Internal oxidation and metal dusting of Fe-Si alloys

Iron and Fe-Si alloys (1, 2, 3 and 5 wt.% Si) were reacted at 680 °C with a gas mixture of 68% CO, 26% H₂ and 6% H₂O (a_C = 2.9, p_O2 = 2 × 10⁻²³ atm). Alloy reaction products consisted of internally precipitated SiO₂, an external scale of Fe₃C + SiO₂ and surface coke deposits containing cementite and silica particles. Coking and metal dusting rates both increased with alloy silicon level. This is proposed to be related to an increase in graphite nucleation sites at Fe₃C/SiO₂ phase boundaries, and the volume expansion accompanying graphite precipitation.     

Metal dusting behaviour of Cr-Ni steels and Ni-base alloys in a simulated syngas mixture

Long-term laboratory exposure tests for various Cr and Ni content steels and Ni-base alloys were conducted at 650 °C in a 60vol.%CO-26%H₂-11.5%CO₂-2.5%H₂O gas mixture simulating syngas environments. Upon isothermal heating, alloys with 15% and 20% Cr had many pits on the surface after a brief exposure, while no pit was found on alloys containing of 60% Ni and more than 23% Cr exposed for up to 5000 h. The thermal cycling accelerated pit initiation drastically, resulting that all test specimens except 30%Cr-60%Ni alloy suffered from metal dusting. From a measurement of pit depths, Ni proved to be an effective alloying element to retard the pit growth: growth rate for 75% Ni alloy has achieved double-digit decrease compared to that for 20% Ni. Microscopic observations has revealed that platelet graphite aligned perpendicular at the boundary of gas/metal of pits. The length of the platelet graphite for high Ni alloys was appreciably longer than that for low Ni steels. This can be interpreted from the difference of super saturation of carbon.     

Corrosion assessment of nitric acid grade austenitic stainless steels

The corrosion resistance of three indigenous nitric acid grade (NAG) type 304L stainless steel (SS), designated as 304L1, 304L2 and 304L3 and two commercial NAG SS designated as Uranus-16 similar to 304L composition and Uranus-65 similar to type 310L SS were carried out in nitric acid media. Electrochemical measurements and surface film analysis were performed to evaluate the corrosion resistance and passive film property in 6 N and 11.5 N HNO₃ media. The results in 6 N HNO₃ show that the indigenous NAG 304L SS and Uranus-65 alloy exhibited similar and higher corrosion resistance with lower passive current density compared to Uranus-16 alloy. In higher concentration of 11.5 N HNO₃, transpassive potential of all the NAG SS shows a similar range, except for Uranus-16 alloy. Optical micrographs of all the NAG SS revealed changes in microstructure after polarization in 6 N and 11.5 N HNO₃ with corrosion attacks at the grain boundaries. Frequency response of the AC impedance of all the NAG SS showed a single semicircle arc. Higher polarization resistance (R_P) and lower capacitance value (CPE-T) revealing higher film stability for indigenous NAG type 304L SS and Uranus-65 alloy. Uranus-16 alloy exhibited the lowest R_P value in both the nitric acid concentration. Auger electron spectroscopy (AES) study in 6 N and 11.5 N HNO₃ revealed that the passive films were mainly composed of Cr₂O₃ and Fe₂O₃ for all the alloys. The corrosion resistance of different NAG SS to HNO₃ corrosion and its relation to compositional variations of the NAG alloys are discussed in this paper.     

Metal dusting on an alumina forming Ni-base alloy

A high-performance commercial alumina-forming Ni-base alloy was studied after a 2 years field exposure at 540 °C in a methanol plant with a gas composition of 10-20%CO and 20-40%H₂O, with some CO₂ and the remainder H₂. The same material was also used in laboratory studies performed at 650 °C using a gas mixture with higher CO and lower H₂O content; 50%CO + 3%H₂O + 47H₂ (carbon activity a_c = 39). Post-exposure metallographic examinations together with thermodynamic calculations were used to identify and describe the metal dusting processes.A growth mechanism for metal dusting in nickel base alloys, which is independent of metal bulk diffusion, is identified. The process involves a separation of the carbon-saturated metal into a network of discontinuous precipitated carbides and a depleted Ni-austenite matrix followed by selective oxidation of the carbide network. The corrosion product consists of Cr-depleted Ni-particles, Cr-rich oxides and free carbon. The estimated metal dusting corrosion rate in the field exposure was 20-25 μm/year, based on metallography and it was correlated to a theoretical model based on boundary diffusion processes.     

