Fireside corrosion of superheater materials in chlorine containing flue gas

Corrosion resistance of three types of candidate materials for superheater sections under simulated waste incineration conditions was evaluated. A 9Cr1Mo steel, an AISI 310SS, and the Ni-based alloy Sanicro 28 were tested on a laboratory and on a pilot scale with different flue gas compositions (up to 2500 mg/Nm³ of HCl and 1500 mg/Nm³ of fly ash). Laboratory tests were carried out in a furnace up to 200 h. Metal and gas temperature were kept constant at 500 °C. Pilot scale tests were carried out by using a 0.3 × 0.3 m cross-sectional combustor, with flue gas velocity of 5 m/s. Air-cooled probes, designed to operate at a metal temperature of 500 °C and facing gas temperatures as high as 600 °C, were used for 200 h as maximum test time. Qualitative correspondence was found between results obtained by the two sets of experimental tests, but quantitative values were not comparable. Metallographic evaluations, metal loss measurements, and weight loss analysis evidenced as the most suitable alloy Sanicro28. Maximum metal loss observed was 240, 182, and 107 μm, respectively, for 9Cr1Mo, AISI310SS, and Sanicro 28 under the most aggressive conditions. Intergranular corrosion attack was evidenced for AISI310SS, limiting the choice of materials to 9Cr1Mo and Sanicro 28, depending upon the lifetime expected at the design stage.     

Recent plant experience and research into fireside corrosion in Japan

The increasing use of heavy oil as a fuel in power stations has given rise to intensified research in the field of fireside corrosion in Japan. The problems which have to be tackled are described in terms of experiences gained in the operation of oil and coal fired boilers. The main types of damage encountered are nonuniform wastage of tubes in connection with carburization. In this context significant interdependences have been found in connection with coal deposition (especially sodium and sulphur contents). On the basis of this experiences and of the results of corrosion tests in the laboratory and in the field it has been found that the measure offering the best prospect for corrosion control might be the use of coextruded tubing which would allow a combination of high corrosion resistance and high creep strength. In addition to that some modified alloys (e.g. Alloy 800 H, CR 30 A or NF709) offer an interesting potential whereby the high chromium content (more than 20%) is the main criterium.     

Experience of superheater tubes in municipal waste incineration plant

Two years after the start of operations at the Tokachi Association for Municipal Waste Disposal and Treatment Services municipal waste incineration plant (name: Kuririn Center), which generates 400°C steam, an investigation of the plant's superheater tubes was conducted. The investigation consisted primarily of analyzing ash deposits, measuring tube wall thickness loss and observing tube sections after removal. The concentration of Cl in the deposited ash was found to increase as the temperature of the gas rose, and the amount of deposited ash tended to increase as the temperature of the gas rose. Tube damage consisted primarily of a uniform loss in thickness. Intergranular corrosion and other local corrosion was not observed. The results of thickness‐loss measurements showed that, after approximately two years in operation, tubes (SUS310) lost a maximum of 0.45 mm in thickness due to high‐temperature corrosion in locations where the steam temperature reached 400°C. Superheater tubes were also apparently damaged from the effects of a soot blower, resulting in an observed maximum loss of 0.9 mm thickness after approximately two years. Furthermore, the rate of thickness loss tended to increase after one year had passed.     

A thermodynamically consistent modelling of stress corrosion tests in elasto-viscoplastic materials

Slow strain rate (SSR) and constant load (CL) tests are the most important techniques used to rank the susceptibility of different materials to stress corrosion cracking in a specific environment. The present paper proposes a thermodynamically consistent phenomenological framework to model both SSR and CL tests of austenitic steels in acid solutions at room temperature. This global one-dimensional approach does not require the computation of local stresses or strains. The goal is to discuss the thermodynamic aspects that allow proposing a one-dimensional model that combine mathematical simplicity with the capability of describing a complex non-linear mechanical behaviour.     

An introduction to fireside corrosion experience in the central electricity generating board

This paper briefly reviews CEGB fireside corrosion experience. It first summarises the numbers and operating conditions of the plants, and indicates the range of materials used in the boilers. Experience of furnace wall and superheater/reheater corrosion in coal fired plant is summarised, emphasising the need to “control” fireside corrosion rather than being able to eliminate it, and the importance of more corrosion resistant materials, particularly as coextruded tube. Tube life prediction techniques in use by the CEGB are outlined, and three current areas of research are described.     

