MgAl2O4 spinel as an effective ceramic bonding in a MgO–CaZrO3 refractory

The influence of MgAl₂O₄ spinel addition as a ceramic bonding in the MgO–CaZrO₃ refractory was established by the evaluation of physical and microstructural characteristics in terms of density, porosity, crystalline phases, phase distribution and morphology. X-ray diffraction analyses and scanning electron microscopy with microanalysis have been used. The mechanical behavior has been evaluated in terms of cold crushing strength at room temperature and modulus of rupture at 25 and 1260 °C. Static and dynamic resistances tested by chemical attack of clinker raw constituents have been carried out at 1450 °C. Results showed that thermo-mechanical properties significantly improved with increasing the content of spinel. Microstructural analysis revealed that spinel phase aided to develop a strong bond between MgO and CaZrO₃ refractory aggregates. Finally, the refractory bodies exhibited a good thermal stability and an excellent chemical resistance against the clinker raw material.     

The Mechanism of corrosion of MgOCaZrO3–calcium silicate materials by cement clinker

The chemical reactions involved in the corrosion of MgOCaZrO₃–calcium silicate materials by cement clinker were studied using a hot-stage microscope up to 1600 °C. The phases formed at 1500 °C were characterized by RLOM and SEM–EDS of the crystalline phases conducted near the reaction front and on unreacted refractory area.The general corrosion mechanism of attack on MgOCaZrO₃–calcium silicate materials involves a mechanism of matter diffusion of the liquid clinker phase through the grain boundaries and pores into the refractory substrate. The liquid phases in the clinker mainly enriched in calcium, iron and aluminium are rapidly diffused and preferentially react with magnesium spinel, calcium zirconate and magnesia, which are the major constituents in the refractory substrates. The dissolution of the CaZrO₃ refractory phase produces the enrichment with zirconium of the liquid phase increasing its viscosity and hindering the liquid phase diffusion.     

水泥窑用MgO-MgAl2O4-ZrO2-La2O3复合耐火材料的研究

根据耐火材料和水泥熟料的反应机理,找到一种既可阻止窑皮中C2S相变,又不损害镁铝质耐火材料的高温性能的添加物,开发了一种基于MgO-MgAl2O4-ZrO2-La2O3体系的新型复合耐火材料。该材料具有优异的耐火性能、抗热震性能、挂窑皮性能、抗侵蚀性能和较高的机械强度,是一种替代镁铬砖的理想材料,适用于水泥窑烧成带。     

The effect of Cr2O3 as a nucleating agent in iron-rich glass-ceramics

In this work, the effect of Cr₂O₃ as a nucleating agent, in iron rich glasses has been investigated by means of DTA, XRD and density measurements. By Cr₂O₃ addition, from 0·4 to 1·0 wt%, a lowering of the crystallisation peak temperature resulted in the DTA trace, the maximum effect corresponding to 0·7 wt%. By evaluating the degree of crystallisation of the glass at 0·7 wt% Cr₂O₃, the highest efficiency in the nucleation process also corresponds. The optimum values for the nucleation and crystallisation time and temperature, determined for 0·7 wt% Cr₂O₃ addition, have been 70 min at 630°C and 30  min at 800°C. The crystalline phases formed at different thermal treatment temperatures of the parent glass have been investigated by XRD; the spinel is the only phase after the nucleation; pyroxene is the major phase after the crystallisation. The results of this study have highlighted that a small percentage of Cr₂O₃ strongly affects the spinel formation thereby reducing the time and temperature of the thermal treatment and enhancing the degree of crystallisation of high iron content glasses. ©     

Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500°C

Hot modulus of rupture of Al₂O₃-spinel castables containing 5–15 wt% alumina-rich magnesia alumina spinel and 1·7 wt% CaO generally increases with increase in spinel content and temperature from 1000 to 1500°C. The magnitudes of hot modulus of rupture of castables containing 15 wt% spinel and 1·7 wt% CaO are 14·3 MPa at 1400°C and 15·6 MPa at 1500°C, while those of castables containing 20 wt% spinel and 1·7 wt% CaO are 12·5 MPa at 1400°C and 14·7 MPa at 1500°C. The former castables contained 15 wt% spinel of −75 μm size, while the latter contained 10 wt% spinel of +75 μm size and another 10 wt% spinel of −75 μm size. The bond linkage between the CA₆ and spinel grains in the matrix is believed to cause both the spinel content and temperature dependence of hot strength of Al₂O₃-spinel castables, as well as fine grain spinel even in amount less than coarser grain spinel to be more effective for enhancing hot strength. The trend of the magnitude of thermal expansion under load (0·2 MPa) above 1500°C of the castables is not necessarily indicative of the magnitude of hot modulus of rupture at 1400 or 1500°C. ©     

