加热时间对高频感应熔覆镍基合金涂层耐腐蚀性能的影响

研究了不同加热时间对高频感应熔覆Ni45B镍基合金涂层组织和耐腐蚀性能的影响。结果表明,用高频感应熔覆的方法得到的合金涂层无裂纹存在,且加热时间较长的合金涂层组织更加均匀;在高温条件下,随着加热时间的延长,涂层和基体之间元素的扩散加剧,使得涂层中Fe元素含量增加,而Ni、Cr元素的含量相对减少;由于合金粉末中含有的Ni、Cr等元素,使得涂层的耐腐蚀性能远高于基体材料Q235A钢,而随着加热时间的延长,扩散引起涂层中Ni、Cr元素减少使得涂层的耐腐蚀性能降低。     

Hot corrosion of materials: a fluxing mechanism?

Hot corrosion is the accelerated oxidation of a material at elevated temperature induced by a thin film of fused salt deposit. Fused Na₂SO₄, which is the dominant salt involved in hot corrosion, is an ionic conductor, so that the corrosion mechanism is certainly electrochemical in nature. Further, the acid/base nature of this oxyanion salt offers the possibility for the dissolution (fluxing) of the normally protective oxide scale. Non-protective precipitated oxide particles are often observed in the corrosion products. In this paper, the status of knowledge for the solubilities of oxides in fused Na₂SO₄ is reviewed, and the effects of various influences on a fluxing mechanism are discussed. An evaluation of a “negative solubility gradient” as a criterion for continuing hot corrosion is made.     

Preparation and hot corrosion behaviour of an Al-gradient NiCoCrAlYSiB coating on a Ni-base superalloy

A gradient NiCoCrAlYSiB coating was prepared on a Ni-base superalloy using arc ion plating (AIP) and subsequent gaseous phase aluminisation techniques. Hot corrosion of normal NiCoCrAlYSiB and the gradient coating in pure Na₂SO₄ and Na₂SO₄/NaCl (75:25, wt./wt.) salts was performed at 900 °C in static air. The corrosion results indicated an enhanced corrosion resistance to both salts for the gradient NiCoCrAlYSiB coating, which the improved performance of it should be attributed to the β aluminide ‘‘pool” at the surface layer. By partially sacrificing Al₂O₃ (i.e. Al), the gradient NiCoCrAlYSiB coating specimen behaved excellently in the two kinds of salts. The grain growth during the gaseous phase aluminisation and the corrosion mechanism, including the role NaCl played in the mixture salt corrosion, are discussed.     

高Cr镍基合金的高温内氧化和内氮化行为

通过对镍基合金进行不同温度的恒温氧化试验、横断面的组织形貌观察及微区成分分析,研究一种高Cr镍基合金在恒温氧化期间的氧化物分布特征、内氧化及内氮化行为。结果表明:该高Cr镍基合金在850、900、950和1 000℃空气中氧化100 h期间,合金表层发生元素的外氧化,且在外氧化膜中出现分层结构,由表及里各层中的主要氧化物分别为Al2O3、Cr2O3、NiCr2O4和NiAl2O4、Cr2O3、CrTaO4和Al2O3;合金在900℃以下为完全抗氧化级,900~1 000℃为抗氧化级。该合金在各温度的恒温氧化期间,均发生元素Al的内氧化和内氮化;与外氧化膜相邻的区域为元素Al的内氧化区,远离外氧化膜的基体内部形成元素Al的内氮化区;随恒温氧化温度的升高,内氧化区和内氮化区的深度增加,内氧化物和内氮化物的尺寸增大。其中,在内氧化物、内氮化物周围形成元素Al的贫化区,在贫化区内发生-′相的分解及贫乏。     

Kinetics and mechanism of high-temperature sulfur corrosion of Fe-Cr-Al alloys

The influence of aluminium on the kinetics and mechanism of high-temperature sulfidation of Fe-Cr alloys containing 20 at.% chromium has been investigated. It has been found that the addition of aluminum greatly improves the scaling resistance of Fe-Cr alloys against attack by sulfur vapors at high temperatures.     

