Influence of Temperature Evolution on Precipitation Behaviour of Second Phase Particles in Grain‐oriented Electrical Steels

A model concerning dynamic precipitation of second phase particles during hot deformation of conventional grain‐oriented electrical steels is proposed. The model involves the solid solubility of the elements forming MnS, the corresponding nucleation driving force, as well as the evolution of dislocation densities during hot deformation, which supplies sites for heterogeneous nucleation of MnS particles. The model describes the dynamic process in which temperature keeps decreasing and dislocation density keeps increasing. The influences of reheating temperature, initial rolling temperature, finishing temperature and deformation duration on the precipitation behaviour are involved. Calculations have been conducted based on the model, to simulate the precipitation behaviour of MnS particles during hot rolling of grain‐orientated electrical steels under different parameters. The results indicate that hot rolling is very important for dispersive precipitation of MnS particles. The increase of particle density is promoted by proper increase of reheating temperature or proper reduction of initial and finishing rolling temperature, in which the driving force and dislocation density are increased. The simulation results agree basically with the experimental observations in hot strip of a grain oriented electrical steel.     

Evolution of MnS inclusions in Ti-bearing X80 pipeline steel

Studies show that manganese sulfide(MnS)inclusions in pipeline steel affect the lateral performance of steel in its rolling deformation,as well as the hydrogen-induced cracking and sulfide stress corrosion cracking resistance performance.To inhibit the precipitation of MnS and its effect on pipeline steel,a quenching experiment and a diffusion couple experiment,which investigated the evolution of MnS inclusions in Ti-bearing X80 pipeline steel,were conducted.The experimental results show that the transformation of the MnS inclusions during solidification is as follows:MnS→titanium sulfide(TiS)→Ti_4C_2S_2.The transition temperatures of MnS to TiS and TiS to Ti_4C_2S_2 are 1 673 and 1 273 K,respectively,and the overall size of the sulfide decreased as well.Thermodynamic calculation results confirm that the transition temperatures of MnS to TiS and TiS to Ti_4C_2S_2 are 1 623 and 1 203 K,respectively.When the sulfur content in the X80 pipeline steel is 0.001 5%,all the sulfur in the steel can be converted into Ti_4C_2S_2 with a titanium content of more than 0.02%.     

Cause Analysis of Low Tensile Plasticity in Normal Direction for Hot-Rolled Thick Plate of HSLA Steel

To investigate the cause for the low tensile plasticity in normal direction of high-strength low-alloy steel thick plate, tensile fracture observation, inclusion statistic, and microstructure observation of thick plate and solidification structure observation of continuous casting slab are carried out. The experimental results reveal that many MnS inclusions are only distributed on the platform of the tensile fracture and they only appear in the center of thick plate together with martensite and severe macrosegregation of elements C and Mn. It is concluded that the aggregated large-sized MnS inclusions are the direct cause for reducing the tensile plasticity. Stress concentration on a single MnS inclusion during tensile testing can occur and cause a limited brittle fracture area. Aggregation of MnS inclusions creates a large brittle fracture area, which significantly reduces the tensile plasticity. The root cause of the aggregation of MnS inclusions is the well-developed columnar crystals of continuous casting slab. The well-developed columnar crystals push high concentration of solutes into the residual liquid-phase zone in the center of continuous casting slab and create severe central macrosegregation which eventually lead to the appearance of aggregated large-sized MnS inclusions with martensite in the center of thick plate.     

