Search Results for secondary reaction zones

Coatings are an essential part of the materials system to protect the turbine blades from oxidation and corrosive attack during service. Inter-diffusion of alloying elements between a turbine blade substrate and their coatings is a potential concern for coated turbine blades at ever increasing operating temperatures because this can cause the formation of undesirable Secondary Reaction Zones (SRZs), which may degrade the mechanical properties of coated Ni-based superalloys. Understanding the effects of each element on the SRZ formation is essential in order to understand both the mechanism and inter-diffusion behaviour between coatings and substrates. In this research, a number of simpler aluminized ternary Ni-Al-X (where X is Co, Cr, Re, Ru or Ta) alloys were investigated in order to elucidate the separate effects of each element on the microstructural evolution, especially at the coating/substrate interface. The aluminized ternary alloys developed distinctive diffusion zones, depending on the third alloy element, ‘X’. Specifically, it has been found that both Ni-Al-Re and Ni-Al-Ta alloys developed a continuous SRZ-like diffusion layer. This diffusion zone persisted in the Ni-Al-Re alloys after high temperature exposure, indicating that Re has a stronger effect on SRZ formation than Ta.

A comprehensive fireside corrosion study was undertaken to better understand the corrosion mechanisms operating on the superheaters and lower furnace walls of advanced coal- fired utility boilers. The study intended to evaluate the fireside conditions generated from burning eight U.S. coals individually in a pilot-scale combustion facility. These coals consisted of a wide range of compositions that are of interest to the utility industry. The combustion facility was capable of producing the realistic conditions of staged combustion existing in coal-fired utility boilers. During each of the combustion tests, gas and deposit samples were collected and analyzed via in-furnace probing at selected locations corresponding to the waterwalls and superheaters. Testing of five of the eight coal groups has been completed to date. Results of these online measurements helped reveal the dynamic nature of the combustion environments produced in coal-fired boilers. Coexistence of reducing and oxidizing species in the gas phase was evident in both combustion zones, indicating that thermodynamic equilibrium of the overall combustion gases was generally unattainable. However, the amount of sulfur released from coal to form sulfur-bearing gaseous species in both the reducing and oxidizing zones was in a linear relationship with the amount of the total sulfur in coal, independent of the original sulfur forms. Such a linear relationship was also observed for the measured HCl gas relative to the coal chlorine content. However, the release of sulfur from coal to the gas phase appeared to be slightly faster and more complete than that of chlorine in the combustion zone, while both sulfur and chlorine were completely released and reacted to form respective gaseous species in the oxidizing zone. The information of sulfur and chlorine release processes in coal combustion generated from this study is considered new to the industry and provides valuable insight to the understanding of fireside corrosion mechanisms.

The article gives a brief overview of the newly developed austenitic material “Power Austenite”. The microstructure of the Power Austenite is characterized by grain boundary strengthening with boron stabilized M23(C,B)6 and secondary Nb(C,N) in combination with sigma phase and Nb(C,N) as the major grain strengthening precipitates. The material shows a significant creep strength at 700 °C (1292 °F) and 650 °C (1202 °F) as well as fireside corrosion resistance which makes it a possible candidate for 700 °C (1292 °F) power plants.

A paste, which contains Pt or Pt-xIr (x = 0-30 at%) alloy nano-powder was sprayed on some Ni-based single crystal superalloys. Then the annealing diffusion treatment at 1100 °C for 1 h in flowing Ar atmosphere was conducted to develop Pt and Pt-Ir diffusion coatings. Cyclic oxidation tests were carried out at 1150 °C in still air in order to investigate the thermal stability and oxidation behavior of the coatings and they were compared with electroplated diffusion coatings. It was found that Ir can retard the formation of voids in both the coatings and substrates. In addition, by replacing the electroplating method to the paste coating method, the crack problem due to the brittle feature of electroplated Pt-Ir coatings could be solved. Therefore, the Pt-Ir diffusion coating prepared by the paste- coating method is promising as the bond-coat material due to suppression of voids, cracks and stable Al 2 O 3 on the surface. The Pt-Ir paste diffusion coatings introduced above have several further advantages: they are easy to recoat, cause less damage to substrates, and offer comparable oxidation resistance. Thus, the method can be applicable to the remanufacturing of blades, which may extend the life of components. The future aspect of the paste coating will also be discussed.