Long-term high-velocity oxidation and hot corrosion testing of several NiCrAl and FeCrAl base oxide dispersion strengthened alloys

Several oxide dispersion strengthened (ODS) alloys have been tested for cyclic, long-term, high gas-velocity resistance to oxidation at 1100°C and hot corrosion at 900°C. Both nominally Ni-16Cr-4Al and Fe-20Cr-4.5Al ODS alloys were subjected up to 2500 cycles, where each cycle consisted of 1 hr in a hot, Mach 0.3 combusted gas stream followed by a 3-min quench in an ambient temperature, Mach 0.3 air blast. For comparison to existing technology, a coated superalloy was simultaneously tested. The ODS iron alloy exhibited clearly superior behavior, surviving 3800 oxidation and 2300 hot corrosion cycles essentially unscathed. While the ODS nickel alloys exhibited adequate oxidation resistance, the long-term hot corrosion resistance could be marginal, since the best life for such alloys under these conditions was only 1100 cycles. However, the hot corrosion resistance of the ODS Ni-base alloys is excellent in comparison to that of traditional superalloys.     

Molten carbonate-induced hot corrosion of nickel

The accelerated oxidation of pure nickel in the presence of a molten carbonate mixture has been studied in O₂ and CO₂-containing atmospheres. The oxidation rate of nickel with carbonate coatings was at least four orders of magnitude faster than that without salt coatings. The extent of oxidation, in terms of unit area weight gain, depended on both the amount of carbonate mixture coatings and the gas atmosphere. The unit area weight gain due to oxidation increased with increasing amounts of salt coatings up to a certain value. These observations suggest that the termination of nickel oxidation results from the exhaustion of either the salt coatings or metallic nickel. Porous and particulate oxide products were observed from scanning electron microscopic (SEM) examinations. The energy-dispersive analysis of x-rays (EDAX) shows that no salt remains on the specimen surface after the oxidation experiment.     

Comparative study on corrosion behaviors of Mg-Al-Zn alloys

A comparative study on corrosion behaviors of various Mg-Al-Zn alloys (AZ21, AZ41, AZ61 and AZ91 series, cast under same cooling conditions and controlled alloying composition) was carried out. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used for microstructural examinations. The corrosion behaviors were evaluated by immersion tests and potentiodynamic polarization measurements in 3.5% NaCl solution. The results showed that the influence of Al addition on corrosion resistance was more pronounced up to 4% (i.e. AZ41) above which its influence was at less extent. The deterioration of the corrosion resistance of the alloys, at higher Al contents, was attributed to the amount and morphology of β-Mg₁₇Al₁₂ intermetallics and the interruption of continuity of the oxide film on the surface of the alloys owing to coarsened β intermetallics.     

The influence of iron and cobalt on the type II hot corrosion behavior of NiCr model alloys

The type II hot corrosion behavior of the alloys NiCr20, NiCr20Co10, and NiCr20Fe10 is investigated at 700°C in synthetic air + 0.5% SO₂ for up to 300 hr. Pure Na₂SO₄ and a eutectic mixture of MgSO₄–Na₂SO₄ are applied as deposits. The kinetics are investigated via dimensional metrology and correlated to the microstructural progression of the corrosion by examining the cross-sections. All alloys exhibit two-stage corrosion kinetics, with initially low and subsequently increased metal losses. Independent of the deposit composition, the metal loss after the longest exposure time is increased by the alloying element cobalt, whereas it is decreased for the iron-containing alloy. All alloys show increased metal losses when exposed to the MgSO₄–Na₂SO₄ deposit. The time to the propagation stage is similar for all tests. During the stage of low metal loss, all alloys develop a chromia scale and internal chromium sulfides. When the propagation stage is reached, chromium and nickel can be found along with oxygen and sulfur within the pit. Nickel is dissolved into the deposit, where it precipitates.     

