Mineralogy and phase transition of oil sands coke ash

Coke obtained from Syncrude and Suncor was investigated to characterize the metals and minerals by ashing it at various temperatures. Samples were collected by high temperature ashing at 100 °C intervals from 400 to 1200 °C. Samples were also obtained from low temperature ashing (LTA) which gives little effect on the mineral assemblage compared to HTA samples. X-ray diffraction patterns of Suncor and Syncrude coke ash were analyzed qualitatively and quantitatively to characterize the mineral phases in the sample and their thermal transition behavior. In Suncor ash, kaolinite, illite, gypsum, anhydrite, microcline, anorthite, hematite, sillimanite and quartz were dominant phases in ash from the LTA temperature up to 700 °C, and mullite, cristobalite, hercynite, albite, anorthite, pseudobrookite and other iron–titanium oxides were dominant mineral phases from 700 to 1200 °C. In Syncrude ash, illite, anhydrite, quartz, anorthite, microcline, sillimanite and hematite were dominant up to 700 °C, and hercynite, anorthite, albite, pseudobrookite and other iron–titanium oxides were dominant up to 1200 °C. The higher quantities of Ca, K and Na, and the lower quantities of V, Fe and Ni in Syncrude ash resulted in higher amorphocity and the different mineral phases.     

Ceramic behaviour of five Chilean clays which can be used in the manufacture of ceramic tile bodies

This study is focussed on the behaviour of ceramic clays from Chile which has an important local ceramic industry. Five deposits of clays with industrial application have been studied. The clays come from San Vicente de Tagua-Tagua (SVTT), Litueche (L), Las Compañías – Río Elqui (LC), La Herradura – Coquimbo (LH) and Monte Patria – Coquimbo (MP). The chemical and mineralogical compositions of clays were determined by X-ray fluorescence (XRD) and X-ray diffraction (XRD), respectively. Also, the plasticity index (PI) was measured for each sample. The chemical and mineralogical compositions of samples differ considerably. Test samples have been prepared by pressing and firing in the range of 800–1150 °C. Linear contraction (LC), water absorption capacity (WAC) and thermodilatometric analysis (TDA) were done in order to characterize clays after firing. A considerable decrease in the WAC coinciding with the beginning of vitrification, is observed between 1050 and 1100 °C. At 1150 °C the porosity of the tile bodies decreases significantly and the tile bodies became earthenware. All studied clays seem to be easily adaptable to a correct dry pressing ceramic process. In particular, illite–kaolinite-rich samples show the best behaviour. Samples SVTT are suitable for the production of fast firing vitreous pieces. L samples present the highest refractory behaviour.     

Influences of quartz and muscovite on the formation of mullite from kaolinite

A kaolin containing muscovite and quartz (K-SZ) and a pure kaolin (K-SX) with the addition of potassium feldspar, K₂SO₄ and quartz, respectively, were used to investigate the influences of muscovite and quartz on the formation of mullite from kaolinite in the temperature range 1000–1500 °C. In K-SZ formation of mullite began at 1100 °C, and in K-SX at 1000 °C. In K-SZ quartz accelerated the formation of cristobalite and restrained the reaction of mullite and silica. Muscovite in K-SZ acted as a fluxing agent for silica and mullite before 1400 °C and accelerated the formation of cristobalite. The FTIR band at 896.8 cm^− 1 was used to monitor the formation of orthorhombic mullite.     

Influence of iron on the occurrence of primary mullite in kaolin based materials: A semi-quantitative X-ray diffraction study

Iron-enriched reference kaolins (KGa-1b, KGa-2 and KF) were used to study the effect of iron on the development of mullite phases during the sintering of kaolin-based materials. Up to 1050 °C, primary mullite formation occurred at earlier temperature within iron-enriched kaolins than in the case of iron-free kaolins. At 1150 °C, the presence of ferric ions tended to promote the transformation of the spinel (γ-Al₂O₃-like) phase into primary mullite. This action was correlated with an enhancement of the diffusion mechanism of the main constitutive species of the samples (Al, Si). In the range 1300–1400 °C, iron-enriched kaolins exhibited an abnormal grain growth of secondary mullite crystals and a partial reduction of hematite (Fe₂O₃) into magnetite (Fe₃O₄). These two iron compounds reacted with mullite and cristobalite, leading to the occurrence of eutectic liquids as expected from phase equilibrium diagrams.     

