Shalaby et al. Bulletin of the National Research Centre (2018) 42:24 Bulletin of the National https://doi.org/10.1186/s42269-018-0030-5 Research Centre RESEARCH Open Access Technological properties of high alumina refractories with different phosphoric acid contents Basel Nour El-Din Ali Shalaby1* , Mohamed Saad El-Maghraby2 and Ali Ismail Mohamed Ismail1 Abstract Background: High alumina refractory batches were prepared from Egyptian clay and imported China calcined bauxite. Three concentrations of phosphoric acid 3, 5, and 7%, were added to study their effects on some of their technological properties. Designed batches tend to form a composition of 76% alumina and ~ 17% silica in addition to the other fluxing and alkali oxides. Chemical and mineralogical composition as well as density and plasticity of both clay and calcined bauxite was performed. Results: Three batches of different phosphoric acid concentrations were fired at 1350 °C for 1 h. Densification parameters of the fired batches as well as the cold crushing strength and thermal shock resistance were carried out. The mineral composition and microstructure of the selected batch were done using XRD as well as SEM and EDAX. It is concluded that by increasing phosphoric acid percentages, the porosities slightly increase and the cold crushing strengths drastically decrease; however, densities and shrinkages exhibit no remarked effects. Conclusions: The mineral composition of the selected fired batch exhibits mullite as a main phase with subordinate amount of corundum, while berlinite, quartz, and cristobalite are in less frequent contents. Microstructure of the selected batch ensures that mullite and corundum are the main mineral phases, in addition to minor phases of phosphate minerals. The fluxing and alkali oxides together with some alumina and silica form a liquid phase, which is responsible for the densification of the batch, while mullite and corundum are the essential formed minerals. Keywords: Egyptian clay, High alumina refractories, Mullite, Corundum, Phosphoric acid Introduction clay mineral (Al2O3·2SiO2·2H2O), e.g., kaolins, fireclays, Refractory materials are inorganic, non-metallic, and and ball clays. In addition, calcined Al2O3-rich raw brittle crystalline solid materials, fired at optimum materials are added to increase the alumina content temperature according to their uses. They are used as and their refractory quality. The additives are mainly face- and back-linings of industrial furnaces at high bauxite (Al2O3·2H2O) and gibbsite (Al(OH)3). These temperature for thermal insulations. They are classi- refractories include fireclay (25–45% Al2O3), aluminous fied according to their chemical composition and fireclay (45–65% Al2O3), and high-alumina (> 72% Al2O3), resistance to attack by the fired materials in contact respectively (Chesters 1974); Kingrey et al. 1976, and Sadik under service conditions into acidic, neutral, and basic et al. 2014). Refractory oxides encompass a broad range of refractories (Shaw 1972 and Chesters 1973). unary, binary, and ternary ceramic compounds that can be Aluminosilicate refractories, rich in silica, are belong- used in structural, insulating, and other applications. ing to acidic refractories, while those rich in alumina Kaolinitic clays are considered as acidic refractories are essentially of neutral type. They are manufactured due to their Al2O3/SiO2 ratio, as well as their limited using refractory clays, which are composed of kaolinite total fluxing and alkali oxide contents, namely, Fe2O3, TiO2,CaO,MgO,Na2O, and K2O. These clays include * Correspondence: [email protected] fireclays, ball clays, and kaolins (Grim 1968). Konta 1Geological Sciences Department, National Research Centre, P.O. 12622, 33 El Buhouth St. Dokki, Giza, Egypt (1979) classified the kaolintic clays for ceramic indus- Full list of author information is available at the end of the article tries according to their content of the total coloring © The Author(s). 2018 Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Shalaby et al. Bulletin of the National Research Centre (2018) 42:24 Page 2 of 7 oxides,i.e.Fe2O3 and TiO2, into two categories; the porosity, and linear shrinkage as well as cold crushing first grade (Seger 1 clays) contains less than 1.2% of the strength and thermal shock resistance were carried out. coloring oxides, e.g., China clay, which is suitable for production of white-ware ceramics, e.g., porcelain Methods tableware and electrical insulators. Clays rich in kaolin- Egyptian clay of Al-Ogybabe area, northeast of Aswan ite containing higher than 1.2% of total Fe2O3 and TiO2 city, south of Egypt, and imported calcined bauxite are classified as Seger 2 clays, which are adequate for were used to produce batch of high alumina refractor- manufacturing colored