Damage in the grade 91 steel partially transformed zone of weld heat affected zones has historically been associated with many different types of microstructural features. Features described as being responsible for the nucleation of creep damage include particles such as laves phase, coarse M 23 C 6 , inclusions, nitrides, or interactions between creep strong and creep week grains, grain boundaries and potentially other sources. Few studies have attempted to link the observations of damage on scales of increasing detail from macro, to micro, to nano. Similarly, assessments are not made on a statistically relevant basis using 2D or 3D microscopy techniques. In the present paper, 2D assessment using scanning electron microscopy (SEM) and quantification techniques such as energy dispersive X-ray spectroscopy (EDS) and electron backscatter diffraction (EBSD) are utilized in combination with 3D serial sectioning of large volumes using plasma focused ion beam milling (P-FIB) and simultaneous EDS to evaluate an interrupted cross-weld creep test. Moreover, the sample selected for examination was from a feature cross-weld creep test made using a parent material susceptible to the evolution of creep damage. The test conditions were selected to give creep brittle behaviour and the sample was from a test interrupted at an estimated life fraction of 60%. The findings from these evaluations provide perspective on the features in the microstructure responsible for the nucleation and subsequent growth of the observed damage.

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 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.

Long-term creep rupture tests up to 10 5 hours at 600℃ and 650℃ were carried out on mod.9Cr- 1Mo steel base metal and weldments from five different materials, consisting of various chemical compositions and heat treatments as well as welding conditions. As a result, positive correlations of creep rupture strength were clarified between the base metal and weldments from the same materials. Microstructural observations and thermokinetic calculations revealed that the strength correlations were attributed to the precipitation strengthening behavior of finely dispersed M 23 C 6 carbides and V-type MX carbonitrides, where their precipitation distribution characteristic in the fine-grained HAZ microstructures partially or almost entirely took over those in base metal. This finding implies that the long-term creep rupture strength of mod.9Cr-1Mo steel weldment might be able to be evaluated as long as the corresponding base metal strength is obtained.

A creep resistant martensitic steel, CPJ7, was developed with an operating temperature approaching 650°C. The design originated from computational modeling for phase stability and precipitate strengthening using fifteen constituent elements. Approximately twenty heats of CPJ7, each weighing ~7 kg, were vacuum induction melted. A computationally optimized heat treatment schedule was developed to homogenize the ingots prior to hot forging and rolling. Overall, wrought and cast versions of CPJ7 present superior creep properties when compared to wrought and cast versions of COST alloys for turbines and wrought and cast versions of P91/92 for boiler applications. For instance, the Larson Miller Parameter curve for CPJ7 at 650°C almost coincides with that of COST E at 620°C. The prolonged creep life was attributed to slowing down the process of the destabilization of the MX and M 23 C 6 precipitates at 650°C. The cast version of CPJ7 also revealed superior mechanical performance, well above commercially available cast 9% Cr martensitic steel or derivatives. The casting process employed slow cooling to simulate the conditions of a thick wall full-size steam turbine casing but utilized a separate homogenization step prior to final normalization and tempering. To advance the development of CPJ7 for commercial applications, a process was used to scale up the production of the alloy using vacuum induction melting (VIM) and electroslag remelting (ESR), and underlined the importance of melt processing control of minor and trace elements in these advanced alloys.

The microstructures of an advanced Ta-added 9Cr-3Co-2W-Mo steel with increased boron content that has been homogenized at different temperatures were investigated. The chains of coarse W-rich particles were observed in the steel after homogenization at 1150°C for 24 h. These particles remained in the microstructure after normalization and tempering. Such additional dispersion hardening in the initial state of the studied steel decreased the creep rate in transient region. However, the duration of steady state creep and overall creep time was increased in the samples homogenized at 1200°C. Despite of the presence of coarse W-rich particles, the impact toughness of the low-temperature- homogenized steel in the tempered condition was significantly higher than that of the steel homogenized at 1200°C

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 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.

