The construction of isothermal quaternary phase diagrams of the Na-M-O-S type for hot corrosion applications

This paper presents a computer program for the calculation of the isothermal phase diagrams of quaternary systems involving sodium, a pure metal, oxygen and sulfur, which are useful for examining the experimental results concerning the hot corrosion of metallic materials. The procedures adopted to calculate the location of the points where four condensed phases are simultaneously present (quadruple points) and to draw the regions of stability of each phase containing the metal are presented by means of examples concerning a practical system. The nature of these quaternary phase diagrams is examined with reference to the various types of quadruple points and to their interconnections with lines of equilibrium involving the participation of three different phases. Examples of phase diagrams of some quaternary systems calculated by means of the present program are given.     

A study of the mechanism of internal sulfidation-internal oxidation during hot corrosion of Ni-base alloys

The hot corrosion of wrought Ni-16Cr-2Nb was studied at temperatures of 910–1020°C using an autoradiography technique. The autoradiographic pictures of the deposits of Na₂SO₄ enriched with³⁵Sshow that sulfur diffuses along the grain boundaries of the alloy preferentially, where it forms metallic sulfides. The sulfides are then oxidized; sulfur atoms are released, forming new sulfides at the grain boundaries or dissolving in grains and migrating inward by volume diffusion. These results provide new evidence for the sulfidationoxidation mechanism of hot corrosion.     

热处理工艺对热轧带钢氧化皮结构及其耐蚀性的影响

利用不同热处理工艺在热轧带钢表面形成不同组成与结构的氧化皮。采用SEM、XRD、LRS、干湿周期浸润腐蚀实验、EIS测试、开路电位测试对不同氧化皮热轧带钢在NaHSO3溶液中腐蚀行为进行了研究。研究表明,慢冷和炉冷所制热轧带钢氧化皮均由Fe2O3、Fe3O4、FeO和Fe组成,其中Fe2O3是微量的,前者含有更多的Fe3O4,后者含有更多的FeO。慢冷所制氧化皮致密、连续、厚度均匀;炉冷制备的氧化皮致密性较差,含有大量的缺陷。慢冷制备的氧化皮热轧带钢的耐蚀性要好于炉冷制备的热轧带钢的耐蚀性。     

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.     

A study on hot corrosion behaviour of Ni–5Al coatings on Ni- and Fe-based superalloys in an aggressive environment at 900 °C

Ni–5Al coating was deposited on Ni- and Fe-based superalloys by high velocity oxy fuel (HVOF) process to enhance their high-temperature corrosion resistance. Hot corrosion studies were conducted on bare as well as HVOF-coated superalloy specimens after exposure to a molten salt environment at 900 °C under cyclic conditions. Each cycles consisted of 1 h heating in the silicon carbide tube furnace followed by 20 min cooling in air. Thermogravimetric technique was used to approximate the kinetics of corrosion. Techniques like X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDAX) were used to characterize the corrosion products. The coatings and the oxide scale formed on the exposed surface were found to be intact with the superalloys. Superfer 800 with Ni–5Al coating has provided a good protection to the superalloys in the given molten salt environment.     

Effect of Y2O3 content in the pack on microstructure and hot corrosion resistance of Y–Co-modified aluminide coating

Y–Co-modified aluminide coatings on nickel base superalloys were prepared by pack cementation method. Effect of Y₂O₃ content in the pack mixture on microstructure and hot corrosion resistance of the coatings was investigated. The results show that with the increase in Y₂O₃ content, the content of Co in the coatings increases. The mass gain of the coatings with Y₂O₃ addition of 1, 2 and 3 wt.% is 0.6, 0.55 and 0.42 mg/cm² after hot corrosion at 1173 K for 100 h, respectively. Y₂O₃ addition accelerates the diffusion of Co and thus increases the hot corrosion resistance of the coating.     

Effect of heat treatment on the Nb distribution and corrosion resistance of Zr-Sn-Nb-Fe zirconium alloy

After being treated in different ways,Zr-Sn-Nb-Fe alloy specimens are exposed in 0.01mol/L LiOH aqueous solution at 350℃ under 16.8 MPa.The examination of microstructures and second phase particles (SPPs) of these specimens was carded out by high-resolution transmission electron microscopy (HR-TEM).The specimens treated at 800℃ before the final cold roiling have a better corrosion resistance than those treated at 680℃,and the specimens treated at 500℃,after the final cold rolling,have a better corrosion resistance than those treated at 560℃.TEM examination shows that the SPPs existing in the 800℃/500℃ specimen,which has the best corrosion resistance,contains a lot of Nb dement,which results in the reduction of the niobium content in the a-Zr solid solution.     

Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.     

Investigation and modelling of edge corrosion of e-coated galvanized steel with respect to the spatial edge orientation

The effect of the spatial orientation of e-coated hot dip galvanized test sheets on edge corrosion is investigated. Therefore paint delamination from corrosion sample edges at different steps in time of samples at different angles relative to the horizontal during a corrosion test is analysed. Two general relations are found: Horizontally oriented edges exhibit significantly increased coating delamination compared with vertically oriented edges. This is due to increased exposure to the electrolyte, resulting from the pinning of electrolyte droplets along the upper edge. With increasing angular displacement relative to the ground, electrolyte exposure and edge delamination decrease. The edges of the upward-facing specimen side showed a higher delamination width compared with the downward-facing side at the same angle. These results are supported by electrochemical impedance spectroscopy and a wetting test. Ultimately, a semi-empirical model to numerically predict the edge delamination over time, incorporating electrochemical impedance spectroscopy and polarization curves, is presented.     

