Thermomechanical and thermophysical characteristics of alumina-carbon monolithic refractory containing surface-modified graphites in matrix

The thermophysical and thermomechanical behavior of graphite-containing refractory castable matrix with 20.0?wt% of graphite had been compared with graphite-free high alumina based castable matrix analogous to it. The thermomechanical properties of similar type of castables with and without 5.0% of graphite had also been evaluated. Graphite was incorporated both as coated and as-received forms, the former having a thin sol-gel derived calcium aluminate coating on graphite flakes. The influence of thermal conductivity, thermal diffusivity and pore size distribution had been critically estimated. The changes in flexural strength, porosity and density of the matrices had also been determined to interpret the castable performance, namely refractoriness under load (RUL), spalling resistance and conventional physical properties. The role of coated graphite on improved densification and thermal tolerance of refractories was further explored by microstructure and phase evolution studies of all kinds of fired samples at 1500?°C. It was further supplemented with the scanning electron microscope (SEM) studies of surface-modified graphites at uncalcined and calcined condition.     

Synthesis and characterization of boehmitic alumina coated graphite by sol–gel method

Non-wettability property makes graphite a good protecting material against the molten metal and/or slag. Properties like high oxidation potential between 600 and 1200 °C and non-wettability with water at room temperatures limits the usage of graphite in castable refractory applications. In this study, sol–gel method, which is a relatively cheaper process, was used. Boehmitic sol was obtained by hydrolyzing and peptiziting the alkoxide AIP (aluminum isopropoxide) used as alumina source. Then natural flake graphite was mixed with the boehmitic solution for coating of graphite. At 120 °C boehmitic sol coated graphite was dried and gelled. Then heat threaded at 550 °C for γ-Al₂O₃ transformation of boehmite. Products that obtained from the studies were characterized with FTIR and XRD tests. Alumina coated graphite samples were made by repeating the same steps and TG analysis were made to investigate the oxidation behaviour of the samples. Finally, SEM–EDS analyses were carried out to investigate the microscopic properties of the alumina coated graphite powders.     

Comparison of solid state and sol–gel derived calcium aluminate coated graphite and characterization of prepared refractory composite

This paper entails an extended investigation on sol–gel thin film of calcium aluminate (CaAl₂O₄) over graphite flakes that improved their oxidation resistance and water wettability. The commercial preparation of calcium aluminate has been compared with the sol–gel synthesis by differential thermal analysis (DTA) and X-ray diffraction (XRD) to assess the feasibility of the latter for coating preparation. Poorly crystalline nanostructured Ca-doped γ-Al₂O₃ is considered to be an important intermediate for this preparation. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) of the calcined gel have been carried out to ascertain its composition. Quantitative chemical analysis of sol gel derived calcium aluminate was also estimated. Atomic force microscopy (AFM) has been conducted to ensure the evolution of hydrophilic nanosized cementitious phases on graphite. Zeta potential values of coated and uncoated graphites with increasing pH have also been determined to distinguish between their compatibility in a refractory castable matrix. Improved physical properties of that high alumina castable containing coated graphite, e.g. apparent porosity (AP), bulk density (BD), cold crushing strength (CCS) have been measured to evaluate the refractory quality. The reasons for its better performance are explored by taking further insight on the microstructural analyses of the fired castable (1500 °C) soaked for an extended period.     

The influence of surface-modified graphites on the rheological pattern of alumina-carbon cementitious refractory castable matrix

The present contribution focused mainly on the fundamental understanding of the influence of surface-modified graphite on rheology of the matrix of a castable slurry in comparison to the same containing the uncoated one. A special observation on the rheology of a graphite-free matrix of similar high alumina castable has been described. The change in rheological behavior due to the presence of other microfine constituents has also been noticed with a particular attention to the refractory cement bond. The variation in viscosity and shear stresses with shear rate of castable matrices containing as-received and surface-modified graphites has been compared. The ‘ball-in-hand’ consistency test of respective castables had also been differentiated. The effect of coated and uncoated graphites on the loss and storage moduli of the respective suspensions has been explored. Zeta potential values of individual constituents as well as the slurries have also been measured and correlated with the flow characteristics of castable matrices. The X-ray diffraction (XRD), SEM (scanning electron microscope) and EDS (energy dispersive spectroscopy) studies of the coated graphite have been observed to substantiate the flow pattern of the slurry. The physical properties of refractory castables at different temperatures have been estimated to supplement the rheological pattern.     

