Search Results for oxidation properties

This paper describes the steam oxidation behavior of two 18Cr-8Ni austenitic fine-grained stainless steels, TP347HFG and SUPER304H, which have been developed for ultra-supercritical (USC) boilers. A field exposure test was conducted by installing these tubes, along with comparative materials, in the tertiary superheater of a utility power boiler. After periodic service, the fine-grained tubes were removed to examine their steam oxidation behavior. Examination of the steam oxidation scale on the inner surface of the tubes indicated an extremely low scale growth rate for the fine-grained steels, even after 10 years of service. The oxidation structure is discussed and compared with conventional materials, TP321H and TP347H. Accelerated steam oxidation tests were conducted using an oxidation test with saturated dissolved oxygen concentration. The combination of fine-grained steel and a shot-peening layer exhibits high steam oxidation resistance at 700°C or higher temperatures.

The microstructural evolution of the MoSiBTiC alloy by rapid solidification and its effect on oxidation and mechanical properties were investigated in this study. A Mo-5Si-10B-10Ti-10C (at%) alloy was produced by a conventional arc-melting technique in an Ar atmosphere, and then it was rapidly solidified by tilt-casting into a rod-shaped copper hearth. Vickers hardness values increased drastically above 1000 Hv due to the microstructure refinement through rapid solidification. They rose from the center toward the outer surface, ranging from about 1100 to 1300 Hv. Interestingly, the oxidation resistance of the rapidly solidified MoSiBTiC alloy at 1100 °C was dramatically improved, probably due to the microstructure refinement effect with ultrafine grains. However, the fracture toughness value of the rapidly solidified MoSiBTiC alloy was about 8 MPa·m 1/2 , less than half of the cast and heat-treated MoSiBTiC alloy previously reported. Heat treatment and composition optimization will further improve the performance of the rapidly solidified MoSiBTiC alloy.

A new 12%Cr steel, VM12, has been developed with the combined strength and oxidation resistance characteristics desired for high-temperature applications. The steel increases chromium content by around 0.2% to improve oxidation properties while alloying with other elements such as cobalt, tungsten, and boron to meet a range of requirements, including extending fatigue life. The steel is designed to have the same creep strength as T/P92 but with better oxidation resistance due to the higher chromium content. It has about a 0.2% increase in mechanical properties compared to T/P92 steel. Results are presented for tubes and pipes cast with a variety of surface conditions. In addition, detailed results are provided on the effects of alloying elements on creep and oxidation resistance.

High gamma prime Ni-based superalloys comprising ≥3.5 % Al are difficult to weld due to high propensity of these materials to weld solidification, heat affected zone liquation, and stress-strain cracking. In this study the root cause analysis of cracking and overview on the developed weldable Ni-based superalloys for repair of turbine engine components manufactured from equiaxed (EA), directionally solidified (DS), and single crystal (SX) materials as well as for 3D AM is provided. It is shown that the problem with the solidification and HAZ liquation cracking of turbine engine components manufactured from EA and DS superalloys was successfully resolved by modification of welding materials with boron and silicon to provide a sufficient amount of eutectic at terminal solidification to promote self-healing of liquation cracks along the weld - base material interface. For crack repair of turbine engine components and 3D AM ductile LW4280, LW7901 and LCT materials were developed. It is shown that LW7901 and LCT welding materials comprising 30 - 32 wt.% Co produced sound welds by GTAW-MA on various SX and DS materials. Welds demonstrated high ductility, desirable combination of strength and oxidation properties for tip repair of turbine blades. Examples of tip repair of turbine blades are provided.

Austenitic heat resistant steels are one of the most promising materials to be applied around 650°C, due to its superior creep strength than conventional ferritic steels and lower material cost than Ni based superalloys. The problem of austenitic steels is its high thermal expansion coefficient (CTE), which leads to high deformation and stress when applied in rotors, casings, blades and bolts. To develop low CTE austenitic steels together with high temperature strength, we chose the gamma-prime strengthened austenitic steel, A-286, as the base composition, and decreased the CTE by introducing the invar effect. The developed alloy, Fe-40Ni-6Cr-Mo-V-Ti-Al-C-B, showed low CTE comparable to conventional ferritic steels. This is mainly due to its high Ni and low Cr composition, which the invar effect is prone even at high temperature region. This alloy showed higher yield strength, higher creep rupture strength and better oxidation resistance than conventional high Cr ferritic steels and austenitic steels. The 2 ton ESR ingot was forged or hot rolled without defects, and the blade trial manufacturing was successfully done. This alloy is one of the best candidates for USC and A-USC turbine components.