冷却强度对超高硫中碳钢方坯凝固过程MnS生长的影响

 中碳超高硫易切削钢SAE144是兼具力学性能与切削性能的结构钢,用于制造汽车发动机密封阀件等,产品多采用转炉/电炉→LF精炼→连铸小方坯→线棒材热轧→冷拉及机加工成型流程生产,近年来市场热度稳步提升。若钢中MnS尺寸过大,零件加工使用过程易发生探伤不合、切削性能差、带状组织严重、力学性能各相异性显著,甚至拉拔加工断裂等问题。MnS夹杂物多在铸坯凝固后期形成,随着轧制与钢基体同步变形,控制该类钢种铸坯内MnS原始尺寸成为控制热轧材中MnS夹杂物形态及尺寸的最关键环节。为控制热轧超高硫中碳钢盘条中MnS夹杂物,利用钢坯凝固数值模拟、第二相析出理论、Ostwald熟化理论计算分析了160 mm2钢坯中硫元素偏析及MnS的生成、长大和熟化过程。计算结果表明,当固相分数f_s为0.446、硫微观偏析比达到2.19时,铸坯在凝固末期生成MnS。凝固过程中MnS的生长过程决定了钢坯中MnS颗粒的直径。理论计算表明,当连铸二次冷却水量固定为0.6L/kg时,拉速为1.6、2.1和2.6 m/min时,160 mm2方坯中心的MnS分别增长到30.6、32.2和34.6 μm,与实际测试结果一致。控制该类钢种线材中MnS尺寸的关键是提高二冷区的冷却强度,降低连铸拉速。基于该系列计算方法,提出了160 mm2钢坯中与MnS直径控制目标相匹配的连铸工艺参数控制范围。     

钢连铸过程的溶质微观偏析模型

建立了钢凝固过程包含δ/γ相变及MnS夹杂析出的溶质微观偏析模型。分析了钢种成分、MnS夹杂物析出及冷却速率对钢凝固过程高温力学性能的影响,模型计算结果与文献报道的实测零强度温度(ZST)和零塑性温度(ZDT)吻合良好。     

热力学分析MnS夹杂物析出与控制

 为了深入研究与控制重轨钢中大尺寸MnS夹杂物,针对目前热力学计算MnS析出行为问题,提出在应用时需要根据实际条件做相应的选择进行计算。在比较了目前几个常用的热力学数据后,基于U75V钢中MnS夹杂物形成过程,建立了适合计算MnS夹杂物析出的分段计算方法。研究表明,采用FactSage 6.4商业软件计算MnS析出温度为1 631 K,与平衡热力学参数计算的结果1 694 K相差63 K。该方法可准确预测MnS的析出行为,降低了热力学分析MnS析出的难度。在1 473、1 573 和1 673 K 3个温度下固溶硫质量分数分别为0.000 67%、0.001 67%和0.010 8%。在铸坯轧制之前的开坯和保温温度为1 563 K时,需要将钢中硫质量分数降低到0.001 67%以下,才能有效控制大尺寸的MnS夹杂物。     

MnS在固态低硫钢中析出的实验室研究

采用高温激光共聚焦显微镜对低硫钢试样抛光表面的MnS夹杂物析出进行了观察,利用高温激光共聚焦观察结果进行了控温轧制M nS析出试验,用SEM-EDS和ASPEX分析了析出物的成分.结果表明,MnS在表面的首次析出发生在1067℃并伴随有表面变形,在859.7℃当界面能随表面变形释放后停止,MnS的第二次析出发生在790...     

Effect of Zr addition on morphology characteristics of MnS inclusions in medium carbon high sulfur free cutting steel

In order to improve the morphology characteristics of MnS inclusions in medium carbon high sulfur free-cutting steel, Zr alloy with different contents were added into the 2kg vacuum induction furnace in laboratory, and the characteristics of oxides and sulfides in steel with different Zr additions were investigated with scanning electron microscope and energy dispersive spectrometer (SEM-EDS). The formation mechanism and process of different MnS inclusions were analyzed with thermodynamic software Thermo-Calc. The results show that sulfides in the experimental steel without Zr element are mainly type II MnS with cluster morphology and a small number of type I MnS with large size, and the size and spatial distribution of the sulfides are extremely uneven. After adding 0.0015 mass% of Zr element, the sulfides in the steel are mainly distributed along the grain boundary with cluster morphology. Complex sulfides account for only 01%. As the Zr content further increases to 0.0051 mass%, fine and pure ZrO2 particles are generated in the steel, which provides a sufficient oxide nucleus for MnS formation, weakens the distribution behavior of sulfides in grain boundary polymers, and improves the distribution uniformity of sulfides. Thus, oxides in steel can be used to improve the morphology of sulfides even under the condition of high S/O ratio. The key is to obtain second phase particles with fine size and efficient nucleation ability.     

