Multi-method approach to study influence of superplasticizers on cement suspensions

Superplasticizers are widely used in concrete processing to increase the rheological properties of hardening pastes. In this study, different techniques (rheology, adsorption, atomic force microscopy—AFM, and ζ-potential) are used to characterize the impact of polycarboxylate-ether based superplasticizer (PCE) on particle suspensions. Results obtained with two cements and two inert powders (MgO and calcite) show that superplasticizer efficiency is strongly influenced by polymer architecture and by the ionic species present in solution. Additionally, experiments performed with AFM and ζ-potential contributed to characterize dispersion forces exerted by superplasticizers at the solid–liquid interface. The application of plateau AFM-tips coated with platinum reveals that dispersion forces depends on the presence of ions in solution, and that multilayer formation occurs with certain superplasticizer types. A further conclusion includes the idea that the PCE has a lubricating effect between adjacent particles and PCE increases surface wettability.     

Correlating cement characteristics with rheology of paste

The influence of cement characteristics such as cement fineness and clinker composition on the “flow resistance” measured as the area under the shear stress-shear rate flow curve has been investigated. Three different types of plasticizers namely naphthalene sulphonate-formaldehyde condensate, polyether grafted polyacrylate, and lignosulphonate have been tested in this context on 6 different cements. The flow resistance correlated well with the cement characteristic (Blaine·{d·cC₃A + [1 − d]·C₃S}) where the factor d represents relative reactivity of cubic C₃A and C₃S while cC₃A and C₃S represent the content of these minerals. It was found to be either a linear or exponential function of the combined cement characteristic depending on plasticizer type and dosage. The correlation was valid for a mix of pure cement and cement with fly ash, limestone filler (4%), as well as pastes with constant silica fume dosage, when the mineral contents were determined by Rietveld analysis of X-ray diffractograms.     

Impact of zeta potential of early cement hydration phases on superplasticizer adsorption

The zeta potential of early hydration products of cement was found to be a key factor for superplasticizer adsorption. A highly positive zeta potential results in a strong superplasticizer adsorption whereas a negative zeta potential does not allow adsorption. Synthetic ettringite precipitated from solution shows a highly positive zeta potential, hence it adsorbs great amounts of negatively charged superplasticizer. Monosulfate (AF_m) has a less positive zeta potential. Therefore, it adsorbs smaller amounts of superplasticizers. For syngenite, portlandite and gypsum, the zeta potential is around zero or negative. These phases do not adsorb superplasticizers. Consequently, a hydrating cement grain is best represented by a mosaic structure, with superplasticizer molecules mainly adsorbed on ettringite and some on monosulfate and C-S-H nucleated at surface.     

Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers

For adsorption of three different allylether-based PCE superplasticizers on CaCO₃ surface, the thermodynamic parameters ΔH, ΔS and ΔG were determined experimentally. The GIBBS standard free energy of adsorption ΔG_0ads, the standard enthalpy of adsorption ΔH_0ads and the standard entropy of adsorption ΔS_0ads applying to an unoccupied CaCO₃ surface were obtained via a linear regression of ln K (equilibrium constant) versus 1 / T (VAN'T HOFF plot). Additionally, the thermodynamic parameters characteristic for a CaCO₃ surface loaded already with polymer (isosteric conditions) were determined using a modified CLAUSIUS-CLAPEYRON equation.For all PCE molecules, negative ΔG values were found, indicating that adsorption of these polymers is energetically favourable and a spontaneous process. Adsorption of PCEs possessing short side chains is mainly instigated by electrostatic attraction and a release of enthalpy. Contrary to this, adsorption of PCEs with long side chains occurs because of a huge gain in entropy. The gain in entropy results from the release of counter ions attached to the carboxylate groups of the polymer backbone and of water molecules and ions adsorbed on the CaCO₃ surface. With increased surface loading, however, ΔG_isosteric decreases and adsorption ceases when ΔG becomes 0. The presence of Ca²⁺ ions in the pore solution strongly impacts PCE adsorption, due to complexation of carboxylate groups and a reduced anionic charge amount of the molecule. In the presence of Ca²⁺, adsorption of allylether-based PCEs is almost exclusively driven by a gain in entropy. Consequently, PCEs should produce a strong entropic effect upon adsorption to be effective cement dispersants. Molecular architecture, anionic charge density and molecular weight as well as the type of anchor groups present in a superplasticizer determine whether enthalpy or entropy is the dominant force for superplasticizer adsorption.     