The physical and mechanical properties of alumina-based ultralow cement castable refractories

In this study, the effects of the type of alumina on the physical, chemical and mechanical properties of the ultralow cement castable (ULCC) refractories were investigated. Brown fused alumina, tabular alumina and rotary bauxite-based ULCC refractories were prepared by mixing each type of alumina with silicon carbide, carbon, cement, metallic silicon and microsilica. The density, porosity and cold crushing strength (CCS) of the refractory castables were measured after drying at 110 °C for 24 h and firing at 1450 °C for 5 h. The slag penetration resistance of the refractory castables was determined using slag corrosion tests. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffractometry (XRD) were used to characterize the castables. It was found that all three refractory castables had strong slag penetration resistance and that the tabular alumina-based refractory castable had the largest specific cold crushing strength with an acceptable percent of porosity among the refractory castables.     

Densification behavior and properties of alumina–chrome ceramics: Effect of TiO2

Highly dense alumina–chrome bodies with low porosity are usually used as corrosion and thermal resistant refractories. Alumina–chrome refractory with molar ratio 1:1 was developed using chemical grade hydrated alumina and chromium (III) oxide by conventional sintering route. Batch materials were attrition milled, isostatically pressed and sintered in the temperature range from 1000 °C to 1700 °C with 2 h soaking at peak temperature. Phase development of the sintered materials with temperature was studied by X-ray diffraction. Sintering temperature, sintering condition and addition of sintering aid (TiO₂) have immense effect on the densification of the alumina–chrome refractory. Highly dense alumina–chrome refractory with almost nil apparent porosity was developed at 1500 °C in reducing atmosphere. Flexural strength of the sintered materials at room temperature and at 1200 °C was also measured. 1 wt% TiO₂ gives the optimum result with respect to densification and flexural strength.     

Significant improvement of refractoriness of Al2O3–C castables containing calcium aluminate nano-coatings on graphite

The performance of alumina-carbon castables containing graphite flakes coated by nanosized Ca-doped γ-Al₂O₃ phases has been investigated in terms of refractoriness under load (RUL) and oxidation resistance tests. The coating characteristics and its beneficial effects in castable matrix have been conceived by water-wettability test, differential scanning calorimetry and some physical characteristics. In this regard, a schematic representation of coated graphite has been proposed to elucidate its sustainability in the refractory mass. The comparative gain in performance of the refractory has also been ascertained by scanning electron microscope (SEM) and X-ray diffraction (XRD) studies of the castable matrix. The sol–gel coating overcomes the pitfalls of including uncoated graphites in castables and should be explored for commercial utilization.     

Effect of SiC–graphite–Al-metal addition on low- and ultra-low cement bauxite castables

Eight batches of low- and ultra-low cement castables were prepared from calcined Chinese bauxite and high alumina cement (HAC). The effect of alumina-cement replacement by SiC, graphite and aluminum metal on the sinterability and properties of these castables was investigated. Physical properties such as bulk density and apparent porosity of hydrated and sintered castables were studied. The sintered castables were also characterized for their solid phase compositions and microstructure using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. In the castables containing SiC, new phases such as mullite (3Al₂O₃·2SiO₂), SiC, and quartz (SiO₂) were formed at the expense of calcium aluminate phases (i.e. CA and CA₂; the main cement phases). Generally, the bulk density of the control castable sample was the highest among all prepared samples, while the batches containing graphite showed the lowest bulk density. The presence of Al-metal reduced the oxidation of SiC and consequently increased the densification of the castables compared with castables containing graphite only. Cold crushing strength (CCS) of the hydrated specimens i.e. green castables, decreased as the additives contents increased at the expense of HAC which is responsible for the bonding at room temperature. The highest CCS value of the sintered castable was obtained for the sample containing 6 wt.% SiC, 3 wt.% CA and 0.5 wt.% Al-metal.     

