Modelling early age hydration kinetics of alite

The modelling platform μic [1] has been used to investigate the mechanisms occurring during the hydration of alite. It is shown that it is possible to obtain a good simulation of the hydration kinetics through the implementation of two mechanisms: a dissolution mechanism combined with nucleation and growth of products. The dissolution rate is varied according to the ratio β, between the ion activity product and the equilibrium solubility product according the theory published by Juilland et al. [2]. The solution concentrations are computed directly from the amount of alite dissolved taking into account the amount of water present and the amount of products formed, with activities and complex ion formation calculated according to standard methods. Saturation index calculations are implemented to compute the time of precipitation of C–S–H and portlandite (CH) individually. For the main heat evolution peak, the rate controlling mechanism switches to a modified form of boundary nucleation and growth. C–S–H grows in a diffuse manner in which the density of packing of the C–S–H phase increases with hydration [3]. The rate of heat evolution obtained from the simulations is compared with isothermal calorimetry data and good agreement is found.     

Evolution of elastic behavior of alite paste at early hydration stages

Elastic behavior is an important aspect of fresh cement-based materials. In this paper, the elasticity development of fresh pure alite paste within 5 hours was monitored in situ by small amplitude oscillation shear. Isothermal microcalorimetry, X-ray diffraction, scanning electronic microscopy, ¹H nuclear magnetic resonance, zeta potential measurements were used to investigate the underlying mechanisms. It was found that the evolution of storage modulus can be characterized by three different stages. The first stage stems from the compression of electrical double layer and the slight increase of solid volume fraction; the second stage is only controlled by the colloidal interaction; and the third stage is associated to the significant growth of solid volume fraction, the enhancement of short-range attraction and the rigidification of calcium silicate hydrate (CSH) network. Moreover, the relationship between the formation of CSH and the growth of elasticity was also quantified.     

Silicate polymerization during the hydration of alite

The influence of admixtures and curing temperature on silicate polymerization during the hydration of alite was studied. Trimethylsilyl derivatives were separated by gel permeation chromatography. The major species identified in the hydrated pastes were dimer, linear pantamer, and linear octamer; at later ages, particularly at higher temperature, higher polymers are formed. A polymerization scheme is proposed. The effect of admixtures on silicate polymerization exactly parallels their effects on hydration.     

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.     

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.     

The influence of sodium and potassium hydroxide on alite hydration: Experiments and simulations

The basic nature of alkali hydroxides (NaOH, KOH) when added to mixing water, increases the pH in proportion to the level of salt addition. For alite (impure tricalcium silicate; MIII-Ca₃SiO₅) hydration, this pH increase accelerates the rate of hydration and reduces the duration of the induction, acceleration and deceleration regimes. This study evaluates alite hydration in solutions of varying compositions and alkalinities (0.1 M, 0.2 M and 0.5 M NaOH and KOH) in context of their heat release behavior and analysis of the solid/liquid phases. The modeling platform, μic, is used to simulate, describe and discriminate the impact of the pore solution chemistry and reaction product formation parameters on alite hydration (Bishnoi and Scrivener, 2009 [1]). Numerical predictions of the solid and liquid phase compositions and the heat release response show good agreement with experimental determinations. The simulations indicate that the effects up to the end of the induction period follow directly from a change in the pore solution composition under a solution controlled dissolution mechanism, which leads to the faster precipitation of portlandite. The changes in the main heat evolution peak appear to be related to an increase in the nucleation density of C–S–H in alkali hydroxide solutions. Examination under the SEM did not indicate significant difference in C–S–H morphology and composition in the presence of NaOH/KOH.     

碱对阿利持—硫铝酸盐水泥熟料矿物形成及水泥性能的影响

以石灰石、粉煤灰、粘土、石膏等为原料,研究了K2O、Na2O对阿利特-硫铝酸盐水泥熟料矿物形成及性能的影响,结果表明,少量碱能改善水泥生料的易烧性,促进fCaO的吸收,过多的碱使C4A3∧-S矿物难以形成;当碱掺加量约1.2%时,NaO有利于C3S矿物的形成,并提高水泥的早期强度,而K2O则使C3S的形成量减少,水泥的强度降低;掺加碱使水泥的凝结时间延长。     

Influence of the reactivity of the amorphous part of mechanically activated alite on its hydration kinetics

The hydration of one mechanically activated alite passing through different drying procedures is examined by heat flow calorimetry and quantitative in-situ XRD analysis. The reactivity of the alite powders is strongly affected by the drying technique. It is shown that the reactivity of the amorphous part of the activated alite sample is particularly affected. Due to the fast initial dissolution of the amorphous “alite” part, the hydration progression is speeded up significantly. However, if the hydration is not speeded up by the amorphous “alite” dissolution, as in the case of surface passivation, the heat released until the transition to the deceleration period will increase. It is discussed that a crystalline alite dissolution by etch pit opening could increase the reactive alite surface and therefore increase the reaction degree at the transition to the deceleration period.     

