超低碳铝硅镇静钢精炼过程中夹杂物的行为及其对钢组织的影响

针对RH精炼并结合典型的渣-钢化学平衡实验,研究了超低碳铝硅镇静钢精炼过程中夹杂物的变化以及钢包顶渣组成对钢中夹杂物的影响. 用激光共聚焦高温扫描显微镜在线观察了再加热过程中钢的微观组织变化,讨论了夹杂物对钢的晶粒长大的影响. 结果表明,本实验条件下精炼前钢中夹杂物是以Fe-Mn氧化物为主的复合夹杂,夹杂物数量和大小受渣碱度、Al2O3含量及CaO/Al2O3比值的影响较大,当碱度为1.5及Al2O3含量为20%时,夹杂物数量最少. 以成分优化的钢包渣与精炼末期钢样进行的平衡实验显示,夹杂物为Al2O3-MgO或Al2O3-MgO-SiO2-MnO为主的复合夹杂,随渣中w(MnO)的增加,复合夹杂中Mn含量有增加的趋势,使钢的晶粒长大过程需要更高的再加热温度. 钢样再加热后,钢中夹杂物变为以Al2O3, MgO, SiO2复合夹杂为主,三者总量占夹杂物总量的90%或以上,复合夹杂中MnO含量受加热制度影响.     

电渣重熔过程增镁及其对夹杂物的影响

通过设计含镁渣系，并在电渣重熔过程添加脱氧剂，氩气保护气氛下进行电渣重熔实验，研究了电渣重熔过程增镁的可能性。用电感耦合等离子体原子发射光谱分析了钢中的镁含量，用ASPEX扫描电镜分析了电渣锭中镁含量对夹杂物尺寸、类型、形貌等的影响。结果表明，渣中含20wt% MgO以上时，即使自耗电极中不含镁，也能使渣中MgO向钢液中传递镁。实验室条件下，分别用55wt% CaF2–15wt% Al2O3–10wt% CaO–20wt% MgO, 65wt% CaF2–10wt% Al2O3–25wt% MgO, 51wt% CaF2–8wt% Al2O3–8wt% CaO–23wt% MgO–10wt% MgF2渣系重熔时，电渣锭中镁含量分别为0.0034wt%, 0.0039wt%, 0.0043wt%。随电渣锭中镁含量增加，夹杂物组成逐渐从以Al–Ca, Al–Mn–S, Al–Mg–Mn–S为主，转变为以含镁夹杂物为主，镁含量最高达98wt%；夹杂物数量大幅减少，直径明显减小，最大直径均小于10 μm，大多数小于5 μm。与含镁0.0003wt%的电渣锭相比，镁含量增至0.0034wt%时，夹杂物从357个降至31个，最大夹杂物直径由11.0 μm降至8.5 μm，平均直径由3.7 μm降至3.2 μm。     

酒钢CSP流程SPCC钢夹杂形成机理

对酒钢CSP流程SPCC两个浇次在LF进站、LF中期、LF出站、中包、铸坯和轧制过程分别取钢样,用SEM-EDS分析其夹杂物及成分. 结果表明,在喂铝线后,钢液中很快形成大量形状不规则Al2O3夹杂物,随着精炼进行夹杂物存在两种变性路线：Al2O3-MgO·Al2O3-CaAlMg复合夹杂物和Al2O3-CA6-CA2-CA-低熔点夹杂物. 经过钙处理后大部分夹杂物可较好地变性到低熔点液相区或固液两相共存区. 夹杂物变性越好,则钢液中夹杂物球形化率越高,总量也越小,夹杂物成分对其尺寸也有重要影响. 分析了外层被钙铝酸盐和CaS包裹的双层夹杂物的形成机理,前者由于钢中Ca还原MgO·Al2O3尖晶石中Mg或Al2O3中Al;后者由于在铸坯凝固过程中温度降低及元素S的偏析,造成液芯中S浓度升高,其与Ca在已有的固体夹杂物核心的表面析出CaS. 在轧制过程中,前者变形能力较好,后者的外层CaS易与内部核心分离,甚至产生微裂纹.     

管线钢夹杂物变性的理论与实验研究

通过对钙处理过程中夹杂物变性的热力学分析,绘制了夹杂物变性过程中钙、铝、氧、硫活度的优势区图及夹杂物变性路径图,并系统分析了钢液温度、铝活度、硫活度等因素对夹杂物变性的影响.管线钢夹杂物变性后,氧化物夹杂为球形或块状的钙铝酸盐,少量的硫化物夹杂为CaS夹杂、CaS均匀分布的CaO·Al2O3CaS复合夹杂和内核为CaO·Al2O3外壳为CaS的复合夹杂.     

