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.

     

Effect of additives on the performance of Dyckerhoff cement,Class G,submitted to simulated hydrothermal curing

Stability of Dyckerhoff cement Class G partially substituted (15 mass%) by metakaolin (MK), silica fume (SF) and ground granulated blast-furnace slag (BFS) was investigated after 7 days of curing under standard and two different autoclaving conditions. Mercury intrusion porosimetry, X-ray diffraction analysis and combined thermogravimetric–differential scanning calorimetry were used to evaluate pore structure development, compressive strength and their dependence on the type of additives in relation to the particular phase composition. Hydrothermal curing led to the formation of α-C₂SH and jaffeite, mostly in the case of referential samples and compositions with addition of slowly reacting BFS. Whilst modest hydrothermal curing (0.6 MPa, 165 °C) favoured formation of α-C₂SH, larger amounts of jaffeite were determined after curing at the highest used pressure and temperature (2.0 MPa, 220 °C). Undesired transformation of primary hydration products was prevented especially by addition of highly reactive and very fine SF. Particular composition attained the best pore structure characteristics and compressive strength after curing at 0.6 MPa and 165 °C. Formation of more stable phases with C/S ratio close to 1 was proved by wollastonite formation during DSC analyses. More severe conditions of curing, however, led to the significant deterioration of microstructure and strength of corresponding sample, probably due to the formation of trabzonite, killalaite and zoisite. Considering the values of hydraulic permeability coefficient and compressive strength, replacement of cement by MK improved significantly the properties of cement when compared with the referential as well as with other blended compositions under the mentioned curing conditions.     

Artificial pozzolanic cement pastes containing burnt clay with and without silica fume

Pozzolanic cement blends were prepared by the partial substitution of ordinary Portland cement (OPC) with different percentages of burnt clay (BC), Libyan clay fired at 700 °C, of 10, 20, and 30%. The pastes were made using an initial water/solid ratio of 0.30 by mass of each cement blend and hydrated for 1, 3, 7, 28, and 90 days. The pozzolanic OPC–BC blend containing 30% BC was also admixed with 2.5 and 5% silica fume (SF) to improve the physicomechanical characteristics. The hardened pozzolanic cement pastes were subjected to compressive strength and hydration kinetics tests. The results of compressive strength indicated slightly higher values for the paste made of OPC–BC blend containing 10% BC The results of DSC and XRD studies indicated the formation and later the stabilization of calcium silicates hydrates (CSH) and calcium aluminosilicate hydrates (C₃ASH₄ and C₂ASH₈) as the main hydration products in addition to free calcium hydroxide (CH). Scanning electron microscopic (SEM) examination revealed that the pozzolanic cement pastes made of OPC–BC mixes possesses a denser structure than that of the neat OPC paste. Furthermore, the addition of SF resulted in a further densification of the microstructure of the hardened OPC–BC–SF pastes; this was reflected on the observed improvement in the compressive strength values at all ages of hydration.     

Effect of BaO on the calcination and hydration characteristic of CA

Phosphoaluminate cement (PAC) clinker had good mechanical properties at early and long-term period. In comparison, the compressive strength of PAC clinker modified by BaO was more prominent. As primary mineral phase for PAC clinker, CA’s mineralogical structure and hydration characteristics were intimately related to the compressive strength of hardened cement paste. In this study, the effects of BaO content on the calcination, mineralogical structure and hydration characteristics of CA were investigated. Experimental results showed that the appropriate calcination temperature of CA was 1400 °C. No more than 11% (the substitution ratio of BaO for CaO) addition of BaO can promote the conversion of C₁₂A₇ to CA and increase the formation ratio of CA. Appropriate content of 7 mol% BaO could endow the hardened paste with excellent compressive strength. In CA mineral phase the high limit addition of BaO was 15 mol%. The addition of BaO decreased and even restrained the formation of C₂AH₈ and C₃AH₆ of CA hydration products and also improved the content of CAH₁₀. The addition of BaO dramatically decreased the hydration velocity and cumulative heat of CA mineral.