Study of oxygen reduction on stainless steel surfaces and its contribution to acoustic emission recorded during corrosion processes

Acoustic emission technique is often used to monitor corrosion processes. Yet, among the potential sources of AE associated to corrosion phenomena, the emissivity of oxygen reduction on metallic surfaces has never been studied up to now. In that context, dissolved oxygen reduction was monitored by acoustic emission (AE) on as polished, pre-reduced, electrochemically or chemically passivated surfaces of AISI 316L austenitic stainless steel. The influence of the composition of the passive film on the oxygen reduction reaction has been confirmed. Moreover, in our experimental configuration, it has been demonstrated that proton reduction or iron oxide reduction were not at the origin of AE signals recorded during cathodic polarization of the specimens. On the other hand, oxygen reduction involving O–O bond rupture and/or atomic oxygen desorption from metallic surface appears to be the source of detected acoustic emission. However, these mechanisms generally occur too slowly during free corrosion processes, such as crevice corrosion, to promote any significant acoustic emission when developing naturally on metallic surfaces.     

Implementation of the quantitative evaluation method of the tempering effect during heating and cooling processes in post-weld heat treatment

In order to evaluate the temper effect during the multiple post-weld heat treatment (PWHT) process, the thermal cycle tempering parameter (TCTP) proposed by the authors, which is derived by extending the Larson–Miller parameter (LMP) to a non-isothermal process, has been used to evaluate quantitatively the temper effect during heating and cooling processes in the process of PWHT. It has been clarified that the temper effect in the multiple PWHT process including long-time heating and cooling processes can be quantitatively evaluated by TCTP. On the basis of the present study, it might be possible to shorten the holding time of the heat treatment for multiple PWHT.     

Effect of magnetic field applied during gas metal arc welding on the resistance to localised corrosion of the heat affected zone in AISI 304 stainless steel

Resistance to localised corrosion at the heat affected zone (HAZ) of AISI 304 stainless steel gas metal arc welded (GMAW) in presence of magnetic fields of different intensity was studied. Samples of HAZ, 8 mm away from the weld centre, were subjected to electrochemical potentiokinetic reactivation to assess the degree of sensitisation (DOS). The application of magnetic field during welding induced lower DOS and better resistance to pitting corrosion in 3.5% NaCl solution than samples welded without it. Experimental findings suggest that magnetic fields enable Cr redistribution in the austenitic base metal during the welding thermal cycle reducing Cr depletion.     

45Mn2V锯片钢相变规律及热处理工艺研究

针对当前锯片用钢油淬工艺污染空气、成本较高等缺点,开发了其水淬工艺。以实际工业生产的15.3 mm厚45Mn2V锯片用钢板为研究对象,结合热模拟试验,对试验钢相变过程进行了研究。同时,结合实验室模拟和工业水淬试验,并与工业油淬进行对比,研究了45Mn2V钢板水淬条件下组织和性能变化。结果表明:采用w(C)=0.43%~0.46%、w(Mn)=1.45%~1.60%、w(V)=0.040%~0.055% 的化学成分设计,热模拟条件下45Mn2V 钢Ac₁=728 ℃、Ac₃=774 ℃、Ar₃=685 ℃、Ar₁=633 ℃,Ms=272 ℃。当冷速不大于3 ℃/s时,试验钢板组织类型为先析铁素体+珠光体;随着冷速的增加,先析铁素体含量减少,珠光体片层间距逐渐变小,向索氏体及屈氏体组织转变;冷速不小于30 ℃/s时,基本得到全马氏体组织。随水淬温度由770 ℃提升至850 ℃,钢板硬度由55.4HRC增加至63.8HRC;回火后钢板硬度变化趋势与淬火态类似,硬度为25.4HRC~-29.3HRC;不同淬火温度下,钢板20 ℃冲击功均在30 J以下;随着淬火温度的升高,钢板冲击韧性逐渐降低;不同温度淬火并经580 ℃回火后,钢板冲击韧性大幅提高。工业生产表明:采用820 ℃水淬+580 ℃回火工艺与850 ℃油淬+550 ℃回火处理的钢板,组织均为回火索氏体,但前者残余奥氏体含量略微增加;力学性能方面,前者强度和硬度略微降低,但冲击韧性更加优异。     

Thermodynamics of the Na2SO4-K2SO4-CoSO4 system and their relevance to low-temperature hot corrosion

Thermodynamic calculations and experiments were performed to determine the SO₃ partial pressures and temperatures at which K₂SO₄-CoSO₄ binary mixed liquid phases form on CoO and Co₃O₄ in the presence of K₂SO₄. The calculations and experiments are in excellent agreement. Similar calculations were also made of the compositions at the liquidus surface and the associated SO₃ partial pressures for the K₂SO₄-Na₂SO₄-CoSO₄ ternary system. These calculations show that the presence of K₂SO₄ substantially reduces the SO₃ partial pressures required to stabilize a liquid salt phase on the surface of oxidized cobalt alloys at 600–800°C. Consequently, at these temperatures the hot corrosion in coal-fired systems, where K levels are high, is expected to be worse than in oil-fired systems, where K levels are low. This prediction was confirmed by experiments in a pressurized fluidized bed coal combustor and in an atmospheric pressure burner rig.