Hydration of Portland cement with high replacement by siliceous fly ash

The effects of two different low calcium fly ashes on the hydration of ordinary Portland cement (OPC) pastes containing 50 wt.% of fly ash were investigated over a hydration time of 550 days. The results were compared with a reference blend of OPC containing 50 wt.% of inert quartz powder allowing the distinction between "filler effect" and pozzolanic reaction.Until 2 days, no evidence of fly ash reaction was measured and its influence on the hydration is mainly related to the “filler effect”. From 7 days on, the effects of the pozzolanic reaction were observed by the consumption of portlandite, the change of the pore solution chemistry, the formation of a presumably water-rich inner hydration product and the change of the C–S–H composition towards higher Al/Si ratio compared to the C–S–H of neat OPC. Additional strength due to the pozzolanic reaction developed after 28 days of hydration.     

The effect of pressure on tricalcium silicate hydration at different temperatures and in the presence of retarding additives

The hydration of tricalcium silicate (C₃S) is accelerated by pressure. However, the extent to which temperature and/or cement additives modify this effect is largely unknown. Time-resolved synchrotron powder diffraction has been used to study cement hydration as a function of pressure at different temperatures in the absence of additives, and at selected temperatures in the presence of retarding agents. The magnitudes of the apparent activation volumes for C₃S hydration increased with the addition of the retarders sucrose, maltodextrin, aminotri(methylenephosphonic acid) and an AMPS copolymer. Pressure was found to retard the formation of Jaffeite relative to the degree of C₃S hydration in high temperature experiments. For one cement slurry studied without additives, the apparent activation volume for C₃S hydration remained close to ~ ? 28 cm³ mol^? 1 over the range 25 to 60 °C. For another slurry, there were possible signs of a decrease in magnitude at the lowest temperature examined.     

Characterization of coal fly ash for possible utilization in glass production

The recycling of three different fly ashes obtained from the coal fired thermal power plants has been studied. Coal fly ashes were vitrified by melting them at 1773 K for 5 h without any additives. After the glass production, glass samples were subjected to a heat treatment process to be able to see whether or not the glasses could be transformed into a microcrystalline structured materials. Produced glass samples were heated to 1423 K and held at this temperature for 2 h to determine the effect of heat treatment process on the properties of glasses. The properties of glass and the heat treated glass samples produced from coal fly ash were investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. DTA study indicated that there were only inflection points of the endothermic peaks in the DTA curves of the glass samples. XRD analysis showed the amorphous state of the glass samples and also the presence of only the diopside phase in the heat-treated glass samples. SEM investigations revealed that small amount of crystallites occurred in the microstructure of the heat treated glass samples in contrast to the amorphous structure of the glass samples. The mechanical, physical and chemical properties of the heat-treated glass samples are found better than those of the glass samples. Toxicity characteristic leaching procedure (TCLP) results showed that the heavy metals of fly ashes were successfully immobilized into both glass and heat treated glass samples. It can be said that glass and heat treated glass samples obtained by the recycling of coal fly ash can be taken as a non-hazardous material. Overall, results indicated that the vitrification technique is an effective way for the stabilization and recycling of coal fly ash.     

Adsorption of an acid dye onto coal fly ash

In this study, we found the raw coal fly ash (CFA) that had not been subjected to any pretreatment process had superior adsorbing ability for the anionic dye Acid Red 1 (AR1) than did two modified coal fly ashes (CFA-600 and CFA-NaOH). The adsorption capacities followed the order CFA > CFA-600 > CFA-NaOH, and they each increased upon increasing the temperature (60 °C > 45 °C > 30 °C). The adsorptions of AR1 onto CFA, CFA-600, and CFA-NaOH all followed pseudo-second-order kinetics. The isotherms for the adsorption of AR1 onto the raw and modified coal fly ashes fit the Langmuir isotherm quite well; the adsorption capacities of CFA, CFA-600, and CFA-NaOH for AR1 were 92.59–103.09, 32.79–52.63, and 12.66–25.12 mg g^?1, respectively. According to the positive values of ΔH° and ΔS°, these adsorptions were endothermic processes. The ARE and EABS error function methods provided the best parameters for the Langmuir isotherms and pseudo-second-order equations, respectively, in the AR1–CFA adsorption system.     

