Influence of CuO on the formation and coexistence of 3CaO·SiO2 and 3CaO·3Al2O3·CaSO4 minerals

The influence of CuO on the formation and coexistence of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals in Portland cement containing 3CaO·3Al₂O₃·CaSO₄ mineral is reported in this paper. The results show that a suitable amount of CuO can lower the clinkering temperature and improve the burn-ability of clinkers. It can also promote the formation of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals and facilitate the coexistence of the two minerals in the clinkers. But adding 1% CuO to the raw material can cause the decomposition of 3CaO·3Al₂O₃·CaSO₄.     

Leaching behavior of heat-treated waste ash

The leaching behavior of heat-treated waste ash was studied to verify the possibility of the thermal treatment of waste incineration ash in existing incinerators and boiler combustion chambers. The influence of temperature, oxygen concentration and treatment time on the leaching behaviors of harmful heavy metals, especially lead (Pb) and chromium(VI) (Cr (VI)) were studied to clarify effective treatment conditions to suppress leaching. By examining the leaching behavior of Pb and Cr from ash heat-treated under various conditions, it was found that leaching can be suppressed by heat-treating the ash under conventional combustion conditions of around 900-1000 °C at 5-10% oxygen concentration. The leaching behaviors of Pb and Cr (VI) from real ash with different particle sizes and from model samples were also investigated in detail to find an effective method to suppress Pb leaching. It was found that the formation and growth of gehlenite (SiO₂·2CaO·Al₂O₃) in the ashes led to the decrease in the amount of Pb leaching. Therefore it was considered that the addition of an inorganic matrix with a high silica content that can promote gehlenite growth in the ash, for example, coal ash or waste glass is effective to suppress of Pb leaching.     

Hydration characteristics of waste sludge ash utilized as raw cement material

In this study, the hydration characteristics and the engineering properties of three types of eco-cement pastes, including their compressive strength, speciation, degree of hydration, and microstructure, were studied and compared with those of ASTM type I ordinary Portland cement. The results indicate that it is feasible to use sludge ash and steel-making waste to replace up to 20% of the mineral components of the raw material of cement. Furthermore, all the tested clinkers met the toxicity characteristic leaching procedure requirements. The major components of Portland cement, C₃S (i.e., 3CaO·SiO₂), C₂S (i.e., 2CaO·SiO₂), C₃A (i.e., 3CaOAl₂O₃) and C₄AF (i.e., 4CaO·Al₂O₃·Fe₂O₃), were all found in the waste-derived clinkers. All three types of eco-cements were confirmed to produce calcium hydroxide (Ca(OH)₂) and calcium silicate hydrates (CSH) during the hydration process, increasing densification with the curing age. The thermal analysis results indicate that the hydration proceeded up to 90 days, with the amount of Ca(OH)₂ and CSH increasing. The chemical shift of the silicates, and the resultant degree of hydration, and the increase in the length of the CSH gels with the curing age, were confirmed by ²⁹Si NMR techniques. Compressive strength and microstructural evaluations confirm the usefulness of eco-cement.     

Influence of MgO on the formation of Ca3SiO5 and 3CaO·3Al2O3·CaSO4 minerals in alite-sulphoaluminate cement

The influence of MgO on the formation of Ca₃SiO₅ and 3CaO·3Al₂O₃·CaSO₄ minerals in alite-sulphoaluminate cement is reported in this paper. The results show that adding a suitable amount of MgO can lower the clinkering temperature, promote the formation of Ca₃SiO₅ and 3CaO·3Al₂O₃·CaSO₄ minerals, and help in the coexistence of the two minerals in the clinker. MgO may obviously decrease the formation of Ca₃Al₂O₆, and increase the SiO₂ content incorporated into the interstitial phase.     

Characterization of sintered coal fly ashes

Çan, Çatala?z?, Seyitömer and Af?in-Elbistan thermal power plant fly ashes were used to investigate the sintering behavior of fly ashes. For this purpose, coal fly ash samples were sintered to form ceramic materials without the addition of any inorganic additives or organic binders. In sample preparation, 1.5 g of fly ash was mixed in a mortar with water. Fly ash samples were uniaxially pressed at 40 MPa to achieve a reasonable strength. The powder compacts were sintered in air. X-ray diffraction analysis revealed that quartz (SiO₂), mullite (Al₆Si₂O₁₃), anorthite (CaAl₂Si₂O₈), gehlenite (Ca₂Al₂SiO₇) and wollastonite (CaSiO₃) phases occurred in the sintered samples. Scanning electron microscopy investigations were conducted on the sintered coal fly ash samples to investigate the microstructural evolution of the samples. Different crystalline structures were observed in the sintered samples. The sintered samples were obtained having high density, low water adsorption and porosity values. Higher Al₂O₃ + SiO₂ contents caused to better properties in the sintered materials.     

