In Situ Coagulation of High-Alumina Zero-Cement Refractory Castables

Coagulation methods originally developed for colloidal processing were investigated in this paper as alternative approaches to consolidate high-alumina refractory castables free of hydraulic binders (zero-cement). Three in situ reactions based on the direct coagulation casting (DCC) technique were evaluated to promote castable coagulation: (1) the autocatalytic hydrolysis of gluconic acid lactone, (2) the gradual dissolution of hydroxyaluminum diacetate particles in water, and (3) the enzyme-catalyzed hydrolysis of urea. The coagulating behavior of castables and matrix-representative suspensions was investigated with the help of zeta potential analysis, pH measurements, castable free-flow evaluation, and oscillatory rheological tests. The enzyme-catalyzed hydrolysis of urea seemed to be the most appropriate mechanism to promote the coagulation of initially self-flow zero-cement refractory compositions.     

Andalusite-Based High-Alumina Castables

Andalusite is easily converted to mullite and silica on heating. A better understanding of the mullitization mechanisms provides new information on use of this mineral in refractory castables. By using specific particle-size distributions for andalusite-based high-alumina castables, the primary mullite formation can be effectively enhanced by a secondary mullite reaction within castables matrices. The influence of ultrafine andalusite grains on thermomechanical properties of specimens is underlined by testing hot modulus of rupture in combination with mineralogical and microscopic analyses. The results demonstrate that andalusite has great promise as a component of high-alumina no-cement- or ultra-low-cement-containing castables.     

Permeability of High-Alumina Refractory Castables Based on Various Hydraulic Binders

This work investigated the changes in the permeability of high-alumina self-flowing refractory castables based on calcium aluminate cement (CAC) and hydratable alumina binder (HAB) pretreated between 110° and 1650°C. Permeability constants k ₁ and k ₂ were fitted from Forchheimer's equation based on airflow tests conducted at room temperature. The results indicated that dehydration was the main contributing factor for increased permeability in bodies pretreated up to 600°C and that sintering effects prevailed between 900° and 1650°C. Castables based on HAB were less permeable than those based on CAC, a behavior ascribed to the type of hydrates formed and to the particle-packing features of the matrix and the matrix–aggregate interfaces.     

Dynamic Permeability Behavior during Drying of Refractory Castables Based on Calcium-Free Alumina Binders

Considerable efforts have been made to understand the dewatering behavior of refractory castables. Modeling of this process must be based on realistic heat and mass transfer data; hence, consistent values of castable properties are required, particularly permeability values, since these are the most important parameters that govern the process. Permeability values, however, are usually obtained at room temperature and therefore may not reflect the remarkable microstructural changes that take place during water removal. The problem has become more critical for castable compositions based on calcium-free binders, in which the dehydration process is still unclear and explosive spalling is more likely to occur. This study has investigated the behavior of the dynamic permeability of high-alumina calcium-free refractory castables subjected to a drying process up to 700°C. Samples were previously treated at temperatures ranging from 110° to 1650°C to provide information on the castables' reversible and irreversible microstructural changes. The results revealed fluctuations and a dramatic decrease in the permeability level near 200°C, which may help to explain the occurrence of explosive spalling in this class of castables.     

Permeability of Refractory Castables at High Temperatures

Temperature is an important factor affectng the permeation of fluids in refractory castables. Because of experimental difficulties, however, permeability parameters are usually obtained at room temperature and then extrapolated to the temperature of interest, with no concern regarding porous structure modification (thermal expansion, etc.). In this work, an apparatus has been developed to evaluate the air-flow permeability of refractory castables at temperatures up to 800°C. The objective is to investigate modifications in the permeability constants obtained by Forchheimer's equation to provide a more realistic relationship with castable processing and molten-metal corrosion parameters.     

Drying Stages during the Heating of High-Alumina, Ultra-Low-Cement Refractory Castables

The purpose of this work was to investigate the drying kinetics of high-alumina, ultra-low-cement refractory castables under continuous heating conditions. Three main drying stages were identified during the castable heat-up and were related to the phase change of free water and to the decomposition of hydrated products present in the body. A clear correlation was found between the actual heating profile inside the castable and the dewatering stages under various heating schedules. Thermal analysis was used to assess the drying temperature that represents the highest risk of steam pressure buildup and, thus, of explosive spalling.     

Synthesis of Magnesium Aluminate Spinel Platelets from α-Alumina Platelet and Magnesium Sulfate Precursors

Spinel platelets were formed from a powder mixture of 3–5 μm wide and 0.2–0.5 μm thick α-Al₂O₃ and 1–8 μm (average 3 μm) MgSO₄ heated 2 h at 1200°C. The hexagonal platelet shape of the original α-Al₂O₃ platelet was maintained in the spinel, although their size was slightly increased and their surface roughened. When a mixture of α-Al₂O₃ platelets and MgO powder was heated 3 h at 1400°C, the spinel formed lost the platelet morphology of the alumina.     

