Investigations of the influence of different fly ashes on cement hydration

Investigations of physico-chemical properties of three kinds of fly ash and their influence on cement hydration were performed in this work. Thermal analysis, microcalorimetry, infrared absorption and others were used. It was confirmed that the kind of coal and combustion conditions essentially influence physico-chemical properties of fly ash and in consequence influence cement hydration. Investigated fly ashes show in cement system so-called pozzolanic activity. Fly ash from combustion of brown coal in fluidized furnace revealed better activity compared to other investigated ones. This work is an introduction to more extensive investigation of fly ash activation.     

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.     

Preparation and characterization of activated carbon from bagasse fly ash

Activated carbons from bagasse fly ash (BFA) were prepared by one step chemical activation using ZnCl₂ as activating agent, or combination method of chemical with CO₂ physical activation (physicochemical activation). The development of porosity was studied in correlation with the method of activation, activation temperature, and also the chemical weight ratio. A typical sample by the combination method at 600 °C and weight ratio of ZnCl₂:BFA = 2 exhibited micropore volume of 0.528 cc/g, mesopore volume of 0.106 cc/g and surface area of 1200 m²/g. For determining the adsorption capacity of the carbon samples in solutions, phenol and methylene blue equilibrium adsorption experiments were conducted. The properties and adsorption capacity of the synthesized activated carbons has been compared to commercial activated carbon (Norit^® SX Plus).     

Microstructure development in mixes of calcium aluminate cement with silica fume or fly ash

The most widely identified degradation process suffered by calcium aluminate cement (CAC) is the so-called conversion of hexagonal calcium aluminate hydrate to cubic form. This conversion is usually followed by an increase in porosity determined by the different densities of these hydrates and the subsequent loss of strength. Mixes of calcium aluminate cement (CAC) and silica fume (SF) or fly ash (FA) represent an interesting alternative for the stabilization of CAC hydrates, which might be attributed to a microstructure based mainly on aluminosilicates. This paper deals with the microstructure of cement pastes fabricated with mixtures CAC-SF and CAC-FA and its evolution over time. Thermal analysis (DTA/TG), X-ray diffraction (XRD) and mid-infrared spectroscopy (FTIR) have been used to assess the microstructure of these formulations.     

Fast physics-chemical characterization of fly ash

This paper analyzes the effect of fly ash chemical character on early Portland cement hydration and the possible adverse effects generated by the addition of gypsum. Behaviour was analyzed for pure Portland cements with varying mineralogical compositions and two types of fly ash, likewise differing in chemical composition, which were previously characterized under sulphate attack as: silicic-ferric-aluminic or aluminic-silicic ash in chemical character, irrespective if they are in nature, siliceous or siliceous and aluminous materials according to the ASTM C 618-94a. The experimental results showed that water demand for paste with a normal consistency increased with the replacement ratio in fly ash with a more aluminic than silicic chemical character, whereas it declined when silicic-ferric-aluminic ash was used. On the other hand, the differences between the total heat of hydration released at the first valley and the second peak also clearly differentiated the two types of ash. While the relative differences increased in the more aluminic than silicic ash, they declined in the more silicic than aluminic. In another vein, the findings indicate that within a comparable Blaine fineness range, the reactive alumina (Al₂O₃^r−) content in pozzolanic additions has a greater effect on mortar strength than the reactive silica (SiO₂^r−) content, at least in early ages up to 28 days. Finally, the adverse effect generated in the presence of excess gypsum is due primarily to the chemical interaction between the gypsum and the C₃A in the Portland cement and the reactive alumina (Al₂O₃^r−) in the fly ash.     

Hydration behaviour of a lime-pozzolan cement containing MSW incinerator fly ash

A lime-pozzolan cement was used to make pastes containing different quantities of MSW fly ash. After setting, the pastes were cured in water at room temperature from 1 h to 260 days. The hydration characteristics and the nature of the hydration products of the various pastes were studied by simultaneous TG/DSC thermal analysis and X-ray diffractometry. The MSW fly ash was found to induce a slowing of the hydration process in lime-pozzolan pastes, and after some days an evident acceleration of hydration reactions occurred. Sulphate and chloride in the MSW fly ash yield hydration products forming a cementitious matrix.The author is grateful to D. Calabrese for assistance with the thermal and XRD analyses.     

