The hydration of slag,part 2: reaction models for blended cement

The hydration of slag-blended cement is studied by considering the interaction between the hydrations of slag and Portland cement clinker. Three reaction models for the slag-blended cement are developed based on stoichiometric calculations. These models correlate the compositions of the unhydrated slag-blended cement with the quantities and compositions of the hydration products. The model predictions are further used to calculate some properties of hydrating slag cement pastes, including the molar fractions of products, the water retention, chemical shrinkage and porosities of pastes. The models are validated by comparing the model predictions with the measurements and proven to be successful in quantifying the hydration products, predicting the composition of the main hydration product (C-S-H) and calculating the properties of the hydration process. The model predictions show that as the slag proportions in the blended cement changes, water retention in the hydration products changes only slightly if compared to that of Portland cement, but the chemical shrinkage can vary in a wide range, depending on the slag hydration degree in the cement.     

Micro-structural development of gap-graded blended cement pastes containing a high amount of supplementary cementitious materials

To clarify the strength improvement mechanism of gap-graded blended cements with a high amount of supplementary cementitious materials, phase composition of hardened gap-graded blended cement pastes was quantified, and compared with those of Portland cement paste and reference blended cement (prepared by co-grinding) paste. The results show that the gap-graded blended cement pastes containing only 25% cement clinker by mass have comparable amount of gel products and porosity with Portland cement paste at all tested ages. For gap-graded blended cement pastes, about 40% of the total gel products can be attributed to the hydration of fine blast furnace slag, and the main un-hydrated component is coarse fly ash, corresponding to un-hydrated cement clinker in Portland cement paste. Further, pore size refinement is much more pronounced in gap-graded blended cement pastes, attributing to high initial packing density of cement paste (grain size refinement) and significant hydration of BFS.     

硬化水泥净浆基于纳米压痕的相态识别与水化程度计算

采用纳米原位压痕手段测量硬化水泥净浆中单一相态的代表性微观力学性能,并采用纳米点阵压痕研究各相态的含量。研究对象囊括水灰比为0.3、0.4、0.5的纯水泥净浆和水灰比为0.3情况下含50%、70%矿渣掺量复合体系,共5种配比,以表征它们的相态分布和微观力学性质的异同点。掺矿渣的试件中含有明显多的复合相,因此提出三相模型测算复合相中未水化物的体积分数。此外,提出基于纳米压痕技术计算纯水泥和掺矿渣水泥试件水化程度的方法,结果吻合于热重分析的结果,其中纯水泥净浆中复合相较少,计算得到的水化程度优于对掺矿渣水泥试件的计算。     

Revisiting the microstructure of hydrated tricalcium silicate––a comparison to Portland cement

The microstructures of 0.40 w/s-ratio pastes of tricalcium silicate (C₃S), alite and Portland cement have been studied at the hydration times 24 h and 1 month. A field-emission SEM (FE-SEM) was used to obtain high-resolution backscattered electron images. Comparison revealed no microstructural differences between C₃S and alite, but there were considerable differences in microstructure between C₃S and Portland cement pastes. The microstructure of the C₃S paste was simpler than that of the Portland cement, and could be described by a few characteristic features. Distribution of the reaction products differed substantially in the two systems. While hollow shells (Hadley grains) were a prominent feature of the Portland cement paste, their occurrence was more limited in the C₃S and alite pastes. Hollow shells were restricted to grains smaller than about 5 μm in the C₃S and alite pastes, and gapped hollow shells were not a common feature.     

The hydration properties of pastes containing municipal solid waste incinerator fly ash slag

This study investigated the hydration properties of Type I, Type III and Type V cements, mixed with municipal solid waste incinerator fly ash, to produce slag-blended cement pastes. The setting time of slag-blended cement pastes that contained 40% slag showed significantly retardation the setting time compared to those with a 10% or even a 20% slag replacement. The compressive strength of slag-blended cement paste samples containing 10 and 20% of slag, varied from 95 to 110% that developed by the plain cement pastes at later stages. An increased blend ratio, due to the filling of pores by C-S-H formed during pozzolanic reaction tended to become more pronounced with time. This resulting densification and enhanced later strength was caused by the shifting of the gel pores. It was found that the degree of hydration was slow in early stages, but it increased with increasing curing time. The results indicated that it is feasible to use MSWI fly ash slag to replace up to 20% of the material with three types of ordinary Portland cement.     

