Fossil fuels continue to be the primary source of energy in the U.S and worldwide. In order to improve the efficiency of fossil power plants, advanced structural materials need to be developed and deployed to meet the need of high temperature creep resistance and corrosion resistance. Examples include creep strength enhanced ferritic (CSEF) steels, austenitic stainless steels, nickel-based superalloys, and oxide dispersion strengthened alloys. Welding is extensively used in construction of fossil power plants. The performance of the weld region can be critical to the safe and economical operation of fossil power plants. Degradations in performance such as reduced creep strength and premature failure in the weld region (e.g. Type IV failure in ferritic steels) are examples of longstanding welding and weldability problems for boiler and other components. In the past, extensive studies have been carried out to characterize the different microstructures in different regions of a weld, and to a certain extent, to establish the correlations between the microstructure and the creep strength. However, the metallurgical or microstructural induced local stress/strain variations have been seldom quantified. In addition, it has been long recognized that, due to the sharp microstructure and property gradients in the weld and HAZ, the standard creep testing procedure for the base metal can produce erroneous results when used for weld testing.

A new martensitic steel for power generation applications was developed: Tenaris High Oxidation Resistance (Thor) is an evolution of the popular ASTM grade 91, offering improved steam oxidation resistance and better long-term microstructural stability, with equal or better creep strength. Thanks to its design philosophy, based on consolidated metallurgical knowledge of microstructural evolution mechanisms, and an extensive development performed in the last decade, Thor was engineered to overcome limitations in the use of ASTM grade 91, above 600 °C, particularly related to scale growth and liftoff. After laboratory development, Thor was successfully validated at the industrial level. Several heats up to 80 metric tons were cast at the steel shop, hot rolled to tubes of various dimensions, and heat treated. Trial heats underwent extensive characterization, including deep microstructural examination, mechanical testing in the as-received condition and after ageing, long-term creep and steam oxidation testing. This paper presents an overview of metallurgical characterization performed on laboratory and industrial Thor material, including microstructural examination and mechanical testing in time-independent and time-dependent regimes. Data relevant to the behavior and the performance of Thor steel are also included.

Inflection is observed at 50% of 0.2% offset yield stress, that is HALF YIELD, on the relation between stress and creep rupture life of creep strength enhanced ferritic steels with tempered martensitic microstructure. Similar shape is generally recognized on the ferritic steels with martensitic or bainitic microstructure, in contrast to ferritic steels with ferrite and pearlite microstructure, as well as austenitic steels and superalloys except for several alloys. Ferritic steel with martensitic or bainitic microstructure indicates softening during creep exposure, however, hardening due to precipitation takes place in the ferritic steels with ferrite and pearlite microstructure and austenitic steels. This difference in microstructural evolution is associated with indication of inflection at half yield. Stress range of half yield in the stress vs. creep life diagram of creep strength enhanced ferritic steels is wider than that of conventional ferritic creep resistant steels with martensitic or bainitic microstructure. As a result of wide stress range of boundary condition, risk of overestimation of long-term creep rupture strength by extrapolating the data in the high-stress regime to the low-stress regime is considered to be high for creep strength enhanced ferritic steels.

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.

This paper summarizes recent efforts to improve creep performance in Grade 91 (Mod. 9Cr-1Mo, ASTM A387) steel weldments via non-standard heat treatments prior to welding. Such heat treatments offer a potential solution for minimizing Type IV failures in creep strength enhanced ferritic (CSEF) steels. A lower temperature tempering (LTT, 650°C) of the 9Cr steels prior to gas tungsten arc welding (GTAW) resulted in improved creep-rupture life at 650°C compared to the samples tempered at a standard condition (HTT, 760°C) before welding. From detailed characterization of precipitation kinetics in the heat affected zone, it was hypothesized that M 23 C 6 carbides in the fine-grain heat-affected zone (FGHAZ) in the LTT sample were fully dissolved, resulting in re-precipitation of strengthening carbides during post weld heat treatment (PWHT). This was not the case in the HTT sample since M 23 C 6 in the FGHAZ was only partially dissolved prior to welding, which caused coarsening of existing M 23 C 6 after PWHT and premature creep failure in the FGHAZ. However, it was also found that the LTT raised the ductile-brittle transition temperature above room temperature (RT). Two different thermo-mechanical treatments (TMTs); two-step tempering and aus-forging/aus-aging, of the modified 9Cr-1Mo steels were attempted, in order to control the balance between creep properties and RT ductility, through control of precipitation kinetics of the M 23 C 6 carbides and/or MX carbo-nitrides. The hardness map of the TMT samples after GTAW and PWHT were evaluated.