中碳高硫易切削钢中Zr添加对MnS夹杂物形貌特征的影响

摘要：为改善中碳高硫易切削钢中MnS夹杂物形貌特征,在2kg真空感应炉开展了钢中添加Zr金属的试验。利用SEM-EDS研究了不同Zr含量下钢中氧化物和硫化物的形貌特征,并利用Thermo-Calc软件分析了中碳高硫易切削钢中不同种类MnS的形成过程和机制。结果表明：不添加Zr元素的试验钢中,硫化物主要为簇状形貌的II类,以及少量大尺寸的I类,尺寸和空间分布都很不均匀。加了质量分数为0.0015%的Zr元素后,钢中硫化物基本上是以沿晶界分布的簇状形貌存在,复合硫化物占比只有0.1%。随着Zr质量分数进一步增加至0.0051%,钢中主要生成细小的、纯ZrO2氧化物粒子,为硫化物提供了大量形核核心,减弱了硫化物在晶界聚集的分布行为,提高了硫化物的分布均匀性。试验结果表明,高硫氧比条件下,同样可以利用钢中氧化物粒子改善MnS形貌,关键是得到细小尺寸、高效形核效果的第二相粒子。     

Thermodynamic Calculation and MnS Solubility of Mn-Ti Oxide Formation in Si-Mn-Ti Deoxided Steel

 Mn-Ti oxides in Si-Mn-Ti deoxidized steels after cooling in the furnace were investigated. The composition and morphology of inclusions were analyzed by using FE-SEM with EDS. Mn-Ti oxides were found to be effective sites to induce intragranular ferrite formation. The thermodynamic calculation was employed to interpret the critical condition for Mn-Ti oxide formation. Mn-Ti oxide formation is controlled not only by [Mn], [Ti] content, but also by total oxygen in steel. When [Mn] and [Ti] were around 1.5 wt% and 0.005~0.01 wt% respectively, Mn-Ti oxide could form as total oxygen was 0.001~0.002 wt%. The experimental results are in good agreement with thermodynamic calculation results. Also MnS solubility was examined in Mn-Ti oxide inclusion system. With MnO content in Mn-Ti oxide increasing, MnS solubility in these oxides increased. High MnO content had an benefit on MnS precipitation in Mn-Ti oxide.     

含钛钢奥氏体中第二相析出的热力学分析和实验研究

基于含钛钢中各析出相之间的相互溶解现象,建立热力学模型,研究了低碳含钛钢中的ＴｉＮ、ＴｉＣ、ＴｉＳ、Ｔｉ４ｃ２ｓ２及ＭｎＳ等第二相在奥氏体中的平衡析出规律,对２０ＣｒＭｎＴｉ钢种成分的计算结果表明：该类含钛钢中的析出相主要为ＴｉＣｙＮ１－ｙ、Ｔｉ４Ｃ２Ｓ２及ＭｎＳ,且钛和硫含量在规格范围内的波动可导致它们析出的次序和数量发生明显的变化,对该钢种的实验研究表明,高温冷却过程中,脱溶析出的细小的沿晶Ｔｉ４Ｃ２Ｓ２等粒子是钢在奥氏体高温塑性恶化的原因之一。     

稀土元素对MnS夹杂物变形能力影响的价电子理论分析

基于固体与分子经验电子理论，计算了MnS及固溶稀土元素的（Mn，RE）S的相空间价电子结构及与合金相硬度和塑性有关的价电子结构参数，即最强键上的共价电子对数和晶格电子密度。用价电子结构参数nA和ρT^L分析讨论了稀土元素使MnS抗变形能力增大的微观本质原因。发现稀土元素溶入后减小了MnS的晶格电子密度，增大了相邻密排面间最强共价键的结合能力，增大了滑移的难度，进而使MnS的抗变形能力增强，并发现随着MnS中固溶稀土量的增多，MnS的抗变形能力逐渐增强。     

