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Materials Research, Volume: 7, Número: 1, Publicado: 2004
  • Editorial

  • High temperature corrosion issues in energy-related systems

    Stringer, John

    Resumo em Inglês:

    The large majority of electric power that is generated world-wide involves heat engines of one kind or another. The significant exceptions are hydroelectric generation; wind; and photovoltaics. The thermal sources for the heat engines include: fossil fuels, nuclear fission, biomass, geothermal sources, and solar radiation. There has been a progressive move to higher overall cycle efficiencies for at least one hundred years, and in the case of fossil fuels this has accelerated recently in part because of concerns about greenhouse gas emissions, notably CO2. For a heat engine, the overall efficiency is closely related to the difference between the highest temperature in the cycle and the lowest temperature. In most cases, this has resulted in an increase in the high temperature, and this in turn has led to increasing demands on the materials of construction used in the high temperature end of the systems. One of the issues is the chemical degradation because of reactions between the materials of construction and the environments to which they are exposed: this is high temperature corrosion. This paper will describe the issues for a range of current heat engines.
  • Oxidation - Nitridation of Ni-Cr-Al alloys

    Han, Susan; Young, David John

    Resumo em Inglês:

    A series of alloys containing 24-36 wt pct Cr and 13.5 - 25.0 wt pct Al was reacted with air at 1100°C for 260 h. The products of isothermal reaction were scales of a-Al2O3 plus small amounts of Cr2O3. These grew according to parabolic kinetics, interrupted by episodic weight losses caused by partial spallation. No nitridation occurred during the isothermal exposures. Reaction during thermal cycling for up to 260 one hour cycles was much more severe. Repeated scale spallation led to subsurface alloy depletion in aluminium and, to a lesser extent, chromium. This caused transformation of the prior alloy three-phase structures (a-Cr+b-NiAl+g-Ni) to single-phase g-nickel solution. Destruction of the external scale allowed gas access to this metal which was able to dissolve both oxygen and nitrogen. Inward diffusion of the two oxidants led to development of a complex internal precipitation zone: Al2O3 and Cr2O3 beneath the surface, then Al2O3 then AIN, then AIN + Cr2N and finally AIN alone in the deepest region. Diffusion-controlled kinetics were in effect initially, but mechanical damage to the internal precipitation zone led to more rapid gas access and approximately linear kinetics in the long term.
  • Gas turbines: gas cleaning requirements for biomass-fired systems

    Oakey, John; Simms, Nigel; Kilgallon, Paul

    Resumo em Inglês:

    Increased interest in the development of renewable energy technologies has been hencouraged by the introduction of legislative measures in Europe to reduce CO2 emissions from power generation in response to the potential threat of global warming. Of these technologies, biomass-firing represents a high priority because of the modest risk involved and the availability of waste biomass in many countries. Options based on farmed biomass are also under development. This paper reviews the challenges facing these technologies if they are to be cost competitive while delivering the supposed environmental benefits. In particular, it focuses on the use of biomass in gasification-based systems using gas turbines to deliver increased efficiencies. Results from recent studies in a European programme are presented. For these technologies to be successful, an optimal balance has to be achieved between the high cost of cleaning fuel gases, the reliability of the gas turbine and the fuel flexibility of the overall system. Such optimisation is necessary on a case-by-case basis, as local considerations can play a significant part.
  • Composite coatings of titanium-aluminum nitride for steel against corrosion induced by solid NaCl deposit and water vapor at 600 °C

    Li, M.S.; Wang, F.H.; Shu, Y.H.; Wu, W.T.

