Hydration and hardening processes of Portland cements obtained from clinkers mineralized with fluoride and oxides

The hydration and hardening processes of Portland cements prepared from clinkers mineralized with sodium fluoride and/or oxides (SnO₂ or CuO) was studied. Type I cements (CEM I) were prepared by grinding with gypsum (5%) of clinkers obtained by the burning of an industrial raw mix with different mineralizers: sodium fluoride, oxides (CuO and SnO₂) or mixtures of sodium fluoride and oxide (NaF + CuO or NaF + SnO₂). The influence of foreign ions on the clinker morphology was assessed by scanning electronic microscopy (SEM) and energy dispersive X-ray spectrometry (EDX). The hydration processes of modified cements were examined by X-ray diffraction analysis (XRD) and thermal analysis techniques (TG and DTA). The main properties of the cements, i.e., flexural and compressive strengths, setting time, and soundness were also determined. A good correlation between the chemically bound water or portlandite content in pastes hydrated 2–28 days and compressive strength developed by mortars was observed. The influence of mineralizers on the kinetic of hydration processes and main properties of cements is different—0.5% NaF and 0.5% SnO₂ and their mixture increase the rate of cement hydration and hardening processes, opposite to 0.5% CuO that reduce the rate.     

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.     

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.     

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.     

Improvement of surface cementitious properties of coarse fly ash by dehydration and rehydration processes

Owing to poor bonding between coarse fly ash particles and hydration products, gap-graded blended cements with fly ash usually show lower compressive strengths than Portland cement. Surface cementitious properties of coarse fly ash were improved by dehydration and rehydration processes in the present study. The results show that during the calcination at 750?°C, C?CS?CH gel is mainly transformed into a new nesosilicate, which is similar to a less crystalline C₂S. The formation of melilite from hydration products is also noticed at 900?°C, however, this will not contribute to rehydration of calcined fly ash. Rehydration of new generated nesosilicate on the surface of coarse fly ash leads to a better bonding between coarse fly ash particles and hydration products. As a result, both early and late mechanical properties of gap-graded blended cements containing 25% cement clinker and 39% calcined coarse fly ash are higher than those of 100% Portland cements.     

Identification of Composite Cement Hydration Products by Means of X-Ray Diffraction

 In this paper the effect of limestone, fly ash, slag and natural pozzolana on the cement hydration products is studied. Four composite cements containing limestone, natural pozzolana from the Milos Island, slag and fly ash have been produced by intergrinding clinker (85%), the above main constituent (15%) and gypsum. The grinding process was designed in order to produce cements of the same 28d compressive strength. The hydrated products, formed after 1–28 days, were studied by means of X-ray diffraction. Unhydrated calcium silicate compounds of clinker and hydration products such as C*H, C*S*H and ettringite are clearly observed. Although there is not significant differentiation among samples hydrated for the same period of time, modifications of calcium aluminate hydrates as well as sulfoaluminate hydrates, are indicated by the XRD patterns. In samples of limestone cement, monocarboaluminate is formed in the first 24 hours and is still present after 28 days.     

Lessons learned from fires of the wood caused by the spontaneous combustion of coal dust in underground mines

The capture of CO₂ and SO₂ from industrial gas effluents has been done usually by lime-containing products. For this purpose, cement pastes also can be used, due mainly to their calcium hydroxide content formed during hydration. To select the best cement for this purpose, TG and DTG curves of different Portland cement pastes (types I, II, III and G), prepared with a water-to-cement ratio (W/C) equal to 0.5, were analyzed at different ages, at same operating conditions. The curves were transformed into respective cement calcined and initial mass basis, to have a common and same composition reference basis, for a correct quantitative hydration data comparison. This procedure also shows that there is an unavoidable partial drying effect of the pastes before starting their analysis, which randomly decreases the W/C ratio at which were prepared, which indicates that, when results are compared on respective paste initial mass basis, assuming that the ratio W/C has not changed, possible calculation errors may be done. Type I, II and G analyzed cements have shown similar hydration characteristics as a function of time, while the analyzed type III cement has shown a different hydration behavior, mainly due to its highest Al₂O₃ and lowest SO₃ contents, promoting the formation of hydrated calcium aluminates, by the pozzolanic action of the excess of alumina, consuming Ca(OH)₂, which final content at 28 days was the lowest one, among the hydrated cements.     

