Microwave and conventional treatment of low-cement high-alumina castables with different water to cement ratios; Part I. Drying

The aim of this study was to determine the effect of the microwave and conventional drying method on the strength, porosity and composition of low-cement alumina castables with various water to cement ratios (wcr). High-alumina low-cement castable samples were prepared with different w/c ratios: 0.64, 0.75, 0.82 and 1.13. Changes in wcr were effected through volumetric replacement of cement with 0–0,045-mm tabular alumina having a comparable particle size. Water content in all the composition was constant (4,5%). After curing, the samples were dried conventionally in a laboratory electric drier or in a laboratory microwave drier. After drying open porosity and modulus of rupture were determined. The pore size distribution, pore median and tortuosity of the samples were measured by the mercury porosimetry method. Phase composition was determined using X-ray diffraction. The Rietveld method was used for quantitative analysis. It was found that at low wcr (0.62) the main hydrate formed in the castable was C₃AH₆, which caused a release of a smaller amount of water during the drying process, mainly pore water, resulting in lower open porosity and lower pore size than in the castables with a high wcr (1.13). At a low wcr, the strenght of castable was higher due to a higher amount of hydrates, low porosity and small pore size. On the other hand, at a high wcr, the strength of castable was lower owing to a higher amount of water released in the drying process, which led to loosening the structure of castable. With an increased water-to-cement ratio the degree of CA₂ hydration decreased. The temperature rise due to cement hydration probably influenced the kinetics of this process.     

Heat resistance and thermomechanical behaviour of ultralow and zero cement castables

Abstract

Knowledge of relative heat resistance as well as thermo-mechanical behaviour of refractory castables is very important for their use as linings in high temperature furnaces and refining vessels in the metallurgical, cement, and petrochemical industries. The present work aims at studying these properties for different types of refractory castable. Two classes of castable were prepared, namely ultralow and zero cement, containing either high alumina cement or hydratable alumina as bonding agent. For each class, two different castable systems were prepared, one containing an alumina-silica mixture in its matrix and the other containing magnesia-alumina. In all castables studied, calcined alumina was used as aggregate. The prepared castable samples were subjected to firing temperatures up to 1500°C. Relative heat resistance, bending strength before and after thermal cycling, hot modulus of rupture, and creep deformation were measured according to international standard specifications. It was concluded that a limited content of cement (ultralow cement castables) is beneficial with the magnesia-alumina mix in the matrix owing to the formation of calcium hexaluminate-magnesium aluminate-corundum (matrix advantage system) that results in excellent relative heat resistance as well as thermome-chanical properties. Zero cement castables on the other hand are recommended for use with the alumina-silica mixture, since the absence of cement improves the chances of mullite formation without glassy phases, thereby enhancing the properties of such refractory castables.     

Comparisons Between Vibration and Self-Flowing Ultra-Low Cement Castables Properties in Al2O3-SiC-C System

In this study, the properties of self-flowing ultra-low cement castables in Al2O3-SiC-C system have been investigated and compared to vibration castables. The major physical and mechanical properties, microstructure and corrosion behavior of these castables against slag have been evaluated. The results showed that the microstructure of Al2O3-SiC-C self-flowing castable is more uniform than the vibrated structure. Also self-flowing castable has smaller pore size and more uniform pore size distribution. Hence, density, strength, oxidation and slag resistance of the self-flowing castables is higher than that of vibration castables. Therefore, besides other benefits such as noise free, easy installation, fewer mold defects and reduced installation costs, Al2O3-SiC-C self flowing ultra low cement castables will have longer service life in comparison with vibration casables.     

The effect of permeability enhancement on dry-out behavior of CA- and microsilica gel-bonded castables as determined by NMR

This investigation deals with refractory monolithic materials that are broadly used in thermal treatment facilities as they are necessary e.g. for iron and steel, glass and cement production, thereby withstanding temperatures between 600 and 2000 °C. In the special case of hydraulic bond refractory castables, the components must be mixed with water for two reasons: firstly, to obtain a mouldable suspension; and secondly, to achieve a green strength via the hydraulic reaction of calcium aluminate cement that is high enough to enable a secure refractoriness of the concrete formwork. Prior to their first use in production, castables must have their pore water and hydraulic bond water carefully removed in order to avoid explosive spalling that can cause severe damages inside the furnaces.In this study, we investigate the one-dimensional drying behavior of two specific refractory castable compositions, a microsilica-containing low- and a no-cement castable (LCC/NCC) during first heat-up in the temperature regime between 20 and 300 °C. First results were already presented in a prior publication that demonstrate a specialized high-temperature Nuclear Magnetic Resonance (NMR) setup capable of continuously measuring moisture and temperature profiles on 74 mm-long cylindrical samples, without touching or moving the sample [1].In this paper we explore how the use of permeability-enhancing agents (fibers and MIPORE 20) beneficially affects the drying behavior and consequently allows higher heating rates. We also demonstrate that the NMR technique as applied here is sensitive enough to resolve differences in the dry-out behavior if said additives are used in the castable formulations.Our results demonstrate that incorporation of fiber and MIPORE 20 significantly alters the dry-out behavior. In particular, it can be resolved that as the fibers begin to melt, there is a noticeable increase in permeability that results in faster drying, as well as a decrease of the drying front temperature and therefore the generated maximum pressure.     

