合金化元素Ti对Laves相Cr_2Nb力学性能及耐蚀性的影响

采用真空非自耗电弧熔炼工艺制备了Cr2Nb-XTi(X=5,10,15,at%)合金,利用光学显微镜(OM),X射线衍射(XRD)仪,扫描电镜(SEM)对电弧熔炼态铸锭的组织进行了研究,探讨了合金化元素Ti的含量对Laves相Cr2Nb力学性能及耐蚀性的影响。结果表明:3种成分的电弧熔炼态合金凝固组织主要由C15-Cr2(Nb,Ti)相和六方的β-(Ti,Nb)以及体心立方结构的β-(Nb,Ti)相组成。在5Ti和10Ti合金冷速较小的铸锭上部凝固组织中出现了亚稳相C14-Cr2(Nb,Ti)。通过对合金力学性能研究表明,随合金化元素Ti含量的增加,Laves相Cr2Nb合金的显微硬度逐渐降低,断裂韧性增大,当Ti含量达到15at%时,合金的断裂韧性达到了3.1 MPa·m1/2,比单相Laves相Cr2Nb提高1倍。另外,对腐蚀性能的测试表明,Ti含量增加材料腐蚀性能下降,但15Ti合金仍表现出良好的耐蚀性。     

High-temperature sulfidation of Fe-Mn alloys

The complete range of binary Fe-Mn alloys were sulfidized in pure sulfur vapor (1 atm) at 700–1000°C. It was found that the corrosion kinetics could be divided into four groups, depending upon the alloy concentration. The first group, up to 11 w/o Mn, had a constant corrosion rate. The second group, up to about 63 w/o Mn, had an exponentially decreasing rate of corrosion with increasing manganese content. In the third group, about 63–80 w/o Mn alloys, the corrosion rate did not follow the parabolic law. The corrosion rates became constant above 80 w/o Mn. These corrosion kinetics were explained by considering the scale structure and alloy substrate.     

含Cr低合金钢的CO2腐蚀产物膜形成及机理研究进展

针对含Cr低合金钢石油专用管的CO₂腐蚀产物膜,介绍了CO₂腐蚀产物膜的形成机理,总结了含Cr低合金钢的CO₂腐蚀产物膜的影响因素,其中包括Cr含量、温度、CO₂分压、pH值、腐蚀时间、Cl^-浓度、流速等对其腐蚀产物膜的影响,并对腐蚀产物膜的结构与成分进行总结,归类了缓蚀剂对含Cr低合金钢石油专用管的保护办法,以期为今后含Cr低合金钢的CO₂腐蚀产物膜的研究提供借鉴。     

Observations on the oxidation behavior of Ni-Cr alloys containing minor additions of group III,IV, or V elements

The corrosion of a number of experimental ternary Ni-15 wt. % Cr-0.5wt. %X alloys (where X= Y, La, Ce, Sm, Th, U, Zr, or V) has been assessed in pure oxygen at 900° C for periods of exposure up to 450 hr, and compared with the behavior of an Ni-15% Cr control alloy. It has been established that while all of the alloys oxidize in accordance with a protective, approximately parabolic regime, considerable differences in oxidation rates are exhibited. In particular, additions of La, Ce, and Th bring about progressively enhanced rates of oxidation relative to the binary alloy, whereas Y, Sm, V, U, and Zr effect increasingly reduced rates of oxidation in the order given. The rate constant for the Th-bearing alloy is about two orders of magnitude larger than that for the alloy containing Zr. Such differences in behavior seem to be associated with subtle variations in the morphology/composition of the corrosion products from alloy to alloy. The observations are considered in the light of earlier published literature concerning the effects of rare-earth and other reactive elements on the oxidation behavior of Ni/Cr alloys.This work has been carried out with the support of Procurement Executive, Ministry of Defence.     

