温度对油管钢CO2腐蚀产物膜的影响

利用静态高压釜对二种油管钢N80、P110和J55进行了CO2腐蚀试验,通过扫描电镜(SEM)对比分析了腐蚀产物膜厚度和表面晶粒尺寸随温度的变化。结果表明,在试验条件下,三种钢的腐蚀产物膜厚度随温度变化情况相近,最大值均在120℃,最小值对应温度则不同;表面晶粒尺寸出现了一峰一谷,峰值均在120℃,谷值对应温度却小同。     

Adhesion of Thermal Oxide Scales on Hot-Rolled Conventional and Recycled Steels

The mechanical adhesion of thermally-formed oxide scales formed on industrial hot-rolled low carbon steel strips produced through the blast-furnace route (conventional steel) or the electric-arc-furnace route (recycled steel) was studied. A new macro-tensile test was compared to a micro-tensile test previously used. It was observed that spallation of scales during straining increased with increasing the tensile strain rate. A higher strain rate resulted in a lower strain inducing the first spallation. As a result, the mechanical adhesion energy of scales actually formed on the recycled steel was in the range 300–700 J m^?2. Comparison at the same strain rate of the conventional and recycled steels showed higher scale adhesion for the recycled steel due to the presence of high amounts of interfacial silica.     

TiAl／TiB2复合材料高温氧化膜的结构和形成机制

利用XRD，SEM，EDS及TEM对TiAl／TiB2复合材料在静止空气中高温氧化后的氧化膜结构及其形成机制进行了研究。结果表明：TiAl／TiB2复合材料的氧化膜主要由TiO2外层与由TiO2和Al2O3混合内层构成。TiO2和Al2O3混合内层为孔洞较多的疏松状结构。TiO2外层亦可分为内外两层，TiO2的内层部分存在一些与TiB2的轮廓相似的“孔洞”，TiO2的外层部分没有此类孔洞。由于TiAl／TiB2复合材料中的TiB2被氧化后生成的B2O3在高温下蒸发掉，使氧化膜中TiB2所处的位置留下了孔洞。因此，氧化膜中的部分孔洞是由于TiB2被氧化后产生的；氧化温度达到1000℃时，TiAl／TiB2复合材料中的TiB2使氧化膜中的孔洞数量增加，复合材料的抗氧化性能急剧下降。     

Effects of Process Parameters on Mechanical Adhesion of Thermal Oxide Scales on Hot-Rolled Low Carbon Steels

The present work investigated the effects of process parameters in a hot-rolling line, finishing and coiling temperatures, on mechanical adhesion of scale on low carbon steel substrate using a tensile test. Modification of our previous model to quantify mechanical adhesion energy was proposed for a system consisting of a cracked scale on a metallic substrate by introducing a distribution function of stress in scale. When a linear distribution was assumed, the quantified mechanical adhesion energy lay in the range of 40–890 J m^?2. Higher finishing temperature had a prominent role on increasing final scale thickness and weakening scale adhesion. For scale with similar thickness, the mechanical adhesion energy was lowered for the sample subjected to higher temperature gradient between finishing and coiling temperatures. This was considered to be from the increased water vapour in atmosphere due to the higher amount of water used to cool down the steel strip. The mechanical adhesion test was further conducted to attest this assumption. It was found that humidified atmosphere during oxidation weakened the scale adhesion to low carbon steel substrate measured at room temperature.     

On the Mechanism of Oxide Films Formation on Pearlitic Steels in Nitrate Solutions

During exposing pearlitic steels to nitrate solutions, three mechanisms of iron transfer from the metal phase into solution are observed, depending on the solution pH and the presence of oxidants. The process yields either bivalent iron, colloid-disperse compounds of trivalent iron, or a lepidocrocite deposit. Oxide films thus formed have different protective value. A mechanism explaining the effect of different factors on the protective effectiveness of the oxide films is proposed.     