Understanding the effect of MPEG-PCE's microstructure on the adsorption and hydration of OPC

Polycarboxylic ethers or polycarboxylate (PCEs) are one of the most employed superplasticizers in construction. However, the understanding of their microstructure–property relationship is still incomplete. Recently, a theoretical model was proposed that relates the microstructure–conformation of the PCE to its effect on the adsorption onto cement particles and cement hydration time. In this work, the effects of a wide range of PCEs with different side chain lengths (P = 5, Group 1; P = 20, Group 2; and P = 45 and 113, Group 3) having flexible backbone worm conformation except one which has stretch backbone worm conformation (P = 113) were experimentally investigated for their effect on adsorption and cement hydration. It is found that PCEs from Group 1 show electrostatic repulsion as dispersing mechanism, unlike PCEs from Groups 2 and 3. Furthermore, the prediction of the theoretical model is also assessed for all the studied PCEs. Only Group 1 PCEs (shortest side chains) showed deviation from the theoretical predictions, and it was attributed to their different behaviors from the standard PCEs for which the theoretical model was developed.     

Studying nucleation and growth kinetics of alite hydration using μic

This paper investigates the applicability of nucleation and growth mechanisms to the hydration of alite. Various possible mechanisms of nucleation and growth were simulated using the recently-developed microstructural modelling platform μic. Comparison with the Avrami equation and the boundary nucleation model demonstrate the limitations of these equations. Experimental measurements of the rates of hydration of alite powders with different particle size distributions were then simulated with a boundary nucleation and growth model in μic. The results show that while the nucleation and growth of C–S–H having bulk densities in the currently accepted range can explain the acceleration during the first few hours of hydration, it cannot explain the later deceleration. It was also found that the resistance to flow of ions offered by the layer of hydrates forming over the surface of the alite particles (diffusion control) cannot explain the deceleration. The deceleration could be reproduced when C–S–H was assumed to be loosely packed in the beginning with its density of packing increasing with hydration. It is proposed that during the early hours of hydration a loosely-packed C–S–H fills a large fraction of the microstructure and the further development of its microstructure occurs due to an increase in its packing.     

冷却速度对熟料中阿利特晶型影响研究

在相同煅烧条件下，同一个样品分别经过室温冷却、冷风下快速冷却和在炉子中慢速冷却制得不同熟料。利用X射线衍射技术分析不同冷却速度对熟料中阿利特晶型的影响，实验结果表明：室温冷却和快速冷却制得的熟料中阿利特晶型为M3型，慢速冷却制得的熟料中阿利特晶型为M1型。     

Effect of polysaccharides on the hydration of cement paste at early ages

This work deals with the relative efficiency of polysaccharides and their influence on cement hydration. Several parameters such as the structure, concentration, average molecular weight, and soluble fraction value of polysaccharides were examined. Cement hydration was monitored by isothermal calorimetry, thermogravimetry (TGA), and Fourier transform infrared (FTIR) spectroscopy. Results clearly show that retardation increases with higher polysaccharide-to-cement weight ratio (P/C). Low-molecular-weight starch showed enhanced retarding effect on the hydration of cement. The retardation effect of polysaccharides is also dependent on the composition of cement.     

Effect of pressure on early hydration of class H and white cement

The change in viscosity of cement slurry with temperature and pressure can be predicted by assuming that hydration can be treated as an activated process and that a given viscosity corresponds to a fixed degree of reaction. For Class H and White cements, chemical shrinkage experiments indicate that the activation energy is 33.8 kJ/mole and rheological measurements yield an activation volume of −30 cm³/mole. With these parameters, it is possible to predict the limit of pumpability of the slurry (which corresponds to a viscosity of about 2.5 Pa s) for arbitrary temperature and pressure cycles. This method of prediction requires that the physics of the process remain the same, but simply change in rate; therefore, the range of applicability is expected to be limited to temperatures below about 100 °C, since new phases occur at higher temperatures.     

粉磨方式对硅酸盐水泥颗粒和 早期水化行为的影响

采用同一批熟料,通过辊压机终粉磨、辊压机—球磨机联合粉磨和实验室球磨三种粉磨方式粉磨。试验发现,在细度相同时,不同粉磨方式制成的水泥颗粒特性具有较大的差异。水泥颗粒形状、形貌对水泥的早期水化行为(如:标准稠度、凝结时间、流动度和水化热)影响较大,但1d的水化总放热量却相差不大。     

Effect of recrystallization on the characters of alite in Portland cement clinker

Alite, as well as belite, undergoes recrystallization during clinkering and grows large at the expense of small crystals. The growth is more noticeable in the direction perpendicular to (0001) than in the direction parallel to it. The crystals that are initially basal tablets become massive granules with the pyramidal faces well-developed. The recrystallization causes a considerable decrease in the concentration of the foreign ions in solid solution and thus occasionally lowers the crystal symmetry of elite to triclinic. These observations give evidence that the chemical composition of alite depends on its kinetics of crystallization from the interstitial melt.     