Fe41Co7Cr15Mo14C15B6Y2块体非晶合金在HCl溶液中的腐蚀行为

采用电化学极化曲线和电化学阻抗(EIS)测试方法研究Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2块体非晶合金在0.5,1,2以及4 mol/L HCl溶液中的腐蚀行为,并比较了1 mol/L HCl溶液中非晶合金和不锈钢的腐蚀行为.极化曲线测试结果表明,Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2块体非晶合金在各种浓度的HCl溶液中都具有很好的耐蚀性,阳极极化曲线表现出明显的钝化特征.随着HCl溶液浓度的增大,其耐蚀性能逐渐下降.在1 mol/L HCl溶液中,非晶合金的自腐蚀电位高于不锈钢,自腐蚀电流密度比不锈钢小1个数量级.EIS结果显示,在开路电位下,Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2非晶合金和不锈钢的Nyquist图均由单一的容抗弧构成,但非晶合金的电化学转移电阻Rt比不锈钢的大2个数量级,这一结果与极化曲线结果一致,说明非晶合金在HCl溶液中的耐蚀性能优于不锈钢.     

Korrosionsuntersuchungen an ausgewählten metallischen Werkstoffen im System Essigsäure/Esigsäureanhydrid

Corrosion tests of selected metallic materials in the system acetic acid/acetic anhydride The corrosion behaviour of the ferritic austenitic stainless steels X2 CrNiMoN 22 5 (UNS S31803) and X2 CrNiMoN 25 7 4 (UNS S32750), the nickel base alloy NiMo16Cr16Ti (alloy C-4) and the titanium grades Ti2 (Grade 2) and Ti2Pd (Grade 7) was investigated by immersion tests in boiling mixtures of acetic acid and acetic anhydride in the presence of air. All materials tested were corrosion resistant in acetic acid and acetic anhydride but were corroded rapidly by the mixtures with a corrosion loss up to 1 mm/a, except the nickel base alloy (alloy C-4). It was corrosion resistant in all solutions with a corrosion loss not exceeding 0.01 mm/a. Electrochemical tests show that all materials tested exhibit stable passivity in glacial acetic acid and active corrosion in the presence of 10% acetic anhydride.     

The oxidation of nickel—tungsten alloys

The oxidation behaviour of NiW alloys and NiWCr alloys containing up to 40 wt%W has been studied in the temperature range 900–1200°C. The parabolic rate constant for oxidation increases with increasing tungsten content in the alloy. Addition of 10 or 15%Cr causes a significant reduction in the oxidation rate.In the Ni—7·5W alloy, spherical internal oxide particle of WO₃ are formed within the alloy, whereas as the tungsten content is increased the tendency to internal oxidation diminishes but the alloy/scale interface develops a highly irregular morphology. The roughened alloy/scale interface is less marked at the higher oxidation temperatures, and also when chromium is present in the alloy. The morphology of the interface is probably related to the relatively low interdiffusion coefficient in NiW alloys.     

Cr含量对CrxMoNbTiZr系高熵合金组织与性能的影响

采用真空电弧熔炼的方法制备了Cr_xMoNbTiZr系高熵合金(x=0, 0.5, 1, 1.5)。利用X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)、显微硬度计以及电化学工作站研究了Cr含量对该高熵合金结构、组织、硬度和耐蚀性能的影响。结果表明,Cr的添加使合金由单相BCC结构转变为富Zr相与富Mo-Nb相的双相BCC结构,随着Cr含量增加,在富Zr相中还有富Cr的Laves相析出;Cr_1.5MoNbTiZr合金具有最高硬度765.53 HV,这是由于第二相析出强化、固溶强化与高熵合金晶格畸变的共同作用;Cr的加入增加了Cr_xMoNbTiZr系高熵合金在质量分数为3.5%NaCl溶液中发生腐蚀倾向,但降低了该系高熵合金的腐蚀速率,同时发现Cr的添加存在一个临界值来保证合金的抗点蚀能力,超过这个临界值合金就会更容易发生点蚀现象。     

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.     

The influence of zirconium on the approach to steady-state scaling in a Ni-Cr alloy and the mechanism of inhibition of corrosion in an oxygen-sulphur environment

The corrosion behaviour of a binary Ni-15 Cr alloy and a ternary Ni-15 Cr'1 Zr alloy has been examined when exposed to a bioxidant O₂:SO₂ atmosphere at 850°C. The patterns of scaling exhibited by the two alloys, especially in the early stages of reaction, have been studied using optical and scanning electron microscopy and EDAX analysis. It has been established that the nucleation of Cr₂ O₃ on, and its subsequent growth over the sample surface was much more rapid with the ternary alloy than the binary material. Furthermore the steady-state scale formed on the ternary alloy was single-layered and contained no NiO, in contrast to the anticipated duplex-layered scale developed on the binary material. It is suggested that the pre-existing intermetallic network in the as-cast microstructure of the Ni-15 Cr-1 Zr alloy is a key factor in promoting the rapid formation of the thin protective layer of Cr₂O₃, free from NiO. These features are responsible for the reduced rate of corrosion of the Zr'bearing material, relative to that exhibited by the binary alloy. The observations are discussed in the light of the published literature concerning the effects of rare earth/reactive metal and inert oxide additions to chromia-forming alloy systems.     