    Resumo em Inglês:

    Composite coatings (Ti,Al)N with different Al content were deposited on a wrought martensite steel 1Cr11Ni2W2MoV by reactive multi-arc ion plating. With the addition of Al to the coatings, the crystallographic structure of them changed from B1 NaCl to B4 ZnS, the relevant hardness and adhesive strength firstly increased then decreased and their oxidation-resistance was also dramatically improved. It was indicated that the introduction of Al was beneficial to (Ti,Al)N coatings against corrosion induced by NaCl(s) in wet oxygen at 600 °C as well as wet corrosion in NaCl solution at ambient temperature.
  • Oxygen-induced intergranular fracture of the nickel-base alloy IN718 during mechanical loading at high temperatures

    Krupp, Ulrich; Kane, William; Pfaendtner, Jeffrey A.; Liu, Xinyu; Laird, Campbell; McMahon Jr., Charles J.

    Resumo em Inglês:

    There is a transition in the mechanical-failure behavior of nickel-base superalloys from ductile transgranular crack propagation to time-dependent intergranular fracture when the temperature exceeds about 600 °C. This transition is due to oxygen diffusion into the stress field ahead of the crack tip sufficient to cause brittle decohesion of the grain boundaries. Since very high cracking rates were observed during fixed-displacement loading of IN718, it is not very likely that grain boundary oxidation governs the grain-boundary-separation process, as has been proposed in several studies on the fatigue-damage behavior of the nickel-base superalloy IN718. Further studies on bicrystal and thermomechanically processed specimens of IN718 have shown that this kind of brittle fracture, which has been termed "dynamic embrittlement", depends strongly on the structure of the grain boundaries.
  • Lifetime modelling for MCrAlY coatings in industrial gas turbine blades

    Krukovsky, Pavel; Tadlya, Konstantin; Rybnikov, Alexander; Kryukov, Iosif; Mojaiskaia, Natalia; Kolarik, Vladislav; Juez-Lorenzo, Maria

    Resumo em Inglês:

    A novel theoretical and experimental approach for lifetime modelling of MCrAlY coatings for stationary gas turbines has been undertaken using the Inverse Problem Solution (IPS) technique. With this technique feasible experimental data acquired after a defined experimental time t e are used as input values for the model parameters estimation. In the first stage of the approach a model, based on the oxidation and diffusion processes (Fick's first and second law) was assumed, which considers the Al concentration profile across the coating. The measured average Al concentration profiles in the two-phase g+b and g - regions of coating as well as base metal were used as input values for the model parameters estimation and calculational prediction of the long term diffusion and oxidation behavior of the coating was performed. The time, when the b-NiAl phase is completely consumed was assumed as the coating lifetime end. Exposure experiments were carried out with a NiCoCrAlY coating (200 micron thickness) with 8% Al in air at 900 °C and 950 °C, currently up to 10000 h. The oxide scale is growing continuously and no other oxides were observed. The average and b-NiAl phase concentration profiles of Al across the coating thickness were determined by electron microprobe and image analysis systems in the initial state after 700 and 10000 h of oxidation. The concentration profile measured after 700 h was used as input values for the model parameters estimation in order to calculate the Al and b-NiAl phase concentration profiles after 10000 h. The computational forecast for 10000 h at 950 °C and 900 °C are in good agreement with the measured data. The approach was applied for NiCoCrAlY (200 micron thickness) coating lifetime modelling at 950 °C and 900 °C as well as for different coating thicknesses at 950 °C.
  • Niobium and chromium rich coatings tailored by laser alloying: XRD analysis at high temperatures

    Costa, Adilson Rodrigues da; Craievich, Aldo; Vilar, Rui

    Resumo em Inglês:

    Laser treatment technologies have been widely used to modify superficial layers of different materials. In this work we prepare Nb and Cr rich coatings according to laser alloying technique using cast iron as substrate material. Nb and Cr are intensive used in order to overcome challenges like good chemical and mechanical performance at high temperatures. Following laser alloying the surface-modified samples were submitted to an "in situ" XRD analysis under controlled high temperature and atmosphere. The phase transitions registered point to transformations that do not implies formation of fragile phases or cracks induced by high volumes modifications.
  • High temperature corrosion in gasifiers

    Bakker, Wate

    Resumo em Inglês:

