Characteristics and cementitious properties of ladle slag fines from steel production

Ladle slag is a by-product from further refining molten steel after coming out of a basic oxygen furnace (BOF) or an electric arc furnace (EAF). Air-cooled ladle slag has a very large portion of fine particles due to the conversion of β-C₂S to γ-C₂S during the cooling process. X-ray diffraction (XRD) analysis of three ladle slag fine samples passing 100, 200 and 325 mesh indicates that the major mineral in ladle slag fines is γ-C₂S, which does not show cementitious property in water. Experimental results have indicated that ladle slag fines show significant cementitious property in the presence of an alkaline activator. The finer the ladle slag is, the better the cementitious property of the slag is.     

重构钢渣的胶凝性分析

在炼钢转炉排渣的同时,将一定比例的电炉还原渣和煤渣加入到渣盘中,利用熔融钢渣的余热对钢渣的组成和结构进行在线重构。结果表明,重构处理明显降低了钢渣中的fCaO含量,改善了钢渣的易磨性和压蒸安定性,钢渣粉的28d活性指数提高了10%～20%。     

Dissolution behavior of silica in molten CaO–SiO2–Fe2O3–MgO–MnO slag

The modification of basic oxygen furnace (BOF) slag by adding silica can improve the properties of BOF slag for applications in the cement industry. The rapid dissolution of silica is essential to hot slag modification. In this work, the dissolution behavior of silica in the molten CaO–SiO₂–Fe₂O₃–MgO–MnO system as synthetic BOF slag was investigated by using the traditional rotating cylinder technique. Effects of rotation speed, temperature, immersion time, and slag basicity on the silica dissolution were studied. Scanning electron microscopy equipped with energy dispersive spectrometer (SEM-EDS) and FactSage simulations were employed to reveal the dissolution mechanism. It was found that the dissolution of the silica rod was affected by both the thermodynamic driving force and the slag viscosity. The silica dissolution rate in molten CaO–SiO₂–Fe₂O₃–MgO–MnO slag increased with increasing the rotation speed and temperature, but first increased and then decreased when decreasing the slag basicity from 2.5 to 1.5. A linear correlation between the logarithm of the dissolution rate and the logarithm of cylinder periphery velocity with a slope of 0.44 was observed, indicating the mass transfer within the boundary layer as the dissolution rate determining step. A direct dissolution way was found during the dissolution of silica in molten CaO–SiO₂–Fe₂O₃–MgO–MnO slag.     

Glass-ceramics produced from thin-film transistor liquid-crystal display waste glass and blast oxygen furnace slag

This study employed waste glass from thin-film transistor liquid-crystal displays (TFT-LCD) and slag from a basic oxygen furnace (BOF) to produce CaO–MgO–Al₂O₃–SiO₂ (CMAS) glass-ceramics through vitrification and further heat treatment of compacts of the obtained glass powders for densification and crystallization. CMAS glass-ceramics are known for their excellent mechanical and dielectric properties. MgO and Al₂O₃ were selected as modifying agents to ensure that the composition of the wastes featured these important characteristics.     

Research on slag-resistance of ZrN-SiAlON-SiC-C composite refractory in different atmospheres

The ZrN-SiAlON composite powder was synthesized using low-grade zircon and bauxite by carbothermal reduction nitridation at first and then ZrN-SiAlON-SiC-C composite refractory were fabricated with the ZrN-SiAlON powder, SiC particles, and a small amount of Si powder as raw materials and sucrose as the binder. The slag resistance of these composites in O₂, N₂ and Ar atmosphere was investigated by X-ray diffraction, scanning electron microscopy, and energy dispersion spectra. The results show that the pores in the inside of ZrN-SiAlON-SiC-C composite refractory were enlarged in oxygen atmosphere due to oxidation, which leads to the decrease in slag resistance. In argon atmosphere, blast furnace slag destroyed the sintered body of zircon, corundum, and cristobalite with the formation of CaZrO₃, then infiltrated into and filled the pores inside the refractory to form a dense layer, which hindered the further erosion of the blast furnace slag. In the reducing atmosphere, the interfacial energy of the gas-liquid phases became larger due to the reactions between blast furnace slag liquid and the gas, resulting in a larger wetting angle which prevented the erosion.     

