/CaSO₄ solution and in deionized water. Scanning electron microscopy (SEM) is used to characterize the early hydration products after 30 min and after 24 h of hydration. Contrary to the hydration reaction with deionized water, in the presence of ionic solutions, the texture and morphology of the clinker surface are significantly altered, and amorphous and crystalline hydration products, mainly ettringite, are formed. The amount and type of ettringite formed are strongly related to solution chemistry and type of superplasticizer. In the presence of superplasticizers, the formation of hydration products and ettringite is reduced and the hydration of the surface is suppressed. Furthermore, the rate of hydration in mortar is studied in the presence of the two admixtures by measuring the temperature evolution as a function of time. The concentration-dependent delay in temperature evolution correlates well with the microscopic observations of different amounts of ettringite formation.     

Determination of dispersion efficiency of cement suspensions by method of centrifugation

In this research, rheological parameters of cement suspensions modified with different doses of two types of superplasticizers (SPs) were evaluated with an alternative method of centrifugation. It was determined that the critical normal and shear stresses (yield values), and the water/solid ratio alter with the additive dose, the additive type as well and the magnitude of centrifugal forces. The results obtained reveal that the method of centrifugation might serve for determination of dispersing effectiveness of SPs and rheological parameters of suspensions in general. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013