    Several commercial scale coal gasification combined cycle power plants have been built and successfully operated during the last 5-10 years. Supporting research on materials of construction has been carried out for the last 20 years by EPRI and others. Emphasis was on metallic alloys for heat exchangers and other components in contact with hot corrosive gases at high temperatures. In this paper major high temperature corrosion mechanisms, materials performance in presently operating gasifiers and future research needs will be discussed.
  • Alloy degradation under oxidizing-sulfidizing conditions at elevated temperatures

    Gleeson, Brian

    Resumo em Inglês:

    Exposure of high-temperature alloys to a low-P O2 oxidizing-sulfidizing environment above about 550 °C is often characterized by an initial period of protective oxidation followed by more rapid corrosion. This paper will provide a brief overview of alloy corrosion in oxidizing-sulfidizing atmospheres, with specific consideration given to the thermodynamic and kinetic aspects of the process, resulting modes of degradation, and alloy selection. The concept of a "critical microstructure" in the subsurface of the alloy as a prerequisite to initiating protective scale breakdown will also be discussed. The paper will conclude with a specific example of alloy development for the filtration of hot oxidizing-sulfidizing gases.
  • High temperature degradation by erosion-corrosion in bubbling fluidized bed combustors

    Hou, Peggy; MacAdam, Stuart; Niu, Yan; Stringer, John

    Resumo em Inglês:

    Heat-exchanger tubes in fluidized bed combustors (FBCs) often suffer material loss due to combined corrosion and erosion. Most severe damage is believed to be caused by the impact of dense packets of bed material on the lower parts of the tubes. In order to understand this phenomenon, a unique laboratory test rig at Berkeley was designed to simulate the particle hammering interactions between in-bed particles and tubes in bubbling fluidized bed combustors. In this design, a rod shaped specimen is actuated a short distance within a partially fluidized bed. The downward specimen motion is controlled to produce similar frequencies, velocities and impact forces as those experienced by the impacting particle aggregates in practical systems. Room temperature studies have shown that the degradation mechanism is a three-body abrasion process. This paper describes the characteristics of this test rig, reviews results at elevated temperatures and compares them to field experience. At higher temperatures, deposits of the bed material on tube surfaces can act as a protective layer. The deposition depended strongly on the type of bed material, the degree of tube surface oxidation and the tube and bed temperatures. With HCl present in the bed, wastage was increased due to enhanced oxidation and reduced oxide scale adherence.
  • Stress and adhesion of chromia-rich scales on ferritic stainless steels in relation with spallation

    Galerie, A.; Toscan, F.; Dupeux, M.; Mougin, J.; Lucazeau, G.; Valot, C.; Huntz, A.-M.; Antoni, L.

    Resumo em Inglês:

    The relation between chromia scale spallation during oxidation or cooling down of ferritic stainless steels is generally discussed in terms of mechanical stresses induced by volume changes or differential thermal expansion. In the present paper, growth and thermal stress measurements in scales grown on different ferritic steel grades have shown that the main stress accumulation occurs during isothermal scale growth and that thermal stresses are of minor importance. However, when spallation occurs, it is always during cooling down. Steel-oxide interface undulation seems to play a major role at this stage, thus relating spallation to the metal mechanical properties, thickness and surface preparation. A major influence on spallation of the minor stabilizing elements of the steels was observed which could not be related to any difference in stress state. Therefore, an original inverted blister test was developed to derive quantitative values of the metal-oxide adhesion energy. These values clearly confirmed that this parameter was influenced by scale thickness and by minor additions, titanium greatly increasing adhesion whereas niobium decreased it.
  • Role of alloying elements and carbides in the chlorine-induced corrosion of steels and alloys

    Grabke, Hans Jürgen; Spiegel, Michael; Zahs, Armin

    Resumo em Inglês:

