Kinetics of inclusion precipitation during steel solidification

The precipitation of non-metallic inclusions (complex oxides, sulphides, nitrides …) during steel solidification is analysed using the multiphase equilibrium code CEQCSI and a nucleation and growth model. The CEQCSI code is based in part on the Irsid slag model, and it provides an evaluation of the composition of inclusions formed at equilibrium, as well as guidelines for industrial treatments in order to reach desirable compositions in semi-killed steel grades. The nucleation and growth model can be applied to the formation, during steel solidification, of stoichiometric compounds or liquid oxide inclusions. Two particularities of this kinetic model are that nucleation and growth are treated simultaneously, and they compete in consuming the supersaturation at each moment, and that a mixed controlled growth model transport/interfacial kinetics at the precipitate/liquid steel interface is considered. The predicted size distribution of TiN precipitates formed in two steel grades is in good agreement with the results of laboratory experiments. In the case of liquid oxide precipitation, the first calculations indicate that the composition of inclusions can be significantly different from that of inclusions assumed to precipitate under equilibrium conditions.     

Computational Thermodynamic Study of Inclusions Formation in the Continuous Casting of SAE 8620 Steel

The general purpose of this work is a thermodynamic study of non‐metallic inclusions in the CC tundish for SAE 8620 steel. Specific purposes are: (1) Obtaining the phases formed and their composition in inclusions by applying computational thermodynamics for SAE 8620 steel; (2) Establishing conditions of steel composition for the improvement of SAE 8620 castability, including the plant validation in terms of the castability index. Thermodynamic studies were performed with the commercial software FactSage and databases. Simulations were carried out by the global chemical composition of SAE 8620 steel in the CC tundish, resulting in both steel composition and non‐metallic inclusions (oxides and sulphides) at the desired temperature. Furthermore, results showed both different solid oxides and liquid phase formation in inclusions by varying calcium content in the steel. Thus, it was possible to determine the inclusion composition as a function of aluminium and calcium content of SAE 8620 steel, and moreover, to establish a range of calcium content in which the inclusions are predominantly formed by liquid phase. In addition, the percentages of liquid and solid phase in inclusions, as well as, oxide compositions could be calculated.     

非钙处理铝脱氧车轮钢夹杂物形成及变形行为

 通过采用扫描电镜对BOF-LF-RH-CC非钙处理工艺生产车轮钢系统取样样品中夹杂物的形貌、尺寸及组成的分析,研究了精炼和凝固过程氧化物夹杂的形成、上浮去除和析出过程,以及轧制过程夹杂物的变形行为。研究发现,在非钙处理条件下,LF精炼过程会形成大量MgO-Al2O3夹杂和CaO-Al2O3夹杂,并且在RH精炼过程中存在MgO-Al2O3夹杂向CaO-Al2O3夹杂的转变过程,最终导致铸坯中出现低变性CaO-Al2O3夹杂;在软吹和镇静过程中,炉渣或空气对钢液的二次氧化与钢液中夹杂物上浮去除存在动态平衡;在钢液凝固过程中,固液界面的Al2O3等氧化物夹杂为MnS的析出提供了异质形核点,形成半包裹状的Al2O3-MnS类复合夹杂物;在轧制过程中,团簇状Al2O3夹杂容易被轧碎在板卷中形成点链状,高熔点半包裹的Al2O3-MnS类复合夹杂物被轧制成小尾巴状,而低熔点的CaO-Al2O3-MnS的复合夹杂形成连续的条状。     

37Mn5钢管内壁鼓包缺陷分析

37Mn5钢管热轧矫直后在内管壁出现鼓包缺陷,为了查找鼓包产生原因,采用显微镜和扫描电子显微镜等设备对鼓包的形貌、微观组织、化学成分及鼓包区域的形貌等内容进行了分析。结果表明:钢管化学成分和组织正常,钢管基体和鼓包区域含有较多相同的夹杂物,夹杂物均含有Ca、O、Fe、Na、K、Mg 等元素,这些元素组成含有多种氧化物和结晶器保护渣的大尺寸复合型夹杂物。进而得知钢管的鼓包缺陷产生原因:由于钢管内存在大量此类复合夹杂物在穿管过程中和钢管基体间的接触层面脱离并逐渐萌生裂纹,裂纹在比较大的周向压力作用下向内壁凸起并形成鼓包。     

