稀土铈对55SiCr高应力弹簧钢夹杂物的改性作用

 55SiCr高应力弹簧钢主要用于制造交通工具的气门、悬架和制动弹簧,钢中的大颗粒复合夹杂物所引起的疲劳破坏和长条形MnS所造成的各向异性与氢致裂纹敏感性等是降低弹簧服役寿命的重要原因。从冶炼环节对此类夹杂物进行改质改性并使其细小、无害化是提高弹簧服役性能的重要途径。基于高温管式炉冶炼试验并结合SEM、EDS检测和热力学计算等方法探究了稀土铈对55SiCr钢中夹杂物的改性机制以及铈含量对夹杂物的影响规律。结果表明,钢水中加入铈后,首先生成大量小尺寸稀土夹杂物;随着反应进行,夹杂物数量逐渐减少,大多数夹杂物得以上浮去除。适量铈可以起到净化钢液作用。此外,铈的添加量对夹杂物特性影响很大。当铈添加量为0.02%时,钢中的夹杂物主要为被铈不同程度改性的MnS夹杂以及Ce-O-S、Ce-S类夹杂,尺寸大多为1~3 μm,呈球形或椭球型;当铈添加量增加至0.26%时,MnS夹杂消失,形成大量有棱角、不规则的Ce-O和Ce-O-S类夹杂,对钢的疲劳性能将产生不利影响。铈通过3种方式改性MnS夹杂, 从MnS四周向内扩散进行、从MnS夹杂物一侧改性以及从MnS中部开始改性。从控制夹杂物无害化角度,建议适宜的稀土添加量为0.01%~0.02%,此时钢中铈质量分数为0.009%~0.014%。     

稀土-镁复合处理对GCr15轴承钢中夹杂物的影响

为了尽可能的去除钢中大颗粒的夹杂物, 在实验条件下通过向GCr15轴承钢中添加适量镁、稀土对夹杂物进行改性, 并利用Aspex夹杂物自动分析仪和扫描电镜对钢中改性后的夹杂物尺寸、类型、形貌等进行了观察、分析, 研究了稀土-镁复合处理对夹杂物的影响规律.研究结果表明, 对轴承钢中加入微量镁处理, 可将未进行镁处理钢中的MnS-Al₂O₃、MnS、Al₂O₃夹杂改性为以含硫、镁复合夹杂物为主, 同时包含少量Al₂O₃、镁铝尖晶石夹杂.进一步采用稀土-镁复合处理后, 钢中的夹杂物转变为主要以含Re-S-O夹杂物为主, Al₂O₃、MnS、镁铝尖晶石夹杂逐步消失, 且夹杂物成球状分布, 绝大多数夹杂物在5 μm以下.稀土-镁复合处理轴承钢后, 10 μm以上的大颗粒夹杂物大大降低, 钢中的夹杂物明显得到细化.钢中镁含量不变时, 随着稀土含量的增加, 大颗粒夹杂物比例明显下降.而在稀土含量相近的情况下, 增加钢中的镁含量也有利于大颗粒夹杂物的去除.稀土-镁的相互作用进一步促进了夹杂物的细化.      

含稀土抽油杆用钢的疲劳试验

包钢开发的含稀土抽油杆用钢疲劳循环周次达到500万次不断。钢中稀土的赋存状态和夹杂物检验结果表明,稀土改变了MnS夹杂物的形态及其尺寸,MnS夹杂物由长条状变性为球状,尺寸明显减小了,因此含稀土抽油杆用钢疲劳寿命获得明显提高。     

含铈IF钢中铈夹杂物的热力学分析及实验研究

研究了含铈IF钢中铈夹杂物生成的热力学规律,以及铈对钢液中Al_2O_3夹杂物的变质机理,并采用扫描电子显微镜及能谱仪观察和分析了IF钢和含铈IF钢中的主要夹杂物,结果表明,铈在氧、硫含量均小于0.0006%的超低氧、硫IF钢中仍能够同时脱氧、脱硫、脱磷,具有净化钢液作用;含铈IF钢中的稀土夹杂物主要为Ce_2O_3、Ce_2O_2S、CeAlO_3夹杂物,各稀土夹杂物呈球状或椭球状,且尺寸均小于2μm,钢中未发现稀土硫化物夹杂;含铈IF钢中的Al_2O_3夹杂物被铈变质为尺寸较小的CeAlO_3夹杂物。     

