Effect of fly ash on the kinetics of Portland cement hydration at different curing temperatures

This paper describes the effect of fly ash on the hydration kinetics of cement in low water to binder (w/b) fly ash-cement at different curing temperatures. The modified shrinking-core model was used to quantify the kinetic coefficients of the various hydration processes. The results show that the effect of fly ash on the hydration kinetics of cement depends on fly ash replacement ratios and curing temperatures. It was found that, at 20 °C and 35 °C, the fly ash retards the hydration of cement in the early period and accelerates the hydration of cement in the later period. Higher the fly ash replacement ratios lead to stronger effects. However, at 50 °C, the fly ash retards the hydration of the cement at later ages when it is used at high replacement ratios. This is because the pozzolanic reaction of the large volumes of fly ash is strongly accelerated from early in the aging, impeding the hydration of the cement.     

矿渣水泥水化动力学的研究

应用恒温导热量热仪对矿渣水泥和波特兰水泥的水化动力学进行了研究。实验结果表明,水泥水化在不同反应阶段具有不同的反应机理,所适用的动力学公式及动力学参数亦不同。加速期由自动催化(auto catalytic)反应控制,减速期由化学反应和扩散过程双重控制,衰减期由扩散过程控制。矿渣水泥对温度的敏感性高于波特兰水泥,原因是矿渣玻璃相具有较高的表观活化能。提高温度(热激发)对矿渣水泥的水化更为有利。在研究中采用两种活性不同的矿渣,它们的活性之差别可以从水化动力学参数K、E与N(与反应机理有关的常数)反映出来。     

纳米SiO_2对硅酸盐水泥水化放热特性的影响

以硅灰为对比,利用微量热仪研究了纳米SiO2对硅酸盐水泥24 h内水化历程、水化放热特性的影响.研究结果表明:掺入纳米SiO2的水泥试样24 h内水化历程也可划分为类似于纯硅酸盐水泥水化的5个阶段;纳米SiO2的掺入,促使诱导期、加速期和减速期的出现提前,缩短了诱导期持续的时间;提高了水化开始时的放热速率,使第二放热峰的出现提前,增大了水化放热量.     

International Summit on Cement Hydration Kinetics and Modeling Special Edition Québec City, July 27, 28 and 29, 2009

The performance of portland cement concrete relies upon a series of complex events that begin with raw minerals and end many years after the concrete is placed. Between these points, the life of this dynamic material is dominated by chemical reactions called hydration. While much is known about hydration, unfortunately, there is no unifying theory that describes the kinetics (rates) of these complex transformations from anhydrous cement to hydrous cement paste. Other industries including metalugy, petrochemicals, pharmaceuticals and semiconductors have asserted process control by developing a fundamental, mechanistic understanding of the kinetics of the chemical reactions and phase transformations that define their products. Might the concrete industry be moving along a similar trajectory?     

A method based on isothermal calorimetry to quantify the influence of moisture on the hydration rate of young cement pastes

Cement hydration needs water to proceed and if water is lost by drying, the hydration rate will decrease. This can be of importance in cases when concrete surfaces are exposed to drying so that their strength development will be retarded. We describe a method based on isothermal calorimetry to assess how the rate of cement hydration is influenced by removal of water (drying) at different times up to three days after mixing. Thin samples of cement pastes are hydrated in a calorimeter and at different times exposed to one hour drying periods. The resulting decrease in thermal power following the removal of water is quantified as a measure of the reduction in hydration rate. The mass loss is found by weighing the samples before and after a measurement, and the change in water activity of a sample during drying can be found from the slope of the thermal power during the drying period.     