Activation of the fly ash pozzolanic reaction by hydrothermal conditions

The effect of hydrothermal treatment on the pozzolanic reaction of two kinds of Spanish fly ashes from coal combustion (ASTM class F) is discussed. Characterization of the compounds formed as a result of hydrothermal treatment and the changes provoked in the starting fly ashes were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and infrared (IR) spectroscopy. α-C₂SH, CSH gel, different solid solutions of katoites (the cubic crystallographic variety of hydrogarnets series (C₃ASH₄)) and a mixed oxide (CaFe₂O₄) were formed depending on the kind of fly ash. The hydrated compounds are precursors of a new kind of low-energy cement called fly ash belite cement (FABC); besides, they have potential properties to intercalate toxic ions and therefore can be used as immobilization systems of these ions.     

Determining suitability of a fly ash for silica extraction and zeolite synthesis

Zeolitic material is obtained from fly ash both by direct conversion of the ash or from SiO₂ extracts obtained from fly ash. This study focuses on determining the suitability of a fly ash for SiO₂ extraction and for zeolite synthesis by direct conversion. The SiO₂ extraction experiments from different fly ashes show that the main parameters governing the SiO₂ extraction are: (a) a high bulk SiO₂ content (>52%, for obtaining an extraction yield of 100 g SiO₂ kg^?1) in the starting fly ash, (b) a high proportion (>55%) of the bulk SiO₂ present in the degradable glass matrix and the highly soluble opaline fraction, and (c) a high bulk SiO₂/Al₂O₃ ratio (>2.0) of the fly ash. The results from experiments of zeolite synthesis by direct conversion demonstrate that the most important criteria for the selection of a fly ash for this process are: (a) a high content of Al₂O₃ and SiO₂(>65%) (b) a high glass content (>63%) and (c) relatively low SiO₂/Al₂O₃ ratio (<2.0). Multivariate analysis confirms the importance of the above‐mentioned variables and shows some additional variables that have influence on ash behaviour under alkaline conditions. It quantifies the use of those variables for determining the suitability of ashes for SiO₂ extraction and zeolite synthesis and is able to distinguish between the two. Copyright © 2004 Society of Chemical Industry     

Mineralogical and elemental composition of fly ash from pilot scale fluidised bed combustion of lignite, bituminous coal, wood chips and their blends

The chemical and mineralogical composition of fly ash samples collected from different parts of a laboratory and a pilot scale CFB facility has been investigated. The fabric filter and the second cyclone of the two facilities were chosen as sampling points. The fuels used were Greek lignite (from the Florina basin), Polish coal and wood chips. Characterization of the fly ash samples was conducted by means of X-ray fluorescence (XRF), inductive coupled plasma-optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), particle size distribution (PSD) and X-ray diffraction (XRD). According to the chemical analyses the produced fly ashes are rich in CaO. Moreover, SiO₂ is the dominant oxide in fly ash with Al₂O₃ and Fe₂O₃ found in considerable quantities. Results obtained by XRD showed that the major mineral phase of fly ash is quartz, while other mineral phases that are occurred are maghemite, hematite, periclase, rutile, gehlenite and anhydrite. The ICP-OES analysis showed rather low levels of trace elements, especially for As and Cr, in many of the ashes included in this study compared to coal ash from fluidised bed combustion in general.     