铈对Fe-28Mn-10Al-1C低密度钢中非金属夹杂物的影响

为了研究稀土铈对Fe-28Mn-10Al-1C低密度钢中非金属夹杂物的影响机理,通过扫描电子显微镜（SEM）、能谱分析仪（EDS）及Image J软件对比分析了稀土处理前后夹杂物的形貌、成分、尺寸和数量,并基于热力学计算阐明了稀土铈对夹杂物的改性机理。研究结果表明,低密度钢中典型夹杂物为AlN和AlN-MnS复合夹杂物,钢中AlN夹杂物较多,尺寸较大,平均直径为3.64μm;向低密度钢中添加（质量分数）0.001 9%铈后,夹杂物以球状AlN-Ce2S3、AlN-Ce2S3-MnS、AlN-MnS复合夹杂物和单一AlN夹杂物为主,整体夹杂物数量最少,夹杂物平均直径及长宽比降低,平均直径为3.08μm;向低密度钢中添加（质量分数）0.013%铈后,夹杂物则以球状Ce2S3、附着态AlN-Ce2S3和单一AlN夹杂物为主,夹杂物数量异常升高,1～4μm夹杂物所占比例较大,平均直径为2.52μm。稀土处理可有效细化夹杂物尺寸并改善大尺寸氮化物和硫化物夹杂的形貌特征,未检测到单一MnS及Al2O3夹杂物。此外,通过FactStage 8.0热力学计算软件分析了稀土铈对Fe-28Mn-10Al-...     

含钇E36船板钢夹杂物改性

为了研究钇对E36船板钢中夹杂物成分和形貌的影响,对钇处理后E36船板钢中典型夹杂物进行热力学计算,并通过扫描电镜及能谱仪对钇处理前后E36船板钢中夹杂物进行检测分析,观察典型夹杂物形态和尺寸。结果表明,未添加稀土钇的E36船板钢主要为长条状MnS夹杂物;添加稀土钇后,钢中夹杂物主要为球状或类球状的含钇复合夹杂物。当钢中钇质量分数为0.007 8%时,夹杂物主要为球状或类球状的Y₂O₂S夹杂物和Y₂O₃夹杂物;当钢中钇质量分数增加至0.037 7%时,夹杂物改性为球状或类球状Y₂O₂S夹杂物、YS夹杂物和Y₂O₃夹杂物。     

稀土对含铜锡铁素体不锈钢中非金属夹杂物的影响

为定量研究稀土元素对含铜锡铁素体不锈钢中变质夹杂物、净化钢液的作用,基于FactSage热力学软件最小吉布斯自由能原理,模拟计算不同稀土添加量条件下钢中夹杂物转变规律。同时,结合实验室小坩埚热模拟试验发现,随着稀土质量分数的增加,含锡铜铁素体不锈钢中Al_2O_3夹杂变质成硬度较低的CeAlO_3,MnS夹杂逐渐转变成CeS。钢中夹杂物逐渐转变为球状的稀土类夹杂,夹杂物尺寸为1~3μm,同时钢中夹杂物总量有所下降。当钢中稀土质量分数增加到0.057%时,CeAlO_3进一步转化成Ce_2O_3,钢中MnS也完全转变成CeS。然而,夹杂物尺寸、数量有所增加,反而使钢液进一步被污染。因此,从夹杂物控制角度考虑,试验钢中稀土最优添加量为0.035%。     

Ce-La合金化处理对取向硅钢夹杂物特征的影响

 为了研究稀土处理对取向硅钢中夹杂物特征的影响,借助FE-SEM/EDS和图像分析软件分析了稀土处理前后热轧取向硅钢夹杂物的成分、形貌、尺寸和数量并解明了影响机理。研究结果表明,未添加稀土的试验钢中,典型的夹杂物为形貌不规则的MnS-AlN复合夹杂物以及片状或条状的AlN夹杂物;添加稀土后,夹杂物则以球状或椭球状的CeS-LaS、CeS-LaS-AlN、Ce₂O₂S-La₂O₂S复合夹杂物和AlN夹杂物为主。稀土处理有效改善了夹杂物形貌,特别是大尺寸氮硫化物的形貌特征,未检测到MnS类夹杂物。尽管加入较多的稀土后夹杂物数量增加,大于5 μm夹杂物的平均尺寸增大量明显(增大0.89 μm),但整体夹杂物的平均尺寸仅增大了0.40 μm。由于稀土的脱硫作用,且稀土硫化物与AlN晶格常数差异大,钢中氮硫化物的数量密度和面积分数降低。稀土降低了AlN在钢中的平衡溶度积,使AlN夹杂物提前析出,导致AlN夹杂物数量增多,且先析出的AlN出现一定程度的长大。稀土对MnS在凝固前沿的析出有抑制作用,有利于热轧和常化过程析出更多用作抑制剂的MnS和AlN。在充分脱氧的取向硅钢中适当降低钢中酸溶铝含量,调整稀土在钢中的用量,在不增加钢中大尺寸夹杂物含量的前提下,发挥MnS、AlN抑制剂作用和Ce-La合金化作用。此外,通过稀土处理控制钢中夹杂物形貌特征,将有望达到改善钢的热轧组织和轧制加工性能的目的。     