ESCA study of oxidation and hot corrosion of nickel-base superalloys

A study of the high-temperature oxidation and Na₂SO₄-induced hot corrosion of some nickel-base superalloys has been accomplished by using ESCA to determine the surface composition of the oxidized or corroded samples. Oxidation was carried out at 900 or 1000°C in slowly flowing O₂ for samples of B-1900, NASA-TRW VIA, 713C, and IN-738. Oxidation times ranged from 0.5 to 100 hr. Hot corrosion of B-1900 was induced by applying a coating of Na₂SO₂ to preoxidized samples, then heating to 900° C in slowly flowing O₂. Corrosion times ranged from 5 min to 29 hr. For oxidized samples, the predominant type of scale formed by each superalloy was readily determined, and a marked surface enrichment of Ti was found in each case. For corroded samples, the transfer of significant amounts of material from the oxide layer to the surface of the salt layer was observed to occur long before the onset of rapidly accelerating weight gain. Some marked changes in surface composition were observed to coincide with the beginning of accelerating corrosion, the most striking of which were a tenfold decrease in the sulfur to sodium ratio and an increase in the Cr(VI) to Cr(III) ratio. Supported by NASA Grant No. NSG-3009     

Localized corrosion mechanism associated with precipitates containing Mg in Al alloys

To clarify the localized corrosion mechanism associated with precipitates containing Mg in Al alloys, the simulated bulk precipitates of S and β were synthesized through melting and casting. Their electrochemical behaviors and coupling behaviors with α（Al） in NaCl solution were measured. Meanwhile, simulated Al alloys containing S and β particles were prepared and their corrosion morphologies were observed. It＇s found that there exist two kinds of corrosion mechanisms associated with precipitates containing Mg. The precipitate of β is anodic to the alloy base, resulting in its anodic dissolution and corrosion during the whole corrosion process. While, there exists a corrosion conversion mechanism associated with the S precipitate, which contains active element Mg and noble element Cu simultaneously. At an initial stage, S is anodic to the alloy matrix at its periphery and the corrosion occurs on its surface. However, during its corrosion process, Mg is preferentially dissolved and noble Cu is enriched in the remnants. This makes S become cathodic to a（Al） and leads to anodic dissolution and corrosion on the alloy base at its periphery at a later stage.     

Electrochemical mechanism of hot corrosion of Bi2O3-deposited copper

An electrochemical mechanism of hot corrosion of the Bi₂O₃-deposited copper is proposed. Oxygen ion transport across the oxide scale with liquid-channel grain-boundary structure (LGBS) is the rate-limiting step in the overall mechanism. The calculated and experimental values of the rate constant for hot corrosion of Bi₂O₃-deposited copper are of the same order of magnitude, which shows agreement between theory and experiment.     

A comprehensive assessment of the performance of corrosion resistant alloys in hot acidic brines for application in oil and gas production

Four stainless steels and alloys (17-4 PH, X4CrNiMo 16-5-1, F6NM and UNS N09935) were evaluated in relation to their application in the oil and gas industry. These materials were tested in solutions exhibiting a range of chloride concentrations, pH values and temperatures of interest for the oil and gas producing environments. The pitting sensitivity was investigated by means of potentiodynamic polarisation measurements, based on the ASTM G61 standard, in conjunction with a morphological study performed by scanning electron and optical microscopy. The resistance to stress corrosion cracking (SCC) was evaluated in compliance with the ASTM G123 standard. Erosion–corrosion was assessed by exposing the materials under electrochemical control to a flux of erodent glass microspheres in a rotating disc electrode device. A ranking of the materials resistance was derived, based on appropriate parameters, devised to effectively and synthetically represent the complex sets of environments of interest for the relevant application. Our results showed, as expected, that UNS N09935 displays the best performance with respect to pitting resistance and susceptibility to SCC as well as a very good resistance to erosion–corrosion. Among the other investigated materials, 17-4 PH showed higher resistance to pitting, X4CrNiMo 16-5-1 and F6NM longer time to SCC failure while 17-4 PH and X4CrNiMo 16-5-1 exhibited superior ability to withstand erosion–corrosion damaging.     

Simulation study on function mechanism of some precipitates in localized corrosion of Al alloys

The function mechanism of different types of aging precipitates in localized corrosion of Al alloys was studied. The function mechanism of the precipitates of θ (Al₂Cu) and η (MgZn₂) is validated. The precipitate of θ containing noble element Cu is cathodic to the alloy base, resulting in the anodic dissolution and corrosion of the alloy base at its adjacent periphery. The precipitate of η containing active element Mg is anodic to the alloy base, anodic dissolution and corrosion occur on its surface. Meanwhile, a localized corrosion mechanism conversion associated with the precipitate of T1 (Al₂CuLi) is advanced, which contains noble element Cu and active element Li simultaneously. The precipitate of T1 is anodic to the alloy base and corrosion occurs on its surface at the beginning. However, during its corrosion process, the preferential dissolution of Li and the enrichment of noble element Cu make its potential move to a positive direction. As a result, the corroded T1 precipitate becomes cathodic to the alloy base at a later stage, leading to the anodic dissolution and corrosion of the alloy base at its adjacent periphery.     