    The high temperature corrosion of steels and Ni-base alloys in oxidizing and chloridizing environments is of practical interest in relation to problems in waste incineration plants and power plants using Cl containing fuels. The behaviour of the most important alloying elements Fe, Cr, Ni, Mo, Mn, Si, Al upon corrosion in an oxidizing and chloridizing atmosphere was elucidated: the reactions and kinetics can be largely understood on the base of thermodynamic data, i.e. free energy of chloride formation, vapor pressure of the chlorides and oxygen pressure pO2 needed for the conversion chlorides -> oxides. The mechanism is described by 'active oxidation', comprising inward penetration of chlorine into the scale, formation of chlorides at the oxide/metal interface, evaporation of the chlorides and conversion of the evaporating chlorides into oxides, which occurs in more or less distance from the surface (depending on pO2). This process leads to loose, fragile, multilayered oxides which are unprotective (therefore: active oxidation). Fe and Cr are rapidly transferred into such scale, Ni and Mo are relatively resistant. In many cases, the grain boundaries of the materials are strongly attacked, this is due to a susceptibility of chromium carbides to chloridation. In contrast the carbides Mo2C, TiC and NbC are less attacked than the matrix. Alloys on the basis Fe-Cr-Si proved to be rather resistant, and the alloying elements Ni and Mo clearly retard the attack in an oxidizing and chloridizing environment.
  • Effect of pre-oxidation on high temperature sulfidation behavior of FeCr and FeCrAl alloys

    Pillis, Marina Fuser; Ramanathan, Lalgudi Venkataraman

    Resumo em Inglês:

    High temperature corrosion of structural alloys in sulfur bearing environments is many orders of magnitude higher than in oxidizing environments. Efforts to increase sulfidation resistance of these alloys include addition of alloying elements. Aluminum additions to iron-chromium alloys bring about increase in sulfidation resistance. This paper reports the effect of pre-oxidation on the sulfidation behavior of Fe-20Cr and Fe-20Cr-5Al alloys in H2-2% H2S environment at 800 °C. The surfaces of sulfidized specimens were also examined. Pre-oxidation of the two alloys results in an incubation period during subsequent sulfidation. After this incubation period, the Fe-20Cr alloy showed sulfidation behavior similar to that when the alloy was not pre-oxidized. The incubation period during sulfidation of the Fe-20Cr-5Al alloy was significantly longer, over 45 h, compared to 2 h for the Al free alloy. Based on the microscopic and gravimetric data a mechanism for sulfidation of these alloys with pre-oxidation has been proposed.
  • High temperature degradation in power plants and refineries

    Furtado, Heloisa Cunha; May, Iain Le

    Resumo em Inglês:

    Thermal power plants and refineries around the world share many of the same problems, namely aging equipment, high costs of replacement, and the need to produce more efficiently while being increasingly concerned with issues of safety and reliability. For equipment operating at high temperature, there are many different mechanisms of degradation, some of which interact, and the rate of accumulation of damage is not simple to predict. The paper discusses the mechanisms of degradation at high temperature and methods of assessment of such damage and of the remaining safe life for operation.
  • The role of alloy composition, environment and stresses for the oxidation resistance of modern 9% Cr steels for fossil power stations

    Schütze, M.; Schorr, M.; Renusch, D.P.; Donchev, A.; Vossen, J.P.T.

    Resumo em Inglês:

    In recent years a new group of ferritic-martensitic chromium steels for the use in fossil power stations has been developed with chromium contents between 9 and 12%. Typical representatives of these steels are P91, E911 and Nf616, which are nowadays widely used in the more advanced power plants. In the development phase the focus was on the mechanical properties of these steels but when taking them to practical operation conditions it turned out that much of the life-time of the materials and components is determined by their oxidation properties. Oxidation resistance is first of all a function of alloy composition. For the steels of this group it is chromium, silicon, manganese and molybdenum that decide their oxidation performance and since the contents especially of the four elements can be significantly different for the different steels there can be clear differences in oxidation behaviour. One of the most important issues from this point of view is how the concentrations of these elements change in the metal subsurface zone during operation/oxidation since if their level drops below a critical level oxidation resistance of the steels will be lost. In the work to be reported the influence of alloy composition and metal subsurface zone concentration as a function of oxidation time up to 10000 h was investigated in dry air and air up to 10% water vapour at 650 °C. The investigations comprised several of the advanced commercial 9% Cr steels including P91, E911, Nf616 and six laboratory melts of Nf616 with different amounts of silicon. As the results of the investigations show humidity, which is omnipresent in combustion environments, can dramatically accelerate oxidation. Silicon as an alloying element reduces the detrimental effect of water vapour significantly while molybdenum has a negative effect. The effects of the key alloying elements in these steels was quantified for conditions with and without water vapour in the environment including the role of mechanical load and recommendations were developed on how to guarantee the optimum oxidation resistance of these steels.
  • Corrosion penetration monitoring of advanced ceramics in hot aqueous fluids