Designing particle sizing and packing for flowability and sintered mechanical strength

In this work, alumina powders in five different commercially available size ranges were used to prepare various refractory castable mixtures, defined using the statistical design of mixture experiments (STATISTICA, StatSoft Inc.) and the EMMA 3.3 software (Elkem Materials). Those mixtures were characterized for packing density, Andreasen particle size distribution modulus (q), flowability and after sintering properties, in order to investigate the relationships between these variables. The optimization of matrix and aggregate sizes and matrix-aggregate proportion, subjected to different property requirements, brought to light the relationships between q, specific surface area (SSA) and maximum paste thickness (MPT). Those relationships were investigated for three fundamental processing steps, namely, dry powders, fresh paste and consolidated dried and sintered bodies. The optimized all-alumina castable was found to require 47.5 wt.% of a fine size matrix with high flowability, which provides the necessary flow bed for 52.5 wt.% of coarse aggregates, resulting in a gap-sized particle size distribution, and presented a fresh paste flowability index above 130% with minimum added water (28 mg/m²) and sintered modulus of rupture above 50 MPa.     

Mullite-based refractory castable engineering for the petrochemical industry

Refractory castables used in fluid catalytic converter (FCC) risers should present suitable particle erosion and thermal shock resistances at temperatures below 900 °C. Considering that calcium aluminate cement (CAC)-bonded refractories usually start their densification above 1200 °C, the use of sintering additives to induce faster densification is a promising technological alternative. Therefore, this work addresses the evaluation of mullite-based castables containing a boron-based sintering additive and CAC and/or hydratable alumina as the binder sources. Hot elastic modulus, cyclical thermal shock, hot modulus of rupture and cold erosion resistance measurements were carried out to evaluate the compositions. According to the attained results, adding 1.5 wt% of the evaluated sintering additive to the designed castables led to a remarkable increase of the hot modulus of rupture (maximum of 40.4 MPa at 800 °C for the CAC-containing refractory) and high erosion resistance (1.5–2.9 cm³) after pre-firing at 800 °C for 5 h. Moreover, the combination of CAC and hydratable alumina gave rise to an improved refractory (M–2CAC–2HA–S) showing a transient liquid formation at an increased temperature, high thermal shock resistance (no E decay after 8 thermal cycles, ΔT=800 °C) and high mechanical strength at 800 °C and 1000 °C.     

Investigation of the structural and mechanical properties of micro-/nano-sized Al2O3 and cBN composites prepared by spark plasma sintering

Alumina-cubic boron nitride (cBN) composites were prepared using the spark plasma sintering (SPS) technique. Alpha-alumina powders with particle sizes of ∼15 µm and ∼150 nm were used as the matrix while cBN particles with and without nickel coating were used as reinforcement agents. The amount of both coated and uncoated cBN reinforcements for each type of matrix was varied between 10 to 30 wt%. The powder materials were sintered at a temperature of 1400 °C under a constant uniaxial pressure of 50 MPa. We studied the effect of the size of the starting alumina powder particles, as well as the effect of the nickel coating, on the phase transformation from cBN to hBN (hexagonal boron nitride) and on the thermo-mechanical properties of the composites. In contrast to micro-sized alumina, utilization of nano-sized alumina as the starting powder was observed to have played a pivotal role in preventing the cBN-to-hBN transformation. The composites prepared using nano-sized alumina reinforced with nickel-coated 30 wt% cBN showed the highest relative density of 99% along with the highest Vickers hardness (H_v2) value of 29 GPa. Because the compositions made with micro-sized alumina underwent the phase transformation from cBN to hBN, their relative densification as well as hardness values were relatively low (20.9–22.8 GPa). However, the nickel coating on the cBN reinforcement particles hindered the cBN-to-hBN transformation in the micro-sized alumina matrix, resulting in improved hardness values of up to 24.64 GPa.     

