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.     

The structure and properties of electroless Ni–Mo–Cr–P coatings on copper alloy

In the present study, the quaternary Ni–Mo–Cr–P alloy coatings were deposited on copper alloy by an electroless deposition process. Crystallization behavior and the effect of heat‐treatment on hardness and corrosion resistance of Ni–Mo–Cr–P deposits were detailedly investigated. X‐ray diffraction (XRD) analysis shows that as‐deposited Ni–Mo–Cr–P coatings are Ni–Mo–Cr–P solid solution and mixed crystal structure; the trend of microcrystallinity increases with the introduction of additional types of metal element; Ni–Mo–Cr–P alloy coatings start to occur in the crystallization with the heat‐treatment temperature increasing. With an increase in the annealing temperature, the hardness improves and reaches the maximum value at 500 °C. Further, it is found that Ni–Mo–Cr–P coatings have superior corrosion resistance than Ni–P and Ni–Mo–P deposits after the analysis of electrochemical measurements. Moreover, corrosion resistance increases before annealed at 400 °C, but heat‐treatment at higher temperatures has a negative effect on the corrosion resistance of Ni–Mo–Cr–P alloy coatings.     

Einfluss der Halbzeugform auf die Korrosionsbeständigkeit hochlegierter Ni‐Cr‐Mo‐Werkstoffe

Effect of semi‐finished products on the corrosion resistance of high‐alloyed Ni‐Cr‐Mo materials The corrosion resistance of different semi‐finished products of six superaustenitic steels and nickel based alloys in the condition of delivery was investigated in some typical standard corrosion tests. The resistance of sheets, plates, strips, seamless tubes and welded tubes to intercrystalline corrosion was tested according to ASTM G 28 methods A and B, as well the resistance to pitting corrosion according to ASTM G 48 method C. The nickel based alloys 625, C‐276 and alloy 59 are resistant to the FeCl₃‐test according to ASTM G 48 method C and therefore a differentiation of these types in regard to their localized corrosion resistance was achieved only in the more aggressive ‘Green‐Death’‐solution. The laboratory experiments confirmed that the corrosion resistance is identical for all semi‐finished products and that it shows only a slight dependence of the surface condition of the materials tested. Additionally, some typical industrial and practical applications of the six high performance materials are presented to demonstrate the excellent corrosion resistance in the manufactured condition.     

Einfluß der Legierungselemente auf die Passivierung und die Korrosionsbeständigkeit der Legierungen auf Eisen-Chrom-Basis

Influence of alloying elements on the passivation and the corrosion resistance of iron chromium base alloys The authors investigated the influence of cathodic alloying (with 0.1–0.5% Pd) on the passivation and the corrosion resistance of alloys of the system FeCr(25–100% Cr) and 25% Cr steels containing Mn, Ni, Mo and N; the experiments have been carried out in hot concentrated sulfuric acid and diluted hydrochloric acid solutions. It has been found that the addition of Pd as a cathodically active component considerably increases the autopassivation tendency as well as the corrosion resistance of the alloys under the particular conditions. Mn gives rise to improved autopassivation of austenitic and austenitic ferritic CrNi and CrNiMo steels, since it is catodically active, too. Cr steels cathodically alloyed with Pd acquire resistance to hydrochloric acid, too.     

Oxidation mechanisms of Cr‐containing steels and Ni‐base alloys at high‐temperatures –. Part I: The different role of alloy grain boundaries

