Materials Science Forum Vols. 522-523

Abstract: In order to improve the durability of high efficiency waste-to-energy boilers, it is essential to develop and apply high temperature corrosion-resistant materials having a long life time according to the intensity of the corrosion conditions. Two types of high Cr-high Si-Fe-Ni base and high Cr-high Si-Ni-Fe base alloy seamless tubes; MAC-N (26Cr-3.5Si-11Fe-Ni base) alloy and MAC-F (23Cr-3.8Si-38Ni-Fe base) alloy respectively which contain no expensive Mo and have better corrosion resistance than the existing alloys under severe corrosive environments of waste combustion gas, have developed. The optimum alloy composition range were defermined by confirming the effect of the alloying elements on the corrosion resistance in the laboratory corrosion tests. Furthermore, the seamless tubes were mounted on the actual superheater of the 500oC/9.8MPa high efficiency waste-to-energy boiler to examine the durability over a period of four years. As a result, it was confirmed that the MAC-N and MAC-F alloys have better corrosion resistance than the Alloy625 and 310HCbN. In addition, it has become clear that corrosion resistance of both alloys is displayed through the formation of SiO2 rich protective scale due to the combined addition of the principal elements, Si, Cr, Fe and Ni. Under conditions of high Cl content molten deposits and severe thermal cycle, the corrosion rate increases as the results of deterioration of protective oxidation scale.

Abstract: Inconel 625 is utilised in both biomass and waste incineration plants in Denmark. In both cases, the performance is good however the morphology of corrosion attack is different which indicates different corrosion mechanisms. In waste incineration plants there is general attack and shallow pitting, and in some cases dendritic attack especially on the fins of waterwalls. The dendritic attack is in the dendritic core. The presence of pits or dendritic attack is linked to the temperature of the metallic surface and the molten salt composition. In a woodchip biomass plant, chromium depletion was observed on the surface of the weld overlay leaving behind a nickel and molybdenum rich porous structure. The corrosion attack was not related to the dendritic microstructure of the weld. In two straw-fired biomass plants, co-extruded Sanicro 63 (alloy 625 type) as well as Inconel 625 weld overlay revealed the same type of attack, again chromium depletion. This indicates that the corrosion mechanism in woodchip and straw power plants are similar. Another interesting result in straw-fired boilers was that Nibas welds (alloy 625 composition) could provoke excessive corrosion in adjacent 18-8 stainless steels indicating a galvanic reaction. The corrosion mechanisms observed in each case are discussed in relation to temperature and corrosive environment.

Abstract: In order to evaluate the damage of molten salt mixtures in waste incineration environments, the alloy 625 was exposed to a molten KCl-ZnCl2 mixture at 650 °C for 200 hours. The corrosion process was monitored by electrochemical impedance spectroscopy (EIS). After exposure the corrosion products were analyzed by X-ray diffraction and SEM. Two different electrochemical impedance models were found to describe the electrochemical processes. In the early stages of corrosion the alloy developed a protective Cr2O3 scale which turned into a porous spinel oxide scale after 100 hours.

Abstract: The influence of gaseous KCl on the high temperature oxidation of alloy Sanicro 28 (27Cr31Ni) at 600°C in 5% O2 (N2 in balance) is reported. The samples were exposed isothermally in flowing gas, the dew point of KCl being 590°C corresponding to a partial pressure of KCl of about 2·10-6 atm. The exposure time was 24, 72 and 168 hours. The samples were investigated by gravimetry, grazing incidence XRD, SEM/EDX and AES. The results show that the oxidation of Sanicro 28 at 600°C is accelerated by KCl(g) at metal temperatures above the dew point of the salt. KCl(g) reacts with the protective chromium rich oxide ((Fe1-xCrx)2O3) forming K2CrO4. The resulting chromium depletion of the oxide gives an increasing oxidation rate but does not trigger “breakaway” corrosion. The distribution of potassium chromate on the sample surface is strongly flow-dependent, showing that the rate of formation of potassium chromate is limited by the rate of transport of KCl(g) to the surface. No evidence for chlorine was found on the corroded samples by AES profiling or EDX.

Abstract: The behavior of three different materials with respect to their Fe, Cr, Ni contents have been studied between 450°C and 700°C, in waste incinerators combustion conditions, where it occurs a main influence of chlorine, sulfur and water vapor. This works analyzes the behavior of these materials which depends on their capability to form melted compounds and on the nature of these melted phases. Also as the corrosion mechanism is influenced by the presence or missing of any corrosive species, the study focalizes on the specific influence of SO2 and alkaline chorine. Effect of additive ashes on the corrosion behavior of tested materials is also studied. The mechanism of corrosion in waste incinerators is supported by thermodynamic calculations performed with the “Thermocalc” software.

