The effect of K2SO4 additive in Na2SO4 deposits on low temperature hot corrosion of iron-aluminum alloys

To understand the effect of K₂SO₄ additive in an Na₂SO₄ deposit on low temperature hot corrosion, the corrosion behavior of Fe-Al alloys induced by Na₂SO₄+K₂SO₄ was compared to that by Na₂SO₄ alone, and sulfation of Fe₂O₃ in the presence of either Na₂SO₄ or Na₂SO₄+K₂SO₄ was studied. It was found that K₂SO₄ additive promoted the low temperature hot corrosion, but did not change the corrosion-mechanism. Experimental results refuted the prior suggestions that the accelerated hot corrosion resulted either from the formation of K₃Fe(SO₄)₃ or from the stimulation of sulfation of Fe₃O₃. The earlier formation of the eutectic melt caused the accelerated hot corrosion, or in other words, the K₂SO₄ additive shortened the induction stage of hot corrosion.     

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.     

The identification of the sulfide NaCrS2 in nickel-base superalloys during corrosion in sulfate melts

The sulfide NaCrS₂ has been identified in the internal corrosion zone of several nickel-base superalloys under basic fluxing conditions at very negative potentials in a 90% Na₂SO₄-10% K₂SO₄ melt at 1173 K. It can also be formed in the presence of carbon-contaminated sulfate. NaCrS₂ can dissolve some Ti, Al, Ni, and Co; other elements, e.g., K, Mo, W, Nb, Ta, and Zr, could not be detected.     

Accelerated oxidation of iron induced by Na2SO4 deposits in oxygen at 750°C—A new type low-temperature hot corrosion

Na ₂ SO ₄ -induced accelerated corrosion of iron in oxygen at 750°C was observed. EDX, XRD, SEM, EPMA and some chemical examinations were carried out to understand the corrosion mechanism. The accelerated oxidation was attributed to the formation of abundant sulfide which has a highly defected lattice and allows rapid diffusion of iron ions. The sulfide resulted in turn from the formation of a liquid phase which was a eutectic melt of Na ₂ SO ₄ and Na ₂ O. The formation of and other possible effects of the melt were discussed. The accelerated oxidation was compared with the usual low-temperature hot corrosion, showing that it has most of the characteristics of low-temperature hot corrosion except that it occurred under basic conditions developed by the removal of sulfur from the sulfate deposits instead of the usual acidic conditions established by the SO ₃ in the atmosphere.     

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     

The Hot Corrosion of Fe-Mn-Al–C Alloy with NaCl/Na2SO4 Coating Mixtures at 750°C

The high-temperature corrosion behavior of Fe-30.1Mn-9.7Al-0.77C alloy initially coated with 2 mg/cm² NaCl/Na₂SO₄ (100/0, 75/25, 50/50, 25/75 and 0/100 wt.%) deposits has been studied at 750°C in air. The result shows that weight-gain kinetics in simple oxidation reveals a steady-state parabolic rate law after 3 hr, while the kinetics with salt deposits all display multi-stage growth rates. The corrosion morphology of the alloy with 100% Na₂SO₄ coating is similar to that of simple oxidation. NaCl acts as the predominant corrosion species for Fe-Mn-Al-C alloy, inhibiting the formation of a protective oxide scale. For the alloy coated with over 50% NaCl in salts, NaCl induces selective oxidation of manganese and results in the formation of secondary ferrite in the alloy substrate as well as void-layers with different densities of voids layer by layer in the secondary-ferrite zone.     

Effect of Na2SO4 and Water Vapor on the Corrosion of Ti3SiC2

The corrosion behavior of polycrystalline Ti₃SiC₂ was studied in the presence of Na₂SO₄ deposit and water vapor at 900°C and 1000°C. The mass gain per unit area of the samples superficially coated with Na₂SO₄ exposed to water vapor was slightly lower than that of the samples corroded without water vapor. The microstructure and composition of the scales were investigated by SEM/EDS and XRD. Pores were observed in the corroded sample surfaces. The main corrosion phases on the sample surface were identified by XRD as TiO₂, Na₂Si₂O₅ and Na₂TiO₃. After Ti₃SiC₂ corroded in the presence of the Na₂SO₄ deposit and water vapor, the scale had a three-layer microstructure, which was different from the duplex corrosion scale formed on Ti₃SiC₂ beneath the Na₂SO₄ film without water vapor. Because water vapor penetrated the corrosion layer and then reacted with SiO₂ to form volatile Si(OH)₄, an intermediate porous and TiO₂-enriched layer formed in the corrosion layer.     