Effects of Al content on non-metallic inclusion evolution in Fe–16Mn–xAl–0.6C high Mn TWIP steel

In the present study, the effects of Al content on the evolution of inclusions formed in Fe–16Mn–xAl–0.6C high Mn TWIP steels were investigated experimentally and discussed based on the thermodynamic calculation with FactSage. The results showed that with the increase of Al content from 0.002 to 2.1?wt-% in the steels, the evolution route of the main oxide inclusions is MnO?→?Al₂O₃?→?MgAl₂O₄?→?MgO, the main sulphide inclusion is changed from MnS to MgS, and the dominant stable inclusion changes along the route of MnO?→?Al₂O₃/MnS?→?MnS?→?AlN. The main inclusion types in thermodynamic calculation results with FactSage are consistent with the observed results in the present experimental steels.     

Modelling of Manganese Sulphide Formation during Solidification,Part II: Correlation of Solidification and MnS Formation

The high temperature properties of steels depend on the solidification parameters and the formation parameters of manganese sulphide precipitates. Therefore, the occurrence of MnS precipitations in relation to primary and secondary microstructures was studied for different steel grades with a primary delta‐ferritic solidification or a primary austenitic solidification. The liquidus and solidus temperatures as well as the δ‐γ‐transformation temperature were calculated thermodynamically and measured by a DTA analysis in order to describe the solidification and transformation temperature range. The MnS formation temperature was calculated thermodynamically and compared to the results of SEM/EDX investigations on fracture surfaces of hot tensile specimens torn at different temperatures after in situ melting and controlled solidification. A special focus of these investigations was the location of MnS precipitates in relation to the primary and secondary grain boundaries. To explain the results, calculations were carried out taking into account the supersaturation of manganese and sulphur during the solidification in residual melt on the primary grain boundaries.     

车轴钢铸锭中MnS的生成、长大、熟化规律分析

 为降低大尺寸MnS夹杂物引起的车轴磁粉探伤不合格率,利用第二相析出理论以及铸锭凝固数值模拟计算相结合,计算分析了车轴钢铸锭中MnS生成、长大、熟化规律。计算结果显示,MnS形核核心尺寸与熟化过程尺寸增加均为纳米级,凝固过程MnS的长大决定凝固完成时MnS粒子直径,理论计算得到车轴钢铸锭竖直中心线上冒口、中心、底部位置对应的MnS长大后尺寸分别为156.35、107.37和94.96 μm,中心处MnS尺寸为连铸工艺条件下的2倍,与实际检测结果相符。钢锭凝固过程缓慢是MnS易于长大的直接原因,显著区别于连铸过程。在现有工艺条件下,为控制车轴钢模铸钢MnS尺寸,关键在于降低钢液硫质量分数以及控制硫偏析。控制车轴成品中MnS夹杂物不超过1.5级,需降低钢液中w([S])至0.004 3%以下。     

Relationship Between Inoculants and the Morphologies of MnS and Graphite in Gray Cast Iron

The influence of oxides and sulfides in gray cast iron on the growth morphologies of MnS and on the nucleation of graphite was experimentally investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDX) analysis with evidences that shows the possible nucleation sites for graphite nucleation. Thermodynamic studies have been done on the influence of varying sulfur concentrations on the nucleation of MnS in the melt and during solidification. The consumption of dissolved oxygen and sulfur in the melt during the cooling process was analyzed and we explored how this influenced the nucleation process of oxides and sulfides. A sequential nucleation concept of oxides and MnS is proposed in relation to the growth morphology of MnS and graphite with respect to the mechanical properties of cast iron. The nucleation of new oxides and sulfides was analyzed using thermodynamics and compared to our experimental results. Graphite nucleation on substrates other than MnS, such as MoS₂ oxides and (Mo,Cr)S, was experimentally analyzed along with the influence of the substrates on graphite nucleation and growth morphology.     