水溶液电解法研究铈对含钛夹杂物的影响

通过水溶液电解法将钛微合金钢中的含钛夹杂物完整地电解提取出来,并采用物理磁选的方法实现夹杂物的无损分离。含钛夹杂物经过超声分散、滴撒夹杂物悬浊液的方式进行制样,并结合扫描电镜研究其形貌。研究发现:随稀土加入量的增加,含钛夹杂物形貌发生不同程度的改变。不添加稀土铈时,钢中含钛夹杂物为典型的长方体形貌。加入0.003 8%稀土铈时,长方体含钛夹杂物转变为正方体含钛夹杂物。稀土加入量为0.005 4%、0.007 2%、0.009 8%时,形成TiC-CeAlO_3、Ti(C,N)-CeAlO_3,含钛夹杂物逐步向椭球形、球形转变,从棱角分明的形状转变为具有光滑曲面的夹杂物并且含钛夹杂物的尺寸减小。随着稀土加入量的增加,钢中含钛夹杂物的析出数量增加,直径小于1μm的含钛夹杂物析出比例增加、含钛夹杂物的平均尺寸逐渐减小。     

钢中不同氧含量对含S钢的MnS夹杂物影响

采用ASPEX自动扫描电镜,分析对比不同氧含量对钢中MnS类夹杂物的组成和形貌的影响。对比结果表明:当钢中氧含量处于高水平时,MnS夹杂物在整个含MnS类夹杂物中所占比例为70.89%,含MnS类夹杂物的尺寸指数为1.98;当钢中氧含量处于低水平时,MnS夹杂物在整个含MnS类夹杂物中所占比例为93.84%,含MnS类夹杂物的尺寸指数为4.5,夹杂物的外观由椭圆型转变为细长型。     

稀土元素铈对钢中非金属夹杂物改性和腐蚀影响的第一性原理研究

通过原位腐蚀观察和基于密度泛函理论的第一性原理计算方法,从微观角度研究了稀土元素铈（Ce）对J5不锈钢中夹杂物的改性和夹杂物诱导腐蚀的机理。采用扫描电子显微镜与能谱分析了稀土元素Ce改性夹杂物的过程中夹杂物成分和类型的变化,观察到的代表夹杂物为CeAlO₃?Ce₂O₂S、Ce₂O₃?Ce₂O₂S、MnS等。根据形成能计算,经稀土元素Ce处理后,生成了稳定的Ce₂O₃、Ce₂O₂S、CeAlO₃夹杂物。通过表面能判断了晶面的稳定性,Fe(100)-2面的表面能经收敛测得为2.4374 J·m?2,该晶面的功函数为4.7352 eV。通过对比夹杂物与钢基体的功函数与计算电势差,分析了不同含Ce夹杂物诱导点蚀的趋势,探讨了不同原子位置、原子数量和不同slab模型对功函数的影响。研究表明,与Fe (100)-2面的电子功函数相比,MnS以及改性后3种夹杂物CeS、Ce₂O₃和Ce₂O₂S电势差大多小于0,CeAlO₃的电势差在0 eV左右。夹杂物不同晶面对功函数影响很大,O、S等非金属原子数量多的晶面功函数平均值较高,添加稀土元素Ce可以有效降低晶面功函数。5种夹杂物和钢基体的平均功函数大小顺序为CeAlO₃>Fe>MnS>CeS>Ce₂O₂S>Ce₂O₃。结合不锈钢中复合夹杂物的实验结果可知,Ce₂O₃诱导点蚀发生的概率最高,CeAlO₃可以有效提高钢的耐腐蚀能。      

Pitting corrosion behavior of Cu-P-RE weathering steels

The weathering steels are prone to pitting corrosion in an environment containing chloride ions.The pitting behavior of Cu-P-RE weathering steels and its effect on the corrosion resistance of steels were investigated by multifarious analytical techniques,such as field emission-scanning electron microscopy(FE-SEM),electron probe microanalysis(EPMA),scanning Kelvin probe force microscopy(SKPFM),electrochemical workstation and a series of immersion tests.The results show that the original stripshap...     