Influence of Portland cement composition on early age reactions with metakaolin

The reactivity of two metakaolins, which vary principally in their surface area, and Portland cements of varying composition were examined via isothermal calorimetry for pastes at water-to-cementitious materials ratio of 0.50 containing 8% cement replacement by weight of metakaolin. Both metakaolins examined appear to have a catalysing effect on cement hydration. Calorimetry showed accelerated hydration, a slight increase in cumulative heat evolved during early hydration, and - for some cements examined - apparently an increased intensity of the heat evolved, particularly during the period typically associated with hydration of calcium aluminates. The higher surface area metakaolin had a greater effect. It is proposed that the presence of metakaolin may enhance dissolution of cementitious phases and/or provide additional, well-dispersed sites for nucleation of hydration products, in addition to increasing the early age concentration of solubilized aluminium (due to metakaolin dissolution). The increased intensity of some of the calorimetry data also suggests that some additional exothermic reactions are occurring, which may be related to an increased reactivity of calcium aluminate phases in the cement as well as the reaction of the metakaolin. This effect is apparently increased as the cement equivalent alkali content increases.     

Properties and hydration of blended cements with calcareous diatomite

In this paper the effect of diatomite addition on blended cement properties and hydration was studied. Calcareous diatomaceous rocks of Zakynthos Island, Ionian Sea, containing mainly CaCO₃ and amorphous silica of biogenic origin with the form of opal-A were used. Cement mortars and pastes, with 0%, 10%, 20% and 35% replacement of cement with the specific diatomite, were examined. Strength development, water demand and setting time were determined in all samples. In addition, XRD, SEM and weight loss at 350 °C were applied in order to study the hydration products and the hydration rate in the cement-diatomite pastes. Blended cements, having up to 10% diatomite content, develop the same compressive strength, as the corresponding Portland cement, while the presence of diatomite leads to an increase of the paste water demand. Diatomite is characterized as natural pozzolana, as it satisfies the requirements of EN 197 1 concerning the active silica content. The pozzolanic nature of the diatomite results to the formation of higher amounts of hydrated products, specifically at the age of 28 days.     

Changes in C3S hydration in the presence of cellulose ethers

The influence of cellulose ethers (CE) on C₃S hydration processes was examined in order to improve our knowledge of the retarding effect of cellulose ethers on the cement hydration kinetics. In this frame, the impacts of various cellulose ethers on C₃S dissolution, C-S-H nucleation-growth process and portlandite precipitation were investigated. A weak influence of cellulose ethers on the dissolution kinetics of pure C₃S phase was observed. In contrast, a significant decrease of the initial amount of C-S-H nuclei and a strong modification of the growth rate of C-S-H were noticed. A slowing down of the portlandite precipitation was also demonstrated in the case of both cement and C₃S hydration. CE adsorption behavior clearly highlighted a chemical structure dependence as well as a cement phase dependence. Finally, we supported the conclusion that CE adsorption is doubtless responsible for the various retarding effect observed as a function of CE types.     

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.     

外加剂对磷铝酸盐水泥中钙、铝析出的影响

用分光光度计等测试技术研究了磷铝酸盐水泥水化时Ca2+,Al3+离子浓度随外加剂掺量不同的变化,并探讨了磷铝酸盐水泥的水化动力学.结果表明:一定掺量的外加剂可调节Ca2+,Al3+离子的析出,改变磷铝酸盐水泥水化加速期的长短,起到了调凝的效果,在磷铝酸盐水泥水化加速期,其水化动力学遵循方程:[1-(1-α)1/3]N=Kt.Ca2+离子的溶出主要受自动催化反应控制,N为1.51～1.67;Al3+离子的溶出则主要受扩散反应控制,N为5.37.     

The hydration of reactive cement-in-polymer dispersions studied by nuclear magnetic resonance

The behaviour of two novel cement-in-polymer (c/p) dispersions, namely cement-in-poly(vinyl acetate) and cement-in-poly(vinyl alcohol) upon exposure to water at room temperature was investigated by a combination of various NMR methods. The swelling, cracking, and the water ingress were monitored non-destructively using ¹H single point imaging. The hydration of the cement matrix was investigated using ²⁹Si NMR whilst ¹³C CPMAS NMR spectra allowed the quantification of the kinetics of the hydrolysis reaction of poly(vinyl acetate) into poly(vinyl alcohol). The polymer controls the rate of water ingress and swelling which in turn determines the behaviour of the c/p dispersions upon exposure to water. For the cement-in-poly(vinyl alcohol), the rates of water ingress and swelling are much faster than the hydration of the clinker whilst for the cement-in-poly(vinyl acetate) the slow rates of the two processes allow the formation of a cementious matrix which assures the stability of the sample.     