    Nickel, Klaus G.; Seipel, Björn

    Resumo em Inglês:

    Advanced ceramics are considered as components in energy related systems, because they are known to be strong, wear and corrosion resistant in many environments, even at temperatures well exceeding 1000 °C. However, the presence of additives or impurities in important ceramics, for example those based on Silicon Nitride (Si3N4) or Al2O3 makes them vulnerable to the corrosion by hot aqueous fluids. The temperatures in this type of corrosion range from several tens of centigrade to hydrothermal conditions above 100 °C. The corrosion processes in such media depend on both pH and temperature and include often partial leaching of the ceramics, which cannot be monitored easily by classical gravimetric or electrochemical methods. Successful corrosion penetration depth monitoring by polarized reflected light optical microscopy (color changes), Micro Raman Spectroscopy (luminescence changes) and SEM (porosity changes) will be outlined. The corrosion process and its kinetics are monitored best by microanalysis of cross sections, Raman spectroscopy and eluate chemistry changes in addition to mass changes. Direct cross-calibrations between corrosion penetration and mechanical strength is only possible for severe corrosion. The methods outlined should be applicable to any ceramics corrosion process with partial leaching by fluids, melts or slags.
  • Rare earth oxide coatings to decrease high temperature degradation of chromia forming alloys

    Fernandes, Stela Maria de Carvalho; Ramanathan, Lalgudi Venkataraman

    Resumo em Inglês:

    The addition of small quantities of reactive elements such as rare earths (RE) to chromia or alumina forming alloys improves the high temperature oxidation resistance. Traditionally, these elements are alloying additions or are added as oxides to form a dispersion. The alloys can also be coated with RE oxides. Several methods can be used to coat alloy substrates with RE oxides and the sol-gel process is considered to be quite efficient, as it generates the very small oxide particles. This paper presents the influence of surface coatings of Ce, La, Pr, and Y oxide gels on the oxidation behavior of an Fe-20Cr alloy at 1000 °C. The morphology of the rare earth (RE) oxide coatings varied with the nature of RE. The oxidation rate of RE oxide coated Fe-20Cr was significantly less than that of the uncoated alloy. The extent of influence the RE oxide coating exercised on the oxidation rate decreased in the following order: La, Ce, Pr, Y. The scale formed in the presence of RE oxide was very thin, fine grained and adherent chromia. A direct correlation between rare earth ion radius and the extent of influence on chromia growth rate at 1000 °C was observed.
  • Simulating steam oxidation of high temperature plant under laboratory conditions: practice and interpretation of data

    Osgerby, Steve; Fry, Tony

    Resumo em Inglês:

    Specimens of ferritic and martensitic steels have been exposed to steam atmospheres at 550 °C using three different experimental procedures. Slight differences in scale growth kinetics were observed but the major differences were in the morphology of the oxide scales that were formed. The microstructures of the scales have been compared with those formed on similar materials during service.
  • Solid particle erosion of plasma sprayed ceramic coatings

    Branco, José Roberto Tavares; Gansert, Robert; Sampath, Sanjay; Berndt, Christopher C.; Herman, Herbert

    Resumo em Inglês:

    Thermal spraying allows the production of overlay protective coatings of a great variety of materials, almost without limitations as to its components, phases and constituents on a range of substrates. Wear and corrosion resistant coatings account for significant utilization of thermal spray processes. Besides being a means to evaluate the coating tribological performance, erosion testing allows also an assessment of the coating toughness and adhesion. Nevertheless, the relationship between the erosion behavior of thermal sprayed coatings and its microstructural features is not satisfactorily understood yet. This paper examines room temperature solid particle erosion of zirconia and alumina-based ceramic coatings, with different levels of porosity and varying microstrucutre and mechanical properties. The erosion tests were carried out by a stream of alumina particles with an average size of 50 µm at 70 m/s, carried by an air jet with impingement angle 90°. The results indicate that current erosion models based on hardness alone cannot account for experimental results, and, that there is a strong relationship between the erosion rate and the porosity.
  • Stress and integrity analysis of steam superheater tubes of a high pressure boiler

    Neves, Daniel Leite Cypriano; Seixas, Jansen Renato de Carvalho; Tinoco, Ediberto Bastos; Rocha, Adriana da Cunha; Abud, Ibrahim de Cerqueira

    Resumo em Inglês:

    Sources that can lead to deterioration of steam superheater tubes of a high pressure boiler were studied by a stress analysis, focused on internal pressure and temperature experienced by the material at real operating conditions. Loss of flame control, internal deposits and unexpected peak charge are factors that generate loads above the design limit of tube materials, which can be subjected to strain, buckling, cracks and finally rupture in service. To evaluate integrity and dependability of these components, the microstructure of selected samples along the superheater was studied by optical microscopy. Associated with this analysis, dimensional inspection, nondestructive testing, hardness measurement and deposit examination were made to determine the resultant material condition after twenty three years of operation.
  • Assessing corrosion in oil refining and petrochemical processing

    John, Randy C.; Pelton, Arthur D.; Young, Arthur L.; Thompson, William T.; Wright, Ian G.; Besmann, Theodore M.

    Resumo em Inglês:

    This paper summarizes the development of an information system used to manage corrosion of metals and alloys by high temperature gases found in many different oil refining, petrochemical, power generation, and chemical processes. The database currently represents about 7.9 million h of exposure time for about 5,500 tests with 89 commercial alloys for a temperature range of 200 - 1,200°C. The system manages corrosion data from well-defined exposures and determines corrosion product stabilities. New models used in the analysis of thermochemical data for the Fe-Ni-Cr-Co-C-O-S-N-H system are being compiled. All known phases based upon combinations of the elements have been analyzed to allow complete assessments of corrosion product stabilities. Use of these data allows prediction of stable corrosion products and hence identification of the possible dominant corrosion mechanisms. The system has the potential to be used in corrosion research, alloy development, failure analysis, lifetime prediction, and process operations evaluations. The corrosion mechanisms emphasized are oxidation, sulfidation, sulfidation/oxidation, and carburization.
  • Nano-structured alloy and composite coatings for high temperature applications

    Gao, Wei; Li, Zhengwei

    Resumo em Inglês:

    Nano-structured materials often possess special properties that materials with identical compositions but ordinary grain size do not have. This paper reports our work on the surface nano-crystallisation and nano-structured alloy and composite coatings. A number of processing methods including magnetron sputtering, thermal spray and pulse electro-spark deposition have been used to produce surface nano-crystalline structure. The compositions and microstructures can be well controlled by using different targets or electrodes, nano-structured composites and adjusting processing parameters. Surface nano-structured coatings can provide special chemical, mechanical and electronic properties such as high temperature corrosion and corrosive wear resistance. It has potential applications such as turbine blades, engine parts for petrochemical, aerospace and electronic device industries. This paper is focused on the study of the interrelations between processing, microstructure and properties. Physical models have been established to explain the effects of nano-crystalline structure on the properties.
  • Corrosion resistance of a steel under an oxidizing atmosphere in a fluid catalytic cracking regenerator