Effect of Chemical Composition on Oxide Transformation and MnS Precipitation Upon Oxide Particles in Fe-Cr Alloy by Heat Treatment

The transformation of nonmetallic inclusions and the change of MnS precipitation ratio on oxide particles during heat treatment were studied by using Fe-10%Cr alloy containing different Si and S content in the present study. The phenomenon of oxide transformation in alloy in this research was characterized according to Si content. When the Si content was lower, the typical inclusions changed from MnO?SiO2 type to MnO?Cr2O3 type by heat treatment. In the case of high S concentration, the obvious MnS area in inclusions was observed after heat treatment. It was more favorable for MnS precipitation as the S content was improved from approximately 20×10-6 to 60×10-6. The MnS precipitation ratio on oxide particles was higher on MnO?SiO2 type than MnO-Cr2O3 type oxide particles. Besides, the ratio on the two kinds of oxides increased with increasing the time for heat treatment at 1473K as a whole. The theoretical Mn content at which MnS can precipitate agrees well with the experimental results.     

Modelling of Manganese Sulphide Formation during Solidification,Part I: Description of MnS Formation Parameters

Precipitations of second phases in steel grades influence the mechanical properties of the material significantly. Manganese sulphides especially affect the ductility properties at high as well as at low testing temperatures. For a sufficient appreciation of the influence of MnS precipitates on the properties, a proper knowledge about the parameters in regard to the size and distribution of MnS precipitates is necessary. This paper proposes a model to describe the solidification of a medium carbon steel grade, the micro‐segregation of manganese und sulphur and the subsequent precipitation of MnS. Especially for the calculation of the mean radius of globular MnS precipitates after solidification, a new approach is presented regarding the MnS size as a function of the manganese and sulphur content, the cooling rate during solidification and the secondary dendrite arm spacing. The model is validated by means of quench tests in combination with light‐optical and scanning electron microscopic evaluations of the size distribution of MnS precipitates as well as EDX analysis for the composition of the formed sulphide phase.     

含硫、稀土、铋等合金元素的易切削奥氏体不锈钢研究

 奥氏体不锈钢是难加工的材料。通过在传统的奥氏体不锈钢中添加硫、稀土和铋,经过钢锭熔炼、切削试验、组织性能检测,对其切削性能和力学性能进行了研究。结果表明,奥氏体不锈钢中的夹杂物主要由MnS组成。稀土包裹在MnS中,金属夹杂物铋以尾状物附于MnS的两端。稀土具有明显的变质作用,易切削奥氏体不锈钢中的夹杂物大部分呈球状或纺锤状。硫、稀土和铋合金元素的添加降低了切削力、减轻了刀具的磨损、改善了切屑的形状。所开发的合金获得了极好的切削性能。由于硫和铋都是软的相,在变形过程中它们并不诱发裂纹的形成。呈球状的夹杂物不仅有利于切削性能的改善,而且还有利于钢获得良好的力学性能。     

Morphological Differences of MnS Inclusions in Medium-Carbon Steel with Different Manganese and Sulfur Contents

The morphology of MnS inclusion is one of the key elements influencing the machinability of steel. Herein, it is shown in the thermodynamic analysis results that the interaction coefficient causes a 1.2% deviation for the precipitation of MnS in low-sulfur-content steel (S1), while the deviation is 14% in high-sulfur steel (S2), and the content of C and Si is the main element causing the deviation. The microstructure of medium-carbon steel is mainly pearlite and ferrite. The increase of manganese and sulfur content leads to the decrease of ferrite content and increase of pearlite content. Almost all MnS inclusions in S1 are polyhedral, while S2 contains spherelike, cluster, and polyhedral MnS inclusions. Manganese and sulfur mainly affect the nucleation rate of MnS inclusion, where the number density of MnS in S2 is higher than that in S1, which increases the probability of viscous sintering of MnS inclusions in S2, and form spherelike- and rodlike-polycrystalline MnS particles. Polyhedron inclusions are mostly octahedron, and it is the final equilibrium morphology of sulfide in S1 and S2.