It is essential for materials used at high‐temperatures in corrosive atmosphere to maintain their specific properties, such as good creep resistance, long fatigue life and sufficient high‐temperature corrosion resistance. Usually, the corrosion resistance results from the formation of a protective scale with very low porosity, good adherence, high mechanical and thermodynamic stability and slow growth rate. Standard engineering materials in power generation technology are low‐Cr steels. However, steels with higher Cr content, e.g., austenitic steels, or Ni‐base alloys are used for components applied to more severe service conditions, e.g., more aggressive atmospheres and higher temperatures. Three categories of alloys were investigated in this study. These materials were oxidised in laboratory air at temperatures of 550°C in the case of low‐alloy steels, 750°C in the case of an austenitic steel (TP347) and up to 1000°C in the case of the Ni‐base superalloys Inconel 625 Si and Inconel 718. Emphasis was put on the role of grain size on the internal and external oxidation processes. For this purpose various grain sizes were established by means of recrystallization heat treatment. In the case of low‐Cr steels, thermogravimetric measurements revealed a substantially higher mass gain for steels with smaller grain sizes. This observation was attributed to the role of alloy grain boundaries as short‐circuit diffusion paths for inward oxygen transport. For the austenitic steel, the situation is the other way round. The scale formed on specimens with smaller grain size consists mainly of Cr₂O₃ with some FeCr₂O₄ at localized sites, while for specimens with larger grain size a non‐protective Fe oxide scale is formed. This finding supports the idea that substrate grain boundaries accelerate the chromium supply to the oxide/alloy phase interface. Finally, in the Ni‐base superalloys deep intergranular oxidation attack was observed, taking place preferentially along random high‐angle grain boundaries.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels Austenitic stainless steels (18% Cr, 12% Ni, Mo gradation between 0.5 to 3.6%) had been gas‐nitrided. By stepwise removal, samples could be prepared with various surface content of nitrogen up to 0.45%. The susceptibility against pitting corrosion of these samples had been tested by two methods: – determination of the stable pitting potential in 0.5 M NaCl at 25°C – determination of the critical pitting temperature in artificial sea water (DIN 81249‐4) The influence of nitrogen to both determined parameter can be described well by PRE = Cr + 3,3 · Mo + 25 · N That means for the investigated steel composition and the used corrosion system there is no influence of molybdenum on the effectiveness of nitrogen.     

Corrosion behavior of nickel alloys in wet hydrofluoric acid

Wet hydrofluoric acid at concentrations below approximately 60% is highly corrosive to glass, reactive metals, carbon steel and stainless steels. Nickel alloys offer moderate corrosion resistance over a wide range of acid concentration and temperature. The corrosion behavior of eleven commercial alloys was quantified through laboratory testing. Variables that were studied included testing time, acid concentration, temperature, vapor and liquid phases and the presence of residual stresses. Results show that the corrosion rate of a Ni‐Cu and a Ni‐Cr‐Mo‐Cu alloy increased with the acid concentration and the temperature. However, both for increasing acid concentration and temperature, the corrosion rate of the Ni‐Cu alloy increased faster than the corrosion rate of the Ni‐Cr‐Mo‐Cu alloy, especially in the vapor phase. Even in unstressed coupons, nickel alloys showed internal penetration in presence of wet HF; the mode of this internal penetration varied from alloy to alloy. Considering all the studied variables that influence corrosion, the highest ranked material for wet HF service was a Ni‐Cr‐Mo‐Cu alloy.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle (Teil II)

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels (Part II) Austenitic stainless steel (18% Cr, 12% Ni, Mo gradation between 0,06 to 3,6%) had been solution nitrided. By step‐by‐step removing, the samples could be prepared with various surface contents of nitrogen from 0.04 to 0.42%. In two test series the influence of nitrogen had been determined. The susceptibility against pitting corrosion of these samples had been tested by the chronopotentiostatical method. For the investigated steel composition and the used corrosion system there is no infuence of molybdenum on the effectiveness of nitrogen. The effectiveness of nitrogen can be described by the factor 25 in the PRE. By the investigation of the surfaces with the XPS analysis, it could be shown that the passivation and the pit nucleation is influenced by nitrogen. In these ranges NO_x, NH_x, and NH_z‐spectra have been detected. Bound Mo was found in steels containing molybdenum. It is assumed that the repassivation mechanisms of N and Mo work independently of each other. With the results efforts are supported to improve the pitting corrosion resistance also at molybdenum poor steels by surface nitriding or nitrogen alloying. The achieved results justify the assumption that the observed positive effect of the nitrogen may be extented to even higher nitrogen contents. A prerequisite for this is avoiding secondary phases in the matrix. The adverse influence of small particles is known well.     

The corrosion behavior of several heat resistant materials in air + 2 vol‐% Cl2 at 300 to 800 °C. Part I – Fe‐base and Fe‐containing alloys

In the present paper the corrosion behavior of 2 1 / 4 Cr1Mo steel, Alloys 800H, AC66, 45TM and 690 was investigated at 300 to 800 °C in dry air and synthetic air with 2 vol.‐% Cl₂. The data reveal that the major role determining corrosion resistance are played by Fe in the alloys. In particular if the same Cr‐contents are present in the alloys it is only the Fe content which decides on resistance against Cl‐attack while additions of even almost 3 % of Si evidently have only little effort.     