    Caminha, Ieda; Zeng, Chaoliu; Paes, Marcelo Piza; Monteiro, Maurício Jesus; Rizzo, Fernando

    Resumo em Inglês:

    In the present work, the corrosion resistance of an ASTM A 387 G11 steel was evaluated under two conditions: an oxidizing atmosphere in a fluid catalytic cracking regenerator of a petroleum processing unit and a simulated atmosphere in the laboratory, at temperatures of 650 °C and 700 °C. The characterization of the phases present in the oxidized layer was carried out by X-ray diffraction (XRD), optical microscopy (OM) and scanning electron microscopy (SEM) with X-ray energy dispersive analysis (EDS). Severe corrosion was observed after exposure to both the real and simulated conditions, with formation of several iron oxides (Fe2O3, Fe3O4 and FeO) in the product scale layer, as well as a slight inner oxidation and sulfidation of chromium in the substrate. Internal nitridation of the silicon and the manganese was observed only in the real condition, probably related to the long-term exposure inside the regenerator.
  • Duplex Al-based thermal spray coatings for corrosion protection in high temperature refinery applications

    Rocha, Adriana da Cunha; Rizzo, Fernando; Zeng, Chaoliu; Paes, Marcelo Piza

    Resumo em Inglês:

    The application of thermal spray coatings has been effective in preventing corrosion of steel and iron products. It has been used in a wide range of applications spreading from the petroleum to the food industry. In this work, the performance and effectiveness of a two-layered aluminum-based thermal spray coating applied to an ASTM A387 G11 steel was evaluated. The coating structure was comprised of an inner Al-Fe-Cr layer and an outer layer of aluminum. Coated samples were tested in the reactor zone of a fluid catalytic cracking unit (FCCU) of a petrochemical plant for 2.5 years. The reactor zone temperature was about 793 K (520 °C) and the environment was a mixed gas containing sulfur, oxygen and carbon. Laboratory-scale tests were also conducted on the coated samples in order to gain a better understanding of the corrosive effect of the gaseous species present in the FCCU atmosphere. Porosity present in the thermal spray coatings allowed the penetration of the atmosphere corrodents, which instigated intergranular corrosion of the steel substrate. The presence of an inner Al-Fe-Cr layer did not prevent coating spallation, which further contributed to the internal corrosion process.
  • Effects of isothermal treatment on microstructure and scratch test behavior of plasma sprayed zirconia coatings

    Veloso, Guilherme; Alves, Heleno Rocha; Branco, José Roberto Tavares

    Resumo em Inglês:

    The increase of the petroleum cost in the last decades revitalized the interest for lighter and more economic vehicles. Simultaneously, the demand for safe and unpolluted transports grows. The application of thermal barriers coatings (TBC) on combustion chamber and on flat surface of pistons reduces the thermal losses of the engines, resulting in higher temperatures in the combustion chamber. This fact contributes to the improvement of the thermal efficiency (performance) and for the reduction of incomplete combustion. Supported on these initial ideas, thermal barriers coatings constituted by CaO partially stabilized zirconia were produced and their microstructure examined. This coating still presents some drawbacks associated with thermal stresses and permeability to oxidizing gases, which will, eventually, lead to failure of the TBC by spallation. The failure may, in general, be associated to one of three factors: oxide growth at the ceramic-metal interface, formed during thermal cycling; stress build-up due to thermal cycling; and metal-oxide interface segregation, mainly of S. However, it is also relevant to understand the behavior of TBC's under isothermal oxidation. Therefore, this paper investigates the effect of oxidation on the adherence of thermal sprayed coatings. The adherence was measured by linear scratching tests, widely used for thin coatings. Plasma sprayed calcia partially stabilized zirconia was used as TBC and Ni-5%Al as bond coat, with Al substrates. Coated samples were submitted to heat treatments at 500 °C, for 50 h. The microstructures were examined by optical light microscopy, X-ray diffraction, profilometry and SEM.
  • Metallic materials in solid oxide fuel cells

