Hilmar Kjartansson Danielsen

Behaviour of Z phase in 9–12%Cr steels

Abstract The literature on the behaviour of modified Z phase Cr(V,Nb)N in creep resistant martensitic 9–12%Cr steels is briefly reviewed. Ten different 9–12%Cr steels were investigated after prolonged exposure at 600–660°C; the modified Z phase was found in all of them. In steels with high Cr content (11–12%), Z phase precipitates much faster than in 9%Cr steels. Precipitation of Z phase is associated with dissolution of MX carbonitrides, and causes a breakdown in long term creep strength in 9–12%Cr steels. High Cr steels show creep instabilities accompanied with Z phase precipitation, whereas low Cr steels show good long term creep stability. A niobium free CrVN variant of the modified Z phase was observed for the first time during the course of this work. The solution temperature of the Cr(V,Nb)N and CrVN modified Z phases was found to be close to 800°C for 11–12%Cr steels, much lower than the 1200–1250°C solution temperature of the unmodified CrNbN Z phase. Above the solution temperature the modified Z phase is replaced by MX particles.

On the crystal structure of Z-phase Cr(V,Nb)N

TheZ-phase Cr(V,Nb)N particles in various 9 to 12 pct Cr creep-resistant steels were investigated with electron diffraction, energy dispersive spectroscopy (EDS), and electron energy loss spectroscopy (EELS). In addition to the well-known tetragonal crystal structure forZ phase, a cubic crystal structure was identified for Cr(V,Nb)N and CrVN particles, but not for CrNbN. The tetragonal and cubic crystal structures were observed to coexist within the same particles, and the orientation relationship between the two lattices was determined. Understanding and controlling the nucleation of Cr(V,Nb)N particles could be of crucial importance to enable improvement of the long-term creep stability of 9 to 12 pct Cr martensitic steels.

Thermodynamic and kinetic modelling: creep resistant materials

Abstract The use of thermodynamic and kinetic modelling of microstructure evolution in materials exposed to high temperatures in power plants is demonstrated with two examples. Precipitate stability in martensitic 9–12%Cr steels is modelled including equilibrium phase stability, growth of Laves phase particles and coarsening of MX, M23C6 and Laves phase particles. The modelling provided new insight into the long term stability of new steels. Modelling of the detrimental precipitation of Z phase Cr(V,Nb)N is described, which points to new approaches in alloy development for higher temperatures. Predictions of interdiffusion between a MCrAlY coating and an IN738 bulk alloy by multicomponent diffusion calculations provide a highly versatile tool for life assessment of service exposed gas turbine components as well as for the development of improved coatings.

Review of Z phase precipitation in 9–12 wt-%Cr steels

For high temperature applications, 9–12 wt-%Cr steels in fossil fired power plants rely upon precipitate strengthening from (V,Nb)N MX nitrides for long term creep strength. During prolonged exposure at service temperature, another nitride precipitates: Cr(V,Nb)N Z phase. The Z phases lowly replace MX, eventually causing a breakdown in creep strength. The present paper reviews the Z phase and its behaviour in 9–12 wt-%Cr steels including thermodynamic modelling, crystal structure, nucleation process and precipitation rate as a function of chemical composition. The influence of Z phase precipitation upon long term creep strength is assessed from several different 9–12wt-%Cr steel grades and alloy design philosophies.

New amorphous interface for precipitate nitrides in steel

According to classical theories precipitate interfaces are described by their degree of coherency with the matrix, which affects their strengthening contribution. Investigations of nitride precipitate interfaces in 12% Cr steels with transmission electron microscopy have shown the nitrides to be enveloped in an amorphous shell a few nm thick, thus leaving them without any coherency with the matrix. The amorphous nature of the shells could be ascertained with high resolution microscopy and dark field techniques. When extracted from the ferrite matrix the amorphous shells were observed to crystallize during electron beam exposure. The amorphous shells were observed around Ta- and Nb-based nitrides, which are considered to have a high interfacial energy with the ferrite matrix. They were not observed around V-based nitrides which have a Baker–Nutting relationship with low-misfit to the matrix.