A remastered external standard method applied to the quantification of early OPC hydration

A promising external standard method, first described by O'Connor [15], was used to determine the quantitative phase composition of a hydrating cement paste. On the basis of the data produced we can conclude that the method used is absolutely to be recommended for the examination of OPC pastes, since it displays many advantages in comparison to internal standard methods and other methods. No reaction of the phase alite could be detected during the initial and the induction periods of the cement hydration. Additionally it was found that the cement phases involved in the aluminate reaction (bassanite, gypsum, anhydrite and C₃A) react successively. The changes detected in the phase composition of the OPC paste could be assigned to the different periods of OPC hydration.     

Relation between the molecular structure and the efficiency of superabsorbent polymers (SAP) as concrete admixture to mitigate autogenous shrinkage

Superabsorbent polymers (SAP) were studied as admixtures for mitigating the autogenous shrinkage of a high-strength concrete. The presence of Ca²⁺ ions in the alkaline solution modified the kinetics of the liquid uptake and release when compared to that in other saline solutions and distilled water. SAP with high density of anionic functional groups took up the cement pore solution quickly, but greatly released it subsequently. The cross-linking density had no pronounced influence on the behaviour of such SAP. SAP with lower density of anionic groups did not release the liquid over the time of experiment. All SAP counteracted autogenous shrinkage during the acceleration period of cement hydration. For the materials which released the absorbed pore solution no effect on autogenous shrinkage was found beyond the initial period. SAP materials which did not release the absorbed solution in the experiments with liquids continued the mitigation of autogenous shrinkage during the deceleration period. The internal curing had no negative effect on the compressive strength of the mortar.     

Investigation into relations among technological properties, hydration kinetics and early age hydration of self-leveling underlayments

Technological properties such as flow value, setting times, compressive strength and early age dimensional stability as linear shrinkage and expansion have been studied for two types of self-leveling underlayments (SLU) in which the kind of calcium sulfates was varied. The influence on hydration kinetics has been measured by isothermal heat flow calorimetry. The results obtained for the technological properties change significantly when different kinds of calcium sulfates are used. The basic trend for the results changes when the composition changes from a calcium aluminate cement system to a Portland cement system. Additionally, there was an interesting relationship to final dimensional stability and shape of heat evolution curve. Moreover the time to reach plateau of dimensional stability was related to the development of compressive strength. In the meanwhile, using hemihydrate in Portland cement systems caused low compressive strength and significant expansion. On the other hand, in the results of XRD measurements, the first genesis of Ettringite corresponded to the first shrinkage of SLU. Interesting results related with technological properties and hydration kinetics or the results of XRD other than these above results were obtained.     

Influence of nucleation seeding on the hydration kinetics and compressive strength of alkali activated slag paste

Addition of pure calcium silicate hydrate (C–S–H) to alkali-activated slag (AAS) paste resulted in an earlier and larger hydration rate peak measured with isothermal calorimetry and a much higher compressive strength after 1 d of curing. This is attributed to a nucleation seeding effect, as was previously established for Portland cement and tricalcium silicate pastes. The acceleration of AAS hydration by seeding indicates that the early hydration rate is controlled by nucleation and growth. For the experiments reported here, the effect of C–S–H seed on the strength development of AAS paste between 1 d and 14 d of curing depended strongly on the curing method. With sealed curing the strength continued to increase, but with underwater curing the strength decreased due to cracking. This cracking is attributed to differential stresses arising from chemical and autogenous shrinkage. Similar experiments were also performed on Portland cement paste.     