水泥水化热对混凝土早期开裂的影响

对于预拌混凝土应用过程出现的早期开裂现象，有些混凝土专家归因于水泥比表面积太大和早期强度太高；而水泥界则认为，我国目前水泥的比表面积和早期强度并不比国外的高，混凝土的早期开裂主要是混凝土施工和养护不当所致。笔者认为，必须通过混凝土生产者和水泥生产商沟通，对早期裂缝的成因达成共识，在水泥生产、混凝土配制及施工养护等环节共同采取措施加以解决。“高强早强、高比表面积”及“水泥磨得太细”，这些都是表面现象，其本质是早期水化热太高及混凝土温度应力大的缘故。     

Effect of early hydration temperature on hydration product and strength development of magnesium phosphate cement (MPC)

This paper investigates the effect of early hydration temperatures on hydration products and strength development of magnesium phosphate cement (MPC). MPC paste specimens with borate contents of 3%, 6%, 9% and 12% are prepared and cured in different air temperatures and in the adiabatic condition. The internal hydration temperatures are measured by pre-embedded temperature probes. MPC samples with different hydration temperatures are also obtained by using thin slice samples. The hydration products in MPC samples with different hydration temperatures are analyzed by X-ray diffractometer (XRD) and scanning electron microscope (SEM) and the strength development is also measured. The results show that NH₄MgPO₄·6H₂O is the major hydration product and beneficial to strength development of MPC at hydration temperature below 70 °C. NH₄MgPO₄·H₂O is another major product, which significantly decreases the strength, when the temperature is higher than a critical temperature between 70 °C and 75 °C. NH₄MgPO₄·H₂O can directly form in the MPC paste, and comes from the decomposition of NH₄MgPO₄·6H₂O when the temperature is above 75 °C. With temperature elevation and duration extension, NH₄MgPO₄·6H₂O decomposes rapidly, and even entirely when the temperature is above 100 °C. The borate content has no effect on the types of major hydration products and the critical temperature.     

分别粉磨与共同粉磨对石灰石硅酸盐水泥颗粒分布及水化性能的影响

试验采用分别粉磨工艺和共同粉磨工艺配制石灰石硅酸盐水泥,分析了石灰石和熟料的粉磨特性差异,并研究了在单位能耗相同情况下,两种粉磨制度下石灰石硅酸盐水泥各组份颗粒分布及水化情况。结果表明,分别粉磨制度能合理控制石灰石硅酸盐水泥颗粒的分布,使熟料处于更细的颗粒范围内,提高了粉磨效率;细的石灰石粉能促进水泥的早期水化反应,而中后期的水化速率主要取决于熟料颗粒的细度;采用合理的分别磨粉工艺配制的石灰石硅酸盐水泥,在相同龄期下,其水化产物含量较多,水化产物之间的连结更紧密,水泥石整体结构更密实。     

利用高铝煤矸石和盐石膏低温烧制阿利特—硫铝酸盐水泥熟料的研究

实验室及工业性试验研究结果表明,利用高铝煤矸石和盐石膏等工业废渣,低温烧制的阿利特－硫铝酸盐水泥熟料,不仅使水泥具有凝结硬化快,早后期强度的均高于硅酸盐水泥的特点,而且具有微膨胀和抗蚀性强的特性,文中对熟料率值和矿物组成算式进行了修正,通过分析认为,在实际生产中控制掺入生料中的石膏较配方设计高出20％左右,熟中C4A2S含量为4－6％,煅烧温度控制在1250－1300度,同时指出了影响水泥质量的工艺隐患。     

The effect of temperature on the hydration rate and stability of the hydration phases of metakaolin-lime-water systems

The paper presents the results of a study carried out to determine the effect of curing temperature on the kinetics of reaction of a metakaolin (MK)/lime mixture. MK and analytical grade Ca(OH)₂ were mixed in a ratio of 1:1 by weight and with a water/binder ratio of 2.37. Specimens were cured at 20 and 60 °C. In the first case, the curing time varied from 2 h up to 180 days and, in the second case, from 2 h up to 123 days. A mathematical model was applied to calculate the rate constant for the hydration reaction. The identity and the amount of the phases present were determined from thermal analysis (TG and DTA) data. The results showed that the rate constant for the samples cured at 60 °C was 68 times greater than the rate constant at 20 °C for the same curing period (up to 9 days). At 20 °C, the sequence of appearance of the hydrated phases was C-S-H, C₂ASH₈ and C₄AH₁₃; while at 60 °C, the sequence was C-S-H, C₂ASH₈, C₄AH₁₃ and hydrogarnet (C₃ASH₆). There is no evidence of further C₂ASH₈ and C₄AH₁₃ transformation into hydrogarnet in the mixture studied for 123 days at 60 °C.