Modification of cement with succinic anhydride‐based hyperbranched polyesteramide

Two hyperbranched polyesteramides (HYP₁ and HYP₂) were prepared by reacting succinic anhydride (ScAn) with both of diisopropanolamine (DiPA) and diethanolamine, respectively, via one‐pot polycondensation reaction. The prepared polymers were analyzed using gel permeation chromatography, infrared spectra, and 1HNMR. The resulting hydroxyl‐ended resins have been successfully applied as polymeric admixtures in two types of cements such as Ordinary Portland cement and Portland limestone cement. The water of consistency decreased by addition of the hyperbranched polymers in both types of cements. Better hydration was observed by incorporation of small amounts of polymers. The infrared spectra and scanning electron microscopy photos of Ordinary Portland cement and Portland limestone cement pastes premixed with HYP₁ and HYP₂ showed no effect on the chemical composition of the cement hydrates where only the morphology and the crystallinity of the formed hydrates were changed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydration study of limestone blended cement in the presence of hazardous wastes containing Cr(VI)

Considering the increasing use of limestone cement manufacture, the present paper tends to characterize limestone behavior in the presence of Cr(VI). The research reported herein provides information regarding the effect of Cr(VI) from industrial wastes in the limestone cement hydration.The cementitious materials were ordinary Portland cement, as reference, and limestone blended cement.The hydration and physicomechanical properties of cementitious materials and the influence of chromium at an early age were studied with X-ray diffraction (XRD), infrared spectroscopy (FTIR), conductimetric and mechanical tests. Portland cement pastes with the addition of Cr(VI) were examined and leaching behavior with respect to water and acid solution were investigated.This study indicates that Cr(VI) modifies the rate and the components obtained during the cement hydration.     

Characterization and Utilization of Polystyrene and Polyacrylamide-Graft-Methoxypolyethylene as Cement Admixtures

A series of polystyrene-g-methoxypolyoxyethylene (PS-g-MPOE) was prepared by solution polymerization technique using benzoyl peroxide as an initiator and another series of polyacrylamide-g-methoxypolyoxyethylene (PAM-g-MPOE) was prepared by using potassium persulfate initiator. The prepared grafted copolymers were characterized by infrared (IR), thermogravimetric analysis (TGA) and rheological properties. The results illustrated that the solution of PS-g-MPOE in water behaved as a Newtonian fluid, but the solution of PAM-g-MPOE as pseudoplastic at higher acrylamide ratios. The TGA analysis showed that the thermal stability of PAM-g-MPOE was highest. Some of these polymers were evaluated as cement admixtures. The water of consistency and setting time of the cement pastes premixed with the polymers decreased sharply than those of the blank, i.e., these polymer admixtures can act as superplastisizers and at the same time as accelerators. The combined water and free lime contents as well as compressive strength of the cement pastes premixed with PS-g-MPOE or PAM-g-MPOE were slightly lower than the blank at the early ages up to 7 d, and then became higher during the later hydration ages. Their total porosities are higher during the early ages and lower during the later ages of hydration. The SEM images confirmed that the addition of the organic polymer solutions to the cement powder does not affect the chemical composition of the normal hydration products, but only affects the physical state, shape or morphology and size of crystals of the formed hydrates.     

碳化过程中大水灰比水泥浆体孔结构的变化(英文)

使用特殊的增黏剂与聚羧酸减水剂,制备了掺加石灰石粉、高炉矿渣、硅灰等混合材的普通波特兰水泥浆体和和低热硅酸盐水泥浆体(水粉比为1.0)。这些水泥浆体在20℃的水中养护4年后基本完全水化。这些硬化水泥浆体在5%(质量分数)CO2、相对湿度66%和温度20℃条件下进行碳化,对比研究碳化前后水泥浆体孔结构的变化。结果显示:碳化浆体内孔直径大于10nm的孔体积明显减少;碳化浆体的孔径分布向大孔径范围偏移;掺加混合材的硬化水泥浆体结构明显趋于松散;与不掺加任何混合材的水泥浆体相比,掺加混合材的水泥浆体的孔径更大。     

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.     

含C_4A_3矿物硅酸盐水泥中混合材反应程度的研究

采用非蒸发水量法测定含硫铝酸钙矿物水泥的水化程度 ,萃取法测定该水泥中混合材的反应程度 ,通过SEM/EDS观察分析水化产物形貌和种类。结果表明 :粉煤灰水泥的水化程度高于同龄期的矿渣水泥的水化程度 ,粉煤灰的反应程度高于矿渣的反应程度。同龄期粉煤灰水泥中的水化产物多于矿渣水泥的水化产物 ,且水化产物发育更良好     

Calcium and silicon concentrations in solution during the early hydration of portland cement and tricalcium silicate

The solution chemistry of Portland cement and C₃S pastes has been studied with particular attention to the concentrations of calcium and silicon in the aqueous phase during early stages of hydration. Results are discussed in relation to solubility data available from studies of OPC and C₃S pastes and from the CaO---SiO₂---H₂O system. It is shown that under normal conditions the concentration of silicon in solution is extremely low (<2ppm) and this remains unchanged even when hydration is accelerated in the presence of CaCl₂. However, retarding admixtures such as oxalic acid and EDTA, which are strong calcium binding agents, release a flush of silicon into solution within the first few minutes of hydration. The results lend support to the osmotic membrane model of cement hydration and also provide insight into the mechanisms by which accelerating and retarding admixtures function.     

