Competitive adsorption between superplasticizer and retarder molecules on mineral binder surface

In a self-levelling mortar based on the ternary binder system ordinary Portland cement (OPC), calcium aluminate cement (CAC) and anhydrite, a polycarboxylate-based superplasticizer (PC) showed no plasticizing effect in combination with citrate retarder while good flowability was observed with tartrate. The mechanism behind the incompatibility between PC and citrate was investigated by means of adsorption and zeta potential measurements. Also, anionic charge densities of the admixtures were compared. Adsorption measurements revealed that, in presence of citrate, PC adsorption drops dramatically to less than 10% of dosage added, implying a complete loss of fluidity in the paste. In presence of tartrate, however, PC adsorption remains high enough to still provide good flowability. In contrast, adsorption of casein biopolymer is not much affected by addition and type of retarder. Thus it provides high fluidity with both retarders. Comparison of specific anionic charge density of Ca²⁺ retarder complexes and PC reveals a direct correlation between their adsorption behaviour and anionic charge density. Admixtures with higher anionic charge density show higher affinity to the binder surface and thus adsorb preferredly. When several admixtures are present, molecules with lower anionic charge density will adsorb only if, after adsorption of the admixture with higher anionic charge, a cationic surface charge and enough adsorption area still exists. The incompatibility problem between PC and citrate in the self-levelling mortar formulation was solved by increasing the anionic charge density of the PC molecule. Similar to casein, adsorption of this modified PC is not much influenced by retarder molecules.     

Effect of complexation on the zeta potential of silica powder

The present paper deals with the surface charge properties and dispersion stability of aqueous silica suspension. The zeta potential was measured versus barium acetate and zinc acetate concentration, at pH 6.0. EDTA was used to chelate the bivalent metal ions, so that the charge of counterion was reduced. The complexation of bivalent counterions favors the increase of the negative zeta potential and the dispersion stability of aqueous silica suspension.     

Electrokinetic potential of hydrated cement in relation to adsorption of chlorides

In this study, surface charge mechanism of cement hydrates and its relations to adsorption of chloride ions are investigated. Hydrated cement paste (HCP) shows net positive surface charge by dissociation and adsorption. In HCP, chlorides bind as Friedel's salt (chemical binding) as well as adsorb on the surface of hydrates (physical binding). A surface complexation model is used to predict the adsorption of chlorides on calcium silicate hydrates (C-S-H). A good agreement between experimental and predicted chloride adsorption isotherm clearly demonstrate that the chlorides adsorb on the surface of C-S-H and bringing additional negative surface charge (SiOHCl⁻). However, chloride ions neutralize the positively charged surfaces of portlandite and Friedel's salt by physical adsorption. From the results, it can be concluded that C-S-H is the dominant phase in terms of chloride adsorption in HCP.     

Effect of zeta potential on properties of foamed colloidal suspension

We reveal that zeta potential has a notable effect on properties of foamed suspension, which remains poorly explored. It is demonstrated low zeta potential is beneficial for foam stability, and the experimental results show that absolute value of zeta potential of 30–40 mV is the boundary between stable foams and unstable foams. High zeta potential above 40 mV gives rise to instability of foamed colloidal suspension, owing to strong interparticle repulsion force that prevents particles from forming a closely packed particle network at liquid/air interfaces. Besides, it is found that high zeta potential leads to low foamability of foamed colloidal suspension. It is also demonstrated herein that stable and uniform foams with thin and homogeneous-thickness wall without agglomerates can be prepared at the isoelectric point (IEP) using long-chain surfactant, which generates weak agglomerated particles that can be re-separated to monodisperse particles due to the steric hindrance effect of surfactant.     

Thermal behavior of cement matrix with high-volume mineral admixtures at early hydration age

Thermal cracks that usually occur in mass concrete are closely related to the thermal behavior of cement matrix, such as heat liberation, temperature rise and thermal shrinkage. Cement pastes added with large-volume mineral admixtures that are usually used for thermal controlling were cast into well-sealed plastic cylinder and covered by heat insulation materials to simulate the pseudo-adiabatic condition of mass concrete. The deformation and temperature rise of cement specimens under the heat insulation condition have been examined at early hydration age. Results show that with addition of fly ash, coal gangue and blast furnace slag the heat liberation and peak temperature of cement paste decrease, while its total shrinkage increases.There is no shrinkage but expansion of the pastes during the temperature rise process, which may be ascribed to the complete compensation of the shrinkage by thermal dilation of the pastes. The thermal dilation coefficient (TDC) of cement paste changes drastically with the hydration duration, and it is also related to the addition of mineral admixtures.     

Impact of admixtures on the hydration kinetics of Portland cement

Most concrete produced today includes either chemical additions to the cement, chemical admixtures in the concrete, or both. These chemicals alter a number of properties of cementitious systems, including hydration behavior, and it has been long understood by practitioners that these systems can differ widely in response to such chemicals.In this paper the impact on hydration of several classes of chemicals is reviewed with an emphasis on the current understanding of interactions with cement chemistry. These include setting retarders, accelerators, and water reducing dispersants. The ability of the chemicals to alter the aluminate–sulfate balance of cementitious systems is discussed with a focus on the impact on silicate hydration. As a key example of this complex interaction, unusual behavior sometimes observed in systems containing high calcium fly ash is highlighted.     