Study on the effectiveness of PNS and LS superplasticizers in air lime-based mortars

Polynaphtalenesulfonate (PNS) and lignosulfonate (LS) were tested as superplasticizers in pastes and mortars of pure air lime and air lime with a pozzolanic additive, nanosilica (NS). LS showed a better plasticizing effect than PNS: the flowability of the samples with LS as well as the slump retention over time was larger. LS strongly hindered carbonation due to its ability to form Ca^2 + complexes. In mortars with NS, PNS was seen to interfere with the C-S-H formation, resulting in lower mechanical strengths. Adsorption isotherms and zeta potential showed that PNS was more adsorbed than LS onto lime and C-S-H particles. PNS acted mainly through electrostatic repulsion owing to its high anionic charge density and flat adsorption. However, LS was more efficient as superplasticizer in air lime media, steric hindrance being the main mechanism responsible for avoiding flocculation. Furthermore, LS yielded high compressive strengths in mortars with NS.     

蒸养条件下两性聚羧酸减水剂对胶砂及混凝土强度的影响

合成了阴离子型和两性型聚羧酸减水剂,研究了两类聚羧酸减水剂对水泥水化热、蒸养胶砂和蒸养混凝土强度的影响.结果表明:在蒸养条件下,与阴离子型聚羧酸减水剂相比,掺两性型聚羧酸减水剂的水泥水化温峰更高;在相同水灰比时,掺两性聚羧酸减水剂的蒸养胶砂和蒸养混凝土的强度也更高.XRD分析可知,掺入两性聚羧酸减水剂在蒸养条件下生成更多的AFm和氢氧化钙,促进了C3S和C2S的水化.     

Incorporation of trace elements in Portland cement clinker: Thresholds limits for Cu, Ni, Sn or Zn

This paper aims at defining precisely, the threshold limits for several trace elements (Cu, Ni, Sn or Zn) which correspond to the maximum amount that could be incorporated into a standard clinker whilst reaching the limit of solid solution of its four major phases (C₃S, C₂S, C₃A and C₄AF). These threshold limits were investigated through laboratory synthesised clinkers that were mainly studied by X-ray Diffraction and Scanning Electron Microscopy. The reference clinker was close to a typical Portland clinker (65% C₃S, 18% C₂S, 8% C₃A and 8% C₄AF). The threshold limits for Cu, Ni, Zn and Sn are quite high with respect to the current contents in clinker and were respectively equal to 0.35, 0.5, 0.7 and 1 wt.%. It appeared that beyond the defined threshold limits, trace elements had different behaviours. Ni was associated with Mg as a magnesium nickel oxide (MgNiO₂) and Sn reacted with lime to form a calcium stannate (Ca₂SnO₄). Cu changed the crystallisation process and affected therefore the formation of C₃S. Indeed a high content of Cu in clinker led to the decomposition of C₃S into C₂S and of free lime. Zn, in turn, affected the formation of C₃A. Ca₆Zn₃Al₄O₁₅ was formed whilst a tremendous reduction of C₃A content was identified. The reactivity of cements made with the clinkers at the threshold limits was followed by calorimetry and compressive strength measurements on cement paste. The results revealed that the doped cements were at least as reactive as the reference cement.     

