Modeling hydration properties and temperature developments of early-age concrete pavement using calorimetry tests

This research aims to evaluate the calorimetry tests for characterizing cement hydration properties and predicting temperature developments of the early-age Portland cement concrete pavement (PCCP). Analytical models are studied to simulate hydration properties, using the measured heat evolution data from both the isothermal and semi-adiabatic tests. HIPERPAV III^® engineering software with these analytical models embedded is used to predict temperature developments of the early-age PCCP. Results show that the maximum hydration time parameter τ corresponds to the maximum activation energy E_a. Semi-adiabatic tests result in a lower hydration shape parameter β yet a higher hydration time parameter τ than isothermal tests. As results, the simulated degree of hydration based on semi-adiabatic tests is higher at the early hours, but lower at later hours compared to that based on isothermal tests. This effect is also reflected from the simulated temperature developments of the early-age PCCP. Three engineering projects in this research show that predicted temperatures of the PCCP using hydration parameters determined from semi-adiabatic tests better match actual measurements than that from isothermal tests.     

Principal component and cluster analyses as supporting tools for co-crystals detection

The effects of super absorbent polymer (SAP) on the early hydration evolution of Portland cement within 72 h were investigated by isothermal calorimetry, thermal analysis and X-ray diffraction analysis. The results show that the SAP definitely affects the early hydration process of Portland cement, increases the hydration heat evolution rate during the acceleration period and during the main exothermic peak, promotes the earlier appearance of the main exothermic peak, but does not affect the lengths of the initial reaction period and the induction period and the onset of the acceleration period. The SAP can accelerate cement hydration to increase the hydration degree within 72 h. But the dosage variation of SAP has minor influence on the hydration heat evolution and hydration degree. The SAP enhances the formation of Ca(OH)₂ after 12 h to keep higher content than that in the reference paste. The SAP does not affect the maximum content of ettringite, but delays the conversion of ettringite to monosulphate to remain ettringite content higher at later hydration time. Besides, no new phases are found to have formed in cement paste with SAP.     

Calorimetry of portland cement with silica fume and gypsum additions

The use of active mineral additions is an important alternative in concrete design. Such use is not always appropriate, however, because the heat released during hydration reactions may on occasion affect the quality of the resulting concrete and, ultimately, structural durability. The effect of adding up to 20% silica fume on two ordinary Portland cements with very different mineralogical compositions is analyzed in the present paper. Excess gypsum was added in amounts such that its percentage by mass of SO₃ came to 7.0%. The chief techniques used in this study were heat conduction calorimetry and the Frattini test, supplemented with the determination of setting times and X-ray diffraction. The results obtained showed that replacing up to 20% of Portland cement with silica fume affected the rheology of the cement paste, measured in terms of water demand for normal consistency and setting times; the magnitude and direction of these effects depended on the mineralogical composition of the clinker. Hydration reactions were also observed be stimulated by silica fume, both directly and indirectly – the latter as a result of the early and very substantial pozzolanic activity of the addition and the former because of its morphology (tiny spheres) and large BET specific surface. This translated into such a significant rise in the amounts of total heat of hydration released per gram of Portland cement at early ages, that silica fume may be regarded in some cases to cause a synergistic calorific effect with the concomitant risk of hairline cracking. The addition of excess gypsum, in turn, while prompting and attenuation of the calorimetric pattern of the resulting pastes in all cases, caused the Portland cement to generate greater heat of hydration per gram, particularly in the case of Portland cement with a high C₃A content.     

Heat of hydration of high reactive pozzolans in blended cements: Isothermal conduction calorimetry

A study was carried out comparing silica fume (SF) and dealuminated kaolin (DK) as pozzolanic materials in blended cements. Ten, 20 or 30 wt% of SF or DK were substituted for Portland cement. The kinetics of hydration up to 45 h were studied using isothermal conduction calorimetry. Blends containing pozzolanic materials usually have decreased heats of hydration compared to pure cement during the period of C₃S hydration, i.e. during the main hydration peak. Depending on the chemical composition and the activity of the pozzolan, the reaction taking place with the lime typically contributes to the heat output after the main hydration peak.The pozzolanic activity of DK is the principal factor and heat evolution increases with respect to pure PC mortar, during the first 15 h. The presence of hydrated silica (silanol groups) in DK increases the pozzolanic activity especially before and during induction period. The acidic silanol sites are capable of a fast acid-base reaction with the alkalis and with any Ca(OH)₂ present in cement during the induction period.     