Characterizations and hot corrosion resistance of Cr3C2-NiCr coating on Ni-base superalloys in an aggressive environment

In the current study, Cr₃C₂-NiCr coating was deposited on the Ni-base superalloys by using high velocity oxyfuel (HVOF) process for high temperature corrosive environment applications. Optical microscopy (OM), x-ray diffraction (XRD), scanning electron microscopy/energy-dispersive analysis (SEM/EDAX), microhardness tester, and electro probe microanalyzer (EMPA) techniques were used to characterize the coating with regard to coating thickness, porosity, microhardness, and microstructure. The thermogravimetric technique was used to establish kinetics of corrosion. The hot corrosion behaviors of the bare and Cr₃C₂-NiCr coated superalloys were studied after exposure to aggressive environment of Na₂SO₄-60% V₂O₅ salt mixture at 900 °C under cyclic conditions. The structure of the as-sprayed Cr₃C₂-NiCr coating mainly consisted of γ-nickel solid solution along with minor phases of Cr₇C₃ and Cr₂O₃. Coating has porosity less than 1.5% and microhardness in the range of 850–900 Hv (Vickers hardness). Some inclusions, unmelted and semimelted powder particles were observed in the structure of the coatings. The Cr₃C₂-NiCr coating has imparted necessary resistance to hot corrosion, which has been attributed to the formation of oxides of nickel and chromium, and spinel of nickel-chromium. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Studies on the hot corrosion of a nickel-base superalloy,Udimet 700

The hot corrosion of a nickel-base superalloy, Udimet 700, has been studied in the temperature range 900–950°C. The effect of the amount of Na ₂SO₄ on the corrosion kinetics was determined. Large weight gains and severe corrosion were associated with two different modes of degradation: (1) formation of large, interconnected sulfides beneath the external scale, and (2) formation of a Na₂MoO₄-MoO₃ melt. The corrosion due to formation of the Na₂MoO₄-MoO₃ melt occurred for all the salt-coating thicknesses, whereas, large sulfides were formed only for the heavier coatings of Na₂SO₄. The formation of Na₂MoO₄-MoO₃ melt required an induction period, and the length of the induction period was observed to be a function of the amount of Na₂SO₄ and of temperature.Work funded under NASA Grant NCC 3-43.     

Influence of pre-oxidation on the hot corrosion of Ti3SiC2 in the mixture of Na2SO4-NaCl melts

Polycrystalline Ti₃SiC₂ suffered from serious hot corrosion attack in the mixture of 75wt.%Na₂SO₄ + 25wt.%NaCl melts at 850 °C. In order to improve the hot corrosion resistance of this material, pre-oxidation treatment was conducted at 1200 °C in air for 2 h. A duplex oxide scale with an outer layer of TiO₂ and an inner layer of a mixture of TiO₂ and SiO₂ was formed during the pre-oxidation. Because the outer oxide layer of the pre-oxidation treated specimens could inhibit hot corrosion process, they exhibited good hot corrosion resistance in the mixture of 75wt.%Na₂SO₄ + 25wt.%NaCl melts at 850 °C for 50 h. However, during the hot corrosion the outer layer of TiO₂ would degrade gradually. Once the outer layer damaged, the hot corrosion rate increased sharply, the corrosion behavior was similar to Ti₃SiC₂ corroded under the same conditions. The microstructure and phase compositions of the hot corrosion samples were investigated by SEM/EDS and XRD.     

K4104镍基高温合金Al-Si渗层组织与抗热腐蚀性能

采用无机盐料浆法对K4104镍基合金进行Al-Si共渗,对Al-Si渗层的微观组织、显微硬度以及1 000℃抗氧化性能和900℃抗热腐蚀性能进行了研究.结果表明,Al-Si渗层连续,硬度比基体高;抗氧化和抗热腐蚀性能高于Al-Si共渗前.     