电渣重熔过程结晶器旋转对钢中夹杂物的影响

基于自行设计的双极串联结晶器旋转电渣重熔炉,采用ASPEX全自动夹杂物分析仪研究了结晶器转速对M2电渣锭洁净度的影响。结果表明,不论结晶器是否旋转,电渣锭中的夹杂物组成基本不变,主要由Al2O3, Al2O3–MnS, Al2O3–SiO2–CaO–MnS, MgO–Al2O3–SiO2–CaO–MnO, MgO–Al2O3–SiO2–CaO–TiO2–MnS, Al2O3–SiO2–CaO–MnO–TiO2组成,其中以Al2O3, Al2O3–SiO2–CaO–MnO–TiO2和Al2O3–MnS数量最多。结晶器静止电渣重熔时,钢中的夹杂物数量较多,且存在50 ?m以上的大颗粒夹杂物,而结晶器转速为6和13 r/min时,夹杂物数量减少,大颗粒夹杂含量大大降低;转速增至19 r/min时,夹杂物数量及尺寸又进一步增加,同时钢中全氧含量、氮含量明显增加。电渣锭中大颗粒夹杂物得以去除的主要原因是结晶器旋转导致金属自耗电极末端的熔融层变薄、熔滴尺寸变小,渣–金接触面积增大,促进了夹杂物被熔渣去除;过快的转速会增加自耗电极氧化、减少渣–金接触时间,从而降低电渣重熔过程的精炼能力。     

高碳连铸坯中夹杂物赋存规律的研究

利用金相法结合非水溶液电解法研究了高碳连铸坯中夹杂物的类型、尺寸、分布、化学成分和来源,确定了高碳连铸坯内部夹杂物情况。结果表明:高碳连铸坯中主要有Al2O3夹杂、硫化物以及Ca O·Al2O3、MgO·Al2O3等复合夹杂物,尺寸大部分小于20μm,在铸坯厚度方向内弧侧1/4处出现聚集,主要来源于采用Si-Ca-Ba系脱氧剂进行脱氧时产生的脱氧产物以及钢液对炉衬和耐火材料的冲刷。     

CaO/Al2O3比对高铝钢连铸保护渣凝固结晶行为的影响

针对目前高铝钢用常规结晶器保护渣中SiO2易被钢液中Al还原导致连铸坯质量缺陷及非反应性保护渣消耗量偏低和润滑差的问题,基于CaO-SiO2-Al2O3三元系相图设计了SiO2含量为20%(w)的CaO-SiO2-Al2O3连铸保护渣,并采用热丝法模拟研究了CaO/Al2O3比对该渣系凝固结晶行为的影响. 结果表明,随CaO/Al2O3比的增加,保护渣的结晶性能增强;CaO/Al2O3比在0.7~1.3范围内其凝固固相分数较小,与现用工业渣具有相似的润滑作用. 综合考虑保护渣的传热和润滑作用,高铝钢保护渣中CaO/Al2O3比范围应为0.7~1.3.     

固/液态夹杂物穿过钢渣界面的分离机理

对液态和固态夹杂物穿过钢?渣界面的分离过程进行了物理模拟实验,研究了钢包内固态夹杂物比液态夹杂物易被去除的原因. 结果表明,固态夹杂物不被钢液润湿,在界面张力的作用下,固态夹杂物与界面之间的钢液在极短的时间内被排尽,导致固体夹杂物瞬间进入渣层. 液态夹杂物易被钢液润湿,界面张力使液态夹杂物与界面之间的钢液不能排尽,形成液膜. 液膜内的钢液在压力的作用下排尽,导致液膜破裂,液态夹杂物瞬间进入渣层. 实际液态夹杂物停留在钢?渣界面处的时间明显长于固态夹杂物穿过钢?渣界面所需时间.     