Preparation of glass-ceramics from red mud in the aluminium industries

The feasibility of recycling red mud and fly ash in the aluminium industries by producing glasses and glass-ceramics has been investigated. The crystallization behavior of glass-ceramics mostly produced from red mud and fly ash was studied by DTA, XRD, optical microscopy techniques. According to DTA curve, nucleation experiments were carried out at various nucleation temperatures at the same crystallization temperature of 900 °C for 2 h, and crystallization experiments were performed at the same nucleation temperature of 697 °C for 2 h followed by crystallization at various temperatures. The nucleation results show that optimum nucleation temperature is near 697 °C, and the crystallization experiments show that the crystallization at a high temperature of over 900 °C results in denser grain size. The major crystallized phases were gehlenite (Ca₂Al₂SiO₇), and augite (Ca(Fe,Mg)Si₂O₆). The XRD results show that with the increase of crystallization temperature, the amount of gehlenite increases, and augite decreases, which is the result of augite transformation into gehlenite.     

Large-scale fine structural alumina matrix ceramic guideway materials improved by diopside and Fe2O3

Diopside and Fe₂O₃ were introduced in alumina matrix ceramic materials. Large-scale fine structural alumina matrix ceramic guideway materials were fabricated by the technology of pressureless sintering, during which liquid phase sintering took place and new phases such as 3Al₂O₃·2SiO₂, CaO·Al₂O₃·2SiO₂ and CaO·6Al₂O₃ were produced by the chemical reactions taking place among alumina and the additives. The hardness, the fracture toughness and the bending strength of the guideway products were tested. The influences of diopside and Fe₂O₃ additions were studied by microstructural observations and mechanical properties evaluations. Meanwhile, the expected improvement of mechanical properties compared with pure alumina was indeed observed. The fracture mechanism and porosity of large-scale fine structural alumina matrix ceramic guideway materials were analyzed.     

Chemical investigation of lignite samples and their ashing products from Kardia lignite field of Ptolemais, Northern Greece

Twenty-six lignite samples were collected from the Kardia lignite field (Ptolemais, Greece). Ash content, moisture and CO₂ were determined. The lignite samples were heated at 900 °C producing 26 ash samples. The chemical composition (major and trace elements) both of the lignite samples and ash products was determined using INAA, ICP-OES and ICP-MS. CaO, SiO₂ and Al₂O₃ are the dominant oxides both in lignite and ash samples. A relative decrease of SiO₂ and Al₂O₃ as well as an increase of CaO was noticed in the deeper lignite samples. Sr, Cr, Ni, V and Ba were found to be the most abundant both in lignite and ash samples. Sr displays a relative increase while Ni and Cr decrease with depth in the lignite samples. In the ash samples, Ni shows the most obvious decrease with depth.     

Fuel mixture approach for solution combustion synthesis of Ca3Al2O6 powders

Single-phase 3CaO·Al₂O₃ powders were prepared via solution combustion synthesis using a fuel mixture of urea and β-alanine. The concept of using this fuel mixture comes from the individual reactivity of calcium nitrate and aluminum nitrate with respect to urea and β-alanine. It was proved that urea is the optimum fuel for Al(NO₃)₃ whereas β-alanine is the most suitable fuel for Ca(NO₃)₂. X-ray diffraction and thermal analysis investigations revealed that heating at 300 °C the precursor mixture containing the desired metal nitrates, urea and β-alanine triggers a vigorous combustion reaction, which yields single-phase nanocrystalline 3CaO·Al₂O₃ powder (33.3 nm). In this case additional annealing was no longer required. The use of a single fuel failed to ensure the formation of 3CaO·Al₂O₃ directly from the combustion reaction. After annealing at 900 °C for 1 h, the powders obtained by using a single fuel (urea or β-alanine) developed a phase composition comprising of 3CaO·Al₂O₃, 12CaO·7Al₂O₃ and CaO.     

Mineralogy of western fly ash

Twenty-six fly ash specimens from North Dakota, Wyoming and Montana lignite and sub-bituminous source coals have been studied in detail by X-ray diffraction. Chemically, these western fly ashes are characterized by higher CaO+MgO+SO₃ contents and lower Al₂O₃+SiO₂ contents than eastern bituminous fly ashes. These western fly ashes have greater proportions of crystalline material. The characteristic phases are quartz, lime, periclase, anhydrite, ferrite spinel, tricalcium aluminate, merwinite and melilite. Alkali sulfates, a sodalite structure phase and hematite also occur in some fly ashes.     

