In order to evaluate long term creep strength of modified 9Cr ferritic steels, the system free energy of creep ruptured specimens at both 650 and 700 °C is evaluated as the sum of chemical free energy, strain energy and surface energy, which are obtained by a series of experiments, i.e., chemical analysis using extracted residues, X-ray diffraction, and scanning transmission electron microscopy. Change ratio of the system free energy and creep stress showed the relationship with one master curve irrespective of creep conditions, indicating that the steel ruptures when the applied stress exceeds a limited stress depending on the microstructural state expressed by the change ratio of system free energy. Furthermore, it was found that dominant factor of the change ratio was the chemical free energy change. On the basis of these results, long term creep strength of the steel was evaluated at 700 °C, for example, 19MPa at 700 °C after 10 5 h. It is concluded that long term creep strength of modified 9Cr ferritic steels can be predicted by the system free energy concept using the ruptured specimens with various creep conditions.

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.

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.

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.

The change in hydrogen desorption characteristic due to creep was investigated to examine the possibility of hydrogen as tracer for detecting and evaluating the creep damage accumulated in high Cr ferritic boiler steel, Gr.91. Hydrogen charging into the creep specimen was conducted by means of cathodic electrolysis. Next, the thermal desorption analyses (TDA) were carried out at temperature range from room temperature to 270°C for measuring the hydrogen evolution curve. The experimental results revealed that the amount of hydrogen desorbed during analysis, C H , increased with increasing creep life fraction, although the trend of increase in C H was strongly dependent on the stress level. Moreover, there was an almost linear correlation between the logarithm of C H measured on the creep ruptured specimen and the Larson-Miller parameter (LMP), which was approximated by “log C H = 0.39 LMP – 13.4”. This can be a criterion for creep rupture and means that as far as the C H does not reach the line, the rupture never occurs.

Prediction of long-term creep strength is an important issue for industrial plants operated at elevated temperatures, although the creep strength of high Cr ferritic steels depends on their microstructural evolution during creep. The state of microstructure in metallic materials can be expressed as numerical values based on a concept of system free energy. In this study, in order to evaluate long term creep strength of 9Cr ferritic steel containing B, change in the system free energy during creep of the steel is evaluated as the sum of chemical free energy, strain energy and surface energy, which are obtained by a series of experiments, i.e., chemical analysis using extracted residues, X-ray diffraction, and scanning transmission electron microscopy. The system free energy decreases with creep time. Change in the energy is expressed quantitatively as a numerical formula using the rate constants which depend on applied stress. On the basis of these facts, long term creep strength of the steel can be evaluated at both 948K(675°C) and 973K(700 °C).

This paper explores the low cycle fatigue (LCF) and creep-fatigue properties of a hot-forged, normalized, and tempered 9Cr-1Mo ferritic steel. This steel offers good performance in high-temperature applications (up to 873K) in power plants and reactors. The steel was forged into 70 mm diameter rods and then heat-treated with normalizing (1313K for 1 hour, air cooling) and tempering (1033K for 1 hour, air cooling). LCF tests were conducted at 300-873K with varying strain amplitudes and strain rates to understand the influence of both factors. Additionally, some specimens were aged at different temperatures for 10,000 hours before testing. Finally, creep-fatigue interaction tests were performed at 823K and 873K using tensile hold times ranging from 1 to 30 minutes.

A compositional modification has been proposed to validate an alloy design which potentially eliminates the requirement of post-weld heat treatment (PWHT) while preserving the advantage of mechanical properties in a reduced activation bainitic ferritic steel based on Fe-3Cr-3W-0.2V- 0.1Ta-Mn-Si-C, in weight percent, developed at Oak Ridge National Laboratory in 2007. The alloy design includes reducing the hardness in the as-welded condition for improving toughness, while increasing the hardenability for preserving the high-temperature mechanical performance such as creep-rupture resistance in the original steel. To achieve such a design, a composition range with a reduced C content combining with an increased Mn content has been proposed and investigated. Newly proposed “modified” steel successfully achieved an improved impact toughness in the as- welded condition, while the creep-rupture performance across the weldments without PWHT demonstrated ~50% improvement of the creep strength compared to that of the original steel weldment after PWHT. The obtained results strongly support the validity of the proposed alloy design.

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.

Microstructure change during creep at 650°C has been examined for a high-B 9%Cr steel by FIB-SEM serial sectioning 3D observation, Nano-SIMS, SEM, EBSD and TEM. The precipitates formed in the steel were M 23 C 6 , Laves phase, and a quite small amount of MX. For as-tempered steel, precipitation of M 23 C 6 on the prior austenite grain boundaries was clearly found, while precipitation of the Laves phase was not confirmed during tempering. The volume fraction of the Laves phase gradually increased with elapsed time, while M 23 C 6 appeared to increase once and decrease afterward, based on the comparison between the 2,754 h ruptured sample and the 15,426 h ruptured sample. Nano-SIMS measurements have revealed that B segregates on the prior austenite grain boundaries during normalizing, and it dissolves into M 23 C 6 .