     

Microstructural,physical, and thermal analyses of Portland cement–fly ash–calcium hydroxide blended pastes

The effect of calcium hydroxide (CH) on the properties of Portland–fly ash cement pastes, at up to high-volume fly ash mixes has been investigated using normal consistency, setting time, compressive strength, thermal analysis and scanning electron microscope. CH as an additive material (5 and 10 wt%), lignite fly ash (FA) up to 50 wt% was used to produce Portland cement (PC)–FA–CH pastes at w/PC + FA ratio of 0.5. Water requirement for normal consistency was found to increase with increasing CH content while a decrease in initial setting time was found. Furthermore, the compressive strengths of all FA mixes with CH were found to be higher than the mixes without CH. Thermal analysis and scanning electron microscope were used to study the hydration of PC–FA–CH system. The results showed that the first phase transition detected by thermal analyses was attributed to ettringite, calcium silicate hydrate, gehlenite hydrate and was found to be higher in PC–FA–CH mixes than in pure Portland–FA cement paste resulting in an increase in compressive strength. Moreover, the hydration phases were also found to increase with increasing curing time. Overall, the results show that the additional of 5 wt% CH in Portland–FA mixes especially at high-volume FA mixes was found to accelerate FA pozzolanic reaction at early ages (7 and 28 days), resulting to an increase in compressive strength.     

Utilization of waste phosphate aluminum slag for cement manufacture

The objective of this study was to investigate the feasibility of application of waste phosphate aluminum slag (PAS) for cement manufacture. To recycle waste PAS and minimize adverse effects on cement hydration induced by phosphate, NH₄OH was used to purify PAS. X-ray diffraction (XRD) analysis was used to determine to confirm the removal of harmful phosphate. The effect of PAS on the hydration product composition, heat release and compressive strength was also investigated. The results demonstrated that NH₄OH was effective in removing harmful AlPO₄ in PAS and 10% NH₄OH was considered as the optimal treatment concentration. In addition, the purification of NH₄OH alleviated the delay in cement hydration caused by AlPO₄ and the heat release curve of purified PAS (PPAS) cement tends to that of OPC. Moreover, the compressive strength of PPAS mortar at 28 days was 49.4 ​MPa, which is 18% higher than the compressive strength of PAS mortar. PAS purified by NH₄OH can be applied to cement manufacturing.     

Effects of reagents’ nature on mechanochemical synthesis of calcium titanate

The effect of alkaline hydrothermal activation of class-C fly ash belite cement was studied using thermal analysis (TG/DTG) by determining the increase in the combined water during a period of hydration of 180 days. The results were compared with those obtained for a belite cement hydrothermally activated in water. The two belite cements were fabricated via the hydrothermal-calcination route of class-C fly ash in 1 M NaOH solution (FABC-2-N) or demineralised water (FABC-2-W). From the results, the effect of the alkaline hydrothermal activation of belite cement (FABC-2-N) was clearly differentiated, mainly at early ages of hydration, for which the increase in the combined water was markedly higher than that of the belite cement that was hydrothermally activated in water. Important direct quantitative correlations were obtained among physicochemical parameters, such as the combined water, the BET surface area, the volume of nano-pores, and macro structural engineering properties such as the compressive mechanical strength.     

Utilization of electric arc furnace dust as an admixture to Portland cement pastes

Electric arc furnace dust (EAFD) is termed as a hazardous waste due to its contamination with heavy metals. Inertization of such very fine dust can be occurred via stabilization and solidification process within the hydrated Portland cement matrix. In this paper, the effect of the addition of various ratios of EAFD on the properties of the hardened Portland cement paste was investigated. Compressive strength, chemically combine water and free lime contents were determined. In addition, phase composition using XRD; DTA analysis; as well as microstructure of the formed hydrates for some selected samples were investigated using SEM. The obtained results showed that the paste containing 1/mass% EAFD give the highest compressive strength values at most hydration ages, specially the later ages, compared to the neat Portland cement blank paste. Whileas, the pastes containing 3 and 5/mass% EAFD showed lower values of compressive strength compared to those of the blank paste.     