Influence of mechanical grinding on pozzolanic characteristics of circulating fluidized bed fly ash (CFA) and resulting consequences on hydration and hardening properties of blended cement

This paper investigates the influence of mechanical grinding on pozzolanic characteristics of circulating fluidized bed fly ash (CFA) from the dissolution characteristics, paste strength, hydration heat and reaction degree. Further, the hydration and hardening properties of blended cement containing different ground CFA are also compared and analyzed from hydration heat, non-evaporable water content, hydration products, pore structure, setting time and mortar strength. The results show that the ground CFA has a relatively higher dissolution rate of Al₂O₃ and SiO₂ under the alkaline environment compared with that of raw CFA, and the pozzolanic reaction activity of ground CFA is gradually improved with the increase of grinding time. At the grinding time of 60 min, the pozzolanic reaction degree of CFA paste is improved from 6.32% (raw CFA) to 13.71% at 7 days and from 13.65 to 28.44% at 28 days, respectively. The relationships of pozzolanic reaction degree and grinding time of CFA also conform to a quadratic function. For ground CFA after a long-time grinding such as 60 min, the hydration heat and non-evaporable water content of blended cement containing CFA are significantly improved. Owing to relatively smaller particle size and higher activity of ground CFA, the blended cement paste has more hydration products, narrower pore size distribution and lower porosity. For macroscopic properties, with increase in grinding time of CFA, the setting time and strength of blended cement are gradually shortened and improved, respectively.     

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.     

Sulphate resistance and passivation ability of the mortar made from pozzolan cement with zeolite

Sulphate resistance and passivation ability of the mortars made from pozzolan cement of CEM IV/A (P) type according to European Standard EN 197-1 (zeolite blended cement with 60.82 mass% of PC clinker, 35.09 mass% of zeolite and 4.09 mass% of gypsum abbreviated as ZBC) and ordinary Portland cement (abbreviated as PC) are introduced. Resistance tests were performed in water and 5% sodium sulphate solution (both 20°C) for 720 days. The increased sulphate resistance of pozzolan cement relative to that of PC was found. The key quantitative insight into the hydrate phase behaviour is given by thermal analysis. This is due to pozzolanic reaction of zeolite with PC resulting in reduction of the formed Ca(OH)₂ opposite to the reference PC. Ability of pozzolan cements with 15 to 50 mass% of zeolite to protect steel against corrosion was verified in 20°C/85% RH-wet air within 180-day cure. Steel was not corroded in the mortars made with pozzolan cement containing up to 35 mass% of zeolite. Pozzolan cement of CEM IV/A (P) type containing 35 mass% of zeolite is a suitable cementitious material for concrete structures exposed to sulphate attack. Steel is protected against corrosion by this pozzolan cement in the same measure as the reference PC.     

A Study on the Hydration of Portland Limestone Cement by Means of TG

Subject of this paper is to investigate the hydration process of Portland limestone cement containing 10-35% limestone. Cements, produced by co-grinding of clinker, limestone and gypsum, were hydrated for periods 6 h to 28 d and were studied by means of TG and XRD. The Ca(OH)₂ content of the cements containing limestone is higher than in pure cements, specifically for 10% limestone content and ages more than 1 day. These results are in accordance with the strength development of the studied cements. In earlier ages the Ca(OH)₂ content is slightly lower in the limestone cements and independent of the limestone content. After 1 day curing, the increase of limestone addition causes a relative increase of the non evaporable water. The XRD patterns indicated the presence of carboaluminates in the hydrated limestone cements. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study on optimization of hydration process of blended cement

To optimize the hydration process of blended cement, cement clinker and supplementary cementitious materials (SCMs) were ground and classified into several fractions. Early hydration process of each cementitious materials fraction was investigated by isothermal calorimeter. The results show fine cement clinker fractions show very high hydration rate, which leads to high water requirement, while fine SCMs fractions present relatively high hydration (or pozzolanic reaction) rate. Cement clinker fractions in the range of 8–24 μm show proper hydration rate in early ages and continue to hydrate rapidly afterward. Coarse cement clinker fractions largely play “filling effect” and make little contribution to the properties of blended cement regardless of their hydration activity (or pozzolanic activity). The hydration process of blended cement can be optimized by arranging high activity SCMs, cement clinker, and low activity SCMs in fine, middle, and coarse fractions, respectively, which not only results in reduced water requirement, high packing density, and homogeneous, dense microstructure, but also in high early and late mechanical properties.     

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.     

Study of a Brazilian spent catalyst as cement aggregate by thermal and mechanical analysis

Fluidized catalytic cracking units of refineries normally use zeolite catalysts to treat heavy oil fractions. This catalyst is regenerated continuously, but due to the reduction of its activity during the process, it is partially substituted by a new catalyst make-up. The spent residue has a high content of silicon and aluminum oxides and usually presents pozzolanic properties. This paper presents the study of a Brazilian spent catalyst, which is being tested as a pozzolanic aggregate in partial substitution to cement. Pastes were prepared with 15, 20 and 25% in substitution to cement mass and analyzed after 28 days of hydration. Hydrated paste samples were analyzed by simultaneous thermogravimetry and differential thermal analysis, to quantify the calcium hydroxide consumption, as well as the content of other main hydrated cement phases. Compressive strength analysis was also performed after 28 days of hydration. Although, as spent catalyst content is increased, the pozzolanic activity is confirmed by the increase of calcium hydroxide consumption on cement mass basis, unlikely to other studied spent FCC catalysts, tested for the same purpose, the compressive strength of respective paste specimens decreases, due to the increase of other hydrated phases formation.     