非球形固态夹杂物穿过钢-渣界面行为研究

为了解释炼钢过程中固态夹杂物比液态夹杂物更易去除的现象,基于分离过程中受力分析,建立了描述八面体和板状夹杂物穿过钢-渣界面行为的数学模型。与传统数学模型相比,本模型考虑了夹杂物周围钢-渣界面变形引起的界面变形阻力。同时,采用该模型研究了各相(钢液、渣和夹杂物)界面张力和顶渣黏度等因素对固态夹杂物穿过钢-渣界面分离行为的影响。结果表明,若忽略固态夹杂物溶解过程,钢液、顶渣和夹杂物体系释放的界面自由能是固态夹杂物穿过钢-渣界面的驱动能,且该动能已足够保证多数固态夹杂物穿过钢-渣界面进入渣层。固态夹杂物溶解过程释放的吉布斯自由能远大于该过程释放的界面自由能,固态夹杂物接触钢-渣界面的瞬间被顶渣吸收去除。     

超纯铁素体不锈钢中含Ti和Nb夹杂物的非水电解分离及其在钢中的析出行为分析

采用非水溶液电解法提取了Ti, Nb稳定化超纯铁素体不锈钢中的夹杂物和析出物,采用场发射扫描电镜观察其形貌,并结合能谱仪分析其成分. 结果表明,高钛型铁素体不锈钢中的夹杂物多为立方结构的碳氮化钛或树枝状的钛氧化物夹杂;Ti,Nb双稳定化铁素体不锈钢中,夹杂物核心由钛氧化物与氮化钛复合而成,棱角上包裹碳氮化铌;高铌型铁素体不锈钢中夹杂物为十字状或树枝状NbC. 利用热力学数据计算了Ti稳定化铁素体不锈钢中复合夹杂物的析出顺序及TiN的析出时机. 计算表明,在1873 K铁素体不锈钢成分条件下TiOx-TiN复合核心中钛氧化物为Ti2O3. 随着温度的降低,Ti, N在钢液中出现偏析富集,在钢液凝固过程中生成TiN,降低钢液中N含量可推迟TiN的析出时机.     

Effect of Tundish Lining on Steel Cleanliness

To clarify the effect of the tundish lining on the steel cleanliness,the MgO based and Al2 O3 based gunning materials( GM) were used as the lining of the alumina crucibles,respectively,in which about 200 g of ultra-low carbon steel was charged at 1 823 K for 2 h in pure argon atmosphere. The chemical analysis was carried out to investigate the change of chemical composition of steel in contact with GM after high temperatures holding experiments. The steel cleanliness in terms of inclusion number density,inclusion size and inclusion size distribution was evaluated by SEM and EDS. It was found that the MgO GM provided more oxygen and showed a stronger oxidizing capacity due to its higher content of reducible oxides( 10. 5 mass% SiO2+ 2 mass%Fe2 O3). The use of Al2 O3 GM resulted in an improved steel cleanliness and consequently Al2 O3 GM could be a promising refractory material in the tundish lining.     

中间包涂料对钢液洁净度的影响

实验研究了镁质、氧化铝质和镁钙质三种中间包内衬涂料与钢水反应,考察了其对钢中T.O, T.N及Al, Ti, Si, Mn含量、夹杂物组成、数量和尺寸分布的影响,并分析了钢水在钢/涂层界面对涂层的渗透和侵蚀程度. 结果表明,在1550℃下,相比于镁质涂料和氧化铝涂料,镁钙质涂料能对钢液T.O和成分有更好的控制,终点氧含量在8.5′10-5,对钢液的二次氧化很少,并有利于细小夹杂物的形成,其中<1 mm夹杂物占98.13%;钢中首先是Al, Ti被氧化,之后是Si, Mn被氧化;氧化铝涂料被损坏的机理主要是冲刷脱落,镁质和镁钙质涂料的损坏则以渗透侵蚀为主. 镁钙质涂料对钢液的二次污染小,有利于洁净钢的生产.     

Dynamic interaction of refractory and molten steel: Effect of alumina-magnesia castables on alloy steel cleanness

High quality alloy steel is an important material needed for social and economic development. It is of great significance to major national projects and defence security. Refractories are used in the smelting process of steel; they are some of the main sources of impurities which have an important effect on the quality of steel. As alumina-magnesia refractories are the main lining materials used for steel refining, the influence of these refractories on the cleanliness of molten steel under dynamic smelting conditions has been studied. The size, quantity, composition, and structure evolution of inclusions in steel are analysed. The results show that after smelting, the content of alloy elements in the steel is stable, and that the total oxygen content and inclusions in the steel are increased by the corrosion of the alumina-magnesia castables. However, the maximum average particle size of the inclusions in the steel was limited to 20?µm, which did not cause large inclusions in the steel or seriously affect the quality of steel. During the dynamic melting process, because of the presence of Si and Mn in the alloy steel, the inclusions changed from homogeneous CaS wrapped Al₂O₃-MgO composite sphere to MnS wrapped egg-shaped structure. The alloy elements in steel were found to be beneficial, as they reduced the effect of alumina and magnesia inclusions on the quality of steel. The results indicate that it is feasible to smelt high quality alloy steel using alumina-magnesia carbon-free castable, and that it would be better to limit the refining time to 45?min during smelting.     