Studies of fly ash using thermal analysis techniques

Improved thermoanalytical methods have been developed that are capable of quantitative identification of various components of fly ash from a laboratory-scale fluidized bed combustion system. The thermogravimetric procedure developed can determine quantities of H₂O, Ca(OH)₂, CaCO₃, CaSO₄ and carbonaceous matter in fly ash with accuracy comparable to more time-consuming ASTM methods. This procedure is a modification of the Mikhail-Turcotte methods that can accurately analyze bed ash, with higher accuracy regarding the greater amount of carbonaceous matter in fly ash. In addition, in conjunction with FTIR and SEM/EDS analyses, the reduction mechanism of CaSO₄ as CaSO₄+4H₂ CaS + 4H₂O has been confirmed in this study. This mechanism is important in analyzing and evaluating sulfur capture in fluidized-bed combustion systems.     

Influence of initial casting temperature and dosage of fly ash on hydration heat evolution of concrete under adiabatic condition

The calorimetric data of binders containing pure Portland cement, 20% fly ash, 20% slag and 10% silica fume respectively are determined at different initial casting temperatures using an adiabatic calorimeter to measure the adiabatic temperature rising of concrete. The calorimetric data of binders with different dosages of fly ash at two water binder ratios (w/b) are determined, too. Elevation of initial casting temperature decreases the heat evolution of binder, enhances the heat evolution rate of binder and increases the heat evolution rate of binder at early age. The dosage of fly ash in concrete has different effects on the heat evolution of binder with different w/b. At high w/b ratio the heat evolution of binder decreases when dosage of fly ash increases. At low w/b ratio the heat evolution of binders increases when dosage of fly ash increases from 0 to 40% of total binder quantity. The heat evolution of binder decreases after the dosage of fly ash over 40%. An appropriate dosage of fly ash in binder benefits the performance of concrete at low w/b ratio.     

Coal fly ash decomposes diethyl phthalate

Decomposition of diethyl phthalate (DEP) exposed to a coal fly ash has been investigated in water by measuring UV-VIS spectra and GC-MS. Alkaline constituents eluted from the fly ash in the liquid phase gradually hydrolyzed DEP to produce monoethyl phthalate and/or phthalic acid. These products were adsorbed on the fly ash and decarboxylated into ethyl benzoate and benzoic acid, respectively, followed by decomposition into benzenes and/or the other compounds of lower molecular weight. The fly ash acts as not only an adsorbent but also a decomposer.     

Speciation of chromium in Australian fly ash

The concentrations of chromium (III) and (VI) in fly ash from nine Australian coal fired power stations were determined. Cr(VI) was completely leached by extraction with 0.01 M NaOH solution and the concentration was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). This was confirmed by determining Cr(III) and Cr(VI) in the extracts of fly ash that had been spiked with chromium salts. These analytical measurements were done using a combination of ion-exchange chromatography and ICP-AES. The elutant was 0.05 M HNO₃ containing 0.5%-CH₃OH. When the column was operated at a flow rate of 1.2 ml min⁻¹ and samples were injected by use of a sample loop with a volume of 100 μl, Cr(III) and Cr(VI) in sample solution was exclusively separated within approximately 10 min. The detection limits (3σ) were 5 ng for Cr(III) (0.050 mg l⁻¹) and 9 ng for Cr(VI) (0.090 mg l⁻¹), respectively. A relative standard deviation of 1.9% (n = 6) was obtained for the determination by IC-ICP-AES of 0.25 mg l⁻¹ Cr(III) and Cr(VI).     