Evaluation of Phosphate Removal Efficiency from Aqueous Solution by Polypyrrole/BOF Slag Nanocomposite

The polypyrrole/basic oxygen furnace slag nanocomposite (PPy–BOFS) was synthesized and characterized by FTIR, SEM, ICP-AES, and X-ray diffraction studies and was employed as an adsorbent for the removal of phosphate ions from aqueous solution by the batch sorption method. The maximal amount of adsorption was found to be 9.13 mg/g (45°C). The Langmuir and Freundlich isotherms were used to describe the adsorption equilibrium. The kinetics of the adsorption process was investigated using the Lagergren rate equation and the Weber Morris intraparticle diffusion model. The FTIR and XRD pattern of the adsorbent before and after the adsorption was recorded to get better insight into the mechanism of the adsorption process. The results of equilibrium and spectral investigations revealed that the removal of phosphate by the nanocomposite involves various mechanisms followed by the nanocomposite and the constituents present in it.     

电石渣激发钢渣-矿渣固化淤泥质土的试验研究

钢渣和矿渣是常见的两种工业废渣,大量堆放且资源化利用困难。以钢渣粉和矿渣粉为基础材料,电石渣粉作为激发剂,可对淤泥质土进行固化处理。通过开展无侧限抗压强度试验,分析固化淤泥质土的强度特性和应力-应变关系,利用X射线衍射(XRD)和扫描电镜(SEM)等微观测试,探索电石渣激发钢渣-矿渣固化淤泥质土的作用机理。结果表明,电石渣粉质量掺量为6%时,电石渣-钢渣-矿渣固化淤泥质土无侧限抗压强度最大,28 d固化淤泥质土强度与同龄期水泥土相当,且具有较好的延性。电石渣可以提供碱性环境和大量钙离子,有效激发钢渣和矿渣的水化活性,促进C-S-H凝胶的大量生成,同时促进离子交换和团粒化作用,使固化淤泥质土强度显著提高。     

Post-mortem analysis of alumina-magnesia-carbon refractory bricks used in steelmaking ladles

Post-mortem studies in secondary steelmaking ladles are an important way to determine the factors related to Alumina-Magnesia-Carbon (AMC) refractory corrosion. AMC refractory bricks installed in the impact zone of a steelmaking ladle bottom were analyzed after 100 castings. X-ray diffraction, X-ray fluorescence chemical analysis, reflected optical light microscopy, scanning electron microscopy, energy dispersive X-ray spectrometry, density and porosity measurements, and mercury porosimetry were used to analyze the chemical and physical characteristics of the slag, the unused refractory and the slag+steel attacked bricks. The corrosion process produced a specific microstructure characterized by: i) a thick discontinuous slag layer composed by secondary spinel+steel+liquid; ii) a thick dense, cracked, and continuous layer consisting of calcium aluminates+steel+liquid at the slag/refractory interface; iii) next to this layer, a wide densified layer with a uniform microstructure in which corundum aggregates and spinel crystals were linked together by elongated CaAl₁₂O₁₉ crystals.The formation of these reaction layers constituted a barrier that effectively suppressed the massive slag penetration and surely reduced the wear rate. Thermodynamic calculations based on simplified and complex condensed phase equilibrium diagrams, were used to further understanding of the corrosion mechanism.     

Dissolution kinetics of alumina in molten CaO–Al2O3–FetO–MgO–SiO2 oxide representing the RH slag in steelmaking process

