Modification of MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> spinel inclusions in Al-killed steel by Ca-treatment

The modification of MgO·Al₂O₃ spinel inclusions in Al-killed steel by Ca-treatment has been studied by industrial trials and thermodynamic calculations. In the industrial trials, samples were taken systematically during the refining process in which the molten steel was treated by calcium, and the characters of the inclusions were analyzed using scanning electron microscopy (SEM) and energy dispersive spectra (EDS). The effects of Ca-treatment were evaluated by tracking the compositions of the inclusions. The results show that the modification of MgO·Al₂O₃ spinel inclusions by Ca-treatment is effective and the transformation sequence of the inclusions during the refining is Al₂O₃→MgO·Al₂O₃→liquid complex inclusions. The modification of spinel inclusions by Ca-treatment was calculated by FactSage6.0 utilizing its free-energy minimization routines. The results of thermodynamic calculations indicate that spinel inclusions are easier to be modified than Al₂O₃ inclusions and the spinel inclusions in 30CrMo steel would transform to liquid complex inclusions when the content of dissolved Ca in the molten steel exceeds 1×10⁻⁶. Also, the results show that adding more calcium into the molten steel would lower the contents of Al₂O₃ and MgO and increase the CaO content of the inclusions, while the change in SiO₂ content is little.     

Determination of inclusions in liquid steel after calcium treatment

Nozzle blocking was eliminated by calcium-treated liquid steel through changing the chemical and phase composition of alumina inclusions in aluminium-killed steel. Three different methods were applied to determine the composition of inclusions in liquid steel: total oxygen content samples, sampling spoon samples, and “lollipop” steel samples. The results show that calcium modification of liquid steel influences the inclusion composition varying from 2wt% to 14wt% depending on the method used. The composition of inclusions contains mainly Al₂O₃-CaO only, or is associated with SiO₂ or MgO depending on the initial input. The methods used in this study are indicators of the inclusion composition but can be improved to quantify the inclusion size.     

不同浇铸阶段高强钢铸坯洁净度研究

采用氧氮分析、金相法、大样电解法、扫描电镜和能谱分析等方法,对不同浇铸阶段高强钢铸坯(头坯、正常坯、尾坯)的洁净度进行研究。结果表明,与正常坯相比较,头坯和尾坯中T[O]含量均有不同程度的提高;头坯中氮含量大幅升高,而尾坯中氮含量变化很小;头坯、尾坯的显微夹杂物均有所增加,显微夹杂物主要为TiN、Al2O3-TiN和球状钙铝酸盐类复合夹杂物;头坯中大型夹杂物最多(8.77mg/10kg),尾坯次之(5.71mg/10kg),正常坯中最少(1.75mg/10kg),大型夹杂物主要为TiN、SiO2、Al2O3-SiO2和Al2O3-SiO2-CaO,另外还有少量的MgO-CaO夹杂物和含有TiO2的复合夹杂物,这些夹杂物主要来源于结晶器卷渣。     

Top slag refining for inclusion composition transform control in tire cord steel

Controlling conditions for inclusion plasticization were calculated by FactSage, and the steel/slag reaction equilibration time was determined by pre-equilibrium experiments. Laboratory experiments with different top slags were carried out in 90 min, and industrial tests were performed based on the results of calculation and laboratory experiments. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) were used to determine the morphology and composition of inclusions in tire cord steel. It is found that the shape of inclusions can be controlled well, and the composition of inclusions varies in the industrial test as the following transformation route:MnO-Al₂O₃-SiO₂→CaO-Al₂O₃-SiO₂→MnO-Al₂O₃-SiO₂. Inclusion plasticization can be achieved by controlling the binary basicity of top slag (CaO/SiO₂ by mass) around 1.0 and the (Al₂O₃) content in top slag below 10wt%. Under these controlling conditions in the industrial test, almost all of inclusions in the wire rods achieve plastic deformation.     

高铝钢精炼渣的热力学计算与分析

为了在高铝钢中得到最低的溶解氧含量,必须找到CaO-Al2O3-MgO体系中Al2O3活度最低点的位置。因此,利用炉渣结构的共存理论,结合CaO-Al2O3-MgO相图,利用Matlab软件计算了CaO-Al2O3-MgO体系中Al2O3活度。通过对不同模型计算出的CaO-Al2O3渣系中Al2O3活度值比较,表明其变化趋势基本相同。由共存理论对CaO-Al2O3-MgO体系中Al2O3活度进行计算得到,在一定的MgO含量下,随着CaO含量增加,炉渣中Al2O3活度降低;在一定的CaO含量下,随着MgO含量增加,炉渣中Al2O3活度降低,且Al2O3活度最低值在CaO和MgO均达饱和的区域。     