The role of alloying elements in commercial alloys for corrosion resistance in oxidizing‐chloridizing atmospheres. Part II: Experimental investigations

In an extensive study the role of the alloying elements in commercial alloys for corrosion resistance was studied in air without and with 0.1 and 2 vol.% Cl₂, respectively. In the first part of this paper [1] the thermodynamic fundamentals were discussed on the basis of the new concept of the quasi‐stability diagrams. The second part which is presented here reports the results from investigations at 650, 800 and 1000°C and testing times up to 1000 hrs where 14 commercial alloys were tested with regard to their corrosion behavior. The materials were selected so that the role of the alloying elements Mo, C, Si, Al, N, Fe, Ni and Cr would be evident from the results. The exposure tests were followed by extensive microstructural analyses of the corrosion scales and the metal subsurface zones so that type, mechanism and extent of corrosion could be characterized in great detail. At the end a ranking was possible of the different materials and with regard to the detrimental or beneficial role of the different alloying elements. The present results thus provide a much deeper insight into materials resistance in oxidizing‐chloridizing environments at high temperatures.     

Cr对钢耐海水腐蚀性的影响

获得了５种含铬低合金钢在海水中暴露１、２、４、８（７）年的腐蚀数据,讨论Ｃｒ对钢耐海水腐蚀的影响,铬钢的耐海水腐蚀性不仅与Ｃｒ的含量有关,还与其他复合合金元素有关。短期浸泡时,钢的耐海水腐蚀性随铬含量（无其他合金元素复合）增加而提高。长期浸泡,Ｃｒ对钢的耐海水腐蚀性有害,约１％Ｃｒ与Ｍｏ（－Ａｌ）复合对钢的耐海水腐蚀性的影响与Ｃｒ的影响没有左别大于２％Ｃｒ与Ｍｏ（－Ａｌ）复合大幅度提高钢在海水中短期浸泡的耐蚀性,并使耐蚀性逆转时间明显推迟.小于1%Cr与Mn-Cu、Cu-Si-V、Ni-Cu-Si、Ni-Mn等复合对钢的耐海水腐蚀性有害。     

Pitting,Crevice and stress corrosion resistance of high chromium und molybdenum alloy stainless steels

This paper presents new data on the resistance of recently developed high-alloy stainless steels to localised corrosion in chloride solutions. Pitting potential was determined in artificial sea water, and critical pitting temperature CPT in very aggressive FeCl₃ solution. Critical crevice corrosion temperature CCT was tested in the same FeCl₃ solution. Stress corrosion measurements, made in a more familiar NaCl solution by the drop evaporation method, demonstrate that alloy stainless steels with high chromium and molybdenum have very long failure times, comparable with those of nickel alloys found to be SCC-resistant under practical conditions. Stainless steels of 20 Cr 25 Ni 6 Mo type showed the best resistance to localised corrosion.     

Corrosion behaviour of alloy 31 – UNS N08031 – under conditions of oil & gas production

The corrosion behaviour of alloy 31 (UNS N08031‐31Ni – 27Cr – 6.5Mo – 1.2Cu – 0.2N – bal. Fe) was tested in laboratory and field tests in seawater with and without additions of CO₂ and/or H₂S in slow strain rate tests, and in SSC (Sulphide Stress Corrosion) tests according to NACE MR0175. The results demonstrate a high resistance of alloy 31 to localised corrosion. Due to the high chromium and molybdenum concentration, its resistance to pitting and crevice corrosion in chloride‐contaminated seawater is significantly higher than that of alloy 28 and alloy 825 and it equals that of typical nickel base alloys like alloy 625. Alloy 31 is not sensitive to chloride‐induced stress corrosion cracking, either with or without H₂S, or sulphide stress cracking. Alloy 31 is approved for sour gas applications up to LEVEL VI in NACE MR 0175. The combination of properties makes alloy 31 an attractive choice for components in oil and gas production including wirelines, umbilicals, tubing, piping and topside application.     

The corrosion behavior of several heat resistant materials in air + 2% Cl2 at 300 to 800 °C. Part 2 – Nickel base alloys

The corrosion behavior of the alloys 59, C‐2000 and HR‐160 was investigated in dry air and in air with 2% Cl₂ at temperatures of 300 to 800 °C. Up to 500 °C Alloy 59 and Alloy C‐2000 do not exhibit any significant attack. At 650 °C in particular HR‐160 is subjected to a marked increase of the corrosion rates. In the latter case the higher amount of C compared to the other two alloys seems to decrease corrosion resistance. At 800 °C the resistance of C‐2000 is inferior to that of Alloy 59 which is attributed to differences in the microstructure consisting of Cr/Mo precipitates in the Ni‐base matrix which are primarily attacked.     

