Na_2SO_4沉积引起的Fe─10Cr合金在700℃的热腐蚀

研究了涂有Na2SO4盐膜的Fe-10Cr合金在700℃,O2-0.5%(SO2+SO3)气氛中的热腐蚀行为。结果表明,该合金在实验条件下发生了“低温”热腐蚀。腐蚀产物分两层,即在熔盐中沉积出的疏松氧化物层和在合金表面直接成长的相对致密的氧化物层。腐蚀形貌观察说明,热腐蚀的发展主要伴随着致密氧化层的增厚。腐蚀动力学和腐蚀形貌特点支持热腐蚀的电化学机理模型。     

Na_2SO_4沉积引起的Fe─10Cr合金在700℃的热腐蚀

研究了涂有Ｎａ２ＳＯ４盐膜的Ｆｅ－１０Ｃｒ合金在７００℃，Ｏ２－０．５％（ＳＯ２＋ＳＯ３）气氛中的热腐蚀行为。结果表明，该合金在实验条件下发生了“低温”热腐蚀。腐蚀产物分两层，即在熔盐中沉积出的疏松氧化物层和在合金表面直接成长的相对致密的氧化物层。腐蚀形貌观察说明，热腐蚀的发展主要伴随着致密氧化层的增厚。腐蚀动力学和腐蚀形貌特点支持热腐蚀的电化学机理模型。     

热腐蚀的电化学机理初探

简要叙述至今仍普遍接受的热腐蚀的盐熔模型,以实验事实为依据较系统地阐述这一机理模型的局限性。根据热腐蚀的特点,吸收盐熔模型的合理成分,并考虑到热腐蚀与高温气体腐蚀的共性,提出热腐蚀的电化学模型。用这一新的模型描述金属和合金的热腐蚀历程。     

α-Fe_2O_3、Fe_3O_4和Cr_2O_3在熔融Na_2SO_4中的溶解度

作者于1200K在1大气压氧和几个低氧压下测定了α-Fe_2O_3及Fe_3O_4及Cr_2O_3在熔融Na_2SO_4中的溶解度与Na_2SO_4熔盐碱度的关系,结果与热力学预示是一致的。在测量溶解度的基础上,确定了这几种金属氧化物在熔融Na_2SO_4中碱性和酸性溶解的溶质形式,计算了它们在该熔盐中的活度系数。金属氧化物溶解行为的研究将有助于了解热腐蚀的盐溶机理和电化学机理。     

表面有Na2SO4沉积时铁基合金的低温热腐蚀行为

研究了工业纯铁、Fe-Cr和Fe-Al合金表面有Na_2SO_4沉积时于O_2/SO_2/SO_3气氛中的低温热腐蚀行为。测定腐蚀动力学曲线,研究温度、气体组成及合金元素对腐蚀动力学的影响,并对腐蚀产物的形貌和组成进行观察与分析。结果表明,在工业纯铁、Fe-Cr和Fe-Al合金的低温热腐蚀过程中都发生金属表面致密氧化层的快速成长和疏松的Fe_2O_3在盐膜中的沉积,且前者对腐蚀的贡献居大。以实验结果为依据,初步提出了电化学机理模型,并用以阐述铁基合金低温热腐蚀过程。     

金属氧化物在熔融Na_2SO_4中的溶解行为

建立了高温Pourbaix型Na-M-S-O系热力学相图,总结了近年来金属氧化物在熔融Na_2SO_4中的溶解度的研究结果,并用高温Na-M-S-O系相图予以解释,还给出了有关金属溶解形式在熔融Na_2SO_4中的活度系数。基于金属氧化物在熔融Na_2SO_4中的溶解行为的研究结果,讨论了由熔融Na_2SO_4引起的热腐蚀的盐溶模型。     

灰铸铁在熔融富铅渣中腐蚀行为的研究

研究分析了灰铸铁在1150℃熔融富铅渣中的热腐蚀行为,并对灰铸铁的腐蚀形貌和腐蚀产物进行了观察和分析。结果表明,石墨及石墨的分布形态对灰铸铁的抗热腐蚀性能有重要影响,PbO和PbO.SiO2是富铅渣中参与腐蚀反应的主要物质。从电化学腐蚀模型讨论了富铅渣对灰铸铁的热腐蚀机理。     

