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.

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.

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.

ASME Grade 91 steel seam-welded elbow pipe, which has been used in a USC plant (A-Plant) for about 6 × 10 4 h, was investigated to clarify the microstructure and remaining creep life of the material at long-term region. SEM and TEM observations were conducted on specimens cut from the welded portions of the intrados and extrados of the elbow, and the number density of creep voids in fine-grained HAZ was measured in the wall-thickness direction. Then, creep rupture tests were performed to examine the remaining life of each portion of the base metal and welded joint. On the basis of the results, it was suggested that the microstructural changes were small and that the cumulative creep damage was also small for the elbow pipe during its use at the USC plant for about 6 × 10 4 h. The present result was compared with the result of an investigation on Grade 91 steel elbow used in another USC plant (B-Plant) for about 5 × 10 4 h. The A-Plant material had a creep life about ten times longer than that of the B-Plant material for not only the base metals but also the welded joint. Through the comparison of the investigation results, it was suggested that the difference in the creep deformation property between the base metals of the elbows was the main reason for the difference in their creep lives.

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.

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.

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.

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.

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.

Development of the advanced USC (A-USC) boiler technology has been promoted in recent years, which targets 700°C steam condition. HR6W (Ni-23Cr-7W-Ti-Nb-25Fe) and HR35 (Ni-30Cr-6W-Ti-15Fe) have been developed for A-USC boiler tubes and pipes. The former alloy is mainly strengthened by Fe 2 W type Laves phase. The latter one employs precipitation strengthening of α-Cr phase in addition to Laves phase. Characteristic alloy design of both alloys, which does not use precipitation strengthening of γ′ phase (Ni 3 Al), leads to superior ductility and resistance to stress-relaxation cracking. Stability of creep strength and microstructure has been confirmed by long-term creep rupture tests. The 100,000h average creep rupture strength of HR6W is 85MPa at 700C. That of HR35 is 126MPa at 700°C which is comparable with conventional Alloy617. Tubes of both alloys have been evaluated by the component test in Japanese national A-USC project with γ′ hardened Alloy617 and Alloy263. Detailed creep strength, deformation behavior and microstructural evolution of these alloys are described from the viewpoint of the difference in strengthening mechanisms. Capability of these alloys for A-USC boiler materials has been demonstrated by the component test in the commercial coal fired boiler as the part of the A-USC project.

Materials with a higher creep strength and sensitization resistance superior to those of 347AP are required in complex refinery such as delayed coker. To optimize material designing, the effect of B addition on the Z phase-strengthened steels has been investigated. B addition significantly improved the creep strength of steel containing Nb despite the absence of M 23 C 6 , whereas the creep strength of steel without Nb showed only a slight change with B addition. The size of Z phase was smaller in the Nb-containing steel with B content than that in B-free steel. It was suggested that the refinement of Z phase contributed to the creep strengthening by B addition in steels containing Nb.

Creep properties and microstructural changes of 25Cr-20Ni-Nb-N steel (KA-SUS310J1TB) were investigated. Creep tests were performed under 20MPa to 380MPa at 600°C to 800°C. Time to rupture was from 53.5h to 23950h. At 650°C or higher, creep strength degraded in the long-term. Rupture elongation and reduction of area decreased with increasing time to rupture at 600°C to 800°C. The reduction of area was lower than 12% after creep rupture for more than 10000h. Creep voids and cracks were observed on grain boundaries in creep ruptured samples. The hardness of head portion of creep ruptured samples increased with increasing time to rupture at 600°C to 800°C. The hardness of gauge portion of creep ruptured samples was higher than that of as received sample. However, the hardness of gauge portion does not strongly depend on time to rupture. No precipitates were observed in as received sample. On the other hand, a large number of precipitates were confirmed after creep rupture at 600°C to 800°C. M 23 C 6 , sigma phase, eta nitride and Z phase were detected in creep ruptured samples. The precipitation was confirmed on grain boundaries after short-term creep. The precipitates were also formed inside grains after long-term creep. It was confirmed by optical microscope that the grain boundary seemed to have band-like structure after short-term creep exposure. The Cr depletion zone was detected around grain boundary after short-term creep exposure. The Cr depletion zone can be visible when Cr rich precipitates such as M 23 C 6 and sigma phase are formed on grain boundaries. However, the bandlike structure was not observed after long-term creep exposure because the Cr depletion zone became unclear after long-term creep exposure. Creep voids were formed on grain boundaries and at the interface between precipitates such as M 23 C 6 and sigma phase and matrix.

In power plants operated at elevated temperatures, the operating life of structural materials increases. Therefore, it is very important to be able to predict creep strength in long term above 100,000 h. Furthermore, it has been reported that in the long term, the actual creep strength is lower than the predicted life. Although this problem has been analysed, the reasons remain unclear. In this study, a fracture energy model is used to evaluate the mechanisms of the creep strength reduction for martensitic steels. In the model, changes in fracture energy with rupture time are expressed by a power law. The energy density rate is calculated using stress, rupture elongation, and rupture time. The model indicates two mechanisms of creep strength reduction. One is the increase in rupture elongation, which leads to reduction in creep strength with ductility; the other is the decrease in reduction of area, which leads to reduction in creep strength with brittleness. Difference between the two mechanisms affects creep-fatigue strength. The study also shows that the equation based on the fracture energy model for creep-fatigue life can be obtained by a parallel translation of that for creep.

