Effect of heat treatment and zircon addition on the properties of low-cement castables based on recycled alumina grog

In this investigation, low-cement castables were prepared using 70% alumina grog aggregates obtained from crushed alumina brick waste. The aggregates were thermally treated at 1550 °C for 3 h. Four types of low-cement castables were prepared with various types of aggregates (alumina grog with or without thermal treatment) and fillers (with or without zircon addition), and they were evaluated in terms of their physical, thermal, and chemical properties. Microstructural analysis via scanning electron microscopy (SEM) was performed on the castables before and after slag attack. Compared to the other fabricated castables, the thermally treated alumina grog castables with zircon showed better physical properties, such as a higher bulk density, cold crushing strength, and modulus of rupture and a lower apparent porosity and water absorption. In addition, they had a higher positive linear thermal expansion, refractoriness under load, permanent linear change, and hot modulus of rupture. The results of the SEM with energy dispersive X-ray analysis of the prepared castables confirmed that the mullite and anorthite phases were predominant when zircon was not added and the zircon–mullite phase additionally appeared upon the incorporation of zircon. A quantitative elemental analysis via X-ray fluorescence spectroscopy was employed to determine the composition of the castables. X-ray diffraction analysis showed that the alumina grog castables had a high mullite and low anorthite content, and the thermally treated alumina grog had a high anorthite, low mullite, and high zircon content. The improvement in the mechanical and thermo-mechanical properties of the castables with thermally treated alumina grog and added zircon can be attributed to the formation of the zircon–mullite phase with a low mullite phase content.     

High-temperature stability of Mg(Al,Cr)2O4 spinel co-existing with calcium aluminates in air

Cr₂O₃ is a well-known corrosion resistant oxide used in refractory applications. However, it can oxidize into toxic and water-soluble Cr(VI) compounds upon reaction with calcium aluminate cement phases in the presence of oxygen, which subsequently causes disposal problems after use. This study describes the extent to which chromium in the spinel Mg(Al,Cr)₂O₄ phase can be oxidized to Cr(VI) when it reacts with the calcium aluminate cement phases C₁₂A₇, CA, CA₂ and free CaO at 1300 °C in air, using XRD, XPS and leaching tests (TRGS 613 standard) as analytical tools. On reaction with CaO, the Mg(Al,Cr^III)₂O₄ spinel mainly transformed into hauyne (Ca₄Al₆Cr^VIO₁₆) and Ca₅Cr₃O₁₂ which contains both Cr(IV) and Cr(VI). The reaction of C₁₂A₇ and CA with the spinel phase also resulted in the formation of Ca₄Al₆CrO₁₆. Conversely, the reaction of Mg(Al,Cr^III)₂O₄ spinel with CA₂ resulted in the formation of only a trace amount of Cr(VI). Water-soluble Cr(VI) leached in large quantities (>100 mg/L) from samples where the Mg(Al,Cr^III)₂O₄ reacted with either C₁₂A₇ or CA. Almost no Cr(VI) leached from the sample when Mg(Al,Cr^III)₂O₄ reacted with CaO, using the standard TRGS 613 leach test, but a significant amount of Cr(VI) was released into solution when leached with a HCl solution for 12 h. Both Cr(IV) and Cr(VI) present in the Ca₅Cr₃O₁₂ dissolved into acidic solution. Only a small amount of Cr(VI) leached from the sample that resulted when spinel was reacted with CA₂, even after a prolonged HCl leach. Cr(III) in spinel Mg(Al,Cr)₂O₄ is very stable and does not leach in either distilled water or acidic solution.     

Effect of in-situ formation of columnar mullite and pore structure refinement on high temperature properties of corundum casatbles

The effects of in-situ synthesis columnar mullite and pore structure on the hot modulus of rupture (HMOR), thermal shock resistance and corrosion resistance of corundum castables have been investigated in this paper. When 2% nano silica was added, the pore diameters of castables could be decreased to 15 nm (at 110 °C), 1 μm (1100 °C) and 6 μm (1500 °C), respectively. The corresponding reducing magnitude of pore size is 98.5%, 83.3% and 33.3%. The HMOR of castables fired at 1500 °C increased by 110% to 3.64 MPa. Furthermore, after three thermal shock cycles, the residual strength ratio of castables increased from 5.2% to 15.3%. A large amount of cross-distributed columnar mullite was formed between nano silica and α-Al₂O₃ by the two-dimensional nucleation mechanism, which remarkably enhanced the high temperature properties. The penetration index reduced from 30.86% to 19.88%, suggesting that smaller pore size and higher viscosity had a great influence to the penetration process.     

A replacement of traditional insulation refractory brick by a waste-derived lightweight refractory castable

Lightweight insulation refractories are essential for high-temperature performance to reduce energy consumption. This study investigates a new insulation material, that is, solid waste rice husk ash (RHA) derived lightweight refractory castable, replacing traditional insulation refractory brick. The RHA is generated after the burning of rice husk as biomass fuel. The RHA is used as an aggregate and alkali-extracted silica sol from RHA as a binder to fabricate the insulation castable. The nanosilica containing (~30 wt%) sol is employed to synthesize the refractory castable by varying the sol amount (2.5-12.5 wt% silica from sol). The castable specimens are cast by a vibro-caster and fired at 900-1200°C in a muffle furnace. The physic-mechanical and thermal conductivity (κ) of the castable is investigated. At 1100°C with 10 wt% dry sol retaining sample shows an excellent apparent porosity (~65%), low bulk density (~ 0.8 g/cm³), and κ (0.136 W/m k) with sustainable compressive strength (6 MPa). The acquired results are a good match with the literature (other wastes-derived insulation materials) and industrial (silica insulation brick) obtained data. These promising outcomes may inspire the refractory industries for using RHA as an aggregate and RHA extracted sol as a binder for making insulation castable.     