合金元素钨对新型Co-Al-W合金热腐蚀行为的影响

研究Co-Al-W和商用MAN900合金在800℃75%Na2SO4+25%NaCl混合熔盐中的腐蚀动力学及热腐蚀行为。结果表明:7.5 W、9.8 W和10.7 W合金经热腐蚀后质量增加量比MAN900合金的质量增加量少,Co-Al-W合金的耐热腐蚀能力比MAN900合金的耐热腐蚀能力强。Co-Al-W合金在熔盐中腐蚀膜结构分成3层,即呈蓬松状由富钴氧化物Co3O4组成的腐蚀膜最外层,由Co、Al、W复杂氧化物组成的中间过渡层和主要由Al及Co氧化物组成较致密的腐蚀膜内层。随着腐蚀时间的增加,合金腐蚀膜最外层由于脱落逐渐变薄;中间过渡层厚度逐渐增加,该层中各元素分布趋于均匀、稳定;腐蚀膜内层致密性增加使该层增厚不明显。     

Improving the Na2SO4-induced corrosion resistance of Ti3AlC2 by pre-oxidation in air

Ti₃AlC₂ suffers severe Na₂SO₄-induced corrosion attacks at temperatures higher than 800 °C in air. A convenient and efficient pre-oxidation method is proposed to enhance the corrosion resistance of Ti₃AlC₂. The corrosion weight-changes of the pre-oxidized samples were decreased by about four orders of magnitude compared with those of the untreated specimens. The mechanism on improvement of corrosion resistance was investigated by means of thermogravimetric analysis, X-ray diffraction and scanning electron microscopy/energy-dispersive spectroscopy. A continuous and adherent α-Al₂O₃ scale was prepared by high-temperature pre-oxidation treatment in air. The preformed dense Al₂O₃ scale has good compatibility with the Ti₃AlC₂ substrate, and consequently, can act as an efficient barrier against corrosion. Long-time corrosion tests demonstrate that the Al₂O₃ scale conserves after corrosion attack and is capable of long-term stability.     

Initial atmospheric corrosion of zinc in presence of Na_2SO_4 and (NH_4)_2SO_4

1 Introduction In view of the widespread use of zinc, as metallic sheet or zinc coatings, it was desirable to study its corrosion behaviour in the wide variety of atmospheres. The atmospheric corrosion of zinc has been studied in field exposures as well …     

Effects of SO2 and SO3 on the Na2SO4 induced corrosion of nickel

The effects of SO₂ and SO₃ in the environment on the hot corrosion behavior of Ni in the temperature range 750–950°C has been studied. Below the melting point of Na₂SO₄ (884°C), rapid corrosion takes place by formation of a Na₂SO₄-NiSO₄ melt, which can penetrate the porous oxide scale and give rise to sulfide information by coming in contact with the metal. The distribution of the sulfides depends on the SO₂ level in the ambient gas. Continued corrosion occurs by a sulfidation-oxidation mechanism. At temperatures above the melting point of Na₂SO₄, accelerated degradation occurs via dissolution of the surface scale, followed by reprecipitation of the oxide in a nonprotective form.Deceased     

The role of NaCl in the hot-corrosion behavior of Nimonic alloy 90

The influence of sodium chloride on the hot-corrosion behavior of Nimonic alloy 90 has been investigated by employing the half-immersion, crucible test. Nimonic 90 samples were hot corroded in the presence of NaCl between 700–900°C. The results showed that the weight-loss plots with both time and temperature were linear indicating the catastrophic nature of attack. An examination of the corroded samples by XRD, XRF, EPMA, SEM, and chemical analysis indicated that as the corrosion time increased, an increase in the depletion of alloying constituents like Cr, Al, Ti, and Co took place with a resultant enrichment of nickel on the alloy surface. The formation of CoCl₂ and Na₂CrO₄ was observed in all the tests. A few experiments were carried out in the presence of Na₂SO₄ and in a 1% NaCl mixture, in order to see the influence of NaCl on Na₂SO₄. The results indicated that Na₂SO₄ is innocuous when compared with NaCl. However, the severe attack was observed in the presence of the 1% NaCl mixture between 700–800°C, i.e., above the eutectic temperature and the m.p. of NaCl (800°C). The corrosion was minimum, when the salt mixture existed in the molten state. All the corroded samples were magnetic in nature. The role of NaCl on the hot-corrosion behavior of Nimonic 90 has been discussed in the light of the above crucible-test investigations.     