15-7PH不锈钢电渣重熔过程夹杂物的行为

为了明晰15-7PH沉淀硬化不锈钢中夹杂物的行为,进一步提高其洁净度,采用超高功率电弧炉初炼→AOD (Argon Oxygen Decarburization)脱碳→LF (Ladle Furnace)精炼→模铸工艺制备了自耗电极,并用带压摆控制的气体保护电渣重熔炉进行重熔。采用HORIBA氧氮氢气体分析仪检测了电渣重熔前后氧、氮等含量的变化;ASPEX扫描电镜分析了夹杂物的尺寸、数目、化学成分、形貌等。结果表明,电渣重熔后15-7PH不锈钢中氧、氮含量有轻微的下降,但夹杂物的组成变化不大,主要由氮化物夹杂物(氮化铝+氮化钛)、氮化物-氧化物复合夹杂物、氧化物夹杂物、硫化物-氧/氮化物夹杂物组成,其中氮化物夹杂物尺寸最大、数量最多,明显高于其他夹杂物。电渣重熔对夹杂物的数量、尺寸有明显影响。重熔后夹杂数量大幅增加,氮化物尤为明显,但大颗粒夹杂物明显减少。氮化物夹杂物大量存在的主要原因在于钢中存在较高的Al, Ti, N等元素,而电渣过程由于熔渣吸附、部分夹杂物溶解,使大颗粒夹杂物减少,重熔过程的快速冷却抑制了夹杂物长大,最终结果是夹杂物尺寸更细小,但数量增加。     

Crushing behavior of alumina inclusions with different porosity during hot compression

Alumina inclusions in commercial as-cast 2.25Cr1Mo0.25V aluminum deoxidized steel exhibited a feature of porous structure. In order to investigate the crushing characteristics of alumina inclusion during hot working, a series of alumina blocks with different porosity whose properties are similar to the alumina inclusions in ingots were prepared using spark plasma sintering. The crushing behavior of alumina blocks during hot compression with quasi-static load was studied. A prediction model of compressive strength of alumina inclusions considering apparent porosity was established on basis of hyperbolic sine Arrhenius equation. A novel crushing mode diagram for alumina inclusions characterized by Z parameter was proposed. The crushing mechanism of alumina inclusions under different deformation parameters was clarified by fracture characteristics. The results showed that the hot compression process of alumina presented a typical brittle fracture, the compressive strength was more sensitive to deformation conditions at lower apparent porosity as compared with the conditions of higher apparent porosity. With the increase of Z, the crushing mode of alumina inclusions gradually changed from intergranular fracture to transgranular fracture.     

Dissolution mechanism of alumina inclusions into CaO–SiO2–Al2O3–FetO–MgO slag via a converter tapping process

Reducing the amount of inclusions during the steelmaking process as much as possible and much earlier plays a vital role in improving the quality of steel products. To reveal the dissolution mechanism of inclusions in slag during the converter tapping process, some comparison experiments were conducted by adding isolated spherical alumina balls as inclusions in CaO–SiO₂–Al₂O₃–Fe_tO–MgO slag, and Fe_tO content up to 10% was contained in slag. The results showed that the dissolution rate of alumina balls in the slag was mainly affected by the diffusion of Al₂O₃, and the diffusion coefficients of Al₂O₃ were 4.2 × 10^–11, 7.5 × 10^–11, and 1.5 × 10^–10 m²/s at 1500℃, 1550℃, and 1600℃, respectively. In addition, the upgraded diffusion-distance-controlled dissolution model (DDD-Model), in which Fe_tO content was introduced and applied in the study. The results illustrated that the Al₂O₃ inclusion apparent dissolution rate was improved by a high Fe_tO content, increasing CaO/SiO₂ and raising the temperature as soon as possible at the early stage of the converter tapping process. It is not necessary to increase the Fe_tO content in the slag to enhance the dissolution rate of the Al₂O₃ inclusion at the last tapping stage. The predicted complete dissolution time of spherical Al₂O₃ inclusions with 1000 µm in diameter based on the upgraded DDD-Model was approximately 1796 s during the actual converter tapping process.