Correlation Between Nonmetallic Inclusions and Localized Corrosion of a Low-Nickel Stainless Steel with Cerium Treatment

The localized corrosion induced by different kinds of inclusions in low-nickel stainless steel is studied through immersion tests and first-principles calculations. The galvanic corrosion between the steel matrix and different kinds of inclusions occurs in the corrosive environment due to the difference in the electron work function of the steel matrix and inclusions. The electron work function of MnS, CeS, and Ce-O-S is smaller than that of the steel matrix, thus, these inclusions first dissolve as the anode. However, the electron work function of cerium-containing oxides is bigger than that of the steel matrix, and the steel matrix dissolves prior to cerium-containing oxides. The order of the volume expansion rate of pits induced by inclusions is CeS > Si-Mn(-Al)-O > MnS > Ce-C-O-S > Ce-Si-Mn(-Al)-O > Ce-O-S. For cerium-containing inclusions, the electron work function of inclusions increases with the increase of the O/Ce ratio and the S/Ce ratio of inclusions. The order of the electron work function of cerium-containing inclusions is cerium oxides > cerium sulfides > cerium oxysulfide.     

稀土在铁素体不锈钢中的研究现状及发展前景

摘要：铁素体不锈钢具有“节镍资源型”特性及优良的综合性能,被广泛应用于轨道运输、汽车、家电和厨具等行业中。稀土作为战略性资源在不锈钢中的应用已有多年,国内外学者在这方面做了大量研究。归纳和总结了稀土对铁素体不锈钢组织和性能等方面的影响,并对其在钢中的作用机制和影响机制进行了简要分析。大量研究表明,稀土能将钢中不规则状且电子功函数较小的A12O3、MnS夹杂改性为电子功函数较大的球状稀土复合夹杂;此外,稀土能降低钢中晶粒尺寸,净化其晶界,对钢的凝固组织、退火组织等金相组织起到明显的细化作用,提高其耐蚀性能和力学性能。最后展望了稀土在不锈钢中的发展前景。     

Effect of Al2O3–SiO2–MnO inclusions on precipitation of MnS in Si–Mn-killed 304 stainless steels

Laboratory experiments and thermodynamic calculation were conducted to investigate the precipitation of MnS inclusions in Si–Mn-killed 304 stainless steels with various Al and S concentrations. Three types of MnS-contained inclusions were detected: MnS phase dissolved in the MnO–SiO₂ inclusion, the Al₂O₃-rich core phase surrounded by a MnS out layer, and the individual MnS. In steel with less than 0.001% Al, the liquid SiO₂–MnO-rich inclusions can hardly influence the precipitation of MnS inclusions during the cooling process of 304 stainless steels. With the increase of Al in steel, more solid Al₂O₃-rich inclusions are formed, which can act as nucleation agents for MnS inclusions and dramatically promote the precipitation of MnS inclusions during the cooling process of Si–Mn-killed 304 stainless steels.     

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%.     

Pitting corrosion behavior of cerium treated HSLA steel induced by sulfide inclusions in 3.5 wt% NaCl solution

Pitting corrosion behavior of Ce treated HSLA steels induced by sulfide inclusions in 3.5 wt% NaCl solution was investigated with potentiodynamic polarization and immersion corrosion test.The results show that Ce added steels exhibit better pitting corrosion resistance with lower corrosion current density and bigger pitting potential compared with steel without Ce,which is mainly attributed to optimized characteristics of spherical Ce-oxysulfide inclusions with less number density,smaller average size and lower pitting corrosion susceptibility.The spherical Ce₂O₂ S inclusions precipitated on the surface of CeAlO₃ inclusions in the Ce added steels induce pits with bigger opening mouth and shallow depth,reducing their tendency of extension to go deeper due to occlusion corrosion battery in the pitting holes.Furthermore,corrosion inhibitor Ce(OH)₃ generated by Ce₂O₂ S hydration can weaken electrochemical corrosion of the matrix micro-region around the pits.To avoid harmful bigger inclusions,Ce content in steels should be regulated within reasonable range,0.015 wt% Ce in present steels effectively modified inclusions to acquire the best pitting corrosion resistance of the steels.     