Crystallisation and microstructure of nepheline–forsterite glass-ceramics

This work presents the results of a study focused on the development of forsterite–nepheline glass-ceramic with the use of rice husk ash (RHA) as a silica source. The glass-ceramics were produced by a sintering process of a glassy frit formulated in the MgO–Al₂O₃–SiO₂ base system with the addition of B₂O₃ and Na₂O to facilitate the melting and pouring processes. The crystallisation study was carried out by depicting the TTT curve (Time–Temperature–Transformation). The mineralogical characterisation of the glass-ceramic materials was carried out using the X-ray diffraction (XRD). The crystallisation activation energies were calculated by the Kissinger method. The results obtained show that devitrification of the RHA glass leads to a glass-ceramic material composed of nepheline (Na₂O·Al₂O₃·2SiO₂) and forsterite (2MgO·SiO₂). A study of the microstructure by scanning electron microscopy (SEM) allowed to establish the morphological evolution in both the shape and spatial arrangement of the nepheline and forsterite crystals on heating.     

Preparation and characterization of fully waste-based glass-ceramics from incineration fly ash,waste glass and coal fly ash

Municipal solid waste incineration (MSWI) fly ash (FA) is a typical hazardous waste due to its high contents of toxic heavy metals, and hence its disposal has attracted global concern. In this work, it was recycled into environmental-friendly CaO–Al₂O₃–SiO₂ system glass-ceramics via adding coal fly ash (CFA) and waste glass (WG). The effects of CaO/SiO₂ ratios and sintering temperatures on the crystalline phases, morphologies, mechanical and chemical properties, heavy metals leaching and potential ecological risks of glass-ceramics were investigated. The results showed that wollastonite (CaSiO₃), anorthite (CaAl₂Si₂O₈) and gehlenite (Ca₂Al₂SiO₇) were the dominant crystals in the glass-ceramics, which were not affected by CaO/SiO₂ ratio and sintering temperature. The compressive strength increased, while the Vickers hardness and microhardness decreased as increasing the sintering temperatures from 850 to 1050 °C, which reached their maximum values of 660.69 MPa, 6.14 GPa, and 7.43 GPa, respectively. However, the increase of CaO/SiO₂ ratio resulted into the reduction of the three mechanical parameters. As varying CaO/SiO₂ ratio from 0.48 to 0.86, the maximum compressive strength, Vickers hardness and microhardness were 611.80 MPa, 5.43 GPa, and 6.56 GPa, respectively. Besides, all the glass-ceramics exhibited high alkali resistance of >97%. The extremely low heavy metals leaching concentrations and low potential ecological risk of glass-ceramics further revealed its environmentally friendly property and potential application feasibility.     

The solubility of selenate-AFt (3CaO·Al2O3·3CaSeO4·37.5H2O) and selenate-AFm (3CaO·Al2O3·CaSeO4·xH2O)

The Se(VI)-analogues of ettringite and monosulfate, selenate-AFt (3CaO·Al₂O₃·3CaSeO₄·37.5H₂O), and selenate-AFm (3CaO·Al₂O₃·CaSeO₄·xH₂O) were synthesised and characterised by bulk chemical analysis and X-ray diffraction. Their solubility products were determined from a series of batch and resuspension experiments conducted at 25 °C. For selenate-AFt suspensions, the pH varied between 11.37 and 11.61, and a solubility product, log K_so=61.29±0.60 (I=0 M), was determined for the reaction 3CaO·Al₂O₃·3CaSeO₄·37.5H₂O+12 H⁺⇔6Ca²⁺+2Al³⁺+3SeO₄²⁻+43.5H₂O. Selenate-AFm synthesis resulted in the uptake of Na, which was leached during equilibration and resuspension. For the pH range of 11.75 to 11.90, a solubility product, log K_so=73.40±0.22 (I=0 M), was determined for the reaction 3CaO·Al₂O₃·CaSeO₄·xH₂O+12 H⁺⇔4Ca²⁺+2Al³⁺+SeO₄²⁻+(x+6)H₂O. Thermodynamic modelling suggested that both selenate-AFt and selenate-AFm are stable in the cementitious matrix; and that in a cement limited in sulfate, selenate concentration may be limited by selenate-AFm to below the millimolar range above pH 12.     