钙处理对20CrMnTiH齿轮钢中非金属夹杂物的影响

铝脱氧齿轮钢中易生成大量的高熔点Al₂O₃类夹杂物,容易导致水口结瘤及钢材性能恶化,目前较常采用钙处理将钢中高熔点的Al₂O₃类夹杂物改性为低熔点的钙铝酸盐类夹杂物。合理的钙处理可以减轻水口结瘤并提高连铸过程钢液的可浇性,工业试验研究了喂钙前钢液中T.Ca含量、喂钙速度、喂钙量、净空高度及渣厚等参数对齿轮钢中钙收得率的影响,并在1.5 m·s?1的喂钙速度条件下研究了不同喂钙量对钙处理过程中齿轮钢中非金属夹杂物改性的影响。研究结果表明,当喂钙前钢液中T.Ca的质量分数小于10×10?6,喂钙速度为1.5 m·s?1,适当降低喂钙量和净空高度和渣厚,钢液中钙收得率均高于20%。当钢液中T.Ca的质量分数高于17×10?6时,钢中生成大量高熔点CaS型夹杂物,三元相图中夹杂物的平均质量分数远离液相区。随着齿轮钢中T.Ca含量的增加,夹杂物的平均尺寸和数密度逐渐增加。热力学计算结果与工业试验钙处理对钢中非金属夹杂物改性效果具有较好的一致性。      

二次氧化过程IF钢中间包中夹杂物演变行为

 为了研究中间包二次氧化对IF钢洁净度的影响,针对中间包连铸过程不同时刻IF 钢钢液成分和夹杂物的性质进行系统的检测分析,结合热力学计算,揭示IF钢二次氧化过程中夹杂物的演变机理。发现开浇过程中的二次氧化主要是由于吸收空气造成的,使得夹杂物中的Al₂O₃夹杂物质量分数增加。这些增加的Al₂O₃一部分是均质形核导致钢中生成了更多小尺寸的Al₂O₃夹杂物;另一部分是非均质形核导致原来的Al₂O₃-TiO_x复合夹杂物表面形成了一层纯的Al₂O₃层,同时使得夹杂物尺寸变大。     

Relationship between Oxygen Chemical Potential and Steel Cleanliness

Control of the oxygen activity andits content inthe molten steel are the main factors in the produc-tion of clean,high quality and homogeneous steel[1].Deoxidation of the steel includes reducing both theoxygen activity and total oxygen in molten steel.Sin…     

Analysis of formation mechanism about Ca-Mg-Al spinel type inclusions in cold thin rolling sheet

The cracking of ultra low carbon Al deoxidized killed steel during cold rolling and stamping was analyzed by SEM and EDS. It was determined that the main inclusions consisted of Al2O3, CaO and MgO, which are Ca-Mg-Al spinel inclusions. The composition of the ladle top slag and corrosion of the tundish covering agent and coating were investigated, and the source of inclusions was discussed. It was found that Al2O3 is the product of deoxidation and secondary oxidation. The source of CaO is the reaction between CaO of higher activity in slag with acid soluble aluminum Als in molten steel, which leads to the entry of element Ca into molten steel and the formation of CaO with oxygen in molten steel. The reaction of MgO, which comes from MgO in tundish covering slag and MgO corroded from tundish coating, with Als in molten steel leads to element Mg entering molten steel, and then MgO is formed with oxygen in molten steel.     

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...     

冷轧薄板钙镁铝尖晶石类夹杂物成因分析

摘要：针对超低碳铝脱氧镇静钢在冷轧冲压过程中出现开裂情况进行了电镜和能谱成分分析,确定了主要夹杂物含有Al2O3、CaO及MgO,为钙镁铝尖晶石类夹杂物。研究了该问题炉次的钢包顶渣组分、中间包覆盖剂及涂层侵蚀情况,讨论了夹杂物的来源。结果显示,Al2O3为脱氧产物及二次氧化的产物;CaO的来源为渣中较高活度的CaO与钢水中酸溶铝Als反应导致Ca元素进入钢水,进而与钢水中的O生成CaO。MgO主要为中间包覆盖剂氧化镁及涂层融蚀的氧化镁进入中间包渣系,与钢水中的Als反应导致Mg元素进入钢水,再与钢水中的O生成MgO。     