A method for predicting the alkali concentrations in pore solution of hydrated slag cement paste

The alkalinity of the pore liquid in hardened cement paste or concrete is important for the long-term evaluation of alkali-silica reaction (ASR) expansion and corrosion prevention of steel bar in steel reinforced structures among others. It influences the reactivity of supplementary cementitious materials as well. This paper focuses on the alkali binding in hydrated slag cement paste and a method for predicting the alkali concentrations in the pore solution is developed. The hydration of slag cement is simulated with a computer-based model CEMHYD3D. The amount of alkalis released by the cement hydration, quantities of hydration products, and volume of the pore solution are calculated from the model outputs. A large set of experimental results reported in different literatures are used to derive the alkali-binding capacities of the hydration products and practical models are proposed based on the computation results. It was found that the hydrotalcite-like phase is a major binder of alkalis in hydrated slag cement paste, and the C?CS?CH has weaker alkali-binding capacity than the C?CS?CH in hydrated Portland cement paste. The method for predicting the alkali concentrations in the pore solution of hydrated slag cement paste is used to investigate the effects of different factors on the alkalinity of pore solution in hydrated slag cement paste.     

Mitigating the effects of system resolution on computer simulation of Portland cement hydration

CEMHYD3D is an advanced, three-dimensional computer model for simulating the hydration processes of cement, in which the microstructure of the hydrating cement paste is represented by digitized particles in a cubic domain. However, the system resolution (which is determined by the voxel size) has a prominent influence on the simulation results and, thus, is difficult to choose a priori. In this paper, it is shown that the effects of system resolution on the simulation results are mainly due to the lack of considerations of the diffusion-controlled reactions in the model. A new concept “hydration layer” is proposed for mitigating the effects of system resolution on the model predictions. By performing simulations with different system resolutions, the robustness of the improved model is demonstrated. Comparisons of model predictions with experimental measurements further demonstrate that the use of hydration layer can successfully mitigate the bias brought by the system resolution.     

Strain and thermal expansion coefficients of various cement pastes during hydration at early ages

Cement pastes undergo elevated temperature histories due to hydration heat liberation at early ages. Thermal expansion coefficients of cement paste and concrete change with age, showing a decrease after mixing, a subsequent minimum and then a gradual increase. These changes contribute to thermal strain. In this study, effects of water–cement ratio and cement type on volume changes in early-age cement pastes were experimentally examined using a newly developed apparatus capable of simultaneously determining both thermal expansion coefficient and total strain of cement pastes. The dependence of the thermal expansion coefficient on hydration was affected by water–cement ratio, cement type, elevated temperature history and particularly by the free water content of the cement pastes, while the relationship between thermal expansion coefficient and free water content varied with water–cement ratio. A notable increase in thermal expansion coefficient at early ages was observed when water–cement ratio was low and alite content in cement was high. At a water–cement ratio of 0.30, low-heat Portland cement paste resulted in a small total strain while moderate-heat and ordinary Portland cement pastes showed larger strains. Because no particular difference was observed in the thermal strains, shrinkage in the low-heat Portland cement paste was attributed to autogenous strain. At a water–cement ratio of 0.40, self-desiccation had a significant influence upon autogenous shrinkage and dependence of thermal expansion coefficient on hydration, and the effect of the mineral composition of cements was notable. However, for cement pastes with a water cement ratio of 0.55, no significant effects of self-desiccation were observed, probably because considerable excess water was present.     

Microstructural Development of Hydrating Portland Cement Paste at Early Ages Investigated with Non-destructive Methods and Numerical Simulation

Microstructure development of hydrating cement paste at early ages is not only an indicator of the reactivity of cement, but also a factor on the workability of fresh concrete. In this study, the microstructure development of hydrating cement paste at early ages is investigated with non-destructive methods including ultrasound P-wave propagation velocity measurement and non-contact electric resistivity tests, together with conventional needle penetration depth and calorimetry tests. The hydration process and microstructural development of the cement paste is modeled with the three-dimensional computer model CEMHYD3D. Evolution of microstructural parameters including the volumetric fraction of phases and their percolation status are analyzed by using the results of the numerical simulation. Microstructural mechanisms of the two non-destructive techniques (ultrasound pulse propagation and electric resistivity measurements) are discussed. The main findings of this study are that the velocity of ultrasound P-wave propagation in hydrating cement paste is a function of the propagation routes in the material and inter-particle forces. The electric resistivity is controlled by the ionic concentrations in the pore solution during the early hours and later by the connectivity of pores. A model for the development of ultrasound P-wave propagation velocity is also proposed.     