Hydration of Portland cement with alkanolamines by thermal analysis

Four types of alkanolamines (i.e., traditional alkanolamines represented by TEA and TIPA and new alkanolamines represented by DEIPA and EDIPA) were added to Portland cement as chemical additives, and their effects on the cement properties and hydration process were investigated. An isothermal calorimeter was used to track the hydration heat flow of the cement pastes with or without alkanolamines. Thermogravimetric analyses were performed to measure the degree of hydration over the course of 28 days. In addition, X-ray diffraction, MIP analysis and SEM were used as auxiliary tests. The results indicated that alkanolamines improved the compressive strength of the cement mortars. It was found that TEA increased the rate of the second hydration of C₃A, and TIPA accelerated the hydration of C₄AF. DEIPA and EDIPA promoted the hydration of both the aluminum and ferrite phases as well as catalyzed the conversion of AFt to the AFm phase. By contrast, the new alkanolamines represented by DEIPA and EDIPA expressed more superior properties.     

Thermodynamics and kinetics of hydrogen absorption–desorption of vanadium synthesized by aluminothermy

This paper studies the addition (0–40% w/w) of natural zeolite (NZ, 84% clinoptilolite) in blended cements made with Portland cement (PC) with low and medium C₃A content. The isothermal calorimetry was used to understand the effect of NZ on the early cement hydration. For low C₃A cement, the addition of NZ produces mainly a dilution effect and then the heat released curve is similar to plain cement with lower intensity. For medium C₃A cement, the curve shows the C₃S peak in advance and a high intensity of third peak attributed to C₃A hydration. The high cation fixed of NZ reduces the ions concentration (especially alkalis) in the mixing water stimulating the PC hydration. The flowability decreases when the NZ replacement level increases. Results of Fratini’s test show that NZ with both PCs used presents slow pozzolanic activity. At early age, XRD and FTIR analyses confirm that hydration products are the same as that of the corresponding PC and the CH is progressively reduced after 28 days and some AFm phases (hemi- and monocarboaluminate) appear depending on the NZ percentage and the PC used. For low replacement levels, the compressive strength is higher than the corresponding PC from 2 to 28 days. For high replacement levels, the early compressive strength is lower than that of corresponding plain PC and the pozzolanic reaction improves the later compressive strength of blended cements.     

Investigation on mechanical properties, durability and micro-structural development of steel slag blended cements

To improve the properties of steel slag blended cements, a chemical activator was added into blended cements, the mechanical properties and durability of steel slag blended cements were investigated. The results show that steel slag in blended cement pastes presents low hydraulic activity and makes practically no contribution to strength development. After the addition of chemical activator, the mechanical properties and durability of ternary blended cements are increased significantly. The hydration process and micro-structural development of blended cement was investigated by isothermal calorimeter and scanning electric microscope, respectively. Steel slag started hydration in the first 3?days in the presence of chemical activator, steel slag and granulate blast furnace slag reacted with Ca(OH)₂ to form a dense microstructure as curing proceeded. Therefore, both early and late compressive strengths of steel slag blended cement with 35% cement clinker and 30% steel slag can be comparable with those of Portland cement.     

Middle stage of Portland cement hydration influenced by different portions of silica fume,metakaolin and ground granulated blast-furnace slag

Present study deals with the influence of metakaolin (MK), silica fume (SF) and ground granulated blast-furnace slag (BFS) on middle hydration of ordinary Portland cement replaced by 45 mass% of particular supplementary cementitious materials (SCMs). Acceleration of cement hydration by SF and MK was proved up to the first 12 h by isothermal calorimetry as well as by thermogravimetric analyses. From the beginning of deceleratory period, when SCMs stopped to act as accelerators, more evident influence of the dilution effect was observed. Nevertheless, the presence of pozzolanic reactions was demonstrated already after 15 h of curing and even when SF and MK were used in the amount equal to 5 mass%. Synergic effect of the used SCMs allowed to increase the quantity of BFS up to 35 mass% without significant changes in their positive action.