Effects of rare earth on inclusions and corrosion resistance of 10PCuRE weathering steel

The types,morphologies and distributions of nonmetallic inclusions in Cu-P weathering steels with and without rare earth were analyzed through a quantitative image analyzer,scanning electron microscopy(SEM)and energy dispersive spectroscopy(EDS)attached to SEM.Solid-soluble content of rare earth in the steels was analyzed by non-aqua electroanalysis and ICP.The results showed that rare earth modified the types and the morphologies of inclusions in the weathering steels.The small spherical rare earth oxysulfides and rare earth sulphides replaced the elongated MnS inclusions in the RE weathering steels.The rare earth inclusions dispersedly distributed and most inclusions were smaller than 2 μm in size.The optimum content of RE was 0.0065%-0.016% for 10PCuRE weathering steels containing about0.002% oxygen and 0.004% sulfur.Solid-soluble content of rare earth in steels was(14-20)x 10-6,which can act as a micro-alloying element.The corrosion resistance of 10PCuRE weathering steels and Q235 were studied by dry-wet cyclic immersion test.Their corrosion rates were obtained respectively.The polarization curves and pitting corrosion behaviors of weathering steels with and without rare earth were measured by electrochemical methods.The corrosion resistance of Cu-P weathering steels was improved by adding an appropriate amount of rare earth.Less and fewer rare earth inclusions largely decreased pitting susceptibility and rate of pit propagation.The pitting potential and the resistance against pitting corrosion of the RE weathering steel were significantly improved due to the modification of rare earth to inclusions.     

Effect of sulfur content on non metallic inclusions of heavy rail steel

Due to the inaccurate control of raw materials and operation in the actual production process, the sulfur content and non-metallic inclusions in the steel fluctuate greatly, which seriously affects the cleanliness of steel. To accurately control the size, shape and quantity of non-metallic inclusions such as manganese sulfide in heavy rail steel, the effect of sulfur content on non-metallic inclusions in heavy rail steel was studied in the laboratory. To investigate the changes of the number and morphology of non-metallic inclusions in steel under different sulfur contents, the sulfur content of test steel was increased to 70×10-6, 110×10-6 and 140×10-6, respectively. During the experiment, the test steel was heated and melted in a tubular furnace according to a certain heating rule, and then cooled naturally in the furnace. Subsequently, the non metallic inclusions in steel were scanned by automatic inclusions analyzer, and the relationship between sulfur content and the composition, size, form and quantity of non-metallic inclusions in steel was obtained. The results indicate that most of the inclusions in the steel are composite MnS with oxides as nucleating cores. With the increase of sulfur content, the quantity density of composite MnS, MnO-SiO2 and MgO-Al2O3-SiO2-CaO inclusions increase, while the CaO-SiO2 and MgO-CaO-SiO2 inclusions decrease. The average size of inclusions increases with the increase of sulfur content, and the number of inclusions with different sizes also increases, especially for inclusions with sizes of 2-10μm which increase obviously. During solidification, MnS can be separated from molten steel with sulfur content of (70-140)×10-6. In addition, the higher the sulfur content is, the earlier MnS inclusions precipitate and the more the MnS content is.     

Effect of Modification Treatment on Inclusions in 430 Stainless Steel by Mg-Al Alloys

 Refining process of 430 stainless steel in AOD (argon oxygen decarburization) was simulated under the experimental condition. Al was chosen as deoxidizer, Mg-Al alloy was added in process of refining, and slag used in oxidation period of AOD was chosen in the experiments. The variation of total oxygen content, the size, morphology and composition of inclusions in refining process and the mechanical properties, pitting corrosion resistance of final samples were studied. The results show that no obvious differences in total oxygen content were observed among all the experiments. Neither chain nor cluster Al2O3 inclusions were found in refining process of experiments treated by Mg-Al alloys, the average size of inclusions in the steel treated by Mg-Al alloys was less than that of inclusions in steel not treated by Mg-Al alloy. 430 stainless steel treated by Mg-Al alloy shows better tensile strength, yield strength, and pitting resistance than that in the contrast experiment.