Role of copper on Laves phase morphology in 9-12%Cr steels

In this work the Laves phase was found to appear in two different morphologies, namely granular shapes and in an elongated shape. No difference in crystallography could be detected between these morphologies. The Laves phase was only observed in its elongated form in Cu-containing steels, where it was the primary morphology present after short term ageing. After long term ageing, the elongated Laves phase was replaced by the granular morphology. It is speculated that Cu precipitates act as nucleation sites for the elongated Laves phase, resulting in an unstable orientation relationship with the matrix, an in the meta-stable elongated morphology of Laves phase precipitates.

Analysis of bearing steel exposed to rolling contact fatigue

The objective of this work is to characterize fatigue damage in roller bearings under conditions of high load and slippage. A test rig constructed for rolling contact fatigue tests of rings is described, and test results are presented for rings taken from two spherical roller bearings. The preparation of the rings and the loading situation are explained. Test conditions are chosen with the aim of achieving pitting formation at the contacting surfaces. During testing the contact pressure, torque and the rotational speed are monitored and recorded. After testing the tested rings have been characterized using X-ray tomography and scanning electron microscopy. The observations confirm that rolling contact fatigue testing at high loads leads to pitting failure at the contacting surfaces. The pitting mostly appears on one side of the contact, attributed to a nonuniform contact pressure in the axial direction.

Synchrotron X-ray measurement of residual strain within the nose of a worn manganese steel railway crossing

Switches and crossings are an integral part of any railway network. Plastic deformation associated with wear and rolling contact fatigue due to repeated passage of trains cause severe damage leading to the formation of surface and sub-surface cracks which ultimately may result in rail failure. Knowledge of the internal stress distribution adds to the understanding of crack propagation and may thus help to prevent catastrophic rail failures. In this work, the residual strains inside the bulk of a damaged nose of a manganese railway crossing that was in service for five years has been investigated by using differential aperture synchrotron X-ray diffraction. The main purpose of this paper is to describe how this method allows non-destructive measurement of residual strains in selected local volumes in the bulk of the rail. Measurements were conducted on the transverse surface at a position about 6.5 mm from the rail running surface of a crossing nose. The results revealed the presence of significant compressive residual strains along the running direction of the rail.

Atomic Resolution Microscopy of Nitrides in Steel

MN and CrMN type nitride precipitates in 12%Cr steels have been investigated using atomic resolution microscopy. The MN type nitrides were observed to transform into CrMN both by composition and crystallography as Cr diffuses from the matrix into the MN precipitates. Thus a change from one precipitate type to another does not necessarily involve nucleation of the new precipitate type followed by dissolution of the old precipitates. By studying the interface between these nitrides and the matrix, it could be observed that the MN and CrMN type precipitates had a few nanometers thick amorphous layer between the crystalline nitride and ferrite matrix. Usually precipitates are described as having (semi) coherent or incoherent interfaces, but in this case it is more energetically favourable to create an amorphous layer instead of the incoherent interface.

Atomic Resolution Investigations of Phase Transformation from TaN to CrTaN in a Steel Matrix

In development of 12%Cr high temperature steels used for fossil fired power plants, the precipitation of large Z-phase particles, CrMN, has been identified as a major problem since they replace small and finely distributed MN particles. This causes a premature breakdown in the long-term creep strength of the steel. The Cr content promotes Z-phase precipitation, making MN strengthening of these materials unfeasible, since 12%Cr is necessary for oxidation resistance. The authors have suggested an acceleration of Z-phase precipitation to obtain a fine and stable distribution of CrMN instead of MN, thus preserving long-term creep strength. This can be done by alloying with Ta instead of Nb and V. Recent investigations have indicated a direct transformation of MN into CrMN to take place, not the traditional nucleation/dissolution process. In this paper atomic resolution microscopy shows how Cr atoms diffuse from the steel matrix into TaN precipitates and physically transform them into CrTaN. The crystal structure of the precipitates changes from that of a typical MN NaCl type crystal structure to a Z-phase crystal structure with alternating double layers of Cr and TaN. Since there is a large contrast between heavy Ta atoms and light Cr atoms, the ordering of the Cr layers inside the TaN particles can clearly be observed.