Effect of the plant waste onto the properties of use and the microstructure of phyllosilicates based ceramics

The present study aimed at using plant waste (Musa Paradisiaca) for manufacturing clay-based ceramics in order to promote lower sintering temperature while preserving the properties of use. Two kaolinic-illitic clays (NZ1 and KO) from Central African Republic were used mixed with 1 to 10 mass% of the plant waste (MP). The clays and the waste exhibited accessory phases: quartz and iron oxides, and K₂O respectively. MP was collected, dried and sieved (<100 μm) previously to its mixture with clays. According to the sintering behavior of KO and NZ1 derived from thermodilatometry, the densification was obtained after firing at 1200°C. Results showed that open porosity decreased from 35% to 17% with increasing temperature in the range 900 to 1200°C for KO and NZ1. This porosity remained in the range 30%-40% while increasing the MP content (firing at 1000°C for 1h.). The optimized MP content was 3 and 5 mass% for KO and NZ1 clay materials respectively. The compressive strength and thermal conductivities were improved compared to clay samples without MP fired at 1200°C. Moreover a significant decrease in the sintering temperature was achieved, leading to energy saving in line with sustainability issues.     

The causes of expansion in fireclay products during firing

Conclusions The expansion of fireclay products during firing is due to the bloating of the grog. Bloating of the dry clays is observed during firing when they are fired in lumps with their natural structure intact.The expansion of the products depends on the conditions of firing the grog, the degree of firing, the time of firing, and the nature of the kiln atmosphere:increasing the temperature of maximum densification of the clay gives rise to bloating of the grog; firing the clay into grog with a fast cycle leads to a bigger expansion that with slow firing; maintenance of a reducing or weakly oxidizing atmosphere during the firing of the clays into grog contributes to a reduction in the growth of the articles.The expansion of the article depends on the firing temperature; in the preparation of grog from biscuit-dry clays, the expansion is noted at firing temperatures of more than 1380°C. The expansion of the articles as a rule is higher, the higher the content of the original raw materials and impurities contributing to sintering.An increase in the grog of fractions finer than 0.088 mm contributes to an increase in the expansion of the articles.The work was shared with O.T. Anosova, M.I. Ivanov, and V.A. Petrova.     

Development of fireclay aluminosilicate refractory from lithomargic clay deposits

Lithomargic clay until now has not been utilised to produce refractory bodies due to its low plasticity. In this work, the development and evaluation of fireclay refractory material produced from lithomargic clay deposit has been studied by addition of clay binder. Three formulations were prepared by mixing, semi-dry moulding, drying and firing at temperatures ranging from 1200 to 1400 °C. The fired samples were investigated to determine their physical properties such as bulk density, apparent porosity, linear firing shrinkage, and cold crushing strength. The chemical and mineralogical compositions were also determined. The results show that the linear firing shrinkage values were within limits acceptable for refractory clays. The cold crushing strength increases as temperature increased to 1400 °C. Cold crushing strength increased with increasing binder content. The increase of the highly refractory phases (cristobalite and mullite) and the densification of the bricks due to the presence of fluxing agents were responsible for the high cold crushing strength values. The investigated properties indicate that lithomargic clay underlying bauxite deposits could be used to produce fire clay aluminosilicate refractories.     

X-RAY INVESTIGATION OF THE EFFECT OF HEAT ON CHINA CLAYS1

X-ray diffraction patterns were obtained from an English china clay and a Georgia sedimentary kaolin, both raw and fired to various temperatures. The chief crystalline constituent of the raw clays was found to be kaolinite. Upon dehydration the kaolinite lattice was destroyed and the clays gave no diffraction pattern. Mullite was formed in both clays at 950°C and the amount increased with increase of firing temperature. In addition to the mullite, free alumina was present in the Georgia clay from 950 to 1100°C and cristobalite at temperatures above 1200°C.     

Preparation and properties of porous mullite-based ceramics fabricated by solid state reaction

In this study, the effect of the alumina particle size on the formation of mullite using a silica gel powder and micro- and nano-scale Al₂O₃ powders as raw materials was investigated. The optimized Al₂O₃ source was then reacted with the silica gel to prepare porous mullite-based ceramics. The results revealed that the highly reactive nano-Al₂O₃ powder could form mullite at a relatively low firing temperature. Therefore, the nano-Al₂O₃ powder was used to prepare porous mullite-based ceramics by firing at 1600 °C, 1650 °C and 1700 °C. The pore size of the prepared porous mullite-based ceramics ranges from tens to hundreds of micrometres, with the apparent porosity being 42.8–58.0%. Further, the mullite content in the samples increased with increasing firing temperature, and a higher firing temperature promoted sintering, resulting in improved strength of the sample. After calcination at 1700 °C, the mullite content in the sample reached 81.8%, and the sample showed excellent thermal shock resistance. The strengths of the samples before and after thermal shock were found to be 23.6 and 15.58 MPa, with the residual strength ratio being 66%.     