In order to effectively remove alumina inclusions suspending in ultra-low C steel during RH process, the dissolution kinetics of alumina in molten CaO–Al₂O₃–Fe_tO–MgO–SiO₂ oxide was investigated. A crucible dissolution technique was used where the alumina crucible was allowed to dissolve in the slag of various conditions ((% CaO)/(% Al₂O₃), (% Fe_tO), temperature). The obtained data were interpreted using a kinetic mass transport equation to obtain the mass transport coefficient (k_m) in each condition. Increasing (% CaO)/(% Al₂O₃), (% Fe_tO), and temperature increased the dissolution rate as well as the k_m provided that the slag composition is not close to its saturation composition by alumina. In order to simulate the dissolution of alumina inclusion in the RH slag, which cannot be measured by a confocal scanning laser microscopy (CSLM) at present due to the opaqueness of the slag, the modified invariant interface approximation was employed. Along with the obtained k_m, the viscosity of slag, and a reference experiment using the CSLM, the dissolution kinetics of alumina inclusion in the Fe_tO-containing RH slag was predicted. The time required for the dissolution of alumina inclusions from liquid steel to RH slag was discussed.     

钢渣对硅酸盐水泥熟料形成的影响研究

研究了钢渣代替铁质原料配料对于硅酸盐水泥熟料形成和熟料性能的影响。研究结果表明,钢渣在煅烧温度低于1300℃时对生料易烧性没有促进作用,但是当煅烧温度在1350℃以上时,钢渣对生料易烧性和阿利特的形成均有促进作用。钢渣对熟料岩相结构的影响主要在于钢渣掺入后熟料中阿利特矿物颗粒大小和分布更加均匀,包裹物减少。     

The formation of alite phase by using phosphogypsum and oil shale

This study aims at gaining in-depth knowledge for the cement clinker production by utilizing phosphogypsum (PG) and oil shale (OS) as raw materials. The raw mixtures (Raw Mixes I and II) were burnt in a muffle furnace and then analyzed by X-ray diffraction (XRD) to observe the phases obtained. While minor amounts of alite (C₃S) and major amounts of anhydrite phases were observed with the Raw Mix I containing 40.72% PG refined with water and lime wash by two and three times, respectively (PGR²³), in N₂ atmosphere at 1300 °C, minor amounts of alite (C₃S), free CaO and major amounts of anhydrite phases were formed in air atmosphere at 1300 °C with the Raw Mix II containing 40.72% PG refined with water and lime wash by three and four times, respectively (PGR³⁴). The change of burning medium and the increase in the number of wash with water and lime, respectively, resulted in any difference in terms of the formation of the alite peaks; however, the intensity and the amount of anhydrite peaks were decreased in N₂ atmosphere due to the more conversion of that to the oxide compared to that in air atmosphere.     

钢渣对水泥生料易烧性的影响

针对高Alite熟料矿物体系,采用不同矿物组成的3种钢渣作为铁质原料进行实验室研究,通过化学分析、X射线衍射和岩相分析等手段对原料和熟料进行测试,分析了不同钢渣的矿物组成及对易烧性的影响规律.分析结果表明：钢渣的主要矿物组成因碱度不同而变化,不同种类的钢渣因其矿物组成不同对生料的易烧性影响也不同.从实验室初步研究结果来看,碱度较高并且微量组分较多的钢渣对生料易烧性影响效果较好.在实验室研究成果的基础上,采用钢渣作为铁质原料进行了工业化试验,生产出了fCaO平均含量＜1%、C3S含量＞60%的优质熟料.     

Tobermorite/jennite- and tobermorite/calcium hydroxide-based models for the structure of C-S-H: applicability to hardened pastes of tricalcium silicate, β-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaolin, or silica fume