Structural study of mullite based ceramics derived from a mica-rich kaolin waste

Mullite-based ceramics have been synthesized by reactive sintering of a mixture containing kaolin and a mica-rich kaolin waste. Samples fired in the temperature range from 1300 to 1500 °C were characterized by X-ray diffraction (XRD). The quantitative phase analysis and unit cell parameters of the mullite were determined by Rietveld refinement analysis of the XRD data. Mullite-based ceramics with 1.2 wt% quartz, 56.3 wt% glass (amorphous phase), 2.64 g/cm³ of apparent density, and 35±1.2 MPa of flexural strength were obtained after firing at 1500 °C. A liquid phase sintering mechanism activated by a total mica content of 13.3 wt% allowed to increase the mullite content to 47.6 wt% (2.3 wt% quartz and 50.1 wt% glass phase) and improve the flexural strength (70±3.9 MPa) after firing at 1400 °C.     

Fabrication and thermal conductivity of highly porous alumina body from platelets with yeast fungi as a pore forming agent

A highly porous alumina body was fabricated by heating a green clinker body consisting of platelets and yeast fungi as a pore forming agent. Four kinds of alumina platelets were used. When green clinker bodies of platelet aggregates (A11) with 10 and 30 mass% of yeast fungi were heated at 1500 °C for 2 h, their porosities reached 72% and 78%, respectively. In contrast, when the green clinker bodies composed of platelets with an average size of 10 µm and an aspect ratio of 25–30 (SERATH①), and 20 mass% of yeast fungi were heated at 1400 °C for 2 h, the porosity of the resultant porous alumina body was also approximately 72%. However, the room temperature thermal conductivities of the porous alumina bodies with 72% porosity derived from A11 and SERATH① were 0.86 and 0.50 W m⁻¹ K⁻¹, respectively. The decrease in the thermal conductivity of the porous alumina body produced from SERATH① is caused by the long path route for heat transfer.     

The system Clinker–MgO–CaZrO3 and its application to the corrosion behavior of CaZrO3/MgO refractory matrix by clinker

Phase relations in the clinker-rich region and the limits between the different stability fields of the isothermal section Clinker (CK)–MgO–CaZrO₃ at 1500 °C were experimentally established. The corrosion behavior by clinker of Portland cement of a CaZrO₃-rich/MgO refractory matrix obtained from both natural and synthetic raw materials were also studied. The attack mechanism to CaZrO₃-rich substrates was discussed in terms of microstructural features of the refractory matrix and the information supplied by the isothermal section Clinker–MgO–CaZrO₃ at 1500 °C.     

High emissivity MoSi2–ZrO2–borosilicate glass multiphase coating with SiB6 addition for fibrous ZrO2 ceramic

To develop a high emissivity coating on the low thermal conductivity ZrO₂ ceramic insulation for reusable thermal protective system, the MoSi₂–ZrO₂–borosilicate glass multiphase coatings with SiB₆ addition were designed and prepared with slurry dipping and subsequent sintering method. The influence of SiB₆ content on the microstructure, radiative property and thermal shock behavior of the coatings has been investigated. The coating prepared with SiB₆ included the top dense glass layer, the surface porous coating layer and the interfacial transition layer, forming a gradient structure and exhibiting superior compatibility and adherence with the substrate. The emissivity of the coating with 3 wt% SiB₆ addition was up to 0.8 in the range of 0.3–2.5 μm and 0.85 in the range of 0.8–2.5 μm at room temperature, and the “V-shaped grooves” surface roughness morphology had a positive effect on the emissivity. The MZB-3S coating showed excellent thermal shock resistance with only 1.81% weight loss after 10 thermal cycles between 1773 K and room temperature, which was attributed to the synergistic effect of porous gradient structure, self-sealing property of oxidized SiB₆ and the match of thermal expansion coefficient between the coating and substrate. Thus, the high emissivity MoSi₂–ZrO₂–borosilicate glass coating with high temperature resistance presented a promising potential for application in thermal insulation materials.     