In-situ Measurement of the Thickness of Aluminum Oxide Scales at High Temperature

Two ways for measuring thickness of aluminum oxide which forms upon the surface of a heating element metal Fecralloy at high temperature over 1000°C are presented. One is LRI (Laser Reflection Interferometer). That is, a He--Ne laser incident to the specimen reflects on the top surface of the aluminum oxide and also on the interface with the substrate. Then these two reflections interfere to yield undulation of the intensity as the oxide grows. As the oxide gets thicker, however, the surface gets rougher and transparency decreases, which results in substantial scatter and low intensity in reflection, respectively. To overcome this problem, a spatial filter was employed on the light path. The other way is EDM (Emissivity Difference Method) which applies the phenomenon that the thermal emissivity of the surface depends upon the oxide thickness and the wavelength of the radiation. The oxide thickness is evaluated from the: difference in temperature indications measured by two infra-red thermometers which respond to different wavelengths, = 8--15 m and = 1.55 m, respectively. The validity of LRI and EDM has been proved by experiments, and some empirical relations are presented. The features and limitations are also discussed.     

氧化温度对SS400钢氧化皮结构及耐蚀性能的影响

以宝钢SS400热轧钢为原料,控制加热温度,在钢表面制备氧化皮.采用SEM分析了氧化皮表面、截面形貌;X射线衍射仪分析氧化皮的相组成;进行室内干湿周期浸润腐蚀试验,对氧化皮试样在NaHSO3(0.01 mol/L)溶液中进行了耐蚀性测试.结果表明,分别在600、700、800℃氧化180 min的过程基本遵循抛物线规律.经过600℃加热保温30 min,所形成的氧化皮厚度小于10μm,700℃时厚度为15μm左右,800℃达到50μm.600、700、800℃制备的氧化皮均含Fe3O4、Fe2O3相和Fe颗粒.同时,800℃制备的氧化皮中保留有少量FeO相.不同温度所制备氧化皮试样耐蚀性能依次为700、600、800℃.     

The Effect of Metallic Co-Coating Thickness on Ferritic Stainless Steels Intended for Use as Interconnect Material in Intermediate Temperature Solid Oxide Fuel Cells

The effect of metallic Co-coating thickness on ferritic stainless steels is investigated. This material is suggested to be used as interconnect material in intermediate temperature solid oxide fuel cells. Uncoated, 200-, 600-, 1000-, and 1500-nm Co-coated Sanergy HT is isothermally exposed for up to 500 h in air at 650 °C. Mass gain is recorded to follow oxidation kinetics, and area-specific resistance (ASR) measurements are conducted on samples exposed for 168 and 500 h. The microstructure of the thermally grown oxide scales is characterized utilizing scanning electron microscopy and energy-dispersive X-ray analysis on broad ion beam-milled cross sections. A clear increase in ASR as a function of Co-coating thickness is observed. However, the increase in ASR, as an effect of a thicker Co-coating, is correlated with thicker (Cr,Fe)₂O₃ scales formed on these materials and not to an increase in Co spinel top layer thickness.     

化学成分对热轧带钢氧化铁皮生长速率的影响

通过氧化模拟实验,观测了试样加热到不同温度时的氧化铁皮起皮情况,绘制了氧化动力学曲线,研究了高温下钢板在不同硅、磷质量分数时对氧化铁皮生长速率的影响。实验结果表明,在1100 ℃且经30 s氧化后,除含硅较低的钢种C外,其它钢种的表面都出现了独立的小气泡;经120 s氧化后各钢种的表面都完全形成了氧化膜。在较高温度(＞1000 ℃)时增硅会促进氧化铁皮的起皮;w（P）≤0005％时,无论在任何温度下都抑制了氧化铁皮起皮。     

Effect of External Stress on the Behavior of Oxide Scales on 9Cr-1Mo Steel

Tensile specimens of 9Cr-1Mo steel weresubjected to oxidation in air at a temperature of 973 Kfor periods of 25, 47, 70, 97, 120, and 140 hr. Theintegrity of the oxide scale was examined by an in-situ technique which involved the recording of theacoustic-emission activity associated with the breakingof the scale. Specimens were also subjected to oxidationfor the same times after subjecting them to an external stress of 40 MPa. The applicationof the external stress was found to alter the integrityof the scale. Spalling of the scale occurred to a lesserextent when external stress was applied due to partial release of growth stresses becauseof the elongation of the specimen. The scale buckledbefore spalling when no external stress was applied. Onthe other hand, the scale developed wedge-type cracks before spalling when subjected toexternal stress during oxidation. Postoxidationexamination of the stressed specimen revealedsubstantial segregation of silicon and chromium at thegrain boundaries (oxide ridges). The specimens, which wereoxidized without external stress, revealed a reductionin the concentration of chromium on the surface. Thisbehavior was attributed to enhanced spalling in the case of the latter specimen compared to theformer.     