The effects of nano-C-S-H with different polymer stabilizers on early cement hydration

A promising approach to accelerate cement hydration known as “seeding technology” has been discovered using nano-particles to provide additional nucleation sites for growing of C-S-H. Two different types of polymer, polycarboxylate (PCE) and polysulfonate (PSE) were used as stabilizer to synthesize nano-C-S-H via co-precipitation process. The obtained C-S-H-polymer composites were characterized by means of XRD, FTIR, thermogravimetric analysis (TGA), TEM, dynamic laser scattering (DLS), and BET. DLS measurement shows that the particle size of the obtained C-S-H-polymer suspension ranges from 82.6 to 589.9 nm. The results of DLS and BET show that the particle size of the C-S-H particles synthesized using PCE polymer as stabilizer is smaller than those synthesized with PSE polymer, and hence the specific surface area is much higher. FTIR and TGA results confirm the presence of the polymers in the obtained C-S-H composites particles. XRD results indicate that the presence of the polymers reduces the crystallinity of C-S-H due to the absence of the d002 peak at 2θ of 7°. The calorimetry results show that the main hydration peak of cement is dramatically increased by the addition of the C-S-H-polymer composites. It is interestingly found that the acceleration effect of the C-S-H-polymer composites is linearly proportional to the total surface area of the nanoparticles introduced into the cement pastes. At the same time, it is found that the secondary hydration peak, usually known as the sulfate-depletion peak, is greatly advanced by addition of the C-S-H nano-particles in comparison with the blank cement paste. The acceleration effect of the nano-C-S-H is further verified in a pure C₃S system.     

Influence of a fine glass powder on cement hydration: Comparison to fly ash and modeling the degree of hydration

This paper reports the results of an investigation carried out to understand the influence of a fine glass powder on cement hydration. The pozzolanicity of the glass powder and a Class F fly ash for comparison was evaluated using strength activity index over a period of time, and a rapid electrical conductivity based method. Flame emission spectroscopy and electrical conductivity tests were used to quantify the alkali release from glass powder, and gain information on the rate of alkali release. It was found that the glass powder releases only a very small fraction of sodium ions into the solution. It was observed that the glass powder modified pastes show higher non-evaporable water contents than the plain paste and fly ash modified pastes, indicating that glass powder facilitates enhancement in cement hydration. An expression has been developed for the change in non-evaporable water content as a result of enhancement in cement hydration and the hydration of the cement replacement material. The efficiency of any cement replacement material with age in the paste system can be quantified using this parameter. Based on this parameter, a 5% cement replacement with glass powder was found to be effective at the chosen water-to-cementing materials ratio (w/cm), whereas at higher replacement levels, the dilution effect dominates. A model to predict the combined degree of hydration of cement pastes incorporating more than one cementing material is outlined. The measured and predicted combined degrees of hydration agree well.     

Analysis of C-S-H gel and cement paste by small-angle neutron scattering

The role of small-angle X-ray and neutron scattering (SAXS and SANS) in the characterization of cement is briefly reviewed. The unique information obtainable from SANS analysis of C-S-H gel in hydrating cement is compared with that obtainable by other neutron methods. Implications for the nature of C-S-H gel, as detected by SANS, are considered in relation to current models. Finally, the application of the SANS method to cement paste is demonstrated by analyzing the effects of calcium chloride acceleration and sucrose retardation on the resulting hydrated microstructure.     

Dissolution theory applied to the induction period in alite hydration

The early hydration of alite, in particular the reason for the onset of the induction period, has been a subject of controversy for many decades. Several theories have been proposed, principally the formation of a protective phase inhibiting dissolution or delayed nucleation and growth, but none have successfully taken into account all the experimental data available. This paper proposes a new mechanism, based on a geochemical approach to crystal dissolution that fully explains the origin of the induction period. It implies that during cement hydration, dissolution is initially dominated by the formation of etch pits on surfaces and later becomes limited to step retreat from such pits. This change in mechanism alone can account for the rapid decrease in reaction after first contact with water, without the need to invoke the formation of a protective phase. Furthermore it can explain all the experimental findings in the literature. While this geochemical view of dissolution explains many features of the induction period it does not account for its end. This remains a question for further research, but the most probable explanation appears to be the onset of rapid growth of C-S-H.