The purpose of this article is to discuss the applicability of the tobermorite-jennite (T/J) and tobermorite-‘solid-solution’ calcium hydroxide (T/CH) viewpoints for the nanostructure of C-S-H present in real cement pastes. The discussion is facilitated by a consideration of the author's 1992 model, which includes formulations for both structural viewpoints; its relationship to other recent models is outlined. The structural details of the model are clearly illustrated with a number of schematic diagrams. Experimental observations on the nature of C-S-H present in a diverse range of cementitious systems are considered. In some systems, the data can only be accounted for on the T/CH structural viewpoint, whilst in others, both the T/CH and T/J viewpoints could apply. New data from transmission electron microscopy (TEM) are presented. The ‘inner product’ (Ip) C-S-H in relatively large grains of C₃S or alite appears to consist of small globular particles, which are ≈4-8 nm in size in pastes hydrated at 20 °C but smaller at elevated temperatures, ≈3-4 nm. Fibrils of ‘outer product’ (Op) C-S-H in C₃S or β-C₂S pastes appear to consist of aggregations of long thin particles that are about 3 nm in their smallest dimension and of variable length, ranging from a few nanometers to many tens of nanometers. The small size of these particles of C-S-H is likely to result in significant edge effects, which would seem to offer a reasonable explanation for the persistence of Q⁰(H) species. This would also explain why there is more Q⁰(H) at elevated temperatures, where the particles seem to be smaller, and apparently less in KOH-activated pastes, where the C-S-H has foil-like morphology. In blended cements, a reduction in the mean Ca/Si ratio of the C-S-H results in a change from fibrillar to a crumpled-foil morphology, which suggests strongly that as the Ca/Si ratio is reduced, a transition occurs from essentially one-dimensional growth of the C-S-H particles to two-dimensional; i.e., long thin particles to foils. Foil-like morphology is associated with T-based structure. The C-S-H present in small fully hydrated alite grains, which has high Ca/Si ratio, contains a less dense product with substantial porosity; its morphology is quite similar to the fine foil-like Op C-S-H that forms in water-activated neat slag pastes, which has a low Ca/Si ratio. It is thus plausible that the C-S-H in small alite grains is essentially T-based (and largely dimeric). Since entirely T-based C-S-H is likely to have different properties to C-S-H consisting largely of J-based structure, it is possible that the C-S-H in small fully reacted grains will have different properties to the C-S-H formed elsewhere in a paste; this could have important implications.     

Densification mechanism of porous alumina plugs by molten steel with different oxygen levels

To investigate the densification of porous alumina plugs, hydrogen measurements, using the Hydris probe system, were performed in molten steel with different oxygen levels at around 1600?°C. The oxygen contents in molten steel were controlled by Al and Fe-Si alloy additions to 664, 296, 92, 51 and 2.5?ppm, respectively. High oxygen levels (>?=?92?ppm) in molten steel were found to favor the infiltration of steel into porous alumina plug. The infiltrating steel interacts with SiO₂-containing phases and Al₂O₃ inside the plug, forming liquid FeO_n-Al₂O₃-SiO₂ slag and FeAl₂O₄ (hercynite). These newly formed phases, along with the infiltrating steel fill the porous structure of the alumina plugs. As a result, severe densification was observed inside the alumina plugs in contact with molten steel containing high oxygen levels. In comparison, no densification occurred in the plugs contacting with the steel having low oxygen contents of 51 and 2.5?ppm.     

Concrete Produced by Steel-Making Slag (Basic Oxygen Furnace) Addition in Portland Cement

A steel-making slag (basic oxygen furnace) obtained from the Kardemir Steelworks was modified to be used as a clinker additive in the cement industry. This study confirmed that the compressive strength values of concretes produced by addition of these steel-making slags up to 30 mass% were within the values of Grade-325 and Grade-425 steel-making slag cement. This is an attractive alternative for cement manufacturers, because calcined material is expensive, and slag substitutes are very often cheaper, in addition to its low or zero-greenhouse-gas emission.     

Selectively enhanced oxygen vacancies in undoped polycrystalline ZnO as a consequence of Multi-Step Sintering

With a motivation to investigate the simultaneous effect of sintering temperature and sintering time in tandem on defect distributions in polycrystalline undoped ZnO a new technique called Multi-step sintering (MSS) has been deliberately designed. Systematic investigations on structural parameters suggest the rigorous defect propagation along a-axis of the unit cell. We report the unwavering nature of Zinc interstitials (Zn_i) and the complexes of Zn_i with oxygen vacancies (V_o) with sintering temperature. The enhanced and broad green emission in Photoluminescence spectroscopy reveals the existence of surplus V_o in the sample. The band gap narrowing at 800 °C and enhanced Raman modes in Raman scattering experiment confirms the existence of excess oxygen vacancies and make MSS successful technique to tailor the intrinsic defects without any extrinsic doping.     

