A new hydration kinetics model of composite cementitious materials,Part 2: Physical effect of SCMs

This paper is the second part of an overall research project that aims to model the hydration kinetics of composite cementitious materials. The new hydration kinetic model of Portland cement was constructed in the first part of this research project. The aim of this part is to characterize the physical effect of SCMs by modifying some kinetic parameters of the hydration kinetic model of cement. In this paper, the filler effect of SCMs is attributed to the “dilution effect”, “nucleation effect” and “accelerated dissolution effect”. The dilution effect is considered by introducing the actual water/cement ratio into the kinetic model. The nucleation surface area, nucleation and growth rates are modified to account for the nucleation effect and accelerated dissolution effect of fillers. The simulative fit results show that the extra contribution of SCMs due to their filler effect on hydration of cement at early ages has an upper limit: at most 20% extra nucleation surface area, 30% extra nucleation ratio and 40% extra growth ratio of calcium silicate hydrate (CSH). The new modified kinetic model and the value-taking method of the newly introduced parameters are verified by simulative fitting to the kinetic data from reference. The apparent activation energies of the nucleation rate, growth rate, and diffusion rate are approximately 35 kJ/mol, 36 kJ/mol and 38.5 kJ/mol, which are slightly smaller than those of the pure Portland cement reported in the first part of this research project.     

Kinetic modeling of calcium aluminate cement hydration

The hydration of iron-rich calcium aluminate cement (CAC) has been investigated by differential calorimeter and quantitative powder X-ray diffraction (QXRD). A simplified stoichiometric model of early age CAC hydration based on reaction schemes of the principal mineral monocalcium aluminate was employed. The CAC characteristic feature of retardation of nucleation and growth mechanism with temperature requires employing more than one kinetic mechanism to describe the resulting complex hydration kinetics. This paper proposes a single equation kinetic model of CAC hydration which comprises simultaneously three main mechanisms: nucleation and growth, chemical interaction and mass transfer. A gradual change between kinetic mechanisms was grasped with a reasonable inter-dependency of the kinetic parameters. The overall hydration kinetics was described relative to the amount of the both reactants, cement and free water.     

Time dependent driving forces and the kinetics of tricalcium silicate hydration

Simulations of tricalcium silicate (C₃S) hydration using a kinetic cellular automaton program, HydratiCA, indicate that the net rate depends both on C₃S dissolution and on hydration product growth. Neither process can be considered the sole rate-controlling step because the solution remains significantly undersaturated with respect to C₃S yet significantly supersaturated with respect to calcium silicate hydrate (C–S–H). The reaction rate peak is attributed to increasing coverage of C₃S by C–S–H, which reduces both the dissolution rate and the supersaturation of C–S–H. This supersaturation dependence is included in a generalized boundary nucleation and growth model to describe the kinetics without requiring significant impingement of products on separate cement grains. The latter point explains the observation that paste hydration rates are insensitive to water/cement ratio. The simulations indicate that the product layer on C₃S remains permeable; no transition to diffusion control is indicated, even long after the rate peak.     

A New Approach to Modeling the Nucleation and Growth Kinetics of Tricalcium Silicate Hydration

The hydration kinetics of tricalcium silicate (C₃S), the main constituent of portland cement, were analyzed with a mathematical "boundary nucleation" model in which nucleation of the hydration product occurs only on internal boundaries corresponding to the C₃S particle surfaces. This model more closely approximates the C₃S hydration process than does the widely used Avrami nucleation and growth model. In particular, the boundary model accounts for the important effect of the C₃S powder surface area on the hydration kinetics. Both models were applied to isothermal calorimetry data from hydrating C₃S pastes in the temperature range of 10°–40°C. The boundary nucleation model provides a better fit to the early hydration rate peak than does the Avrami model, despite having one less varying parameter. The nucleation rate (per unit area) and the linear growth rate of the hydration product were calculated from the fitted values of the rate constants and the independently measured powder surface area. The growth rate follows a simple Arrhenius temperature dependence with a constant activation energy of 31.2 kJ/mol, while the activation energy associated with the nucleation rate increases with increasing temperature. The start of the nucleation and growth process coincides with the time of initial mixing, indicating that the initial slow reaction period known as the "induction period" is not a separate chemical process as has often been hypothesized.     