Fabrication of superhydrophobic surfaces on Mg alloy substrates via primary cell corrosion and fluoroalkylsilane modification

The present work reports a simple and safe two‐step process to render magnesium (Mg) alloy surfaces superhydrophobic via primary cell corrosion and subsequently cover it with a fluoroalkylsilane (FAS) film. The surfaces were characterized by scanning electron microscopy (SEM), optical microscopy, energy‐dispersive X‐ray spectroscopy (EDS), Fourier‐transform infrared spectrophotometry (FTIR), X‐ray diffraction (XRD), and optical contact angle measurements. The power generated via the primary cell corrosion of copper and Mg alloys was also measured using a digital multimeter. The results show that micro/nanometer‐scale binary rough structures and an FAS film with a low surface energy were present on the Mg alloy surfaces, both of which confer good superhydrophobicity with a water contact angle of 162.8° and a tilting angle of 2°. The micro/nanometer‐scale binary rough structures consisted of micrometer‐scale grains, cluster‐like structures composed of nanometer‐scale needles, and network‐like structures composed of nanometer‐scale sheets. Superhydrophobicity was analyzed by the Cassie–Baxter theory. Findings show that only about 6.3% of the water surface was in contact with the Mg alloy substrates, while the remaining 93.7% was in contact with the air cushion. The unique advantage of the proposed method is that power can be generated during the machining process of the superhydrophobic surfaces on the Mg alloy substrates.     

Effects of cooling rate on the precipitation behavior of grain boundary carbide and corrosion resistance of 5Cr15MoV stainless steel

High-carbon and high-chromium alloy steels are prone to pitting and intergranular corrosion, which reduces corrosion resistance. The precipitation behavior of the carbides of high-carbon and high-chromium alloy steels is one of the main factors affecting pitting and intergranular corrosion of stainless steel. In this study, 5Cr15MoV stainless steel was heated to 1,200℃ and then cooled by cooling rates varying from 25 to 150°C/min. The precipitation behavior of grain boundary carbides of 5Cr15MoV steel at different cooling rates, and its effect on the corrosion resistance of materials was studied. The results show that the carbides of 5Cr15MoV steel mainly precipitate along the grain boundaries, which leads to the formation of chromium-depleted zones near the grain boundaries and reduces resistance to intergranular corrosion. It has been found that a higher cooling rate shortens the width of the Cr-depleted zone near the boundary from 0.871 to 0.569 μm, reduces the Cr-concentration gradient near the grain boundary from 36.422% to 12.667%, and suppresses the nucleus growth rate of grain boundary carbides. As the cooling rate increases, the corrosion current density decreases from 13.29 to 2.42 μA/cm². The corrosion rate is the lowest, while the cooling rate is 150°C/min. The corrosion rate decreases from 218.339 to 158.488 mm/a. The phenomenon of intergranular corrosion and pitting corrosion was found to be weakened; and thereby, it is shown that an intensive cooling rate can improve the corrosion resistance of 5Cr15MoV steel.     

The oxidation of micro-crystalline Co–Cr alloys under balanced oxygen pressure of Co2O3/Co powders