Oxidation behavior of TiC particle-reinforced 304 stainless steel

TiC particle-reinforced 304 stainless steels were prepared using a new developed in situ technology and exhibited the uniform distribution of TiC particles in the matrix. The oxidation behavior of 304SS-2TiC and 304SS-6TiC (all in weight percentage) was compared with that of 304SS at 850 °C in air for 96 h using thermogravimetry analysis. For 304SS, the rate of weight gain was very slow initially, but accelerated suddenly to a very high level, forming breakaway oxidation. The addition of TiC particles to 304SS resulted in no breakaway oxidation and maintained a low oxidation rate in the whole reaction time investigated. Examination of oxide scale morphology and cross-section analysis by scanning electron microscopy and optical microscopy showed a significant scale spallation and a deep oxide penetration in the case of 304SS, but a rather continuous, dense and adherent oxide layer formed on the surface of TiC particle-reinforced alloys. XRD analysis revealed the presence of Cr₂O₃ together with spinel-type oxides in the oxide scale. For TiC-containing alloys, fine TiO₂ was also found on the surface and the amount of this oxide increased with TiC addition. The TiC addition developed finer matrix structure before oxidation, which accelerates chromium diffusion. As a result, scale adherence was improved and oxidation resistance was increased.     

Metal dusting behaviour of several nickel‐ and cobalt‐base alloys in CO?H2?H2O atmosphere

The metal dusting behaviour of total 11 nickel‐ and cobalt‐base alloys at 680 °C in a gas of 68%CO? 31%H₂? 1%H₂O (a_C = 19.0, = 5.4 × 10^?25 atm) was investigated. All samples were electropolished and reacted in a thermal cycling apparatus. On the basis of their reaction kinetics, these alloys can be classified into three groups: the first, with rapid carbon uptake and significant metal wastage, consists of alloys of relatively high iron content (AC 66, 800H and NS‐163); the second, with intermediate rates, consists of some Co‐base alloys (HAYNES 188, HAYNES 25 and ULTIMET) and the third, with very low reaction rates, consists of nickel‐base alloys with high chromium levels (601, HAYNES HR 160, 230, G‐35 and EN 105). An external chromia scale protected group 3 alloys from carburization and dusting. However, this protective scale was damaged and not rehealed for group 1 and group 2 alloys, allowing carbon attack. In all cases, coke deposited on the surface with two typical morphologies: filaments and graphite particle clusters. Subsurface spinel formation in high iron‐content alloys led to rapid dusting due to the significant volume expansion. Alloy carbon permeability was calculated from a simple law of mixtures, and shown to correlate reasonably well with initial dusting rate except for one cobalt‐base alloy in which iron spinel formation was significant.     

Oxidation, carburisation and metal dusting of 304 stainless steel in CO/CO2 and CO/H2/H2O gas mixtures

The oxidation and carburisation behaviour of 304 stainless steel was studied during thermal cycling in CO/CO₂ at 700 °C, and also in CO/H₂/H₂O at 680 °C. Thermal cycling caused repeated scale separation which accelerated chromium depletion from the alloy subsurface regions. The CO/CO₂ gas, with a_C=7 and , caused internal precipitation of oxides and carbides, some surface damage, but no dusting. In contrast, the CO/H₂/H₂O gas, with a_C = 19 and caused rapid graphite deposition and metal dusting. This was accompanied by internal oxidation and carburisation. The internal oxide was identified as spinel, which forms in the short term, but not at long reaction time. Its formation produced a significant volume expansion, which disrupted the material and resulted in surface damage in both gas atmospheres. In CO/H₂/H₂O, however, direct graphite deposition and metal disintegration into dust was the main reaction. The very different reaction morphologies produced by the two gas mixtures are discussed in terms of competing gas-alloy reaction steps.     