Nucleation and growth models for hydration of cement

The hydration of cement is often modeled as a nucleation and growth process. In this paper, we examine the applicability of the boundary nucleation and growth model, in which nucleation is assumed to occur only on the surfaces of the cement particles. This theory has been shown to give good fits to calorimetric and chemical shrinkage data, with the assumption that the nucleation and growth rates are constant. However, we will show that slightly better fits are obtained when it is assumed that growth occurs from a fixed number of nuclei. We present a version of the model that allows for anisotropic growth, with different rates on each side of the particle surface. This type of model must only be used during the period when the reaction is dominated by a single phase, but this is approximately valid during the time when the paste is setting.     

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。     

Multi-phase hydration model for prediction of hydration-heat release of blended cements

Recently, the heat release during cement hydration and the so-caused temperature rise was exploited for (i) identification of material properties of early-age cement-based materials (stiffness, strength), and (ii) determination of the diameter and the cement content of jet-grouted structures. In this paper, the underlying hydration model for determination of the heat release and its rate is refined for Ordinary Portland Cements (OPC) and extended towards blended cements. Hereby, the overall degree of hydration with one kinetic law is replaced by a multi-phase hydration model, taking the hydration kinetics of the main clinker phases into account. As regards blended cements, which are commonly used in engineering practice, the effect of slag hydration is incorporated into the presented multi-phase model. The developed hydration model for both plain and blended cement is validated by means of differential-calorimetry (DC) experiments.     

Early hydration and setting of oil well cement

A broad experimental study has been performed to characterize the early hydration and setting of cement pastes prepared with Class H oil well cement at water-to-cement ratios (w/c) from 0.25 to 0.40, cured at temperatures from 10 to 60 °C, and mixed with chemical additives. Chemical shrinkage during hydration was measured by a newly developed system, degree of hydration was determined by thermogravimetric analysis, and setting time was tested by Vicat and ultrasonic velocity measurements. A Boundary Nucleation and Growth model provides a good fit to the chemical shrinkage data.Temperature increase and accelerator additions expedite the rate of cement hydration by causing more rapid nucleation of hydration products, leading to earlier setting; conversely, retarder and viscosity modifying agents delay cement nucleation, causing later setting times. Lower w/c paste needs less hydration product to form a percolating solid network (i.e., to reach the initial setting point). However, for the systems evaluated, at a given w/c, the degree of hydration at setting is a constant, regardless of the effects of ambient temperature or the presence of additives.     

Cement hydration in the presence of high filler contents

To realise self-compacting concrete, high filler contents are often used, and in order to avoid problems with excessive heat development during hardening, inert filler materials can be used. In this research two different filler types, limestone and quartzite, are considered in combination with different Portland cements. Although the filler material has often been considered to be inert, experimental results show that it does influence the hydration processes. On the one hand the reaction rate is influenced due to a modified nucleation possibility, and on the other hand, in some cases, the reaction mechanisms are altered, with a new hydration peak occurring. Based on isothermal conduction calorimetry on different cement-filler systems, an existing hydration model for blended cement is modified for these systems. Within the degree of hydration based hydration model, the cement/powder ratio seems to be an important parameter for the cement-filler systems. The model accurately predicts the heat of hydration during the hardening process.     

The Filler Effect: The Influence of Filler Content and Surface Area on Cementitious Reaction Rates

Finely ground mineral powders are known to accelerate cement hydration rates. This “filler effect” has been attributed to the effects of dilution (w/c increase) when the cement content is reduced or to the provision of additional surface area by fine powders. The latter contribution (i.e., surface area increase) is speculated to provide additional sites for the nucleation of the hydration products, which accelerates reactions. Through extensive experimentation and simulation this study describes the influence of surface area and mineral type (e.g., quartz or limestone) on cement reaction rates. Simulations using a boundary nucleation and growth (BNG) model and a multiphase reaction ensemble (MRE) indicate that the extent of the acceleration is linked to the: (1) magnitude of surface area increase and (2a) capacity of the filler's surface to offer favorable nucleation sites for hydration products. Other simulations using a kinetic cellular automaton model (HydratiCA) suggest that accelerations are linked to: (2b) the interfacial properties of the filler that alters (increases or decreases) its tendency to serve as a nucleant, and (3) the chemical composition of the filler and the tendency for its dissociated ions to participate in exchange reactions with the calcium silicate hydrate product. The simulations are correlated with accelerations observed using isothermal calorimetry when fillers partially replace cement. The research correlates and unifies the fundamental parameters that drive the filler effect and provides a mechanistic understanding of the influence of filler agents on cementitious reaction rates.     