燃煤飞灰中铁质微珠的显微结构及其组成研究

选用我国三个典型燃煤煤种的电厂飞灰中铁质微珠,进行显微结构与物相组成等方面的研究。揭示出铁质微珠中存在空心微珠、子母珠和实心微珠三种显微颗粒类型,在这些显微颗粒表面可识别出以微粒状和八面体自形晶两种方式存在的赤铁矿和磁铁矿析晶;元素分析表明,燃烧褐煤电厂铁质微珠主要由Fe、Ca、Al、和Si元素组成,燃烧烟煤和无烟煤的电厂铁质微珠主要由Fe、Al和Si元素组成;物相分析发现,Fe在铁质微珠中以四种存在形式：Fe3O4、α-Fe2O3、γ-Fe2O3和Fe3+-玻璃相。这些物相在三个电厂飞灰中呈现出不同的分布特征,反映出不同的燃煤煤种在锅炉中燃烧温度的差异。随着温度的升高,Fe3O4先氧化为γ-Fe2O3,或γ-Fe2O3与Fe3O4的固熔体,然后再转变为α-Fe2O3,当温度超过 1 400 ℃时,Fe2O3又转化为Fe3O4。     

Determination of arsenic in fly ash by hydride generation in a slurry

We have studied the generation of arsenic hydride on a fly ash slurry from a thermal power plant burning lignite. The conditions for the formation of the slurry were optimized and the influence of the presence of various surfactants on the formation and stability of slurry (particle size-analytical signal ratio) were investigated.The As content in the ash was 78.7 g/g, with an rsd of 5.6% and a detection limit of 2.8 ng. The proposed method was successfully applied to the determination of arsenic in a certified ash sample (BCR-38). This method was applied to fly ash from a thermal power plant burning anthracite.     

Flame retardancy of polycarbonate enhanced by adding fly ash

We have developed a flame‐retardant polycarbonate resin whose flame retardancy is greatly enhanced by adding fly ash (a by‐product from thermal power plants). Fly ash with comparatively small average particle sizes (<10 µm) raised the flame retardancy of polycarbonate because of the hydrogen bond that forms between the polycarbonate and the hydroxy group on the fly ash surface. This bond primarily improves the heat resistance of the polycarbonate and also isomerizes the polycarbonate to promote carbonization. The polycarbonate with 25 wt% of the fly ash showed good other main characteristics, such as mechanical properties and moldability, comparable to those of a flame retardant polycarbonate reinforced with glass fiber, used for electronic products such as desktop computers, etc. Applying the fly ash eliminates the need to use current retardants such as organic halogen compounds and thus promotes the perceived environmental safety of flame‐ retardant polycarbonate. In addition, being able to use less raw resin by adding the fly ash means that less energy is required to manufacture flame‐retardant polycarbonate. Copyright © 2007 John Wiley & Sons, Ltd.     

Investigations into the role of activated carbon in a moisture-blocking cement formulation

Physical deterioration is a natural consequence of moisture attack in finished concrete. Moisture is retained in open voids in prepared cement during mixing and hydration stages. Further atmospheric moisture uptake occurs following dehydration under use conditions in polymer-containing cement formulations, since polymers act as conduits for moisture ingress. The initial attribute of added strength from the polymer in improved cement formulations is thus nullified. Customary solution to the moisture problem has centered around improving moisture resistance by significant reduction of inherent macro defects. A more complete method of moisture blocking by the reaction of activated carbon with a vinyl polymer included in the cement formulation is described here. The moisture blocking action is due to the mitigation of open voids by the occlusion of a carbon-vinyl additive, essentially resulting in filled voids or no voids in the prepared cement, producing a durable finished concrete product. Supporting evidence for the above by thermal, polarization, X-ray and SEM are reported in this paper. This revised version was published online in July 2006 with corrections to the Cover Date.     

Specific features of adsorption of azo dyes on fly ash

A possibility to utilize fly ash (FA) formed at coal-fired power plants as a cheap adsorbent for the purification of wastewater containing azo dyes methylene blue (MB) and methyl red (MR) was considered. The effect of an FA additive on the adsorption capacity of active carbon was studied. The efficiency of FA as an adsorbent for the purification of aqueous solutions from MB and MR was shown. The adsorption is also fairly efficient when active carbon is partially replaced by FA. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 545–548, March, 2007.     