硬化水泥浆体弹性模量细观力学模型

应用复合材料力学理论和有孔介质力学(Poromechanics)理论建立了一个描述硬化硅酸盐水泥浆体弹性模量的细观力学模型, 将硬化水泥浆体从不同尺度上划分为4个层次, 即C-S-H凝胶、 水泥水化产物、 水泥浆体骨架和水泥浆体, 分别应用不同的细观力学模型予以描述: 将C-S-H视为饱和的有孔介质; 应用Mori-Tanaka模型描述水泥水化产物的弹性性质; 应用三相模型(Three-phase model)模拟水泥浆体骨架的有效弹性模量; 最后, 再次应用Mori-Tanaka模型和有孔介质理论, 计算水泥浆体的排水和不排水弹性模量(Drained and undrained elastic moduli)。该模型所需要的参数为水泥浆体各个组成部分的自身弹性性质, 使用方便。通过预测文献中的实测结果, 证明了该模型的有效性。      

Modeling the influence of limestone filler on cement hydration using CEMHYD3D

The ASTM C150 standard specification for Portland cement now permits the cement to contain up to 5% of ground limestone. While these and much higher levels of limestone filler substitution have been employed in Europe and elsewhere for many years, changing the ASTM standard has been a slow process. Having computational tools to assist in better understanding the influence of limestone additions on cement hydration and microstructure development should facilitate the acceptance of these more economical and ecological materials. With this in mind, the CEMHYD3D computer model for cement hydration has been extended and preliminarily validated for the incorporation of limestone at substitution levels up to 20% by mass fraction. The hydration model has been modified to incorporate both the influence of limestone as a fine filler, providing additional surfaces for the nucleation and growth of hydration products, and its relatively slow reaction with the hydrating cement to form a monocarboaluminate (AFmc) phase, similar to the AFm phase formed in ordinary Portland cement. Because a 20% limestone substitution substantially modifies the effective water-to-cement ratio of the blended mixtures, the influence of limestone substitutions on hydration rates is observed to be a strong function of water-to-solids ratio (w/s), with significant acceleration observed for lower (e.g., 0.35) w/s, while no discernible acceleration is observed for pastes with w/s = 0.435.     

Hydration characteristics of municipal solid waste incinerator bottom ash slag as a pozzolanic material for use in cement

This study investigated the pozzolonic reactions and engineering properties of municipal solid waste incinerator (MSWI) bottom ash slag blended cements (SBC) with various replacement ratios. The 90-day compressive strengths developed by SBC pastes with 10% and 20% cement replacement by slags generated from the bottom ash were similar to that developed by ordinary Portland cement pastes. Thermal analyses indicated that the hydrates in the SBC pastes were mainly portlandite (Ca(OH)₂) and calcium silicate hydrate (C–S–H) gels, similar to those found in ordinary Portland cement paste. It is also indicated that the slag reacted with Ca(OH)₂ to form C–S–H. The average length (in terms of the number of Si molecules) of linear polysilicate anions in C–S–H gel, as determined by ²⁹Si nuclear magnetic resonance, increased in all the SBC pastes with increasing curing age, which outperformed that of ordinary Portland cement at 90 days. It can thus be concluded from the study results, that municipal solid waste incinerator bottom ash can be processed by melting to obtain reactive pozzolanic slag, which may be used in SBC to partially replace the cement.     