Mineral admixtures in mortars: Effect of inert materials on short-term hydration

This work is the first part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The separation of the different physical effects responsible for the modification of cement hydration, when chemically inert quartz powders are used in mortars, is presented. The phenomenological approach, based on semi-adiabatic calorimetry, is only associated with first-order phenomena, and the study excludes the complex physicochemical details involved in the chemistry of cement. The results, obtained for a wide range of fineness (between 180 and 2000 m²/kg) and replacement rates (up to 75%), show that short-term degrees of hydration in mortars containing a chemically inert mineral admixture (quartz) are always higher than for a reference mortar. This study confirms that cement hydration is enhanced by inert mineral admixtures. The two main physical effects responsible for the modification of the hydration of cement are identified as the dilution effect and heterogeneous nucleation. The dilution effect of the cement is highlighted with a coarse mineral admixture. The heterogeneous nucleation effect, although it increases with fineness of mineral admixtures, presents an optimum depending on the replacement rate. In the following part of this work, these results will be used for the development of an empirical model allowing us to quantify both physical effects.     

The Effect of Magnesium and Zinc Ions on the Hydration Kinetics of C3S

Impure tricalcium silicate (C₃S) in portland cement may contain various foreign ions. These ions can stabilize different polymorphs of C₃S at room temperature and may affect its reactivity. In this paper, the effects of magnesium and zinc on the polymorph type, hydration kinetics, and the hydrate morphology of C₃S were investigated. The pure C₃S has the T1 structure while magnesium and zinc stabilize polymorphs M3 and T2/T3, respectively. The two elements have distinct effects on the hydration kinetics. Zinc increases the maximum heat released. Magnesium increases the hydration peak width. The C–S–H morphology is modified, leading to longer needles in the presence of zinc and thicker needles in the presence of magnesium. Zinc is incorporated into C–S–H, while magnesium is only incorporated slightly, if at all, but rather seems to inhibit nucleation. Implementing experimentally measured parameters for C–S–H nucleation and growth in the μic hydration model captured well the observed changes in hydration kinetics. This supports C–S–H nucleation and growth to be rate controlling in the hydration of C₃S.     

石灰石粉-粉煤灰细度变化对水泥基胶凝材料体系水化动力学的影响

为研究混磨不同细度石灰石粉-粉煤灰对水泥基胶凝材料水化进程和早期力学性能的影响规律,本文采用等温量热法测定了不同细度复合胶凝体系在水化温度为20 ℃时的水化放热速率和放热量,根据Krstulovic-Dabic提出的水化动力学模型计算了复合胶凝体系水化反应各阶段的动力学参数。结果表明:增加石灰石粉和粉煤灰的细度可促进复合胶凝体系水化产物的结晶成核与晶体生长,缩短水化诱导期结束时间和达到最大放热速率时间,加速水泥的水化反应速率。石灰石粉和粉煤灰细化会缩短相边界反应过程时间,使复合胶凝体系在水化程度更高时发生反应控制机制转变。抗压强度试验表明增加细度可明显提高胶砂试件的早期强度,其后期强度保持稳定。     

Metallocene polypropylene crystallization kinetic during cooling in rotational molding thermal condition

This article is part of an ambitious project. The aim is to simulate mechanical properties of rotomolded part from microstructure consideration. Main objective here is to consider metallocene polypropylene crystallization kinetic (PP) during cooling stage in rotational molding. Crystallization kinetic of metallocene PP is so rapid that microscopy cannot help to observe nucleation and growth. Crystallization rate can be estimated by a global kinetic. Given that cooling in rotational molding is dynamic with a constant rate, Ozawa law appears more appropriate. Ozawa parameters have been estimated by differential scanning calorimetry. In rotational molding thermal condition, Avrami index identifies a complex nucleation intermediate between spontaneous and sporadic. Ozawa rate constant is 68 times higher than this obtained for Ziegler–Natta PP. By coupling transformation rate from Ozawa model and a thermal model developed earlier, the difference between theory and experimental is less than 1%. To optimize rotational molding, study has been completed by sensitivity to adjustable parameters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Kinetics and Activation Energy of Magnesium Oxide Hydration

