还原性气氛中HCl和H2S导致Fe-Cr合金在700℃的加速失效

研究了Fe-8Cr,Fe-12Cr和Fe-18Cr合金在700℃含氯和两种硫含量还原性气氛中的腐蚀行为.气氛中H2S含量增加导致合金发生加速腐蚀,尤其造成Fe-18Cr合金表面氧化铬膜退化.合金的加速腐蚀与膜中生成的硫化物和氯化物密切相关.合金的腐蚀速率随其Cr含量的升高而降低.通过计算气氛中平衡时的氯势、氧势、硫势预测了合金与气氛可能发生的反应,并解释了腐蚀机制.     

Fe-15Ce合金的氧化-硫化腐蚀

研究了Fe-15Ce合金及纯Fe、纯Ce在600和700℃下H 2-H2S-CO2中的腐蚀行为.Fe-15Ce合金的腐蚀速度比纯Fe慢但比纯Ce快得多.腐蚀后合 金表面形成多层的腐蚀产物膜,最外层是基体金属的硫化物（FeS）,中间层为两种金属化 合物组成的混合区,最内层为Ce在O和S作用下的内腐蚀区.合金中15 mass%的Ce不足以阻止 基体金属的硫化,这主要与Ce在Fe中有限的溶解度及合金中存在富Ce相有关.     

钢材在N-甲基二乙醇胺中的腐蚀行为

应用电化学测量技术研究了炼油厂中常用材料(20#钢、渗铝20#钢、304、321、316L)在含N-甲基二乙醇胺的RNH2-CO2-H2O、RNH2-H2S-H2O、RNH2-H2S-CO2-H2O三种介质中的电化学腐蚀行为。试验结果表明,渗铝钢在此类腐蚀介质中表现出较好的耐蚀性能。     

The corrosion of a Fe-15 wt.% Ce alloy in coal gasification type atmospheres at 600 to 800 °C

The corrosion of a Fe-15 wt.% Ce alloy and of the two pure metals have been studied at 600 to 800 °C in H₂-H₂S-CO₂ mixtures providing high-sulfur and low-oxygen activities that are typical of coal gasification atmospheres. The alloy corrodes more slowly at 600 to 700 °C than pure Fe, more rapidly than pure Ce, while at 800 °C it corrodes at about the same rate as pure Fe. The scaling kinetics of Fe-15Ce are irregular and generally intermediate between linear and parabolic. The scale formed on Fe-15Ce shows a multilayered structure, including an outermost layer of base metal sulfide (FeS), an intermediate complex layer composed of a mixture of compounds of the two metals, and finally an innermost region of internal attack of Ce by both oxygen and sulfur. Ce is not able to diffuse outward in the metal substrate and remains in the alloy consumption region. In the intermediate region, FeS forms a continuous network that allows the growth of an external iron sulfide layer. A Ce content of 15 wt.% is insufficient to prevent the sulfidation of the base metal. These results as well as the scale microstructure are interpreted by taking into account the limited solubility of Ce in Fe and the presence of Ce-rich intermetallic compounds in the alloy examined.     

The corrosion of a Fe-15 wt.% Ce alloy in coal gasification type atmospheres at 600 to 800 °C

The corrosion of a Fe-15 wt.% Ce alloy and of the two pure metals have been studied at 600 to 800 °C in H₂-H₂S-CO₂ mixtures providing high-sulfur and low-oxygen activities that are typical of coal gasification atmospheres. The alloy corrodes more slowly at 600 to 700 °C than pure Fe, more rapidly than pure Ce, while at 800 °C it corrodes at about the same rate as pure Fe. The scaling kinetics of Fe-15Ce are irregular and generally intermediate between linear and parabolic. The scale formed on Fe-15Ce shows a multilayered structure, including an outermost layer of base metal sulfide (FeS), an intermediate complex layer composed of a mixture of compounds of the two metals, and finally an innermost region of internal attack of Ce by both oxygen and sulfur. Ce is not able to diffuse outward in the metal substrate and remains in the alloy consumption region. In the intermediate region, FeS forms a continuous network that allows the growth of an external iron sulfide layer. A Ce content of 15 wt.% is insufficient to prevent the sulfidation of the base metal. These results as well as the scale microstructure are interpreted by taking into account the limited solubility of Ce in Fe and the presence of Ce-rich intermetallic compounds in the alloy examined.     