     

Calorimetric and thermogravimetric study on the influence of calcium sulfate on the hydration of ye’elimite

Calcium sulfoaluminate (CSA) cements, which represent a CO₂-friendly alternative to conventional Portland cements, are produced by blending CSA clinker with gypsum and/or anhydrite. The hydration kinetics and the hydrated phase assemblages of the main hydraulic phase ye’elimite (calcium sulfoaluminate) with calcium sulfate were studied by isothermal conduction calorimetry, thermogravimetric analysis, X-ray diffraction analysis and thermodynamic modelling. Two calcium sulfates with different reactivities (gypsum and anhydrite) were applied. It was found that the pure phase without any calcium sulfate addition exhibits very slow hydration kinetics during the first 10 h. The hydration can be accelerated by the addition of calcium sulfate or (less effective) by increasing the pH of the aqueous phase. The amount of the calcium sulfate determines the ratio between the hydration products ettringite, monosulfate and amorphous aluminium hydroxide. The reactivity of the added calcium sulfate determines the early hydration kinetics. It was found that the more reactive gypsum was better suited to control the hydration behaviour of ye’elimite.     

Influence of superplasticizers on the course of Portland cement hydration

A multicell isoperibolic — semiadiabatic calorimeter was used for the measurement of temperature and the determination of the hydration heat evolution at earlier period of cement pastes setting and hardening. The measurements were aimed at the determination of the effect of superplasticizers (SPs) on the course of the Portland cement hydration. Commercial polycarboxylate SP was added to the mixtures and the heat effect was measured. With the increasing content of SP, the hydration temperature increased up to a certain value and then decreased. In case of a sufficient amount of water in the mixture to achieve complete hydration of cement, samples with the highest values of the maximum hydration temperature reached the highest values of the released total heat. If there is not a sufficient amount of water to achieve complete hydration, the samples with the highest values of the maximum hydration temperature reach the lowest values of the released total heat.     

Simultaneous effect of silica fume,metakaolin and ground granulated blast-furnace slag on the hydration of multicomponent cementitious binders

Portland cement was partially replaced by metakaolin (MK), silica fume (SF) and ground granulated blast-furnace slag (BFS). Globally, two amounts of SF (5 and 10 mass%) and total substitution level of 35 mass% were used to prepare blended samples. Their early and 28 days hydration was studied by means of isothermal calorimetry and thermal analysis. Developed phase composition was assessed using compressive strength measurements. Acceleration of cement hydration in early times was proved and reflected higher amounts of finer additives. Despite dilution effect, the presence of more reactive SF and MK resulted in pozzolanic reactions manifesting already before 2 days of curing and contributing to the formation of strength possessing phases. The influence of BFS addition showed later and thanks to the synergic effect of all the used additives; it was possible to increase its content up to 25 mass% by keeping the compressive strength values near that of referential one.

     

Effect of addition of nano-magnetite on the hydration characteristics of hardened Portland cement and high slag cement pastes

In this investigation the effect of addition of magnetite nanoparticles on the hydration characteristics of both ordinary Portland cement (OPC) and high slag cement (HSC) pastes was studied. The cement pastes were prepared using a water/solid (W/S) mass ratio of 0.3 with addition of 0.05, 0.1, and 0.3 % of magnetic fluid Fe₃O₄ nanoparticles by mass of cement. An aqueous stable magnetic fluid containing Fe₃O₄ nanoparticles, with a mean diameter in the range of super-paramagnetism, was prepared via co-precipitation method from ferrous and ferric solutions. The admixed magnetite-cement pastes were examined for compressive strength, chemically combined water content, X-ray diffraction analysis, and differential scanning calorimetry. The results of compressive strength revealed that the hardened pastes made from OPC and HSC admixed with different amounts of magnetic fluid have higher compressive strength values than those of the neat cement OPC and HSC cement pastes at almost all ages of hydration. The results of chemically combined water content for the admixed cement pastes showed almost the same general trend and nearly comparable values as those of the neat cement pastes. From the XRD diffractograms obtained for the neat OPC and HSC cement pastes, the main hydration products identified are calcium silicate hydrates, portlandite, and calcium sulfoaluminate hydrates. Addition of magnetic fluid nanoparticles to both of OPC and HSC did not affect the main hydration products of the neat OPC or HSC cement in addition to one main basic difference, namely, the formation of calcium iron hydroxide silicate as a new hydration product with a reasonable hydraulic character.     

