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.     

陶瓷梗对致密浇注料性能的影响

对比研究了添加莫来石质陶瓷梗和不锈钢纤维分别对刚玉质超低水泥浇注料和高铝质超低水泥浇注料性能的影响 ,并从显微结构分析了其影响机理。研究表明 :莫来石陶瓷梗能显著改善烧成后致密浇注料的抗热震性和体积稳定性 ;而含不锈钢纤维的浇注料烧成后 ,纤维氧化成氧化铁和氧化铬 ,促进了烧结以及纤维与基体之间的结合 ,使浇注料的刚性增加 ,高温抗折强度提高 ,但抗热震性下降 ,同时 ,高温下钢纤维氧化生成更大体积的氧化铁 ,导致了浇注料本体的膨胀 ,使其烧成线变化增加。     

How effective is the addition of nanoscaled particles to alumina–magnesia refractory castables?

The addition of nanoscaled alumina and magnesia particles to the matrix of alumina–magnesia refractory castables drastically reduces the residual expansion related to the in situ spinel formation. Nonetheless, as their benefits on other relevant properties have not been reported so far, the effectiveness of such nanoengineering design for castables applied in steel ladles is still uncertain. In the present work, not only the expansion level, but also the corrosion resistance, the hot modulus of rupture and the creep deformation of different nanoparticle-containing castables were evaluated and compared with the results attained by refractory materials designed only by micrometric-scaled Al₂O₃ and MgO. Although the addition of a nanoalumina and nanomagnesia mixture ensured the best results regarding to the expansive behavior, thermo-mechanical and thermo-chemical properties, its performance was only slightly superior to the castable containing micrometric alumina and magnesia particles. Therefore, as the cost–benefit ratio is one of the main requirements for the end users, the nanotechnology use in the refractory production must be previously carefully analyzed.     

In situ spinel bonded refractory castable in relation to co-precipitation and sol–gel derived spinel forming agents

This paper deals with the preparation and characterization of two types of in situ spinel bonded low cement high alumina based castable refractories. Semidried magnesium aluminate mass was prepared from cheaper precursors via coprecipitation and sol–gel routes for application in a refractory castable composition in different concentrations. The pH, average particle size, solid content, DTG analysis and XRD patterns of those two additives were observed. After being fired at elevated temperatures those two kinds of in situ spinel bonded castables were characterized and compared in terms of bulk density, apparent porosity, cold crushing strength, flexural strength, volume shrinkage, spalling resistance, and XRD phase analysis. Scanning electron microscopy of some selected fired samples was done to analyse the mode of interaction of in situ spinel bonds in castable microstructure. The corrosion resistance of the castables was estimated by heating with blast furnace and converter slags.     

Use of alumina dispersant in alumina-spinel castable: Comparison between in situ and preformed spinels

The role of alumina dispersant as a flow modifier, completely replacing fume silica, on the properties of preformed and in situ spinel-containing low cement high alumina castables was investigated with variations in spinel content and granulometry. Both 10 and 20 wt.% spinel-containing compositions were prepared using preformed spinel or magnesia in alumina castable compositions with vibratable and self-flowing consistency. The castables underwent conventional processing methods and accessed for various refractory-related parameters post-heat treatments. No glassy phase was observed in the castables upon firing. The presence of self-flowing consistency led to improved characteristics. Preformed spinel-containing compositions showed improved density, strength, hot strength, and thermal shock resistance properties, whereas slag corrosion and penetration resistances were found to be higher for in situ spinel-containing castable.     

Preparation and characterization of HA bonded Al2O3–MgO based castables with superior slag resistance for the working lining of Si-killed stainless steel ladles

The study prepared Al₂O₃–MgO based castables bonded by hydratable alumina (HA) instead of calcium aluminate cement (CAC) for the working lining of Si-killed stainless steel ladles. The microstructure, phase composition, mechanical properties, and slag resistance of castables were investigated by SEM, XRD, and thermodynamic software FactSage®. The results indicated that the HA bonded castables showed superior hot flexural strength, thermal shock resistance and slag resistance than the CAC bonded castables, due to the optimized pore characteristics, less liquid content, and higher liquid viscosity of the castable matrix and the formation of a continuous insulating layer.     