Alloying with copper to reduce metal dusting of nickel

Copper is thought to be noncatalytic to carbon deposition from gas atmospheres, and owing to its extremely low solubility for carbon, inert to the metal dusting reaction. Thus, the addition of copper to nickel, which forms a near perfect solid solution, may be able to suppress or greatly retard the metal dusting of the alloy, without the need for a protective oxide scale on the surface. The dusting behaviour of Ni‐Cu alloys containing up to 50 wt% Cu, along with pure Cu, was investigated in a 68%CO‐31%H₂‐1%H₂O gas mixture (a_C: 19) at 680°C for up to 150 h. Surface analysis showed that two types of carbon deposits, graphite particle clusters and filaments, were observed on pure Ni and Ni‐Cu alloys with Cu contents of up to 5 wt%. Alloys with more than 10 wt% Cu showed very little coking, forming filaments only. SEM and TEM analyses revealed metal particles encapsulated by graphite shells within the graphite particle clusters, and metal particles at filament tips or embedded along their lengths. A kinetic investigation showed that alloy dusting rates decreased significantly with increasing copper levels up to 10 wt%. At copper concentrations of more than 20 wt%, the rate of metal dusting was negligible. Although pure copper is not catalytic to carbon formation, scattered carbon nanotubes were observed on its surface. The effect of copper on alloy dusting rates is attributed to a dilution effect.     

Coke formation and metal dusting of electroplated Ni3Al-CeO2-based coatings in CO-H2-H2O

Coke formation and metal dusting of electrodeposited pure, 5 μm CeO₂-dispersed, and 9-15 nm CeCO₂-dispersed Ni₃Al coatings were investigated in CO-H₂-H₂O at 650 °C for a period of 500 h. All Ni₃Al coatings showed the inferior long-term resistance to coke formation and metal dusting to the Fe-Ni-Cr alloy due to failure to form a continuous Al₂O₃ scale. CeO₂-dispersed Ni₃Al coatings, especially 9-15 nm CeCO₂-dispersed coatings, exhibited more severe coke formation and metal dusting than the pure Ni₃Al coating. The detrimental effect of CeO₂ is believed to be caused by the enhanced formation of NiO/Ni crystals on the coating surfaces or at the grain boundaries, which catalysed the carbon deposition and promoted the carbon attack on Ni₃Al coatings.     

High temperature corrosion properties of ionic liquids

The corrosion behaviour of several metals and metal alloys (copper, nickel, AISI 1018 steel, brass, Inconel 600) exposed to a typical ionic liquid, the 1-butyl-3-methyl-imidazolium bis-(trifluoromethanesulfonyl) imide, ([C₄mim][Tf₂N]), has been investigated by electrochemical and weight-loss methods. Corrosion current densities have been determined by extrapolation from Tafel plots and by polarization resistance measurements and 48 h immersion tests were performed at 150, 250, 275 and 325 °C. Room temperature results show low corrosion current densities (0.1-1.2 μA/cm²) for all the metals and alloys investigated. At 70 °C, the corrosion current for copper dramatically increases showing a strongly dependence on temperature. At 150 °C copper shows significant weight-loss while nickel, AISI 1018, brass and Inconel do not. At higher temperatures (?275 °C), the copper sample crumbles and localized corrosion occurs for the other metals and alloys.     

The stress corrosion cracking behavior of austenitic stainless steels in boiling magnesium chloride solutions

The change in the mechanism of stress corrosion cracking with test temperature for Type 304, 310 and 316 austenitic stainless steels was investigated in boiling saturated magnesium chloride solutions using a constant load method. Three parameters (time to failure; t_f, steady-state elongation rate; l_ss and transition time at which a linear increase in elongation starts to deviate; t_ss) obtained from the corrosion elongation curve showed clearly three regions; stress-dominated, stress corrosion cracking-dominated and corrosion-dominated regions. In the stress corrosion cracking-dominated region the fracture mode of type 304 and 316 steels was transgranular at higher temperatures of 416 and 428 K, respectively, but was intergranular at a lower temperature of 408 K. Type 310 steel showed no intergranular fracture but only transgranular fracture. The relationship between log l_ss and log t_f for three steels became good straight lines irrespective of applied stress. The slope depended upon fracture mode; −2 for transgranular mode and −1 for intergranular mode. On the basis of the results obtained, it was estimated that intergranular cracking was resulted from hydrogen embrittlement due to strain-induced formation of martensite along the grain boundaries, while transgranular cracking took place by propagating cracks nucleated at slip steps by dissolution.     