High temperature corrosion mechanisms and effect of alloying elements for materials used in waste incineration environment

Corrosion products on two typical materials, SA213-T12 steel and alloy 625 exposed to the actual combustion gas, were analyzed in addition to laboratory tests for penetration of corrosive matter. It has been clarified that corrosion products of oxides containing a little chlorides and sulphides show lamellar structures and that at the alloy-scale interface, chlorination, sulphidation, and oxidation occur under a low P_O2-high P_Cl2 condition. The formation of scale structures and the effect of corrosion-resistant alloying elements can be explained according to the stability tendencies of metals, chlorides, and oxides in the M-Cl-O equilibrium diagrams. The severity of corrosion environments at the interface is influenced by the penetration extent of corrosive matters through deposits and scales, and the protective effects of oxide films derived from alloying elements play an important role in preventing the corrosion. On the other hand, it has been shown that thermal fluctuation characterized in this kind of environment makes the lamellar scale structures and sometimes breaks and peels off the scale, and thus accelerates the corrosion. On the basis of the above mentioned knowledge, a new corrosion model is presented.     

A time-dependent corrosion wastage model for seawater ballast tank structures of ships

For assessment of time-dependent reliability or risk of aging ship structures, it is essential to have a mathematical model which provides the statistical characteristics (mean, variance, distribution) of corrosion wastage as a function of time (i.e., ship age). The aim of the present work is to develop such a model for low alloy carbon steel plates used for the structure of seawater ballast tanks in ships. Measurement data of structural wastage due to corrosion for such ship steel plates is collected and the statistical characteristics of corrosion loss and rate are quantified by statistical analysis in terms of ship age. The results and insights developed in the present study will be useful for predicting the wastage of corrosion in seawater ballast tank structures of ships. They will also be useful for designing corrosion tolerant structures subjected to the seawater environment.     

High temperature failures of heat resistant steel castings in waste incinerators

In waste incinerators, heat resistant cast steel grates and side wall plates are exposed to uncontrollable temperatures up to approx. 1000°C and also to various corrosion attacks. Considerable temperature gradients may generate cracks, elevated Cl-contents or S-contents will produce high loss of wall thicknesses. Since failures may result from very different causes, all-round recommendations as to material selection cannot be given.     

Comparison of Different boiler tube materials and the corrosion resistance in burning of municipal waste

The aim of this paper is to investigate the corrosion risks in burning of pretreated municipal waste as additional fuel together with bark in a fluidized-bed boiler. It was deduced that the burning of bark alone did not cause corrosion in the materials tested. When the waste was burnt the corrosion of steels was insignificant when providing that the surface temperature of material was below 300°C. When the surface temperature was over this temperature, the burning of municipal waste caused corrosion in the conventional boiler steel. The stainless steels were not corroded even in these conditions. The impact of waste combustion on flue gas releases was also studied.     

Fireside corrosion in dutch waste incinerations

The total installed capacity in the (eleven) Dutch waste incineration plants is 3.6 × 10⁶ t/y. About 70% of the waste is household, the remainder industrial and coarse waste. From the view point of fireside corrosion the furnace atmosphere may be characterized as follows: flue gas temperature 800–1000 °C, excess ait 50% P_HCl 10^?3–10^?5 bar, P 10^?4 bar. Two case histories concerning superheater failures are described. It has been found that fire side corrosion failures do occur in Dutch waste incinerators but they account for only part of the unforeseen plant unavailability. Improvements can be achieved by optimizing burning conditions, slag transport, gratings and, if necessary, by installation of more corrosion-resistant tube materials in (certain parts of) the boiler.     

Material corrosion issues for nuclear waste disposition in Yucca Mountain

For more than two decades, an extensive scientific effort has been underway to determine whether Yucca Mountain, Nevada, is a suitable site for a deep underground repository for spent nuclear fuel and high-level radioactive waste. Even though the geologic site is stable, additional engineered barriers are planned, including waste packages, drip shields, and tunnel inverts that will be within the emplacement tunnels. Research is under way into the best materials for corrosion prevention in those engineered barriers to ensure their long-term mechanical integrity.     