Conventional time-temperature-parameter (TTP) methods often overestimate long-term creep rupture life of creep strength enhanced high Cr ferritic steels. The cause of the overestimation is studied on the basis of creep rupture data analysis on Gr.91, 92 and 122 steels. There are four regions with different values of stress exponent n for creep rupture life commonly in stress-rupture data of the three ferritic steels. Activation energies Q for rupture life in the regions take at least three different values. The values of n and Q decrease in a longer-term region. The decrease in Q value is the cause of the overestimation of long-term rupture life predicted by the conventional TTP methods neglecting the change in Q value. Therefore, before applying a TTP method creep rupture data should be divided into several data sets so that Q value is unique in each divided data set. When this multi-region analysis is adopted, all the data points of the steels can be described accurately, and their long-term creep life can be evaluated correctly. Substantial heat-to-heat and grade-to-grade variation in their creep strength is suggested under recent service conditions of USC power boilers.

As long term laboratory creep data became available the original estimates of the allowable stresses for creep strength enhanced ferritic steels (CSEF) had to be reduced. Thus, even in properly processed steel, the long term performance and creep rupture strength is below that originally predicted from a simple extrapolation of short term data. One of the microstructural degradation mechanisms responsible for the reduction in strength is the development of creep voids. Nucleation, growth and inter linkage of voids also result in a significant loss of creep ductility. Indeed, elongations to rupture of around 5% in 100,000 hours are now considered normal for long term creep tests on many CSEF steels. This relatively brittle behaviour, and the associated creep void development, promotes burst rather than leak type fracture in components. Moreover, the existence of significant densities of voids further complicates in-service assessment of condition and weld repair of these steels. The present paper examines background on the nucleation and development of creep voids in 9 to 12%Cr martensitic steels and discusses factors affecting brittle behavior.

Creep strength enhanced ferritic steels like T/P 91 and T/P 92 are widely used for the fabrication of pressure vessel components in the petro-chemical and thermal power industry. Today, a new generation of 9-12% Cr CSEF steels like MARBN, Save12AD, G115 and Super VM12 are entering into the market. All CSEF steels require an accurate post-weld heat treatment after welding. This paper discusses the impact of chemical composition on Ac1 as well as the transformation behavior during post-weld heat treatment in a temperature range below and above Ac1. The Ac1 temperature of weld metals with variations in chemical composition has been determined and thermodynamic calculations has been carried out. Simulations of heat treatment cycles with variations in temperature have been carried out in a quenching dilatometer. The dilatation curves have been analyzed in order to detect any phase transformation during heating or holding at post weld heat treatment. Creep rupture tests have been carried out on P91 and Super VM12 type weld metals in order to investigate the effect of sub- and intercritical post weld heat treatment on creep rupture strength.

The Creep Strength Enhanced Ferritic steel grade 91 is widely used for both retrofit applications and primary construction on high temperature power plant. Although to date most structural integrity issues with this material have been associated with welds, as the operating hours of these plants accumulate, there will be a growing need for remanent creep life assessment of the base material. Arguably this is already the case for aberrant grade 91 material entering service in an incorrectly heat treated condition. In these circumstances the strength may fall below the normally accepted lower bound of the creep strength range and some indication of actual strength may be required. One strategy to address potential base material failure is to use small scale sampling of individual components, followed by small scale creep testing, to investigate the current creep strength present. The data can be compared with the equivalent data produced for well characterised material known to be at the lower bound of the creep strength range. This paper describes a methodology for using the impression creep data obtained to provide both creep strength ranking and an estimate of absolute creep strength for individual grade 91 components. This will enable appropriate judgements to be made by plant operators on repair/run decisions. For those components remaining in service, it allows for the weakest items to be given priority for early re-inspection at future outages. The ultimate goal is to identify base material creep damage development at as early a stage as possible and well in advance of failure in service.