Influence of raw material type and of the overall chemical composition on phase formation and sintered microstructure of mullite aggregates

Dense mullite aggregates with varied (47–70%) alumina contents have been prepared by a conventional dry-powder pressing technique followed by heat treatments at temperatures in the range of 1450–1725 °C. Different types of clays, beach sand sillimanite (BSS) and a high purity aluminium hydroxide were used as starting materials. Mullites derived from BSS consisted of equi-axed grains whereas those obtained from clay containing precursor mixtures exhibited elongated grains. The bulk density (BD), apparent porosity (AP) and water absorption (WA) capacity of sintered mullites were found to be strongly influenced by the pre-mullitization step of the precursors and in a less extent by the type of raw material, its hydration degree and the impurity contents of Fe₂O₃, CaO and Na₂O. Mullite aggregates obtained from the three different types of aluminosilicate raw materials (i.e., ball clay, china clay and beach sand sillimanite) through a double-stage heat treatment process exhibited better sintered properties in terms of bulk density, apparent porosity, water absorption capacity and higher mullite contents in comparison to those obtained following a single-stage firing process.     

Mineralogy and physico-chemical properties of alluvial clays from Sanaga valley (Center,Cameroon): Suitability for ceramic application

Alluvial clays from four localities along the Sanaga River (Center Cameroon) were studied by physico-chemical, mineralogical and technological characterization in order to assess their suitability as ceramic raw materials. The chemical compositions indicated that SiO₂ (65–70%) and Al₂O₃ (12–15%) are major elements while Fe₂O₃ is less (4–7%). Kaolinite, quartz and feldspar are the main minerals. Particle size distribution and chemical composition are indicative of “plastic red clays” belonging to heavy sandy clays group. Their medium to high plasticity is suitable for fired earth and fine ceramics products. Pressed samples were fired at temperatures ranging between 900 and 1100 °C for coarse ceramic products. Linear shrinkage, flexural strength and water absorption indicated that the clays from one site (Mbandjock) are good for brick making. Clays from the three other localities present poor technological properties (higher shrinkage and cracks), they need degreasers before use as ceramic raw materials. Although water absorption and flexural strength parameters are good for all the studied samples, firing shrinkage needs to be improved.     

The effect of boron waste in phase and microstructural development of a terracotta body during firing

In the present study, a dewatering sieve waste (TSW) of Etibor Kırka Borax company (Turkey) was employed in different amounts in order to develop an experimental terracotta floor tile body composition in combination with a feldspathic waste provided from a local sanitaryware plant and a ball clay. Several formulations were prepared and shaped by dry pressing under laboratory conditions. The obtained samples were fired at selected peak temperatures (1050, 1100 and 1150 °C) to establish their optimum firing temperatures. Some technological properties of the resultant products, namely linear firing shrinkage, water absorption and breaking strength were determined as a function of increasing TSW content in place of the sanitaryware waste at these temperatures. The phase content of the starting raw materials and that of the fired compositions was determined by XRD. The relevant polished surfaces of selected fired samples were also examined using SEM. According to the results, increased presence of TSW compared to the standard mixture of clay and the sanitaryware waste, as a co-fluxing material, in the experimental terracotta body considerably accelerated the vitrification process. The overall results indicated a prospect for using the TSW as a raw material in mixtures with both clay and sanitaryware waste for the production of a terracotta floor tile body.     

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.     

Influence of fluorine source and TiO2 on glass ceramics based on red clay and magnesite

Abstract

Within the Fe₂O₃–BaO–Al₂O₃–SiO₂ glass system, the influence of different fluorine source and TiO₂ on the crystallisation behaviour and thermal expansion characteristics has been investigated. These aluminosilicate glasses, with different nucleation catalysts (TiO₂, AlF₃ and NH₄F), were successfully prepared from Saudi Arabia raw materials (red clay and magnesite). Thermal behaviour, crystalline phases, microstructures, and thermal expansion coefficient were studied by DTA, XRD, SEM techniques, as well as a dilatometer. Spinel, hexacelsian, monocelsian, kinoshitalite, and Ba-osumilite were developed in glass ceramic samples. Spinel was the early phase formed in all glasses; however, with increasing temperature, hexacelsian and kinoshitalite were developed in fluorine free glasses and fluorine containing glasses respectively. Ba-osumilite was developed and hexacelsian was converted into monocelsian during lengthy heat treatment at 1150°C. A bulk crystalline microstructure was obtained; however, a microscale structure was observed in fluorine free samples and a homogeneous nanoscale microstructure was developed in fluorine containing samples. The coefficient of thermal expansion (CTE) varied according to the phases and the heat treatment parameters. Development of spinel, hexacelsian and kinoshitalite in glass ceramic samples gave CTE values between 86·44 × 10^?7 and 52·53 × 10^?7°C^?1, whereas crystallisation of Ba-osumilite and monocelsian gave CTE values between 51·29 × 10^?7 and ?7·35 × 10^?7°C^?1.     

