Synergistic corrosion behavior of coated Ti60 alloys with NaCl deposit in moist air at elevated temperature

In the present paper, the corrosion behavior of Ti60 alloys with an aluminide, TiAlCr, and enamel coatings in moist air containing NaCl vapor at 700-800 °C were studied. The results showed that the TiAlCr and aluminide coatings failed to protect the substrate from corrosion due to the cyclic formation of volatile products during corrosion at 800 °C. However, an uneven continuous protective Al₂O₃ scale could form on the aluminide coating during corrosion at 700 °C. And the enamel coating could protect Ti60 from corrosion due to its high thermochemical stability and matched thermal expansion coefficient with substrates of Ti-base alloys during corrosion.     

Corrosion behaviour of intermetallic aluminide coatings on nitrogen-containing austenitic stainless steels

The present work reports the effect of aluminide layers on the aqueous corrosion behaviour of four different 316L stainless steels containing various nitrogen contents (0.015%, 0.1%, 0.2% and 0.56% N). Diffusion annealed aluminide layers are generated over the surface by heat treatment of the aluminium precoated alloys at 750 °C for 25 h in nitrogen atmosphere. X-ray diffraction patterns of the surface modified samples showed the presence of AlN, Al₁₃Fe₄ and FeAl₂ phases. Diffusion of aluminum into the alloy, and the formation of AlN by the reaction of aluminium with matrix nitrogen, was identified using secondary ion mass spectrometry (SIMS). The nitrogen peak in the diffused layer was found to increase with increasing nitrogen content of the base alloy. SEM observation of cross-sectionally mounted alloys showed the presence of spherical AlN phase in addition to iron aluminide intermetallic phases. The role of such a composite surface layer containing intermetallic aluminides and nitride on the corrosion resistance of austenitic stainless steels in 0.5 M NaCl and 0.5 M sulphuric acid is discussed in greater detail based on open circuit potential (OCP)–time measurements, potentiodynamic polarisation studies and electrochemical impedance spectroscopy (EIS) investigations. The aluminide layered alloy with 0.1% N content showed better corrosion performance. The presence of nitrogen was found to have a positive effect in enhancing the hardness of the composite layer. Role of matrix nitrogen on the microstructure and microchemical distribution at the surface, and its role on corrosion resistance in acidic and chloride media are discussed in detail.     

Impact of Deposits and Their Morphology on the Active Corrosion of Iron in Chlorine- and Sulfur-Containing Atmospheres in the Temperature Range of 350–500 °C

Iron-based alloys have shown high corrosion rates under ash deposits typical for waste-to-energy plants. The ashes on superheater tubes in waste incineration are multicomponent systems including alkali and alkali–earth chlorides and sulfates. Under and within such salts, the corrosive effect on the alloy is induced by a complicated interplay of such ash products. On the one hand, in chlorine-containing atmospheres iron-based alloys are believed to be attacked by the so-called active corrosion, including the formation of volatile corrosion products and their transformation into stable iron oxides. At the same time, they form complex scales, involving among other compounds iron sulfides, chlorides, and oxides. Thus, in order to directly investigate the influence of a deposit on the corrosion in waste-to-energy plants and to reproduce the scales observed on field tested superheaters, this work compares the scale formation and metal wastage under different chemically inert alumina deposits with different grain sizes to a synthetic salt as well as to an actual deposit taken from a superheater tube in a plant.     