Early hydration of portland cement — effects of water/cement ratio

The water/cement ratio at which Portland cement is hydrated is shown to influence the early hydration behaviour. Results have been obtained with both an ordinary Portland cement and a white Portland cement. As the water/cement ratio was progressively raised from 0.3 through 0.4 to 0.5, increased quantities of ettringite were formed at all the hydration times studied up to two hours. The results have been interpreted on the basis of a through solution mechanism for the formation of ettringite.     

Effect of lignosulfonate, calcium chloride and their mixture on the hydration of RHA-blended portland cement

Hydration of 10 wt.% rice husk ash (RHA)-blended Portland cement has been studied in the presence of 2 wt.% CaCl₂, 1 wt.% lignosulfonate (LS) and a mixture of the two admixtures by using different methods. Free lime determinations and differential thermal analysis have shown that CaCl₂ accelerates the pozzolanic reaction of Ca(OH)₂ and RHA. In the presence of mixture of two admixtures, lower amount of water is required for consistency of the paste. IR spectral studies have supported that the mixture of the two admixtures act as a strong accelerator for cement hydration. The compressive strength is highest in the presence of a mixture of the two admixtures at 28 days of hydration. The admixtures did not prevent the deterioration of the blended cement in corrosive atmosphere.     

Modeling the hydration of concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are industrial by-products that have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, the hydration of concrete containing fly ash or slag is much more complex compared with that of Portland cement. In this paper, the production of calcium hydroxide in cement hydration and its consumption in the reaction of mineral admixtures is considered in order to develop a numerical model that simulates the hydration of concrete containing fly ash or slag. The heat evolution rates of fly ash- or slag-blended concrete is determined by the contribution of both cement hydration and the reaction of the mineral admixtures. The proposed model is verified through experimental data on concrete with different water-to-cement ratios and mineral admixture substitution ratios.     

Reaction mechanisms of concrete admixtures

Concrete admixtures influence the kinetic of cement hydration mainly during the dormant period. The dominant influence of admixtures seems to lie in different bound forces between dissociated ions in the pore water solution. Repulsive forces characterize the solvation process while attractive forces dominate during crystallization. These changes of ion bound forces lead twice to volume changes during phase transitions of hydration. Volume changes measured with an immersion weighing setup show clearly the effect of concrete admixtures on cement reaction. Retarder agents produce a volume swelling while accelerators force an immediate shrinkage behaviour. A mechanism as introduced by Le Chatelier involving a solution-crystallization step seems to describe the hydration process most adequately. As long as repulsive forces dominate, a volume swelling occurs and no strength gain can take place. The dormant period is defined by the length of the swelling process. Hardening and strength growth start at the point at which volume shrinkage appears.     

Effect of polysaccharides on the hydration of cement suspension

This work compares the effects induced by polysaccharides on the hydration of cement. It also brings new insights into the interaction mechanisms between these two components. Several parameters such as structure, concentration, average molecular weight, and the soluble fraction value of the polysaccharides were examined. The hydration of cement was monitored by conductivity measurement, and ionic chromatography. The influence of polysaccharide structure on the kinetics of cement hydration was revealed. The extent of retardation increases when polysaccharide concentration rises. Dextrins with lower average molecular weights compared with starches favor a higher soluble fraction value and further retard hydration. The growth of hydrates seemed to be more affected by the presence of these admixtures than did the dissolution of anhydrous particles or the nucleation of former hydrates.     

防腐阻锈剂对混凝土性能影响试验研究

将防腐阻锈剂按照不同比例等量取代普硅水泥配制混凝土,研究其对混凝土抗压强度、抗硫酸盐侵蚀系数、氯离子渗透系数、腐蚀电量等性能指标的影响,并通过SEM扫描电镜观察混凝土3 d、7 d、28 d的水泥水化产物形貌.研究结果表明:掺入防腐阻锈剂后,混凝土的工作性能、后期力学性能、抗硫酸盐侵蚀性能、氯离子渗透性能、抗氯盐侵蚀性能明显优于基准混凝土;防腐阻锈剂的掺入消耗了水泥中的C3A、水泥水化产生的Ca(OH)2,生成钙矾石和C-S-H凝胶,产生微膨胀效应使混凝土结构更加致密,提高了抗硫酸盐、氯盐侵蚀性能.     