Sintering behavior of spark plasma sintered alumina with graphene nanoplatelet reinforcement

Graphene nanoplatelet (GNP) reinforced alumina is synthesized by spark plasma sintering (SPS) using process conditions of 1100–1500 °C, 3–10 min dwell time, and 45–90 MPa in order to investigate the effects of GNP on sintering behavior. High volume fractions of GNP (5–15 vol%) are utilized in order to accentuate effects of GNPs. GNP effects on sintering behavior are assessed by evaluating microstructural evolution, grain growth kinetics, and microhardness. The addition of GNPs is found to suppress grain growth by a grain wrapping mechanism resulting in a 10% increase in activation energy when GNP content is increased beyond 5 vol %. Grain growth suppression partially mitigates a decrease in hardness due to the introduction of the soft GNP phase. Evidence of GNPs serving as a sintering aid are seen at short sintering times (3 min), while densification and grain size are observed to level off with extended sintering time (10 min). The application of higher pressures enhances densification, which enables GNPs to more effectively wrap around grains resulting in enhanced grain growth suppression.     

The influence of MgO,Y2O3 and ZrO2 additions on densification and grain growth of submicrometre alumina sintered by SPS and HIP

Spark plasma sintering followed by hot isostatic pressing was applied for preparation of polycrystalline alumina with submicron grain size. The effect of additives known to influence both densification and grain growth of alumina, such as MgO, ZrO₂ and Y₂O₃ on microstructure development was studied. In the reference undoped alumina the SPS resulted in some microstructure refinement in comparison to conventionally sintered materials. Relative density >99% was achieved at temperatures >1200 °C, but high temperatures led to rapid grain growth. Addition of 500 ppm of MgO, ZrO₂ and Y₂O₃ led, under the same sintering conditions, to microstructure refinement, but inhibited densification. Doped materials with mean grain size <400 nm were prepared, but the relative density did not exceed 97.9%. Subsequent hot isostatic pressing (HIP) at 1200 and 1250 °C led to quick attainment of full density followed by rapid grain growth. The temperature of 1250 °C was required for complete densification of Y₂O₃ and ZrO₂-doped polycrystalline alumina by HIP (relative density >99.8%), and resulted in fully dense opaque materials with mean grain size<500 nm.     

Molten salt corrosion of high density graphite and partially stabilized zirconia coated high density graphite in molten LiCl–KCl salt

Corrosion studies were performed on uncoated high density graphite and plasma sprayed partially stabilized zirconia (PSZ) coated high density graphite with NiCrAlY bond coat in molten LiCl–KCl eutectic salt at 600 °C for periods of 250 h, 1000 h and 2000 h under inert argon atmosphere. High density graphite showed weight loss while PSZ coated high density graphite showed weight gain. There is no significant attack and degradation of top PSZ coating in molten salt, however microcracks were observed at the bond coat-substrate interface after 2000 h of exposure. PSZ coated high density graphite exhibited excellent corrosion resistance in molten LiCl–KCl salt due to chemical stability and absence of phase transformation as confirmed from scanning electron microscopy, X-ray diffraction and laser Raman studies, however adhesion of the coating has to be improved.     

Investigating the effect of SPRM on mechanical strength and thermal conductivity of highly porous alumina ceramics

For recycling waste refractory materials in metallurgical industry, porous alumina ceramics were prepared via pore forming agent method from α-Al₂O₃ powder and slide plate renewable material. Effects of slide plate renewable material (SPRM) on densification, mechanical strength, thermal conductivity, phase composition and microstructure of the porous alumina ceramics were investigated. The results showed that SPRM effectively affected physical and thermal properties of the porous ceramics. With the increase of SPRM, apparent porosity of the ceramic materials firstly increased and then decreased, which brought an opposite change for the bulk density and thermal conductivity values, whereas the bending strength didn’t decrease obviously. The optimum sample A2 with 50 wt% SPRM introducing sintered at 1500 °C obtained the best properties. The water absorption, apparent porosity, bulk density, bending strength and thermal conductivity of the sample were 31.7%, 62.8%, 1.71 g/cm³, 47.1 ± 3.7 MPa and 1.73 W/m K, respectively. XRD analysis indicated that a small quantity of silicon carbide and graphite in SPRM have been oxidized to SiO₂ during the firing process, resulting in rising the porous microstructures. SEM micrographs illustrated that rod-like mullite grains combined with plate-like corundum grains to endow the samples with high bending strength. This study was intended to confirm the preparation of porous alumina ceramics with high porosity, good mechanical properties and low thermal conductivity by using SPRM as pore forming additive.     