甘油三酸脂对硅溶胶的分散作用

通过对硅溶胶泥浆的流变性实验确定了硅溶胶泥浆的流变模型，验证并分析了加入少量经过低温氧化过的甘油三酸脂（ＧＴＯ）不改变硅溶胶泥浆的流变模型，但能有效地改善其流变性能。因此，ＧＴＯ可作为硅溶胶结合浇注料的高效减水剂。     

溶胶-凝胶结合耐火浇注料抗CO侵蚀性能研究

研究了新型溶胶．凝胶结合耐火浇注料的抗CO侵蚀性能，同时也与传统的水泥结合耐火浇注料进行了对比试验，并从侵蚀前后的表观特征、理化性能和微观结构等多方面探讨了其CO侵蚀作用机理。结果表明，浇注料中的铁氧化物含量，CO气氛的浓度等多种因素决定了CO侵蚀反应的强度。而在同等实验条件下，溶胶-凝胶结合耐火浇注料的抗CO侵蚀性能要大大优于水泥结合的耐火浇注料，因此是替代传统浇注料的理想材料。     

Effect of spinel content on the properties of phosphoric acid bonded high alumina castables

In order to study the effect of fused spinel on the properties of phosphoric acid bonded high alumina castables, samples with different contents of fused spinel were prepared. The results show that when the contents of the fused spinel are between 8% and 16% (mass fraction), the castables have good properties. The castables overcome the shortages of the phosphoric acid bonded high alumina castables with bauxite cement as a hardening promoter. The experiments demonstrate that most of the service properties of the castables with fused spinel are better than those of the normal phosphoric acid bonded castables which use bauxite cement as a hardening promoter. The examination of the materials indicates that free MgO inclusions in the spinel powder can promote the hardening of the castables.     

Reconstruction and hydration of hydrotalcite response to thermal activation temperature: Enhancement of properties for magnesia castables

Optimization binding system for refractory castables is significant to enhance the service performance. Hydrotalcite has been considered a promoter for high-temperature performance of basic castables, however, its binding property remains to be improved before practical application. In this work, the thermal activated Mg–Al hydrotalcites were incorporated in magnesia castables, and the mutual influence of pre-calcination temperature on the hydration, microstructure, and strength of castables was investigated. The obtained results indicated that the reconstruction of calcined hydrotalcite took place in the hydration process and effectively motivated the hydrolysis. Hydrate was thus promoted and a relatively dense microstructure of magnesia castables was confirmed by X-ray computed tomography analysis. Hydrotalcite pre-calcinated at 300 °C contributed to the highest early strength for castable, and the high-temperature properties also performed better than that of other pre-calcinated hydrotalcite-adding. The enhancement mechanisms of calcined hydrotalcite were attributed to the two following reasons: (ⅰ) the modified microstructure of magnesia castables from the early stage by hydration process, (ⅱ) the further enhanced sinterability inspired by the appropriate thermal activation effect.     

Role of cement content on the properties of self-flowing Al2O3 refractory castables

In this work, Al₂O₃ self-flowing castables (SFCs) were produced based on various cement contents. The SFCs were sintered at 1273 K, 1573 K and 1773 K and the exhibited properties were experimentally determined. Among the properties determined in this work are bulk density (BD), apparent porosity (AP), water absorption (WA), cold crushing strength (CCS), modulus of rupture (MOR) and fracture toughness (K_IC). It is found that additions of 5% cement lead to SFCs with maximum MOR and K_IC values after firing at 1773 K. Firing at 1573 K leads to a reduction in both, MOR and K_IC. In SFC containing 3% cement, maximum K_IC values of 3.53 MPa m^1/2 were achieved after firing at 1573 K. In the low cement SFCs (1 wt%) after firing at 1773 K the exhibited K_IC values were below those obtained in either the SFC-3 or SFC-5, but they were significantly high (3.43 MPa m^1/2).     

低水泥浇注料中纯铝酸钙水泥和SiO_2微粉的“老化”试验

为了探讨纯铝酸钙水泥结合的低水泥浇注料"老化"的原因和影响因素,将SiO2微粉以及不同粒度、不同物相组成(CA相含量)、不同新鲜程度的纯铝酸钙水泥在温度为(20±1)℃、相对湿度>75%的潮湿环境中摊成厚度为2.5 cm左右的料层,放置一定时间(分别为0、3、7、14、28 d)使其老化,然后分别将它们与特级矾土(≤5、≤0.088 mm)、磷酸盐分散剂和减水剂等其他原料一起配制成浇注料,通过测定浇注料的可工作时间、初始流动性和早期(6 h)养护强度,来表征这些原料的老化速度.结果表明:(1)纯铝酸钙水泥的cA含量和细度越高,其老化速度越快.(2)"新鲜"的铝酸盐水泥比存放一段时间后的水泥的老化速度更快.(3)SiO2微粉的老化会导致浇注料的流动性变差,可工作时间变短.