Microprocesses of metal dusting on iron

In strongly carburizing atmospheres iron and steels are subject to ‘metal dusting’, a catastrophic carburization, leading to disintegration into a dust of carbon and metal particles. TEM investigations of iron foils in different states of this corrosion process have clearly shown now that unstable cementite is an intermediate in the reaction. The carbide is formed at the iron surface after supersaturation (a_C > 1), its disintegration is started by graphite deposition on its surface (a_C = 1). The carbon atoms from Fe₃C disintegration are attached to the graphite planes which are vertically oriented to the cementite surface, the iron atoms diffuse through the graphite and agglomerate to small particles (～ 20 nm) which act as catalysts for further carbon deposition from the atmosphere, till they are densely covered with graphite. The TEM investigations are in good agreement with preceding studies concerning kinetics and mechanisms of metal dusting.     

Study on the friction and wear properties of the surface nanocrystallized 1.0C-1.5Cr steel induced by the surface mechanical attrition treatment

Nano-structured layers are fabricated on the surface of 1.0C-1.5Cr steel by using the surface mechanical attrition treatment(SMAT)technology,and the microstructures of the surface nano-crystallization layers are characterized by means of X-ray diffraction(XRD)and transmission electron microscopy(TEM).The friction and wear properties are also investigated by a UMT-2 friction and wear tester.Experimental research has indicated that the average diameter of nanocrystalline grains in the surface layer after being treated for 15 min is in the range of 10-20 nm,and ferrite and cementite grains can not be identified by their morphologies.The wear-resistance of the specimen treated for 15 min has been doubled,compared with that of the matrix due to the grain refinement to a nano-sized scale.The lowest friction coefficient is 0.27,which is for the specimen treated for 30 min,resulting from the dissolution of the cementite phase and the formation of a relative homogenous structure.The SMAT technique for enhancing the wear-resistance of the 1.0C-1.5Cr steel has an optimum processing time,which is in the range of 15-30 min.The dominant wear mechanism of the specimen treated for 15 min changes from adhesive wear into particle wear.     

Evaluation of Metal Dusting Behavior in Reformer Tube Made of HP–Nb Alloy on the Outer Surfaces

The metal dusting behavior of Iron–Chromium–Nickel heat resistant HP–Nb steel specimen was investigated at the outer surfaces while the methane gas was passed inside the hole of the specimen. After an exposure of 130 h in a flowing methane (CH₄) gas at 680 °C, different dispersed corrosion products were formed on the outer surface of the specimen near the hole. Conventional metallography and scanning electron microscopy were used to identify the microstructure of the reaction products. Energy dispersive X-ray spectroscopy was used for microchemical analysis. The phases produced on the surface were identified by X-ray diffraction. Some of reaction products found as surface deposits on the outer surfaces of specimen near the hole contained Fe and Cr carbides, Fe, Cr and Ni oxides, scale of Ni, Fe particles and free C. Results revealed that carbon nano-filaments materials could be formed during disintegration of heat resistant HP–Nb steel under metal dusting environment.     

Corrosion Products and Formation Mechanism During Initial Stage of Atmospheric Corrosion of Carbon Steel

The formation and development of corrosion products on carbon steel surface during the initial stage of atmospheric corrosion in a laboratory simulated environment have been studied by scanning electron microscopy （SEM） and Raman spectroscopy. The results showed that two different shapes of corrosion products, that is, ring and chain, were formed in the initial stage of corrosion. MnS clusters were found in the nuclei of corrosion products at the active local corrosion sites. The ring-shaped products were composed of lepidocrocite （γ-FeOOH） and maghemite （γ-Fe2O2 ） transformed from lepidocrocite. The chain-type products were goethite （α-FeOOH）. A formation mechanism of the corrosion products is proposed.     

Microstructure Evolution and Microhardness of Ultrafine-grained High Carbon Steel during Multiple Laser Shock Processing

Surface microstructure and microhardness of(ferrite+cementite)microduplex structure of the ultrafinegrained high carbon steel after laser shock processing(LSP)with different impact times were investigated by means of scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD)and microhardness measurements.Equiaxed ferrite grains were refined from 400 to 150nm,and the cementite lamellae were fully spheroidized,with a decrease of the particle diameter from 150 to 100nm as the impact times increased.The cementite dissolution was enhanced significantly.Correspondingly,the lattice parameter ofα-Fe and microhardness increased with the impact times.     