9-10%Cr-3%Co martensitic steels are the prospective materials for elements of boilers, tubes and pipes for fossil power plants which are able to work at ultra-supercritical parameters of steam (T=620-650°C, P=25-30 MPa). The effect of creep on the microstructure of the 10 wt.%Cr-3Co- 3W-0.2Re martensitic steel was investigated in the condition of 650°C and an applied stress of 140 MPa, time to rupture was more than 8500 h. Previously, this steel was subjected to the normalizing at 1050°C and tempering at 770°C. This heat treatment provided the hierarchical tempered martensite lath structure with the mean size of prior austenite grains of 59 μm and with high dislocation density (2×10 14 m -2 ) within martensitic laths. Boundary M 23 C 6 and M 6 C carbides and randomly distributed within matrix Nb-rich MX carbonitrides were detected after final heat treatment. The addition of Re in the steel studied positively affected creep at 650°C/140 MPa and stabilized the tempered martensite lath structure formed during 770°C-tempering. The formation of the subgrains in the gage section was accompanied by the coarsening of M 23 C 6 carbides and precipitations of Laves phase with fine sizes during creep. No depletion of Re and Co from the solid solution during creep was revealed whereas W content decreased from 3 to 1 wt.% for first 500 h of creep. Reasons of improved creep as well as mechanisms of grain boundary pinning by precipitates are discussed.

The size and distribution of the Laves phase particles in a 9.85Cr-3Co-3W-0.13Mo-0.17Re- 0.03Ni-0.23V-0.07Nb-0.1C-0.002N-0.008B steel subjected to creep rupture test at 650°C under an applied stresses of 160-200 MPa with a step of 20 MPa were studied. After heat treatment consisting of normalizing of 1050°C and tempering of 770°C, M 23 C 6 and Fe 3 W 3 C carbides with the mean sizes of 67±7 and 40±5 nm, respectively, were revealed along the boundaries of prior austenite grains and martensitic laths whereas round NbX carbonitrides were found within martensitic laths. During creep metastable Fe 3 W 3 C carbides dissolved and the stable Laves phase particles precipitated; volume fraction of Laves phase increases with time. The Laves phase particles nucleated on the interfacial boundaries Fe 3 W 3 C/ferrite during first 100 h of creep and provided effective stabilization of tempered martensitic lath structure until their mean size less than 150 nm.

Modified 9Cr-1Mo steel (ASTM Gr.91) is widely used in components of fossil fueled power plants around the world today. This grade of steel has however been shown to exhibit significant variations in creep life and creep ductility, which has led to premature in-service failures. The aim of this work is to define potential metallurgical risk factors that lead to this variation in performance. To achieve this, a set of creep test samples that represent a wide range in this variation of creep behavior in this steel grade have been studied in detail. As a first stage in this characterization the macro-scale chemical homogeneity of the materials were mapped using micro-XRF. Understanding the segregation behavior also allows quantification of microstructural parameters in both segregated and non-segregated areas enabling the variations to be determined. For example this showed a significant increase in the number per unit area of Laves phase particles in high compared with low Mo content areas. To study the effect of MX particles on segregation a methodology combining SEM and TEM was employed. This involved chemically mapping the larger V containing particles using EDS in the SEM in segregated and unsegregated areas and then comparing the results to site-specific TEM analysis. This analysis showed that although the average size of the V containing samples is in the expected 0-50 nm size range, these particles in some samples had a wide size distribution range, which significantly overlaps with the M 23 C 6 size distribution range. This together with the segregation characteristics has important implications for determining meaningful quantitative microstructural data from these microstructurally complex materials.

For VM12-SHC 11-12 wt. % Cr steel, there have been no systematic investigations to define the regions or characterise the microstructures within the heat-affected zone (HAZ) of weldments. In similar steels, these regions relate to the Ac 1 and Ac 3 transformation temperatures and can affect weldment performance. In this study, controlled thermal cycles were applied to VM12-SHC parent metal using a dilatometer and the Ac 1 and Ac 3 temperatures were measured for various heating rates. The Ae 1 and Ae 3 temperatures were also calculated by thermodynamic equilibrium modeling. Through dilatometry, thermal cycles were then applied to simulate the microstructures of the classically defined HAZ regions. The microstructural properties of each simulated material were investigated using advanced electron microscopy techniques and micro-hardness testing. It was found that the simulated HAZ regions could be classified as; (1) the completely transformed (CT) region, with complete dissolution of pre-existing precipitates and complete reaustenitisation; (2) the partially transformed (PT) region, exhibiting co-existing original martensite with nucleating austenite microstructures with partial dissolution of precipitates; and (3) the over tempered (OT) region, with no phase transformation but precipitate coarsening and decreased hardness.