Optimization of Intensified Silicon Deoxidation

For demanding wire applications steel cleanliness should be very high and the inclusions inevitably found in steel should be harmless. This means strict control of inclusions' size, quantity, and composition, pursuing deformable inclusions in rolling conditions. Primary inclusions are formed during steel treatment in the ladle. Most of these are removed to the ladle slag or on the lining. However, the rest of the inclusions still remain through the successive process stages, and some new inclusions are formed during casting and solidification. Conventionally, deformable inclusions are produced by Si–Mn deoxidation resulting in MnO–SiO₂–Al₂O₃ inclusions. This leaves, however, the oxygen content too high for demanding applications. In order to get really clean steel, the Si deoxidation needs to be strengthened by lowering the activity of SiO₂ forming in steel. This can be done by bringing the steel in intimate contact with a slag containing SiO₂–MnO–Al₂O₃ and additionally CaO and some MgO. With this kind of intensified Si deoxidation it is possible to produce steels with low oxygen content having inclusions that will elongate at rolling. In this paper thermodynamic examination of potential slag systems and compositions to equilibrate with steels having medium carbon and high silicon were scrutinized. The optimal slag composition for producing low‐O steels with deformable inclusions was evaluated by using FactSage thermodynamic calculation program. The lowest SiO₂ activities at the region in which slag is still liquid at 1400°C, can be found when slag composition is approximately 36–40 wt% SiO_2, 6–18 wt% Al₂O_3, 30–40 wt% CaO, 6–8 wt% MgO, and 2–4 wt% MnO. Industrial heats using intensified Si deoxidation and slag based inclusion engineering were produced in a steel mill with 60 tons heat size. Inclusions and slag compositions were in satisfactory accordance with the theoretical examinations, though some scattering was discovered.     

非金属夹杂物三维形貌及其包裹的非夹杂物颗粒物来源分析

钢中非金属夹杂物的分离提取过程,需要解决外来因素的干扰问题,准确判断是否来源于钢中,是夹杂物检测与表征方法的重点。分析了在实验室环境下,以U75V重轨钢为代表,采用酸溶法和非水溶液电解法分离提取出钢中非金属夹杂物,利用扫描电镜对夹杂物的基本形貌和成分进行了系统的分析研究。结果表明,利用电磁搅拌装置的酸溶法能有效得到耐酸类的夹杂物形貌和成分,其最佳溶液配比为盐酸(1+1);采用非水溶液电解法能够得到耐酸类和不耐酸类的微米和纳米尺度的非金属夹杂物,电解时间控制在8～10 h。与此同时,U75V重轨钢的酸溶和电解法分析结果表明,夹杂物中存在大尺寸不规则状的颗粒物,经分析判断该类是外来的颗粒物,被定义为非夹杂物,主要来源于空气中、自来水、干燥箱和电解槽内等,其成分为MgO、CaO、SiO₂和Al₂O₃,与钢中的氧化物夹杂物成分接近,从而对生产过程中控制夹杂物的措施易造成不准确的指导。因此,在分离提取钢中夹杂物的过程中,需要严格的保护操作,杜绝不利因素的干扰,准确得到钢中夹杂物的三维形貌、尺寸、化学成分等详细信息,能够为工艺改进或实验研究提供有效的支持。     

Effect of vanadium on modification of inclusions in Mn- and Si-deoxidized steel during heat treatment at 1473 K

The effect of vanadium (V) on the modification of oxide inclusions in steels with different concentra-tions of Mn, Si, and V was determined before and after heat treatment at 1473 K.Changes in the morphology, size, and composition of these inclusions were analyzed.Equilibrium relations between the inclusions and steels at 1873 K and 1473 K were calculated using available thermodynamic data to roughly approximate the stable oxide inclusions in the steels.The results revealed that the concentra-tions of V and Si in the steel are critical for controlling the modification of the inclusions during heat treatment at 1473 K.MnO-SiO2-type oxide inclusions gradually transformed into MnO-V2O3-type or Mn-SiO2- and MnO-V2 O3-type inclusions in low-Si high-V steels heat-treated for 60 min.In addi-tion, the morphology of the inclusions changed from spherical to irregular.A Si-accumulated zone and a V-depleted zone formed close to the interface in the steel matrix.The experimental and calcula-tion results indicated that, during the heat treatment, an interface chemical reaction occurred be-tween the Fe-Mn-Si-V steel and the MnO-SiO2-type oxide inclusion.     