Investigations on role of HVOF sprayed Co and Ni based coatings to combat hot corrosion

Abstract

This paper aims to investigate the hot corrosion resistance of high velocity oxy-fuel (HVOF) sprayed cobalt based (Stellite-6) and nickel based (Ni–20Cr) coatings deposited on the superalloy Superni-718 (Ni–19Cr–18˙5Fe–5˙13Ta–3˙05Mo–0˙9Ti–0˙5AI–0˙18Mn–0˙18Si–0˙15Cu–0˙04C) in the Na₂SO₄–60%V₂O₅ salt environment at 900°C under cyclic conditions. The X-ray diffractometry, scanning electron microscopy/energy dispersive analysis and electron probe microanalyser techniques were used to study the corrosion products with respect to their morphology, phase composition and element concentration. The thermogravimetric technique was used to establish the kinetics of corrosion. The bare alloy underwent severe hot corrosion attack. The Ni–20Cr coating shows excellent hot corrosion resistance with negligible spallation, whereas Stellite-6 coating reveals less hot corrosion resistance and more spallation. The hot corrosion resistance of Ni–20Cr coating has been attributed to the formation of oxides of chromium, nickel and spinel of nickel chromium. The oxides of silicon, chromium, cobalt and spinels of cobalt–chromium and nickel–chromium have contributed for hot corrosion resistance of Stellite-6 coatings.     

Effect of Mo on corrosion behavior of Ni20Cr–xMo alloys in air with NaCl–KCl–CaCl2 vapor at 570°C

The effect of Mo on the corrosion behavior of Ni20Cr–xMo alloys in an oxidizing chlorine-containing atmosphere using air mixed with the salt-vapor mixture of NaCl–KCl–CaCl₂ at 570°C was investigated. The results revealed that the corrosion performance of the Ni20Cr alloys in the oxidizing chlorine atmosphere was improved by Mo addition of up to 3 wt%. The Mo-free alloy formed a potassium chromate during corrosion as a result of the reaction between the Cr₂O₃ scale and KCl vapor. The chromate formation increased the chlorine potential at the scale surface and induced the breakdown of the protective Cr₂O₃ scale, resulting in internal chromium chloride precipitates and a Cr-depleted zone. In contrast, the presence of Mo resulted in the formation of a NiO scale, which did not react with the salt vapors and, therefore, prevented the formation of chromates. The beneficial effect of Mo on the high-temperature chlorination of Ni–Cr alloys in salt-vapor-containing atmospheres was ascribed to the suppression of chlorine generation due to NiO scale formation.     

Erosion–corrosion characteristic of nano‐particulates reinforced Ni–Cr–Mo–Cu surface alloying layer in acidic flow and acidic slurry flow

In order to improve the corrosion and erosion–corrosion resistance of 316L stainless steel in engineering application, two kinds of composite alloying layers were prepared by a duplex treatment, consisting of Ni/nano‐SiC and Ni/nano‐SiO₂ predeposited by brush plating, respectively, and a subsequent surface alloying with Ni–Cr–Mo–Cu by double glow process. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were performed on the two kinds of composite alloying layer using 10 wt% HCl solution to assess the corrosion behavior. Erosion–corrosion tests were carried out by erosion–corrosion test rig in acidic flow and acidic slurry flow for test time of 20 h at four different rotational speeds. Results of electrochemical tests indicated that the corrosion resistance of composite alloying layer with brush plating Ni/nano‐SiO₂ particles interlayer approximated to that of single Ni‐based alloying layer, whereas the corrosion resistance of the composite alloying layer with brush plating Ni/nano‐SiC particles interlayer was apparently inferior to that of Ni‐based alloying layer in 10 wt% HCl solution at static state. Under the conditions of acidic flow and acidic slurry flow, the mass losses of tested samples increased with increase in the time of erosion–corrosion tests and the rotational speeds of samples. The mass losses of composite alloying layer with brush plating Ni/nano‐SiO₂ particles interlayer were lower than that of single Ni‐based alloying layer at all rotational speeds, except at 1.88 m/s in acidic flow. The mass losses of composite alloying layer with brush plating Ni/nano‐SiC particles interlayer were higher than that of single Ni‐based alloying layer at all rotational speeds, but were obviously lower than that of AISI 316L stainless steel. The influences of second phase on the corrosion and erosion–corrosion of the two kinds of composite alloying layer were discussed in this paper.     