The impact of time on the heat resistance of self-compacting high-performance concrete incorporated with recycled martials

The influence of time on the mechanical behavior of concrete after exposure to elevated temperatures has been studied. Twenty-one self-compacting high-performance concrete mixtures with different incorporation amounts of coarse recycled concrete aggregate (RCA) and three unprocessed waste powder materials have been tested at age of 270 days for residual compressive and flexural strength after exposure to fire. The results have been compared to the results for the same concrete, which have been studied at age of 90 days. A new parameter has been introduced for comparing the responses of concrete to elevated temperatures at different ages; this parameter was the “heat resistance” which expresses the total area under the curve of the relative residual strength (compressive or flexural) after exposing to six temperature degrees (20, 150, 300, 500, 600, and 800 °C). The results showed that the age of concrete has an influence on the response of concrete to elevated temperatures. The heat resistance of compressive strength enhanced with age but the concrete behaved with a tendency different to that at the age of 90 days. The heat resistance of flexural strength has not been affected or slightly decreased but not with more than 10% to that at the age of 90 days. The used waste powder materials were unprocessed waste fly ash, waste cellular concrete powder and waste perlite powder; they proved that using any of them up to 15% as a replacement for cement with 0% or 25% of RCA enhanced the concrete resistance for the fire with time. The main two reasons for changing of residual strength with the time were the changing of water content and the proceeding of hydration of the binder. In general, long ages testing properties of concrete simulate the real behavior of concrete structures accurately.

     

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.     

Synthesis and calorimetric study of hydration behavior of sulfate-rich belite sulfoaluminate cements with different phase compositions

Sulfate-rich belite sulfoaluminate (BSA) cements with varied phase compositions were synthesized in this work. The presence of sulfate in the clinker is in the form of anhydrite in addition to calcium sulfoaluminate. The aim of this paper is to study the effect of mineral composition on cement properties. Experimental results indicate that the improvement of early-age strengths mainly depends on the hydration of ye’elimite. The increase of ferrite content promotes the compressive strength after 7 days of hardening, but has adverse effect on cement strength at early ages. The optimum content of ferrite is between 10 and 20% for BSA cement containing approximately 35% ye’elimite. Different amounts of natural gypsum were added to the synthetic sulfate-rich BSA clinkers and we found that anhydrite formed in BSA clinkers can replace natural gypsum to facilitate the hydration of ye’elimite.     

Hydration heat evolution of high-belite cement–phosphate slag binder

The influence of phosphate slag with different finenesses and activators on the hydration of high-belite cement has been studied by using the hydration heat of binders, the DTA curves, the SEM images, and the specific strength. Results indicated that doped phosphorus slag in the cement will reduce heat of hydration. The activity of phosphate slag was low at early stage, but pozzolanic activity of phosphorus slag is higher than that of fly ash. Increasing the specific surface area and curing time and using Ca(OH)₂ combined with gypsum can clearly promote the hydration degree of phosphorus slag. The findings in this paper show that since phosphorus slag can promote the hydration of high-belite cement, the strength contribution of cement is increased. Moreover, the greater the specific surface area is, the more significant the promotion effect at 90 d is.

     

Studies on the influence of different fly ashes and Portland cement on early hydration of calcium aluminate cement

The influence of three mineral additives, i.e. fly ashes from pulverized combustion and from fluidized combustion of hard coal as well as Portland cement, on early hydration (up to 28th day) of calcium aluminate cement was investigated. Cement pastes containing 0, 5 and 25 wt% of additives were studied by the use of calorimetry, thermal analysis and infrared spectroscopy methods. It was confirmed that hydration of calcium aluminate cement is closely dependent on the type of addition and its amount. The influence of additives of different properties on cement hydration was discussed basing on received results and other literature reports.     

Effects of nano-limestone on hydration properties of tricalcium silicate

In this research, the influences of nano-limestone (NC) on tricalcium silicate (C₃S) hydration, including early hydration rate, setting time, Ca(OH)₂ content, quantification of C–S–H, micrographs of hydration products and compressive strength, were investigated by different methods. Calorimetry results show that the first and second exothermic peak of C₃S with 1 mass% NC is ~29 and ~5% higher than that of control sample and the second peak appears 32 min in advance. Besides, the total hydration heat of C₃S with 1 mass% NC increases by 10.08% compared to control sample at 72 h. The initial and final setting time of C₃S with 1 mass% NC shortens by 23 and 17 min, respectively. In addition, thermal analysis results show that adding NC leads to higher Ca(OH)₂ and C–S–H content at all ages (1, 3 and 28 days). All of the above results imply that the hydration progress of C₃S is accelerated by NC. Correspondingly, the compressive strength of C₃S with 1 mass% NC increases by 9.88% at 28 days. Besides, EDS results reveal that the Ca/Si ratio of C–S–H gel decreases after NC modification. However, excessive content NC (4 mass%) reduces the acceleration effect of NC on C₃S hydration and finally leads to relative low content of Ca(OH)₂ and C–S–H compared with C₃S sample containing 1 mass% NC.     

