Analysis of Largest Sulfide Inclusions in Low Carbon Steel by Using Statistics of Extreme Values

The statistics of extreme values was applied for the determination of the largest sulfide inclusions with different morphology in low carbon steel samples by using both two‐dimensional (2D) observations on the polished cross section and three‐dimensional (3D) observations on a surface of a film filter after electrolytic extraction of the samples. It was found that the globular, rod‐like and dendritic sulfides in the molten steel sample as well as the elongated sulfides in the rolled steel sample can be successfully extracted from the both samples, and analyzed precisely by using extreme value analysis in 3D. Based on the geometrical considerations of the probability for measurement of the true length of rod‐like and elongated inclusions on a cross section, it was found that this probability for inclusions decreases dramatically with an increasing real aspect ratio value of them. Particularly for the determination of the true length for elongated inclusions in the rolled steel sample by 2D investigations on a metal cross section, it is required to be cut investigating section of steel sample within ± 1 degree against rolling direction. Therefore, a 3D observation is considered to be more preferable and accurate than the conventional cross sectional observation in 2D, due to the possibility for the measurements of the real size of them.     

Review of investigations on the thermodynamics of reduction of copper from oxides and sulfides

The thermodynamics of reduction of copper from oxides and sulfides at T = 298–1273 K is considered. The absence of a correlation between the values of ΔG ⁰ of the reduction of copper from oxides and those of their formation is confirmed. The reducing ability of sulfide, elementary sulfur, and sulfite sulfur is investigated with respect to copper in oxides Cu(I) and Cu(II). The presence of an interrelation between the probability of reduction of metal and stability of the reducing agent is established. The possibility of reduction of copper from sulfides with the use of hydrogen and metals, as well as with the use of electron donor properties of sulfide sulfur, is investigated. The conditions for realization of reduction are found.     

Processing oxide-sulfide copper ores using ammonium chloride

The method of processing copper raw material into copper oxide is suggested and investigated. This method is based on the decomposition of copper oxide and sulfide by ammonium chloride with the subsequent leaching of chloride compounds of copper and the precipitation of copper hydroxide from the solution. The thermodynamics is calculated, and a thermogravimetric analysis of the processes is carried out. The kinetics of chlorination of copper and iron sulfides, as well as calcium oxide with ammonium chloride, is investigated experimentally. A process flowsheet of the closed cycle of processing the copper-containing raw material using ammonium chloride is suggested.     

镁处理对钢中夹杂物以及HAZ组织和性能的影响

近年来镁处理的氧化物冶金技术研究非常活跃,为了总结镁处理氧化物冶金研究的最新成果,综述了镁处理对钢中夹杂物以及HAZ组织和性能的影响研究.通过镁处理形成的微米级含镁氧化物和硫化物复合夹杂物可以诱导晶内针状铁素体析出;镁处理过程中形成的纳米析出物,通过对奥氏体晶界的钉扎作用可以抑制原奥氏体晶粒长大,钉扎粒子多为300 n...     

硫系易切削钢中氧含量对硫化物形成的影响

 硫化物夹杂对低碳高硫易切削钢的切削性能具有非常重要的影响,实际生产中希望得到纺锤形或球形的硫化物。钢中的氧含量能显著影响硫化物的种类和形态,主要研究了在铸态和线材中,不同氧含量下,硫化物的成分、粒径、长宽比、圆度的变化情况。结果表明,钢中氧含量的增加,有利于形成纺锤形或球形的硫化物夹杂,在wO=00140%时,能够得到理想的硫化物。     

