Impact of zeta potential of early cement hydration phases on superplasticizer adsorption

The zeta potential of early hydration products of cement was found to be a key factor for superplasticizer adsorption. A highly positive zeta potential results in a strong superplasticizer adsorption whereas a negative zeta potential does not allow adsorption. Synthetic ettringite precipitated from solution shows a highly positive zeta potential, hence it adsorbs great amounts of negatively charged superplasticizer. Monosulfate (AF_m) has a less positive zeta potential. Therefore, it adsorbs smaller amounts of superplasticizers. For syngenite, portlandite and gypsum, the zeta potential is around zero or negative. These phases do not adsorb superplasticizers. Consequently, a hydrating cement grain is best represented by a mosaic structure, with superplasticizer molecules mainly adsorbed on ettringite and some on monosulfate and C-S-H nucleated at surface.     

Effects of the clinker - gypsum grinding temperature upon early hydration of Portland cement

The temperature at which Portland clinker and gypsum are ground together to produce Portland cement is shown to influence the subsequent early hydration behaviour. Raising the grinding temperature from 90°C to 130°C and thence to 170°C has resulted in increased ettringite being present at all the hydration times examined up to two hours. The results have been interpreted on the basis of a through solution mechanism involving primarily the reaction of tricalcium aluminate from the cement clinker component with available soluble Ca²⁺ and SO₄^2? ions in the aqueous medium.     

Influence of the availability of calcium on the hydration of tricalcium aluminate (C3A) in seawater-mixed C3A–gypsum system

This work examined the effects of seawater (SW) on the hydration of tricalcium aluminate (C₃A) in C₃A–gypsum and C₃A–gypsum–Ca(OH)₂ systems through the characterization of hydration heat release, the evolution of aqueous phase composition and hydration products with the hydration time. It was found that SW increased the dissolution driving force of C₃A and solubility of gypsum, which accelerated the early hydration of C₃A and the formation of ettringite (AFt), leading to a higher hydration degree of C₃A at an early age compared with the deionized (DI) water–mixed pastes. After gypsum depletion to form AFt, and in the absence of Ca(OH)₂, the formation of chloroaluminate hydrates was slower due to the insufficient Ca resulted in an accumulation of Al in solution. This would delay the subsequent transformation of AFt to monosulfate (SO₄–AFm) and the formation of hydrogarnet (C₃AH₆), which would further reduce the hydration degree of the C₃A at the later ages. However, in the presence of Ca(OH)₂, the hydration degree of C₃A–gypsum–Ca(OH)₂ at later ages was increased, which was similar to that of the corresponding DI pastes. This can be inferred that the amount of Ca available in SW-mixed cement concrete can affect the hydration degree of C₃A in cement.     

玻璃粉水泥浆的初期水化产物和浆体结构

采用SEM、XRD研究了玻璃粉水泥浆的初期水化产物、浆体结构.并用化学结合水量和有效结合水法来定性和定量分析玻璃粉对水化初期复合体系及水泥的促进或抑制作用以及作用程度.研究表明:在水化反应初期(1d内),因为玻璃粉的掺入既由此而产生的稀释作用使有效水灰比增加而产生的对水泥熟料水化的促进作用,因此,硅酸盐水泥熟料的水化程度较高,但从整体来看,大掺量(50%)的玻璃粉延缓了复合胶凝材料总水化程度;水化开始(6 h~1 d)时,水化反应开始加速进行,水化产物的数量迅速增加,主要为纤维状CSH凝胶、针棒状钙矾石晶体和Ca(OH)2,这些水化产物彼此间相互搭接、交错生长,部分未水化的水泥颗粒镶嵌其中,并将玻璃粉粘结成整体,构成体系骨架.     

Very High Volume Fly Ash Cements. Early Age Hydration Study Using Na2SO4 as an Activator

The early age ambient temperature hydration of a hybrid cement formulation containing very high volumes of coal fly ash (~80% by dry mass) and activated by Na₂SO₄ is presented. The Na₂SO₄ salt acts as a safe and convenient in situ source of alkali to activate fly ash glassy phases without undesirable effects on cement clinker hydration. Comparison to a reference paste with gypsum instead of sodium sulfate revealed that Na₂SO₄ reduced setting times, shortened the induction period, and increased early alite hydration and compressive strength development, but also restricted ettringite formation. When replacing the active fly ash component for milled sand of a similar particle size, the Na₂SO₄‐activated pastes set even quicker, no ettringite was observed, and early strengths were considerably reduced. Possible reaction mechanisms in the hybrid pastes are discussed.     