碳含量和组织类型对低合金钢耐蚀性的影响

研究了不同碳含量和显微组织的低合金钢的耐腐蚀性能和腐蚀行为,并与商业耐候钢09CuPCrNi进行了相应的比较.通过金相显微镜、扫描电镜观察,轧后水冷钢的主体组织为板条状贝氏体,轧后空冷钢为针状铁素体、粒状贝氏体、M/A小岛和少量渗碳体(珠光体)的混合物.用干湿循环加速腐蚀实验对耐蚀性测定结果表明:低碳钢(0.03%C)和轧后水冷的较高碳含量钢(0.1%C)的耐蚀性均明显优于09CuPCrNi;低碳含量钢的组织类型对其耐蚀性影响不大;较高碳含量情况下,单相贝氏体钢的耐蚀性优于由铁素体、渗碳体(珠光体)等构成的复相组织钢;轧后水冷时,不同碳含量的钢耐蚀性差别不大;轧后空冷时,低碳含量钢的耐蚀性优于较高碳含量钢.用扫描电镜对锈层进行观察,可以看出耐蚀性较好的样品在腐蚀后期形成了致密的内锈层.     

Research on the dissolution behavior of cementite in the GCr15 steel surface layer induced by surface nanocrystallization

Dissolution of cementite was found in the surface layer of 1.0C-1.5Cr steel plates during the process of surface mechanical attrition treatment(SMAT),and its evolution was characterized by transmission electron microscope(TEM),three-dimensional atom probe(3DAP)and Mssbauer spectroscopy.The average grain size contained in the top surface of SMAT specimen was 10nm,and no diffraction ring corresponding to cementite grain was identified in the selected area election diffraction(SAED)pattern,which indicated the disappearance of cementite.3DAP analysis showed the average carbon concentration in ferrite(0.75 at%)after SMAT,which was almost 100 times higher than that in matrix(0.008 at%),which suggested cementite dissolve in the process of SMAT.The results of Mssbauer spectroscopy indicated that partial cementite dissolved in the process of SMAT,the saturation of cementite dissolution is about 47%.Evolution of cementite involved three sub-stages:①inoculation stage,in the first 5 min of treated duration,cementite fraction is reduced only by 0.4%;②dissolution stage,within the following 25 min cementite fraction significantly is reduced from 14.6% to 8.4%;③saturation stage,when treatment exceeds 30 min,the fraction of cementite nearly remains the same.     

酸雨对低碳钢腐蚀行为的影响

利用金相显微镜(OM)、扫描电镜(SEM)、X射线衍射(XRD)等分析手段及电化学方法研究了低碳钢在模拟酸雨环境中的腐蚀行为.研究结果表明:碳钢在酸雨环境中腐蚀是一个局部腐蚀和均匀腐蚀并存的过程,溶液中的SO24-和Cl-离子的存在加速了碳钢表面腐蚀坑的形成和生长,腐蚀坑优先出现在铁素体上.腐蚀产物主要有Υ-FeOOH...     

Observations of Surface Relief of Proeutectoid Widmanstätten Cementite Plates in a Hypereutectoid Carbon Steel

Proeutectoid Widmanstätten cementite in a hypereutectoid carbon steel was found to be associated with a surface relief effect. A hot-stage microscope was used for heat treatment and in situ observation. Widmanstätten cementite plates were obtained near the surface of the specimen. The surface relief effect of Widmanstätten cementite plates was quantitatively characterized by atomic force microscopy. It was found that the relief had either a typical tent shape or apex-lost tent shape. The relief tilt angles were of considerable dispersion, ranging from 20 deg to 50 deg.     

石墨化钢石墨化过程的金相分析及其动力学方程

在650、680和710 ℃不同温度条件下对碳质量分数为0.66%的淬火高碳钢进行了石墨化处理,并利用场发射扫描电子显微镜、电子探针、X-射线衍射仪和透射电子显微镜对其石墨化过程的组织进行金相分析,以及利用组织转变动力学理论,绘制了其石墨化过程的动力学曲线,并建立了相应的动力学方程。研究结果显示:在石墨化过程中,淬火马氏体首先向析出碳化物的稳定状态转变,且在碳化物为渗碳体Fe₃C时,石墨粒子析出速度开始明显增加;基体组织中针叶状α-Fe发生再结晶,由等轴状铁素体逐步代替针叶状的α-Fe;铁素体中的碳含量随着石墨化时间的延长而逐步降低,即由过饱和状态转变为稳定态,碳含量在石墨粒子中突变增为峰值,而铁含量则突变降为谷值,由此表明,渗碳体分解的碳向石墨核心扩散,铁自石墨核心处扩散出来,而形成石墨粒子;石墨粒子面积分数随时间变化的曲线呈S形状,即该动力学过程符合动力学模型JMAK（Johnson-Mehl-Avrami-Kolmogorov）方程,且该方程中的n值为1.5～1.7。      