A combined pilot-scale combustion test and long-term laboratory study investigated the impact of oxy-firing on corrosion in coal-fired boilers. Four coals were burned under both air and oxy-firing conditions with identical heat input, with oxy-firing using flue gas recirculation unlike air-firing. Despite higher SO 2 and HCl concentrations in oxy-firing, laboratory tests showed no increase in corrosion rates compared to air-firing. This is attributed to several factors: (1) Reduced diffusion: High CO 2 in oxy-firing densified the gas phase, leading to slower diffusion of corrosive species within the deposit. (2) Lower initial sulfate: Oxy-fired deposits initially contained less sulfate, a key hot corrosion culprit, due to the presence of carbonate. (3) Reduced basicity: CO 2 and HCl reduced the basicity of sulfate melts, leading to decreased dissolution of metal oxides and mitigating hot corrosion. (4) Limited carbonate/chloride formation: The formation of less corrosive carbonate and chloride solutes was restricted by low O 2 and SO 3 near the metal surface. These findings suggest that oxy-firing may not pose a greater corrosion risk than air-firing for boiler materials.

Direct-fired supercritical CO 2 (sCO 2 ) cycles are expected to result in sCO 2 with higher impurity levels compared to indirect-fired cycles. Prior work at ambient pressure showed minimal effects of O 2 and H 2 O additions, however, a new experimental rig has been built to have flowing controlled impurity levels at supercritical pressures at ≤800°C. Based on industry input, the first experiment was conducted at 750°C/300 bar in CO 2 +1%O 2 -0.25%H 2 O using 500-h cycles for up to 5,000 h. Compared to research grade sCO 2 , the results indicate faster reaction rates for Fe-based alloys like 310HN and smaller increases for Ni-based alloys like alloys 617B and 282. It is difficult to quantify the 310HN rate increase because of scale spallation. Characterization of the 5,000 h specimens indicated a thicker reaction product formed, which has not been observed in previous impurity studies at ambient pressure. These results suggest that more studies of impurity effects are needed at supercritical pressures including steels at lower temperatures.

The paper deals with microstructural evolution in the AISI 316LN + 0.1 wt.% Nb steel during long-term creep exposure at 600 and 625°C. The following minor phases formed: Z-phase (NbCrN), M 23 C 6 , M6X (Cr3Ni2SiX type), η-Laves (Fe2Mo type) and σ-phase. M6X gradually replaced M 23 C 6 carbides. Primary Z-phase particles were present in the matrix after solution annealing, while secondary Z-phase particles formed during creep. Precipitation of Z-phase was more intensive at 625°C. The dimensional stability of Z-phase particles was excellent and these particles had a positive effect on the minimum creep rate. However, niobium also accelerated the formation and coarsening of σ-phase, η-Laves and M6X. Coarse particles, especially of σ-phase, facilitated the development of creep damage, which resulted in poor long-term creep ductility.

As many nuclear power plants are in the license renewal operating period and some are entering subsequent license renewal, there is increased probability that repairs will be needed on components that have been exposed to significant neutron fluence. The neutron-driven transmutation of nickel and tramp boron in austenitic materials commonly used in reactor internals can lead to the generation of trapped helium and the associated risk of helium-induced cracking (HeIC) during weld repairs. In the weld heat affected zone, where temperatures are insufficient to allow the helium to diffuse out of the material, the helium can remain trapped. Upon cooling, the residual stresses, combined with weakened grain boundaries due to helium coalescence, can lead to cracking. The current ASME limit for helium content for Code repairs is 0.1 appm. Prior work has demonstrated a strong inverse correlation between helium content and permissible weld heat input for avoidance of HelC. The helium concentration in the material to be repaired is thus a critical input to the development of weld repair processes to be applied to these materials. The reliable measurement of helium in irradiated materials at concentrations relevant for the evaluation of HeIC risk is a specialized process. It is important to demonstrate that the capability is available and can be practically leveraged to support emergent repairs. This paper presents on the execution and results of a multi-laboratory test program aimed at demonstrating the industry capability of acquiring accurate, repeatable, and timely measurements of relatively low concentrations of helium (< ~20 appm) within austenitic materials commonly used in reactor internals. Participating laboratories were supplied with equivalent specimens extracted from boron-doped coupons that were irradiated to drive the boron-to-helium transmutation reaction. The results and lessons learned from the program are expected to support the development of industry guidance for the acquisition of similar measurements supporting nuclear component repairs.