How to increase the hydration degree of CA — The influence of CA particle fineness

It is shown that the hydration degree of CA is directly dependent on the fineness of CA-particles. Finer particles lead to an increased degree of hydration and also an increased hydration rate.The reaction of a sample with mainly coarse particles of CA (d₅₀ = 50 μm) is characterized by a low hydration rate and only 34 rel.-% of CA dissolved after 22 h. Whereas in a very fine CA-sample (d₅₀ = 4 μm) hydration starts delayed but then shows the highest hydration rate and a dissolution of 62 rel.-% CA. The behaviour is explained by the coverage of CA-particles with a dense hydrate layer of C₂AH_x and AH_x. This reacted CA-rim is supposed to have the same thickness for different sized CA-particles. Optimization of Gauss distribution curves, which were applied to simulate a more realistic particle size distribution, leads to a reacted rim thickness of 1.3 μm until reaction is stopped.     

Synthesis of monocrystalline Ca3SiO5 using the optical floating zone method

Alite (Ca₃SiO₅/C₃S with low concentrations of foreign ions) is the main constituent of Ordinary Portland Cement. Normally it forms during sintering but with quite low crystal sizes (ca. 30 μm). For experiments on alite hydration behavior monocrystalline grains are required. Due to its incongruent melting behavior and its thermodynamic instability below 1250 °C it is very challenging to obtain large alite single crystals.In the present study, the floating zone method was used for annealing polycrystalline rods of monoclinic and triclinic C₃S just below the melting point of the phase. Large monocrystalline grains (> 500 μm) of the monoclinic (Al, Mg-doped) and triclinic polymorphs could successfully be obtained. Monocrystallinity was demonstrated by electron backscatter diffraction (EBSD). The chemical composition regarding incorporation of foreign ions and thus the resulting crystallographic modification of the C₃S can easily be adjusted. Chemical homogeneity of the synthesized monocrystalline grains was proven by electron probe microanalysis (EPMA).     

Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C.The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling.The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity.     

Filtration of fly ash using fluidized bed at 300–500 °C

The filtration of the coal-burning fly ash using fluidized beds with silica sand of 770 μm under temperatures of 36, 300, 400, and 500 °C was studied. The variations of the outlet concentration and particle size distribution (PSD) with time were measured to evaluate the dynamic characteristics of the process. Experimental results showed that the overall collection efficiency decayed with the operation time, revealed the effect of the elutriation of fly ash on particle filtration. The collection efficiency rose when the temperature increased from 36 °C to 500 °C. The strong attrition at high temperature released more small particles than that at room temperature, increased the concentration of the particles less than 10 μm (PM₁₀) at high temperature. The removal efficiency of the particles in a size of 4–7 μm, not the submicron particles, is the lowest because they are most easily elutriated from fluidized beds.     

The effect of temperature on the rate of sulfate attack of Portland cement blended mortars in Na2SO4 solution

Sulfate attack on Portland cement and Portland blended cement concretes is a well-researched field. However, the effect of varying temperature on the rate of sulfate attack requires further attention. This laboratory experiment studied temperatures of 23 °C, 10 °C, 5 °C, and 1 °C. Both Portland and Portland limestone cements were studied in combination with several supplementary cementing materials. The mortar bars were submerged in 5% Na2SO4 (33,800 ppm SO₄^2 −) solution for 15–30 months. At higher temperatures the supplementary cementing materials, particularly the fly ashes, greatly improved the resistance to external sulfate attack. At lower temperatures the metakaolin improved the resistance to sulfate attack; the fly ashes had little to no effect on the low-temperature sulfate resistance. The alterations to sulfate resistance are attributed to: dilution of Portland cement in the presence of supplementary cementing materials; additional nucleation sites provided by finely ground SCMs; and the pozzolanic and hydraulic reactions of the SCMs.     