Utilization of recycled paper processing residues and clay of different sources for the production of porous anorthite ceramics

Production of porous anorthite ceramics from mixtures of paper processing residues and three different clays are investigated. Suitability of three different clays such as enriched clay, commercial clay and fireclay for manufacturing of anorthite based lightweight refractory bricks was studied. Porous character to the ceramic was provided by addition of paper processing residues (PPR). Samples with 30–40 wt% PPR fired at 1200–1400 °C contained anorthite (CaO·Al₂O₃·2SiO₂) as major phase and some minor secondary phases such as mullite (3Al₂O₃·2SiO₂) or gehlenite (2CaO·Al₂O₃·SiO₂), depending on the calcite to clay ratio. Anorthite formation for all clay types was quite successful in samples with 30–40 wt% of paper residues fired at 1300 °C. A higher firing temperature of 1400 °C was needed for the fireclay added samples to produce a well sintered product with large pores. Gehlenite phase occurred mostly at lower temperatures and in samples containing higher amount of calcium (50 wt% PPR). Compressive strength of compacted and fired pellets consisting of mainly anorthite ranged from 8 to 43 MPa.     

Fabrication and characterization of anorthite-based ceramic using mineral raw materials

The purpose of this study is to design a novel single crystalline phase ceramic based on anorthite whose properties fulfill the tableware market requirements such as high appearance quality, strength and thermal shock resistance. To obtain the single phase anorthite ceramic, ball clay, quartz, calcite, feldspar and alumina were used as raw materials. The single phase anorthite ceramic was fabricated by slip casting and sintering at 1230 °C for 1 h. It has a high flexural strength of 103 MPa, which is higher than that of the conventional porcelain. The single phase anorthite ceramic had relatively low (4.9 × 10^?6 K^?1) thermal expansion coefficient which can be matched with applicable glaze easily. Furthermore, the single phase anorthite ceramic had high degree of whiteness (L* = 94) and excellent translucency behavior which could achieve a high-quality decorative effect.     

Formation of high-temperature crystalline phases in ceramic from illite clay and dolomite

The formation of ceramic with the prevailing cordierite/mullite in the crystalline phase is greatly dependent on the raw materials used. In the present work the cordierite and mullite (or their solid—solutions accordingly with spinels and corundum) formation processes from compositions of natural raw materials (illite clay, dolomite) with synthetic additives (MgO, Al(OH)₃, K₂CO₃) are studied. It is shown that the illite clay acts as a low viscosity liquid medium as well as a precursor for cordierite and mullite crystallisation in ceramics.The phase development using XRD—analysis and the SEM is studied. Particles size distribution of staiting powder and some properties of ceramic obtained are also demonstrated. It is shown that formation of the above mentioned phases starts at temperatures 1050–1080 °C and remarkably increases at 1200 °C for mullite and at 1300 °C for cordierite.     

Characterization of transparent glaze for single-crystalline anorthite porcelain

The objective of this work was to design a transparent glaze for matching single-crystalline anorthite porcelain. Excessive amounts of quartz were used in glaze to improve surface hardness. Technological properties including hardness and thermal shock resistance were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies were also carried out to analyze the microstructure. The phases found in glaze were aluminosilicate glass, quartz and cristobalite crystals. The Vickers hardness of the transparent glaze was about 2.48 GPa, which was much higher than that of commercial soft glaze and was close to hard porcelain glaze due to forming dispersed crystal particles (quartz and cristobalite) in the glass matrix. Moreover, the thermal expansion coefficient of the glaze was slightly lower than that of porcelain body which was easy to produce compressive stress in glaze surface to increase the strength of porcelain. And no cracks were observed on glaze surface after heat exchange three times from 220 °C to 25 °C, presenting excellent thermal shock resistance.     

The change of phase composition in kaolinite- and illite-rich clay-based ceramic bodies