硫化氢质量浓度和温度对碳钢在NACE溶液中腐蚀行为的影响

采用动电位极化曲线和电化学阻抗谱等电化学实验方法以及扫描电镜和能谱等表面分析技术对20^#碳钢在不同H₂S质量浓度(0,95.61,103.22,224.16 mg·L^-1)、不同温度(25,35,45℃)下的NACE溶液(含CO₂)中腐蚀行为进行了研究,同时对该环境下腐蚀产物的形成机制进行了探讨.发现在含有CO₂的NACE溶液中,加入少量H₂S,能加剧碳钢腐蚀,加速阳极铁的溶解和阴极氢气的析出.随着H₂S质量浓度的增加,腐蚀电流密度增大,碳钢腐蚀加剧.温度升高,腐蚀极化电阻变小,腐蚀也会加剧.腐蚀试样外层絮状腐蚀产物主要是铁碳化物,接近基体表面的腐蚀产物主要是铁硫化物.     

表面纳米化诱导GCr15钢渗碳体溶解行为研究

高能机械球磨表面纳米化过程中发现表面纳米晶层内渗碳体发生溶解现象,采用TEM、三维原子探针和穆斯堡尔谱对渗碳体的溶解进行了表征。TEM观察结果表明,在纳米化的最表层平均晶粒为10 nm,在选区电子衍射花样中没有发现渗碳体的衍射环,表明渗碳体可能发生溶解。三维原子探针分析表明,表面纳米化处理后,铁素体中的碳含量为0.75at%,是基体铁素体碳含量的100倍,表明表面纳米化过程中渗碳体发生了溶解,通过穆斯堡尔谱分析结果表明,渗碳体的溶解量约为47%。表面纳米化过程中渗碳体的溶解可分为三个阶段：①诱导阶段,在表面机械研磨的最初5 min,渗碳体的溶解分数仅为0.4%;②溶解阶段,在表面纳米化处理的5-30 min,渗碳体大量溶解,其体积分数由14.6%降低到8.4%;③饱和阶段,当处理时间达到30 min以上,渗碳体的体积分数基本保持不变。     

Atom probe and transmission electron microscopy investigations of heavily drawn pearlitic steel wire

Transmission electron microscopy (TEM) and atom probe field ion microscopy (APFIM) observations of pearlitic steel wire show that drawing to a true strain of 4.22 causes fragmentation of cementite lamellae into nanoscale grains. The drawing strain amorphizes some portions of the cementite lamellae in regions where the interlamellar spacing is very small, but most of the cementite lamellae are polycrystalline with nanoscale grains. The carbon concentration in the ferrite is inhomogeneous and varies from 0.2 to 3 at. pct; the carbon concentration in nanocrystalline cementite is less than 18 at. pct, significantly lower than that in stoichiometric Fe₃C. Silicon is segregated to ferrite/cementite boundaries, but, in regions with a small interlamellar spacing, the silicon concentration is uniform across the lamellae. Annealing at 200 °C for 1 hour does not cause noticeable changes in the microstructure. Annealing at 400 °C or above for 1 hour causes spherodization of the cementite lamellae, and the carbon concentrations in ferrite and in cementite return to the predeformation values.     

Chromium partitioning during isothermal transformation of a eutectoid steel

Partitioning of chromium between ferrite and cementite during the isothermal decomposition of austenite to pearlitic or pearlitic/bainitic decomposition products has been studied in a 1.4 wt pct Cr eutectoid steel using analytical electron microscopy on two-stage extraction replicas. Chromium was observed to segregate preferentially to cementite at the pearlite reaction front for temperatures in the range 730 to 550 °C. Although the extent of partitioning decreased with decreasing reaction temperature, a no-partition temperature could not be identified for the steel. It is clear that previous studies on thin foils have underestimated the temperature range over which partitioning of chromium can occur. At high reaction temperatures measured values of pearlite growth rates were found to be in excellent agreement with those calculated, using the assumption that phase boundary diffusion of chromium was rate controlling. At lower reaction temperatures models based on volume diffusion of carbon and on phase boundary diffusion of chromium both gave reasonable predictions of measured growth rates. However, it seems likely that solute drag effects influence pearlite growth at temperatures in the austenite bay region which the chromium addition produces in the T.T.T. diagram. Measurements made on upper bainite which co-existed with pearlite following transformation at 500 and 550 °C showed that preferential partitioning of chromium to cementite did not occur during this reaction. Formerly Graduate Student, University of Manchester     

大气腐蚀下耐候钢的初期行为规律

 研究了耐候钢在40 ℃ 和100%RH高温高湿环境中初期大气腐蚀行为规律。结果表明,耐候钢初期大气腐蚀行为符合幂函数规律,随着Cu含量的增加,代表腐蚀发展趋势的n值减小,说明Cu有助于减缓耐候钢的腐蚀发展趋势。通过SEM扫描电镜和显微激光拉曼光谱分析模拟大气腐蚀初期腐蚀产物的形成和发展得知,在大气腐蚀初期,腐蚀产物形貌为团状和链状,团状腐蚀产物主要由γ Fe2O3和γ FeOOH构成,而链状腐蚀产物为α FeOOH。     