Investigation of PEG adsorption on the surface of zinc oxide nanoparticles

The influence of polyethylene glycol (PEG) on the adsorption at zinc oxide/polymer solution interface has been determined. PEG macromolecules bond with the solid surface mainly via the -OH group of the surface of ZnO nanoparticles, which may interact with PEG through hydrogen bonding. Adsorption isotherms demonstrate the marked influence of the PEG molecular weight and the concentration of polymer solution on the extent of adsorption. The thickness of the adsorbed polymer layer on ZnO nanoparticles was calculated on the basis of measurements of their suspension viscosities in the absence and presence of adsorbed polymer. Results show that the thickness of the adsorption layer increased with increasing polymer molecular weight and the concentration of polymer solution. The main factors responsible for the changes in zeta potential were determined on the basis of the data obtained. The shift of the slippage plane away from the surface of ZnO nanoparticles plays major role below pH_iep. Above pH_iep, the blockage of the adsorption sites is the predominant factor.     

Critical zeta potential and the Hamaker constant of oxides in water

The critical zeta potential characterises the flocculated-dispersed state transition of a colloidal dispersion. For many colloidal dispersions, yield stress displayed a linear relationship with the square of zeta potential, indicating that they obeyed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From this relationship, the critical zeta potential is obtained from the intercept at the zeta potential axis at a yield stress of zero. The critical zeta potential is a measure of the repulsive potential required to exactly counter the maximum attractive potential between particles in dispersion in the flocculated state. When the forces of interaction between particles in the dispersion are only the van der Waals and electrostatic forces, then the critical zeta potential is indirectly a measure of the van der Waals attractive potential and, hence, it may be used to determine the Hamaker constant of solids in water. This potential is proportional to the square root of the solids Hamaker constant in water. At present, only the ratio of Hamaker constant between two oxides was obtained and compared with that obtained by other techniques. These oxides were ultrapure anatase TiO₂ and γ-Al₂O₃, and they displayed a linear relationship between yield stress and the square of zeta potential. At the conductivity (or ionic strength) of about 3000 μS/cm, the critical zeta potential for both TiO₂ and Al₂O₃ is ∼47 and ∼32 mV, respectively. These critical zeta potential data give a value of 2.2 for the ratio of Hamaker constant of anatase TiO₂/H₂O/TiO₂ to γ-Al₂O₃/H₂O/γ-Al₂O₃. This ratio compares well with a value ranging from 1.0 to 2.18 for rutile TiO₂/H₂O/TiO₂ to α-Al₂O₃/H₂O/α-Al₂O₃ where their Hamaker constants were calculated from the Lifshitz theory using full optical spectral data.     

Water chemical potential: A key parameter to determine the thermodynamic stability of some hydrated cement phases in concrete?

The CaO-Al₂O₃-SO₃-H₂O system at 25 °C under 1 bar of pressure has been investigated with phase diagrams software (Zen + k) based on chemical potentials (or activities). The reported invariant points are similar to those obtained previously using equilibrium calculations. However Zen + k enables us to calculate systems at different relative humidities, and in conditions where water is not in excess, calcium monosulfoaluminate could be a stable phase and thus, as observed experimentally, remain for long times in an ordinary Portland cement paste.     

The fluidity of fly ash-cement paste containing naphthalene sulfonate superplasticizer

The zeta potential measurement indicated that the surface potential of fly ash was different from ordinary Portland cement (OPC) in both sign and value. Hence, the Derjaguin-Landau-Verway-Overbeek (DLVO) theory for dispersion-flocculation of heterogeneous particles with different surface potentials was applied to explain the influence of fly ash on the rheology of cement paste containing naphthalene sulfonate superplasticizer. For the fly ash-cement paste without superplasticizer, the sign of zeta potential of fly ash was different from OPC. Thus, the extent of the potential energy barrier between particles was small or even showed negative value, and the change in the rheology of the fly ash-cement paste was mainly dependent on the bulk solid volume of fly ash, which was related to available free water for fluidizing paste. For the fly ash-cement paste with naphthalene sulfonate superplasticizer, fly ash and cement had the same sign and dispersed well due to higher potential barrier. The extent of potential energy barrier depended on the absolute value of surface potential, which was represented by a function of the amount of adsorbed superplasticizer. The bulk solid volume of fly ash also affected the change in flow ability, but the effect of potential energy barrier between particles was superior to that of the bulk solid volume of fly ash.     

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.     

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.     

Investigation of relation between both sulfur removal and adsorption capacity with surface morphology of a pyrolysed Turkish lignite

In considering with morphological physicochemical transformations of the coal samples pyrolysed in CO₂ atmosphere at different temperatures, the change of their adsorptive capacities have been investigated. It was seen that the change occurred in the monolayer adsorption capacities as parallel to morphological transformations of the coal surface is particularly connected with the amount of organic sulfur present in the coal matrix. Adsorption capacity is not affected from the contents of pyritic sulfur and ash of coal samples. The measurements of zeta potential of the pyrolysed coal samples also showed that pyrolysis modified the functional groups on surface of the coal, depending on the pyrolysis temperature.     