超细矿渣粉对硅酸盐水泥性能和微观结构的影响

通过掺入不同量的超细矿渣粉,研究其对普通硅酸盐水泥凝结时间、标准稠度用水量以及水泥胶砂流动性和强度的影响。结果表明,水泥浆体的初凝、终凝时间在矿渣粉掺量为5%(质量分数,下同)时有所缩短,而随着超细矿渣粉掺量的增加,初凝时间都有所延长,在掺量为20%时初凝时间最长。然而终凝时间的变化不大,只有掺量为30%时稍有延长;水泥的标准稠度用水量先减少后增加,在掺量为20%时最小;随着超细矿渣粉掺量的增大,水泥胶砂的各龄期抗折强度、3d抗压强度不断提高,7d、28d抗压强度在掺量为20%时达到最大值,之后有所降低。掺入超细矿渣粉后,能通过填充以及与水泥水化产物氢氧化钙发生反应,使水泥中氢氧化钙含量明显降低,水泥微观结构更加密实。     

The early-age short-term creep of hardening cement paste: AC impedance modeling

Impedance spectra were monitored at early ages on hydrating Portland cement pastes subjected to a sustained load. The pastes were prepared with two different water-cement ratios (0.35 and 0.50). The experiments were conducted in a controlled chamber maintained at (96±2)% relative humidity. The three ages at loading investigated were 18, 24 and 30 hrs. Real-time changes in paste microstructure due to sustained load were followed through the coupling of an AC impedance frequency analyzer with a miniature loading system. Cement paste specimens were in the form of T-shaped columns with a minimum thickness value (for the web and flanges) less than 1.25 mm. The impedance analysis included an assessment of the relevance of the high frequency arc depression angle to an understanding of the creep and shrinkage behavior of cement paste. Electrical models were developed in order to predict the creep coefficient of normal (w/c = 0.50) and high strength (w/c = 0.35) cement pastes from early age data.     

In situ observation of cement particle growth during setting

The evolution of the cement paste microstructure is a complex phenomenon, which governs the setting of concrete. During setting, cement particles tend to flocculate and agglomerate due to their surface charges, attraction forces and variety of other reasons. However, it is still unclear how these developments in cement paste microstructure influence the setting of concrete. In order to better understanding the correlation between cement paste microstructure development and corresponding concrete behavior during setting, in situ observations on cement particles behaviors are essential. In this study, in situ observations on microstructure development of fresh pastes were made on three different cement pastes by using a newly developed Quantomix WETSEM? capsuling system in a conventional scanning electron microscope. Further, by employing image analysis techniques on the captured images, microstructure changes of these cement pastes were investigated quantitatively. During the study single and multiple particle growth, hydration rate of different cement particles, and total solids growth in association with various solid concentrations and corresponding heat of hydration were studied quantitatively and as well as qualitatively. The purpose of this quantitative study is to investigate the feasibility of using such a new technology to evaluate the factors influencing the cement paste microstructure evolutions during setting.     

Optimization of calcium chloride content on bioactivity and mechanical properties of white Portland cement

This research investigates the optimization of calcium chloride content on the bioactivity and mechanical properties of white Portland cement. Calcium chloride was used as an addition of White Portland cement at 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10% by weight. Calcium chloride was dissolved in sterile distilled water and blended with White Portland cement using a water to cement ratio of 0.5. Analysis of the bioactivity and pH of white Portland cement pastes with calcium chloride added at various amounts was carried out in simulated body fluid. Setting time, density, compressive strength and volume of permeable voids were also investigated. The characteristics of cement pastes were examined by X-ray diffractometer and scanning electron microscope linked to an energy-dispersive X-ray analyzer. The result indicated that the addition of calcium chloride could accelerate the hydration of white Portland cement, resulting in a decrease in setting time and an increase in early strength of the pastes. The compressive strength of all cement pastes with added calcium chloride was higher than that of the pure cement paste, and the addition of calcium chloride at 8 wt.% led to achieving the highest strength. Furthermore, white Portland cement pastes both with and without calcium chloride showed well-established bioactivity with respect to the formation of a hydroxyapatite layer on the material within 7 days following immersion in simulated body fluid; white Portland cement paste with added 3%CaCl₂ exhibited the best bioactivity.     