Atom probe and transmission electron microscopy investigations of heavily drawn pearlitic steel wire

Transmission electron microscopy (TEM) and atom probe field ion microscopy (APFIM) observations of pearlitic steel wire show that drawing to a true strain of 4.22 causes fragmentation of cementite lamellae into nanoscale grains. The drawing strain amorphizes some portions of the cementile lamellae in regions where the interlamellar spacing is very small, but most of the cementite lamellae are polycrystalline with nanoscale grains. The carbon concentration in the ferrite is inhomogeneous and varies from 0.2 to 3 at. pct; the carbon concentration in nanocrystalline cementite is less than 18 at. pct, significantly lower than that in stoichiometric Fe₃C. Silicon is segregated to ferrite/cementite boundaries, but, in regions with a small interlamellar spacing, the silicon concentration is uniform across the lamellae. Annealing at 200 °C for 1 hour does not cause noticeable changes in the microstructure. Annealing at 400 °C or above for 1 hour causes spherodization of the cementite lamellae, and the carbon concentrations in ferrite and in cementite return to the predeformation values.     

耐候钢和碳钢在竖直方向上的腐蚀行为

为研究耐候钢和碳钢在竖直方向上的腐蚀行为,利用干湿循环腐蚀试验,模拟研究了耐候钢和碳钢在表面受到雨水反复冲刷的条件下,竖直方向上不同位置的腐蚀行为特征以及锈层的形成和演变。结果表明,耐候钢试样和碳钢试样在干湿循环一定周期后,上部腐蚀程度较轻,底部腐蚀程度较重,而中部的腐蚀程度则随竖直方向位置的下移而明显加重;碳钢试样底部的腐蚀程度随腐蚀时间的延长而加重,但耐候钢试样底部的腐蚀至一定程度后几乎不再继续;碳钢试样锈层形貌随竖直方向位置的下移而逐渐粗化,锈层形态和致密度变化较小,耐候钢试样的锈层形貌则随竖直方向位置的下移而逐渐细化,锈层形态由球状变为块状,致密度明显增加,这也导致了耐候钢的锈层电阻明显高于碳钢的锈层电阻;在干湿循环过程中,湿润时间会影响腐蚀产物的类型,湿润时间较短时,腐蚀产物以β-FeOOH为主,随着湿润时间的延长,腐蚀产物逐渐向γ-FeOOH转变。     

Influence of microalloying on the corrosion resistance of steel in saturated calcium hydroxide

The influence of microalloying vanadium or titanium on improving the corrosion resistance of mild steel in saturated calcium hydroxide solution was investigated. Potential-time, potentiodynamic polarization, and impedance measurement techniques were employed. The corrosion products have been examined by infrared and X-ray diffraction analysis and by scanning electron microscopy. It has been shown that the grain refining, due to microalloying, plays an important role in enhancing the corrosion resistance of steel. Scales of calcite and iron oxides on top of a protective oxide are formed on the investigated steels.     

Slag corrosion of dolomite-carbon refractories

Seven industrial doloma refractory samples, coming from three European suppliers, and with different carbon, or graphite, or binder content, are subjected to the action of a slag required for the desulfurization of the steel in the secondary metallurgy at 1600°C. Three tests have been carried out within two induction furnaces. The corrosion depth, at the slag-steel interface, has been measured; the graphite-containing samples display a better resistance than the graphite-free pitch or resin-bonded refractories. Among the graphite-containing samples correlations have been found with the carbon content and with the resistance to oxidation by CO–CO₂ at 1100–1200°C. The slag-refractory interface has been investigated by X-ray diffraction, optical microscopy and electron microprobe analysis; the observed phases are CaO, MgO, Ca₂SiO₄, Ca₃SiO₅ and Ca₁₂Al₁₄O₃₃ (outside graphite and iron). The corrosion mechanism is linked to the reaction of slag with lime, followed by infiltration of the refractory and dispersion of periclase grains in the slag.     

稀土对低碳钢耐工业大气腐蚀性的影响

研究了在江津地区暴晒2年低碳钢和稀土钢的大气腐蚀行为。结果表明:稀土可以有效提高低碳钢耐工业大气腐蚀性,试验钢的腐蚀数据符合动力学模型D=Atn。采用扫描电镜、极化曲线、XRD及Fourier变换红外光谱等手段对腐蚀产物进行研究。发现稀土能促进稳定的保护性腐蚀产物α-FeOOH生成,降低锈层中具有反应活性的Fe3O4含量;并可以增加锈层致密性。从锈层反应的角度阐述了稀土提高低碳钢耐蚀性的机理。