Characteristics of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, MnS,and TiN inclusions in the remelting process of bearing steel

The Al₂O₃, MnS, and TiN inclusions in bearing steel will deteriorate the steel's mechanical properties. Therefore, elucidating detailed characteristics of these inclusions in consumable electrode during the electroslag remelting process is important for achieving a subsequently clean ingot. In this study, a confocal scanning violet laser microscope was used to simulate the remelting process and observe, in real time, the behaviors of inclusions. The obtained images show that, after the temperature exceeded the steel solidus temperature, MnS and TiN inclusions in the specimen began to dissolve. Higher temperatures led to faster dissolution, and the inclusions disappeared before the steel was fully liquid. In the case of an observed Al₂O₃ inclusion, its shape changed from angular to a smooth ellipsoid in the region where the solid and liquid coexisted and it began to dissolve as the temperature continued to increase. This dissolution was driven by the difference in oxygen potential between the inclusion and the liquid steel.     

LF精炼过程中SAE8620钢所含MgO复合夹杂物分析

采用非水溶液电解的方法,萃取分离出SAE8620齿轮钢中含MgO复合夹杂物,利用扫描电镜、能谱分析仪对夹杂物的组成、类型和形貌特征进行分析。结果表明,SAE8620齿轮钢在LF精炼过程中,含MgO复合夹杂物中MgO、CaO含量逐渐增加,SiO2含量逐渐减少,Al2O3含量呈先上升后下降的趋势;夹杂物的形貌多不规则,呈块状且棱角分明;夹杂物类型主要为SiO2-Al2O3-MgO、SiO2-MgO、SiO2-Al2O3-CaO-MgO等,此类夹杂物的尺寸较大、熔点较高,直接影响钢材的质量和使用性能。     

提高高铝钢可浇性工艺技术研究

为了提高高铝钢可浇性,在转炉出钢及LF精炼过程对钢包渣进行改质处理,连铸采用专用高铝钢保护渣,中间包采用塞棒吹氩+密封圈等水口防堵工艺。工艺试验结果表明,夹杂物组成可控制在12CaO·7Al2O3、3CaO·Al2O3低熔点组成区域,浇铸时长为4.5~6h时,液面状况正常,无结团,渣条较少且无硬渣条,铸坯表面质量优良,连续浇铸炉数不低于6炉。     

Dissolution of Al<Subscript>2</Subscript>TiO<Subscript>5</Subscript> inclusions in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags at 1823 K

Al-Ti-O inclusions always clog submerged nozzles in Ti-bearing Al-killed steel. A typical synthesized Al₂TiO₅ inclusion was immersed in a CaO-SiO₂-Al₂O₃ molten slag for different durations at 1823 K. The Al₂TiO₅ dissolution paths and mechanism were revealed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Decreased amounts of Ti and Al and increased amounts of Si and Ca at the dissolution boundary prove that inclusion dissolution and slag penetration simultaneously occur. SiO₂ diffuses or penetrates the inclusion more quickly than CaO, as indicated by the w(CaO)/w(SiO₂) value in the reaction region. A liquid product (containing 0.7–1.2 w(CaO)/w(SiO₂), 15wt%–20wt% Al₂O₃, and 5wt%–15wt% TiO₂) forms on the inclusion surface when Al₂TiO₅ is dissolved in the slag. Al₂TiO₅ initially dissolves faster than the diffusion rate of the liquid product toward the bulk slag. With increasing reaction time, the boundary reaches its largest distance, the Al₂TiO₅ dissolution rate equals the liquid product diffusion rate, and the dissolution process remains stable until the inclusion is completely dissolved.     

高级别管线钢钙处理效果评价标准

对X70管线钢进行了六炉钙处理实验.结果表明:钙处理后管线钢生产的后续工序中钢中钙含量显著下降,夹杂物组成和形貌发生显著变化;二次氧化会降低管线钢钙处理效果,但钢中溶解钙和较高CaO含量的CaO-Al2O3复合夹杂可对钢水二次氧化产生的Al2O3发生改性作用;高级别管线钢钙处理效果与钢中钙含量、氧含量、硫含量、钢水二次氧化程度以及钙处理后续时间等有关,采用钢中Ca含量、[%Ca]Tot/[%Al]s、[%Ca]Tot/T[O]、ACR和[%Ca]Tot/[%S]作为钙处理效果的评判标准均存在缺陷.本文建议钙处理效果评判标准为:①铸坯中心部位或轧后板带中心部位不存在单纯的MnS夹杂;②中间包和结晶器中夹杂的nCaO/Al2O3应该与12CaO.7Al2O3相近;③钙处理后夹杂的nCaO/Al2O3应稍高于12CaO.7Al2O3的夹杂.同时还必须注意钙处理应在最后精炼工序的后期进行,尽量防止钢水的二次氧化.     