Microstructural characterization and crystallization behaviour of (1 − x)TeO2–xWO3 (x = 0.15, 0.25, 0.3 mol) glasses

DTA, XRD and SEM investigations were conducted on the (1 − x)TeO₂–xWO₃ glasses (where x = 0.15, 0.25 and 0.3). Whereas the 0.75TeO₂–0.25WO₃ and 0.7TeO₂–0.3WO₃ glasses show no exothermic peaks, an indication of no crystallization in their glassy matrices, two crystallization peaks were observed on the DTA plot of the 0.85TeO₂–0.15WO₃ glass. On the basis of the XRD measurements of the 0.85TeO₂–0.15WO₃ glass samples heated to 510 °C and 550 °C (above the peak crystallization temperatures), α-TeO₂ (paratellurite), γ-TeO₂ and WO₃ phases were detected in the sample heated to 510 °C and the α-TeO₂ and WO₃ phases were present in the sample heated to 550 °C. SEM micrographs taken from the 0.85TeO₂–0.15WO₃ glass heated to 510 °C showed that centrosymmetrical crystals were formed as a result of surface crystallization and were between 3 μm and 15 μm in width and 12 μm and 30 μm in length. On the other hand, SEM investigations of the 0.85TeO₂–0.15WO₃ glass heated to 550 °C revealed the evidence of bulk massive crystallization resulting in lamellar crystals between 1 μm and 3 μm in width and 5 μm and 30 μm in length. DTA analyses were carried out at different heating rates and the Avrami constants for the 0.85TeO₂–0.15WO₃ glass heated to 510 °C and 550 °C were calculated as 1.2 and 3.9, respectively. Using the modified Kissinger equation, activation energies for crystallization were determined as 265.5 kJ/mol and 258.6 kJ/mol for the 0.85TeO₂–0.15WO₃ glass heated to 510 °C and 550 °C, respectively.     

Assessment of the protective effect of carbonation on portlandite crystals

The kinetics of many reactions important to cement hydration and use are not well understood: this is in part due to the great complexity of many supposedly “simple” processes. One such process, carbonation of portlandite, Ca(OH)₂, in moist air at ~ 23 °C has been investigated by microscopy and microchemical analysis. Single crystals of portlandite were grown, carbonated at relative humidities between ~ 25 and ~ 90%, and the transport properties of the self-generated calcite, CaCO₃, product film were determined.The calcite films thus grown within days or weeks varied in thickness but typically were polycrystalline and epitaxial: a variety of morphologies and surface features are recorded. Permeation was measured by determining the time taken for Ca^2 + ions, arising from the Ca(OH)₂ substrate, to diffuse through the calcite coat into initially pure water. The spontaneous formation of self-protecting films on concrete has long been envisaged: results demonstrate that passivation can actually be achieved.     

SEM investigation of domain structure in (Ba,Ca,Pb)TiO3

In the present paper the microstructure and domain structure in modified BaTiO₃ with Pb and Ca as additives have been investigated using SEM technique. The (Ba,Pb)TiO₃ and (Ba,Ca,Pb)TiO₃ ceramics show a slight difference in grain size, being smaller in composites with Ca additives which acts as grain growth inhibitor. The domain configuration is almost the same. The small grain microstructure with tiny domains have been observed in specimen sintered at 1300°C and the average grain size is in the range 1–3 μm. For those specimens sintered at 1320°C the homogenous microstructure is also obtained with grain size around 2–4 μm. For both types of specimens, the single domain structure is associated with grain which size is lower than 2 μm. The banded domain structure could be observed in grains with size bigger than 3 μm. The bar shape grains and elongated grains together with some large region in microstructure are free of domain structure. The observed domain patterns reveal mainly the straight domain boundary lines with 90° domains walls. The wall thickness ranged from 0·03 μm to 0·15 μm, while the domain width is in the range of 0·1 μm–1 μm.     