Thermodynamic evaluation and properties of refractory materials for steel ladle purging plugs in the system Al2O3-MgO-CaO

The influence of iron oxide in the phase relationships of Al₂O₃-MgO-CaO and Al₂O₃-MgO purging plug refractory material has been studied by the thermodynamic analysis tool FactSage. Results showed that the system without CaO to be advantageous on the onset temperature of liquid phase, and on the liquid content at defined chemical composition and temperature. Therefore, CaO negatively influences the iron-rich slag resistance of the purging plug material. Analysis of used purging plugs proved the thermodynamic results. They showed that spinel solid solution and calcium hexaluminate as stable phases were formed in the reaction with iron oxide slag.Corundum-spinel castables with and without calcium aluminate cement were investigated in the laboratory to compare the relevant technical properties. In the cement bonded castable, the curing and drying strength are increased by increasing the cement content. However high cement addition requires higher water demand, which results in higher open porosity and a lower hot modulus of rupture (HMoR). In the CaO-free, no-cement castable with hydratable alumina binder, the water demand is slightly higher when compared to the ultra-low cement castable. However, the curing and drying strength are still slightly higher for the no-cement castable. As there is no significant difference in HMoR with various hydratable alumina binder additions, low dosage of such binder in the range of two to four percent is normally recommended to avoid excessive water addition. Cement bonded castables (with CaO) show some advantages to the no-cement castable (non-CaO) regarding HMoR, however the no-cement castable could have advantages regarding the iron-rich slag resistance and thermal shock resistance.     

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.     

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.     

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.     

耐火材料用有机-无机复合结合剂的研制

以水泥为结合剂的浇注料中含有CaO,在烧成过程中能够生成低共熔相而影响了其高温性能。为了提高浇注料的高温使用性能,需要在保证浇注料具有一定的常温强度的基础上,研制低水泥或者无水泥的新型结合剂来替代水泥结合剂。以丙烯酰胺体系为基础,探讨了丙烯酰胺系有机-无机结合剂在矾土基浇注料中的实际使用效果。结果表明,浇注料在110℃烘干后的体积密度、显气孔率、耐压和抗折强度等常温性能良好,尤其是抗折强度得到很大的提高。在不同高温烧成后,有机结合剂的浇注料性能得到提高。     

h-BN加入量对低水泥刚玉质浇注料性能的影响

为了提高低水泥刚玉质浇注料中温处理后的强度和抗热震性,在其配料中引入不同量的h-BN粉(其质量分数分别为0、0.5%、1%、1.5%和2%),经成型、养护、脱模、烘干、750℃热处理后,检测试样的体积密度、显气孔率、常温抗折强度、常温耐压强度、抗热震性,并进行XRD分析。结果表明:随着h-BN加入量的增加,750℃处理后试样的显气孔率有所减小,体积密度逐渐减小,常温耐压强度逐渐增大,常温抗折强度也呈增大趋势,抗热震性逐渐改善。可见,加入h-BN有助于提高低水泥刚玉质浇注料中温处理后强度和抗热震性。     

Cement-free spinel-based refractory materials

Channel induction furnaces can operate at temperatures as high as 2000 °C, which requires the use of high-temperature refractory materials resistant to corrosion. CaO, a conventional component of the corundum-containing refractory castables, produces a degrading effect on high-temperature properties; for this reason, low-and ultralow cement materials fail to meet the needed requirements. Therefore a cement-free refractory of the DALCAST series in the Al₂O₃-MgO binary system based on an Al₂O₃ fully hydratable binder has been developed. Physical properties (strength and hardening behavior) of a standard low-cement castable and a newly developed product based on the results of their practical use in channel induction furnaces are compared and discussed. __________ Translated from Novye Ogneupory, No. 6, pp. 95–98, June, 2005.     