Vaporization Processes and Pressure Buildup during Dewatering of Dense Refractory Castables

This work describes an experimental investigation on the dewatering kinetics of high-alumina refractory bodies under several heating conditions. The drying stages involving the removal of unbound water have been correlated with the two consecutive thermal processes by which liquid water transforms into vapor during heating: evaporation and ebullition. Thermogravimetric data have been used as the basis for a discussion of the parameters that affect the performance of both vaporization processes and guide the design of suitable heating schedules aimed at minimizing the drying time and the risk of harmful pore pressurization.     

Thermal Expansion Characteristics of Alumina–Magnesia and Alumina–Spinel Castables in the Temperature Range 800°–1650°C

The thermal expansion of Al₂O₃–MgO castables containing 5.5 wt% MgO and 1.36 wt% CaO and Al₂O₃–spinel castables containing 20 wt% spinel having 95 wt% Al₂O₃ and 1.7 wt% CaO was measured in the temperature range of 800–1650°C by dilatometry. A sharp increase in expansion from around 1425° to 1525°C, followed by a sharp decrease with further increasing temperature, is characteristic of Al₂O₃–MgO castables. The sharp increase in expansion is believed to be caused by the bond linkage between the CA₆ and spinel grains in the bonding matrix, while the sharp decrease is apparently related to liquid-phase sintering. The sharp increase and decrease in expansion were not observed in Al₂O₃–spinel castables because of the much lower MgO (around 1 wt% MgO) and impurity contents. The magnitude of thermal expansion of calcium aluminate bonded castables containing self-forming or preforming spinels or both is dictated by the MgO content of the castables.     

Fluid Dynamics and Thermal Aspects of the Dewatering of High-Alumina Refractory Castables: Removal of Physically Absorbed Water

This article reports on an experimental investigation of the dewatering process of cement-free high-alumina refractory castables. Simultaneous fluid dynamic, thermal, and mass loss effects were investigated during the removal of physically absorbed water at temperatures of 25° to 700°C. The release of steam was decisively affected by the castable's permeability level and the heating rate applied. The analysis of fluid dynamics revealed that at 1°C/min, the main bulk of physical water was released as steam under saturated conditions at 100°C. However, at 5°C/min, steam was trapped within the pores, and water loss was chaotically released and shifted to higher temperatures. Thermal analysis showed that the endothermic boiling of water may result in a critical thermal shock in the castable's structure. Both steam entrapment and thermal shock were more severe with the reduction in the castable's permeability level.     

无水泥高铝浇注料的热机械性能

测定了高铝质无水泥自流浇注料的机械性能,并将其结果与相似组成的超低水泥（ULC）浇注料的机械性能做了对比。     

Influence of the Characteristics of Spinels on the Slag Resistance of Al2O3–MgO and Al2O3–Spinel Castables

The XRD patterns at ambient temperature and at 1500°C showed that the spinel in the Al₂O₃–MgO castables fired at 1500°C for 3 h has the higher peak intensity, compared to those in Al₂O₃–spinel castables; the interplanar distance in the set (311) is 2.43 Å for the spinel in Al₂O₃–MgO castables as well as the spinels in Al₂O₃–spinel castables using spinels containing 73, 90, and 94 wt% Al₂O₃, respectively. The corresponding alumina contents of the spinels in these castables were estimated to be around 75 wt%. The smaller grain size of the spinel in Al₂O₃–MgO castables compared to that in Al₂O₃–spinel castables is evidenced by the recrystallization of the in situ spinel only occurring in Al₂O₃–MgO castables as revealed by the XRD patterns at ambient temperature and at 1500°C. The larger amount and smaller grain size of the in situ spinel in the matrix mostly account for the better slag resistance of Al₂O₃–MgO castables, compared to Al₂O₃–spinel castables.     

Influence of Air Compressibility on the Permeability Evaluation of Refractory Castables

Air compressibility is important in attaining an accurate quantification of the permeability parameters for refractory castables. Nevertheless, this effect is often neglected in the permeability equations that are found in ceramics literature. The consequences of omitting the compressibility effect in two of the main permeability equations are highlighted and discussed. The permeability to air flow of high-Al₂O₃ ultra-low-cement refractory castables has been quantified by Darcy's law according to U.S. ASTM C577–96 and European PRE-16th permeability methods, which propose distinct approaches for air compressibility. Forchheimer's equation, which establishes a more realistic dependence between fluid pressure and fluid velocity, also has been used to obtain the permeability constants k ₁ and k ₂. Results show that equations proposed by the ASTM and the PRE methods may yield very distinct values of Darcian permeability k ₁ for the same sample. Forchheimer's equation for compressible fluids provides the best fitting with experimental data.     