Performance characteristics of cement grouts made with various combinations of high-range water reducer and cellulose-based viscosity modifier

Cellulose-based viscosity-modifying admixtures (VMA) are used to increase the viscosity of cement-based systems, hence, reducing the risk of material separation during handling and transport and thereafter until the onset of hardening. To ensure proper fluidity such admixtures are incorporated along with high-range water reducers (HRWRs). The ability of the VMA to ensure the required rheological properties depends on the type and interaction with the incorporated HRWR. Good understanding of such interaction is essential to ensure adequate performance. Limited knowledge is available on the effect of cellulose-based VMA and HRWR on physico-chemical characteristics and cement hydration.

The performance of grouts made with 0.40 water/cement (w/c) ratio containing a liquid-based cellulose material was investigated for mixtures made with polynaphtalene sulfonate (PNS) and polymelamine sulfonate (PMS) HRWR. The grouts are tested for fluidity, rheological properties, stability, setting and rate of hydration. The grouts were also tested for strength and pore-size distribution, and microstructural characteristics.

This paper summarizes the results of the study regarding the influence of the type and dosage of HRWR on key characteristics of grouts made with the cellulose-based VMA.     

Filler cement: The effect of the secondary component on the hydration of Portland cement: Part 2: Fine hydraulic binders

In Part 1 of this paper, it was shown that enhanced hydration was achieved by blending a fine non-hydraulic filler into an ordinary Portland cement. This enhancement was considered to be a particle size effect and associated with the presence of fine particles of filler which provided the additional nucleation sites. The filler, rutile, had a variable cement equivalence and reached a maximum value of 0.9kg/kg after hydration had proceeded for three days. In this second part, the same Portland cement was blended seperately with latent hydraulic binders (two pulverized fuel ashes and a ground granulated blastfurnace slag, a Lurgi slag and a volatilized silica). The apparent overall reactivity of these binders was seen to have two components, the first being the particle size effect with its influence on the hydration of the Portland cement and the second the inherent hydraulicity of the secondary material.     

Effect of delaying addition of some concrete admixtures on the rheological properties of cement pastes

The effect of delayed addition of two concrete admixtures, namely melamine formaldehyde sulfonate (MFS) and naphthalene formaldehyde sulfonate (NFS), on the rheological and adsorption properties of ordinary Portland cement (OPC), sulfate-resisting cement (SRC) and silica fume-ordinary Portland cement (SF-OPC) pastes was investigated. The admixture addition was delayed by 1, 3, 6, 10 and 13 min after the addition of mixing water. The shear stress, as well as the apparent viscosity of these cement pastes, was determined at different shear rates. Total organic carbon (TOC), Ca²⁺ concentration and conductivity of the filtrate and the combined water content of the precipitated cement pastes were determined. The results show that delaying the admixtures addition increases the cement pastes workability than that of simultaneous addition.     

-3 ℃养护下考虑矿物掺合料影响的水泥水化程度计算模型

针对多年冻土地区工程施工时混凝土养护的问题,采用10%、20%、30%的矿粉和粉煤灰替代量等量替代水泥,测试了-3 ℃恒温养护条件下0.38水胶比水泥浆体在各个龄期的水泥水化热,计算了水泥水化程度;分析了龄期及矿物掺合料对水泥水化程度的影响规律,建立了综合考虑龄期和矿物掺合料替代量的水泥水化程度计算模型.结果表明:-3 ℃恒温养护下,矿物掺合料等量替代水泥,水泥浆体的水化程度会降低,粉煤灰降低水化程度的值要比矿粉高;在相同矿物掺合料替代量下,随着龄期的增长,矿物掺合料对水泥水化程度的影响逐渐减弱;同一龄期时,随着矿物掺合料的增加,矿物掺合料对水泥水化程度的影响逐渐增强;利用建立的模型计算了分别掺入15%矿粉和粉煤灰的水泥水化程度,与实测值相比,计算值偏离值较少,预测精度较高.     

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.     

Early hydration behaviour of portland cement containing tartaro- and titanogypsum

Portland cements containing tartaro- and titanogypsum were respectively hydrated for up to two hours at a water: cement ratio of 0.5. They were compared with a Portland cement containing high grade natural gypsum hydrated similarly. The cement containing tartarogypsum produced much more ettringite than those with titanogypsum and natural gypsum. Comparisons were made with previous examinations of the hydration of Portland cements containing other by-product gypsums. Reasons for the observed hydration behaviour of the Portland cements with tartaro- and titanogypsum are discussed.     

Water dynamics in cement paste at early age prepared with pozzolanic volcanic ash and Ordinary Portland Cement using quasielastic neutron scattering

Early age hydration kinetics of Portland cement with pozzolanic volcanic ash was examined using quasielastic neutron scattering. Volcanic ash consisting of two different particle sizes was used to prepare cement pastes with different ratios of Portland cement to volcanic ash. The concentration of the volcanic ash played a major role in the bound water index and self-diffusion coefficients of hydration water confined in the cement paste. An increase in the particle size of the volcanic ash affected the degree of hydration by allowing more free and mobile water in the gel pores, suggesting that volcanic ash may not have completely reacted during the experimental time frame. This study shows that the particle size along with variation in volcanic ash composition governs the early age hydration process in volcanic ash cements.