Basic slag attack of spinel-containing refractory castables

The better performance of spinel-containing refractory castables when in contact with basic slag is mainly associated with their higher corrosion resistance. Although the literature has shown various studies related to this subject, only few of them evaluated the overall microstructural effect on the corrosion resistance. Considering this aspect, four different compositions were produced, in order to evaluate the binder source influence (calcium aluminate cement or hydratable alumina), the silica fume addition and spinel incorporation method (in situ or pre-formed) effects. Based on the physical properties (apparent porosity, linear thermal expansion and pore size diameter distribution) and also on the phases generated (detected by SEM, before and after corrosion), a basic slag corrosion mechanism, for the set conditions, is proposed. The results pointed out that lower penetration can be attained by reducing the pore size diameters, whereas chemical corrosion resistance is a consequence of higher content of fine alumina, lower amount of calcium aluminates and the lack of liquid phase in the castable matrix. This study stresses that the castable formulation design and the proper raw material selection are of utmost importance to understand and master the performance of this class of refractory castables.     

高铝水泥浇注料损坏现象研究

分析了在实际生产现场发生损坏的高铝水泥浇注料的表面析出物 ,证实了造成这一现象的直接原因是浇注料水化物的碳酸化、硫酸化和盐析效应。研究认为 ,改善养护条件以及水源质量可以减少浇注料损坏现象的发生。     

Slag attack evaluation of in situ spinel-containing refractory castables via experimental tests and thermodynamic simulations

Although the in situ spinel formation in alumina-magnesia refractory castables induces an expansive behavior, many investigations highlight its positive role in the corrosion resistance of such materials. Thus, this work addresses the slag attack evaluation of four designed in situ spinel-containing castables (containing hydratable alumina or calcium aluminate cement as a binder source and 0 or 1 wt% of silica fume) when in contact with a Fe_xO rich industrial slag. Corrosion cup-tests, microstructural characterization and a two-step thermodynamic simulation model were used in order to investigate the reactions taking place during the slag-refractory interactions. According to the attained results, hydratable alumina seems to be a suitable binder to improve the corrosion resistance of such castables, as it induces densification and the formation of an alumina-rich spinel phase at the slag-matrix interface. Moreover, the thermodynamic calculations matched to the experimental observations, attesting the efficiency of the proposed simulation model for the evaluation of the in situ spinel-containing castable corrosion behavior.     

Microstructure and refractory properties of spinel containing castables

The bauxite-based and kaolin-based refractory castables investigated were carefully prepared. They are composed of 90 wt.% well-graded (coarse, medium, and fine) bauxite or kaolin aggregates, 10 wt.% binding matrix and adequate amount of distilled water. The binder mixture was calcium aluminate cement (CAC) containing 80% alumina and magnesium-aluminate spinel (MA-spinel) either preformed or in situ. The castable batches were cast into cubes (25 mm × 25 mm × 25 mm), left at 100% relative humidity for 24 h cured for 7 days under water, and dried at 110 °C for 24 h. The samples were then subjected to firing at 1550 °C for a soaking time of 1 h.     

Synthesis of mullite aggregates from fly ash: effect on thermomechanical behaviour of low cement castables

Abstract

Refractory aggregates were synthesised from beneficiated fly ash by reaction sintering with calcined alumina at 1600°C, and 83% mullite yield was achieved. The aggregates had low porosity, low thermal expansion and good refractoriness. To study compatibility in castable refractories, the aggregates were used in high alumina cement based low cement castables and their thermomechanical behaviour was studied. Microstructural characterisation revealed that the emergence of new bond phases such as mullite and calcium hexa-aluminate had a beneficial effect on the hot modulus of rupture and creep resistance of castables. An attempt was made to establish a structure–property relationship.     