Long term corrosion of X70 steel and iron in humid supercritical CO2 with SO2 and O2 impurities

Abstract

The corrosion of X70 steel and iron in supercritical CO₂/SO₂/O₂/H₂O environment were investigated after a 454 h exposure. Optical microscopy was applied to observe the morphology of etch pits and synthesise the three-dimensional morphology. X-ray diffraction and X-ray photoelectron spectroscopy were employed to detect the composition of product scales. Experimental results verified that the localised corrosion occurred on the X70 steel sample under corrosion product deposits. Ferrous sulphate, sulphur and iron sulphide were detected as the corrosion products.     

The corrosion of Ni3Al in a combustion gas with and without Na2SO4-NaCl deposits at 600–800°C

The corrosion behavior of Ni₃Al containing small additions of Ti, Zr, and B in combustion gases both with and without Na₂SO₄–NaCl deposits at 600–800°C has been studied for times up to four days. The corrosion of the saltfree Ni₃Al leads to the formation of very thin alumina scales at 600°C but of mixed NiO–Al₂O₃ scales containing also some sulfur compounds at higher temperatures, while the rate increases with temperature up to 800°C. The presence of the salt deposits considerably accelerates the corrosion rate, especially at 600 and 800°C. The duplex scales formed at 600°C are composed mostly of a mixture of NiO and unreacted salt in the outer layer and of alumina and aluminum sulfide with some nickel compounds in the inner layer. The scales grown at 700°C contain only one layer of complex composition, while those grown at 800°C are similar but have an additional outer layer containing similar amounts of nickel and aluminum. At 600 and 700°C NiSO₄ can be detected also in the salt layer. The samples corroded at 700°C and 800°C also show an Al-depleted zone containing titanium sulfide precipitates at the surface of the alloy. The hot corrosion of Ni₃Al involves a combination of various mechanisms, including fluxing of the oxide scale as well as mixed oxidation-sulfidation attack. At all temperatures Ni₃Al shows poor resistance to hotcorrosion attack as a result of the formation of large amounts of Ni compounds in the scales.     

The corrosion of Nb-modified Ti3Al in a combustion gas with and without Na2SO4−NaCl deposits at 600–800°C

The corrosion behavior of a Nb-modified Ti₃Al intermetallic compound containing 11 at.% Nb in a simulated combustion gas with and without deposits of a Na₂SO₄–NaCl mixture was examined at 600–800°C for times up to four days. In the absence of salt deposits the corrosion rates were rather low and increased only slightly with temperature, producing very thin scales of mixed oxides of Ti, Al, and Nb without sulfides. The presence of the salt deposits produced higher weight gains during an initial stage of one to two days at 600 and 700°C, after which the reaction stopped. A more important and longlasting effect was observed instead at 800°C, when the kinetics of hot corrosion became nearly linear. The scales formed by hot corrosion were complex mixtures of various corrosion products at all temperatures and showed a porous outer region containing a mixture of unreacted salts with oxides (mainly TiO₂), an intermediate region of a mixture of variable composition of oxides of the three metals, and a TiO₂-rich layer beneath it. At 800°C the scales tended to form a thin, discontinuous Al₂O₃-rich layer in the middle and contained an additional innermost region presenting a large concentration of sulfur, very likely as Nb and Ti sulfides. The high rate of hot corrosion at 800°C is attributed to the appearance of sulfides in the inner region of the scale and to a more efficient scale fluxing.     

On the reaction mechanism of nickel with SO2+O2/SO3

High-purity nickel has been reacted with 96% O₂+4% SO₂ at 700–900°C. The reaction has been studied at 700°C as a function of the total gas pressure (0.06–1 atm) and at 1 atm as a function of temperature (700–900°C). The reaction mechanism changes with the effective pressure of p(SO₃) in the gas. When NiSO₄ (NiO + SO₃ = NiSO₄) is formed on the scale surface, the scale consists of a two-phase mixture of NiO + Ni₃S₂; in addition, sulfur is enriched at the metal/scale interface. A main process in the reaction is rapid outward diffusion of nickel through the Ni₃S₂ phase in the scale; the nickel reacts with NiSO₄ to yield NiO, Ni₃S₂, and possibly NiS as an intermediate product. When NiSO₄ cannot be formed, the scale consists of NiO, and small amounts of sulfur accumulate at the metal/scale interface. It is proposed that the reaction under these conditions is primarily governed by outward grain boundary diffusion of nickel through the NiO scale, and in addition, small amounts of SO₂ migrate inward through the scale—probably along microchannels.