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.

     

Calcite,vaterite and aragonite forming on cement hydration from liquid and gaseous phase

Cement hydration products were studied as influenced by the hydration conditions (hydration time in liquid phase; relative humidity, RH, in gaseous phase). The formation of calcium hydroxide (portlandite, P) and its transformation to calcium carbonates is mainly discussed here. More hydration products, including P, were formed in liquid phase (paste) than in water vapor (powder), due to the higher availability of water molecules. Full hydration was observed only in the paste hydrated for 6 month, otherwise the P content, estimated from its water escape, DM(400-800°C), increased after storage in water vapor of the prehydrated paste. All the three polymorphs of CaCO₃ (calcite, vaterite and aragonite) were found on prolonged contact with air of the hydrated powder (XRD, HRTEM). Their content was dependent on sequence of RH conditions on hydration: higher after water retention, WR, on lowering RH=1.0→0.95→0.5, than after water sorption, WS, on increasing RH in the inverse order. It increased also on wetting and drying, both of hydrated powder and paste. Ca was found to accumulate on the micro-surfaces of WR samples (SEM, TEM), whereas more Al was observed on WS samples and the crystallinity of hydration products was here higher (ED). Dissolution-diffusion-recrystallization was possible: small Al-ions concentrated at one end and the bigger Ca ions - at the other end of some needles (TEM). At 400-500°C the P in cement transforms in air into CaCO₃, which decomposes at 600-700°C. Thus the sensitivity to carbonation was estimated from ΔM(600-800°C). This value was similar in pastes hydrated for 1 month and in powder (WR). It was lower in powder WS and much lower in the paste (6 months). It increased pronouncedly when the prehydrated paste was stored in water vapor in WS. The nanocrystals of portlandite, vaterite and aragonite, embedded in the amorphous matrix, were observed by HRTEM in the hydrated powder. They may contribute to the cement strength. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚羧酸减水剂在水泥水化过程中的微观表现

采用SEM、IR、XRD、pH值和电导率等分析手段研究了聚羧酸减水剂对水泥水化初期的影响,结果表明,聚羧酸减水剂具有减缓水泥的初期水化作用,水泥水化产物的聚合度随水化时间增加而增大,但晶型不改变。在水泥中添加0．3％聚羧酸减水剂,32．5#水泥3d、7d和28d的抗压强度分别提高了50．9％、40．4％、35％。     

The Effect of Different Bentonites on Cement Hydration During Solidification/Stabilization of Tannery Wastes

In the present work, a Portland cement blended with calcium carbonate is being used to study the solidification/stabilization (S/S) of a Brazilian tanning waste arising from leather production. Chromium is the element of greatest concern in this waste, but the waste also contains a residual organic material. Using thermogravimetry (TG) and derivative thermogravimetry (DTG) to identify and quantify the main hydrated phases present in the pastes, this paper presents a comparative study between the effects of Wyoming and Organophilic bentonites (B and OB) on cement hydration. Samples containing combinations of cement, B, OB and waste have been subjected to thermal analysis after different setting times during the first 28 days of the waste S/S process. Both bentonites affect the cement hydration, with no significant differences in hydration degree after 1 week. This work shows further examples of the great utility of thermal analysis techniques in the study of very complex systems containing both crystalline and amorphous mineral materials as well as organics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Early stages hydration of high initial strength Portland cement

Thermogravimetry (TG) and derivative thermogravimetry (DTG) were used to analyze the early stages of hydration of a high-initial strength and sulphate resistant Portland cement (HS SR PC) within the first 24 h of setting. The water/cement (W/C) mass ratios used to prepare the pastes were 0.35, 0.45, and 0.55. The hydration behavior of the pastes was analyzed through TG and DTG curves obtained after different hydration times on calcined cement mass basis to have a same composition basis to compare the data. The influence of the W/C ratio on the kinetics of the hydration process was done through the quantitative analysis of the combined water of the main hydration products formed in each case. TG and DTG curves data calculated on calcined mass basis of all the results were converted to initial cement mass basis to have an easier way to analyze the influence of the W/C ratio on the free and combined water of the different main hydrated phases. The gypsum content of the pastes was totally consumed in 8 h for all cases. A significant part of the hydration process occurs within the first 14 h of setting and at 24 h the highest hydration degree, indicated by the respective content of formed calcium hydroxide, occurs in the case of the highest initial water content of the paste.     

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.