Drying-induced changes in the structure of alkali-activated pastes

Drying of cement paste, mortar, or concrete specimens is usually required as a pre-conditioning step prior to the determination of permeability-related properties according to standard testing methods. The reaction process, and consequently the structure, of an alkali-activated slag or slag/fly ash blend geopolymer binder differs from that of Portland cement, and therefore there is little understanding of the effects of conventional drying methods (as applied to Portland cements) on the structure of the geopolymer binders. Here, oven drying (60 °C), acetone treatment, and desiccator/vacuum drying are applied to sodium silicate-activated slag and slag/fly ash geopolymer pastes after 40 days of curing. Structural characterization via X-ray diffraction, infrared spectroscopy, thermogravimetry, and nitrogen sorption shows that the acetone treatment best preserves the microstructure of the samples, while oven drying modifies the structure of the binding gels, especially in alkali-activated slag paste where it notably changes the pore structure of the binder. This suggests that the pre-conditioned drying of alkali activation-based materials strongly affects their microstructural properties, providing potentially misleading permeability and durability parameters for these materials when pre-conditioned specimens are used during standardized testing.     

Assessing the effect of biomass ashes with different finenesses on the compressive strength of blended cement paste

This study assesses the effect of biomass ashes with different finenesses on the compressive strength of blended cement paste. rice husk ash (RHA), palm oil fuel ash (POFA) and river sand (RS) were ground to obtain two finenesses: one was the same size as the cement, and the other was smaller than the cement. Type I Portland cement was replaced by RHA, POFA and RS at 0%, 10%, 20%, 30% and 40% by weight of binder. A water to binder ratio (W/B) of 0.35 was used for all blended cement paste mixes. The percentages of amorphous materials and the compressive strength of the pastes due to the hydration reaction, filler effect and pozzolanic reaction were investigated. The results showed that ground rice husk ash and ground palm oil fuel ash were composed of amorphous silica material. The compressive strength of the pastes due to the hydration reaction decreased with decreasing cement content. The compressive strength of the pastes due to the filler effect increased with increasing cement replacement. The compressive strengths of the pastes due to the pozzolanic reaction were nonlinear and were fit with nonlinear isotherms that increased with increasing fineness of RHA and POFA, cement replacement rate and age of the paste. In addition, the model that was proposed to predict the percentage compressive strength of the blended cement pastes on the basis of the age of the paste and the percentage replacement with biomass ash was in good agreement with the experimental results. The optimum replacement level of rice husk ash and palm oil fuel ash in pastes was 30% by weight of binder; this replacement percentage resulted in good compressive strengths.     

Near-infrared spectroscopy investigation on the hydration degree of a cement paste

Near-infrared spectroscopy is a fast and easy-to-perform technique characterized by high sensitivity regarding water containing systems and for this reason it is a suitable tool for investigating structural modifications of hydrating cementing materials, even if the lack of knowledge in this field makes the interpretation of NIR vibrational bands very difficult. In this paper, the NIR spectrum of a hydrated ordinary Portland cement is extensively investigated and an interpretation of the different bands is proposed on the basis of both experimental evidence and reference to literature. The obtained results were applied to the investigation of cement hydration lasting up to 28 days, analyzing the variations detectable in the shape of the spectrum as the reaction went on. The degree of this variation, quantified through area calculations of the main significant bands, revealed a broad agreement with the degree of hydration of the paste measured by thermal methods. The findings of this research supply a solid foundation for future in-field application of NIR spectroscopy, for example, for investigations on cements with different hydration behavior, or to evaluate the effect of additives on cement pastes and, at a further level, for cement quality control.     

Influence of alkalis on porosity percolation in hydrating cement pastes

Loss-on-ignition (LOI) measurements and low temperature calorimetry (LTC) are used to study the properties of hydrating cement pastes with various quantities of alkalis. In addition to the well-known acceleration of early age hydration and “retardation” of later age hydration, the alkalis are observed to have a significant effect on the percolation of the porosity in the hydrating systems, as assessed using the LTC technique. At equivalent degrees of hydration, the capillary pores in cement pastes with sufficient added alkalis may depercolate while those in lower alkali cement pastes remain percolated. A simple dissolution/precipitation three-dimensional microstructural model is applied to examine the potential effects of hydration product morphology (random, needles, and plates or laths) on pore space percolation. The model suggests that the observed experimental results could be consistent with the higher alkali levels modifying the morphology of the C–S–H gel to produce more lath-like hydration products, as has been observed by others previously using electron microscopy. Potential implications for the transport properties and durability of these materials are discussed.