Processing and properties of glass-bonded silicon carbide membrane supports

Porous SiC membrane supports were fabricated from SiC and glass frit at a temperature as low as 850 °C in air by a simple pressing and heat-treatment process. The effects of the initial SiC particle size and frit content on the porosity, flexural strength, and air permeation of the membrane supports were investigated. During heat-treatment, the glass frit transformed to a viscous glass phase, which acted as a bonding material between SiC particles and as a protecting layer for severe oxidation of SiC particles. The porosity of the porous SiC membrane supports could be controlled within a range of 37–46% with the present set of processing conditions. The typical flexural strength, permeability, and specific air flow rate of the porous membrane supports fabricated using 23 μm SiC particles with 15 wt% glass frit were 75 MPa, 4.2 × 10⁻¹³ m², and 32.4 L/min/cm², respectively.     

Effects of different particle size of spinel and Y2O3 additive of the periclase-spinel refractory on the sintering densification and corrosion resistance to copper smelting slag

In order to analyze the sintering densification and copper smelting slag corrosion resistance of periclase-spinel refractories, the periclase-spinel refractories were prepared with fused magnesia, magnesia-rich spinel, industrial alumina, and yttrium oxide as the main raw materials. The different particle sizes of spinel in material and with or without Y₂O₃ additive were studied. The study demonstrated that: (1) The different particle sizes of spinel in periclase-spinel refractories can result in different effects. Adding particle spinel to the refractory can improve the strength and corrosion resistance of the periclase-spinel refractories. The addition of spinel and magnesia powders in the matrix resulted in cracks due to the great difference of coefficient of thermal expansion between magnesia and spinel. The reduction in bulk density and strength of the material decreased slag penetration resistance because of its poor sintering properties. While adding the alumina in the matrix can further fill the crack and prevent slag penetration by the volume expansion of in-situ reaction to form spinel. (2) The periclase-spinel refractories can be reacted with Cu slag to form a Mg₂FeO₄ insulating layer as the iron ion becomes oxidized. Adding Y₂O₃ in periclase-spinel refractories can result in grain boundary phase reconstruction, which can promote sintering densification, improve the slag physical infiltration resistance, and improve the chemical corrosion resistance of materials.     

Investigating the effect of porosity level and pore former type on the mechanical and corrosion resistance properties of agro-waste shaped porous alumina ceramics

The strength integrity and chemical stability of porous alumina ceramics operating under extreme service conditions are of major importance in understanding their service behavior if they are to stand the test of time. In the present study, the effect of porosity and different pore former type on the mechanical strength and corrosion resistance properties of porous alumina ceramics have been studied. Given the potential of agricultural wastes as pore-forming agents (PFAs), a series of porous alumina ceramics (Al₂O₃-xPFA; x=5, 10, 15 and 20 wt%) were successfully prepared from rice husk (RH) and sugarcane bagasse (SCB) through the powder metallurgy technique. Experimental results showed that the porosity (44–67%) and the pore size (70–178 µm) of porous alumina samples maintained a linear relationship with the PFA loading. Comprehensive mechanical strength characterization of the porous alumina samples was conducted not just as a function of porosity but also as a function of the different PFA type used. Overall, the mechanical properties showed an inverse relationship with the porosity as the developed porous alumina samples exhibited tensile and compressive strengths of 20.4–1.5 MPa and 179.5–10.9 MPa respectively. Moreover, higher strengths were observed in the SCB shaped samples up to the 15 wt% PFA mark, while beyond this point, the silica peak observed in the XRD pattern of the RH shaped samples favored their relatively high strength. The corrosion resistance characterization of the porous alumina samples in hot 10 wt% NaOH and 20 wt% H₂SO₄ solutions was also investigated by considering sample formulations with 5–15 wt% PFA addition. With increasing porosity, the mass loss range in RH and SCB shaped samples after corrosion in NaOH solution for 8 h were 1.25–3.6% and 0.44–2.9% respectively; on the other hand, after corrosion in H₂SO₄ solution for 8 h, the mass loss range in RH and SCB shaped samples were 0.62–1.5% and 0.68–3.3% respectively.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.     