Deformation mechanism and quantitative characterization of Al2O3 inclusions in powder metallurgy superalloys

By means of implanting inclusions artificially, the evolution law of three-dimensional morphology and size of Al₂O₃ inclusions in FGH96 powder metallurgy (PM) superalloy during hot iso-static pressing (HIP), hot extrusion (HEX) and hot isothermal forging (HIF) process was investigated by SEM and quasi in situ Micronano-CT. The size change of inclusions during different stages was studied quantitatively, the three-dimensional (3D) morphology of the inclusions was characterized, and the deformation mechanism was proposed. The results showed that the inclusions in powder stage were long stripe or plate-like shape. During HIP, Al₂O₃ inclusions were mechanically bonded to the alloy matrix, and its chemical composition, morphology and size remained unchanged. During HEX, Al₂O₃ inclusions were broken and elongated into chain shape due to shear stress. The quantitative relationship between inclusion size after extrusion and extrusion ratio as well as original inclusion size was established. During HIF, the relationship between 3D morphology, size, orientation and deformation of a single inclusion during forging compression was quantitatively characterized by quasi in-situ micronano-CT for the first time. The above evolution law provides theoretical basis and technical support for improving the purity level of powder turbine disk.     

不同碱度精炼渣系对弹簧钢夹杂物的影响

哈贝马斯对《启蒙辩证法》的否定性解读,使得该著中的拯救逻辑遭到歪曲。由哈贝马斯的解读所延伸出的对《启蒙辩证法》拯救逻辑的美学化和精神分析化的重构与阿多尔诺的哲学思想相矛盾,由此我们必须重新反思哈贝马斯的解读模式。《启蒙辩证法》并非仅仅局限于工具理性批判,它通过有规定的否定达到了对现代启蒙当中现实权力因素的内在批判,它因此并没有彻底否定启蒙也没有重新树立新的乌托邦。对自然的回忆的拯救逻辑意味着思想必须对自身展开批判,以达到重新正视社会现实中的苦难现象,从而解构抽象主体的优先地位。     

Characteristics of inclusions in high-Al steel during electroslag remelting process

The characteristics of inclusions in high-Al steel refined by electroslag remelting (ESR) were investigated by image analysis, scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The results show that the size of almost all the inclusions observed in ESR ingots is less than 5 μm. Inclusions smaller than 3 μm take nearly 75% of the total inclusions observed in each ingot. Inclusions observed in ESR ingots are pure AlN as dominating precipitates and some fine spherical Al₂O₃ inclusions with a size of 1 μm or less. It is also found that protective gas operation and slag deoxidation treatment during ESR process have significant effects on the number of inclusions smaller than 2 μm but little effects on that of inclusions larger than 2 μm. Thermodynamic calculations show that AlN inclusions are unable to precipitate in the liquid metal pool under the present experimental conditions, while the precipitation of AlN inclusions could take place at the solidifying front due to the microsegregation of Al and N in liquid steel during solidification.     

Thermodynamic analysis on the formation mechanism of MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> spinel type inclusions in casing steel

MgO·Al₂O₃ spinel type inclusions in casing steel were analyzed by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). The results show that there are three forms. One is pure MgO·Al₂O₃ spinel, another is the composite oxide of the Mg-Al-Ca-Si-O system, and the third is the complex with oxide as a core covered by sulfide. The formation mechanisms were studied. The influences of slag basicity and vacuum degree on the magnesium content during the vacuum treatment of molten steel and furnace lining in molten steel were calculated with the coexistence theory of slag structure. The results show that the magnesium content increases with the increase in slag basicity and aluminum content in molten steel, and decreases with the increase in CO partial pressure.     

Development of inclusions in 3104 alloy melt during heating and holding treatments

Developments in the contents of different typical inclusions in 3104 alloy melt were described during heating and holding processing. The settling process of inclusion particles was investigated by measuring the contents of inclusions in the surface, center, and bottom layers of the molten metal. In the results, main inclusions observed and determined by Prefil and PoDFA methods are MgO, Al₂O₃, spinel (MgAl₂O₄), and TiB₂ particles or thin films. It is found that some small particles of Al₂O₃ and MgO are transformed into spinel particles, and the formation rate increases as the temperature and the holding period of melt increase. The content of inclusions increases from 3.37 mm2·kg-1 to 7.54 mm2·kg-1 and then decreases to 3.08 mm2·kg-1 after holding for 90 min. This is attributed to a settling phenomenon and a significant increase in settling velocity after holding for 60 min. The content of inclusion particles decreases by means of settlement and flotation in liquid aluminum with an increase in holding time. The theoretical analysis and experiment results are in essential agreement with those from industrial production.     