The recently developed 12%Cr steel VM12-SHC is characterized by very good creep properties at temperatures up to 620°C. This new material development exhibits an excellent oxidation resistance in steam atmospheres at the typical application temperature but also at temperatures up to 650°C. In comparison to the existing 9% Cr grades T/P91 and T/P92, VM12-SHC steel opens due to its excellent oxidation behavior, new possibilities for its application as a heat exchanger boiler component. It was found that outside its application temperature range VM12-SHC also shows, as all 9-12%Cr steels, the appearance of the so called Z-phase. This effect was investigated to understand its influence on creep properties of this class of ferritic/martensitic steels aiming at controlling the microstructure stabilities for future grade developments. Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected crept specimens have been investigated using light optical microscopy, SEM with EDX and TEM. In this study, the oxidation behavior of a number of typical martensitic 9-12%Cr steels was compared with the newly developed 12% Cr steel VM12-SHC. The compositions and morphologies of oxide scales formed after 5000 h exposure steels in simulated steam environments as function of temperature were characterized by light optical metallography and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX).

Improvement of thermal efficiency of new power plants by increasing temperature and pressure of boilers has led us to the development of high creep strength steels in the last 10 years. HCMA is the new steel with base composition of 1.25Cr-0.4Mo-Nb-V-Nd, which has been developed by examining the effects of alloying elements on microstructures, creep strength, weldability, and ductility. The microstructure of the HCMA is controlled to tempered bainite with low carbon content and the Vickers hardness value in HAZ is less than 350Hv to allow the application without preheating and post weld heat treatment. The HCMA tube materials were prepared in commercial tube mills. It has been demonstrated that the allowable stress of the HCMA steel tube is 1.3 times higher than those of conventional 1%Cr boiler tubing steels in the temperatures range of 430 to 530°C. It is noted that creep ductility has been drastically improved by the suitable amount of Nd (Neodymium)-bearing. The steam oxidation resistance and hot corrosion resistance of the HCMA have been proved to be the same level of the conventional 1%Cr and 2%Cr steels. It is concluded that the HCMA has a practical capability to be used for steam generator tubing from the aspect of good fabricability and very high strength. This paper deals with the concept of material design and results on industrial products.

In the “Boiler Materials for Ultrasupercritical Coal Power Plants” program, sponsored by the U.S. Department of Energy and the Ohio Coal Development Office, various materials are being assessed for their suitability in the high-temperature, high-pressure environment of advanced ultrasupercritical (A-USC) boilers. Beyond mechanical properties and fireside corrosion resistance, these materials must also exhibit adequate steamside oxidation and exfoliation resistance. A comprehensive database of steamside oxidation test results at temperatures relevant to A-USC conditions has been compiled over recent years. These tests have been conducted on ferritic and austenitic materials with chromium content ranging from 2 to 26%. The specimens were evaluated for oxidation kinetics and oxide morphology. The findings indicate that steamside oxidation behavior is significantly affected by temperature, the chromium content of the material, and the ability of chromium to diffuse through the material's crystallographic lattice structure. Additionally, surface treatments have been applied to enhance the steamside oxidation resistance of certain materials. While these treatments have shown potential, their effectiveness can be limited by the operational temperatures.

SMST is producing Ni alloy Boiler tubes since more than 10 years with application in several test loops and R&D programs. This paper will give an overview about the experience with the common grades A617 as well as C263 plus some additional information on the new developed austenitic material “Power Austenite MoW”.

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.

Development of steels used in the power generation industry for the production of boilers characterized by supercritical parameters poses new challenges. The introduction of new combinations of alloying agents aimed at obtaining the best possible mechanical properties, including creep resistance, affects the weldability of new steels. Each of the latter has to undergo many tests, particularly as regards bending and welding, in order to enable the development of technologies ensuring failure-free production and assembly of boiler systems. Martensitic steels containing 9% Cr, used in the manufacturing of steam superheaters, are characterized by excellent creep resistance and, at the same time, low oxidation resistance at a temperature in excess of 600°C. In turn, steels with a 12% Cr content, i.e., VM12-SHC or X20CrMoV12-1 are characterized by significantly higher oxidation resistance but accompanied by lower strength at higher temperatures, which translates to their limited application in the production of boilers operating at the most top parameters.X20CrMoV12-1 was withdrawn from most of the power plants, and VM12-SHC was supposed to replace it, but unfortunately, it failed in regards to creep properties. To fulfill the gap a new creep strength-enhanced ferritic steel for service in supercritical and ultra-supercritical boiler applications was developed by Tenaris and it is designated as Thor115 (Tenaris High Oxidation Resistance). This paper covers the experience gained during the first steps of fabrication, which includes cold bending and welding of homogenous joints.

