Interactions of Li2O volatilized from ternary lithium-ion battery cathode materials with mullite saggar materials during calcination

In recent years, the rapid development of Li(Ni_xCo_yMn_1-x-y)O₂ (LNCM) materials for application in ternary lithium-ion batteries has led to an increased demand for refractory kiln saggars in industries. However, saggars used for firing ternary Li-ion battery cathode materials are often subjected to severe corrosion and spalling. To investigate the damage mechanism of the saggar materials, non-contact corrosion experiments were designed to study the effects of the precursor additions, calcination temperature, and number of calcinations during the interaction between mullite saggar and LNCM materials. The phase composition and microstructure of the mullite saggar specimens before and after corrosion were characterized using X-ray diffraction and scanning electron microscopy, respectively, to obtain a comprehensive understanding of the causes of the deterioration of mullite saggar materials during corrosion.     

Low shear rheological behaviour of two-phase mesophase pitch

The low shear rate rheology of two phase mesophase pitches derived from coal tar pitch has been investigated. Particulate quinoline insolubles (QI) stabilised the mesophase spheres against coalescence. Viscosity measurements over the range 10–10⁶ Pa s were made at appropriate temperature ranges. Increasing shear thinning behaviour was evident with increasing mesophase content. At low mesophase contents the dominant effect on the near Newtonian viscosity was temperature but at higher contents it was the shear rate; temperature dependence declined to near zero. The data indicated that agglomeration could be occurring at intermediate mesophase volume fractions, 0.2–0.3. The Krieger–Dougherty function and its emulsion analogue indicated that in this region the mesophase pitch emulsions actually behaved like ‘hard’ sphere systems and the effective volume fraction was estimated as a function of shear rate illustrating the change in extent of agglomeration. At the higher volume fractions approaching the maximum packing fraction, which could only be measured at higher temperatures, the shear thinning behaviour changed in character and it is considered that this is possibly due to shear induced deformation and breakup of dispersed drops in the shear field.     

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.     

Producing fully-lamellar microstructure for wrought beta-gamma TiAl alloys without single α-phase field

Fine-grained fully-lamellar (FL) microstructure is desired for TiAl components to serve as compressor/turbine blades and turbocharger turbine wheels. This study deals with the process and phase transformation to produce FL microstructure for Mo stabilized beta-gamma TiAl alloys without single α-phase field. Unlike the α + γ two-phased TiAl or beta-gamma TiAl with single α-phase field, the wrought multi-phase TiAl–4/6Nb–2Mo–B/Y alloys exhibit special annealing process to obtain FL microstructure. Short-term annealing at temperatures slightly above β-transus is recommended to produce the desired FL microstructure. The related mechanism is to guarantee the sufficient diffusion homogenization of β stabilizers during single β-phase annealing, and further avoid α decomposition by α → γ + β when cooling through α + β + γ phase field. The colony boundary β phase contributes to fine-grained nearly FL microstructure, by retarding the coarsening of the α phase grains.     

Corrosion resistance of Al–Cr-slag containing chromium–corundum refractories to slags with different basicity

Al–Cr slag is the solid waste generated by the smelting of Cr metal. It presents a range of environmental hazards. This study addressed the corrosion resistance of Al–Cr slag containing chromium–corundum refractories to slags with different basicity. Herein, we provide suggestions for the use of Cr–corundum of different basicity in kilns. Al–Cr slag, brown fused Al₂O₃, and chrome green were used as the raw materials, with pure calcium aluminate cement being used as a binder. The brick samples, prepared using different blends of chrome green and corundum, were fired at 1600?°C, and subsequently subjected to a slag corrosion test. After corrosion by slag of different basicity, the phase composition and microstructure of the sample were analyzed by X-ray diffraction, energy dispersive spectrometer and scanning electron microscopy. There were two major findings. First, Cr–corundum brick made from Al–Cr slag has a better slag corrosion resistance than that made from Cr₂O₃ and brown fused Al₂O₃. Second, Cr–corundum brick made from Al–Cr slag has superior corrosion resistance to slag with a CaO:SiO₂ ratio of 2:1.     

高炉开炉装料计算软件的设计

高炉开炉装料计算工作繁琐、复杂,手工计算耗费时间长、容易出错,难以得到最佳方案,影响高炉顺利开炉。通过高炉开炉装料计算软件的开发实践,介绍了装料计算模型的建模步骤;讨论了软件的功能需求;阐述了选用三层网络结构的原因,从而描述了装料计算软件的设计方法。软件投入运行后,能够快速、准确地计算、分析开炉数据,取得了满意的效果。     

In situ formation of multi scale reinforcing phases to improve performance of Al2O3-SiC C castables

In order to improve the physical properties and slag corrosion resistance of refractory materials for hot metal pretreatment, different contents of composite metal powders (CMP) were introduced into Al2O3-SiC-C refractory castables. The effect of CMP on the microstructure, physical properties and slag corrosion resistance of Al2O3-SiC-C refractory castables were studied. The results show that the multi scale reinforcing phases including flake crystals, rod shaped fibers, filamentous fibers and whiskers are in situ formed in the samples with addition of CMP, which result to the improvement of the cold modulus of rupture and cold crushing strength. When the addition of CMP is 6 wt.%, the high temperature modulus of rupture increases by 231%, the thermal shock resistance increases by 77% after thermal shock by water cooling 5 times and the percentage of the slag resistant area reduces by 37.2%.     

Formation mechanism of 21R AlN-polytypoids in aluminothermic reduction and nitridation process

Synthesis of 21R AlN polytypoids was investigated using Al and ultrafine SiO₂ powder in a flowing nitrogen atmosphere by means of thermal gravity (TG), differential scanning calorimeter (DSC), X-ray diffractometer (XRD) and scanning electronic microscope (SEM) linked with energy dispersive spectrometer (EDS). The results showed that the formation mechanism of AlN polytypoids was different from that in reaction sintering process using Si₃N₄, AlN, Al₂O₃ and other sintering additive as raw materials. It was suggested that firstly Al reduce SiO₂ into Si and is also nitrided into AlN, then AlN, Al₂O₃ and SiO₂ dissolve into silicon liquid until the AlN polytypoids precipitate in saturated liquid in a flowing nitrogen atmosphere at lower than 1700 °C.     

Synthesis of Mg-α-sialon from the mixture of silicon, aluminum and magnesia powders in a flowing nitrogen atmosphere

Synthesis of Mg-α-Sialon has been investigated by the mixture of silicon, aluminum and magnesia powders in a flowing nitrogen atmosphere in the range of 1300–1600 °C, when Mg-α-Sialon is designed with a chemical formulation of Mg _x Si_12−3x Al_3x O _x N_16−x in present work. The results showed that Mg-α-sialon initially occurred at 1400 °C and basically increased with elevated temperatures. For the samples of x = 0.6, 0.8 and 1.0 the products mainly consisted of Mg-α-Sialon with small amounts of Si, AlN and 21R AlN-polytypoid phases at 1600° C. However, in final products of x = 1.2, 1.4 and 1.6 only a little of Mg-α-Sialon formed and a great amount of Si remained in these samples at all the fired temperatures. Fortunately, the content of Mg-α-Sialon in these samples were obviously increased by adding a small amount of α-Si₃N₄ as seeds before nitridation.