Raw material for ceramics consists mainly of kaolinite, illite, quartz and feldspar. Three representative clays, a high kaolinitic (HB), illitic- and quartz-rich (KW) and naturally mixed kaolinite–illite (P1) clays of Westerwald area, were chosen for this study [Kromer, H., 1980. Tertiary clays in the Westerwald area. Geol. Jb. D. Rhei D Hanover, 69–84]. The largest and oldest clay mining area of Germany is in the Westerwald area. These clays were mixed with each other and also with K, and Ca–Na feldspar. The high temperature phases of the mixed bodies were of three groups: crystalline phase, amorphous/glassy phase and porosity.The aim of this study was to determine: (1) the effect of kaolinite–illite–quartz ratios, (2) the effect of heat treatment and (3) the effect of feldspar on the fired mineralogy of the fired products. The crystalline phases are cristobalite, mullite, quartz, hematite and anatase. The bodies consist of crystalline phases such as quartz, mullite and cristobalite in a composite structure where crystals and pores are often embedded in amorphous/glassy phase. The formation of mullite and cristobalite is very distinctive in kaolinitic clay, and the structure is dominated by the spiky primary mullite. In the illite/sericite-rich mixtures, the high K content causes a large amount of melt superimposed on the mullite formation. The cristobalite formation is completely suppressed in illite/sericite-rich bodies. After dehydroxylation, metakaolinite and illite/sericite anhydride structures are formed. The persistence of illite/sericite anhydride peaks above 950 °C in KW clay indicates the presence of sericite/muscovite mineral. The disappearance temperatures and firing behaviour of K and Ca–Na feldspar observed within the XRD patterns of mixed bodies are different. K feldspar lines disappear earlier in HB bodies than in KW bodies, but Ca–Na feldspar shows a reverse behaviour. While Ca–Na feldspar peak intensity gradually decreases but persists at 1150–1250 °C, K feldspar suddenly disappears at 1150 °C.     

Crystalline phases and physical properties of modified stoneware body with glaze sludge

Ceramic stoneware body has been modified with ceramic and glass industrial wastes by replacing 25–100% as flux in the formula. The effects of solid wastes added to the bodies were studied after firing in the temperature range 950–1280 °C. The physical properties of linear shrinkage, bulk density, apparent porosity, water absorption and 3-point bending strength were determined. A composition which related to the general stoneware properties was found when using soda-lime cullet and glaze sludge. It had a firing range lowered to 1050–1100 °C. SEM results demonstrated the sintered microstructure increased in density with increase in solid waste in the modified body. XRD results after firing showed the crystalline phases comprised of mullite, albite calcian and quartz. Thermal expansion was measured in the range 6.53–6.67 × 10^?6 K^?1 at 30–500 °C. The modified bodies were capable of forming prototype products by slip casting and jiggering.     

Time-resolved powder neutron diffraction study of the phase transformation sequence of kaolinite to mullite

Mullite formation from kaolinite was studied by means of high-temperature in situ powder neutron diffraction by heating from room temperature up to 1370 °C. Neutron diffractometry under this non-isothermal conditions is suitable for studying high-temperature reaction kinetics and to identify short-lived species which otherwise might escape detection. Data collected from dynamic techniques (neutron diffraction, DTA, TGA and constant-heating rate sintering) were consistent with data gathered in static mode (conventional X-ray diffraction and TEM). The full process occurs in successive stages: (a) kaolinite dehydroxylation yielding metakaolinite in the ∼400–650 °C temperature range, (b) nucleation of mullite in the temperature range ∼980–992 to ∼1121 °C (primary mullite) side by side with a crystalline cubic phase (Si-Al spinel) detected in the ∼983–1030 °C temperature interval; (c) growth of mullite crystals from ∼1136 °C, (d) high (or β) cristobalite crystallization at T > ∼1200 °C and (e) secondary mullite crystallization at T > ∼1300 °C. The calculated activation energy for the kaolinite dehydration was 115 kJ/mol; for the mullite nucleation was 278 kJ/mol and for the growth of mullite process was 87 kJ/mol; finally for cristobalite nucleation the calculated apparent activation energy was 481 kJ/mol.     

Fabrication and characterization of anorthite–mullite–corundum porous ceramics from construction waste

In this work, anorthite–mullite–corundum porous ceramics were prepared from construction waste and Al₂O₃ powders by adding AlF₃ and MoO₃ as mineralizer and crystallization catalyst, respectively. The effects of the sintering temperature and time on open porosity, mechanical properties, pore size distribution, microstructure, and phase composition were characterized in detail. The results showed that the formation of the mullite whiskers and the properties of the anorthite–mullite–corundum porous ceramics depended more on the sintering temperature than the holding time. By co-adding 12 wt% AlF₃ and 4 wt% MoO₃, mullite whiskers were successfully obtained at sintering temperatures upon 1350 °C for 1 h. Furthermore, the resultant specimens exhibited excellent properties, including open porosity of 66.1±0.7%, biaxial flexural strength of 23.8±0.9 MPa, and average pore size of 1.32 µm (the corresponding cumulative volume percent was 37.29%).     