简单/改性铝化物涂层的研究现状

航空发动机各部件高温结构材料在苛刻环境下服役时,会遭受严重的高温氧化和热腐蚀.在合金表面施加铝化物涂层后,高温下表面能够生成一层致密且生长缓慢的Al2O3氧化膜,从而隔绝腐蚀介质,以防止合金被快速氧化腐蚀.概述了铝化物涂层的优点,包括制备简单、成本低廉.重点综述了以Ni、Fe、Ti/TiAl为合金基体的铝化物涂层微观结构.涂层的微观结构主要由渗铝工艺、基材成分及后处理工艺等因素决定,渗铝工艺包括渗剂成分、渗铝温度和渗铝时间.在高温下渗铝,Al的活度较低,涂层主要以基体元素向外扩散形成外扩散型涂层为主;在低温下渗铝,Al的活度较高,涂层主要以Al向内扩散形成内扩散型涂层为主.还归纳了不同渗铝涂层在干燥空气和水蒸气环境中的高温氧化行为,阐述了水蒸气对铝化物涂层高温氧化行为的影响,比较了Ni-Al系和Fe-Al系涂层的抗高温氧化性能.同时介绍了Cr-Al、Si-Al和Pt-Al 3种改性铝化物涂层的研究进展,包括制备方法、微观结构及抗高温氧化和腐蚀性能.最后,展望并总结了高温防护涂层的发展趋势.     

Field test of superheater corrosion in a CFB waste boiler: Part I – Metal loss characteristics

The corrosion was investigated on a superheater test coil in a CFB waste boiler. The alloys ranged from ferritic steel T22 to nickel‐based Alloy 65 and the metal temperatures were between 460 and 540°C. The thickness of the deposit was alloy and temperature dependent. The low‐alloyed steels developed thick deposits at all temperatures while the deposit thickness increased with the temperature on the high‐alloyed steels and the nickel‐based alloy. The corrosion attack was alloy dependent and related to the deposit crest. The nickel‐based Alloy 65 was preferentially attacked directly under the crest of the deposit while the other alloys were preferentially attacked at the edge. The corrosion rate increased with temperature for X20, Alloy 304L, Alloy 310 and Alloy 825; decreased on Alloy 65; and was bell shaped on T22 and Alloy 28. Alloy 310 suffered from severe pitting corrosion in a line following the edge of the deposit crest. The best overall corrosion resistant alloy was Alloy 28.     

Long‐term exposure of austenitic steels and nickel‐based alloys in lignite‐biomass cofiring

The aim of this study was to assess the long‐term impact that the addition of biomass provokes on superheater materials exposed to fireside corrosion environments. Alloys covering a broad range of commercially available materials were investigated. Their corrosion kinetics under different corrosive deposits and atmospheres was evaluated, and their corrosion products analyzed to deepen understanding of the underlying corrosion mechanisms. Therefore, three nickel‐based alloys and three austenitic steels containing 20–24 wt.% Cr were tested at 650°C for 7,000 hr. The long‐term exposure shows new mechanistic aspects of Type II hot corrosion that were revealed by accelerated material depletion. The formation of Ni–NiS eutectic and the formation of a Cr depleted zone close to the substrate corrosion product interface are indicative of the breakaway occurrence. Differences in the corrosion behavior are related to the balance of Ni, Mo, Co, and Cr and can serve as the material selection argument. The evaluation concluded with the finding that alloys presenting Mo and Ni might be preferentially used in fireside corrosion in the presence of biomass, whereas the use of austenitic steels suffer less corrosion if no biomass is present in the corrosive atmosphere.     

High Temperature Corrosion Problems in the Process Industries

This paper reviews a wide variety of high-temperature corrosion problems frequently encountered in the process industries. Problems in metallurgical processing, chemical and petrochemical processing, industrial heating, waste incineration, glass manufacturing, and pulp and paper industry are presented. Examples of component failures are given to illustrate the major modes of corrosion attack. The corrosion modes cover such complex environments as aluminum remelting flue gases (recuperator problems) and municipal waste incineration flue gases (superheater tube problems). The behavior of various alloys in various processing environments is also reviewed.     

Microstructural investigation of PGM‐based alloy coatings for oxidation protection

It is well known that Pt addition significantly improves the resistance of aluminide coatings to high‐temperature oxidation and hot corrosion, which has led to the widespread application of Pt modified aluminide coatings on the superalloy components of advanced gas turbine engines. Other platinum group metals (PGMs) such as Ir and Ru attract researchers for high temperature applications. In this study, oxidation properties of Pt‐Ir and Pt‐Ru based alloy coatings were investigated. Pt, Ru, and Ir were electroplated on a directionally solidified Ni‐base superalloy DZ125. The cyclic oxidation test revealed that both Pt‐Ir and Pt‐Ru alloys exhibited good oxidation performance. The effect of substrate alloy and coating compositions on microstructural changes during cyclic oxidation tests were discussed.     