Abstract: After examining practical structural materials for use in the high-temperature environments of waste incinerators, it was found that a Ni-Cr-W casting alloy is promising. However, the corrosion reaches its peak in the vicinity of 900°C. This peak is related to the behavior of chlorides that form in the interior of the alloy. As the chlorides continuously generate and decompose, the Cl recycles, accelerating corrosion. It is thought that when the temperature rises, the chlorides vaporize outside the alloy, suppressing Cl recycling and thus reducing the amount of corrosion. Adding Al to the alloy generates highly volatile AlCl3, making it possible to prevent the accumulation of chlorides in the vicinity of 900°C and lower the corrosion peak. As a result of conducting exposure testing for a year at an actual incinerator, it was demonstrated that adding Al is an effective way to improve corrosion resistance.

Abstract: Corrosion/deposition field tests have been carried out in the superheater region of a commercial waste-fired 75MW CFBC boiler using air cooled probes. The influence of material temperature (450-500°C), flue gas temperature, temperature variations (i.e. thermal cycling) and additives to the fuel (elemental sulphur and dolomite) on deposition and corrosion was studied. The results presented here mainly consider the influence of sulphur additions to the fuel. The fuel was a mixture of 50% household waste and 50% industrial waste. After exposure the samples were analyzed by ESEM/EDX, XRD, AAS, FIB and IC. With no additional sulphur, alkali chlorides made up a large part of the deposit/corrosion product layer and in some cases chromate (VI) was detected. It is suggested that the chromate (VI) has formed by reaction of the protective oxide with alkali chlorides in the deposit. Adding sulphur to the fuel changed the composition of the deposits, alkali chlorides being largely replaced by alkali sulphates. No chromates(VI) were detected in the sulphur-added runs. It is suggested that adding sulphur to the fuel may decrease fireside corrosion because it changes the composition of the deposit. Alkali sulphates are much less corrosive than alkali chlorides partly because they do not form chromate(VI).

Abstract: This paper gives an overview of the different processes of metal dusting (MD) that operate on low and high alloyed iron and nickel base alloys exposed in CO+H2–containing environments with or without water vapour. MD of pure metals like iron and nickel occur with a solely carbon-induced corrosion mechanism. However, in high alloyed materials with strong oxide formers such as Cr and Al, a more complex MD-process takes place which involves both carbon and oxygen in close collaboration. The “alloyed” carbides, i.e normally Cr-containing carbides, formed in such materials are thermodynamically stable with respect to the carbon activity. However, in the reaction front of a MD-pit with non-protective spinel oxide, they destabilise and dissolve due to the influence of the low oxygen activity determined by CO-dissociation. Based on recent results in the field of MD a chart with tentative MD mechanisms is presented as a function of alloy composition and temperature.

Abstract: The present study focuses on a new technique for the prevention of metal dusting in carbonaceous gas environments at intermediate temperature. Preliminary laboratory metal dusting test was conducted for Ni-x%Cu binary alloys and Ni-Cr alloys with various Si and Cu content in a simulated 60%CO-26%H2 -11.5%CO2-2.5%H2O (in vol.%) gas mixture at 650°C. Specimens of the binary alloys containing low Cu were entirely covered with coke and showed rough metal surfaces due to the degradation of metal. Alloys of 20% and more Cu, on the contrary, had no coke deposition and smooth metal surfaces, suggesting alloys with an adequate Cu do not react with CO in the syngas mixture without an oxide scale barrier. Based on these results, we conclude that Cu does not protect by formation of the oxide scale but has a “Surfactant-Mediated Suppression” against metal dusting. This effect can be explained in terms of atomistic interaction of CO with transition-metal surfaces by electronic structure analyses. For the Ni-Cr alloy, both addition of Si and Cu played a role of preventing pit formation in the simulated syngas atmosphere. The concept can be also useful for the practical material design of Ni-Cr-Si-Cu alloy with excellent metal dusting resistance.

Abstract: Low carbon steel, S15CK, was carburized at 1203K up to 12.93ks in a commercial furnace where RX gas converted from propane was employed as carrier gas. Gas compositions in the furnace were changed intentionally; consequently carbon potential changed from 0.8 to 1.2 mass%. The carbon content profiles were determined by a succession of grindings and carbon analyses of the ground surfaces with a vacuum type emission spectrometer. A mathematical model for calculation of carbon content profiles is proposed to describe carburizing behavior under time-variant gas compositions in a furnace. The calculated profiles were in good agreement with the experimental ones except the surface and its vicinity. This result indicates that the present model can be applied to gas carburizing in the furnace where gas compositions were changed.