SULFIDATION OF Co-15wt%Y ALLOY IN H_2-H_2S MIXTURES AT 600-800℃

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Fe-15Ce合金的高温硫化腐蚀

研究了含15wt%Ce的Fe-Ce合金在600～800℃、H2-H2S气氛中的硫化行为,其硫的分压为10-3Pa.结果表明,Fe-15Ce合金的腐蚀速度比纯Fe慢,但比纯Ce快得多,随温度升高其腐蚀速度加快.该合金硫化后形成复杂的腐蚀产物膜,最外层为纯Fe的硫化物层,其下为Ce的硫化物与Fe的硫化物的混合物层;内层为Ce的内硫化区,与之相邻的基体金属层中没有贫Ce现象发生.Ce不能从合金的腐蚀区中向外扩散,而是在腐蚀区内原位地形成Ce的硫化物与Fe的硫化物的混合物.与纯Fe相比,尽管Fe-Ce合金的腐蚀速     

Fe-25Cr-9Mn三元合金高温硫化特性

研究了Fe-25Cr-9Mn合金在800℃、10-3─1Pa硫分压的H2-H2S混合气体中的硫化行为,并与Fe-25Cr合金进行了对比。结果表明:Mn的加入提高了Fe-25Cr合金的抗硫化性能,但作用并不显著。在Fe-25Cr-9Mn合金的多层结构硫化层中形成了较厚且独立的α-(Mn.Fe)S层,但它并没有效地阻挡Fe2+和Cr3+向外的扩散。文中讨论了这种现象的原因以及硫化层分层对铁铬合金硫化行为的影响。     

在600-800℃低氧压下Co-Nb合金的氧化

研究了含15与30wt%Nb的两种Co-Nb合金在600-800℃低氧压F的氧化性能选择的氧压低于相应温度的氧化钴分解压,由H2-CO2混合气获得,在600℃为10-24atm,而700与800℃为10-20atm.两种合金在600与700℃氧化结果仅产生由α-CO与氧化铌(NbO2与Nb2O5)混合物组成的内氧化带在700℃尚可能生成双元氧化物CONb2O6在内氧化带界而无贫Nb层可见.两会金,尤其是Co-30Nb在800℃时发生了由内氧化向外氧化的转变,伴随有贫Nb的单相区出现于合金的表层.从Co中N     

Ce对Fe-Cr合金高温氧化行为的影响

Fe-15Cr 和 Fe-30Cr 合金在1000至1200℃空气中氧化时,表面富铁氧化伤的发展导致保护性Cr_2O_3层衰退,氧化速率增大。添加 Ce 可延迟衰退过程的发生,从而大幅度减低氧化速率。随氧化温度和合金成份变化,Cr_2O_3层衰退的开始时间和发展特征随之改变,Ce 对氧化行为的影响因而呈现出规律性的变化。研究发现,合金中 Cr 的内氧化使 Cr_2O_3层形成小舌包卷合金并使其氧化成富铁氧化物。这是Cr_2O_3层衰退的原因之一。含 Ce 合金中 Ce 的优先内氧化则降低自氧化层进入合金的氧浓度,抑制Cr 的内氧化。氧浓度降低还能促进 Si 的内氧化物在氧化层/合金界面集聚。     