Electrostatic repulsion between particles in cement suspensions: Domain of validity of linearized Poisson-Boltzmann equation for nonideal electrolytes

To understand the dispersion of cement particles by superplasticizers, proper quantification of the possible mechanisms involved (electrostatic, steric, and depletion forces) is required. This is an important objective to help understand the origin of unexpected incompatibilities between some cement and superplasticizer combinations and more generally predict the rheological behavior. The relative importance of the electrostatic interaction with respect to steric hindrance is currently under much debate. The debate centered on this topic has not fully explored how the nonideal electrolyte found in cement suspensions effects the simplified Debye-Hückel approximation for evaluation of electrostatic repulsion. In this article, the nonideality of the cement aqueous phase—suspension electrolyte—has been taken into account based on solubility equilibria of the possible ionic species present in typical cement suspensions. By replacing the normally assumed symmetric electrolyte (1:1, 2:2, or 3:3) with a noninteger symmetric electrolyte, the simple Debye-Hückel approach has been shown to remain valid for negative potentials down to around 30 mV. Significant deviations are found for positive potentials greater than 10 mV.     

Influence of superplasticizers on rheological behaviour of fresh cement mortars

To assure required workability of high performance concrete (HPC), various superplasticizers are used. Only by using superplasticizers can rheological properties of HPC mix be adequately adjusted to the methods and conditions of concrete processing. Thus, the key element in efficient workability shaping is the complex knowledge how superplasticizers influence the rheological properties of fresh concrete in different technological circumstances.In the paper, the methodology and test results of an investigation into the influence of chemically different superplasticizers on the rheological properties of standard mortars are presented and discussed. The rheological parameters of mortars yield value g, and plastic viscosity h were determined using VISCOMAT PC rotational rheometer. In the research, the influence of the performance of superplasticizers was investigated taking into account following factors: chemical origin of superplasticizers (SNF/naphthalene sulfonic acid/, AP/polycarboxylate acid, PC/policarboxylate ester/), superplasticizer dosage, W/C ratio, cement type (CEM I, CEM II and CEM III), cement physical and chemical properties and temperature.The results presented in the paper show that by testing rheological parameters of mortars with rotational viscometer, it is possible to complex and precisely determine the performance of superplasticizers. On the ground of obtained results, it is possible to optimise the composition of mortars and concretes from workability point of view.     

Filler-elastomer interactions: influence of oxygen plasma treatment on surface and mechanical properties of carbon black/rubber composites

In this work, the influence of oxygen plasma treatment on the surface and adsorption properties of carbon blacks was investigated using X-ray photoelectron spectroscopy (XPS), ζ-potential, and BET isotherms. Then the mechanical properties [tensile strength and tearing energy (G_IIIC)] of carbon black/acrylonitrile butadiene rubber (NBR) composites were measured. As a result, it was found that oxygen plasma treatment generated oxygen-containing functional groups, such as, carboxyl, hydroxyl, lactone, and carbonyl groups, on the carbon black surfaces, resulting in a decrease in the equilibrium spreading pressure or London dispersive component of surface free energy. The tearing energy of the carbon black/NBR composites improved as the oxygen-containing functional groups on the carbon black surfaces increased. This revealed that there is a relatively high degree of interaction between the polar NBR and the oxygen-functional groups of carbon blacks.     

Adsorption of cationic-anionic surfactant mixtures on activated carbon

This paper reported the adsorption of cationic-anionic surfactant mixtures, such as octyltriethylammonium bromide/sodium dodecylbenzenesulfonate (OTEAB/SDBS) and dodecylpyridinium chloride/sodium octanesulfonate (DPC/SOS), on activated carbon (AC) in deionized water and in mineralized water systems. The AC surface chemistry was characterized by X-ray photoelectron spectroscopy and ζ-potential determinations. It was observed that in deionized water solution, the addition of SOS obviously promoted the adsorption of DPC, while the existence of OTEAB increased the adsorption of SDBS first and then decreased that slightly with increasing SDBS concentration. In mineralized water solution, the addition of cationic (anionic) surfactants reduced the adsorption of anionic (cationic) surfactants. It was shown that the adsorption of the surfactants on the AC was predominated mainly by the hydrophobic interaction between AC surface and surfactants because of the low oxygen content and very low ζ-potential on the AC surface. There might exist synergism between cationic and anionic surfactants when adsorbing on AC in deionized water due to the electrostatic interaction between oppositely charged surface active ions. Such synergism might be greatly weakened when a large number of inorganic salts exist owing to the “screen” effect of the counter ions of the salt on the electrostatic attraction of oppositely charged surface active ions.     