含Ca汽车控制臂用钢中复合硫化物控制机理

 汽车控制臂由于形状复杂,切削量大,部分汽车控制臂用钢在加入质量分数0.03%硫元素的基础上,又进一步添加了少量钙元素,希望将钢中常见的细长条状MnS转变为纺锤状(Ca, Mn)S以增加零件的切削性能。然而,硫质量分数为0.03%时,钙元素在钢液中的溶解度很低,冷却和凝固过程单一的纯(Ca, Mn)S生成量极少。因此,提出了利用钢液中生成的含CaO类的氧化物来诱导(Ca, Mn)S在其外围形核长大,形成大量双层结构复合硫化物的形貌控制机理。为了研究最佳双层结构复合硫化物形成机理,选取了3炉不同冶炼工艺的汽车控制臂用钢,利用带能谱分析的电子扫描显微镜观察了铸坯和轧材中典型复合硫化物形貌、成分特征,并手动测量了其尺寸,最后利用热力学软件FactSage计算了钢中夹杂物的生成行为。研究结果表明,当钢中不进行钙处理时,复合硫化物内部氧化物主要为Al₂O₃或低MgO比例的镁铝尖晶石,外围硫化物为纯MnS,轧制后成细长条状。当钢中进行钙处理后,可以得到两种不同类型的复合硫化物。一种内部氧化物中CaO组元含量较高,外围硫化物主要是高CaS比例的(Ca, Mn)S,基本不变形,成典型的D类或Ds类形貌;另一种核心氧化物中CaO组元低,外围硫化物主要是低CaS比例的(Ca, Mn)S,轧制后成纺锤状。控制钙处理后钢液氧化物中合适的CaO比例使得氧化物既具有高效的硫化物形核能力,又能促进合适CaS比例的(Ca, Mn)S在其外围生成,这是钢中得到大量纺锤状双层结构复合硫化物的关键。当钢中Ca/S比约为0.07时,外围硫化物中的钙元素质量分数为2%~5%最为理想。     

Morphology and Precipitation Kinetics of MnS in Low-Carbon Steel During Thin Slab Continuous Casting Process

The morphology of manganese sulfide formed during thin slab continuous casting process in low-carbon steel produced by compact strip production （CSP） technique was investigated. Using transmission electron microscopy analysis, it was seen that a majority of manganese sulfides precipitated at austenite grain boundaries, the morphologies of which were spherical or close to the spherical shape and the size of MnS precipitates ranged from 30 nm to 100 nm. A mathematical model of the manganese sulfide precipitation in this process was developed based on classical nucleation theory. Under the given conditions, the starting and finishing precipitation temperatures of MnS in the continuous casting thin slab of the studied low-carbon steel are 1 189 ℃ and 1 171 ℃, respectively, and the average diameter of MnS precipitates is about 48 nm within this precipitation temperature range. The influences of chemical components and thermo-mechanical processing conditions on the precipitation behavior of MnS in the same process were also discussed.     

硫化物形貌对非调质钢力学性能各向异性的影响

为了明确硫化物变性处理前后材料力学性能各向异性的变化规律,利用金相显微镜、SEM、拉伸及冲击试验机研究了工业生产的具有不同硫化物形貌特征(硫化物变性与未变性处理)的35MnVS非调质钢锻态力学性能的各向异性。结果表明,经变性处理后硫化物由未经变性处理的细长条状向短棒状或纺锤状转变,硫化物长宽比在1～8范围内的个数比例由未经变性处理的不到40%提高到变性处理后的90%以上,且分布更加均匀,组织有所细化。硫化物变性处理能够明显地降低试验钢塑性和韧性的各向异性,断面收缩率和冲击功的各向异性分别减小了约10%和34%,横向断口形貌由脆性的朽木分层状向韧窝韧性断裂转变。     

Isothermal precipitation behavior of copper sulfide in ultra low carbon steel

Copper and sulfur are typical residual elements or impurity elements in steel.Sufficient removal of them during steelmaking process is difficult for copper and costly for sulfur.Utilization of copper and sulfur in steel, especially in steel scrap,has been an important issue for a long period for metallurgists.Copper and sulfur may combine to form copper sulfide,which may provide a prospect to avoid the detrimental effects of copper and sulfur in steel.Unfortunately the formation mechanism of copper sulfide in steel has not been completely clarified so far. In the present paper,solution treatment of samples containing copper and sulfur are firstly performed at 1623 K for 2.7×10~3 s followed by quenching into water.The samples are then isothermally heat-treated at 673 K,873 K, 1073 K,1273 K and 1373K for different time followed by quenching into water again.The size,morphology, constituent and crystallography of sulfide precipitates in these samples are investigated by scanning electron microscope(SEM) and TEM equipped with EDS.Fine copper sulfides(less than 100 nm) are observed to coexist with silicon oxide in samples even isothermally heat-treated at 1 373 K for 1.44×10~4 s;Film-like copper sulfides are generally observed to co-exist with iron sulfide in all samples;Plate-like copper sulfides are observed especially in sample isothermally heat-treated at 1 073 K for 1.44×10~4 s.The formation mechanisms of these copper sulfides have been discussed.     