Surface micro-crystallizing was applied to Co–5Cr, Co–10Cr and Co–15Cr alloys by electro-spark deposition (ESD) and the oxidation behaviors of both cast and micro-crystalline alloys were investigated at 1000 °C under balanced oxygen pressure of Co₂O₃/Co-mixed powders. Surface and cross-section SEM morphologies, EDS and XRD analysis show that micro-crystallizing promotes both the external oxidation and internal oxidation of Co–5Cr alloy. Micro-crystallizing provides more grain boundaries so that the diffusion is enhanced. The inwards diffusion of O makes internal oxidation zone thicker while the outwards diffusion of Cr makes external oxidation more prominent for the micro-crystalline Co–5Cr alloy. For both the cast and micro-crystalline Co–10Cr and Co–15Cr alloys, 10 wt.% Cr is enough to form complex selective oxides (AO/AB₂O₄/BO) scales and 15 wt.% Cr is still not enough to form a single Cr₂O₃ oxide scale. Micro-crystallizing promotes the outwards diffusion of Cr and selective Cr₂O₃ scales are easier to form so that the external oxides scales of micro-crystalline Co–10Cr and Co–15Cr alloy are much thinner and their Cr/Co ratios are higher. The oxidation model of A–B alloy under oxygen pressure that both A and B can be oxidized is also proposed.     

Ni基合金在900 ℃75%Na2SO4+25%NaCl盐膜下的热腐蚀

研究了纯Ni、Ni-10Cr和Ni-10Cr-5Al合金在900 ℃空气中涂敷Na2SO4+25%NaCl盐膜时的热腐蚀行为。结果表明,Ni-10Cr合金的腐蚀动力学曲线近似服从抛物线规律,而纯Ni和Ni-10Cr-5Al合金的腐蚀动力学曲线分段服从抛物线规律。Ni-10Cr的腐蚀增重最小,抗热腐蚀性能最好,Ni-10Cr-5Al次之,纯Ni的腐蚀增重最大。Ni-10Cr-5Al合金热腐蚀24 h后氧化产物分为3层,外层氧化产物主要是NiO,中间层氧化产物为Cr2O3和Al2O3,最内层有少量Cr2S3和Al2S3。Ni-10Cr合金热腐蚀24 h后氧化膜分为3层,外层氧化产物是NiO,中间层是不连续的Cr2O3,内腐蚀区有少量Cr2S3。由于熔盐中NaCl的存在,Ni-10Cr-5Al和Ni-10Cr合金的腐蚀产物会变得疏松多孔。     

Corrosion of low alloy steel in stagnant artificial or stirred natural seawater: The role of Al and Cr

Carbon steel and low alloy (containing Al and Cr) steel coupons were immersed for 6–7 months in stagnant artificial seawater or in natural marine site. The corrosion processes were studied via the combination of electrochemical techniques and the analysis of corrosion product layers by µ‐Raman spectroscopy and X‐ray diffraction. In natural seawater, the low alloy steel showed better resistance to corrosion and the best results were obtained when the mill scale was removed from the steel surface. This shows that improved corrosion resistance is due to a protective layer that forms spontaneously in the environment. In stagnant artificial seawater, the behavior of low alloy steel coupons (without mill scale) was compared with that of carbon steel coupons. The polarization resistance of the carbon steel coupons remained approximately constant over time. The corrosion product layer proved to be mainly composed of magnetite, an electronic conductor that does not hinder oxygen reduction. In contrast, the polarization resistance of the low alloy steel coupons increased with time, as the growing corrosion product layer, enriched with insulating FeOOH compounds, hindered oxygen diffusion.     

Corrosion behavior of a CuCrNiAl alloy in the presence of NaCl deposit

The corrosion behavior of a CuCrNiAl alloy with NaCl deposit at 700 and 900℃ was studied by means of metalloscope, XRD, SEM/EDX, and thermogravimetric analysis. The results indicated that the corrosion of the CuCrNiAl alloy beneath the NaCl deposit is severe; the corrosion production is loose and easy to scale off; the Cr phase is easier to erode than the Cu phase, and the contents of Cu and Cr decrease when the content of Ni increases in the matrix of the alloy beneath the corrosion region. The effects of distortion on the corrosion of the CuCrNiAl alloy were discussed, and the acceleration mechanisms of NaCl on the corrosion were also discussed.     