Temperature and Chromium-Content Effect on the Corrosion of Steels in an Ammonia-Chloride Medium

The joint effect of the alloying with chromium, operation time, and temperature on the steel corrosion rate in an ammonia-chloride medium is determined, and a long-term quantitatively predictive mathematical model of the corrosion damage to chromium steels is developed. The model can be used in choosing a steel for and predicting the residual operating life of the equipment for the evolution stage of the continuous production of aromatic diamine.     

The Effect of Low Temperature Sensitization on Corrosion Resistance of Ultrafine-Grained Type 321 Stainless Steels

The ultrafine grain 321 stainless steel was produced by cold rolling. The microstructure, after 87% cold rolling and annealing at 380 and 450 °C, has been characterized using transmission electron microscopy and x-ray diffraction. The degree of sensitization (DOS) was investigated by means of double loop electrochemical potentiokinetic reactivation test. The results showed that the DOS was higher in samples annealed at 380 °C than that in samples annealed at 450 °C. The strain-induced martensite promoted sensitization at 380 °C and the reversion-transformed austenite-restrained sensitization or promoted healing of chromium-depleted zone at 450 °C. Although the activation and reactivation current densities in samples sensitized at 450 °C were higher than those in samples sensitized at 380 °C, higher corrosion resistance of the former was attributed to lower DOS, which was proven further by electrochemical impedance spectroscopy experiment.     

微晶化对Ni20Cr合金热生长氧化膜应力的影响

利用氧化膜应力原位测量装置对Ni20Cr微晶涂层/合金体系在1000℃空气中氧化过程中发生的弯曲挠度变化进行测量.结果表明,微晶涂层1000℃氧化所形成的Cr_2O_3氧化膜中存在压应力,应力绝对值高于相同厚度的合金表面的热生长氧化膜,其原因在于涂层/Cr_2O_3界面结合好,应力释放较小.降温冷却过程中,通过微晶涂层...     

铁硅合金初次再结晶对立方织构形成的影响

Fe-3.2%Si合金通过真空退火发生二次再结晶,最终可形成立方织构电工钢.其中初次再结晶后的晶粒是发生二次再结晶的晶核.通过电子背散射衍射(EBSD)技术和取向成像显微(OIM)技术研究了硅钢初次再结晶对最终立方织构形成的影响.通过冷轧压下量70%和不同退火温度的工艺处理,研究了退火温度对初次再结晶的影响;发现在低温650 ℃下初次再结晶,形成的初次再结晶晶核有利于最终形成立方织构.     

高温高压H2S/CO2腐蚀产物膜对低铬钢氢渗透行为的影响

目的探讨含Cr腐蚀产物膜对油管钢氢渗透行为的影响。方法对80SS、P110-3Cr和P110-7Cr油管钢试样进行高温高压H_2S/CO_2腐蚀模拟实验,并利用双电解池技术测量试样腐蚀前、后的氢渗透电流密度。通过扫描电子显微镜、能谱分析仪和X射线衍射仪对腐蚀产物膜的微观形貌、成分和物相组成进行分析。结果三种材料的腐蚀产物主要由亚稳态的马基诺矿型硫铁化合物构成,没有发现典型的CO_2腐蚀产物FeCO_3晶体,在P110-3Cr(7.4%Cr)和P110-7Cr(14.75%Cr)钢的腐蚀产物膜中有Cr元素富集。随着钢中Cr含量的提高,120℃腐蚀后,试样的表观扩散系数减小。80SS、P110-3Cr和P110-7Cr油管钢试样表面无腐蚀膜时,吸附氢浓度分别为0.98×10~(-5)、9.54×10~(-5)、9.3×10~(-5) mol/cm~3。120℃腐蚀后,带有腐蚀膜试样的膜层/基体界面钢基体侧的吸附氢浓度分别为0.93×10~(-5)、5.17×10~(-5)、8.52×10~(-5) mol/cm~3。结论三种油管钢的腐蚀过程均由H_2S控制。腐蚀产物膜中Cr元素富集有助于降低带有腐蚀膜试样的表观扩散系数。与不带腐蚀膜的试样相比,三种带腐蚀膜试样的膜层/基体界面钢基体侧的吸附氢浓度降低,腐蚀产物膜对氢渗透具有明显的阻碍作用。     