For last half century the development of creep strength enhanced ferritic steels has been continued and presently ASME grades 91, 92 and 122 extremely stronger than conventional low alloy steels have extensively been used worldwide in high efficient power plants. However the use of these creep strength enhanced 9-12%Cr steels is limited to around 630°C or 650°C at maximum in terms of high temperature strength and oxidation resistance. Consequently the appearance of ferritic steels standing up to higher temperature of around 700°C to substitute of high strength austenitic steels is strongly desired. Under the state, the addition of high nitrogen to ferritic steels is attracting considerable attention because of improving high temperature strength and oxidation resistance of them. This work was done to evaluate the oxidation resistance of high nitrogen steels and to investigate the effect nitrogen and microstructure on oxidation resistance using 9-15%Cr steels with about 0.3% nitrogen manufactured by means of Pressurized Electro- Slag Remelting (PESR) method in comparison with ASME grades 91 and 122. As a result, high nitrogen ferritic steels showed excellent oxidation resistance comparing with nitrogen-free steels and ASME grades 91 and 122. The oxidation resistance of 9%Cr ferritic steels depends on the nitrogen content in the each steel. That is, the weight gain decreases with an increase in nitrogen content. Moreover, the oxide scale of high nitrogen steel contained a high concentration of Cr. It is conjectured that, in high temperature oxidation, nitrogen plays a key role in promoting the formation of the oxide scale which has high concentration of Cr, inhibiting oxidation from proceeding. And also it was found that the oxidation resistance of the high nitrogen steels does not depend greatly on Cr content but on their microstructure. The oxidation resistance of high nitrogen ferritic heat-resistant steels increased as the fraction of martensite structure increased. These results indicate for high nitrogen steels Cr diffusion along grain boundaries is further promoted resulting in the formation of protective oxide scale having high Cr concentration. Furthermore as new findings it was confirmed that the Cr diffusion in substrate of steels to form Cr concentrated oxide scale on the metal surface is accelerated by nitrogen while suppressed by carbon in matrix of steel.

Grade 91 steel has achieved broad acceptance within the modern boiler industry to fabricate a variety of critical pressure components including tubing, piping and headers, particularly in Ultra Super Critical (USC), Advanced Ultra Super Critical (A-USC) and Combined Cycle Power Plants (CCPP). The applications for which this material is used enforce severe requirements on strength, corrosion, creep properties and thermal stability during service. The properties of Creep Strength Enhanced Ferritic steels (CSEF) such as Grade 91 are critically dependent on manufacturing factors like steelmaking, heat treatments and welding: poor control of these parameters can severely compromise material properties. In scientific literature, several studies correlate low creep ductility to high content of trace elements such As, Sn, Sb, Pb, Cu, P and S. Since the current reference Codes, namely ASTM/ASME, don’t require particular restrictions for these elements, Electric Power Research Institute (EPRI) has issued guidelines for grade 91 which enforce a significant reduction of impurities and trace elements. This paper discusses steelmaking operating challenges to produce Grade 91 steel with very low contents of the above mentioned residual elements, starting from the furnaces charges, up to the chemical composition measuring equipment used in the steel shop laboratories.

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.

Modified 9Cr-1Mo alloy steel has been developed over the last few decades and has since gained wide acceptance in the boiler industry for the production of a variety of pressure-critical components, including tubing, piping and headers. The properties of creep-strength enhanced ferritic steels such as grade 91 are critically dependent on manufacturing parameters such as steelmaking, hot deformation, heat treatment and welding. Since the applications for which this material is used impose strict requirements in terms of resistance, corrosion, and creep behavior, poor process control can severely compromise the service behavior. This work discusses the impact of total deformation during the rolling process, and heat treatment parameters on time-independent and time-dependent properties for grade 91. For this study, two heats with similar chemical composition were produced with different reduction ratios: to which, several normalizing and tempering combinations were applied. For each combination, the microstructure was characterized, including evaluation of segregation by metallographic examination, and analysis of secondary phase precipitates by means of X-ray powder diffraction. Mechanical testing and creep testing were performed. A comparison of results is presented, and recommendations on the optimal process parameters are provided to ensure reliable performance of grade 91 material.

Metallurgical factors affecting the fusion boundary failure and damage mechanism of DMWs (Dissimilar Metal Welds) between the CSEF (Creep Strength Enhanced Ferritic) steels and austenitic steels were experimentally and theoretically investigated and discussed. Long-term exservice DMWs up to 123,000 hours were investigated; the precipitates near the fusion boundary were identified and quantitatively evaluated. Comparing with the other generic Ni-based weld material, MHPS original filler metal HIG370 (Ni bal.-16Cr-8Fe-2Nb-1Mo) showed superior suppression effect on fusion boundary damage of DMWs, which was verified by both of the microstructure observation and thermodynamic calculation. Based on the microstructure observation of crept specimen and ex-service samples of DMWs, temperature, time and stress dependence of fusion boundary damage of DMWs were clarified. Furthermore, fusion boundary damage morphology and mechanism due to precipitation and local constituent depletion was discussed and proposed from metallurgical viewpoints.

The use of the bainitic class of creep strength enhanced ferritic steels T/P23 and T24 has increased over the last decade in a wide range of applications including replacement headers, superheater and reheater tubing and in waterwall tubing. Many issues have been reported in one or both of these materials including hydrogen induced cracking, reheat cracking and stress corrosion cracking. To appropriately address these issues, work has been initiated that includes a literature review, development of a database of phase transformation temperatures, investigation of tempering behavior, and an analysis of the effect of phase transformation on residual stresses. Such information will be provided in the context of understanding why these two materials appear highly susceptible to these cracking mechanisms.

