超纯铁素体不锈钢夹杂物控制的研究进展

论述了超纯铁素体不锈钢夹杂物控制的热力学,着重于脱氧、TiN析出、尖晶石夹杂物形成及钙处理的热力学研究。介绍了VOD炉内夹杂物行为的数学模拟研究,分析了超纯铁素体不锈钢中夹杂物引起的产品缺陷、夹杂物形成规律及特征,指出TiN或Ti(CN)容易在MgO、Al2O3-MgO、Ti2O3基体上析出,形成包裹型复合夹杂物。最后提出了今后开展超纯铁素体不锈钢夹杂物研究的几点建议。     

典型含钛超纯铁素体不锈钢冶炼-连铸过程夹杂物衍变研究

通过热力学分析、扫描电镜和EDS能谱分析等方法,系统研究了一种典型含钛超纯铁素体不锈钢（/%:≤0.01C,17.5～18.5Cr,0.40～0.55Nb,0.10～0.25Ti）80 t K-OBM-S-VOD-LF-200 mm×1 240 mm CCM过程夹杂物的衍变。结果表明,VOD还原期采用Si-Al复合脱氧,夹杂物类型以Al2O3-CaO-SiO2-MgO和Al2O3-CaO-MgO为主,钛合金化后夹杂物转变为Al2O3-CaO-TiOx-MgO,由于此类夹杂物熔点高、尺寸大,且很难通过钙处理变性,容易聚集造成水口堵塞。通过提高铝钛比至0.11以上,降低钛合金化前钢中全氧含量至25×10-6以下,使用纯净的钛铁合金可以避免形成大尺寸的含TiOx夹杂物。     

脱氧方式对高铝钢中非金属夹杂物的影响

摘要：为了研究不同脱氧方式对高铝钢中非金属夹杂物的影响,采用高温试验和热力学计算相结合的方法,对比分析了先SiMn后Al和先Al后SiMn两种脱氧方式下高铝钢中夹杂物形貌、类型、数量和尺寸特征。结果显示：先加入SiMn后,生成大量液态球形的Mn-Si-Al-O系复合夹杂物,再加入Al后夹杂物演变为Al2O3,且夹杂物数量明显减少;采用先Al后SiMn脱氧方式时,高铝钢中夹杂物始终以Al2O3为主,夹杂物最终数量相对较低。2种脱氧方式钢中夹杂物平均等效圆直径和尺寸分布相差不大。此外,采用先SiMn后Al进行脱氧时,发现尺寸较小的AlN颗粒附着在Al2O3夹杂物表面形成Al2O3-AlN复合夹杂物。而采用先Al后SiMn脱氧方式时,高铝钢中发现单一AlN夹杂物和Al2O3-AlN复合夹杂物,AlN夹杂物的形成与钢水中的氧势和合金原料有关。     

SUS436L超纯铁素体不锈钢夹杂物的形成机理

采用金相显微镜、扫描电子显微镜和能谱面扫描等仪器设备研究了钛稳定化SUS436L超纯铁素体不锈钢板材的夹杂物类型,结合热力学计算分析各类夹杂物的生成机理。结果表明,SUS436L不锈钢的夹杂物主要包括纯TiN颗粒、TiN包裹MgO·Al_2O_3尖晶石的复合夹杂以及Al_2O_3-CaO-TiO_2复合氧化物;当w([N])为0.007 0%、钢液温度为1 600~1 650℃时,平衡钛质量分数为0.23%~0.38%;当钢液温度为1 600℃、w([Al])为0.02%时,w([Mg])大于0.000 8%时生成MgO·Al_2O_3,w([Mg])大于0.004 4%则生成MgO;当钢液温度为1 600℃、w([Al])为0.02%时,钙处理后w([Ca])为0.000 14%~0.000 36%、大于0.000 36%时分别生成低熔点的12CaO·7Al_2O_3及3CaO·Al_2O_3,且在钛合金化后易生成低熔点的Al_2O_3-CaO-TiO_2复合氧化物。     

含钛超纯铁素体不锈钢的铝脱氧及钙处理实验研究

通过500 kg真空感应炉对0.007%～0.015%C-15.96%～16.94%Cr-0.08%～0.36%Ti-0.015%～0.124%Al铁索体不锈钢的铝脱氧和钙处理实验,以及相应的热力学计算,对Al、Ti竞争氧化及夹杂物改性进行了研究.结果表明,当[Ti]/[Al]低于2.50时,氧化物夹杂主要为Al2O3,随[Ti]/[Al]的增加,钢中的主要夹杂由Al2O3向MgO-Al2O3-TiOx及Al2O3-TiOx转变,夹杂物平均尺寸逐步减小;钙处理后随[Ca]/[Al](0.01～0.08)的升高,钢中含钙复合夹杂的数量比例增加;包裹形复合夹杂的中心为氧化物,周边为TiN或Ti(CN).     