Physicochemical methods for studying the mineral composition and pore structure for the argillaceous part zircon-ilmenite ore gravitation tailings

It is established that the argillaceous part zircon-ilmenite ore gravitation tailings (ZIG) is a refractory clay, but it has a complex mineral composition, including in contrast to traditional refractory clays more than ten minerals and an increased amount of Fe₂O₃ (>5%). The main clay mineral of ZIG is kaolinite, which is poorly crystallized. An increase in ZIG ceramic specimen firing temperature to 1300°C promotes pore size uniformity.     

Reduction of the porcelain firing temperature by preparation of the raw materials

An innovative way of reduction of firing temperature of porcelain tableware is reached by preparation of raw materials down to submicron- and nanoscaled powder for higher reactivity. In this study a common slurry was ground in an agitator ball mill from d₅₀ = 5.0 μm to 0.9 μm, green bodies were prepared, and glost firing was simulated in a dilatometer. The sintering temperature has been decreased by approximately 180 °C. A reflection between ball mill and agitator ball mill regarding the grinding cost shows no difference which means that the ball mill could be replaced. The energy consumption during the grinding process will be discussed regarding to energy savings resulting from reduced firing temperature. Furthermore a comparison between experimental and literature data will be done. The effect of grinding of raw material is finally evaluated concerning sintering behaviour and material properties.     

Phase formation,structure and properties of light-weight aluminosilicate proppants based on clay-diabase and clay-granite binary mixes

One of the drawbacks of fusible clays is the narrow sintering interval due to a sharp increase in the amount of iron-silicate melt at a temperature of 1000–1100 °C, which hardens in the form of a glass phase upon cooling. This leads to a relatively low mechanical strength of the calcined samples and causes the danger of melting the granular material surface from such clays during the firing process. To increase the strength of samples of fusible clays, the influence of diabase and granitoid rocks was considered. It was found that the strengthening effect of diabase and granitoid rock additives in an amount of 20–50% in a mixture with fusible clay is due to an increase of total content of the crystalline phase (mullite, cristobalite and residual quartz) from 18–20% in clays without additives to 22–28 % - in mixtures with diabase and to 28–34% - with granitoid additives) at a temperature of 1050–1100 °C. This increase is due to the activation of synthesis processes of secondary mullite and crystallization from alkali-rich feldspar melt of amorphous silica, released from the structure of clay minerals. The established influence of the igneous rocks used made it possible to develop compositions and propose process flow sheet for producing aluminosilicate proppants based on fusible clays. The use of granitoid and diabase rocks in an amount of 20–70% with fusible clays produces lightweight aluminosilicate proppants with bulk density of 1.40–1.46 g/cm³ at temperature range of 1050–1100 °C, which can endure destructive pressures up to 34.5–52 MPa.     

Low-valued raw materials challenge the common eligibility criteria for triaxial ceramics

In this work, two low-valued natural raw materials were used, namely a low plasticity and high iron content clay and a powdered rock waste generated during crushing of igneous rocks to produce construction aggregates. After characterization (chemical, mineralogical, thermal and granulometric), mixtures containing up to 75 wt% of rock powder were prepared and extruded closely following industrial practice, and fired for 60 min from 900 to 1100 °C. Property development was evaluated on as-extruded, dried and fired pieces. The results obtained were interpreted based on chemical compositions, the estimates from the Al₂O₃–SiO₂–CaO phase diagram and presumed reaction kinetics. Such interpretation showed that physical characteristics dominate not only during shaping and drying, but also during low temperature firing (slow reaction kinetics), when rock additions act as inert material; at high firing temperatures, however, the rock promotes liquid phase development after first melting (fluxing effect) and thermodynamics prevail. The dominant fluxing effect results in improved fired properties, which were shown to depend almost linearly on the liquid phase content, predicted by the phase diagram and determined by the chemical composition. These results enabled the identification of behavioural composition ranges to best exploit the materials’ industrial use potential and demonstrate that current paradigms in raw material evaluation and processing in traditional ceramics industries need a re-assessment.     

Preparation of machinable cordierite/mica composite by low-temperature sintering

In order to fabricate machinable cordierite/mica composite at low temperatures, the mica-composition glass powder was mixed with the conventional magnesia, alumina and silica powders which are raw materials of cordierite, compacted and fired in a sealed platinum container. By the addition of the 40 mass% mica-composition glass powder, machinable cordierite/mica composite was obtained. The machinability was caused by the interlocking microstructure of mica developed in the composite. In the firing process, mica crystallized at about 730 °C, cordierite was suddenly formed at 1050–1100 °C and the densification progressed markedly at 1000–1100 °C. The formation and sintering of cordierite were strongly promoted by a small amount of gaseous fluorine and/or fluorides. It was considered that fluorine and fluorides such as AlF₃ evaporated from the mica-composition glass at >800 °C and gaseous HF was formed in the sealed platinum container by the reaction of fluorine with water evaporated from the glass.     