铈提高Fe-15Cr合金抗氧化能力的作用机理

利用真空热天平、扫描电镜和X-射线衍射仪研究了Fe-15Cr和Fe-15Cr-0.3 Ce合金在1000和1100℃的氧化行为。结果表明,在Fe-15Cr合金表面,Cr_2O_3膜形成后不久便广泛变形、频繁开裂,使富铁氧化物瘤子不断产生。与此相应,氧化动力学曲线反复发生曲折,对抛物线产生正偏离。铈使Cr_2O_3膜变形,开裂和形成瘤子的倾向减小,产生较光滑的动力学曲线,较小的氧化速率。 进一步的研究发现,铈促进Cr_2O_3膜的晶粒成为柱状晶,抑制在膜表面形成新氧化物,并绽膜中(1010)、(104)、(116)等晶面具有较强的择优取向。由此推断出铈具有阻止膜中铬离子扩散、减小膜的生长应力等作用。认为这是铈减轻膜发生变形和开裂的倾向,减小氧化速率的原因。     

Corrosion behavior of Fe-20Cr and Ni-20Cr alloys in Ar-H2O-HBr gas mixtures at 1000 K

Discontinuous mass-change measurements and corrosion-product analyses were made for Fe-20Cr and Ni-20Cr alloys after exposing them to Ar-H ₂ O-HBr gas mixtures at 1000 K for 24 hours. Predominantly chromia scales formed on both alloys. Upon cooling, the scales remained adherent to the Fe-20Cr alloy but spalled extensively from Ni-20Cr samples. After tests in HBr-rich gas mixtures, bromine-rich corrosion products were found underneath chromia scales on both alloys while nickel evaporation was observed from Ni-20Cr samples. Preoxidation of the Ni-20Cr alloy prior to exposure to Ar-H ₂ O-HBr gas mixtures increased chromia scale adherence but did not prevent nickel loss from the alloy. Chromia scales formed on the Fe-20Cr alloy were more protective due to the absence of iron oxides in the scale. Large NiO crystals formed over the Ni-20Cr alloy decreased chromia-scale adherence and increased nickel loss from the alloy due to the low stability of NiO in HBr-containing gas mixtures.     

Effect of enamel coating on long-term oxidation and hot corrosion behavior of Ti-24Al-17Nb-0.5Mo alloys

The effect of enamel coating on long-term isothermal oxidation at 700 ℃ and cyclic oxidation at 800 ℃ in air and hot corrosion resistance of Ti-24Al-17Nb-0. 5Mo in 75% (Na2SO4 K2SO4 ) 25% NaCl (mass fraction) molten mixed salts at 700 ℃ was investigated. The results indicate that Ti-24Al-17Nb-0.5Mo alloy exhibits relatively poor long-term oxidation resistance due to the formation of Al2O3 TiO2 Nb2O5 mixed scales and poor hot corrosion resistance due to the spallation of scales formed in molten (Ns, K)2 SO4 NaCl. Enamel coating can effectively protect Ti-24Al-17Nb-0.5Mo alloy from long-term oxidation at high temperature in air and remarkably improve the hot corrosion resistance of Ti-24Al-17Nb-0. 5Mo alloy, and can act as the barrier to suppress the migration of oxygen and corrosive ions into the substrate.     

Fe-Y合金在600～800℃H_2-CO_2-H_2S中的腐蚀

研究了纯Fe、纯Y、Fe-15Y和Fe-30Y合金在600～800℃高硫压(10-3Pa)-低氧压(10-19Pa于600℃或10-15Pa于700℃和800℃)混合气中的腐蚀行为.Y在600℃和700℃发生加速腐蚀,但在800℃形成的腐蚀膜有保护性.加入Y能够降低合金的腐蚀速率,但在所有条件下,合金都形成FeS最外层膜、由两金属的化合物组成的中间层和由α-Fe和Y的硫氧化物的细微混合物所组成内硫化-氧化区.Fe似以相当高的速率穿过中间层形成FeS外层.在合金/氧化膜界面内侧不产生Y的贫化现象.从Y在Fe     

The corrosion of a Co–15 wt% Ce alloy in mixed oxidizing-sulfidizing gases at 600–800°C