Soda-lime-silica-glass/quartz particle size and firing time: Their combined effect on sanitary-ware ceramic reactions and macroscopic properties

This paper describes how soda-lime-silica (SLS) glass particle size in combination with firing time and quartz particle size influence sanitary-ware ceramic reactions (mullite/glass formation rate and activation energy), and affect some relevant ceramic bodies’ macroscopic properties (water absorption, WA; linear thermal expansion, α; linear shrinking, LS). The study is focused on the system kaolinite, quartz (d₅₀ = 28 and 4 µm), Na-feldspar and SLS-glass (d₅₀ = 35, 23 and 16 µm). SLS-glass in partial replacement of Na-feldspar accelerates the mullite formation rate and the same effect is achieved by decreasing the quartz-d₅₀, which leads to a higher reactivity of the starting slip and to a lesser vitrification grade. In general, mullite formation rate increases with a decrease in SLS-glass-d₅₀. Secondary mullite occurs more abundantly and better shaped in samples with small quartz and SLS-glass d₅₀-values. The technological properties here considered exhibit a complex dependence on SLS-glass/quartz particle size and firing time; in general, they result more sensitive to the former than to the latter. The issues of this work show that one can (i) notably tune WA−α−LS as a function of SLS-glass/quartz particle size and firing time cycle, and (ii) achieve a 30–90 K lowering of firing temperatures (curbing CO₂-emissions), making it possible to tailor a reuse of SLS-glass as a function of final ceramic targets.     

The microstructure,coefficient of thermal expansion and flexural strength of cordierite ceramics prepared from alumina with different particle sizes

Cordierite ceramics were produced from alumina with 5 and 0.65 μm particle sizes or AlOOH and talc, clays and feldspar, to determine the influence of the alumina particle size on the microstructure, coefficient of thermal expansion (CTE) and flexural strength (FS) of the ceramics. After sintering at 1300 °C the ceramics made from 5-μm-sized alumina consisted of cordierite, glass, quartz, mullite and alumina, and had the highest density, FS and CTE. The alumina grains act as inclusions, from which the trajectories of the cracks were deflected or terminated, which increases the FS and CTE. The ceramics from sub-micrometre-sized alumina or AlOOH contained a negligable amount and no alumina, respectively, together with other phases. This is reflected in the low CTE and FS. The cordierite ceramic with the lowest CTE of ∼2.0 × 10⁻⁶ K⁻¹ and a high FS of 100 MPa was prepared from the 0.65-μm-sized alumina particles.     

Nickel aluminate spinel formation during sintering of simulated Ni-laden sludge and kaolinite

Incorporating Ni-laden waste sludge into kaolinite-based construction ceramic materials appears promising based on the identified nickel bearing phases, evaluated incorporation efficiency and nickel leachability of the products. Nickel aluminate spinel (NiAl₂O₄) results from sintering kaolinite and nickel oxide between 990 and 1480 °C, with more than 90% incorporation efficiency achieved at 1250 °C and 3 h sintering. At lower temperature (990 °C), NiAl₂O₄ formed from the reaction between nickel oxide and the defect spinel generated from the kaolinite–mullite reaction series. In addition to sintering temperature and time, four raw material mixing procedures were employed, and the ball-milled slurry samples had the highest nickel incorporation efficiency. Prolonged leach testing of NiO, NiAl₂O₄ and the product from sintered kaolinite + NiO mixtures was carried out using the TCLP extraction fluid #1 (pH 4.9) to evaluate the product stability, and the results revealed the superiority of spinel products over NiO in stabilizing nickel.     

Investigation on cristobalite crystallization in silica-based ceramic cores for investment casting

In this work, cristobalite crystallization and its effects on mechanical and chemical behaviour of injection moulded silica-based ceramic cores were investigated. In order to simulate casting process condition, the sintered samples at 1220 °C were also heated up to 1430 °C. Flexural strength test was carried out on both sintered and heat treated samples. Chemical resistance of the cores was evaluated by leaching the samples inside 43 wt% KOH solution at its boiling point. Phase evolution and microstructure were investigated by thermal analyses (DTA and DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical microscopy (OM). Results showed that cristobalite was crystallized on the surface of fused silica grains at about 1380 °C. Flexural strength of the sintered cores was decreased after simulated casting heat treatment due to cristobalite phase transformation. The formed cristobalite on the surface of fused silica grains dramatically decreased the leachability of ceramic cores.     