掺煅烧石膏水泥早期水化过程的研究

利用DTA，XRD，IR测定水泥水化浆体的化学结合水和Ca(OH)2的生成量，研究了煅烧石膏，二水石膏对硅酸盐水泥早期水化过程的影响。结果表明：在水化龄期相同时，掺煅烧石膏水泥浆体中水化产物同掺二水石膏相比，Ca(OH)2生成量大；在1d前无钙钒石（AFt)生成，结合水量在1d前，前者高于后者，而1d后则相反。指出了煅烧石膏加快水泥水化产物形成的机理在于：由于它的溶解度较低，在水泥水化初期（1d前），存在于水泥中的铝酸盐相不能形成AFt，从而减缓了AFt对水泥水化的延缓作用，加速了整个熟料矿物相的水化。     

Analysis of C3A hydration using soft X-rays transmission microscopy: Effect of EVA copolymer

The hydration of pure C₃A (Ca₃Al₂O₆) in calcium hydroxide-gypsum saturated solution was analyzed using soft X-ray microscopy. The images show the presence of at least two different types of ettringite crystals during the first 4 h of hydration. They differ in morphology and growing rate. When poly(ethylene-co-vinyl acetate) (EVA) is present, there is a significant change in the hydration kinetics and morphology of the hydration products. EVA particles inhibited or even prevented the formation of ettringite crystals during the early stage of hydration. A cloud of small, bright particles are observed concentrated around the hydrating C₃A grains. The particles are most likely to be a product of reaction between EVA and inorganic species in solution.     

Contribution to the hydration of expansive cement on the basis of metakaolinite

The study of hydration of expansive cement prepared from 64% portland cement clinker, 23% metakaolinite and 13% CaSO₄.2H₂O is described. It was found that in the course of a 10-day hydration period, all the gypsum entered the reaction with the formation of ettringite. In 7–10 days, after the termination of the expansion processes, typical stalk-like crystals were transformed into leaf-shaped or other formations. Ettringite was identified even after 4 months of hydration. Monosulphate (3CaO.Al₂O₃.CaSO₄.12H₂O) was found in none of the investigated high-expansion cement paste samples.     

Hydration of calcium sulfoaluminate cements — Experimental findings and thermodynamic modelling

Calcium sulfoaluminate cements (CSA) are a promising low-CO₂ alternative to ordinary Portland cements and are as well of interest concerning their use as binder for waste encapsulation. In this study, the hydration of two CSA cements has been investigated experimentally and by thermodynamic modelling between 1 h and 28 days at w/c ratios of 0.72 and 0.80, respectively.The main hydration product of CSA is ettringite, which precipitates together with amorphous Al(OH)₃ until the calcium sulfate is consumed after around 1-2 days of hydration. Afterwards, monosulfate is formed. In the presence of belite, strätlingite occurs as an additional hydration product. The pore solution analysis reveals that strätlingite can bind a part of the potassium ions, which are released by the clinker minerals. The microstructure of both cements is quite dense even after 16 h of hydration, with not much pore space available at a sample age of 28 days.The pore solution of both cements is dominated during the first hours of hydration by potassium, sodium, calcium, aluminium and sulfate; the pH is around 10-11. When the calcium sulfate is depleted, the sulfate concentration drops by a factor of 10. This increases pH to around 12.5-12.8.Based on the experimental data, a thermodynamic hydration model for CSA cements based on cement composition, hydration kinetics of clinker phases and calculations of thermodynamic equilibria by geochemical speciation has been established. The modelled phase development with ongoing hydration agrees well with the experimental findings.     

Preparation and performance of slag-based binders for the cementation of fine tailings

To achieve effective cementation of fine tailings, slag-based binders were prepared using Portland cement clinker stimulation, early strength activator (ESA, mixture of anhydrite and triethanolamine at 97:3 (w/w)) activation and slag pulverization methods. The compressive strength, hydration products, slag reaction degree and non-evaporable water content of the consolidated samples under different curing times were analyzed to clarify the application performance and early strength action mechanisms of this slag-based binder. The results showed that clinker alone was able to effectively stimulate the slag’s cementitious property, but the cementation strength was relatively low. The addition of ESA in the clinker activated slag promoted the conversion of C₄AH₁₃ into ettringite (AFt) and accelerated the consumption of Ca(OH)₂, all of which significantly improved the early cementation strength of fine tailings. Slag pulverization promoted the slag reaction degree and increased the yield of hydrated products, which led to a further increase in the early strength of the slag-based binder. Eventually, a more efficient and higher early strength slag-based binder was prepared with the composition of 27% clinker, 10% ESA and 63% pulverized slag, and the cementation strength at 3 curing days for the fine tailings sample was 231% more than that of P.O 42.5 Portland cement.     