The corrosion behavior of a Co–Ce alloy containing approximately 15 wt% Ce has been studied at 600–800°C in several H₂–H₂S–CO₂ mixtures, providing sulfur pressures of 10⁻⁸ atm at 600, 700 and 800°C and of 10⁻⁷ atm at 800°C, and oxygen pressures of 10⁻²⁴ atm at 600°C and 10⁻²⁰ atm at 700 and 800°C. At 600°C, the alloy corrodes more slowly than pure cobalt but more rapidly than pure cerium while, at 700°C, it corrodes at about the same rate as pure cerium, but much faster than pure cobalt. At 800°C under 10⁻⁸ atm S₂, i.e. a value below the stability of the cobalt sulfides, the alloy corrodes rather slowly but, under 10⁻⁷ atm S₂, the rate is very high, although slightly lower than that of pure cobalt. The scaling kinetics are generally intermediate between linear and parabolic but are sometimes irregular. The corrosion of this alloy produces multilayered scales, containing an outermost layer of almost pure cobalt sulfide, an intermediate complex layer composed of a mixture of compounds of the two metals and, finally, an innermost region of internal attack of cerium by both oxygen and sulfur. Cerium is not able to diffuse outwards and remains in the alloy consumption region. In the intermediate region cobalt sulfide forms a continuous network which allows the growth of the external CoS_y layer, although at rates that are reduced with respect to those of pure cobalt. Thus, a cerium content of 15 wt% is not sufficient to prevent or even to significantly reduce the sulfidation of the base metal. These results, as well as the details of the microstructure of the scales, are interpreted by taking into account the limited solubility of cerium in the base metal and the presence of an intermetallic compound, rich in cerium, in the alloy.     

Yb/Dy掺杂改性Fe-Cr合金热生长氧化膜的电化学阻抗谱研究

研究了掺杂0.2 mass%Yb和Dy对Fe-20Cr合金在900℃空气中的氧化性能的影响,应用电化学阻抗技术研究在中性硫酸钠溶液中合金表面氧化膜的电导率,对高温氧化膜的性能进行描述并建立适当的等效模型。结果表明,加入元素Yb和Dy有助于促进合金表面富Cr氧化膜的形成,提高氧化膜的粘附性,从而改善合金的抗氧化性能,其中元素Dy的作用效果比Yb更好。Fe-20Cr 和Fe-20Cr-0.2Yb合金表面氧化膜在溶液中的电化学阻抗谱不能看到明显的双容抗弧特性,而Fe-20Cr-0.2Dy的双容抗弧特性明显,表明氧化膜是双层结构,且其表面氧化膜的电导率最小,显示更好的抗氧化性能,这与氧化动力学测量结果一致。通过与其它高温氧化分析方法进行比较,发现对于研究氧化膜的结构特点、孔隙率、缺陷性等电化学阻抗谱有其独特的优势。     

800H合金的高温抗氧化性能

利用X射线衍射仪(XRD)、扫描电镜(SEM)和能谱仪(EDS)等,对800H合金高温氧化膜的增厚动力学、形貌及氧化物组成进行了分析。结果表明,700和800℃下形成的氧化膜相近,由(Cr,Fe)2O3和Mn-Cr氧化物组成;900℃时的氧化膜急剧增厚,里层依然是Cr2O3,中间层则是Cr-Fe-Mn氧化物,外层为富Ti的氧化物。通过热力学和动力学计算,提出了800H合金氧化膜形成的模型,发现TiN的存在改变了氧化膜的结构。     

Formation of Fe-19 wt%Cr-9 wt%Ni Nanocrystalline Alloy with Excellent Corrosion Resistance: Phase Transition and Microstructure