The heats of hydration of cement constituents

Integral heats of hydration and time courses of heat power function were directly measured for a series of nine cements in a heat-conduction calorimeter. Both the heat power and the integral heat of hydration of cement constituents C₃S, C₂S, and C₃A+C₄AF were evaluated by the thermochemical analysis method. The rate of heat evolution courses for the cement constituents, evaluated by the thermochemical analysis method, were found to differ from those recorded for the cement-constituting minerals hydrated individually. This fact may be helpful in the interpretation of the mechanism of cement hydration processes.     

Design and function of novel superplasticizers for more durable high performance concrete (superplast project)

In this article we shall describe our quest and ultimate success in furthering our understanding of the action of superplasticizers on the rheology of cement and concrete. By specifically producing superplasticizers with varied architectures, we have been able to show the important structural features of the macromolecules that lead to a successful superplasticizer or water reducing agent. Both polycarboxylate and lignosulfonate polymers have been investigated. Using both non-reactive model MgO powders, three different types of cement blends, the adsorption behaviour and the effect on the rheological properties of these two important superplasticizer families have been used to further develop a conceptual model for superplasticizer — cement behaviour. This paper will deal mainly with the conceptual model, the materials and methods used to asses the polymer adsorption behaviour and rheological properties of the systems studied. We shall briefly describe the adsorption of the polymers onto the different surfaces and their influence on surface charge and rheology and the influence of the various ionic species found in cement pore solutions that may influence polymer-cement affinity. The key factors are shown to be the effective adsorbed polymer thickness and the induced surface charge which can be influenced by the polymer architecture, the pore solution composition and the initial particle surface charge.     

The effect of the kind of calcium sulfate in cements on the dispersing ability of poly β-naphthalene sulfonate condensate superplasticizer

Many studies have been carried out to prevent the incompatibility problem between poly β-naphthalene sulfonate condensate superplasticizer (PNS) and cements. Several of them suggested that the effect of SO₄²⁻ concentration on adsorption equilibrium might be more important for the performance of PNS than the effect of ionic strength on electrostatic repulsion. In this study, the influence mechanism of the kind of calcium sulfate in cements on the performance of PNS was analyzed in regards to SO₄²⁻ concentration change with time elapse. It was found that SO₄²⁻ concentration change was affected by two kinds of calcium sulfate, gypsum and hemihydrate. In case of using the cement containing mainly hemihydrate, SO₄²⁻ concentration in the solution phase of cement paste initially after mixing is high; however, it decreases rapidly with time elapse. The adsorbed amount of PNS onto surface of cement particle is limited just after mixing because the SO₄²⁻ concentration is high and increases with decreasing SO₄²⁻ concentration. As a result, the flow loss of cement paste decreases.     

Ungewöhnliche Adsorptions‐ und Trenneigenschaften des Molekularsiebs ZIF‐8

Low‐temperature rectification represents the state‐of the‐art in olefin/paraffin separation. Adsorption on microporous coordination polymers could be a less energy and cost‐intensive alternative. Especially zeolitic imidazolate frameworks, such as ZIF‐8, exhibits an interesting adsorption behavior since alkanes are preferentially adsorbed in comparison with the corresponding olefins. The single‐component adsorption isotherms and mixed gas breakthrough experiments of C₂ to C₄ hydrocarbons show the potential of ZIF‐8 for olefin/paraffin separation.     