Formation and thermodynamics of CaS-bearing inclusions during Ca treatment in oil casting steels

Industrial experiments were carried out to investigate the formation of CaS-bearing inclusion during Ca double modification in oil casting steels using polished cross sections and electrolytic extraction. Immediately after Ca addition, the role of newly generated CaS as an intermediate reaction product, which modified the Al_2O_3 inclusion into a liquid calcium aluminate, was confirmed. The formation of transient CaS was attributed to the high surface segregation of S at the liquid steel-calcium vapor interface, where a simple site coverage model based upon the Langmuir adsorption equation was established. Moreover, a CaS outer layer surrounding the liquid calcium aluminate was attained mainly in the tundish, which was distributed unevenly on the surface of liquid particles according to the three-dimensional mapping results. The surface of a well-modified calcium aluminate with higher CaO activity and Al_2O_3 activity under bulk composition conditions in the tundish acted as a favorable site for the generation of CaS. Additionally, CaS could be precipitated directly onto existing inclusions during solidification of the steel, which led to various morphologies of CaS-bearing inclusions in slabs. Furthermore, the phase transformation of inclusions during solidification was strongly influenced both by the S content and the Ca/S ratio in the tundish via thermodynamics.     

AlMnCa合金脱氧和非金属夹杂物控制技术

在1873K下,MoSi2电阻炉内用70mm×100mmMgO坩埚和AlMnCa合金开展了3炉低碳低硅钢脱氧实验.结果表明,用1#AlMnCa脱氧后,钢中溶解氧和全氧含量均较低,终点全氧质量分数为37×10-6.用AlMnCa脱氧后钢中夹杂物大部分为球形的含有CaO的复合夹杂物.用AlMnFe脱氧后,钢中主要是Al2O3或Al2O3-MnO等构成的复合夹杂物,其形状仅有少量为球形.实验终点钢中89.1%的夹杂物尺寸小于10μm,无大于50μm的夹杂物.用1#AlMnCa在25t转炉上进行了6炉TGD07钢脱氧工业试验,脱氧后钢中氧质量分数平均为23.8×10-6,最低达到8×10-6.与未用...     

Clogging behavior of submerged entry nozzles for Ti-bearing IF steel

The nozzle clogging behavior of Ti-bearing IF steel was studied by metallographic analysis, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). According to the experimental results, nozzle clogging primarily appears three layers. There are a lot of large-sized iron particles in the inner layer and mainly slag phase in the middle and outer layers. The principal clog constituents of the inner layer are loose alumina cluster inclusions and granular shaped alumina inclusions, containing iron particles. The clog constituents of the middle layer are mainly dendrite alumina inclusions. The primary phases existing in nozzle clogging are FeO·TiO₂ and FeO·Al₂O₃ besides α-Al₂O₃ and α-Fe. The FeO·TiO₂ phases among the deposits adhere the deposits together firmly enough to lead to the inferior castability of Ti-bearing ultra low carbon steel compared with that of Ti-free low carbon Al-killed steel.     

TT610L大梁钢冷弯裂纹原因分析

TT610L汽车大梁钢板经冷弯加工时在折弯部位外侧出现裂纹,为查找开裂原因,对试验钢进行了力学性能、OM、SEM及EDS分析.结果表明:对沿厚度方向开裂的试样来说,其夹杂物主要为Al2O3和SiO2,对表皮开裂的试样来说,其夹杂物主要为SiO2,由于这些夹杂物的异常偏聚造成了TT610L大梁钢的冷弯开裂.通过连铸工艺的优化,稳定了拉速,有效地解决了试验钢冷弯裂纹开裂问题.     

Novel mechanism for the modification of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based inclusions in ultra-low carbon Al-killed steel considering the effects of magnesium and calcium

Many researchers have explored the inclusion modification mechanism to improve non-metallic inclusion modifications in steelmaking. In this study, two types of industrial trials on inclusion modifications in liquid steel were conducted using ultra-low-carbon Al-killed steel with different Mg and Ca contents to verify the effects of Ca and Mg contents on the modification mechanism of Al₂O₃-based inclusions during secondary refining. The results showed that Al₂O₃-based inclusions can be modified into liquid calcium aluminate or a multi-component inclusion with the addition of a suitable amount of Ca. In addition,[Mg] in liquid steel can further reduce CaO in liquid calcium aluminate to drive its evolution into CaO-MgO-Al₂O₃ multi-component inclusions. Thermodynamic analysis confirmed that the reaction between[Mg] and CaO in liquid calcium aluminate occurs when the MgO content of liquid calcium aluminate is less than 3wt% and the temperature is higher than 1843 K.