Iron role on mechanical properties of ceramics with clays from Ivory Coast

Three clays from Gounioubé deposits were used for the manufacture of floor tiles. The strength distributions by the Weibull statistical model are interpreted in relation to clay chemical and mineralogical compositions and particularly to the iron role by Mössbauer spectroscopy. With clays without additions, results of mechanical strength of sintered materials show that clays alone are not really suitable for the manufacture of ceramics. But clay calcite mixes (10 wt% of CaCO₃) favor a significant increase of mechanical resistance, which are similar to used standards. This behavior is due to the formation of a three-dimensional network of anorthite crystals within the silico-aluminate materials. Beside the anorthite role, the iron oxide content of the clays influences the mechanical strength. With Gounioubé clays, it is shown that the increase of iron content in clays causes a decrease of the ceramic strength. This behavior is related to the clay compositions, which contain iron in the form of goethite. During the thermal transformations, part of the iron is involved in both the structural transformations and the densification phenomenon of the silico-aluminate phase. But the most part of iron readily transforms into hematite crystallites, which are embedded within the silico-aluminate. They accentuate the heterogeneous nature of the material and favor the decrease of the mechanical strength.     

Sintered material from alkaline basaltic tuffs

The possibility to obtain sintered material from alkaline basaltic tuffs is demonstrated. The parent rock was milled for 10–15 min, the resulting powder was pressed at 100 MPa and the obtained samples were heat-treated in the range of 1000–1140 °C. The sintering behaviour and the phase formation were studied by pycnometry, dilatometry, DTA, XRD and SEM.The final material was obtained by sintering at 1100 °C and is characterized by zero water absorption, 8–9 vol.% closed porosity and a structure similar to a glass-ceramic. Due to high crystallization trend of used composition, phase formation takes place during the sintering and cooling steps; this leads to a crystallinity of ～60% and formation of different crystal phases (pyroxene, anorthite, spinel and hematite).Despite the low-cost production cycle the obtained material is characterized by high mechanical properties: bending strength of 100 MPa and Young modulus of 90 GPa.     

A kinetic study of the quartz–cristobalite phase transition

Cristobalite is a common silica polymorph in ceramics, as it can crystallize in SiO₂-rich systems during high temperature processes. Its occurrence in final traditional ceramic bodies remarkably affects their thermal expansion, thus playing an important role in the shrinkage upon cooling. The quartz–cristobalite transformation kinetics is investigated by in-situ isothermal X-ray powder diffraction experiments and then correlated to the average particle size (〈d〉) of the starting quartz using a model here developed. An Avrami-like rate equation, i.e. α(t) = 1 ? exp(? k × t)ⁿ, in which the n-term is assumed to account for the dependence on the average particle size, has provided the best fitting of theoretical to experimental data, yielding activation energy values that range from 181 to 234 kJ mol^?1, and exponential n-coefficients from 0.9 to 1.5. Ex-situ observations have demonstrated that the formation of cristobalite from quartz after 50 min, 2, 4 and 6 h at 1200 and 1300 °C, exhibits a remarkable dependence on 〈d〉 of quartz, showing comparable behaviours in the case of 〈d〉 equal to 15.8 and 28.4 μm, but significant differences for 〈d〉 of 4.1 μm. The formation of cristobalite is boosted remarkably at temperature higher than 1200 °C, with an increase by weight even of 500%, with respect to its content at lower temperature. The method of sample preparation (dry powder, wet powder and tablet of compressed dry powder) seems to influence the results only at temperature > 1200 °C and in the case of fine powder.     

Diphasic aluminosilicate gels with two stage mullitization in temperature range of 1200–1300 °C

The crystallization of mullite in amorphous diphasic gel aged for 6 months has been studied using non-isothermal differential scanning calorimetry (DSC) and powder X-ray diffraction with Rietveld structure refinement analysis. The diphasic premullite gels undergo structural changes by aging even when they are calcined at 700 °C. These changes imply segregation of the sample to Al₂O₃-rich and SiO₂-rich regions. From the Al₂O₃-rich region crystallizes poorly defined AlSi spinel at 977 °C followed by two-step mullite crystallization in the temperature interval of 1200–1300 °C. Two overlapped exothermic peaks on DSC scan of aged gel were observed; the first at 1233 °C and the second at 1261 °C. The former is attributed to mullite crystallization by transformation of AlSi spinel, by which excess alumina occurs, which in the second step of mullitization reacts with amorphous SiO₂-rich phase. The activation energy for mullite crystallization in the first step was E_a=935±14 kJ mol⁻¹ and the Avrami exponent n=2.5. The values E_a=1119±25 kJ mol⁻¹ and n=1.2 were obtained for mullite formation in the second step. If amorphous SiO₂-rich phase is extracted from the sample, the value E_a=805±26 kJ mol⁻¹ is obtained. Mullite crystallizing from AlSi spinel (when SiO₂-rich phase has been extracted) differentiates compositionally from that formed by both reactions. Smaller unit cell parameters and higher amount of oxygen vacancies are incorporated into tetrahedral positions of mullite structure, as was determined by Rietveld structure refinement method.