Functionalized sepiolite for heavy metal ions adsorption

Surface modification of clays has become increasingly important due to the practical applications of clays such as fillers and adsorbents. The surface modification of sepiolite with [3-(2-aminoethylamino)propyl]trimethoxysilane has been employed. The modified sepiolite surface was investigated by FTIR, XRD and DTA/TG analysis. It was found that the chemical bonding takes place between the hydroxyl groups and/or oxygen atoms within the structure of sepiolite and methoxy groups of [3-(2-aminoethylamino)propyl]trimethoxysilane. The changes on electrokinetic properties of modified sepiolite particles were studied by measuring the zeta potential of particle as a function of metal concentration and equilibrium pH of solution. It was found that the zeta potential of the clay particles was always negative independent of the metal concentration in solution. This study also provides some evidence for the adsorption of metal ions on modified sepiolite. The adsorption of metal ions onto modified sepiolite has varied with the type of metal cations. The available basic nitrogen centers covalently bonded to the sepiolite skeleton were studied for Co(II), Cu(II), Mn(II), Zn(II), Fe(III) and Cd(II) adsorption from aqueous solutions. It was found that the amount of metal ion adsorbed onto modified sepiolite increases with increase in solution equilibrium pH and temperature, whereas it generally decreases with the ionic strength. The experimental data were correlated reasonably well by the Langmuir adsorption isotherm and the isotherm parameters (q_m and K) were calculated. The ability to adsorb the cations gave a capacity order of Zn(II) > Cu(II) ~ Co(II) > Fe(III) > Mn(II) > Cd(II) with affinities of 2.167×10⁻⁴, 1.870×10⁻⁴, 1.865×10⁻⁴, 1.193×10⁻⁴, 0.979×10⁻⁴ and 0.445×10⁻⁴ mol g⁻¹, respectively.     

Impact of hydroxypropylguars on the early age hydration of Portland cement

Hydroxypropylguars (HPG) are used as admixtures in factory-made mortars. These molecules present water retention properties comparable to those obtained with commonly used cellulosic water-retaining agent.The influence of HPG on cement hydration was investigated in order to improve understanding on the delayed effect induced by polysaccharides. Hydration kinetics were characterized by means of conductivity and isothermal calorimetry measurements. The influence of polymer concentration and predissolution was studied. A weak influence of HPG on the germination of hydrates was observed. In contrast, HPG induced a significant decrease in the hydrates growth rate. Strong effects of the polymer concentration and predissolution were noticed too. From these results, we supported the hypothesis that HPG adsorption on hydrated phases via polar interactions should be responsible for the delayed effect observed.     

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.     

Effects of polycarboxylate-type superplasticizer on fluidity and hydration behavior of cement paste

Polycarboxylate (PC)-type superplasticizers were synthesized with different average molecular weight of polyethylene oxide (PEO) graft groups, the molar ratios of graft group to carboxylic group, and then the chemical structure, polymerization condition, and physical and chemical properties were analyzed. In order to evaluate the effects of PC-type superplasticizers in cement paste, the adsorption, the initial plasticity and slump retention characteristics and the degree of hydration reaction were investigated. As the average molecular weight of graft group decreased and molar ratio increased, the conversion rate to copolymers, the adsorption amount of PC-type superplasticizer on cement particles improved; on the other hand, the hydration reaction was delayed.     

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.     

The zeta potential and surface properties of asphaltenes obtained with different crude oil/n-heptane proportions

We have investigated some surface properties of asphaltenes precipitated from crude oil with different volumes of n-heptane. According to the crude oil/n-heptane proportions used, asphaltenes are identified as 1:5, 1:15 and 1:40. Zeta potential results indicate that the amount of n-heptane determines the electrokintetic behaviour of asphaltenes in aqueous suspensions. Asphaltene 1:5 exhibits an isoelectric point (IEP) at pH 4.5 whereas asphaltenes 1:15 and 1:40 show an IEP at about pH 3. Surface charge on asphaltenes arises from the dissociation of acid functionalities and the protonation of basic functional groups. The presence of resins remaining on the asphaltene molecules may be responsible for the different IEP of asphaltene 1:5. Both sodium dodecyl sulfate (an anionic surfactant) and cetylpyridinium chloride (a cationic surfactant) were found to adsorb specifically onto asphaltenes. They reverse the sign of the zeta potential under certain conditions. These surfactants may be potential candidates to aid in controlling the stability of crude oil dispersions. Critical micelle concentration, interfacial tension measurements, and Langmuir isotherms at the air-water interface confirm the different nature of asphaltene 1:5, which also showed more solubility and a larger molecular size.     

A note on early hydration of cement

In this note it is shown that the hydration of portland cement and of blastfurnace slag cement can be traced using the flotation of cement from mortars and concretes. The various stages of the hydration reaction, i.e. initiation, induction period, formation of an initial gel structure and the final hardening process can be detected clearly.