Chemical characterization of density separated submicrometer coal fly ash

A new geometrical particle size separation method in the range of submicrometer has been developed for coal fly ash. Coal fly ash particles prefractionated less than 5m in geometrical diameter were fractionated with a coupling of supersonical dispersion in methyl alcohol and filtration through antistatic Nucleopore filter into >1.0, 1.0–0.8, 0.8–0.6m.Submicrometer (1.0–0.6m) and micrometer coal fly ash (25–20m) were separated into six density fractions and their compositions measured by SEM-EDX were compared. For the both size fractions, for the low density fractions (<2.8 g/cm³) consisted mainly of aluminosilicates and the fractions of 2.8–3.2 g/cm³ consisted of oxides of aluminum, silicon and calcium, and in the fraction above 3.2 g/cm³ iron was rich. In submicrometer fly ash, phosphor and sulfur concentrated to the particles rich in calcium. In the heaviest fraction, the particles containing over 30 wt% titanium as oxide observed among the particles rich in iron. These fractions were revealed not as a single component, but as mixtures of several components.     

垃圾焚烧飞灰颗粒的微观形态特征及能谱研究

利用SEM/EDX，观察了垃圾焚烧飞灰颗粒的微观形态特征，探讨了其主要组成元素及其质量分数。实验结果表明，飞灰颗粒形态多样化，其中以不规则形状聚合体居多，球形体、絮状集合体相对较少，少数颗粒为棒状集合体。球形飞灰颗粒很少有重金属分布，不规则形状聚合体或絮状集合体的表面易分布重金属。从飞灰颗粒表面、内部组成元素的质量分数来看，Si、Ca、Al为主要元素。飞灰颗粒表面、内部有重金属Pb、Cu等分布，局部测定点其质量分数可高达16.2%和14.5%。     

褐煤SHELL气化飞灰黏附影响因素的研究

通过激光粒度仪、X射线荧光光谱仪、扫描电子显微镜等现代化分析测试技术对褐煤样、飞灰样以及换热废锅中的积灰样进行了粒度分布、化学组成、晶体矿物组成、微观形貌、微区化学组成等特征的分析,研究影响飞灰黏附特性的因素。并通过引入富集系数,描述各个元素在煤灰、正常飞灰、废锅积灰中的迁移富集情况。结果表明,在废锅积灰中有含铁矿物的生成,同时Na、K、Fe、S、P元素在废锅积灰中发生富集,在飞灰与积灰颗粒边缘处有大量的Fe、Na元素的富集。     

Effect of nano-metakaolin addition on the hydration characteristics of fly ash blended cement mortar

The effect of nano-metakaolin (NMK) addition on hydration characteristics of fly ash (FA) blended cement mortar was experimentally investigated. The amorphous or glassy silica, which is the major component of a pozzolan, reacts with the calcium hydroxide liberated during calcium silicate hydration. It is believable to add FA and NMK particles in order to make high performance concrete. The physico-mechanical properties of FA blended cement mortars made with different percentages of NMK were investigated. The experimental results showed that the compressive and flexural strengths of mortars containing NMK are higher than those of FA blended cement mortar at 60 days of hydration age. It is demonstrated that the nanoparticles enhances strength than FA. In addition, the hydration process was monitored using scanning electron microscopy and thermal gravimetric analysis (TG). The results of these examinations indicate that NMK behaves not only as a filler to improve microstructure, but also as an activator to promote the pozzolanic reaction.     

Determination of total mercury in coal fly ash by gold amalgamation cold vapour atomic absorption spectrometry

A method for the determination of total mercury in coal fly ash by gold amalgamation cold vapour atomic absorption spectrometry (CV-AAS) was optimized. Most of the experiments were performed on NBS SRM 1633a Coal Fly Ash with a certified value of 160 ± 10 ng Hg g^?1. The main attention was focused on the decomposition of the sample. The efficacy of pressure decompositions in closed silica and sealed Pyrex tubes using various combinations of acids (HNO₃, HCl, HClO₄) was compared with oxidative combustion of the coal fly ash. Notwithstanding the incomplete mineralization of the sample in sealed tubes, the results obtained showed good agreement with the certified value and results obtained by neutron activation analysis (NAA), which suggests that mercury is quantitatively released from the sample into solution. Lower results were obtained using decomposition in closed (but not hermetically sealed) silica tubes owing to losses of mercury by volatilization during decomposition. Interferences from some metal ions (nickel, lead, copper, silver, palladium, zinc and antimony) were also examined. The results showed a serious depression of the mercury signal only when gold, palladium and platinum were present at higher concentrations, which never or very seldom occur in fly ash matrices, and therefore do not represent a limitation of the method.