Effects of slag content,fineness and additive to cement pastes on the corrosion behaviour of embedded reinforcing steel

Previous studies proved that the slag content of the blast furnace slag-Portland cement mix could be increased, while retaining the engineering properties of the produced slag cement pastes within the normal range and increasing the fineness of the mix. The corrosion behaviour of reinforcing steel embedded in the cement pastes giving the optimum mechanical properties was studied using the galvanostatic polarisation technique. The most corrosion-resistant mix has been determined. The effect of adding CaCl₂ to a paste of this mix on the corrosion behaviour of embedded reinforcing steel has been investigated. For the purpose of comparison, anodic polarisation tests were carried out using pastes having the composition of the most corrosion-resistant mix but at the Blaine area of the ordinary slag cement. Portland and normal slag cements were also tested. The threshold concentration of CaCl₂, below which breakdown of steel passivity did not occur, has been determined. The results of this study might have practical implications in the field.     

Effect of modified zeolite on the expansion of alkaline silica reaction

Effect of modified zeolite (MZ) on the ASR expansion was analyzed, and comparison between MZ and other mineral admixtures such as fly ash and ground blast furnace slag was made according to ASTM C441. It is shown that the modified zeolite derived from immersion of natural zeolite(NZ) in 2 N NH₄Cl solution might decrease the concentration of soluble alkalis in pore solution more effectively, as the alkali ions could be exchanged by NH₄⁺ existed in MZ with formation of NH₃·H₂O, as a result, the expansion due to alkali-silica reaction (ASR) was controlled consequently. In ASTM C441 test, the 14-day expansion of the specimen incorporating 5% of MZ was less than 0.1%, while the percentage of the fly ash and blast furnace slag with the same efficiency was about 25% and 40%, respectively. Physical properties of cement incorporating 5% of MZ, such as normal consistency, setting time, bending and compressive strength also met the requirement of the Chinese national standard.     

Erosion mechanism of tabular alumina of various microstructures under different basicity of blast furnace slag

In this study, three types of commercial tabular alumina aggregates with different microstructural characteristics were selected for corrosion tests on blast furnace slags with varying basicities. A corrosion mechanism with different microstructural characteristics is proposed, and the dominant microstructures in high- and low-basicity environments are evaluated. The pore structure was found to have a crucial influence on the dissolution of tabular alumina aggregates in the blast furnace slag. Under low-basicity (0.5–0.7) conditions, a small amount of clustered pore structure was beneficial for obtaining the maximum thickness (40–60 μm) of the isolation layer between the tabular alumina aggregate and slag. Under high-basicity (0.9–1.1) conditions, the circular pore structure tended to form a uniform and stable double-layer isolation structure of calcium hexaaluminate and MgAl₂O₄ spinel.     

Slag corrosion mechanism of lightweight Al2O3–MgO castable in different atmospheric conditions

The slag resistance of ladle lining refractory in different atmospheric conditions is of utmost importance due to the strong variation of atmospheric environment in ladle during the process cycle. In this study, by adopting dynamic induction furnace corrosion test, the corrosion mechanism of lightweight Al₂O₃–MgO castable with different environmental oxygen partial pressure was investigated through macro and microanalysis, XRD, and thermodynamic simulation. The atmospheric condition was set to P (O₂) = 0.21 atm or P(Ar) = 1.0 atm. The attained results showed that a reduced slag corrosion but intensified slag penetration happened at low environmental oxygen partial pressure condition. With P(O₂) = 0.21 atm, Mn and Fe in slag were present in the form of divalent and/or trivalent cations and were incorporated into spinel to form MnFe₂O₄ solutions and MgAl₂O₄ solutions during the corrosion process. Since Fe, Mn ions were largely consumed, liquid with high viscosity formed and the continuing infiltration was suppressed. Under P(Ar) = 1.0 atm, Fe ions in the slag were totally reduced into elemental iron while Mn existed mainly in the state of MnO, and the amount of liquid slag was therefore reduced, leading to significantly weakened corrosion on castable aggregates. Corrosion reaction products under this condition were mainly MgAl₂O₄ and CA₆.