Investigation of the HCl (g) attack on pre-oxidized pure Fe, Cr, Ni and commercial 304 steel at 400 °C

The paper presents the results from an investigation studying the ability of pre-oxidized metals and alloys to withstand chlorine attack in the form of gaseous HCl. The materials under investigation were pure Fe (s), Cr (s), Ni (s), and a commercial 18Cr-10Ni-Fe (304) alloy. The samples were pre-oxidized in different well defined environments, dry 10 vol.% O₂ (g) + N₂ (bal.), 10 vol.% O₂ (g) + 5 vol.% H₂O (g) + N₂ (bal.) and 10 vol.% O₂ (g) + 250 vppm SO₂ (g) + N₂ (bal.) for 24 h at 400 °C using a horizontal tube furnace. Afterwards the oxide films were characterized by GI-XRD, FEG-SEM, XPS and ToF-SIMS. The samples were then exposed further in 10 vol.% O₂ (g) + 500 vppm HCl (g) + x (x = 5 vol.% H₂O (g), 250 vppm SO₂ (g)) + N₂ (bal.). The exposure time was 100 h and after the exposures during the cool down process the reaction chamber was flushed with dry 10 vol.% O₂ (g) + N₂ (bal.). The corroded samples were then examined by the same techniques mentioned before. HCl (g) showed mainly to be aggressive toward the Fe (s) samples that form a relatively thick and porous oxide scale consisting of layered Fe₂O₃ (s)/Fe₃O₄ (s) during pre-oxidation, and the aggressiveness did not depend on the pre-oxidation conditions. All the other materials formed thin and dense oxides (20-100 nm) during pre-oxidation, and they did not suffer accelerated oxidation caused by HCl (g) during the subsequent exposure. The only exception was Ni (s) that had been pre-oxidized in an atmosphere containing SO₂ (g), in this case Ni sulphides and sulphates were formed during pre-oxidation which in turn caused accelerated oxidation to Ni when subsequently exposed to HCl (g). HCl (g) readily reacts with NiSO₄ (s) and Ni₃S₂ (s) and forms NiCl₂ (s) and SO₃ (g).     

Kinetics and mechanisms of nickel metal dusting I. Kinetics and morphology

The kinetics of nickel metal dusting were investigated at different gas compositions at 680 °C. The carbon uptake rate on nickel exposed to supersaturated H₂/CO/H₂O gas mixtures (nominal a_C = 19) increased as p_CO increased from 0.31 to 0.68 atm, but decreased with further increase in p_CO. This behaviour was ascribed to the existence of parallel, independent reaction paths, and the rate was well described by

     

Relation between corrosion behavior and microstructure of Mg-Zn-Y alloys prepared by rapid solidification at various cooling rates

The relation between corrosion resistance and microstructure of Mg-Zn-Y alloys with a long period stacking ordered (LPSO) phase has been investigated. In order to clarify the influence of microstructure evolution by rapid solidification on the occurrence of localized corrosion such as filiform corrosion, several Mg_97.25Zn_0.75Y₂ (at. %) alloys with different cooling rates were fabricated by the gravity casting, copper mould injection casting and melt-spinning techniques and their corrosion behavior and microstructures were examined by the salt immersion tests, electrochemical measurements, XRD and TEM. When the cooling rate was less than 3 × 10⁴ K s⁻¹, filiform corrosion propagated in the early stage of salt immersion test, due to formation of a massive block-shaped LPSO phase during casting. On the other hand, when the cooling rate was increased up to 3 × 10⁴ K s⁻¹, rapidly solidified (RS) alloys exhibited excellent corrosion resistance because of grain refinement and formation of a supersaturated single-phase solid solution. Large-sized Mg_97.25Zn_0.75Y₂ alloys fabricated by consolidation of the RS ribbons also exhibited excellent corrosion resistance with passivity. Enhancement of microstructural and electrochemical homogeneities in the Mg-Zn-Y alloys by rapid solidification techniques results in the passivity of substrate materials.     