The kinetics of hydration of magnesium oxide (MgO) powder to form magnesium hydroxide (Mg(OH)₂) were measured using isothermal calorimetry at different temperatures, and the morphology of the powders before and after hydration were examined. The hydration kinetics of light‐burned MgO exhibit a hydration rate peak similar to that of portland cement hydration, whereas the hydration kinetics of hard‐burned MgO are comparatively slower at the same temperature, and exhibit a continuously declining hydration rate after the first several minutes of reaction. The hydration kinetics of both light‐burned and hard‐burned MgO can be fit using a boundary nucleation and growth model that has previously been applied to the hydration of portland cement and tricalcium silicate. Activation energy values for MgO hydration were determined from the fitted rate constants and were also measured directly using small temperature excursions according to a recently proposed method. For light‐burned MgO the resulting values are in good agreement and indicate a value of 77 kJ/mol. For the hard‐burned MgO the activation energy values vary considerably depending on temperature and how the activation energy is measured, but are always lower than the value obtained for the light‐burned MgO.     

Kinetic model for thermal dehydrochlorination of poly(vinyl chloride)

In this paper, a novel method for calculating degradation kinetics is presented. The method has been applied to the thermal dehydrochlorination of two different samples of PVC. It has been observed that this dehydrochlorination is complex and involves two different processes. A model that accounts for the entire dehydrochlorination is proposed. This model involves nucleation and growth and diffusion controlled mechanisms. The kinetic parameters are obtained from linear heating rate, isothermal and sample controlled thermal analysis experiments. Kinetic results obtained from the macroscopic thermal analysis measurements demonstrate the correlation between the kinetics of the thermal dehydrochlorination of PVC and the structure of this macromolecule.     

Mineral admixtures in mortars: Quantification of the physical effects of inert materials on short-term hydration

This work is the second part of an overall project, the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The first part presented the separation of the different physical effects responsible for changes in cement hydration when chemically inert quartz powders are used in mortars. This second part describes the development of an empirical model, based on semiadiabatic calorimetry measurements, which leads to the quantification of the enhancement of cement hydration due to the heterogeneous nucleation effect at short hydration times. Experimental results show that not all the admixture particles participate in the heterogeneous nucleation process. Consequently, the concept of efficient surface S_eff is introduced in the model. S_eff is the total admixture surface S (m² of mineral admixture/kg of cement) weighted by a function ξ(p). The efficiency function ξ(p) depends only on the replacement rate p and is independent of time, fineness and type of mineral admixture used. It decreases from 1 to 0: Low replacement rates give an efficiency value near 1, which means that all admixture particles enhance the hydration process. An efficiency value near 0 is obtained for high replacement rates, which indicates that, from the hydration point of view, an excess of inert powder does not lead to an increase in the amount of hydrates compared with the reference mortar without mineral admixture. The empirical model, which is mainly related to the specific surface area of the admixtures, quantifies the variation of the degree of hydration induced by the use of inert mineral admixtures. One application of the model, coupled with Powers' law, is the prediction of the short-term compressive strength of mortars.     

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.     

The effect of gyrolite additive on the hydration properties of Portland cement

The influence of gyrolite additive on the hydration properties of ordinary Portland cement was examined. It was found that the additive of synthetic gyrolite accelerates the early stage of hydration of OPC. This compound binds alkaline ions and serves as a nucleation site for the formation of hydration products (stage I). Later on, the crystal lattice of gyrolite becomes unstable and turns into C–S–H, with higher basicity (C/S ~ 0.8). This recrystallization process is associated with the consumption of energy (the heat of reaction) and with a decrease in the rate of heat evolution of the second exothermic reaction (stage II). The experimental data and theoretical hypothesis were also confirmed by thermodynamic and the apparent kinetic parameters of the reaction rate of C₃S hydration calculations. The changes occur in the early stage of hydration of OPC samples and do not have a significant effect on the properties of cement stone.