Starting in 2010 a new generation of coal fired power plants in Europe operating at a steam temperature of up 620°C was commissioned. During that commissioning process many cracks occurred in welds of T24 material which was extensively used as membrane wall material in nearly all of the new boilers. The cracks were caused by stress corrosion cracking (SCC) only occurring in the areas of the wall being in contact to high temperature water during operation. The question which step of the commissioning process really caused the cracking was not answered completely even several years after the damage occurred. To answer this question and to define parameters which will lead to cracking in high temperature water many tests were conducted. Generally it was found that slow tensile tests in controlled environment are well suited to get information about materials SCC sensitivity in the laboratory. In the present paper, first the influence of the cracking of welded T24 material in acidic environment containing well-defined amounts of H2S is investigated to address the question if a chemical cleaning process prior to the testing might lead to hydrogen induced SCC. As a second step, cracking behaviour in high temperature water is being investigated. Here the influence of the temperature, the oxygen concentration of the water, the deformation speed of the sample, the heat treatment and the condition of the material on the SCC is analysed.

In 9~12% Cr containing martensitic stainless steels, Laves phase usually occurs after long term high temperature exposure, while in the present work, some sparse relatively large particles of (Fe,Cr)2Mo type Laves phase were observed in virgin FB2 steel. It is speculated that the large Laves phase particles formed in casting process due to dendritic segregation. Then the evolutionary behavior of Laves phase during welding thermal cycle was studied and constitutional liquation of Laves phase was found, suggesting a liquation crack tendency in FB2 steel. At last, the hot ductility tests showed that the area where constitutional liquation occurred would act as crack initiation site, and the tested specimen fractured without any obvious plastic deformation. This work provided some guidance for the practical production of welded turbine rotors made of FB2 steel.

Because of the problems experienced with steam-side oxidation in commercial power plants, there has been continuing interest in better understanding the steam oxidation behavior of creep strength enhanced ferritic steels such as grades 23, 24 and 91 as well as 300-series stainless steels such as 347H and 304H. Analysis of field-exposed tubes has provided information on the oxidation reaction products but relatively few specimens are available and there is limited information about the kinetics. Specimens have included tube sections with a shot peened surface, a treatment that is now widely used for austenitic boiler tubes. To complement this information, additional laboratory studies have been conducted in 1bar steam at 600°-650°C on coupons cut from conventional and shot-peened tubing. Exposures of 1-15 kh provide some information on the steam oxidation kinetics for the various alloys classes. While shot-peened type 304H retained its beneficial effect on oxidation resistance past 10,000 h at 600° and 625°C, the benefit appeared to decline after similar exposures at 650°C.

Xcel Energy’s Comanche Unit 3 experienced widespread cracking of T23 membrane wall tubes within the evaporator section, initially occurring during the boiler construction phase, primarily at shop and field tube butt welds. The majority of the tube cracking was attributed to stress-corrosion cracking (SCC), and a lesser number of fabrication-related hydrogen induced cracking (HIC), weld solidification cracking, and brittle cracking within tube swage sections were also experienced. Hundreds of tubes were replaced prior to Unit commissioning, due to both actual tube leaks and those replaced due to weldment cracking and other identified weld defects during radiographic testing. Elevated stress levels and material susceptibility (i.e. hardness in the as-welded condition) were considered the critical factors in the tube cracking.

Diffusion aluminide coatings have been evaluated as a strategy for improving the oxidation resistance of austenitic and ferritic-martensitic (FM) steels, particularly in the presence of steam or water vapor. The objective was to evaluate the strengths and weaknesses of these coatings and quantify their performance and lifetime. Long-term diffusion and oxidation experiments were conducted to study the behavior of various model diffusion coatings and produce a better data set for lifetime predictions. The key findings are that (1) thin coatings (<50μm) with relatively low Al contents appear to be more effective because they avoid high thermal expansion intermetallic phases and have less strain energy to nucleate a crack; and (2) the low Al reservoir in a thin coating and the loss of Al due to interdiffusion are not problematic because the low service temperatures of FM steels (<600°C) and, for austenitic steels at higher temperatures, the phase boundary between the ferritic coating-austenitic substrate inhibits Al interdiffusion. Unresolved issues center on the effect of the coating on the mechanical properties of the substrate including the reaction of N in the alloy with Al.