非调质钢中夹杂物生成热力学

为了研究非调质钢中非金属夹杂物的演变规律和生成条件,实现对钢中夹杂物的精准控制,揭示了非调质钢冶炼全过程非金属夹杂物的形貌和成分转变。初始钢中夹杂物主要为镁铝尖晶石夹杂物,随着冶炼反应的进行,钢中逐渐出现部分含有CaO和CaS的夹杂物,同时还伴有MnS析出相生成。系统地通过热力学计算了1 873 K下一元脱氧钢中Al、Ti、Mg和Ca与O的平衡关系,二元脱氧钢中Al-Mg、Al-Ti、Al-Ca和Al-Mg-Ca脱氧夹杂物的生成区域。可为非调质钢脱氧过程脱氧剂的加入、钢液中溶解氧含量的控制以及非调质钢中不同夹杂物的生成和控制提供理论指导。     

铝含量对TWIP钢中夹杂物特征及AlN析出行为的影响

采用扫描电镜、X射线能谱仪以及扫描电镜配置的夹杂物自动扫描统计软件(INCAFeature)表征了Fe-Mn-C(-Al)系TWIP钢中夹杂物的成分、形貌和数量,考察了Al质量分数在0.002%~1.590%的四种TWIP钢中夹杂物的特征和Al含量对AlN析出行为的影响.并在此基础上,采用了适合TWIP钢中高锰高铝特点的热力学参数对AlN夹杂物进行了系统的热力学分析.研究表明,在含有相似N质量分数(0.0078%~0.0100%)的TWIP钢中,当钢中Al质量分数升高至0.75%时,AlN夹杂物开始在钢中析出,并在MnS(Se)-Al₂ O₃上局部析出形成MnS(Se)-Al₂ O₃-AlN复合夹杂;当Al质量分数升高至1.07%时,热力学计算表明AlN已经可以在TWIP钢液相中形成,经不断长大后在MnS(Se)夹杂物表面局部析出形成MnS(Se)-AlN复合夹杂物;在Al质量分数为1.59%的TWIP钢中,AlN的平衡析出温度比其液相线温度高出42℃,在液相中形成的AlN可以作为异质核心,MnS(Se)夹杂在其表面包裹形成MnS(Se)-AlN复合夹杂物.另外,在Fe-18.21% Mn-0.64% C-1.59% Al体系的TWIP钢中,AlN在液相中析出所需的最低氮的质量分数仅为0.0043%.因此,在TWIP钢的冶炼过程中,应尽可能的降低钢中的氮含量,避免生成过量的AlN夹杂.      

石油钻杆钢冶炼过程中夹杂物的析出和衍变

系统分析了国内某钢厂复合脱氧工艺下Cr Mo石油钻杆钢夹杂物在EAF-LF-VD-CC流程中的析晶和衍变规律.由于铝酸盐的上浮,LF冶炼前钢中T[O]含量较低,冶炼过程中氮含量逐渐升高.电镜下钢中大尺寸夹杂物（50μm左右）只出现在LF-VD阶段,主要为低熔点的硅锰酸盐、包含Na₂O的混合物和含有少量CaO的镁铝尖晶石,中间包阶段大尺寸夹杂物完全消失.小尺寸夹杂物（<10μm）出现在精炼全过程中,主要成分是Mg、Al、Si和Ca的复合氧化物、CaS以及二者的复合物,LF冶炼前到中间包阶段小尺寸夹杂物粒径相似,铸坯中其粒径稍微增加.随着精炼过程的进行,钢中小尺寸夹杂物的成分逐渐向复合氧化物的低熔点区域转移,夹杂物中CaO和MgO含量存在竞争关系.铸坯中大型夹杂物（>100μm）包括卷渣引起的复合夹杂,耐材剥落产生的MgO-CaO夹杂和钢液内生的铝酸盐夹杂.内生铝酸盐与精炼过程中小尺寸夹杂物成分相似,外层包覆Ca S,轧制过程中容易破碎成链状引发钻杆钢裂纹.建议适当延长VD处理后钢液的镇静时间,以去除钢中大型铝酸盐夹杂,提高钻杆钢质量.      