On the role of free calcium oxide in expansive cements

Results of research, tending to elucidate the effect of free CaO content in portland cement clinker upon the expansion of specimens of expansive cements, prepared in semi-commercial scale by intergrinding of portland cement clinker, C₄A₃$\text{S}$-phase containing special clinker and gypsum, by means of examination of liquid phase composition and porosity of mortars, have been presented. Special clinker was obtained by burning a mix of limestone, fly ash with high Al₂O₃ content and gypsum. Obtained results confirm the advantageous effect of free lime upon the hydration process and properties of expansive cements. The concentration of CaO in the liquid phase seems to influence rather the rate of ettringite formation than the size of its crystals.     

The hydration of Portland cement,C3S and C2S in the presence of a calcium complexing admixture (EDTA)

The effect of EDTA, a calcium chelating agent, on the early hydration of Portland cement, C₃Sand β-C₂S has been studied by solution analysis and electron microscopy. EDTA is a retarded of cement hydration. Under normal conditions of hydration, the silica levels in solution are very low (<0.05 M) but in the presence of EDTA an initial flush of silica appears in the bulk aqueous phase. On continued hydration, following the saturation of EDTA with calcium, the appearance of ‘free’ calcium causes precipitation of C-S-H gel from the bulk solution and changes in microstructure of the colloidal gel around clinker particles in C₃S and β-C₂S pastes are observed. The action of EDTA as a retarding admixture is explained in terms of the membrane model of cement hydration.     

环氧乳液改性水泥基材水化过程的硬化机理

极端环境和复杂荷载条件对混凝土结构的材料性能提出了更高的要求,聚合物通过改性水泥基材提高混凝土性能的方法已经得到了广泛应用。本研究为揭示环氧乳液改性水泥基材水化过程的硬化机理,通过等温放热试验分析环氧乳液对水泥水化放热过程的影响,结合原位XRD技术跟踪水泥主要矿物熟料和水化产物在水化反应早期的相含量发展。研究结果表明,环氧乳液对水泥水化的阻滞作用与环氧颗粒、水泥矿物熟料和水化产物之间的相互作用有关,并随着水化时间的延长,相互作用效果越明显。在水泥胶凝体系中,环氧乳液会减缓水化放热速率,降低水化放热峰值,减少累积放热量。环氧乳液通过抑制水泥矿物(C₃S、C₃A、石膏)的溶解和水化产物(钙矾石、氢氧化钙)的析出,延缓硅酸盐反应和铝酸盐反应;环氧乳液对水泥水化的影响随着其掺量的增加而增强。     

The impact of Fe dosage on the ettringite formation during high ferrite cement hydration

Illustrating the influence of Fe dosage and temperature on the formation of sulfoaluminate hydrates is of great significance to understand the early hydration process of high ferrite cement under steam curing. Herein, the impact of Fe dosage on the ettringite formation at different temperatures was revealed through the combination of experiments and computational simulations. A Fe dosage no more than 20% conspicuously accelerated the crystal growth of ettringite by increasing the surface energy in the (0 0 1) direction, whereas a higher dosage suppressed the formation of ettringite as the high incorporation of Fe ions into the ettringite crystal was energetically unstable. The chemical environment analysis of Fe in products shows that Fe(OH)₆³⁻, compared with Al(OH)₆³⁻, prefers to participate in the formation of Al₂O₃-Fe₂O₃-mono than ettringite, which is also confirmed by the calculated thermodynamic properties’ results. The understanding of the impact and mechanism of Fe on the formation of ettringite under steam curing conditions plays a pivotal role in the utilization of high ferrite cement.     

In situ synchrotron X-ray powder diffraction study of the early age hydration of cements blended with zeolitite and quartzite fines and water-reducing agent

A comparison was made between the early-age hydration of cements blended with micronized zeolitite and quartzite powders. The Portland cement replacement in the mixes was 30%, and the effect of introducing a superplasticiser to lower the required water to solid ratio was assessed. The cement pastes were hydrated at 40 °C and monitored in situ by time-resolved synchrotron X-ray powder diffraction combined with Rietveld quantitative phase analysis.The quantitative evolution of phase weight fractions showed that the addition of the zeolite tuff accelerated the hydration rate of the main C₃S cement component. Blending with the quartzite powder of similar fineness did not affect the C₃S hydration rate. Reduction of the water to solid ratio by introduction of the superplasticiser had a retarding effect on the hydration of the zeolitite-blended cement over the early hydration period up to 3 days.The AFt or ettringite reaction products, formed promptly after the addition of water to the mixtures, underwent a crystal structural modification over the induction period up to 4 to 6 hours of reaction. The continuous contraction of the c-cell parameter and expansion of the a-cell parameter towards the ideal values for AFt or ettringite reflects the structural adaptation of the AFt to the changing availability of sulphate over the course of the first hours of hydration. The observed structural changes were less pronounced in the zeolitite blended cement. This is related to the dilution of the overall sulphate content in the blended cement and highlights the need to control and optimise sulphate additions in blended cements.     