This study presents a characterization of the microstructural evolutions taking place in a 9%Cr martensitic cast steel subjected to fatigue and creep-fatigue loading. Basis for this study of investigation is an extensive testing program performed on a sample heat of this type of steel by conducting a series of service-like high temperature creep-fatigue tests. The major goal here was to systematically vary specific effects in order to isolate and describe relevant damage contributing mechanisms. Furthermore, some of the tests have been interrupted at several percentages of damage to investigate not only the final microstructure but also their evolution. After performing those tests, the samples were examined using transmission electron microscopy (TEM) to characterize and quantify the microstructural evolutions. The size distribution of subgrains and the dislocation density were determined by using thin metal foils in TEM. A recovery process consisting of the coarsening of the subgrains and a decrease of the dislocation density was observed in different form. This coarsening is heterogeneous and depends on the applied temperature, strain amplitude and hold time. These microstructural observations are consistent with the very fast deterioration of creep properties due to cyclic loading.

The global electric power production is largely dependent on the operation of fossil-fired generation units. Many coal-fired units are exceeding 300,000 hours, which is beyond the expected design life. This has caused a continuous need to inspect steam touched components operating at high temperature and pressure. State-of-the-art coal and combined cycle gas units are specifying ever-greater amounts of the Creep Strength Enhanced Ferritic (CSEF) steels such as Grade 91 or Grade 92. The martensitic 9%Cr CSEF steels were developed to provide greater strength than traditional low alloy power plant steels, such as Grades 11, 12 and 22. The enhanced strength allows for a reduction in overall wall thickness in new or replacement components. Extensive research in both service failures and laboratory testing has shown that time-dependent creep damage can develop differently in Grade 91 steel when compared to low alloy steels. Furthermore, the creep strength in Grade 91 can vary by more than a factor of 10 between different heats. This wide variation of creep strength has led to extensive research in understanding the damage mechanisms and progression of damage in this steel. In this study, large cross weld samples were fabricated from thick wall piping in Grade 91 steel using two different heats of material. One weld was fabricated in a ‘damage tolerant’ heat and another weld was fabricated in a ‘damage intolerant’ heat of material. The samples were subjected to a post-weld heat treatment (PWHT) at a temperature of 745°C (1375°F) for 1.50 hours. Hardness maps were collected on the cross-welds in the as-welded and PWHT condition for both weldments. Cross-weld creep test conditions were selected to develop accelerated damage representative of in-service behavior. The test samples were interrupted at multiple stages and nondestructively evaluated (NDE) with advanced phased-array ultrasonic techniques. Samples were developed to variable levels of damage (50% to 100% life fraction) in both weldments. Metallographic sections were extracted at specific locations to validate the NDE findings using light emitting diode, laser and scanning electron microscopy. This research is being used to help validate the level of damage that can be reliably detected using conventional and advanced NDE techniques.

The effect of boron nitrides (BN) and aluminum nitrides (AlN) on long-term creep life and rupture ductility has been investigated for martensitic 9 to 12Cr steels at 550 to 700 °C. The BN particles form in 9 to 12Cr steels during normalizing heat treatment at 1050 to 1150 °C, suggesting no change in the amount of BN particles during creep. On the other hand, the AlN particles gradually form during creep at 550 to 700 °C, decreasing the concentration of nitrogen free from the AlN particles. The degradation in creep life takes place more significantly with test duration in the steels containing high Al but not in those containing the BN particles. The rupture ductility is evaluated by using a semi-logarithmic diagram of the RA and total elongation, showing the necking dominant and void swelling dominant regions. The BN and AlN particles are responsible for the degradation in RA at low stresses and long times by accelerating the formation of creep voids at interfaces between the BN and AlN particles and alloy matrix.