Composition and microstructure of a periclase–composite spinel brick used in the burning zone of a cement rotary kiln

The composition and microstructure of a periclase–composite spinel brick used in the burning zone of a cement rotary kiln were investigated and compared to the original brick. The results indicate that cement clinker and alkali salts are two important agents that cause corrosion especially of the bonding phase of refractories in cement rotary kilns. When the molar ratio of alkalis to anions ((Na+K)/(Cl+2S)) is more than one, alkali salts accumulated in the pores, cracks and grain boundaries of the refractory but the severe corrosion of the bonding phase of the refractory did not occur in zones with lower temperatures. The interaction between the cement clinker and the refractory formed a liquid, which, together with alkali salts, improved sintering. The reaction between the cement clinker and the refractory formed a dense reaction layer. Cracks formed in the dense layer and extended through the boundary between the reaction and non-reaction (penetrated) layers by mechanical and thermal stress, which caused the spalling of the reaction and coating layer from the refractory. The recurrence of this process during service leads to degradation of the refractory.     

The solid state structure of polycarbonate blends with lead phthalocyanine

The physical properties of polycarbonate blends containing the nonlinear optical dye lead tetracumylphenoxy phthalocyanine were characterized. Blends with up to 20 wt% dye were prepared and characterized in terms of density, refractive index, glass transition temperature, loss modulus, subambient relaxation behavior, and free volume hole size from positron annihilation lifetime spectroscopy. The dye strongly affected the physical properties of the blend. The initial 0.1 wt% dye produced a dramatic increase in the density. A similar trend in the refractive index was accounted for by the change in density using a relationship between density and refractive index derived from the Lorentz–Lorenz equation. Increasing the dye content to 8 wt% led to a large reduction in the glass transition temperature. An increase in E′ and a decrease in the subambient γ-relaxation intensity accompanied the large decrease in T_g. This behavior fit the conventional concept of antiplasticization, which has been described for other low molecular weight diluents in PC. Recognizing that the dye was present as a mixture of monomer, dimer and higher aggregates, it was shown that the monomer form was responsible for the antiplasticization. In the glass, dimer and higher aggregates were viewed as nanoparticle fillers. It was confirmed that the antiplasticization effect was due to a reduction in excess hole free volume of the polymer.     

Evolution of elastic properties and microstructural changes versus temperature in bonding phases of alumina and alumina–magnesia refractory castables

The microstructural evolutions of high alumina refractory concretes, based on the systems CaO–Al₂O₃ and CaO–Al₂O₃–MgO, have been studied by the way of ultrasonic high temperature measurements. Since such a refractory concrete can be considered as a composite material with two constituents, a continuous matrix (so called bonding phase) and aggregates, investigations of matrices made of mixtures containing cement, reactive alumina and/or magnesia, constitute a preliminary study which is presented in this paper. The elastic behaviour of these matrices has been followed from room temperature to 1550 °C via a specific ultrasonic method. During the first thermal treatment, different changes of slope are observed in the curve E = f(T). Between 200 °C and 400 °C, dehydration mechanisms involve a microstructural reorganisation correlated with a strong decrease of the elastic properties. At high temperature, the Young's modulus evolutions are associated with the expansive formations of CA₂^b and/or in-situ spinel at 1100 °C and then CA₆ (see endnote b) at 1450 °C, which directly depend on the CaO/Al₂O₃ and MgO/Al₂O₃ ratios in the mix. The forming of bond linkage between CA₆ and in-situ spinel grains in the matrix is believed to enhance the elastic properties at high temperature.     