Evolution of fluorine emissions during the fast firing of ceramic tile

The present paper examines the emission–adsorption phenomena of fluorine compounds in various ceramic tile body compositions with different fluorine and calcium contents, processed by fast firing cycles in an electric laboratory batch kiln and in continuous fast-cycle industrial combustion kilns (roller kilns). In the roller kilns, fluorine emission was monitored by analysing the fluorine content in both solid and gas samples throughout the kilns.It was found that fluorine emission during firing in air atmosphere in the laboratory batch kiln began at temperatures above 800 °C and increased progressively up to peak firing temperature. In the roller kilns, however, the emissions started at lower temperatures and decreased in certain kiln zones. This decrease indicates that there are regions in these kilns in which fluorine is adsorbed rather than emitted by the material being processed.A fluorine adsorption process is thus shown to occur in the preheating stage in the roller kilns, despite the rapid heating rate. However, encouraging this adsorption process in order to foster the formation of crystalline phases is ineffective in abating fluorine emissions when ceramic tiles are fired at peak temperatures exceeding 1100 °C.     

The influence of different CaO source in the production of anorthite ceramics

The effects of starting raw materials and firing conditions on anorthite (CaAl₂Si₂O₈) phase formation are investigated by differential thermal analysis (DTA)–thermogravimetry (TG) and X-ray powder diffraction (XRD). Four different sources of CaO were used for anorthite production such as Ca(OH)₂, CaCO₃, marble powder and gypsum mould waste. The mixture of raw materials was prepared in stoichiometric ratio of anorthite. Sintering of samples was carried out at various temperatures (1000–1300 °C). In all samples before the formation of anorthite phase, formation of layered alimunosilicate phase (LAS) and of gehlenite phase were observed at low temperatures (<1200 °C). All the samples showed similar crystallization behaviour at 1200 °C. The densification characteristic and the flexural strength of samples were affected by the nature of starting raw materials. The maximum density (～80%) was reached in sample ACH which was prepared from Ca(OH)₂.     

碳化硅质高温陶瓷膜的低温烧成

本文以碳化硅骨料、章村土系结合剂和核桃壳粉为原料,通过等静压成型工艺和 低温烧结制备了碳化硅质高温陶瓷膜材料。研究了成型压力对坯体强度以及成型压力和烧成温 度对膜材料强度、孔径、气孔率和透气阻力的影响。结果发现,当成型压力为 70 MPa、烧成温 度为 1250~1270?C 时,制品综合性能较优。     

PROPERTIES OF NATURAL ALUNITIC CLAYS

The mineral and chemical compositions and some of the refractory and firing properties of eight alunite-bearing clays were investigated. It was found that alunite raises the softening temperature of clays. Secondary expansion occurs in reheating the clays at temperatures higher than the original firing temperature and the degree of expansion seems to depend uot only on the alunite concentration in the clay but also on its characteristics. This expansion is believed to be due to SO₂ or/and SO₂ gases released by the body in refiring; these gases expand at high temperature causing bloating of the body. The usefulness of thermal analysis in detecting small amounts of alunite is pointed out.     

Influence of Synthesis Conditions and Cerium Incorporation on the Properties of Zr-Pillared Clays

Zr-pillared clays were prepared from ZrOCl₂ pillaring solutions by adopting different preparative conditions. Ce³⁺ ions are introduced to Zr-pillared clays by co-intercalation method. The resulting samples were characterized by XRD, TGA, N₂ sorption and UV-VIS-Diffuse reflectance spectroscopy techniques. Basal spacings in the range of 18–21 Å were observed depending upon the preparative condition. TG analysis shows three weight loss regions corresponding to removal of various types of water molecules. All pillared clays show Type-I sorption isotherm typical of microporous materials. Pillaring under refluxing condition is found to have beneficial effect on the surface area and pore volume of the Zr-pillared clay. The chemical environment and location of Ce³⁺ ions is studied by UV-VIS-DRS. The Ce³⁺ ions are found to be present in the micropores of the Zr-pillared clays. However heat treatment at higher temperature may result in peripheral interaction between Ce³⁺ ions and Zr-pillars. Catalytic activity of these pillared clays was evaluated for cyclohexanol dehydration which correlates well with the Brønsted acidity of these materials. The Zr-Pillared clay containing Ce³⁺ ions show good catalytic activity and stability with reaction time which has been ascribed to the stabilazition of the Brønsted acidic centers.