脱氧制度对H08C焊丝钢连铸水口结瘤的影响

采用两种脱氧制度试制了H08C焊丝钢,方案1为先采用硅、锰预脱氧,再用钛进行终脱氧;方案2为先采用铝深脱氧,再进行钛合金化。用扫描电镜(SEM/EDS)分析了不同脱氧制度下钢液中夹杂物的形貌、成分以及连铸水口结瘤物的组成,采用电解的方法提取了钢中夹杂物并进行了定量分析。结果表明:精炼结束后,两种脱氧制度钢液中夹杂物的类型相同,都为MnO-Al2O3-SiO2-TiOx、MgO-Al2O3-TiOx夹杂物,方案1钢液中w(TiOx)=0.003 3%,方案2钢液中w(TiOx)=0.000 8%;两种方案结瘤物中的非金属相组成与钢液中的夹杂物成分相同,但方案1的结瘤物中含有较多的金属相,而方案2基本不含金属相。采用方案2的脱氧制度有利于改善连铸过程中水口的结瘤问题。     

Q345精炼过程中非金属夹杂物生成热力学及工业实践

Q345钢采用铝硅锰复合脱氧,在LF精炼过程中,钢—渣—夹杂物—耐火材料—合金—空气多元体系下夹杂物成分会发生转变。由于纯铁液脱氧热力学不能指导工业生产实践,且目前实际钢液的脱氧热力学没有系统化,需要进行深入研究。结合Factsage7. 0热力学计算,分析了Q345钢LF精炼脱氧、耐材侵蚀、钙处理等引起的钢液[Al]、[Si]、[Mg]、[Ca]含量变化对夹杂物成分的影响。转炉出钢采用铝硅锰复合脱氧,脱氧产物主要为Al2O3,随着钢中[Mg]含量上升,夹杂物由Al2O3转变为MgO·Al2O3尖晶石。钙处理会将夹杂物由MgO·Al2O3尖晶石转变为液态Ca-Al-Mg氧化物,但当喂钙过量时,夹杂物中CaO含量偏高,会影响夹杂物改性效果。利用Factsage7. 0热力学软件分析出的夹杂物成分与直接检测结果一致。     

精炼渣对SUS444铁素体不锈钢中夹杂物的影响

在1 873K,MgO坩埚内进行了VOD精炼渣与SUS444铁素体不锈钢之间的脱氧平衡试验,考察了精炼渣对不锈钢中T.O含量及夹杂物组成、数量和尺寸分布的影响。结果表明,脱氧终点钢中w(T.O)=0.006 3%~0.007 4%,提高精炼渣碱度,降低渣中Al2O3的活度,有利于降低钢中T.O含量。精炼渣碱度增加,试样中单位面积夹杂物的个数及夹杂物的平均面积分数都减小。降低渣中Al2O3含量,夹杂物平均粒径也降低。加入脱氧合金后,钢中夹杂物主要为Al2O3、MgO·Al2O3及含有少量SiO2、MnO的复合氧化物;钙处理后,钢中夹杂物主要为球形的MgO·Al2O3-CaO。随着精炼渣中a(MgO)/a(Al2O3)的增加,MgO·Al2O3夹杂物中xMgO/xAl2O3随之增加。根据试验,R=3.5、w(Al2O3)=10%、w(MgO)=10%、w(CaF2)=5%的精炼渣具有良好的精炼效果。     

不同RH脱氧方式对含铝电工钢的影响

摘要：研究了RH脱氧方式（铝脱氧,先铝后硅;硅脱氧,先硅后铝）对含铝电工钢洁净度、渣成分、夹杂物演变及连铸过程的影响。2种脱氧方式下钢包顶渣的氧化性相似,热力学计算表明硅脱氧的顶渣对铝酸盐夹杂物的吸收能力强于铝脱氧渣。铝脱氧钢中夹杂主要为Al2O3 CaO CaS复合氧化物,硅脱氧钢中夹杂物主要是Al2O3。2种脱氧方式下,热轧钢卷中的典型夹杂物都是AlN、MnS和复合铝酸盐。由于脱氧方式和钢中N、S含量的差异,铝脱氧热轧卷中夹杂物的含量是硅脱氧的2～3倍,这与理论的预测结果完全吻合。由于钢液中Ca含量不同,硅脱氧的钢水在CSP连铸过程中会引起中包塞棒上涨,因此建议在传统的连铸工艺中采用硅脱氧,在CSP工艺中采用铝脱氧。     