Investigation of slag-refractory interactions for the Ruhrstahl Heraeus (RH) vacuum degassing process in steelmaking

In order to determine the effect of slag composition during the RH process on refractory wear, magnesia–carbon and magnesia–chromite refractories were immersed for 10 min at 1600 °C in a ladle slag, two FeO-rich slags (20 and 40 wt% FeO) and two CaO–Al₂O₃ slags. Corrosion of magnesia–carbon refractory by the ladle and CaO–Al₂O₃ slags was limited as the refractory carbon phase efficiently prevented slag infiltration. Severe degradation was observed in contact with FeO-rich slags. FeO oxidized the carbon phase with formation of Fe droplets at the hot face. Regarding magnesia–chromite refractory, the corrosion mechanism consisted of severe slag infiltration, high temperature inactivation of the secondary chromite and primary chromite dissolution in the infiltrating slag. The FeO-rich slags seem to have generated more severe conditions as the infiltrating slag pushed apart the periclase grains, leading to severe refractory erosion. The degradation mechanisms are discussed by combining experimental results and thermodynamic calculations.     

Direct mineralogical composition of a MgO-C refractory material obtained by Rietveld methodology

Magnesia-graphite refractory materials are used in large quantities in the steelmaking process. The chemical characterization of this type of refractories is an arduous task that requires a rigorous set of laboratory tests and analyses. In the present paper, proper characterization of magnesia-graphite refractories has been approached by X-ray powder diffraction combined with Rietveld methodology. The quantitative phase analysis of a MgO-graphite refractory has been 68.3 wt% of MgO, 8.1 wt% of graphite, 13.5 wt% of Al₂O₃, 4.4 wt% of SiC, 0.6 wt% of Si, 1.2 wt% of Al, 1.5 wt% of AlPO₄ and 2.4 wt% of silicone. These results have been checked and validated with those obtained by other analysis procedures used to determine the crystalline and non-crystalline phases present in these materials.     

Compressive strength and microstructure of alkali-activated mortars with high ceramic waste content

The present work investigated alkali-activated mortars with high ceramic waste contents. Tile ceramic waste (TCW) was used as both a recycled aggregate (TCWA) and a precursor (TCWP) to obtain a binding matrix by the alkali-activation process. Mortars with natural siliceous (quartz) and calcareous (limestone) aggregates, and with other ceramic waste materials (red clay brick RCB and ceramic sanitaryware CSW waste), were also prepared for comparison purposes. Given the lower density and higher water absorption values of the ceramic aggregates, compared to the natural ones, it was necessary to adapt the preparation process of the recycled mortars by presaturating the aggregate with water before mixing with the TCWP alkali-activated paste. Aggregate type considerably determined the mechanical behaviour of the samples cured at 65 °C for 3 days. The mortars prepared with the siliceous aggregate presented poor mechanical properties, even when cured at 65 °C. The behaviour of the limestone aggregate mortars depended heavily on the applied curing temperature and, although they presented the best mechanical properties of all those cured at room temperature, their compressive strength reached a maximum when cured at 65 °C, and then decreased. The mechanical properties of the mortars prepared with TCWA progressively increased with curing time (53 MPa at 65 °C for 28 days). An optimum 50 wt% proportion was observed for the limestone/TCWA mortars (≈43 MPa, 3 days at 65 °C), whereas the mechanical properties of that prepared with siliceous particles (10 MPa) progressively increased with the TCWA content, up to 100 wt% substitution (23 MPa). Limestone particles interacted with the binding matrix, and played an interesting beneficial role at the 20 °C curing temperature, with a slight reduction when cured long term (28 days) at 65 °C. The results demonstrated a potential added value for these ceramic waste materials.     

Thermomechanical and corrosion inhibition properties of graphene/epoxy ester–siloxane–urea hybrid polymer nanocomposites

The effect of graphene on the corrosion inhibition properties of a hybrid epoxy–ester–siloxane–urea polymer was investigated. The weight fraction of graphene was varied from 1 to 2 wt%. Direct current polarization (DCP) and electrochemical impedance spectroscopic (EIS) techniques were used to measure the polarization and coating resistance of the coated aluminum alloy substrate. The grapheme/hybrid polymer composite coatings showed much higher corrosion inhibition property when compared to the neat hybrid polymer coating. An increase in glass transition temperature and rubbery region modulus was also observed for composites containing 1–2 wt.% of graphene. A direct correlation between the rubbery plateau modulus of free standing composite thin films and corrosion resistance of the composite coatings was made, indicating that the corrosion protection mechanism is due to restriction of the polymer chain motion by graphene which causes a decrease in coating permeability.