Characteristics of precipitated calcium carbonate by hydrothermal and carbonation processes with mega-crystalline calcite using rotary microwave kiln

In the conventional kiln, mega-crystalline calcite (m-CC) breaks apart easily during calcinations, and cannot be easily converted to CaO due to that it requiring a lot of heat. In this study, m-CC was calcined to CaO of around 1 mm using the rotary microwave kiln. Furthermore, CaCO₃ was produced by the carbonation process and hydrothermal process, and the form of CaCO₃ was characterized.Calcination of m-CC using the rotary microwave kiln resulted in CaO (97 wt%) of relatively fine size.CaCO₃ of colloidal-shaped and 6 μm in size could be prepared by applying the carbonation process to Ca(OH)₂ using a bubble reactor at 25 °C. As the carbonation temperature increased from 25 to 80 °C, the shape of prepared CaCO₃ changed from a colloidal-type to spindle-type of 1 μm due to self-assembly. Also, hexagonal-shaped aragonite could be prepared by the hydrothermal process with the supersaturated Ca(HCO₃)₂ solutions.     

Characterization of porous silicon nitride ceramics by pressureless sintering using fly ash cenosphere as a pore-forming agent

A new method for fabricating porous silicon nitride ceramics has been developed by using fly ash cenosphere (FAC) with mean diameter of 87 μm as a pore-forming agent. Sintering was carried out at 1780 °C for 2 h under a nitrogen atmosphere. FAC can also act as a sintering aid besides a pore-forming agent. X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies showed that YSiO₂N forms instead of Y₂Si₃O₃N₄ when FAC is incorporated. Microstructural analysis revealed that large spherical cavities are scattered in a relative dense matrix. Porous Si₃N₄ ceramics with density of 2.17–2.30 g/cm³, Young’s modulus of 141–150 GPa and strength of 180–320 MPa were obtained by changing the FAC content.     

Effects of components on the rate of heat liberation of the hydration in the system of glass/gypsum/lime

Slag-simulated glasses in the system of CaO–Al₂O₃–SiO₂ were prepared. Their rates of heat liberation were measured in the system with gypsum and lime, especially in the excess gypsum system. They have a period with constant rate of heat liberation. These rates depend on the components of the glass. The effects of the components on the rate of heat liberation were discussed.The rates of constant heat liberation depend on the composition of glass especially the contents of CaO and Al₂O₃. The period of this process was controlled by the amount of lime addition. During this stage, the solid Ca(OH)₂ was completely consumed. In this sulfate-excess system, the reaction equation, during Ca(OH)₂ consumption, should be written as; glass + gypsum + lime ⇒ C–S–H with a C/S ratio of 1.42 and Ettringite.     

Effect of micro-sized alumina powder on the hydration products of calcium aluminate cement at 40 °C

In this work, the effect of different micro-sized alumina powders on the hydration products of calcium aluminate cement (CAC) during hydration at 40 °C is studied. The cement hydration at the designated times is terminated by the freeze-vacuum method. The phase development and microstructure evolution during the cement hydration are investigated by XRD and DSC, and SEM, respectively. It is found that 3CaO·Al₂O₃·6H₂O (C₃AH₆) is the dominant product of the pure CAC after hydration at 40 °C for 3.5 h. But 2CaO·Al₂O₃·8H₂O (C₂AH₈) is the dominant hydrate and C₃AH₆ is not found in the mixtures of CAC and micro-sized alumina powder under the same condition. The results indicate that the addition of alumina powders promotes the formation of C₂AH₈ and retards the conversion of C₂AH₈ to the C₃AH₆ phase. Moreover, such phase development with alumina addition is discussed.     

Effect of BaCO3 on C3A hydration

Ba ions are known to immobilise sulfates by forming BaSO₄. The use of BaCO₃ as a full or partial substitute for gypsum to regulate C₃A (3CaO·Al₂O₃) hydration was consequently studied with a view to establishing its correct dosage in sulfate-resistant cements presently under development.The hydration rate of synthetic C₃A was determined in the presence of varying percentages of gypsum, BaCO₃, and gypsum + BaCO₃ by running conduction calorimetry analyses on early age (up to 20 h) samples. The hydration products were subsequently identified with XRD, FTIR and DTA/TG.The addition of (20–42 wt.%) BaCO₃ to C₃A neither regulated the speedy reaction of the latter with water nor reacted with the aluminate. Gypsum + BaCO₃ blends proved able to regulate C₃A hydration; the heat flow curves for the mixes studied exhibited an induction period, an indication that gypsum acted as a C₃A hydration regulator whilst at the same time reacting with BaCO₃ to form barite.     