Effects of nitrogen and fluorine on crystallisation of Ca-Si-Al-O-N-F glasses

The effect of nitrogen and fluorine substitution on the crystallisation of a new generation of oxyfluoronitride glasses in the Ca-Si-Al-O-N-F system has been studied. Glasses were nucleated for 5 h at the nucleation temperature of Tg + 50 °C and crystallised for 10 h at the maximum crystallisation temperature (900-1050 °C depending on the glass composition) determined from differential thermal analysis. For the oxide glass, crystallisation results in formation of wollastonite (CaSiO₃), gehlenite (Ca₂Al₂SiO₇) and anorthite (CaAl₂Si₂O₈) along with a small amount of residual glass. For crystallisation of oxyfluoride glasses (0 equiv.% N), when fluorine content increases, cuspidine (Ca₄Si₂O₇F₂) is the major crystalline phase at the expense of gehlenite while in oxyfluoronitride glasses containing 20 equiv.% N, gehlenite is always the dominant crystalline phase at different fluorine contents. At constant fluorine content (5 equiv.%), an increase in nitrogen content favours the formation of gehlenite rather than anorthite or wollastonite suggesting that this phase may be able to accommodate N into its crystal structure. While a small amount of nitrogen substitution for oxygen can be assumed in the gehlenite structure, the residual glass in the glass-ceramic is expected to be very N-rich. In terms of properties, hardness is shown to be more sensitive to changes in microstructure, phase morphology and crystal size compared with elastic modulus which is related to the amounts of constituent phases present.     

Mineralogical characteristics of Ettringites synthesized from solutions and suspensions

Due to the wide technical importance of Ettringite (3CaO·Al₂O₃·3CaSO₄·32H₂O) in hydrated cement based systems, four different synthesis methods were applied to get a better overview on how and under what favoring conditions Ettringite can be formed. In the first step different precipitation methods resulting in Ettringite were established. For all methods Al³⁺ was supplied by aqueous CO₂-free solution of Al₂(SO₄)₃·18H₂O. As a source of CaO-supply a clear solution and otherwise a Ca(OH)₂-suspension was utilized. Four synthesis routes with and without sucrose were employed.Variation of reaction parameter like temperature, time of reaction, pH-value of synthesis solution and influence of additional Gypsum were investigated. The qualitative phase analysis was performed by X-ray diffraction method (XRD). Morphological aspects of some synthesis products were studied by scanning electron microscopy (SEM). Finally lattice and structural parameter of the Ettringites were determined by refinement of XRD-pattern using the Rietveld-Method.     

Microwave-assisted zeolite synthesis from coal fly ash in hydrothermal process

Coal fly ashes, which include much amount of silica and alumina, can be converted into zeolite by hydrothermal alkaline treatment. In the present work, the effect of microwave irradiation on the zeolite formation was investigated with emphasis on the change in yield of zeolite during the reaction. The fly ash was mixed with 2 M NaOH solution and heated by oil bath or microwave for 2 h. Zeolite Na-P1 formed after the conventional treatment using oil bath, but no zeolitic product was obtained by microwave heating. When microwave was applied in the course of hydrothermal treatment, zeolitization was promoted by the early-stage irradiation. This is due to the stimulated dissolution of SiO₂ and Al₂O₃ from coal fly ash. On the other hand, the microwave irradiation in the middle to later stage retarded the crystallization of zeolite. The microwave is effective to produce the zeolite from coal fly ash in a short period by control of irradiation schedule in the early stage.     

Gunited concrete linings of conveyer sintering machines

Conclusions The construction of unique heating equipment requires the development of composite programs with a single center of control, coordination, and financing of all work: scientific research, planning and design, construction and assembly, and start-up and adjustment. Further introduction of gunited concrete linings requires standard production by the refractory industry of guniting mixtures, for which successful use may be made of VTs-75 cement of ferroalloy production clinker, using additional working with the addition of special inspection on the basis of petrographic or x-ray diffraction analyses or on the basis of the criterion M (limits of variation 3.2–4.1). In mineral composition the clinker must meet the following requirements: 73–78.2% CaO·2Al₂O₃; 5% max·CaO·6Al₂O₃; 3% max· MgO·Al₂O₃; 6–9% CaO·Al₂O₃; up to 4% chromium regulus.As the result of the work conducted, a method was developed for guniting linings of various degrees of complexity with a refractory layer thickness up to 200 mm operating at a temperature up to 1450°C in an oxidizing, iron, gas, and dust atmosphere.The method may find wide use for lining of thermal equipment both in the steel industry and in other branches of industry.Translated from Ogneupory, No. 4, pp. 51–57, April, 1988.