Flotation of Sulfide Components of Copper Ore in the Presence of n-Dodecane

Influence of n-dodecane aqueous emulsion on flotation of sulfide minerals present in the copper ore from the Legnica-Glogow Copper Basin (LGOM), carried out on the laboratory scale, was investigated. Five flotation experiments performed in the presence of different doses of n-dodecane were conducted and compared. Next, mineral analysis of selected flotation products were conducted and discussed. The best flotation selectivity was obtained for bornite, tennantite and chalcocite using 600 g/t of n-dodecane. In the case of non-copper sulfides, the maximum selectivity was observed for sphalerite and galena. Measurements of the rest potential of copper sulfide conducted to explain the differences between recoveries of each sulfide mineral were performed. It was observed, that with increasing sulfide rest potential, the recovery was decreasing. The study provided information hitherto poorly available in literature on flotation of sulfides from the LGOM area with n-dodecane.     

Behavior of sulfide inclusions during thermomechanical processing of AISI 4340 steel

The morphological and compositional modifications of sulfides in AISI 4340 low alloy steel, in which the sulfur level was raised to about 0.1 pct, were studied during hotrolling at 1223 K followed by homogenization at 1583 K for various lengths of time. The relative plasticity of sulfide inclusions with respect to the steel matrix increased with cooling rate during solidification, hence with iron content. The number of sulfides first increased with homogenization time, reached a maximum and subsequently decreased. Inclusion size exhibited the opposite variation. The sulfide matrix interface area per unit volume of sulfide decreased continuously with homogenization time. These variations were in agreement with observed morphological modifications of sulfides during homogenization. During early stages of homogenization the flattened and elongated sulfide plates in the as-rolled material coarsened and became cylindrical. The cylindrical sulfides, broken into segments which spheroidized and coarsened with time, assumed finally a faceted morphology. During homogenization iron was rejected from the sulfide phase into the surrounding matrix, whereas manganese was accepted, causing the formation of manganese depleted zone around the inclusions. This paper is based on a Ph.D. Thesis submitted by Y. V. Murty to the Department of Metallurgy, University of Connecticut.     

铜萃余液综合回收铜、锌试验研究

采用硫化沉淀工艺对铜萃余液中的铜、锌等有价金属进行了回收试验研究,考察了硫化沉淀pH值、硫化钠加入量和硫化反应时间等因素以及铜、锌共沉淀和分步沉淀对铜、锌回收率和精矿品位的影响。试验结果表明,铜、锌分步沉淀时,萃余液pH=2．5,加入1．2倍硫化钠用量,反应20min,沉铜效果最好,铜回收率98．33％,精矿铜品位38．88％;pH=3．5,加入1．4倍硫化钠用量,反应20min,沉锌效果最好,锌回收率为98．36％,精矿锌品位33．17％。该工艺可有效回收萃余液中的铜、锌等有价金属。、     

Slags and mattes in vanyukov’s process for the extraction of copper

Slags and matte in Vanyukov’s process, an autogeneous method of processing sulfide concentrates of nonferrous metals used in a specially designed furnace at the Balkhash copper-smelting plant (Kazakstan), have been characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The liquid matte was shown to have contained 3.6 wt pct of slag inclusions and about 4 wt pct of magnetite. The solid matte is a mixture of sulfide phases. The liquid-waste slag was shown to have contained 0.6 wt pct of matte inclusions and about 3 wt pct of magnetite. The silicate field of the solid slag consists of two phases, identified as iron orthosilicate and iron metasilicate. It was shown that most slag formation occurred before the emulsion reached the settling tank of the furnace. Thermodynamic calculation of the exchange reactions for the oxide and sulfide components of the slag showed that zinc and lead dissolved in the slag are present mainly as oxides, but with only a small part (10 to 20 pct) in the form of sulfides. By contrast, copper is present in the slag as dissolved sulfides and also as matte reguli. The results of these thermodynamic calculations are supported by the experimental data.     