Extensive research and development has been undertaken in the UK on MarBN steels. These were first proposed by Professor Fujio Abe from NIMS in Japan. Within the UK, progress has been made towards commercialisation of MarBN-type steel through a series of Government funded industrial collaborative projects (IMPACT, IMPEL, INMAP and IMPULSE). As part of the IMPACT project, which was led by Uniper Technologies, boiler tubes were manufactured from the MarBN steel developed within the project, IBN1, and installed on the reheater drums of Units 2 and 3 of Ratcliffe-on-Soar Power Station. The trial tubes were constructed with small sections of Grade 91 tubing on either side of the IBN1 to allow direct comparison after the service exposure. This is the world’s first use of a MarBN steel on a full-scale operational power plant. In September 2018 the first tube was removed having accumulated 11,727 hours operation and 397 starts. This paper reports microstructural and oxidation analysis, that has been undertaken by Loughborough University as part of IMPULSE project, and outlines future work to be carried out.

This work deals with the potential of microstructurally based modeling of the creep deformation of martensitic steels. The motivation for the work stems from the ever increasing demand for higher efficiency and better reliability of modern thermal power plants. Service temperatures of 600°C and stress levels up to 100 MPa are currently the typical requirements on critical components. High creep and oxidation resistance are the main challenges for a lifetime 10+ years in steam atmosphere. New materials may fulfill these requirements; however, the save prediction of the creep resistance is a difficult challenge. The model presented in this work takes into consideration the initial microstructure of the material, its evolution during thermal and mechanical exposure and the link between microstructural evolution and creep deformation rate. The model includes the interaction between the relevant microstructural constituents such as precipitates, grain- lath- and subgrain boundaries and dislocations. In addition, the material damage is included into the model. The applicability of the model is then demonstrated on standard creep resistant alloys. Contrary to phenomenological models, this approach can be tested against microstructural data of creep loaded samples and thus provides higher reliability. Nevertheless, potential improvements are discussed and future developments are outlined.

In response to the strong needs for the life assessment of various components in fossil power plants, studies on Grade 91 and Grade 92 steels have been jointly performed by EPRI and CRIEPI for a last decade. These studies have been covering the effects of load variation (creep- fatigue) and stress multiaxiality as well as the behavior under uniaxial creep conditions. Based on abundant test data accumulated in this period and associated analytical evaluation, approaches based on inelastic strain energy have been developed for accurately assessing creep damage and failure lives under various conditions. The essence of these efforts is presented in this paper.

In this study, creep rupture behaviors and rupture mechanisms of dissimilar welded joint between Inconel 617B and COST E martensitic steel were investigated. Creep tests were conducted at 600 ℃ in the stress range 140-240 MPa. Scanning electron microscopy (SEM) and micro-hardness were used to examine the creep rupture behaviors and microstructure characteristics of the joint. The results indicated that the rupture positions of crept joints shifted as stress changed. At higher stress level, the rupture position was located in the base metal (BM) of COST E martensitic steel with much plastic deformation and necking. At relatively lower stress level, the rupture positions were located in the fine-grained heat affected zone (FGHAZ) of COST E or at the interface between COST E and WM both identified to be brittle fracture. Rupture in the FGHAZ was caused by type Ⅳ crack due to matrix softening and lack of sufficient precipitates pinning at the grain boundaries (GBs). Rupture at the interface was related to oxide notch forming at the interface.

Advanced martensitic 9% chromium steels have been identified as the most favored group of materials for high temperature applications in thermal power plants. To extend the temperature range of martensitic steels up to 650°C large effort was put on the development of new alloy concepts. The so-called MARBN concept (Martensitic steel with defined Boron/Nitrogen relation) provides increased creep rupture strength due to higher solid solution strengthening and improved microstructural stability. The major improvement is the reduction of type IV cracking in welded joints, which shifts the focus to the creep rupture strength of the weld metal. This paper illustrates the process experience of the steel foundry for production of heavy cast components in latest state of the art 9-12%Cr-MoCoVNbNB-alloyed cast steel grades and the newest state of development and prototype components in MARBN cast steel grades. Metallurgy, solidification, heat treatment and welding are main items to be considered for development of new, complex steel grades for foundry processing with the help of empiric processing in test programs and thermo-physical simulation. As welding is an essential processing step in the production of heavy steel cast components a good out-of-position weldability is required. Moreover a stress-relieve heat-treatment takes place subsequently after welding for several hours. This contribution also deals with the development of matching welding consumables for the production of heavy cast components and discusses the challenges of defining appropriate welding and heat treatment parameters to meet the requirements of sufficient strength and toughness at ambient temperature. Additionally, first results of creep rupture tests are presented.