In this paper, microstructure characteristics and phase transitions of Fe-19 wt%Cr-9 wt%Ni nanocrystalline alloy are comprehensively studied during the mechanical alloying and hot pressing sintering processes. Corrosion resistance of the sintered Fe-19 wt%Cr-9 wt%Ni nanocrystalline alloy samples is further analyzed. During the mechanical alloying process, Fe-19 wt%Cr-9 wt%Ni nanocrystalline alloy powders mainly composed of metastable ferrite phase are obtained after mechanical alloying for 8, 16 and 24 h, respectively. In the subsequent hot pressing sintering process, the phase transitions(from ferrite to austenite) occur from 650 to 750 °C for Fe-19 wt%Cr-9 wt%Ni alloy powders milled for 24 h. When the sintering temperature is raised to 1050 °C for 1 h, the ferrite phase has transformed into austenite phase completely, and the obtained grain size of sintered Fe-19 wt%Cr-9 wt%Ni alloy is around 40 nm. Electrochemistry test of the sintered Fe-19 wt%Cr-9 wt%Ni alloy has been operated in 0.5 mol L~(-1) H_2SO_4 solution to show the corrosion resistance properties. Results show that the sintered Fe-19 wt%Cr-9 wt%Ni alloy exhibits excellent corrosion resistance, which is proved by higher self-corrosion potential, lower self-corrosion current density and larger capacitive reactance, compared with that of commercial 304 stainless steel.     

The Oxidation of Two Fe-Y Alloys Under Low Oxygen Pressures at 600-800°C

The corrosion of pure yttrium and of two Fe-basealloys containing approximately 15 and 30 wt.% Y wasstudied at 600-800°C in H₂-CO₂mixtures providing an equilibrium oxygen pressure of10^-24 atm at 600°C and 10^-20 atm at 700 and800°C. The corrosion of yttrium under these lowoxygen pressures resulted in the growth ofY₂O₃ scales and presented twoapproximately parabolic stages at 800°C, while at 600-700°C it was faster andnonprotective. The corrosion of the two alloys followedapproximately the parabolic rate law, except for Fe-15Yat 600°C which oxidized nearly linearly. At 600 and700°C, when the gas-phase oxygen pressure was in thefield of stability of iron oxide, the alloys formed alsoa thin external Fe₃O₄ layer, whileat 800°C, when the oxygen pressure was below thestability of FeO, a thin outermost layer of pure iron wasobserved to form. Under all conditions a region ofinternal oxidation formed in the alloy, in which theyttrium-rich phases were transformed into a mixture ofiron metal and oxides, which included double Fe-Yoxides as well as Y₂O₃. Themicrostructure of the internal-oxidation region followedclosely that of the original alloys, which moreover didnot undergo any yttrium depletion. These results are examinedby taking into account the low solubility of yttrium iniron and the presence of intermetallic compounds in thealloys.     

低H2S、高CO2超深井环境中P110SS抗硫钢的腐蚀行为

目的研究高温条件下抗硫低合金钢P110SS在低H2S、高CO_2环境中的腐蚀行为。方法模拟我国西部酸性油田工况环境,利用高温高压设备,通过失重法测试腐蚀速率,并用SEM、EDS和XRD分析腐蚀产物。结果在8 MPa的纯CO_2环境中,腐蚀速率随温度升高而降低,210℃时为0.35 mm/a,腐蚀产物为碳酸盐。当加入6 k Pa硫化氢时,腐蚀速率依然随温度升高而降低,150℃时为0.74 mm/a,腐蚀产物呈现双层结构,内层为结晶良好的FeCO_3,外层为FeS。当硫化氢分压升至165 k Pa时,腐蚀加剧,且腐蚀速率随温度升高而增大,210℃时达2.78 mm/a,腐蚀产物主要为铁的硫化物,同时随腐蚀时间延长至2160 h,腐蚀速率有所降低。结论在纯CO2环境中,高温时生成的内层碳酸盐腐蚀产物膜相对完整,对基体的保护能力较强。当加入6 k Pa硫化氢时,腐蚀由CO_2主导,呈现与纯CO_2环境中相同的腐蚀速率规律,内层的FeCO_3细密均匀。当硫化氢分压升至165 k Pa时,腐蚀由H_2S和CO_2混合控制,疏松破损的铁的硫化物无法对基体形成良好的保护,因此腐蚀速率显著升高。