FeSi中铝对不锈钢连铸和热轧板表面缺陷影响

 针对硅脱氧条件下304不锈钢中出现的Al2O3夹杂物和热轧板表面存在分层缺陷的问题,通过对铸坯的大样电解、热轧板取样、扫描电镜检测分析以及FactSage软件计算等方法,主要研究了FeSi合金中残余铝质量分数对Al2O3夹杂物生成的影响,并分析了Al2O3夹杂物对不锈钢连铸和热轧板表面分层缺陷的影响。研究表明,硅脱氧条件下生产的304不锈钢整个冶炼过程中,产生Al2O3夹杂物的主要环节为GOR还原初期含有较高铝质量分数的FeSi合金的脱氧过程。通过FactSage软件计算得到了避免Al2O3生成时FeSi合金中所允许的最大铝质量分数。根据计算结果和现场试验得出以下结论：FeSi合金中的铝质量分数超过1.8%时,钢液中会产生Al2O3夹杂物,Al2O3进入具有较高碱度的结晶器保护渣熔渣层造成局部保护渣黏度和熔化温度快速增加形成块状的夹杂物,这些夹杂物被卷入钢液内部或者被新生铸坯表面捕捉,从而造成热轧过程中轧板的表面分层缺陷形成。当FeSi合金中的铝质量分数小于1.5%时,钢液中难以产生Al2O3类夹杂物,有效抑制了这类表面缺陷的产生。     

Investigation on Variation of Inclusions and Total Oxygen in IF Steel After RH Deoxidization

The variational regulation of inclusions and total oxygen in the IF Molten Steel during the RH refining process after deoxidization was studied. The results show that the relationship between total oxygen content and time is in accord with the following equation, T.O=271.25e-1.53t+23.49, R2=0.9966.The inclusion analysis investigation during RH pure circulation process indicates that the main inclusion of the IF molten steel after 2 minutes from the beginning of deoxidization is cluster inclusions of pure Al2O3 system. After 6 minutes from the aluminum deoxidization, the quantity of inclusion decreases and the inclusion style changes into block inclusions of Al2O3 system with the size of 5μm. In the other hand, some inclusions are of Al2O3-MgO. Complex inclusions of Al2O3-TiOx with the size of below 5μm, and the single particle or cluster complex inclusions with the typical square shape of Al2O3-TiN system are found after 3 minutes from titanium-ferrous alloy added. Then, the content of titanium of complex inclusions of Al2O3-TiOx decreases and the aluminum content rises along with the RH pure circulation time process. That means the inclusions of Al2O3-TiOx is not steady, and it trends to transfer into Al2O3.     

Effects of AlMnCa and AlMnFe Alloys on Deoxidization of Low Carbon and Low Silicon Aluminum Killed Steels

 To confirm the effects of AlMnCa and AlMnFe alloys on the deoxidization and modification of Al2O3 inclusions, experiments of 4 heat low carbon and low silicon aluminum killed steels deoxidized by AlMnCa and AlMnFe alloys were done in a MoSi2 furnace at 1 873 K. It is found that the 1# AlMnCa alloy has the best ability of deoxidization and modification of Al2O3 inclusions than 2# AlMnCa and AlMnFe alloys. Steel A deoxidized by 1# AlMnCa alloy has the lowest total oxygen content in the terminal steel, which is 37×10-6. Most of the inclusions in the steel deoxidized by 1# AlMnCa alloy are spherical CaO containing compound inclusions, and 891% of them are smaller than 10 μm. The diameter of the inclusion bigger than 50 μm is not found in the final steels deoxidized by AlMnCa alloys. Whereas, for the steels deoxidized by AlMnFe alloys, most inclusions in the terminal steel are Al2O3 or Al2O3 MnO inclusions, and a few of them are spherical, and only 768% of them are smaller than 10 μm. Some inclusions bigger than 50 μm are found in the steel D deoxidized by AlMnFe alloy.     