The present study presents a detailed investigation on the evolution of the microstructure during welding on virgin and long-term service exposed (creep aged 1 = 535°C; 16.1 MPa; 156 kh and creep aged 2 = 555°C; 17.0 MPa; 130 kh) 12% Cr (X20CrMoV11-1) martensitic steel. This study was carried out in order to understand the impact of welding on prior creep exposed Tempered martensite ferritic (TMF) steel and to explain the preferential failure of weldments in the fine grained heat affected zone (FGHAZ) of the creep aged material side instead of the new material side. Gleeble simulation (Tp = 980°C; heating rate = 200 °C/s; holding time = 4 seconds) of the FGHAZ was performed on the materials to create homogeneous microstructures for the investigation. Quantitative microstructural investigations were conducted on the parent plate and simulated FGHAZ materials using advanced electron microscopy to quantify: a) voids, b) dislocation density, c) sub-grains, and d) precipitates (M 23 C 6 , MX, Laves, Z-phase) in the materials. Semi-automated image analysis was performed using the image analysis software MIPARTM. The pre-existing creep voids in the creep aged parent material and the large M 23 C 6 carbides (Ø > 300 nm) in the FGHAZ after welding are proposed as the main microstructural contributions that could accelerate Type IV failure on the creep aged side of TMF steel weldments.

Recent in-service experiences have revealed critical vulnerabilities in creep-strength enhanced ferritic (CSEF) steels, with cracking potentially occurring surprisingly early in a component's operational life. Fabrication irregularities have been found to introduce substantial property deficiencies compared to average material performance, raising serious concerns among industry users regarding personnel safety and equipment reliability. In response, a collaborative research program between the Electric Power Research Institute and Structural Integrity Associates, Inc. has been initiated to comprehensively address these critical material challenges. The program's extensive scope encompasses a holistic approach to material management, including rigorous investigations spanning material procurement, shop fabrication, field erection, and appropriate quality assurance procedures for each implementation phase. The research will systematically examine the behavior of both base and weld metals, with a strategic focus on developing a comprehensive life prediction methodology and optimizing maintenance protocols. Beyond its core technical objectives, the program is designed to facilitate knowledge exchange through regular participant workshops, where both program-generated findings and global utility experiences will be critically reviewed and discussed to ensure the research maintains optimal direction and relevance. This collaborative effort aims to establish a robust framework for understanding, mitigating, and managing the complex challenges associated with CSEF steel materials in high-performance industrial applications.

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.

In the present study a creep resistant, ferritic steel, based on the chemical composition of Crofer 22 H, was analysed regarding microstructure and particle evolution. Because of the preceding hot-rolling process formation of sub-grain structures was observed, which disappears over time. Additionally formation of particle-free zones close to high angle grain boundaries was observed. These zones are considered to be responsible for long-term material failure by lacking particle hardening and thus a concentration of deformation. Therefore in-depth analyses by transmission and scanning electron microscopy were performed to investigate dislocation behaviour in these areas

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.

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.

New Monte Carlo models have recently been developed to predict microstructural evolution in steels and aluminum alloys during heat treatment and high-temperature service. These models can control precipitate type and size distribution, distinguishing between pure lattice and grain boundaries. Consequently, they can forecast the precipitate size distribution within grains and on grain boundaries as a function of time. This paper describes the model validation for ferritic Fe-9Cr P92 steels. The model provides new information over a range of time intervals adding up to the total plant lifetime in an ultra-supercritical plant. This information can be incorporated into continuum damage mechanics models for predicting creep rate and stress rupture life. The paper discusses how this technique is used as a materials development tool to forecast necessary compositional modifications for improving creep properties in ferritic steels.

Creep behavior and degradation of creep properties of advanced 9-12%Cr ferritic steels are phenomena of major practical relevance, often limiting the lives of power plant components and structures designed to operate for long periods under stress at elevated temperatures. Because life expectancy is, in reality, based on the ability of the material to retain its high-temperature creep strength for a period of at least twice the projected design life, methods of creep property assessment based on physical changes in the material that are likely to occur during service exposure rather than simple parametric extrapolation of the short-term data are necessary. This work attempts to highlight the problem areas just in this respect. The proposed approaches are illustrated by recent experimental results on advanced high creep strength 9-12%Cr ferritic- martensitic steels (P91 and P92).

Creep deformation behavior of the T122 type steels with different matrix phases such as α’ (martensite) and α’+δ (martensite and delta-ferrite) at different stress levels has been studied comparing with those of the model steels with the initial microstructures consisting of the various combination of matrices such as ferrite (α), martensite (α’) and austenite (γ), and precipitates such as MX and M 23 C 6 . The heterogeneous creep deformation is found to be pronounced at lower stress level in the steel with a dual phase matrix of α’+δ, resulting in a complex sigmoidal nature in the creep rupture life. The creep deformation process of the steel with the dual phase matrix is similar to that of the model steel with the α phase matrix which exhibits a typical heterogeneous creep deformation and the early transition to the acceleration creep at a very small creep strain. Such a heterogeneous creep deformation is much pronounced along the interfaces between the soft δ ferrite and the hard martensite (α’) phases, and has a viscous nature in creep deformation which was first identified in P91 steel. It is concluded that the homogeneous microstructure is a key for achieving the long-term creep strength in the advanced ferritic steels at elevated temperatures over 600°C.

The highest creep rupture strength of recent 9-12% Cr steels which have seen practical application is about 130 MPa at 600°C and 100,000 h. While the 630°C goal may be realized, much more work is needed to achieve steam temperatures up to 650°C. Conventional alloy development techniques can be slow and it is possible that mathematical models can define the most economical path forward, perhaps leading to novel ideas. A combination of mechanical property models based on neural networks, and phase stability calculations relying on thermodynamics, has been used to propose new alloys, and the predictions from this work were published some time ago. In the present work we present results showing how the proposed alloys have performed in practice, considering long term creep data and microstructural observations. Comparisons are also made with existing enhanced ferritic steels such as Grade 92 and other advanced 9-12%Cr steels recently reported.