Supercritical CO 2 (sCO 2 ) is of interest as a working fluid for several concepts including the direct- fired Allam cycle as a low-emission fossil energy power cycle. Over the past 10 years, laboratory exposures at 300 bar sCO 2 have found reasonably good compatibility for Ni-based alloys at <800°C, including an assessment of the sCO 2 impact on room temperature mechanical properties after 750°C exposures. However, initial screening tests at 1 and 20 bar CO 2 at 900°-1100°C showed poor compatibility for Ni-based alloys. In an open cycle, the introduction of 1%O 2 and 0.1- 0.25%H 2 O impurities at 300 bar increased the reaction rates ≥2X at 750°C. At lower temperatures, steels are susceptible to C ingress and embrittlement. Creep-strength enhanced ferritic steels may be limited to <550°C and conventional stainless steels to <600°C. Two strategies to increase those temperatures are higher Ni and Cr alloying additions and Al- or Cr-rich coatings. Alloy 709 (Fe- 20Cr-25Ni) shows some promising results at 650°C in sCO 2 but reaction rates were accelerated with the addition of O 2 and H 2 O impurities. Pack aluminized and chromized Gr.91 (Fe-9Cr-1Mo) and type 316H stainless steel show some promise at 600°-650°C but further coating optimization is needed.

Structural changes in P92-type steel after creep at temperature of 600°C under a stress of 140 MPa were investigated. The steel was solution treated at 1050°C and tempered at 780°C. The structure in the grip portion of the creep specimen changed scarcely after creep exposure for 6876 h. In contrast, the structural changes in the gage and neck sections were characterized by transformation of the tempered martensite lath structure into relatively coarse subgrain structure. The formation of a well-defined subgrain structure in the gage and neck sections was accompanied by the coarsening of M 23 C 6 carbides and precipitations of Laves phase during creep. Mechanisms of grain boundary pinning by precipitates are discussed.

In both direct- and indirect-fired supercritical CO 2 (sCO 2 ) cycles, there is considerable interest in increasing the size and efficiency of such systems, perhaps by increasing the peak temperature to >700°C. However, relatively little experimental data are available under these conditions with pressures of 200-300 bar. Furthermore, impurities such as O 2 and H 2 O in the CO 2 may greatly alter the compatibility of structural alloys in these environments. While an experimental rig is being constructed that can measure and control the impurity levels in sCO 2 at 200-300 bar, initial 1 bar experiments at 700°-800°C for 500 h have been conducted in high-purity and industrial grade CO 2 , CO 2 +0.15O 2 and CO 2 +10%H 2 O and compared to exposures in dry air and 200 bar sCO 2 . These results, focusing on Fe- and Ni-base structural alloys and commercial chromia- and alumina-forming alloys, indicate that modifications in the environment did not strongly affect the reaction products at 700°-800°C.

In dissimilar welds between martensitic stainless steel F6NM and nitrogen-strengthened austenitic stainless steel FXM-19, type 209 austenitic welding consumables are used to align with the mechanical properties and chemical composition of FXM-19, with F6NM welds requiring post-weld heat treatment (PWHT) to restore ductility and toughness, raising concerns about sigma embrittlement in ER209 butter welds. This study investigated the mechanical properties and microstructure of F6NM+FXM-19 dissimilar welds, finding no detrimental sigma phase formation in the butter (PWHT) and groove weld metal (as welded) across various welding processes, indicating no sigma phase transformation due to PWHT. Submerged arc welding (SAW) and gas tungsten arc welding (GTAW) demonstrated good mechanical properties, while Gas Metal Arc Welding with 100% Ar gas shield (GMAW 100% Ar) could not be properly evaluated due to weld defects. SAW and GTAW were deemed suitable for this dissimilar weld joint, with several welding processes providing acceptable results using ER209 filler material for fabricating pressure vessels requiring F6NM to XM-19 joints.