Influence of Submicron Fibrillated Cellulose Fibers from Cotton on Hydration and Microstructure of Portland Cement Paste

This paper reports the influence of submicron hydrophilic fibers on the hydration and microstructure of Portland cement paste. Submicron fibrillated cellulose (SMC) fibers was prepared by the acid hydrolysis of cotton fibers in H₂SO₄ solution (55% v/v) for 1.5 h at a temperature of 50 °C. The SMC fibers were added into cement with a dosage of 0.03 wt.%, and the effect of SMC on the hydration and microstructure of cement paste was investigated by calorimeter analysis, XRD, FT-IR, DSC-TG, and SEM. Microcrystalline cellulose (MCC) fibers were used as the contrast admixture with the same dosage in this study. The results show that the addition of SMC fibers can accelerate the cement hydration rate during the first 20 h of the hydration process and improve the hydration process of cement paste in later stages. These results are because the scale of SMC fibers more closely matches the size of the C-S-H gel compared to MCC fibers, given that the primary role of the SMC is to provide potential heterogeneous nucleation sites for the hydration products, which is conducive to an accelerated and continuous hydration reaction. Furthermore, the induction and bridging effects of the SMC fibers make the cement paste microstructure more homogeneous and compact.     

Effect of ZnO on the hydration of Portland cement

ZnO added to the system Portland cement — water changes the kinetics of the hydration process substantially. Amorphous zinc hydroxide is formed and inhibits the reaction of tricalcium silicate with water, resulting in an induction period prolongation. This effect depends on the amount of ZnO added to the hydrated paste. The transformation of zinc hydroxide into calcium hydrozincate provokes the further hydration.

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Zusammenfassung Durch den Zusatz von ZnO zum System Portlandzement-Wasser wird die Kinetik des Hydratationsprozesses grundlegend verändert. Amorphes Zinkhydroxid wird gebildet, was einen Inhibitor für die Tricalciumsilikatreaktion mit Wasser darstellt, wodurch die Induktionsperiode verlängert wird. Dieser Effekt hängt von der Menge ZnO ab, die dem Zementbrei zugesetzt wurde. Die Umwandlung von Zinkhydroxid zu Calciumhydrozinkat führt eine weitere Hydratation herbei.

     

Physical and chemical studies on cement containing sugarcane molasses

Molasses is generally used as a grinding aid in cement and as a water reducer and retarder in concrete. In China, the output primarily consists of sugarcane molasses. In this paper, the effects of sugarcane molasses on the physical performance and hydration chemistry of conventional Portland cement were investigated. The setting times, the normal consistency of cement pastes, the compressive strengths and fluidities of the mortars were respectively determined according to Chinese Standard GB/T 1346, GB/T17671 and GB/T 2419. The effect of molasses on the hydration kinetics of cement was investigated using a calorimeter. The hydration products and pore size distribution of the cement pastes were analysed by X-ray powder diffraction, differential scanning calorimetry and a mercury injection apparatus. The results show that a small amount of sugarcane molasses retards the setting and hardening of cement paste and increases the fluidity of cement mortar, while excess molasses accelerates the setting and hardening. Molasses improves significantly the compressive strength at 3d due to the decrease of porosity. The addition of 1.0 % molasses accelerates the formation of ettringite, prevents the second hydration of aluminate phase and delays the hydration of C₃S.     