不同碳材料对铝碳浇注料性能的影响

含碳浇注料因碳材料的水润湿性差及高温氧化引起的材料性能差等问题一直备受关注。分别以热氧化石墨、ZrC包覆改性石墨和水热碳化生物质碳材料为碳源制备铝碳浇注料,研究不同碳材料对铝碳浇注料显气孔率、物理性能、物相组成,以及抗氧化性和抗渣侵蚀性能的影响。结果表明:引入热氧化石墨的浇注料具有最高的加水量,残留孔隙破坏了材料内部结构,浇注料机械性能较差;添加ZrC表面改性石墨可以降低浇注料的加水量,抗氧化性能较好,但对力学性能的提升无显著影响;以生物质碳材料为碳源可以显著提高浇注料的物理性能,相比于添加石墨的试样,生物质碳材料并未显著提升试样的抗渣侵蚀性能。     

Al2O3-SiC-C质湿式喷射浇注料的研究和应用

以高纯莫来石、碳化硅、SiO2微粉、Al2O3微粉、纯铝酸钙水泥、白刚玉细粉和球沥青等为原料,研究了q值为0.23、0.25、0.27、0.29和0.31时湿式喷射浇注料的流变性能;进一步研究了q值为0.27时,SiC加入量(质量分数分别为12%、15%、18%、21%)对其流变性能、常温物理性能和高温抗折强度、抗热震性能、抗渣侵蚀性能的影响。结果表明:根据Andreassen方程,当q=0.27时,配制的浇注料具有较好的流变性能;加水量为6.5%(w)时,研制浇注料的流变性能类似于宾汉姆流体,适于管道输送;SiC加入质量分数为18%时,浇注料具有较高的高温抗折强度、抗渣侵蚀性能和抗热震性能;经对鱼雷罐和出铁沟的喷补使用证明,研制的湿式喷射浇注料施工性能好,使用性能优异。     

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.     

CaO含量对Al2O3-MgO-CaO系浇注料性能的影响

高纯度的Al2O3-MgO-CaO系浇注料正广泛应用于精炼钢包的透气砖、座砖、工作衬及包壁修补料等,纯铝酸钙水泥既是Al2O3-MgO-CaO系统浇注料的结合剂,同时又是浇注料中CaO的主要来源.本试验通过改变纯铝酸钙水泥的加入量来改变CaO的含量,探究高温下形成的CA6等矿相对体系性能的影响.结果发现:氧化钙以本研究中的纯铝酸水泥形式引入时,随其引入量的增加,材料经110 ℃处理后的物理性能呈现优化的趋势;CA6形成产生的体积膨胀在促进结构的致密化的同时,当达到一定程度时,会导致材料结构劣化,因此材料经1550 ℃处理及5次热循环后,其物理性能呈现先提高后降低的趋势.综合各项性能认为,纯铝酸钙水泥加入量在5wt%~8wt%时其高温强度及抗热震性能较为优异.     

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。     

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。     

Does a tiny amount of dispersant make any change to refractory castable properties?

A growing demand for refractory castables with specific behaviors has given rise to a continuous technological evolution, mainly due to the broad knowledge of hydraulic binders available nowadays. The high alumina cements remain as the most important hydraulic binders for castables. Nevertheless, calcium aluminate bound castables still show a characteristic drop of strength at intermediate temperatures, which could also be affected by the castable chemical additive. Thus, this paper aims to highlight the influence of dispersants on the refractory castable properties with the firing temperature. It was noticed that the hydrates formed during the curing process of castable depends on the dispersing additive used. The FS60, a polycarboxylate ether, induced the AH₃ formation and its decomposition resulted in a more stable hydrate (AH), which increased the splitting strength with the thermal treatment temperature. At a high temperature, the CA₂ and CA₆ formation is also favored in the presence of this additive. However, it did not bring benefits to the castables creep behavior, resulting in a less tough structure.     

化学合成高纯铝酸钙水泥的特性及应用

研究了化学合成高纯铝酸钙水泥的物理特 性,包括强度发展、凝结时间、水化结合水量和水化放 热特性,并与市售的以传统烧结法生产的水泥进行了 在典型耐火浇注料中的应用比较。结果表明:(1)化 学合成高纯铝酸钙水泥胶砂的强度发展快且充分,早 期强度高;(2)化学合成高纯铝酸钙水泥的水化放热 速率在水化2h时最大,放热快且放热量集中;(3)化 学合成高纯铝酸钙水泥的水化活性较高;(4)化学合 成纯铝酸钙水泥用于耐火浇注料中,浇注料表现出较 高的烘干强度,且浇注料的烧后强度等性能指标也与 用传统烧结水泥的大体相当。     

Application of New Calcium Aluminate Cement CA-670 in Low Cement Castables

A new calcium aluminate cement CA-670 was studied in the system of tabular alumina,white fused alumina( WFA),and bauxite based low cement castables.The flow ability,strength development,and hot strength( HMOR) were investigated. Different types of additives were used for the CA-670 bonded castables. The results show CA-670 provides a good workability for each type of castables. CA-670 displays a good compatibility with different types of additives. Testing on different batches of CA-670 shows good reproducible properties in each castable,which manifests good consistency and reliability of CA-670.