Working mechanism of calcium nitrate as an accelerator for Portland cement hydration

Precast concrete, cold weather concreting, and the emerging technique of concrete additive manufacturing are applications in which the acceleration of cement hydration plays a critical role. To allow precise control of early cement hydration in these applications, a thorough understanding of the working mechanisms of cement hydration accelerators is required. This study contributes to the understanding of the mechanism by which calcium nitrate (Ca(NO₃)₂) influences early cement hydration. The influence of Ca(NO₃)₂ on the hydration of an ordinary Portland cement has been followed by isothermal calorimetry, in situ X-ray diffraction (XRD), quantitative XRD, compressive strength testing, and the analysis of the pore solution composition. Further, the initial pore solution, the initial phase composition, and the phase composition in the fully hydrated cement have been estimated by thermodynamic calculations to corroborate the experimentally obtained results. The results indicate that Ca(NO₃)₂, especially at the highest analyzed dosage of 5 wt.%, enhances the formation of ettringite and a nitrate-containing AFm phase. Furthermore, Ca(NO₃)₂ accelerates alite hydration. Besides the increased Ca concentration in solution, it has been found that a reduction of the Al concentration in the initial pore solution by Ca(NO₃)₂ possibly contributes to the accelerating effect of Ca(NO₃)₂ on alite hydration.     

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.     

The microstructure of dispersed and non-dispersed fresh cement pastes — New insight by cryo-microscopy

This study aims to give new insights to the microstructural development of fresh cement pastes without and with polycarboxylate-type (PCE) of superplasticizers. Qualitative comparisons of the particulate structure of such cementitious systems were carried out by using cryo-FIB and cryo-SEM techniques. The natural structure of fresh cement pastes was preserved by high pressure freezing.It is illustrated that non-dispersed cement systems tend to form hydration rims on the surface of the clinker grains immediately after mixing. This leads to an interlocking of the particles. In contrast, in the dispersed systems the early hydrates precipitate in the pore solution and thus, agglomeration is prevented. These microstructural observations are important aspects of the fluidization effect of superplasticizers.     

Effect of CuO on the formation of clinker minerals and the hydration properties

The purposes of this study are to explore the mechanisms of Cu element in clinker burning and hydration processes and to make effective use of waste containing copper in cement production. The effect of CuO on clinker mineral composition, C₃S polymorph and size, Cu element distribution and state, compressive strengths, hydration products, non-evaporable water quantity and hydration heat release rate was analyzed by XRD, SEM, DTA, isothermal heat-conduction calorimetry, etc. Results show that as the amount of CuO increases the formation and growth of C₃S grain are accelerated, R C₃S is gradually transformed into M₃ and the content of C₄AF increases; a small quantity of CuO increases the 3-day and 28-day strengths and the hydration degree of clinker, but excessive CuO has adverse effects. Those effects of CuO on clinker burning process are attributed to the formation of low-melting Cu₂O and the dissolution of CuO in C₄AF which decrease the formation temperature of liquid phase and increase its quantity. The effects on hydration process result from the combined action of the following factors: the induction period is prolonged; the hydration reactions in the initial and acceleration periods are accelerated.     

The effectuation of seawater on the microstructural features and the compressive strength of fly ash blended cement at early and later ages

The current work scrutinizes the effectuation of seawater on morphological properties, pore structure, and compressive strength during the hydration process of fly ash blended cement at 3, 7, 28, 56, and 90 days to better understand the influence of salinity conditions of seawater on the microstructural modification and strength development of the hydration products as well as the total porosity. The chemical reaction's mechanism of mightily soluble salts, for example, Mg₂SO₄ and NaCl, with hydrated fly ash and blended cement (calcium-bearing phases) was also confirmed. Fourier-transform infrared spectroscopy has been appointed to observe and characterize the energetics of variation in the formulation of portlandite (CH), calcium silicate hydrate, gypsum (Gy), ettringite (AFt), and calcium chloroaluminate (Friedel's salt [FS]) throughout the hydration process of fly ash blended cement with seawater in comparison with deionized water. X-ray diffraction analysis exposed that the peak intensities of FS, portlandite, and some particular phases of the hydrated fly ash blended cement in seawater are higher and sharper than the comparable peaks in deionized water. Mercury intrusion porosimetry-measurements have been appointed that the total porosity of artificial seawater (ASW) was decreased from 28.9% at 3 days to 19.4% at 56 days. In addition, the average, median, and critical pore diameter were decreased in ASW while compared to deionized water (DIW). The reaction products of this work were also characterized using scanning electron microscopy, EDS, compressive strength, and isothermal calorimeter.