    Quadakkers, Willem Joseph; Pirón-Abellán, Javier; Shemet, Vladimir

    Resumo em Inglês:

    Fe-Cr alloys with variations in chromium content and additions of different elements were studied for potential application in intermediate temperature Solid Oxide Fuel Cell (SOFC). Recently, a new type of FeCrMn(Ti/La) based ferritic steels has been developed to be used as construction material for SOFC interconnects. In the present paper, the long term oxidation resistance of this class of steels in both air and simulated anode gas will be discussed and compared with the behaviour of a number of commercial available ferritic steels. Besides, in-situ studies were carried out to characterize the high temperature conductivity of the oxide scales formed under these conditions. Main emphasis will be put on the growth and adherence of the oxide scales formed during exposure, their contact resistance at service temperature as well as their interaction with various perovskite type contact materials. Additionally, parameters and protection methods in respect to the volatilization of chromia based oxide scales will be illustrated.
  • Degradation of some ceria electrolytes under hydrogen contact nearby anode in solid oxide fuel cells (SOFCs)

    Malta, Luiz Fernando Brum; Ogasawara, Tsuneharu

    Resumo em Inglês:

    This work is concerned with thermodynamic analysis of the stability of some ceria electrolytes under contact with hydrogen gas nearby anode in fuel cells. It was considered the following types of ceria-electrolytes: pure ceria, strontium-doped ceria, calcium-doped ceria and calcium-bismuth-doped ceria. The equilibrium Log (pH2O/pH2) vs. T diagrams were constructed for x = 0.1 and 0.01, where x is the fraction of initial ceria converted to Ce2O3 (proportional to the ratio between activities of Ce3+ and Ce4+ in the ceria electrolyte, which is proportional to the fraction of electronic conduction in the electrolyte at a given temperature). The predictions of the diagrams are as follows: (a) Ce1.9Ca0.1Bi0.8O5.1 and Ce0.9Sr0.1O1.9 are less stable than pure ceria for the whole temperature range (from 0 to 1000 °C); (b) Ce0.9Ca0.1O1.9 is more stable than pure ceria below about 650 °C for x = 0.1 and below about 400 °C for x = 0.01; (c) at each temperature in the considered range the pressure ratio pH2O(g)/pH2(g) has to be higher than thermodynamically predicted in order to keep CeO2 stable in the electrolyte contacting hydrogen gas. Thermodynamic predictions are entirely capable of explaining experimental data published on the subject (irreversible cell degradation in the case of SrO-doped ceria; weight loss from doped-ceria electrolyte above 700 °C; oxygen gas release during sintering of ceria).
  • Influence of the starting materials on performance of high temperature oxide fuel cells devices

    Seo, Emília Satoshi Miyamaru; Yoshito, Walter Kenji; Ussui, Valter; Lazar, Dolores Ribeiro Ricci; Castanho, Sonia Regina Homem de Mello; Paschoal, José Octavio Armani

    Resumo em Inglês:

    High temperature solid oxide fuel cells (SOFCs) offer an environmentally friendly technology to convert gaseous fuels such as hydrogen, natural gas or gasified coal into electricity at high efficiencies. Besides the efficiency, higher than those obtained from the traditional energy conversion systems, a fuel cell provides many other advantages like reliability, modularity, fuel flexibility and very low levels of NOx and SOx emissions. The high operating temperature (950-1000 °C) used by the current generation of the solid oxide fuel cells imposes severe constraints on materials selection in order to improve the lifetime of the cell. Besides the good electrical, electrochemical, mechanical and thermal properties, the individual cell components must be stable under the fuel cell operating atmospheres. Each material has to perform not only in its own right but also in conjunction with other system components. For this reason, each cell component must fulfill several different criteria. This paper reviews the materials and the methods used to fabricate the different cell components, such as the cathode, the electrolyte, the anode and the interconnect. Some remarkable results, obtained at IPEN (Nuclear Energy Research Institute) in São Paulo, have been presented.
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