Electrochemical and XPS surface analytical study on the reactivity of Ni‐free stainless steel in artificial saliva

Nowadays, there is a strong demand to replace CrNi stainless steels used for biomedical applications such as brackets in orthodontics with a new generation of more biocompatible austenitic, nickel‐free alloys. The aim of this work is the investigation of the growth and stability of the surface films formed on DIN 1.4456 Ni‐free stainless steel (18% Cr, 18% Mn, 2% Mo) in artificial saliva (pH 7.9) at 37 °C by electrochemistry and XPS surface analyses and the assessment of the ions that leach from the steel. These results show that the open circuit potential asymptotically increases and the corrosion current density decreases from 1 to 24 h exposure time to the artificial saliva. XPS provides evidence that the surface film present on the surface after mechanical polishing transforms into a passive film that becomes progressively enriched in Cr (III) oxy‐hydroxides whereas iron and manga­nese oxides are depleted. It is found that the instantaneous corrosion rate decreases exponentially with the amount of Cr (III) in the passive film. The results are discussed regarding the biocompatibility, thus the release of ions into solution, of the new nickel‐free stainless steel. Based on the results presented in this paper and literature evidence, a comprehensive model is proposed that substantiates the biocompatibility of these alloys.     

Susceptibility of highly alloyed austenitic stainless steels to caustic stress corrosion cracking

Slow Strain Rate tests (5 × 10⁻⁶ to 4 × 10⁻⁸ s⁻¹) in 300 g/L sodium hydroxide at 200°C were conducted on highly alloyed austenitic stainless steels with various nickel and chromium concentrations: N08904 (20Cr‐25Ni‐4Mo), N8825 (22.5Cr‐40Ni‐3Mo), N08028 (27Cr‐30Ni‐3.5Mo), R20033 (32.5Cr‐31Ni‐1.5Mo). Stress Corrosion Cracking (SCC) resistance of studied alloys increases in the following order: N08904 → N8825 → N08028 → R20033 in accordance with increasing chromium content. The SCC susceptibility indexes decrease gradually with decreasing of strain rate. In materials exhibiting higher SCC resistance, tests should be conducted at very low strain rates ( < 2 × 10⁻⁷ s⁻¹) to observe indications of SCC. When sulphide ions are added the R20033 steel exhibiting an excellent corrosion behaviour in pure caustic solution, becomes highly susceptible to SCC, even at = 5 × 10⁻⁶ s⁻¹.     

Besonderheiten im Korrosionsverhalten hochchrom- und molybdänhaltiger Legierungen in heißer 92, 5%iger Schwefelsäure

Peculiarities in the corrosion behaviour of high chromium and molybdenum containing alloys in hot 92.5% sulfuric acid In laboratory tests at temperatures above 50°C unusual high corrosion rates of passivating stainless steels and nickel alloys containing more than 26% Cr were observed in 92.5% sulphuric acid. In order to investigate the cause of this phenomenon further corrosion tests and additional chemical analyses were performed. The H₂SO₄ concentration tested displays a relative maximum of the electrical conductivity, the reason being a stronger dissociation of the sulfuric acid. Electrochemical investigations revealed an enhanced activity of the cathodic reactions which lead to higher corrosion rates. The cathodic reactions are strongly dependend on alloy constitution with special emphasis on the contents of Cr, Ni and Mo. Mo containing stainless steel show potential oscillations (of the open circuit potential) between ?50 and +550 mV_H. These alloys corrode under development of SO₂ (reduction of H₂SO₄ molecules) and formation of several sulfur compounds with different oxidation numbers (6+ and 2?). Alloys with chromium contents above 26% develop additionally hydrogen gas due to a lower hydrogen overvoltage of these alloys. With increasing nickel content the overvoltage for the reduction reaction of H₂SO₄ molecules will be lowered. This fact results in an elevation of the exchange current density for the Alloy NiCr45 and therefore to the highest corrosion rate observed. Alloy B-2 shows the best resistance, i.e. very low corrosion rates. Obviously high levels of molybdenum can compensate the influence of nickel on the overvoltage of the reduction reaction or even hinder the cathodic reaction.