CHARACTERISTICS AND FORMATION MECHANISM OF CORROSION SCALES ON LOW--CHROMIUM X65 STEELS IN CO2 ENVIRONMENT

利用高温高压CO₂腐蚀模拟实验以及ESEM, EDS, XPS和SEM等分析技术, 研究了4种不同含Cr量的X65管线钢的腐蚀速率、腐蚀形态和腐蚀产物膜结构特征. 结果表明: 含Cr量高的钢平均腐蚀速率小, 无Cr和含1\%Cr的钢的腐蚀形态为局部腐蚀, 含3%和5%Cr的钢的腐蚀形态为全面腐蚀. 在高温高压CO₂腐蚀环境中, 含Cr钢的腐蚀产物膜为FeCO₃和Cr(OH)₃竞争沉积形成的多层结构, 其中1Cr-X65和3Cr-X65的腐蚀膜具有3层结构, 5Cr-X65的腐蚀膜是双层结构. Cr在腐蚀产物膜层中出现局部富集, 远高于基体中的Cr含量. 高含Cr量使腐蚀产物膜中的Cr(OH)₃含量高, 并提高了腐蚀膜的保护性能, 从而引起腐蚀形态发生转变, 腐蚀速率降低. FeCO₃和Cr(OH)₃共沉积层膜对低铬钢的抗CO₂腐蚀性能具有关键的影响.     

Al/Cr复合涂层对Ti2AlNb合金抗热腐蚀性能的影响

目的改善Ti2AlNb合金在高温腐蚀盐环境中的耐热腐蚀性能。方法在Ti2AlNb合金表面通过双层辉光等离子渗铬及磁控溅射镀铝技术制备Al/Cr复合涂层,分析涂层热腐蚀前后的微观形貌和物相组成,并探究涂覆Na2SO4盐膜的试样在不同温度下(750、850、950℃)的热腐蚀行为。结果Al/Cr复合涂层组织均匀致密,且与基体结合良好,厚度约73μm,由表及里依次由Al沉积层、Al/Cr合金层、Cr沉积层、Cr扩散层四部分组成。经不同温度Na2SO4盐热腐蚀后,Al/Cr复合涂层腐蚀程度均显著小于合金基体。涂层试样经750~850℃Na2SO4盐热腐蚀后质量变化较小,850℃腐蚀增重仅0.525 mg/cm^2,而经历950℃、40 h熔盐热腐蚀后失重达到73.571 mg/cm^2,且试样截面出现剥离、脱落现象,Al/Cr复合涂层抵抗热腐蚀能力减弱。结论具有涂层保护的试样抗热腐蚀性能明显优于合金基体。Al/Cr复合涂层在750~850℃Na2SO4盐环境中具有良好的热腐蚀抗力,而更高温度段(850~950℃)的热腐蚀抗力下降。Al/Cr复合涂层在Na2SO4盐环境中良好的抗热腐蚀性得益于涂层中Al、Cr元素氧化形成以Al2O3、Cr2O3为主的混合氧化膜,有效阻碍外界氧气及腐蚀性介质侵入基体。     

Study of passive film on stainless steels and high grade nickel base alloy using X-ray photoelectron spectroscopy

Abstract

In the present study an assessment has been made of the air formed passive film and the passive film existing after a short exposure to a synthetic sea water environment on austenitic (UNS S31603), superaustenitic (UNS S31254 and UNS S32654) and superduplex (UNS S32760) stainless steels and a Ni base alloy (UNS N06625) using X-ray photoelectron spectroscopy. Assessment of their corrosion behaviour has been made through use of electrochemical accelerated tests supported by post-test microscopy. The passive film on the Ni base (low Fe) UNS N06625 alloy is remarkably similar to those formed on the high Cr and Mo stainless steels. It has been demonstrated that the Fe/Cr ratio in the passive film is dependent on alloy composition and on the conditions to which the material has been exposed, and a general correlation between passive film constitution and corrosion resistance is evident.     

Investigation into the Hot salt corrosion of Cr?Al,Cr?Ni?Mn and Mn?Al steels

The hot salt corrosion behaviour in a KCl · K₂SO₄ · Fe₂O₃ melt at 755 °C has been investigated as a function of alloy composition for three groups of refractory steels: 24Cr1.3Al, 27Cr12Ni(4 or 6)Mn and (20: 33)Mn(7 : 10)Al. Mn. Al-steels with a maximum Mn-content of 30% and CrNi6Mn-steels displayed a marked superiority in corrosion resistance in terms of weight loss as well as depth of internal deterioration. The protective mechanism of manganese is apparently related to its high-rate uniform segregation to the metal/melt interface inhibiting internal sulphidation along preferential paths.