and heavy clay-based ceramics ies (> 72% Al2O3). The starting materials were received and aluminosilicate refractories. The Egyptian kaolins from Normatic Co. for building materials and refract- and fireclays are mainly belonging to Seger 2 kaolinitic ories, Helwan, Cairo, Egypt. Phosphoric acid of 85% clays (Carniglia and Barna 1992,Routschka2004,and concentration was received from El-Gomhoryia Company Elmaghraby and Ismail 2016). for chemicals. Phosphoric acid reacts with metal oxides to form High alumina refractory > 72% Al2O3 was proc- salts which function as a bonding agent. Phosphoric essed using Egyptian raw clays and calcined bauxite. acid and aluminum hydroxide react readily but alu- Calcined bauxite and Egyptian clay were crushed, mina and phosphoric acid are only slowly reactive at ground to pass through 200 mesh. The used clay ordinary temperature. When temperature rises, phos- acts as a plastic-bonding material for the refractory phoric acid undergoes dehydration and reacts with alu- batch. High alumina refractories were produced as mina to form mono aluminum phosphate, which starts standard from the corresponding calcined bauxite above 127 °C and continues till 427 °C. Between 732 and clay by mixing with different percentages (3, 5, and 1327 °C, aluminum orthophosphate is formed. and 7%) of 85% phosphoric acid concentration, Aluminum orthophosphate resembles silica in struc- semi-dry, pressed, and dried. They were then fired ture. It corresponds to quartz to form berlinite; it has for 1 h at 1350 °C. ortho-polymorphs of cristobalite and tridymite forms Chemical and mineralogical compositions of the (Schacht 2004, Sahnoun and Bouaziz 2012,andLuza starting materials were carried out using XRF and et al. 2015). Refractory concretes based on binder XRD, while the phase composition of the selected modified with orthophosphoric acid improve the batch was done by using XRD and scanning electron thermo-mechanical and physicochemical properties microscope as well as EDAX. (Trepalina et al. 2016). The amount of water that rendered the raw clay The scope of the present research is to prepare high material plastic (i.e., plasticity) was determined using alumina batch using Aswan clay and China calcined the Atterberg method (BS 1377 1975). Bulk densities bauxite as well as to study the effect of different of the calcined bauxite and the clay raw material were phosphoric acid percentages on the technological determined. Densification parameters of the fired properties of the fired samples, through monitoring high alumina batch were investigated as bulk density the densification parameters, cold crushing strengths, and apparent porosity using the water displacement and thermal shock resistance. To achieve these pa- (Archimedes) method according to European Stand- rameters, chemical and mineralogical compositions of ard No. BS En No. 993-1/1993 (Serry et al. 2006). the starting materials were determined using XRF and XRD, respectively. The plastic and liquid limits as well as the plasticity of the clay were determined to Table 1 Chemical composition of the used materials detect the amount of water required for making the Oxide % Clay Calcined bauxite clay as plastic material. The density of the used clay SiO2 52.97 7.20 and the calcined bauxite was also measured. The high Al2O3 29.07 85.39 alumina batch was designed from the Egyptian clay TiO2 1.48 4.08 and the China calcined bauxite according to their Fe O 3.92 2.45 composition. Three different concentrations of 3, 5, 2 3 CaO 0.50 0.07 and 7% of phosphoric acid were added to the pre- formed high alumina batch to form three different MgO 0.20 0.16 concentration batches. The designed batches of differ- Na2O 0.06 0.02 ent phosphoric acid concentrations were fired at K2O 0.28 0.27 1350 °C for 1 h. The phase composition of the SO3 0.76 – selected batch was done using XRD and a scanning LOI 10.62 – electron microscope as well as EDAX. The densifica- Total 99.86 99.64 tion parameters in terms of bulk density, apparent Shalaby et al. Bulletin of the National Research Centre (2018) 42:24 Page 3 of 7 Fig. 1 XRD pattern of the raw clay material Thermal shock resistance at 1000 °C in terms of The calcined bauxite is used to enrich, adequately, the number of heating and coaling cycles was deter- these refractories; it is composed of Al2O3 up to mined using an air-quenching technique. Cold 85.39%, as well as 7.20% SiO2 and nearly 7.0% total im- crushing strengths of the fired bricks were also per- purity oxides (Fe2O3,TiO2,CaO,MgO,Na2O, and formed to detect the maximum load-bearing capacity K2O). XRD patterns of the raw clay and calcined baux- of the batch. ite materials (Figs. 1 and 2) show that clay is composed mainly of kaolinite and halloysite as clay minerals in Results addition to quartz as a non-clay mineral.