Phase composition of bauxite-based refractory castables

The bauxite-based refractory castables are composed of 90 wt.% well-graded (coarse, medium, and fine) bauxite aggregate, 10 wt.% binding matrix and adequate amount of distilled water. The binder mixture was calcium aluminate cement (CAC) containing 80% alumina and magnesium-aluminate spinel (MA-spinel) or mullite either preformed or obtained in situ.The phase composition of the prepared castable samples was investigated by using X-ray diffraction (XRD) analysis, scanning electron microscopy, energy dispersive X-ray analysis, differential thermal analysis (DTA) and thermal gravimetric analysis.The XRD patterns indicated the formation of the corundum phase along with mullite phase in all of bauxite-based castable samples. The scanning electron microscopy (SEM) micrographs show densely packed microstructures with an abundant of corundum grains of comparable sizes, rounded and sub-rounded, homogeneously embedded in the matrix. Some needle-shaped mullite crystals are distributed from place to place. The DTA curve of the castable samples showed three endotherms due to the release of free or the physically absorbed water, the dehydroxylation of the chemically bound water and due to some dehydration and dehydroxylation reactions.     

The effect of nano-size additives on the electrical conductivity of matrix suspension and properties of self-flowing low-cement high alumina refractory castables

Influence of two nano-size additives on electrical properties of suspension matrix of self-flowing low-cement high alumina refractory castable is investigated. For this purpose, castament FS 10 and FS 20 on the basis of polycarboxylate ether were considered. The self-flow value, workability and mechanical strength of the castable are evaluated and their relations with electrical conductivity are determined. Using these relations, the type and optimum amount of proper additive for these refractory castables are determined. It was shown that if the electrical conductivity of matrix suspension is less than 0.71 mS/cm, high alumina low-cement self-flowing refractory castable can be obtained. The best self-flow, sufficient working time and adequate mechanical strength in the castables are obtained with 0.08 wt.% FS 20.     

Low Temperature Synthesis of High Alumina Cements by Novel Co‐Melt Precursors and Their Implementation as Castables with Some Micro Fine Additives

In the present investigations nano size high alumina cements (HAC) were prepared by very effective co‐melt precursor sintering technique from their metal nitrate precursors. The prime cementing phases observed were CA, CA₂, and C₁₂A₇. The addition of nano structured cements in refractory castables has improved the thermo‐chemical‐mechanical properties to a significant extent. Each batch of low cement castables (LCC) was prepared from calcined Chinese bauxite, HAC, and superfine additives. The effect of HAC in bauxite castable with the additives similar to Silicon Carbide, reactive alumina, and micro‐fine silica on the sinterability and properties of these castables was investigated. Physical properties such as apparent porosity and bulk density, mechanical properties such as hot modulus of rupture (HMOR), cold and hot modulus of rupture (CMOR), and cold crushing strength (CCS) 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 FE‐SEM, respectively. In the castables new phases such as mullite, α‐alumina were formed at the expense of bauxite and silica. Solid solution of mullite formed at high temperature acts as a bonding phase and is accounted for high HMOR, CMOR, and CCS values. These excellent properties of such castables may enable their uses in various applications such as refractory lining for fabrication of steel, aluminium, copper, glass, cement, chemicals, and ceramics.     

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.     

Effects of different additives on properties of magnesium aluminate Spinel–Periclase castable

Bauxite- and alumina-based spinels were employed as refractory aggregates, and sintered magnesia fine powder, calcium aluminate cement, microsilica, and activated α-Al₂O₃ were utilized as matrices. The effects of alumina powder, analytically pure zinc oxide, and analytically pure zirconia on the properties of magnesium aluminate spinel–periclase castables were studied. The results demonstrated that the addition of the three additives promoted the sintering of magnesium aluminate spinel–periclase castables. Simultaneously, the three additives significantly improved the high-temperature properties of the samples. The thermal shock resistance of the alumina powder sample increased by 200%, that of the pristine zinc oxide sample by 75%, and that of the zirconia sample by 125%. The additives effectively improved the thermal shock resistance of the magnesium aluminate spinel–periclase castable. In addition, the slag resistance depths of the samples with alumina powder and zirconia were 41% lower than that of the sample without additives, which significantly improved the slag resistance of the magnesium aluminate spinel–periclase castable.     