In Europe between 2006 and 2012 several ultra-super-critical (USC) coal-fired power plants were built employing T24 (7CrMoVTiB10-10 / DIN EN 10216-2:2014-03 / VdTÜV sheet 533/2) in membrane walls. During commissioning stress corrosion cracking (SCC) on the tube-to-tube butt welds appeared. The widespread damages required the development of a new patented commissioning procedure to avoid recurring damages. Although this commissioning procedure was employed successfully and the power plants are in operation since then, a debate about the implementation of a hardness limit for such butt welds was initiated. According to the European standards butt welds of T24 boiler tubes with wall thickness < 10 mm (0.3937 in) do not require any post-weld heat treatment (PWHT) and no hardness limits are given. When looking at manufacturing related issues such as an imminent risk of cold cracking after welding of micro-alloyed steels a widely applied but coarse hardness limit is 350 HV. Based on laboratory tests, some authors reallocated this 350 HV hardness limit for addressing SCC susceptibility of low-alloyed steels. This article describes typical hardness levels of T24 boiler tube TIG butt welds and the SCC behavior in high temperature water. Further the effect of the stress relief heat treatment (SRHT) of the boiler membrane walls between 450 °C and 550 °C (842 °F and 1022 °F) on its hardness values and on the SCC behavior is discussed, showing that the hardness values should not be used as an indicator for SCC susceptibility of T24 boiler tube butt welds.

Development activities initiated over a decade ago within the COST 522 program and continuing through the COST 536 Action have yielded significant progress in constructing a new generation of steam power plants capable of operating under advanced steam conditions. These innovative plants promise substantially improved thermal efficiency, with steam temperatures reaching up to 620°C (1150°F). Recent successful power plant orders in Europe and the United States stem from critical advancements, including the development, testing, and qualification of 10% Cr steels with enhanced long-term creep properties for high-temperature components such as turbine rotors and valve casings. Extensive in-house development efforts have focused on fabrication, weldability, mechanical integrity, and fracture mechanics evaluations of full-sized forged and cast components. These materials will be implemented in several new coal-fired power plants, notably the Hempstead plant in the USA, which will operate with live steam temperatures of 599°C (1111°F) and reheat steam temperatures of 607°C (1125°F). The improved creep properties enable the construction of casings with reduced wall thicknesses, offering greater thermal flexibility at lower component costs and facilitating welded turbine rotors for high-temperature applications without requiring cooling in the steam inlet region. Looking forward, further efficiency improvements are anticipated through the introduction of nickel alloys in steam turbine and boiler components, with the European AD700 project targeting reheat steam temperatures of 720°C (1328°F) and the US Department of Energy project aiming even higher at 760°C (1400°F). The AD700 project has already demonstrated the technical feasibility of such advanced steam power plants, with engineering tasks progressing toward the construction of a 550 MW demonstration plant, while DOE activities continue to address boiler concerns and focus on rotor welding, mechanical integrity, and steam oxidation resistance.

With nearly half of the world's electricity generation fueled by coal and an increasing focus on limiting carbon dioxide emissions, several technologies are being evaluated and developed to capture and prevent such emissions while continuing to use this primary fossil energy resource. One method aimed at facilitating the capture and processing of the resulting carbon dioxide product is oxy-combustion. With appropriate adjustments to the process, the approach is applicable to both new and existing power plants. In oxy-combustion, rather than introducing ambient air to the system for burning the fuel, oxygen is separated from the nitrogen and used alone. Without the nitrogen from the air to dilute the flue gas, the flue gas volume leaving the system is significantly reduced and consists primarily of carbon dioxide and water vapor. Once the water vapor is reduced by condensation, the purification and compression processes otherwise required for carbon dioxide transport and sequestration are significantly reduced. As an introduction to and overview of this technology, the paper summarizes the basic concepts and system variations, for both new boiler and retrofit applications, and also serves as an organized review of subsystem issues identified in recent literature and publications. Topics such as the air separation units, flue gas recirculation, burners and combustion, furnace performance, emissions, air infiltration issues, and materials issues are introduced.