耐火浇注料的干燥性能

对浇注料干燥性能的了解是帮助耐火材料生产商优化加热过程的一个重要因素，由此可将在生产过程中替代损毁砖所花费的时间和能源费用降至最低。     

Mechanochemical Synthesis of Magnesium Aluminate Spinel Powder at Room Temperature

MgAl₂O₄ spinel was successfully synthesized using a mechanochemical route that avoided the formation and calcination of its precursors at high temperatures. The method involved a single step in which γ-Al₂O₃–MgO, AlO(OH)–MgO, and α-Al₂O₃–MgO mixtures were milled at room temperature under air atmosphere. The formation of MgAl₂O₄ occurred faster with γ-Al₂O₃ than with AlO(OH) or α-Al₂O₃. After 140 h, the mechanochemical treatment of the γ-Al₂O₃–MgO mixture yielded 99% of MgAl₂O₄.     

Permeable Porosity of Refractory Castables Evaluated by the Water-Expulsion Porosimetry Technique

In this work, the water-expulsion porosimetry technique was used to quantify the permeable pores of self-flow ultralow-cement refractory castables that were treated at 600°–1650°C. Results have shown that the method as proposed in previous works was not valid, because water was not removed continuously from pores, relative to increased pressure. Nevertheless, the maximum pore diameter obtained according to ASTM Method E128-89 could be successfully correlated with other castable physical properties (such as the permeability constants from the Forchheimer equation) and the apparent porosity obtained via the Archimedes technique. Although the apparent porosity decreased as the thermal treatment temperature increased, the pore morphology changed continuously, with the generation of less-tortuous and more-permeable paths for fluid flow.     

Corrosion Resistance and Microstructure of High-Alumina Refractories, Based on the Rotary Slag Test

The corrosion resistance and microstructure of four highalumina and two chromia-containing high-alumina refractories were evaluated. Analysis of the refractories after exposure in the rotary slag test showed that the chromia-containing products had better slag resistance than the chromia-free products. Three factors contributed to this conclusion, including formation of a Cr-spinel layer at the slag/refractory interface, formation of an impermeable mullite layer just below the interface, and improved matrix bonding from chromia-alumina solid-solution formation.     

Thermomechanical Behavior of Refractory Concrete Linings

A numerical analysis model was developed for predicting the behavior of dual-component, refractory-lined coal-gasification vessels. The temperature-dependent constitutive law, failure criteria, creep behavior, thermal expansion contraction behavior, and shrinkage characteristics of refractory concrete were formulated. To verify the proposed model, a three-dimensional simulation analysis was made of an experimental gasifier vessel. The model was then used to study parameters on a circular, dual-component, refractory concrete-lined coal-gasification vessel. The effects of shrinkage, creep, temperature distributions, vessel shell temperatures, bond barriers and anchor spacing, size, and shape on the performance of the gasifier vessel were studied. Design recommendations are made to aid in improving the mechanical reliability of refractory concrete-lined coal-gasification vessels.     

Assessment of Mass Loss and Permeability Changes during the Dewatering Process of Refractory Castables Containing Polypropylene Fibers

This work describes the use of a new permeametry technique to evaluate microstructural changes that take place in castables with high alumina-fiber content during the dewatering process. It is shown that the mass loss due to cement dehydration and the permeability increase caused by fiber burnout can be independently assessed, based on the fluid dynamic conditions established for the experiment. Control of the pressure drop through the sample was the key procedure used to analyze the phenomenon of interest.     

Synthesis of Zinc Aluminate Spinel Film through the Solid-Phase Reaction between Zinc Oxide Film and α-Alumina Substrate

We synthesized spinel ZnAl₂O₄ film on α-Al₂O₃ substrate using a solid-phase reaction between the pulsed-laser-deposited ZnO film and α-Al₂O₃ substrate. Auger electron spectroscopy showed that the atomic distribution in the spinel ZnAl₂O₄ was inhomogeneous, which indicated that the reaction was diffusion controlled. Based on X-ray fluorescence measurements, the apparent growth activation energy of ZnAl₂O₄ was determined as 504 kJ/mol. X-ray diffractometry spectra showed that, as the growth temperature increased, the ZnAl₂O₄ film became disoriented from the single (111) orientation. The ZnAl₂O₄ (333) diffraction peak shifted toward a small angle, and its full-width at half-maximum decreased from 1.30° to 0.37°. At the growth temperature of 1100°C, the morphology of the ZnAl₂O₄ was initially transformed from islands to stick structures, then to bulgy-line structures with increased growth time. X-ray diffractometry spectra showed that these transformations were correlated with changes of ZnAl₂O₄ orientation.