钙处理对成品无取向硅钢夹杂物特性的影响

通过取样检测结合热力学计算,分析了钙处理对成品无取向硅钢中夹杂物特征及硫化物夹杂的析出机制的影响。结果表明,钢中尺寸大于3μm的有害夹杂物主要是AlN、MgO-SiO2、CaO-Al2O3-SiO2类复合夹杂物及其与MgS、MnS、CaS的复合析出物。钙处理钢中没有检测到单独的Al2O3、SiO2及铝酸钙类夹杂物。钙处理钢中形成的液态3CaO·Al2O3、MgO·SiO2和Al2O3夹杂物被精炼渣吸收,改性去除了钢中大尺寸Al2O3夹杂物。钙处理钢中尺寸大于3μm的氧化物夹杂主要是含CaO和(或)CaS的Al2O3-SiO2类夹杂。硫化物在MgO-SiO2类氧化物表面的析出有利于其形貌趋于规则。钢中不同形貌的AlN夹杂物呈多尺度分布,钙处理对大尺寸AlN的析出特性影响不大。氧硫化物及其与AlN复合析出并定向长大的过程,与其晶体结构有关。氧化物夹杂的硫容量决定了其与硫复合的难易程度。钙处理钢中CaS在氧化物表面呈局部包裹析出和局部吸附析出。     

Phase equilibria in the metal-sulfur-oxygen system and selective reduction of metal oxides and sulfides: Part I. The carbothermic reduction and calcination of complex mineral sulfides

The difference in the standard Gibbs free energy for the formation of any two oxides or sulfides is the chemical potential for selective reduction of metals from complex minerals. The magnitude of the Gibbs free energy difference is shown by plotting the univariant relationships for relevant sulfides and oxides. In this investigation, three examples of mineral sulfides are considered, and the experimental results are compared with the predicted thermodynamic calculations. These examples include the reduction conditions for nickel and iron sulfides and pentlandite (Fe,Ni)₉S₈ and chalcopyrite (CuFeS₂) minerals. The reduction behavior of mineral sulfides, such as those of nickel, cobalt, iron, and copper, is illustrated by referring to both the sulfide and alloy phase equilibria. In particular, the solution thermodynamic properties of the metallic phase equilibria are featured for determining the physical chemistry of preferential or selective reduction of the metal oxides and sulfides. The mechanism for the reduction of the aforementioned sulfide minerals is explained with the aid of the governing phase equilibria for the calcination process. The results from the carbothermic reduction of sulfide minerals are also compared. The important roles of lime and calcium sulfate in controlling the emission of sulfurous gases during the reduction reaction are explained. A qualitative analysis of reduction reactions of nickel and iron sulfides is reviewed to provide a comparison of the mechanism for complex nickel-bearing minerals. The importance of these results in producing alloy and pure metallic phases is also examined.     

Thermodynamics for Precipitation of CaS Bearing Inclusion and Their Deformation During Rolling Process for Al‐Killed Ca‐Treated Steel

Thermodynamics for CaS bearing inclusions precipitation and their deformative behaviors during compact strip production (CSP) rolling process for Al‐killed calcium treatment steel were researched using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) combined with the results of industrial trials. In addition, thermodynamic software FactSage was applied to calculate component activities of an inclusion and to analyze properties of sulfide‐oxide duplex inclusions. It is possible for CaS bearing inclusion precipitation during secondary refining and continuous casting in two manners: the first is that Ca and S react directly after calcium treatment; the other is as the well modified calcium aluminates react with dissolved sulfur and aluminum in liquid steel. Correspondingly, two types of sulfide‐oxide duplex inclusion were observed in casting slab. For the first type duplex inclusion, nearly no chemical reactions occur between outer CaS layer and solid inclusion core, thus the outer CaS rich layer is easily separated even taken off from the inner core during rolling process, and a crack may be generated correspondingly. The later one performs a better deformation during rolling process.     

镁改质对Y1Cr13易切削不锈钢中硫化物的影响

 为了研究镁对Y1Cr13易切削不锈钢中硫化物的改质作用,采用金相显微镜、Image-Pro Plus图像分析软件、扫描电子显微镜、FactSage热力学软件分析了添加镁前后钢中硫化物的分布规律、整体形貌以及析出条件。结果表明,向Y1Cr13易切削不锈钢中加入一定量的镁可将Al₂O₃改质成细小弥散的Al₂O₃·MgO,钢中典型硫化物MnS在钢液凝固末期会以其为形核质点析出,析出温度为1 448 ℃,形成的MnS-Al₂O₃·MgO复合夹杂物具有外软内硬的结构,这种结构使得MnS在轧制过程中不易变形,在轧材中仍然保持球状或椭球状,并且随着镁质量分数的提高,Al₂O₃·MgO的析出温度区间越大,其析出量越多,对MnS形态的改善也越明显;硫化物评级由未改质前的细系5.5、粗系4.5下降到改质后的细系3.5、粗系1.0,并且随着其质量分数的提高,评级进一步下降至细系2.5、粗系0.5,轧材成材率由原来的70%提升至90%。因此,适当提高镁的添加量有利于提高其改质效果。     