Assessment of Titanium Aluminide Alloys for High-Temperature Nuclear Structural Applications

Titanium aluminide (TiAl) alloys exhibit high specific strength, low density, good oxidation, corrosion, and creep resistance at elevated temperatures, making them good candidate materials for aerospace and automotive applications. TiAl alloys also show excellent radiation resistance and low neutron activation, and they can be developed to have various microstructures, allowing different combinations of properties for various extreme environments. Hence, TiAl alloys may be used in advanced nuclear systems as high-temperature structural materials. Moreover, TiAl alloys are good materials to be used for fundamental studies on microstructural effects on irradiation behavior of advanced nuclear structural materials. This article reviews the microstructure, creep, radiation, and oxidation properties of TiAl alloys in comparison with other nuclear structural materials to assess the potential of TiAl alloys as candidate structural materials for future nuclear applications.     

Compositional effects on the Type I hot corrosion of β-NiAl alloys

Cast alloys of nominal compositions Ni-36Al, Ni-36Al-5Co, Ni-36Al-5Pt, Ni-36Al-5Co-5Pt, and Ni-36Al-5Cr (at.%) were tested under Type I (900 °C) hot corrosion conditions in order to determine the influence of various elements commonly found in diffusion aluminide coatings on the resistance to this mode of attack. Chromium was found to be the most effective element in conferring hot corrosion resistance, but improvements in performance were also found with the addition of Co and/or Pt. Experimental evidence is presented which suggests that each of these elements increase the hot corrosion resistance of β-NiAl alloys primarily by increasing their ability to rapidly form a thermally grown Al₂O₃ scale and to heal this scale in the event of damage. Potential explanations for this enhanced scale formation and healing capability are discussed.     

渗铝、渗铬工业纯铁的耐低温热腐蚀性能

分别采用热浸法和固渗法在工业纯铁上制备了铝的扩散涂层;工业纯铁上铬的扩散涂层是用固渗法获得的。对渗铝和渗铬的工业纯铁在有K_2SO_4-Na_2SO_4 盐膜存在时的低温热腐蚀行为进行了研究。结果表明,渗铝的工业纯铁仍遭受低温热腐蚀,这一热腐蚀的发生归因于K-Na-Al-Fe 四元低熔点复合硫酸盐的形成。而渗铬的工业纯铁表现出优异的耐蚀性能,这归因于涂层表面完整的富Cr_2O_3 氧化膜的快速形成。据此有理由认为,渗铬是铁基合金低温热腐蚀防护的一个有效途径。     

Improving high temperature oxidation and hot corrosion resistance of Ni-base super alloy INC738LC with Cr-Si-RE modified aluminide coatings produced by single step pack cementation process

The Cr-Si-Zr (or Y) modified aluminide coatings were produced on Ni-base INC738 by a novel single step pack cementation process and their behavior was evaluated in cyclic oxidation and hot corrosion conditions. A dual layer pack with different composition was applied to produce Cr-Si-Zr or Cr-Si-Y modified aluminide coatings. A mixture of salts 75%Na₂SO₄-20%NaCl-5%V₂O₅ at 950°C was used as a hot corrosion environment. The results show that oxidation and corrosion rate of Cr-Si-Zr or Cr-Si-Y modified aluminide coatings produced by dual layer pack process are lower than those of uncoated or simple aluminide coatings. Coatings with higher Al content and uniformly dispersed Cr-Si rich phases show better hot corrosion resistance.     