热处理对轧制态Mg5Gd合金腐蚀行为的影响

通过浸泡试验、电化学测试、扫描电化学显微镜和腐蚀形貌分析等手段研究热处理工艺对轧制态Mg5Gd合金在3.5 wt.％NaCl饱和Mg(OH)2溶液中腐蚀行为的影响及机理,以期达到提高镁合金耐蚀性的目的.结果表明:固溶处理能显著降低Mg5Gd合金的腐蚀速率,并且使其腐蚀变均匀,腐蚀坑变浅,这主要归因于固溶处理可以熔解镁基...     

High-temperature sulfide corrosion of cobalt-chromium alloys

The kinetics and mechanism of high-temperature sulfidation of cobaltchromium alloys were investigated. It has been found that the sulfidation rate of low-chromium alloys, up to 2% Cr, is higher than that of pure cobalt. The one-layer homogeneous scale on these alloys is a solid solution of chromium sulfide in cobaltous sulfide. In the case of alloys containing more chromium, up to 43%, sulfidation rate decreases gradually with chromium content, the scale consisting of two layers. The growth mechanism of scales as well as the influence of chromium concentration on sulfidation rate is discussed.This work was carried out under contract No. 03.10 coordinated by the Institute of Physical Chemistry, Polish Academy of Sciences.     

Effect of pre-oxidation on the hot corrosion of CoNiCrAlYRe alloy

The effect of pre-oxidation on the resistance to hot corrosion was examined by corroding the CoNiCrAlYRe alloy at 900 °C in molten Na₂SO₄. Preoxidized specimens featured strong adhesion of oxide scale with uniform multi-layered structure. The time of pre-oxidation was crucial for controlling Al content sufficient for subsequent hot corrosion. However, direct corrosion yielded a defective and non-protective oxide scale, which allowed detrimental penetration of sulfur into substrate. Sulfur migrating along phase boundary was trapped by yttrium to diminish slightly sulphidation. Thus, two advantages of proper pre-oxidation treatment were presented, as keeping repairing for Al₂O₃ scale and inhibiting sulfur penetration.     

激光熔敷镍基碳化钨的腐蚀磨损行为

测定了Ｎｉ６０＋２０％ＷＣ合金激光熔敷层的腐蚀磨性能，用扫描电镜研究了冲击速度和介质浓度对腐蚀磨损表面形貌的影响。结果表明，激光熔敷合金层的腐蚀磨损速率随冲击速度Ｖ和硫酸浓度Ｃ的提高而增大，符合Ｗ＝０．０２８７Ｖ＾２．０８７＋３．９３２Ｖ＾０．４３６Ｃ０．３３１Ｖ＾０．３１６的定量关系。其磨损机制为犁削磨损，腐蚀机制为均匀腐蚀和坑穴腐蚀，磨损对腐蚀有明显的激化作用。     

递归法研究钛合金应力腐蚀机理

利用递归法(Recursion)计算了α-Ti中刃位错及裂纹区的电子结构(Fermi能级、结构能、环境敏感镶嵌能等),计算并分析了合金元素Mo,V对α-Ti与β-Ti相原子结合能的影响.结果表明:氢原子在位错处的环境敏感镶嵌能较低,易于在位错处聚积,形成氢原子气团.裂纹尖端Fermi能级高于裂纹其他区域,电子从裂纹尖端流向裂纹其他区域造成电位差,在电解质作用下裂纹尖端阳极分解腐蚀.拉应力与裂纹处的氢气压使裂纹解理或沿晶延伸,促进应力腐蚀的发展.合金元素Mo,V有利于α-Ti合金中β相的形成,阻止裂纹在α相中扩展,提高合金应力腐蚀抗力.