The application of electrochemical noise resistance to evaluate the corrosion resistance of AISI type 304 SS in nitric acid

The paper presents the application of noise resistance to evaluate the corrosion behaviour of sensitized AISI type 304 SS in nitric acid of varying concentration (4 N, 12 N, 16 N) and temperature (298 K, 323 K, 348 K). Electrochemical noise data was acquired from a three identical electrode configuration in the required conditions at open circuit potential. The noise resistance was evaluated as the ratio of the standard deviation of the potential to that of the current noise after removing the DC component. The inverse relationship between noise resistance and corrosion rate was exploited to qualitatively assess the corrosion behaviour of AISI type 304 SS in nitric acid. Noise resistance decreased with increase in concentration implying an increase in corrosion rate with increase in nitric acid concentration. An increase in temperature from 298 K to 323 K and 348 K decreased the noise resistance in 4 N and 12 N nitric acid implying higher corrosion rates at higher temperatures. The corrosion rates were similar at 323 K and 348 K in these concentrations. The simultaneous measurement of current and potential noise facilitated the evaluation of the frequency dependence of the noise data to determine the spectral noise resistance (R_sn) and the DC limit of the spectral noise resistance . The results from R_sn and also indicated higher corrosion rates at higher concentration and temperature. Also R_n and correlated well in 4 N and 12 N nitric acid at 323 K and 348 K while disparity was observed at room temperature in 4 N and 12 N nitric acid.     

Accelerated corrosion of five commercial steels under a ZnCl2-KCl deposit in a reducing environment typical of waste gasification at 673-773 K

The corrosion of five Fe-Cr commercial steels containing 0-18 wt.% Cr at 673-773 K has been studied in a reducing H₂-HCl-CO₂ atmosphere under a ZnCl₂-KCl deposit typical of waste gasification environments. In comparison with the behavior of the same steels in a similar gas mixture without salt deposit, all steels suffered from accelerated corrosion induced by the salt and formed porous scales with poor adherence to the underlying steels. Some Cl was detected close to the steels/scale interface, indicating that Cl-containing species were able to go through the scale down to the metal matrix. Even though the corrosion rates generally decreased with increasing Cr content, the high-Cr stainless steel SS304 was still unable to provide a good corrosion resistance against the ZnCl₂-KCl deposit. The reaction mechanisms are discussed on the basis of thermodynamic considerations and of the “active oxidation” model.     

Electrochemical response of AlNiLa amorphous and devitrified alloys

The electrochemical response of Al_94−xNi₆La_x alloys (x = 4, 5, 6, 7) after different stages of devitrification was studied in 0.05 M Na₂SO₄ as well as in different concentrations [0.001 M, 0.01 M and 0.1 M] NaCl solutions. Complementary crystallization studies were carried out to elucidate the composition dependent phase evolution in these alloys. It was observed that the primary crystallization did not cause any deterioration in the corrosion resistance of the alloys as compared to the amorphous alloys. In the case of Al₈₇Ni₆La₇, there was actually an improvement in the passivating ability in benign media. The various primary crystalline phases in the different alloys investigated did not cause different electrochemical responses. However, the onset of secondary crystallization caused a reduction in the corrosion resistance in the NaCl media through a loss in passivating ability of all the alloys. This is due to increased galvanic activity as well as the loss of the amorphous phase.     

Subsurface microstructural changes in a cast heat resisting alloy caused by high temperature corrosion

A cast HP ModNb alloy (Fe-25Cr-35Ni-1Nb, wt.%) was oxidised and carburised in CO-CO₂ corresponding to a_C = 0.1 and p_O2 = 3 × 10⁻¹⁶ atm at 1080 °C. Formation of an external, chromium-rich oxide scale led to depletion of this metal in a deep alloy subsurface zone. Within that zone, secondary chromium-rich carbides dissolved, primary carbides oxidised, solute silicon and aluminium internally oxidised, and extensive porosity developed. Pore volumes correspond to the difference between metal loss by scaling and metal displacement by internal oxidation, assuming the scale-metal interface to be fixed. The pores are concluded to be Kirkendall voids.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.