Improvement of the durability of glass fiber reinforced cement using blended cement matrix

Blended cements prepared with two fly ashes were used as matrices in glass fiber reinforced cement (GRC) composites in an attempt to improve their durability. The hydrated matrices from the two blended cements investigated here had similar strength and composition. Both fly ashes reduced the Ca(OH)₂ content to the same extent but in both cases the pH level was only slightly reduced compared to the portland cement matrix. In spite of these similarities, the GRC prepared with one fly ash showed considerable improvement in durability while the other one had only a small positive effect. SEM observations indicated that the improved durability in one case was associated with modification in the microstructure of the hydration products deposited in between the glass filaments, resulting in a much more open structure compared to that of portland cement matrix or the other blended cement. It is therefore suggested that the potential of the blended cement matrix to improve the durability of GRC is associated with its ability to modify the microstructure of the paste at the glass interface. This characteristic is not necessarily related to the overall composition of the blended cement matrix and to the reactivity of fly ash with Ca(OH)₂.     

Continuous experiment regarding hydrogen production by Coal/CaO reaction with steam (II) solid formation

Integration of coal gasification and CO₂ separation reactions in one reactor may produce a high concentration of hydrogen. To design a reactor for this new reaction system, it is necessary to know all reaction behaviors in the integrated reaction system. In our previous study, we performed a continuous reaction experiment of coal/CaO under high steam pressure and confirmed that H₂ concentration higher than 80 vol% with little CH₄ was produced; and that almost all CO₂ was fixed by adding CaO. In this study, the behaviors of solid products during the continuous experiment were investigated. It was found that, CaO first reacted with high-pressure steam to form Ca(OH)₂ (hydration), then the Ca(OH)₂ absorbed the CO₂ generated by coal gasification to form CaCO₃. The hydration of CaO restored sorbent reactivity. Eutectic melting of Ca(OH)₂/CaCO₃ was found to occur in the experiment at 973 K, and this eutectic melting led to the growth of large particles of solid materials. However, at the relatively low temperature of 923 K, eutectic melting could be avoided. Carbon conversion of the coal in the continuous reaction of the coal/CaO mixture with steam was high as 60–80%, even at the lower temperature of 923 K.     

Mineralogical and engineering characteristics of dry flue gas desulfurization products

Fifty-nine coal combustion products were collected from coal-fired power plants using various dry flue gas desulfurization (FGD) processes to remove SO₂. X-ray diffraction analyses revealed duct injection and spray dryer processes created products that primarily contained Ca(OH)₂ (portlandite) and CaSO₃·0.5H₂O (hannebachite). Most samples from the lime injection multistage burners process contained significant amounts of CaO (lime), CaSO₄ (anhydrite), and CaCO₃ (calcite). Bed ashes from the fluidized bed process were often dominated by CaSO₄ but also contained CaCO₃, CaO (lime), and MgO (periclase). Cyclone ashes were similar in composition to the bed ashes but contained more unspent sorbent and CaSO₄ and less MgO. Fly ash in all samples ranged from 10 to 79 wt%. Samples usually exhibited two distinct swelling episodes. One occurred immediately after water was applied due to hydration reactions, especially the conversion of CaO to Ca(OH)₂ and CaSO₄ to CaSO₄·2H₂O (gypsum). The second began between 10 and 50 d later and involved formation of the mineral ettringite (Ca₆[Al (OH)₆](SO₄)₃·26H₂O). The final pH after 112 d ranged from 10.0 to 12.1. If samples are incubated under ‘closed’ (i.e. incomplete recarbonation with atmospheric CO₂) and alkaline weathering conditions, gypsum and portlandite are initially formed followed by the conversion of the gypsum to ettringite. Closed, alkaline conditions typically can occur when FGD products are placed in confined settings such as a road embankment or buried as a discrete layer as occurs in some surface mine reclamation projects.