Influence of cement and superplasticizers type and dosage on the fluidity of cement mortars—Part I

Concrete quality is controlled by the flow behavior of cement paste, which is related to the dispersion of cement particles. Superplasticizers (SPs) provide the possibility of a better dispersion of cement particles, thereby producing paste of higher fluidity. With the development of high strength, high performance concrete, SPs are becoming indispensable. SPs are adsorbed on the cement particles. This adsorption is uneven and depends upon the clinker composition of cement and the type of SP used. This work is focused on the study of the influence of lignosulfonic acid (LS)- and melamine sulfonic acid (SMF)-based SPs on the fluidity of mortars made with ordinary Portland (OPC), low alkali (LAC) and white cement (WC) at different water to cement ratio. It is shown that LS are more effective than SMF in providing better fluidity. Further WC has given the highest fluidity among the cements used. It is attributed to the lower C₃A+C₄AF and alkali content, and higher SO₃ content.     

Synthesis,working mechanism and effectiveness of a novel cycloaliphatic superplasticizer for concrete

In this study, the synthesis, performance and mode of action of a new type of superplasticizer is presented. From cyclohexanone, formaldehyde and sulfite, a high molecular weight polycondensate (M_w ≈ 220,000 g/mol) was synthesized. The resulting CFS superplasticizer was characterized by size exclusion chromatography and anionic charge density measurement. Performance of CFS in cement was probed by mini slump test and by determining the maximum water reduction achievable. The working mechanism was identified via adsorption and zeta potential measurements. The results show that CFS behaves like a typical polycondensate superplasticizer such as BNS. It enhances the fluidity of cement due to electrostatic repulsion. Advantages of this novel type of superplasticizer are simple preparation method, effectiveness at low water-to-cement ratio, huge water reducing capability and stable performance in the presence of clay.     

Hydration characteristics of waste sludge ash utilized as raw cement material

In this study, the hydration characteristics and the engineering properties of three types of eco-cement pastes, including their compressive strength, speciation, degree of hydration, and microstructure, were studied and compared with those of ASTM type I ordinary Portland cement. The results indicate that it is feasible to use sludge ash and steel-making waste to replace up to 20% of the mineral components of the raw material of cement. Furthermore, all the tested clinkers met the toxicity characteristic leaching procedure requirements. The major components of Portland cement, C₃S (i.e., 3CaO·SiO₂), C₂S (i.e., 2CaO·SiO₂), C₃A (i.e., 3CaOAl₂O₃) and C₄AF (i.e., 4CaO·Al₂O₃·Fe₂O₃), were all found in the waste-derived clinkers. All three types of eco-cements were confirmed to produce calcium hydroxide (Ca(OH)₂) and calcium silicate hydrates (CSH) during the hydration process, increasing densification with the curing age. The thermal analysis results indicate that the hydration proceeded up to 90 days, with the amount of Ca(OH)₂ and CSH increasing. The chemical shift of the silicates, and the resultant degree of hydration, and the increase in the length of the CSH gels with the curing age, were confirmed by ²⁹Si NMR techniques. Compressive strength and microstructural evaluations confirm the usefulness of eco-cement.     

抗泥型聚羧酸减水剂的制备及性能

以甲基丙烯酸（MAA）、甲基丙烯酸羟乙酯（HEMA）为单体,过氧化氢（H₂O₂）/抗坏血酸（Vc）为引发剂,甲基烯丙基磺酸钠（SMAS）为链转移剂,合成了一种抗泥型聚羧酸减水剂,通过红外光谱（FTIR）、凝胶渗透色谱（GPC）对聚合物进行结构表征,通过水泥净浆流动度、蒙脱土层间官能团、X射线衍射和吸附量测试,对其分散性能及抑制蒙脱土机理进行了探究。结果显示：合成的抗泥型聚羧酸减水剂在摩尔比为2.5：1时分散性能最佳,当减水剂折固掺量为0.25%时,水泥初始净浆流动度为268mm;与普通聚羧酸减水剂相比,合成的抗泥型减水剂对蒙脱土敏感性较低,与蒙脱土作用后的层间未出现抗泥型减水剂的特征官能团,层间距为1.40nm,抗泥型减水剂在蒙脱土上的吸附量远小于普通减水剂的吸附量。