Effect of preparation route on the properties of slip-casted Al2O3/YAG composites

Alumina composites containing 5, 10 and 20 vol.% YAG were produced by a slip-casting process. Two different routes for adding the YAG phase were chosen. Either by mixing of alumina with previously produced YAG powder or by coating of an adequate amount of yttria to form YAG precipitates during the calcining step. The mechanical properties of the sintered samples were measured and compared. Independent from the preparation route Al₂O₃/10 vol.% YAG composites showed best mechanical properties. Significant differences in the densification behavior appeared between the two different manufacturing technologies. The presence of intermediately formed phases like YAM and YAP during the powder preparation step of coated composites is probably the reason why mixed composites showed higher mechanical properties than coated composites.     

Microstructure and mechanical properties of alumina 5 vol% zirconia nanocomposites prepared by powder coating and powder mixing routes

Zirconia toughened alumina (ZTA) nanocomposites are attractive structural materials which combine the high hardness and Young's modulus of the alumina matrix with an additional toughening effect by the zirconia dispersion.In this study two approaches to prepare ZTA are compared. For the first approach, an ultrafine alumina powder was coated with 5 vol% zirconia by a wet chemical method. For the second one, the reference material was prepared by intensively mixing and milling the same alumina with nanoscale zirconia powder. Samples were consolidated at 1350–1600 °C by hot pressing and their mechanical properties, microstructure and transformation behavior were compared. Toughness increments derived from different toughening mechanisms are also briefly discussed. Besides better sinterability, the mixed material exhibited a finer grain size of both matrix and dispersion and thus higher hardness and strength. The alumina matrix was under compressive hydrostatic residual cooling stress, whereas zirconia was under tensile one. The coated material, however, showed higher transformability, deeper transformation zones and thus higher fracture toughness. In addition, it contained more monoclinic zirconia so the matrix was under tension.     

Wear behavior of graphene/alumina composite

In the present work, the dry sliding behavior of a graphene/alumina composite material was studied against alumina in air. The tests were carried out in a reciprocating wear tester with an applied load of 20 N, a sliding speed of 0.06 m s⁻¹ and a sliding distance of up to 10 km. Under the testing conditions, the graphene/ceramic composite showed approximately half the wear rate and a 10% lower friction coefficient than the monolithic alumina. It has been found that this behavior is related to the presence of graphene platelets adhered to the surface of friction that form a self-lubricating layer which provides enough lubrication in order to reduce both wear rate and friction coefficient, as compared to the alumina/alumina tribological system.     

Nano carbon containing MgO-C refractory: Effect of graphite content

Development of low carbon containing MgO-C refractories has been studied containing a fixed 0.9 wt% of nano carbon and 1–9 wt% of flake graphite. Refractory compositions were prepared and processed as per the conventional manufacturing techniques of MgO-C refractory. Properties of the different compositions were evaluated and also compared against the conventional MgO-C refractory containing 10 wt% graphite prepared under exactly similar conditions. Addition of 3 wt% of flake graphite in combination with 0.9 wt% of nano carbon black was found to be optimum and resulted in better/comparable properties to that of conventional MgO-C refractory.     

Electrical conductivity of gelcast alumina sintered under inert atmosphere

Electrically conductive alumina ceramic has been successfully fabricated by sintering of dried gelcast alumina in an inert atmosphere. The process was developed similar to the conventional gelcasting method except for varying the amount of monomer in the premix solution. The sintering treatment was carried out in argon gas from 1100 °C to 1700 °C. Van der Pauw's method was used to measure the electrical resistivity. The results showed that increasing monomer addition and sintering treatment were significantly affecting in lowering electrical resistance. Using the lowest monomer addition and increased sintering treatment, the measured electrical resistivities were in the range from 1.94 Ω-cm to 0.37 Ω-cm. The material exhibited ohmic behavior and rendered two regimes of Arrhenius profile in the plot of electrical conductivity against increasing temperature from 20 °C to 600 °C. All conduction processes were governed by the presence of carbon that caused the alumina grains in polygonal morphology typical of densification. Furthermore, physical tests were conducted to describe the electrical conduction behavior of the material.