Effect of cerium addition on the corrosion behaviour of carbon-alloyed iron aluminides

The effect of Ce addition on the microstructure and corrosion behavior of carbon-alloyed iron aluminides Fe-20.0Al-2.0C, Fe-18.5Al-3.6C and Fe-19.2Al-3.3C-0.07Ce (in at.%) has been studied. The potentiodynamic polarization behaviour of the alloys was evaluated in freely aerated 0.25 mol/l H₂SO₄. A 0.05% C steel was used for comparison purposes. All the alloys exhibited active-passive behaviour in the acidic solution. The addition of Ce destroyed passivity as indicated by lower breakdown potentials in polarization studies. This has been related to the finer distribution of the carbides in the microstructure. Corrosion rates were evaluated by immersion testing. The iron aluminide with Ce addition exhibited a lower corrosion rate compared to the aluminides without Ce addition. This has been attributed to modifications in surface film with Ce addition. Scanning electron microscopy of corroded surfaces indicated that the carbon-alloyed intermetallics were susceptible to localized galvanic corrosion due to the presence of carbides in the microstructure.     

High-temperature coating for titanium aluminides using the pack-cementation technique

The practical application of titanium aluminide metal-matrix composites (MMCs) at high temperatures requires suitable surface coatings to provide the needed oxidation resistance. Without a coating, the titanium aluminide alloys suffered from rapid oxidation attack at elevated temperatures, particularly under thermal cyclic conditions. The pack-cementation coating process was utilized to aluminize the surface region of a Ti₃Al-base alloy to TiAl₃, the most oxidation-resistant phase. With the existence of an adherent conversion coating, a thin protective alumina scale formed on the outer surface, and a significant improvement in the corrosion resistance was observed. Excellent coating efficiency and geometric flexibility were demonstrated in this study by the pack-cementation technique. Further development of the cementation process will focus on the elimination of surface cracking in the coating.     

The Protection of Aluminides by Alloying with Molybdenum in High Chlorine Containing Atmospheres at 1,000 °C

Nickel aluminides are widely employed as coatings to enhance the oxidation resistance of alloys at high temperatures. However, some modern processes require the use of extremely high levels of chlorine in the process gas. This evokes a type of attack that no classical coating system can withstand. Nickel aluminide with molybdenum addition has been reported to be a potential candidate material before, but the corrosion mechanism of this system has not yet been investigated. To evaluate the influence of the molybdenum content on the corrosion behavior of NiAl, coupons were manufactured using an arc-melting process. The degradation mechanisms of these samples in synthetic air with 10 % chlorine gas at 1,000 °C are reported and discussed. It was found that molybdenum addition to NiAl changes the mechanisms of the attack and highly decelerates the corrosion rate under such demanding conditions.     

CLAM钢表面铝化物涂层的制备与铅液相容性研究

目的探索铝化物涂层的制备工艺,研究其是否能有效抑制铅液对CLAM钢的腐蚀。方法用配制的渗剂对CLAM钢进行包埋渗铝,并通过随后的热扩散和原位氧化处理,在CLAM钢表面制备铝化物涂层,研究不同渗铝时间和热扩散时间对涂层厚度的影响。通过静态氧化试验和铅液腐蚀试验,分别评价铝化物涂层的抗氧化性能及其与铅液的相容性,采用XRD、SEM和EPMA分析涂层的相组成以及铅液腐蚀前后的微观形貌和元素分布。结果包埋渗铝+热扩散+原位氧化处理制备的铝化物涂层主要由约30μm的FeAl相层和约70μm的α-Fe(Al)固溶体层组成。在热处理过程中,由于Al和Fe的互扩散现象,涂层中的Fe-Al相依次经过了Fe₂Al₅、FeAl₂、FeAl、Fe₃Al和α-Fe(Al)的转变。在600℃空气中静态氧化120 h后,铝化物涂层试样氧化质量增量为0.028 mg/cm²,比CLAM钢的氧化质量增量降低了1个数量级,铝化物涂层使CLAM钢的氧化动力学曲线由直线规律转变为抛物线规律。经550℃铅液腐蚀600、1800 h后,铝化物涂层的腐蚀质量增量分别为0.058、0.077 mg/cm²,仅约为CLAM钢的1/120。CLAM钢表面产生了疏松多孔的铁氧化物层,而铝化物涂层没有发生明显的腐蚀,但是腐蚀1800 h后,随着表面铝含量的不断消耗,Al₂O₃层厚度逐渐减小。结论铝化物涂层具有良好的抗氧化性能及与铅液的相容性,能够有效抑制铅液对CLAM钢的腐蚀。     