This paper addresses the limitations of P92 steel used in ultra-supercritical power plants, particularly ferrite formation in thick components and its impact on short- and long-term properties. A guideline for determining ferritic content in P92 steel is presented. Furthermore, a novel 12% Cr boiler steel grade, VM12-SHC, is introduced. This new material offers good creep properties and oxidation resistance, overcoming the limitations of P92 steel. Finally, the development of matching filler metals for welding P92 and VM12-SHC steels is presented, ensuring optimal weld compatibility and performance in power plant applications.

Constricted steam oxidation resistance and finite microstructural stability limits the use of 9 - 12 wt.-% chromium ferritic-martensitic steels to steam temperatures of about 620 °C. Newly developed 12 wt.-% Cr steels are prone to Z-phase precipitation, which occurs at the expense of the strengthening precipitates, and therefore suffer an accelerated decline in strength during longterm operation. While the concept of ferritic-martensitic chromium steels thus seems to hit technological limitations, further improvement in steam power plant efficiency necessitates a further increase of steam pressure and temperature. Furthermore increasing integration of intermitting renewable energy technologies in electrical power generation poses a great challenge for supply security, which has to be ensured on the basis of conventional power plant processes. Besides improved efficiency for resource preservation, load flexibility, thermal cycling capability and downtime corrosion resistance will play key roles in the design of tailored materials for future energy technology. Under these preconditions a paradigm shift in alloy development towards improvement of cyclic steam oxidation and downtime corrosion resistance in combination with adequate creep and thermomechanical fatigue strength seems to be mandatory. The steam oxidation, mechanical and thermomechanical properties of fully ferritic 18 - 24 wt.-% chromium model alloys, strengthened by the precipitation of intermetallic (Fe,Cr,Si)2(Nb,W) Laves phase particles, indicate the potential of this type of alloys as candidate materials for application in highly efficient and highly flexible future supercritical steam power plants.

The U.S. Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) are sponsoring the “Boiler Materials for Ultrasupercritical Coal Power Plants” program. This program is aimed at identifying, evaluating, and qualifying the materials needed for the construction of critical components for coal-fired boilers capable of operating at much higher efficiencies than the current generation of supercritical plants. Operation at ultrasupercritical (USC) conditions (steam temperatures up to 760°C (1400°F)) will necessitate the use of new advanced ferritic materials, austenitic stainless steels and nickel-based alloys. As well as possessing the required mechanical properties and fireside corrosion resistance, these materials must also exhibit acceptable steamside oxidation resistance. As part of the DOE/OCDO program, steamside oxidation testing is being performed at the Babcock & Wilcox Research Center. More than thirty ferritic, austenitic and nickel-based materials have been exposed for up to 4,000 hours in flowing steam at temperatures between 650°C (1202°F) and 800°C (1472°F). In addition to wrought materials, steamside oxidation tests have been conducted on weld metals, coated materials and materials given special surface treatments. Exposed specimens were evaluated to determine oxidation kinetics and oxide morphology. High chromium ferritic, austenitic and nickel-based alloys displayed very good oxidation behavior over the entire temperature range due to the formation of a dense chromium oxide. With increasing steam temperature, low chromium ferritic materials experienced breakaway oxidation, and low chromium austenitic materials experienced significant oxide exfoliation. Special surface treatments that were applied to these materials appeared to have a beneficial effect on their oxidation behavior.

Advances in materials for power plants include not only new materials with higher-temperature capabilities, but also the use of current materials at increasingly higher temperatures. This latter activity builds on extensive experience of the performance of the various alloys, and provides a basis for identifying changes in alloy behavior with increasing temperature as well as understanding the factors that ultimately determine the maximum use temperatures of the different alloy classes. This paper presents results from an effort to model the exfoliation processes of steam-side oxide scales in a manner that describes as accurately as possible the evolution of strains in oxides growing inside small-diameter tubes subjected to large thermal gradients and to thermal transients typical of normal steam boiler operation. One way of portraying the results of such calculations is by plotting the evolving strains in a given oxide scale on an ‘Exfoliation Diagram’ (of the type pioneered by Manning et al. of the British Central Electricity Research Laboratory) to determine the earliest time at which the trajectory of these strains intersects a criterion for scale failure. Understanding of how such ‘strain trajectories’ differ among different alloys and are affected by the major variables associated with boiler operation has the potential to suggest boiler operating strategies to manage scale exfoliation, as well as to highlight the mode of scale failure and the limitations of each alloy. Preliminary results are presented of the strain trajectories calculated for alloys T22, T91, and TP347 subjected to the conditions experienced by superheaters under assumed boiler operating scenarios. For all three alloys the earliest predicted scale failures were associated with the increased strains developed during a boiler shut-down event; indeed, in the cases considered it appeared unlikely that scale failure would occur in any practically meaningful time due to strains accumulated during operation in a load-following mode in the absence of a shut down. The accuracy of the algorithms used for the kinetics of oxide growth appeared to be a very important consideration, especially for alloy TP347 for which large effects on oxide growth rate are known to occur with changes in alloy grain size and surface cold work.