热腐蚀中的微电池过程

热腐蚀中存在的微电池过程，主要由热腐蚀过程中金属及合金表面形成的不同氧化物、硫化物及氧化膜中的不均匀性及缺陷等因素引起。提出了预氧化金属及合金试样在熔盐中的电位模型，实验结果基本与理论模型相一致。通过热腐蚀微电池模型，可以解释一些热腐蚀现象。     

Ni-xCr-6.8Al基合金热腐蚀行为

研究铸态和预氧化态Ni-xCr-6.8Al基合金在Na2SO4＋25%NaCl混合盐中873K时的热腐蚀行为。结果表明：NixCr6.8Al基合金的质量损失随着Cr元素含量的增加而减少,预氧化可以明显改善材料的抗热腐蚀性能,并且与Cr含量无关。Ni12Cr6.8Al基和Ni16Cr6.8Al基合金的热腐蚀动力学遵循抛物线规律,Ni-20Cr-6.8Al基合金遵循指数规律,所有的预氧化试样的热腐蚀动力学都符合对数规律。铸态合金热腐蚀的机理可以用酸碱熔融模型解释,而预氧化合金的热腐蚀机理在很大程度上由预氧化过程中形成的氧化层的性质决定。     

高温合金热腐蚀性能影响因素的研究进展

高温合金是一种复杂组元多相组织材料,在高温下的热腐蚀行为是制约其发展的重要因素。国内外学者对高温合金的热腐蚀性能做了大量研究,先后提出了多种腐蚀机理模型,但对于不同种类高温合金腐蚀机制间的相互关系仍缺乏成熟的理论表述。从高温合金的特点和用途对热腐蚀的影响因素进行了综述,并对目前高温合金主要的涂层、预氧化等耐热腐蚀防护措施进行了讨论。最后,从实际应用角度展望了未来提高合金热腐蚀性能的方法。     

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.     

铸造镍基合金K-3的热腐蚀及防护研究

用光学显微镜、X 光衍射、扫描电镜、能谱分析和化学分析等多种手段,对经热腐蚀后的K-3合金试样及渗铝的 K-3合金涡轮叶片进行了分折研究。结果表明叶片失效的原因是硫化及熔盐引起的热腐蚀;低铬、富难熔金属的 K-3合金的热腐蚀机制是硫化、碱性熔解和酸性熔解的综合作用。用 RFL 燃气腐蚀装置对不同的保护涂层进行抗热腐蚀性能的对比试验表明:渗铝的防护效果并不理想,而富硅的扩散型和融烧型料浆铝硅涂层则具有良好的抗热腐蚀性能。     

Hot corrosion of materials: Fundamental studies

Hot corrosion is the accelerated oxidation of materials at elevated temperatures induced by a thin film of fused salt deposit. Because of its high thermodynamic stability in the mutual presence of sodium and sulfur impurities in an oxidizing gas, Na₂SO₄ is often found to be the dominant salt in the deposit. The corrosive oxyanion-fused salts are usually ionically conducting electrolytes that exhibit an acid/base chemistry, so that hot corrosion must occur by an electrochemical mechanism that may involve fluxing of the protective oxides. With the aid of high-temperature reference electrodes to quantify an acid/base scale, the solubilities for various metal oxides in fused Na₂SO₄ have been measured, and these show remarkable agreement with the theoretical expectations from the thermodynamic phase stability diagrams for the relevant Na-Metal-S-O systems. The solubilities of several oxides infused Na₂SO₄-NaVO₃ salt solutions have also been measured and modeled. Such information is important both in evaluating the corrosion resistance of materials and in interpreting any oxide fluxing/reprecipitation mechanisms. Various electrochemical measurements have identified the S₂O₇ ^2? anion (dissolved SO₃) as the oxidant that is reduced in the hot corrosion process. Electrochemical polarization studies have elucidated the corrosion reactions and clarified the corrosion kinetics of alloys. Mechanistic models for Type I and Type II hot corrosion are discussed briefly.     

Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-Deposit-Induced Corrosion of Mo-Containing Alloys

Disk alloys used in advanced gas turbine engines often contain significant amounts of Mo (2 wt% or greater), which is known to cause corrosion under Type I hot corrosion conditions (at temperatures around 900 °C) due to alloy-induced acidic fluxing. The corrosion resistance of several model and commercial Ni-based disk alloys with different amounts of Mo with and without Na₂SO₄ deposit was examined at 700 °C in air and in SO₂-containing atmospheres. When coated with Na₂SO₄ those alloys with 2 wt% or more Mo showed degradation products similar to those observed previously in Mo-containing alloys, which undergo alloy-induced acidic fluxing Type I hot corrosion even though the temperatures used in the present study were in the Type II hot corrosion range. Extensive degradation was observed even after exposure in air. The reason for the observed degradation is the formation of sodium molybdate. Transient molybdenum oxide reacts with the sodium sulfate deposit to form sodium molybdate which is molten at the temperature of study, i.e., 700 °C, and results in a highly acidic melt at the salt alloy interface. This provides a negative solubility gradient for the oxides of the alloying elements, which results in continuous fluxing of otherwise protective oxides.     

Corrosion of Ni–Al high velocity oxyfuel (HVOF) thermal spray coating by fly ash and synthetic biomass ash deposits

Abstract

Corrosion of a thermal spray (HVOF) Ni–Al coating has been investigated at 600°C under both biomass generated fly ash and synthetic biomass ashes and has been monitored as a function of reaction time for up to 1000 h. Detailed microstructral and compositional analyses have been carried out to investigate the hot corrosion mechanism. Various microstructural defects and compositional inhomogeneities are found to play an important role in the initiation of hot corrosion. Deposition of molten reactants from the ashes creates the aggressive environment. Molten salts cause initial rapid hot corrosion via fluxing reactions between planar interlamellar porosity resulting in debonding of the surface lenticular splats followed by subsequent slow dissolution. Comparison between the performance of the coating in the fly ash and the synthetic ashes provides information for improved laboratory corrosion tests.     

Hot Corrosion Behavior of a Ni3Al-Based IC21 Alloy in a Molten Salt Environment

Ni₃Al-based alloys have become important candidates for hot components in turbine engines, owing to their low densities and outstanding mechanical properties in service environments. The hot corrosion behavior of a Ni₃Al-based IC21 alloy in a molten salt environment of 75 wt% Na₂SO₄ and 25 wt% NaCl at 900 °C was studied, via oxidation kinetics analyses, scanning electron microscope observations and energy dispersive as well as diffraction analyses by X-ray. A multilayer corrosion oxide scale and dendritic morphology internal corrosion zone formed after hot corrosion, and inter-phase selective corrosion phenomena were also observed. Salt fluxing and oxidation-sulfidation processes were inferred to be the essential hot corrosion mechanisms of the alloy. Moreover, additions of Cr and Y proved to be beneficial to the hot corrosion resistance of the IC21 alloy, while the Mo content should be strictly controlled.     

大气腐蚀研究方法进展

综述了近几十年来国内外大气腐蚀研究方法的发展，重点介绍了大气腐蚀的加速试验方法、电化学研究方法和实时监测技术．湿热试验、盐雾试验、周期喷雾复合腐蚀试验、干湿周浸循环试验和多因子复合加速腐蚀试验是目前使用较多的加速试验，而多因子复合加速试验是模拟大气腐蚀加速试验方法以后发展的方向；发展了研究薄液膜的电化学测试技术，大气腐蚀监测电池ACM和Kelvin探头参比电极技术，极化和阻抗测量方法通常用于干湿交替加速试验中，也用于测试带锈试样在浸渍液中的电化学行为；原位动态实时监测技术的发展促进了从微观水平对材料大气腐蚀机理的研究工作的开展．最后提出了今后大气腐蚀研究方法的发展趋势．