Change of Inclusion Characteristics during Vacuum Degassing of Tool Steel

The inclusion characteristics were studied during vacuum degassing by interrupting the operation at five different times after the start of operation. Slag and steel samples were collected and thereafter assessed with respect to steel and slag composition, total oxygen content, size distribution of inclusions and chemical composition of inclusions. The main conclusion is that the number of inclusions in the different size classes as well as the total oxygen content seem to reach a minimum value after around ten minutes of vacuum degassing. Furthermore, it seems to be a consistent trend that, during vacuum degassing, the top slag influences the inclusion composition.     

不同铝含量的脱氧剂对钢液洁净度的影响

铝具备较强的脱氧能力,被广泛应用于炼钢过程中钢液的脱氧。然而铝脱氧产生的高熔点、大尺寸Al₂O₃夹杂物不仅会严重降低钢液的洁净度、恶化钢材韧性和疲劳寿命,还容易造成水口结瘤,影响连铸工艺的顺行。考虑到局部过饱和度对夹杂物的形核和长大等有着重要的影响,采用纯铝和Fe-30%Al合金(质量分数)对钢液进行脱氧,且实际加入的铝量保持一致,通过对不同脱氧时间(30、60 s)的钢液成分和夹杂物特征进行分析,研究了不同铝含量的合金对钢液洁净度的影响。结果表明,相较于纯铝脱氧,Fe-30%Al合金在相同时间节点下脱氧效果更好,合金中铝元素溶解速度更慢。此外,在目前试验条件下使用纯铝脱氧的钢样中夹杂物尺寸可达到9μm,而使用Fe-30%Al合金脱氧的夹杂物尺寸最大只有4μm。采用纯铝脱氧60 s后钢中夹杂物平均尺寸为Fe-30%Al合金脱氧的1.35倍,且单位面积夹杂物数量多了23%。两种合金在脱氧过程中残留在钢液中的夹杂物均以多面体夹杂为主,并有少量碰撞聚集形成的松散型团簇状夹杂。使用Fe-30%Al合金脱氧比纯铝脱氧更有利于钢液洁净度的提高,这取决于两...     

钢液凝固与冷却过程及固体钢加热过程钢中非金属夹杂物成分动力学转变的几个概念和特征曲线

利用钢中非金属夹杂物成分变化的集成模型,介绍了夹杂物成分随时间和冷却速率的变化,提出了夹杂物成分转变分数的概念,然后介绍了夹杂物成分转变的等温转变曲线（TTT）、连续冷却转变曲线（CCT）和等径转变曲线（TDT）的概念及应用.该集成模型考虑了钢液流动、传热、凝固和元素偏析,也考虑了钢与夹杂物反应的热力学和动力学.然后以管线钢、重轨钢和轴承钢为例,进一步分析讨论了钢液凝固与冷却过程中的冷却速率、固体钢加热过程中的加热温度和加热时间、钢成分以及夹杂物尺寸等参数对夹杂物成分转变的影响.这些概念和特征曲线能够直观展示在钢液凝固冷却过程及固体钢加热过程钢中非金属夹杂物的成分转变,将钢中夹杂物的控制方略从钢液拓展到固体钢中.     

帘线钢生产过程中氧化物夹杂的演变规律

 使用ASPEX PSEM explorer研究了帘线钢中氧化物夹杂的成分及形态在炼钢与轧制过程的变化。结果表明,连铸坯夹杂物中SiO2质量分数较中间包有增加趋势,并在铸坯中发现MnO-SiO2-Al2O3和SiO2构成的复合夹杂物,轧制盘条中出现未很好变形的SiO2夹杂物。热力学分析表明：由于连铸过程钢液和夹杂物间的传质作用,导致铸坯夹杂物中SiO2质量分数增加,MnO-SiO2-Al2O3系夹杂在浇铸过程较CaO-SiO2-MnO-Al2O3系夹杂物更易析出SiO2相,形成MnO-SiO2-Al2O3为基体的复合夹杂物。CaO-SiO2-Al2O3-MnO和MnO-SiO2-Al2O3夹杂物在盘条中呈长条状,MnO-SiO2-Al2O3和SiO2析出相构成的复合夹杂在轧制过程将发生相分离,形成“眼睛状”或单颗粒状夹杂。