The use of the bainitic creep strength enhanced ferritic steel T/P23 has increased over the last decade in a wide range of applications including headers, superheater and reheater tubing and in waterwall tubing. Many issues have been reported in weldments of this material, such as hydrogen induced cracking, reheat cracking and stress corrosion cracking. In order to help characterize high temperature cracking phenomena, including reheat cracking, a limited number of laboratory creep crack growth tests are being conducted as part of an ongoing project. Tests were run on as-welded sections with the test specimen crack-tip located in select zones of the weldment. Test temperatures are intended to bookend the range of applications from a waterwall condition of ~482°C (900°F) to the superheat/reheat condition of 565°C (1050°F). This paper describes the results of some early testing at 482°C (900°F). The tests provided useful insight into the cracking susceptibility of the material at this temperature with respect to not only time-dependent cracking, but also fatigue crack growth and fracture toughness. The paper includes details of the test method and results, as well as findings from post-test metallographic examinations of the tested specimens.

Creep strength of Grade 91 steels has been reviewed and allowable stress of the steels has been revised several times. Allowable stress regulated in ASME Boiler and Pressure Vessel Code of the steels with thickness of 3 inches and above was reduced in 1993, based on the re-evaluation with long-term creep rupture data collected from around the world. After steam leakage from long seam weld of hot reheat pipe made from Grade 122 steel in 2004, creep rupture strength of the creep strength enhanced ferritic (CSEF) steels has been reviewed by means of region splitting method in consideration of 50% of 0.2% offset yield stress (half yield) at the temperature, in the committee sponsored by the Ministry of Economy, Trade and Industry (METI) of Japanese Government. Allowable stresses in the Japanese technical standard of Grade 91 steels have been reduced in 2007 according to the above review. In 2010, additional long-term creep rupture data of the CSEF steels has been collected and the re-evaluation of creep rupture strength of the steels has been conducted by the committee supported by the Federation of Electric Power Companies of Japan, and reduction of allowable stress has been repeated in 2014. Regardless of the previous revision, additional reduction of the allowable stress of Grade 91 steels has been proposed by the review conducted in 2015 by the same committee as 2010. Further reduction of creep rupture strength of Grade 91 steels has been caused mainly by the additional creep rupture data of the low strength materials. A remaining of segregation of alloying elements has been revealed as one of the causes of lowered creep rupture strength. Improvement in creep strength may be expected by reducing segregation, since diffusional phenomena at the elevated temperatures is promoted by concentration gradient due to segregation which increases driving force of diffusion. It has been expected, consequently, that the creep strength and allowable stress of Grade 91 steels can be increased by proper process of fabrication to obtain a homogenized material free from undue segregation.

Type IV damage is observed in creep-strength-enhanced ferritic (CSEF) steel used in USC plants and the research on the evaluation of such damage has been carried out in the world. Type I failure is recently reported in welded joint of Gr.91 so that the importance of the evaluation of the creep strength of the weld metal is increasing. In this study, the change in hardness with aging and creep strength before and after aging were evaluated to determine the creep strength of the weld metal of Gr.91. The hardness of the weld metal subjected to aging significantly decreased compared with that of the base metal and the heat-affected zone (HAZ). The creep strength of the weld metal was also decreased by aging. From these results, it is suggested that the failure morphology of Gr.91 steel welded joint used for a long term may change from type IV to type I.

Early supercritical units such as American Electric Power (AEP) Philo U6, the world’s first supercritical power plant, and Eddystone U1 successfully operated at ultrasupercritical (USC) levels. However due to the unavailability of metals that could tolerate these extreme temperatures, operation at these levels could not be sustained and units were operated for many years at reduced steam (supercritical) conditions. Today, recently developed creep strength enhanced ferritic (CSEF) steels, advanced austenitic stainless steels, and nickel based alloys are used in the components of the steam generator, turbine and piping systems that are exposed to high temperature steam. These materials can perform under these prolonged high temperature operating conditions, rendering USC no longer a goal, but a practical design basis. This paper identifies the engineering challenges associated with designing, constructing and operating the first USC unit in the United States, AEP’s John W. Turk, Jr. Power Plant (AEP Turk), including fabrication and installation requirements of CSEF alloys, fabrication and operating requirements for stainless steels, and life management of high temperature components

Preface for the 2016 Advances in Materials Technology for Fossil Power Plants conference.