Progress in corrosion resistant materials for supercritical water reactors

Supercritical water reactors (SCWRs) are a kind of high-temperature, high-pressure water-cooled reactors that operate above the thermodynamic critical point of water (374 °C, 22.1 MPa). Corrosion and degradation of materials used in supercritical water environments are determined by several environment- and material-dependent factors. In particular, irradiation-induced changes in microstructure and microchemistry are major concerns in a nuclear reactor. Many structural materials including alloys and ceramics have been proposed for use as SCWR components or materials for applying protective coatings in SCWRs. Various surface modification processes are also explored to change the chemical composition and microstructure of the near surface regions. This article aims to provide an overview of recent materials developments for supercritical water reactors focusing mainly on the nuclear reactor applications. The emphasis is placed on the corrosion and degradation mechanisms and the selection criteria of materials. In addition, the development of new processes for surface modification of materials in SCWRs is also briefly reviewed. Finally, some perspectives on the direction of future research in this area are also outlined.     

Microbial-induced corrosion in nuclear power plant materials

The long construction times associated with nuclear plants and the large number of redundant or standby systems where water is allowed to remain stagnant for long periods of time produce conditions under which microbial-induced corrosion (MIC) can occur. Carbon and low-alloy steels, stainless steels and copper alloys are all susceptible to MIC in raw-water applications. Visual examination is particularly useful in performing preliminary assessments of MIC. If properly diagnosed, MIC can be effectively treated during plant construction, operation and temporary shutdowns.     

A thermodynamic approach on vapor-condensation of corrosive salts from flue gas on boiler tubes in waste incinerators

Thermodynamic equilibrium calculation was conducted to understand the effects of tube wall temperature, flue gas temperature, and waste chemistry on the type and amount of vapor-condensed “corrosive” salts from flue gas on superheater and waterwall tubes in waste incinerators. The amount of vapor-condensed compounds from flue gases at 650-950 °C on tube walls at 350-850 °C was calculated, upon combustion of 100 g waste with 1.6 stoichiometry (in terms of the air-fuel ratio). Flue gas temperature, rather than tube wall temperature, influenced the deposit chemistry of boiler tubes significantly. Chlorine, sulfur, sodium, potassium, and calcium contents in waste affected it as well.     

The corrosion of materials in spallation neutron sources

Efforts to measure the real-time corrosion rates of alloy 718 during 800 MeV proton radiation at currents up to 1 mA are reported. Specially designed corrosion probes, which incorporate ceramic seals, were mounted in a water manifold that allowed samples to be directly exposed to the proton beam at the Los Alamos Neutron Science Center. The water system that supplied the manifold provided a means for controlling water chemistry, measuring dissolved hydrogen concentration, and measuring the effects of water radiolysis and water quality on corrosion rate. Real-time corrosion rate measurements during proton irradiation showed an exponential increase in corrosion rate with proton-beam current. These results are discussed within the context of water radiolysis at the diffusion boundary layer/beam-spot interface. However, additional factors that may influence these parameters, such as oxide spallation and charge build-up in the passive film, are not ruled out. Scott Lillard earned his Ph.D. in materials science and engineering from Johns Hopkins University in 1992. He is currently a technical staff member at the Materials Corrosion and Environmental Effects Laboratory, Los Alamos National Laboratory. Darryl P. Butt earned his Ph.D. in ceramic science from Pennsylvania State University in 1991. He is currently a technical staff member at the Non-Proliferation and International Security Division, Los Alamos National Laboratory.     

Hot corrosion of materials: Fundamental studies

Hot corrosion is the accelerated oxidation of materials at elevated temperatures induced by a thin film of fused salt deposit. Because of its high thermodynamic stability in the mutual presence of sodium and sulfur impurities in an oxidizing gas, Na₂SO₄ is often found to be the dominant salt in the deposit. The corrosive oxyanion-fused salts are usually ionically conducting electrolytes that exhibit an acid/base chemistry, so that hot corrosion must occur by an electrochemical mechanism that may involve fluxing of the protective oxides. With the aid of high-temperature reference electrodes to quantify an acid/base scale, the solubilities for various metal oxides in fused Na₂SO₄ have been measured, and these show remarkable agreement with the theoretical expectations from the thermodynamic phase stability diagrams for the relevant Na-Metal-S-O systems. The solubilities of several oxides infused Na₂SO₄-NaVO₃ salt solutions have also been measured and modeled. Such information is important both in evaluating the corrosion resistance of materials and in interpreting any oxide fluxing/reprecipitation mechanisms. Various electrochemical measurements have identified the S₂O₇ ^2? anion (dissolved SO₃) as the oxidant that is reduced in the hot corrosion process. Electrochemical polarization studies have elucidated the corrosion reactions and clarified the corrosion kinetics of alloys. Mechanistic models for Type I and Type II hot corrosion are discussed briefly.