Effects of Mg Addition on Inclusions Formation and Resultant Solidification Structure Changes of Ti-stabilized Ultra-pure Ferritic Stainless Steel

The effects of Mg addition on the formation of nonmetallic inclusions and solidification structure of Ti-stabilized ultra-pure ferritic stainless steels were investigated by experimentally casting ingots with different compositions.Thermodynamic analyses on the formation of complex inclusions after adding Mg into steels were carried out combined with the scanning electron microscopy-energy dispersive spectrometry(SEM-EDS)analysis.And the EDS analysis showed that in steel samples with Mg addition,a new spinel crystal phase combined with Al2O3-TiOx formed.It was also found that after Mg addition,the proportions of equiaxed grain zone of 409L,4003,439 and 443NT steels increased from 10.2%,21.8%,13.4% and 18.6% to 84.3%,92.3%,91.1% and 100.0%,respectively.Since the planar disregistry between spinel and TiN is 5.1%,spinel could promote the precipitation of TiN and increase the number density of TiN inclusions in steel melts.The mechanism of solidification structure refinement after adding Mg into steels supposed that the complex inclusions of spinel and TiN in high number density enhanced columnar-to-equiaxed transition,since the planer disregistry betweenδphase and spinel is 1.4%.     

Inclusions for Ultra-pure Ferritic Stainless Steels Containing 21% Chromium

As stabilizing elements added into ultra-pure ferritic stainless steels, niobium and titanium react with carbon and nitrogen to form carbonitrides and have great effects on the ratio of equiaxed zone and the grain size of solidification structure of ingots, which remarkably affect the quality of cold-rolled sheets. Combined with thermodynamic calculation, style and precipitation progress of inclusions in ultra-pure ferritic stainless steels were investigated by optical microscopy, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy. The results indicate that the inclusions are mainly Ti-Al-N-O system inclusions in ultra-pure ferritic stainless steels. Al₂O₃ starts to precipitate firstly and then TiO_x and TiN precipitates sequently. The inclusions are mainly single TiN particles and complex inclusions with Al₂O₃-Ti₂O₃ as cores and covered with TiN under the condition of 0.31% titanium addition and mainly Al₂O₃ under the condition of 0.01% titanium addition. A few (Nb, Ti) N particles precipitate because of no enough titanium to react with nitrogen when titanium addition is 0.01%. In addition, fine Nb(C, N) particles with size of less than 500 nm precipitate at relatively low temperature.     

Inclusion control of ferritic stainless steel by aluminum deoxidation and calcium treatment

A thermodynamic equilibrium between aluminum and oxygen and inclusion morphology in the Fe-16Cr stainless steel were investigated to understand the fundamentals of the aluminum deoxidation technology for ferritic stainless steels. Further, the effect of calcium addition on the changes in chemistry and morphology of inclusions was discussed. The measured results for the aluminum-oxygen equilibria exhibit relatively good agreement with the calculated values, indicating that an introduction of the first-and second-order interaction parameters, recently reported, is reasonable to numerically express the aluminum deoxidation equilibrium in a ferritic stainless steel. In the composition of dissolved aluminum content greater than about 60 ppm, pure alumina particles were observed, while the alumino-manganese silicates containing Cr₂O₃ appeared at less than 20 mass ppm of dissolved aluminum. The formation of calcium aluminate inclusions after Ca treatment can be discussed based on the thermodynamic equilibria among calcium, aluminum, and oxygen in the steel melt. In the composition of steel melt with relatively high content of calcium and low aluminum, the log ( ) of inclusions linearly increases by increasing the log [a _Ca/a _Al ² ·a _O ² ] with the slope close to unity. However, the slope of the line is significantly lower than the expected value in the composition of steel melt with relatively low calcium and high aluminum contents.     

Ultra-Pure Ferritic Stainless Steels Grade, Refining Operation, and Application

The grades of ultra-pure ferritic stainless steels, especially the grades used in automobile exhaust system, were reviewed. The dependence of properties on alloying elements, the refining facilities, and the mechanism of the reactions in steel melts were described in detail. Vacuum, strong stirring, and powder injection proved to be effective technologies in the melting of ultra-pure ferritic stainless steels. The application of the ferritic grades was also briefly introduced.     

Thermodynamic Properties of Inclusions Formed Aluminum-Titanium Deoxidation of Molten Steel

Titanium alloyed steel has been widely used as automobile sheet steels, thick plate steels, and also stainless steels to improve the mechanical and chemical properties of many grade steels. Since Ti has strong affinity with oxygen, Ti is normally alloyed after Al deoxidation to keep the high yield of Ti. Therefore, Al-Ti deoxidation is one of the common and important secondary refining processes. Although the chemical stability diagram for this system has been reported by many researchers, these diagrams are inconsistent significantly each other. In the present study, the stability region of Al2TiO5 oxide was measured by equilibrating Fe-Al-Ti alloy and Al2TiO5 pellet in Al2O3 crucible at 1873 K. However, inclusions in metal after equilibration were Ti-containing Al2O3 or Al-containing TiOx. The precise phase diagrams and related thermodynamic data for the Al2O3-TiOx-FeO system should be determined.     

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...