The current work presented a study of isothermal-oxidation behavior of the additive manufactured (AM) Alloy718 in air at 800°C. The oxidation behavior of Alloy718 specimens produced by selective laser melting (SLM) and electron beam melting (EBM) process were comparatively examined. No significant differences were observed in oxidation kinetics while different microstructures of the oxide scale were found. Coarse and columnar chromia grains developed on SLM specimens, whereas the chromia scale of EBM specimens consisted of extremely fine grains. Glow Discharge Optical Emission Spectrometry (GD-OES) analysis revealed that SLM specimens contain a higher content of Ti in chromia compared with EBM specimens. Process-induced supersaturation in SLM specimens might lead to a relatively high concentration of Ti in the chromia, which may affect the grain morphology of oxide scale in the SLM specimen.

The increasing steam parameters in modern high-efficiency fossil fuel power plants demand advanced materials with enhanced creep strength for operation under extreme temperature and pressure conditions. Tenaris has focused on developing ferritic-martensitic and austenitic grades for tube and pipe applications. At TenarisDalmine, efforts on ferritic-martensitic steels include ASTM Grade 23, a low-alloyed alternative to Grade 22 with 1.5% W, offering good weldability, creep resistance up to 580°C, and cost competitiveness. Additionally, ASTM Grade 92, an improved version of Grade 91, provides high creep strength and long-term stability for components like superheaters and headers operating up to 620°C. At TenarisNKKT R&D, austenitic steel development includes TEMPALOY AA-1, an improved 18Cr-8NiNbTi alloy with 3% Cu for enhanced creep and corrosion resistance, and TEMPALOY A-3, a 20Cr-15Ni-Nb-N alloy with superior creep and corrosion properties due to its higher chromium content. This paper details the Tenaris product lineup, manufacturing processes, and key material properties, including the impact of shot blasting on the steam oxidation resistance of austenitic grades. It also covers ongoing R&D efforts in alloy design, creep testing, data assessment, microstructural analysis, and damage modeling, conducted in collaboration with Centro Sviluppo Materiali.

The newly developed 12%Cr steel Super VM12 is characterized by excellent creep rupture strength properties (better than Grade 92) and enhanced steam oxidation resistance of 12%Cr steels such as VM12-SHC. Balanced properties profile of the new steel development in comparison to the existing well-established steels such as Grade 91 and Grade 92, opens opportunities for its application as construction material for components in existing or future high-efficiency power plants. In this study the oxidation behavior of typical 9%Cr steels was compared with the new steel development. The oxide scale morphologies and compositions of different oxide layers as function of temperature and exposure time in steam-containing atmospheres were characterized using light optical metallography, Scanning Electron Microscopy (SEM). Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected creep specimens were investigated using the Transmission Electron Microscopy and the Atom Probe Tomography techniques.

Refractory metal, such as molybdenum and tungsten, are used in increasingly severe environments. Therefore, these materials are required to have superior mechanical properties, long life and excellent reliability. In this study, we developed newly Mo alloy dispersed Mo-base intermetallic compound for material forming such as hot extrusion die. This newly Mo alloy “MSB” exhibited superior mechanical properties compared with convention Mo alloy at temperatures below 1000℃. In addition, by adding a titanium alloy to the MSB, we have developed another alloy “T-MSB” that has high mechanical properties at higher temperatures. In the hot extrusion of brass, die made of these Mo alloys had 2.5 times longer tool life than the conventional Mo alloy die.

New Fe-base ferritic alloys based on Fe-30Cr-3Al-Nb-Si (wt.%) were proposed with alloy design concepts and strategies targeted at improved performance of tensile and creep-rupture properties, environmental compatibilities, and weldability, compared to Grade 91/92 type ferritic-martensitic steels. The alloys were designed to incorporate corrosion and oxidation resistance from high Cr and Al additions and precipitate strengthening via second-phase intermetallic precipitates (Fe2Nb Laves phase), with guidance from computational thermodynamics. The effects of alloying additions, such as Nb, Zr, Mo, W, and Ti, on the properties were investigated. The alloys with more than 1 wt.% Nb addition showed improved tensile properties compared to Gr 91/92 steels in a temperature range from 600-800°C, and excellent steam oxidation at 800°C as well. Creep-rupture properties of the 2Nb-containing alloys at 700°C were comparable to Gr 92 steel. The alloy with a combined addition of Al and Nb exhibited improved ash-corrosion resistance at 700°C. Additions of W and Mo were found to refine the Laves phase particles, although they also promoted the coarsening of the particle size during aging. The Ti addition was found to reduce the precipitate denuded zone along the grain boundary and the precipitate coarsening kinetics.