Oxidation and hot corrosion of coated and bare oxide dispersion strengthened superalloy MA-755E

Cyclic hot corrosion and oxidation testing of an experimental oxide dispersion strengthened (ODS) superalloy MA-755E were conducted in a hot gas stream at Mach 0.3. The response of the ODS alloy, bare or with protective coatings, was similar to that of a conventional cast alloy, IN-792, in hot corrosion at 900°C. However, during oxidation at 1100 and 1150°C the ODS alloy differed from the cast alloy by developing a greater amount of subsurface porosity. Compared with a diffused aluminide coating, an electron beam vapor deposited NiCrAlY coating offered superior oxidation protection and decreased porosity formation. In additional testing, the tendency to form porosity was associated with the large grains of recrystallized powder metallurgy alloys but was independent of the presence of an oxide dispersion.     

垃圾焚烧电厂过热器腐蚀影响因素及防护涂层研究进展

垃圾焚烧电厂过热器管道的高温腐蚀一直是制约电厂焚烧温度的关键问题,因此研究开发耐高温、耐腐蚀、长寿命的关键服役材料是保证垃圾焚烧炉正常有序运转及安全生产的关键。对近年来垃圾焚烧电厂腐蚀问题的研究现状进行了梳理,对近期垃圾焚烧电厂过热器腐蚀与防护的研究成果进行了综述。首先,从过热器腐蚀影响因素的角度,归纳了焚烧环境中存在氯、硫、温度、水蒸气等诸多因素影响下的腐蚀特点,对各个影响因素下的腐蚀机理进行了概述,氯作为影响腐蚀的关键因素,重点对氯导致腐蚀的活性氧化机理和电化学机理进行了阐述。其次,讨论了应用在过热器表面的涂层制备技术的发展,包括热喷涂、热扩散、堆焊、激光熔覆等,探讨了制备方法,以及应用技术的优缺点。分析了材料成分(Ni、Mo、Cr、Al、Si、Pt等元素)的添加与涂层耐腐蚀性能之间的关系。再次,从焚烧垃圾预处理的角度,进一步讨论前期可通过对垃圾脱水、添加共燃剂等方法,达到脱硫、脱氯的目的,以此降低烟气中硫、氯的含量,减小其对腐蚀的影响。最后,对垃圾焚烧电厂过热器管道材料和涂层的选择进行了总结和展望。     

Hot Corrosion Behavior of a Cr-Modified Aluminide Coating on a Ni-Based Superalloy

A Cr-modified aluminide coating is prepared on a Ni-based superalloy using arc ion plating and subsequent pack cementation aluminizing.Hot corrosion behavior of the Cr-modified aluminide coating exposed to molten Na2SO4/K2SO4(3:1) or Na2SO4/NaCl(3:1) salts at 900 °C in static air are evaluated as well as the aluminide coating.The results indicate that compared with the aluminide coating,the anti-corrosion properties of the Cr-modified aluminide coating in the both salts are improved,which should be attributed to the beneficial effect of the Cr in the coating.The corrosion mechanism of the Cr-modified aluminide coating,especially the role of Cr in the mixture salt corrosion,is discussed.     

Danish experience with fireside corrosion

Fireside corrosion has not been a severe problem in Danish power plants. Furnace wall corrosion has only been seen in one unit caused by insufficient control of the burners. High temperature corrosion has only been seen in units, where the final stage of superheater/reheater was placed in gas temperatures above 1300°C or where the difference in tube length was too big. Since 1970 the final stages of superheater and reheater are made of X20 CrMo V 12.1, which has showed excellent behavior. For estimation of the remaining service life of superheater/reheater, they are examined after 100,000 h in service.