Development of waste derived nano-lakargiite bonded high alumina refractory castable for high temperature applications

This work provides a new binder system, i.e., nano-lakargiite (NL) [CaZrO₃] for unshaped refractories. NL powder formulation is done through a green and facile route, i.e., solution mixing technique, which is easily capable of recycling the byproducts. The waste eggshells are practiced as a source of CaO for the preparation of NL. The characteristics such as differential thermal/thermogravimetric (DTA-TGA) analysis, X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM) of the synthesized NL powder are accomplished. The single phase orthorhombic crystal structure with the Pnma space group of nano CaZrO₃ (avg. crystallite size ∼19 nm) is attained at 1100 °C. High alumina castable specimens are formulated through the replacement of calcium aluminate cement (CAC) by the NL and heat treated at 1600 °C. The different physico-mechanical properties of the prepared castables are comprehensively investigated. The corrosion resistance in the molten glass at 1400 °C is also examined. The properties are also equated with the different advanced bonding systems of high alumina refractory castables. Significant progress in terms of densification, hot strength, and thermal shock resistance is achieved for the NL bonded refractory castables.     

Self-formed mullite containing refractory barium silicate cements and their castable applications

Abstract

Six batches consisting of different percentages of barite, kaolin and calcined alumina were sintered at 1500–1600°C for 3 h to produce self-formed mullite containing barium silicate cements. The compositions of the cement mixes were investigated using X-ray diffraction. Physicomechanical, sintering and refractory properties were tested according to standard specifications. Each of the mixes, composed mainly of varying proportions of mullite and dibarium silicate minerals, showed different behaviour. The best compromise between cementing, sintering and refractory properties was provided by the mix prepared from 60 wt-% barite, 25 wt-% kaolin and 15 wt-% calcined alumina, consisting of about 54 wt-% dibarium silicate and 33 wt-% mullite. Self-formed mullite containing castable prepared from 15 wt-% of a fine powder of the chosen mix as the cement and 85 wt-% of graded aggregate of the same mix showed good volume stability, high mechanical properties, high thermal shock resistance as well as high loadbearing capacity.     

不同结合系统刚玉-方镁石-尖晶石浇注料的性能

对比研究了水泥结合和水合氧化铝结合的刚玉 -方镁石 -尖晶石浇注料的性能。结果表明 :二者相比 ,水合氧化铝结合浇注料的需水量较大 ,流动性较差 ,烧结致密化温度高 ,在 1 5 5 0℃下烧结后的强度和致密度低 ,但其抗热震性能及抗渣性能较好。     

Study of the castable selection for blast furnace blowpipe

The contradictory properties required of castable refractories makes selecting castable refractories for industrial applications challenging. This paper seeks to describe the material selection for a blast furnace blowpipe application that is subjected to sudden temperature changes and must prevent heat loss. Three commercial high alumina castables containing andalusite or mullite from different manufacturers were characterized. Thermal shock damage resistance was evaluated using thermal shock damage resistance theory and experiments. The castables’ coefficient of thermal expansion was estimated using quantitative X-ray diffraction. Crack propagation resistance was measured using the work-of-fracture technique. Thermal shock damage was experimentally evaluated by measuring the modulus of elasticity and rupture prior to and after thermal cycles. Ultimately, the microstructure of the castables was related to the thermal shock damage behavior by estimating the aggregate size and the fracture toughening mechanisms using light optical and scanning electron microscopes. Heat loss was evaluated by calculating the blowpipe shell temperature using a one-dimensional steady-state heat conduction model. The best commercial castable refractory for blowpipe showed high thermal shock damage resistance and low thermal conductivity. The results in this study agreed with thermal shock damage resistance parameters and showed a correlation between coarse microstructure with large aggregate and higher thermal shock damage resistance.