The Sulfidation Behavior of Several Commercial Ferritic and Austenitic Steels

The sulfidation behavior of C-steel, 1Cr-0,5Mosteel, 12Cr-1Mo-0.25V steel, 18Cr-10Ni-Ti steel, thebinary alloys Fe-20Cr, Fe-25Cr, Fe-30Cr, and pure Cr wasinvestigated between 400 and 700°C in a94Ar-5H₂-1H₂S gas mixture. All steels sulfidize according tocomplex kinetics which, after a period with decreasingrate, can be approximated by a linear rate law. Thescale of the three ferritic steels consists of two layers, an outer outward-growing one of FeSwith traces of dissolved Cr and an inner, inward-growingone, which contains in addition to Fe the alloyingelements Cr and Mn. Most of the outer FeS layer is separated from the inner layer and can be splitinto several partial layers, the number increasing withincreasing sulfidation time and temperature. The scaleon the austenitic 18Cr-10Ni-Ti steel differs insofar as that of the ferritic steels as theouter FeS layer contains some Ni and that a third layerof the spinel FeCr₂S₄ is formedbetween the outer and the inner layer. This intermediatelayer is responsible for the lower sulfidation rate of this materialcompared with that of the ferritic steels. The scale ofthe binary Fe-Cr alloys is similar to that of theaustenitic steel. From AE-measurements it can be deduced that the separation of the outer FeSlayer occurs during isothermal sulfidation and isaccompanied by an increase in the AE event rate. Theseparation is a consequence of the formation and growth of pores in the region close to the inner/outerlayer interface and the development of compressivegrowth stresses in the outer FeS layer. While detachmentof the FeS layer on the ferritic steels was already observed at 400°C, the austenitic steelshowed a similar separation of the FeS layer only at600°C. The detached FeS layer is obviously rathergas tight. Differences in the sulfur partial pressure ofthe bulk gas and the gas in the cavity between theinner and separated outer layer lead to a reduction ofFeS at the inner surface of the detached FeS layer. TheFe ions and electrons, produced by this reaction, diffuse outward, forming new FeS on the outerFeS surface. This process not only shifts the detachedFeS layer continuously away from the core of thespecimen but offers also the possibility of healing cracks in the separated FeS layer. This scaledetachment does not stop scale growth. After scaleseparation the total sulfidation reaction consists of atleast seven partial reactions: phase-boundary reaction at the outer surface, diffusion of iron ionsand electrons outwards in the detached FeS layer,formation of H₂S at the inner surface of thedetached layer, gas diffusion in the cavity, formationof FeS on top of the porous inner layer, gas diffusionin the channels of the porous inner layer, FeS formationat the metal/scale interface. When the new FeS layer ontop of the porous inner layer exceeds a critical thickness, the detachment of the FeSlayer from the inner porous layer repeats. This processcan take place several times, leading to an outer FeSpartial scale, split into several layers, which are separated by relatively large cavities andkept together only locally by FeS bridges. The overallreaction rate is controlled by the phase-boundaryreaction at the outermost FeS surface.     

In-situ Impedence Spectroscopy Study of Electrical Conductivity and Ionic Transport in Thermally Grown Oxide Scales on a Commercial FeCrAl Alloy

In-situ impedance-spectroscopy measurements were performed at temperatures between 600 and 1,000 °C to investigate ionic transport in oxide scales formed on Kanthal AF alloy. The samples were pre-oxidized at 800, 900 and 1,000 °C in air. The impedance spectra of the oxide formed at 1,000 °C exhibited essentially one semicircle, whereas samples oxidized at lower temperatures showed an additional semicircle at high frequencies suggesting a more heterogeneous oxide. The ionic-transference number, derived by measuring the voltage across the oxide scale, indicates that the oxide is a predominant electronic conductor. Ionic diffusivity in the oxide scales formed at different pre-oxidizing temperatures was calculated, using the ionic-transference number. The ionic diffusivities obtained in this way are in reasonable agreement with literature data acquired by other methods. The oxide-formation temperature has a significant influence on the conductivity and ionic-transport properties of the oxide scale.