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).

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.

High precision stress relaxation tests (SRT) at temperatures between 550C and 700C were performed on serviced and reheat treated T91, 9%Cr steel. The service exposure was 116,000 hours at steam temperatures to 550C. Constant displacement rate (CDR) tests were also run at 600C on notched specimens for the two conditions. Specimens, heat treated after service, were stronger at the lower test temperatures in terms of both tensile strength and creep strength. This difference was reflected in the CDR results, which also suggested a lower fracture resistance in the heat treated condition. Thus, service exposure appears to have softened the alloy and enhanced its resistance to fracture, with no evidence of embrittling reactions. Based on the analysis of the SRT tests, projections were made of the times to 1% creep and the times to rupture as well as direct comparisons with minimum creep rate data'. When plotted on the basis of a Larson- Miller parameter (C=30), the calculated values compared well with actual long time rupture testing for exposed and re-heat treated specimens, and generally showed higher precision. The longest test time was about eighteen months for the stress rupture data compared with the use of one machine for a few weeks for the SRT data. The latter actually covered a far greater range of creep rates and projected lives. The SRT test is especially consistent at higher parameter values, i.e., higher temperatures and/or lower stresses. This method of accelerated testing is now being applied to a wide range of alloys for fossil power plants for composition and process optimization, design analysis, and life assessment.

The effect of Cr content on the creep strength at 650°C was examined with high Cr heat resistant steels for the USC high-temperature rotor shafts. The amount of Cr was varied from 8.5% to 11.5%, and then, the alloying effect of Cr was investigated on the stability of the precipitates at 650°C. Within the present range of the Cr content, the short-term creep rupture life under the higher applied stress increased with the Cr content in the steels, whereas the long-term creep rupture life under the lower applied stress decreased with the Cr content in the steels. For example, under the applied stress of 98MPa, the 9%Cr steel exhibited the longest creep rupture life among the experimental steels. Also, it was found from the experiment using the extracted residues that the degree of solution strengthening and the sorts of precipitates scarcely changed regardless of the Cr content in the steels. The Laves phase precipitated finely in the lath was enlarged in the 11.5%Cr steel even after a short-term creep. This result indicates that the coarsening of precipitates such as the Laves phase promotes the recovery of the lath in the early stage of creep deformation. It was suggested that 9%Cr is desirable content in the ferritic steel for suppressing the degradation of creep strength in 98MPa at 650°C.

Effects of Ni content and heat treatment condition on impact toughness and creep strength of precipitation strengthened 15Cr ferritic steels were investigated in order to discuss a possibility of improvement in both mechanical properties. Both creep strength and impact toughness of the developing steels were improved drastically by solid solution treatment with water quenching. However, an addition of Ni reduced the long-term creep strength of the steels, though Ni was effective in improvement in impact toughness. It was found that water quenching suppressed formation of coarse block type particles and precipitate free zones around them, and precipitation of plate type fine particles and thermal stability of them within ferrite phase were promoted by solid solution treatment with water quenching. However, martensite phase with sparsely distributed coarse block type particles were formed in the Ni added steels, and such microstructure reduced the precipitation strengthening effect slightly. On the other hand, increase in impact values of the steel indicated no relation to volume fraction of martensite phase. It was supposed that the impact toughness of ferrite phase itself was improved by solid solution treatment and addition of Ni.

The demand for higher efficiency and reduced emissions in coal-fired power boilers will result in the use of higher steam temperatures and pressures. A significant materials effort is required to reach a target steam condition of 760°C/35MPa. These new Ultrasupercritical (USC) units will require the use of nickel-based superalloys. Long-term creep strength will be a determining factor in achieving the highest possible steam conditions. To this end, the creep strength of commercially available (Haynes 230), modified/controlled chemistry (CCA617/Maгco 617), and new (INCONEL 740) alloys, including weldments, are being investigated at Oak Ridge National Laboratory (ORNL). Creep tests at ORNL show that the CCA617 provides a significant improvement in strength over the standard alloy 617 at 650°C to possibly 750°C. The strength of alloy 230 is well characterized, thus the testing on 230 has focused on specific specimen configurations for evaluating the high temperature behavior of weldments. Creep testing on INCONEL alloy 740 has shown good strengths (higher than 230 or CCA617) that may meet the target steam conditions. Microstructural analysis by electron microscopy on aged and tested material is being used to further understand the structure-properties relationship in these materials and determine long-term stability of the microstructures.

The effect of a reduced-temperature austenization treatment on the microstructure and strength of two ferritic-martensitic steels was studied. Prototypic 9% and 12% Cr steels, modified 9Cr-1Mo (ASME T/P91) and Type 422 stainless (12Cr-1Mo-W-V), respectively, were austenized at the standard 1050°C and an off-normal 925°C, both followed by tempering at 760°C. The reduced austenization temperature was intended to simulate potential inadequate austenization during field construction of large structures. The microstructure, tensile behavior, and creep strength were characterized for both steels treated at each condition. While little change in microstructure was observed for the modified 9Cr-1Mo steel, the creep strength was reduced at higher temperatures and in long duration tests. The microstructure of the Type 422 stainless in the off-normal condition consisted of polygonized ferrite instead of tempered martensite. In this case the creep strength was reduced for short duration tests (less than ~1000 hr), but not for long duration tests. Slight reductions in tensile strength were observed at room temperature and elevated temperatures of 450,550, and 650°C.