Simultaneous measurements of heat of hydration and chemical shrinkage on hardening cement pastes

Isothermal calorimetry and chemical shrinkage measurements are two independent techniques used to study the development of hydration in cementitious systems. In this study, calorimetry and chemical shrinkage measurements were combined and simultaneously performed on hydrating cement paste samples. Portland cement pastes with different water to cement ratios and a cement paste containing calcium sulfoaluminate clinker and anhydrite were studied. The combined calorimetry/chemical shrinkage test showed good reproducibility and revealed the different hydration behavior of sealed samples and open samples, i.e., samples exposed to external water during hydration. Large differences between sealed and open samples were observed in a Portland cement paste with low water to cement ratio and in the calcium sulfoaluminate paste; these effects are attributed to self-desiccation of the sealed pastes. Once the setup is fully automatized, it is expected that combined calorimetry/chemical shrinkage measurements can be routinely used for investigating cement hydration.     

Study of the hydration of Portland cement blended with blast-furnace slag by calorimetry and thermogravimetry

The hydration of ordinary Portland cement (OPC) blended with blast-furnace slag (BFS) is a complex process since both materials have their own reactions which are, however, influenced by each other. Moreover, the effect of the slag on the hydration process is still not entirely known and little research concerning the separation of both reactions can be found in the literature. Therefore, this article presents an investigation of the hydration process of mixes in which 0–85% of the OPC is replaced by BFS. At early ages, isothermal, semi-adiabatic and adiabatic calorimetric measurements were performed to determine the heat of hydration. At later ages, thermogravimetric (TG) analyses are more suitable to follow up the hydration by assessment of the bound water content w _b. In addition, the microstructure development was visualized by backscattered electron (BSE) microscopy. Isothermal calorimetric test results show an enhancement of the cement hydration and an additional hydration peak in the presence of BFS, whilst (semi-)adiabatic calorimetric measurements clearly indicate a decreasing temperature rise with increasing BFS content. Based on the cumulative heat production curves, the OPC and BFS reactions were separated to determine the reaction degree Q(t)/Q _∞ (Q = cumulative heat production) of the cement, slag and total binder. Moreover, thermogravimetry also allowed to calculate the reaction degree by w _b(t)/w _b∞. The reaction degrees w _b(t)/w _b∞, Q(t)/Q _∞ and the hydration degrees determined by BSE-image analysis showed quite good correspondence.     

Reactivity of fly ash in cement paste studied by means of thermogravimetry and isothermal calorimetry

Four paste mixtures with varying replacement level of the cement content by fly ash have been studied. Due to fly ash, the acceleration period decreased and a third hydration peak was noticed with isothermal calorimetry. The total heat after 7 days increased with increasing fly ash content. From 1 to 7 days, thermogravimetry showed a higher chemically bound water and Ca(OH)₂-content for the pastes with fly ash. Between 7 and 14 days the calcium hydroxide started to be depleted due to the pozzolanic reaction. A unique relation was found between calcium hydroxide and total heat development.     

Influence of borax and citric acid on the hydration of calcium sulfoaluminate cement

The hydration of calcium sulfoaluminate cement in the presence of borax and citric acid has been studied using isothermal calorimetry, X-ray diffraction, thermogravimetric analysis, Fourier transfer infrared spectrometry and mercury intrusion porosimetry. The results suggest that the formation of complex between calcium and citrate in the solution adsorbed on the solid surface delayed the C₄A₃ \( \bar{S} \) and anhydrite dissolution and AFt nucleation. At the same time, the presence of borate replaced sulfate anion in ettringite (AFt) to form B-AFt. These reactions have an effect on the setting times and the mechanical strength values. The setting times of the calcium sulfoaluminate cement increased when the mineral admixtures increased in the cement. The effect of borax and citric acid on the strength development at different hydration stages presented different results, namely a decreased strength in an early stage and an increased strength at 3 and 28 days.     

A novel evidence for the formation of semi-permeable membrane surrounding the Portland cement particles during the induction period

This letter presents strong novel evidence for the semi-permeable membrane surrounding Portland cement during the induction period. In the cement hydration, heat curve obtained through high-resolution differential scanning calorimetry under isothermal conditions, one main and some other smaller endothermic peaks were detected. These endothermic peaks are believed to be caused by the osmotic expansion that occurs after the semi-permeable membrane forms, not the precipitation of calcium hydroxide or the imbibition of water during the induction period.