Precipitation Characteristic of Sulfide in Medium-Carbon Sulfur-Containing Steel

Herein, the precipitation characteristic of sulfide is investigated by confocal laser scanning microscopy for a typical medium-carbon sulfur-containing 42CrMo steel under different cooling rates (100, 200, 600 °C min⁻¹) and sulfur contents (0.0018 and 0.0249 wt%). Thermodynamic calculations show that increasing sulfur content can enlarge the liquid–solid-phase zone and enhance the initial precipitation temperature of MnS in 42CrMo steel. Phase diagram of Mn–Mo–S demonstrates that the sulfides contain Mn, Mo, and S elements can be formed. The experimental results indicate that with an increase of the sulfur content from 0.0018 to 0.0249 wt%, more (Mn, Mo)S sulfides are formed in the steel due to the significant enhancement of supersaturation. Moreover, it is revealed that the average size of (Mn, Mo)S inclusions decreases from 16.11 to 3.55 μm when the cooling rate increases from 100 to 600 °C min⁻¹. The typical of large-size rodlike (Mn, Mo)S inclusions is observed in a low cooling rates of 100–200 °C min⁻¹. As the cooling rate increases to 600 °C min⁻¹, smaller globular (Mn, Mo)S inclusions with an average size of 3.55 μm are appeared which can act as a core to promote the ferrite formation.     

易切削不锈钢1Cr17MoS的硫化物形态对力学性能的影响

易切削不锈钢1Cr17MoS中硫化物随冶炼控制方式的差异会呈现不同的形态。采用正常冶炼方式对1Cr17MoS钢进行锻制,硫化物呈细长条形状,长度一般为50～80 μm,长宽比为5～12;夹杂物尺寸为1～5 μm,大部分夹杂物小于3 μm。在冶炼中通过添加微量元素使1Cr17MoS钢经过锻制后的硫化物呈纺锤状、点球状,长度为10～30 μm,长宽比为2～5;夹杂物尺寸为3～20 μm,大部分夹杂物为10～20 μm。通过对不同硫化物形态的1Cr17MoS钢进行纵向和横向拉伸试验,结果表明,2种形态下1Cr17MoS钢的纵向拉伸断口均为韧窝断口,韧窝数量和大小受硫化物数量和宽度的影响,其形态与力学性能没有明显关系;1Cr17MoS的横向拉伸断口以准解理断口为主,还存在部分韧窝断口。传统冶炼方式中,冶炼过程未经过硫化物形态处理,细长条状硫化物破坏了试验钢基体的连续性,加速了横向拉伸的脆性断裂。而经过硫化物形态处理的冶炼方式中,纺锤状和点球状硫化物以韧窝形态出现,保留了试验钢的塑性特征,使其具备较好的横向拉伸性能。     

Copper,Boron, and Cerium Additions in Type 347 Austenitic Steel to Improve Creep Rupture Strength

Type 347 austenitic stainless steel (18Cr-12Ni-Nb) was alloyed with copper (3 wt pct), boron (0.01 to 0.06 wt pct), and cerium (0.01 wt pct) with an aim to increase the creep rupture strength of the steel through the improved deformation and cavitation resistance. Short-term creep rupture strength was found to increase with the addition of copper in the 347 steel, but the long-term strength was inferior. Extensive creep cavitation deprived the steel of the beneficial effect of creep deformation resistance induced by nano-size copper particles. Boron and cerium additions in the copper-containing steel increased its creep rupture strength and ductility, which were more for higher boron content. Creep deformation, grain boundary sliding, and creep cavity nucleation and growth in the steel were found to be suppressed by microalloying the copper-containing steel with boron and cerium, and the suppression was more for higher boron content. An auger electron spectroscopic study revealed the segregation of boron instead of sulfur on the cavity surface of the boron- and cerium-microalloyed steel. Cerium acted as a scavenger for soluble sulfur in the steels through the precipitation of cerium sulfide (CeS). This inhibited the segregation of sulfur and facilitated the segregation of boron on cavity surface. Boron segregation on the nucleated cavity surface reduced its growth rate. Microalloying the copper-containing 347 steel with boron and cerium thus enabled to use the full extent of creep deformation resistance rendered by copper nano-size particle by increase in creep rupture strength and ductility.