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.     

A comparison of early hydration properties of cement–steel slag binder and cement–limestone powder binder

The early hydration properties of cement–steel slag composite binder and cement–limestone powder composite binder were compared in this study by determining the hydration heat of binder within 3 days, the pore structure of paste and the compressive strength of mortar at the age of 3 days. Results show that at the curing temperature of 25 °C, the early hydration heat of the binder containing steel slag is smaller, and the early pore structure of the paste containing steel slag is coarser, but the early compressive strength of the mortar containing steel slag is higher compared with the mix containing limestone powder. Though the early reaction degree of steel slag is low, its chemical contribution to the strength of mortar cannot be neglected. At the curing temperature of 50 °C, the early hydration heat of the binder containing steel slag is larger, and the early pore structure of the paste containing steel slag is finer, and the early compressive strength of the mortar containing steel slag is even higher compared with the mix containing limestone powder. Raising curing temperature can enhance the role played by steel slag more significantly than that played by limestone powder in the hydration and hardening of the composite binder.     

Calorimetric and thermal analysis studies on the influence of waste aluminosilicate catalyst on the hydration of fly ash–cement paste

Binders containing large amounts of cement substitutes have been a subject of interest for many years because of the possibility to reduce the amount of cement in concrete, and in consequence decrease negative influence of cement production on natural environment. In this work, studies related to hydration of binders where 80 % of cement was substituted by blended pozzolana were carried out. The aim of this work was to investigate activation of fly ash–cement system by addition of spent aluminosilicate catalyst, using calorimetry and thermal analysis as main methods of investigations. It was demonstrated that spent fine-grained fluidised catalytic cracking catalyst acts acceleratingly on early hydration of binder. It seems to be beneficial to use up to 10 mass% of this spent catalyst. Higher amounts may cause changes in the mechanism of early hydration. Because Ca(OH)₂ in such systems is quickly consumed due to pozzolanic reaction it seems beneficial to modify composition of binders by introducing additional amounts of Ca(OH)₂ or cement.     

Calorimetry in the studies of cement hydration

Calorimetry was applied to an investigation of the early hydration of Portland cement (PC)–calcium aluminate cement (CAC) pastes. The heat evolution measurements were related to the strength tests on small cylindrical samples and standard mortar bars. Different heat-evolution profiles were observed, depending on the calcium aluminate cement/Portland cement ratio. The significant modification of Portland cement heat evolution profile within a few hours after mixing with water was observed generally in pastes containing up to 25% CAC. On the other hand the CAC hydration acceleration effect was also obtained with the 10% and 20% addition of Portland cement. As one could expect the compressive and flexural strength development was more or less changed—reduced in the presence of larger amount of the second component in the mixture, presumably because of the internal cracks generated by expansive calcium sulfoaluminate formation.     

Deposition of cesium and cobalt sorbed on zeolite in matrices of blast furnace slag

¹³⁷Cs and⁶⁰Co were sorbed from model solutions and waste water on chemically treated granular zeolite. The zeolite was incorporated into cement slurries based on blast furnace slag (BFS). The compressive and bending strength were measured after different times of hydration. The leaching tests were performed in water, base and acid solutions. The leachability was more pronounced only for samples in acidic solutions.     

Influences of fly ash and fluorgypsum on the hydration heat and compressive strength of cement

The hydration heat of pure cement, fly ash single-doped cement, as well as fly ash and fluorgypsum co-doped cement were investigated by means of micro-calorimetry with an eight-channel micro-calorimeter. The results showed that the hydration heat and the hydration rate could be reduced significantly by fly ash and fluorgypsum. However, the reduction was not proportional to the loading of dopant. The exothermic peak of the co-doped cement was appeared earlier than that of the single-doped cement. As the temperature decreased, the hydration heat and the hydration rate of both the doped cement were reduced, and the exothermic peak appeared later. The effect of fly ash and fluorgypsum on the compressive strength of cement was also investigated. The results revealed that the early compressive strength of concrete made up of the co-doped cement was largely higher than that of the single-doped cement. Based on the experiment results obtained in this article, we could conclude that fluorgypsum is a suitable additive for the single-doped cement.