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    18. ‐ 20. 5.

 2010, Rožnov pod Radhoštěm, Česká Republika 

, Vít JAN

VUT, FSI, UMVI, Technická 2896/2, 616 69 Brno, Česká republika,
The paper presents results of study of structural stability of creep-resistant steels P24, P22, P91 and their
weld joints P24/P22 and P22/P91. The microstructural changes during annealing at temperatures of 500–
900°C and 16–1000 hours were examined. During high temperature exposure, carbon diffuses in the
direction of its chemical potential gradient and carbon enriched and carbon depleted zones are formed in the
weld interface area. In the case of P24/P22 joint, the P22 steel is carburised, in case of P22/P91 joint, P91
steel is carburised. Redistribution of carbon causes changes of mechanical properties in the weld interface
area through changes of phase composition. Calculations of phase diagrams shape, phases composition,
weight and volume fractions of minor phases and temperature dependence of carbon activity were
performed using the Thermo-Calc software. The DICTRA software was used for simulations of diffusion
redistribution of carbon across the welds. These calculations were used for theoretical predictions of
expectable behaviour of investigated materials and welds during their long time high temperature
exploitation. These were consequently verified by structural and phase analysis of investigated samples. The
computed results were compared with published data with satisfactory agreement.
Keywords: Microstructural stability, creep-resistant steel, weld joint, Thermo-Calc
At present time, large number of power generating facilities undergo reconstruction and refitting. The most
widely used materials in these applications are creep-resistant steels which are often connected by dissimilar
weld joints. Generally, the necessary high creep-strength of these materials and their joints is ensured by
microstructural stability.
In this work a microstructural stability of creep-resistant steels P24, P22, P91 and their dissimilar welds is
examined. As a suitable tool for evaluation of microstructural stability, computational modelling of phase
composition at thermodynamical equilibrium was selected. This modelling approach forms nowadays one of
the standard tools of material designing process. The Thermo-Calc software, which uses the CALPHAD
method [1], [2] presents a generally accepted standard software used for computational phase equilibria
determination. By use of the add-on package DICTRA [3], it is possible to simulate diffusion and its effects
on chemical and phase composition. Thermodynamic database STEEL12 [4] and kinetic database Dif were
used in the calculations.
P24, P22 and P91 steels of standard purity were used as experimental material. The chemical composition
of the used steels is in Table 1. The steels were supplied in heat-treated state. Cylindrical samples with one
polished basis were machined out of the materials. The samples were resistance-welded to form the
experimental welds of P24/P22 and P22/P91. These were subsequently annealed in evacuated glass
capsules at temperatures 500 – 900°C, for 16 – 1000 hours (see Table 2). After annealing the samples were
rapidly cooled down in water. Samples were cut up from the heat treated samples perpendicularly to the
    18. ‐ 20. 5. 2010, Rožnov pod Radhoštěm, Česká Republika 

weld interface. Metalographical evaluation of microstructure, microhardness measurements and chemical
analyses were performed on the samples across the weld interface.
Table 1 Chemical composition of the used steels

Table 2 Annealing conditions of the experimental joints
Sample joint type annealing conditions Sample joint type annealing conditions
1 P22/P91 900°C/16h 6 P24/P22 900°C/16h
2 P22/P91 625°C/160h 7 P24/P22 625°C/160h
3 P22/P91 575°C/320h 8 P24/P22 575°C/320h
4 P22/P91 500°C/1000h 9 P24/P22 500°C/1000h
The microstructure of samples was evaluated by means of light and SEM microscopy. The carbon
concentration profiles perpendicularly to the weld interface were measured using WDX method on samples
“3” and ”6”.
3.1 Phase diagram calculations of the base materials
The P24 steel
The P24 steel is a low alloyed
steel with chemical composition
0,5Cr-0,5Mo-0,25V. The phase
diagram of the steel calculated
in Thermo-Calc is in the Fig. 1.
According to the phase diagram,
MC carbines are stable in matrix
up to 900°C. The M
C carbides
are stable up to 680°C; up to
730°C a small amount of M

carbide is present in the matrix.
The matrix of the microstructure
of the experimental samples consisted of ferrite and bainite mixture. The largest fraction of minor phases
was found in samples annealed at 500°C. Very fine particles dispersed on grain boundaries were observed
and more particles in clusters inside grains were observed. With increasing temperature the amount of
observed particles decreased and their inter-particle distance increased. A small amount of fine particles was
found in the microstructure undissolved also in samples annealed at 900°C (MC carbides).

Fig. 1. Phase diagram and weigth fraction of minor phases for steel P24
(Thermo-Calc calculation)
    18. ‐ 20. 5. 2010, Rožnov pod Radhoštěm, Česká Republika 

The P22 steel
The P22 steel is a low
alloyed steel of the 2,25Cr-
1Mo type. Fig. 2 shows the
phase diagram of the steel
calculated in Thermo-Calc.
According to the calculated
diagram, the M
carbide is
the main minority phase in
this material. At 520°C the
molybdenum rich M
carbide starts to precipitate
and is stable to 720°C. At
the usual operating
temperatures of 550°C the undesirable Laves phase is also stable.
The microstructure of all the samples was formed by bainitic matrix. The highest fraction of minority phases
was found at the 500°C temperature. The volume of the minority phases decreased with increasing
temperature of annealing. Particles on grain boundaries were found stable up to higher temperatures. At
625°C the matrix was partially recrystallized.
The P91 steel
The P91 steel belongs in the
group of 9-12%Cr steels and
it is regarded as a distinctive
step in creep resistant steels
development [5]. According to
computed diagrams in Fig. 3,
the material is hardened by
carbides and MX
carbonitrides which are
present in the martensitic
matrix. Up to 620°C the Laves
phase is also stable. The
calculations predicted also the
presence of nitridic Z-phase instead MX carbonitrides. According to previously published results [6], the
Z-phase is thermodynamically more stable than MX carbonitrides at temperature around 800°C. Precipitation
of this phase starts in the steel P91 at 650°C after 10 000 hours [6] and generally is regarded to cause a loss
of creep strength. The presented calculated phase diagram is consistent with phase state of the material in
the beginning of the operation time.
The microstructure of all samples of the P91 steel had fine-grained martensitic matrix. The highest fraction of
the minor phases was found at 500°C. Very fine particles were dispersed in the matrix. The particles on the
grain boundaries formed almost a continuous network. Particle size and interparticle distance grew at 575
and 625°C. A small amount of undissolved precipitates was kept even at 900°C.

Fig. 2. Phase diagram and weigth fraction of minor phases for steel P22
(Thermo-Calc calculation)

Fig. 3. Phase diagram and weigth fraction of minor phases for steel P91
(Thermo-Calc calculation)
    18. ‐ 20. 5. 2010, Rožnov pod Radhoštěm, Česká Republika 

3.2 The weld joints
Considering the high values of carbon mobility at the usual operating temperatures of creep resistant steels
(500 – 700°C); carbon redistribution can be expected during high-temperature exposure of heterogeneous
welds of the materials in question. Carbon will diffuse in the direction of its thermodynamical activity gradient
- disregarding the direction of the concentration gradient - and carbon enriched (CEZ) and carbon depleted
zones (CDZ) will be formed in the weld interface area [7]. The temperature dependences of carbon
thermodynamical activity of used steels calculated in Thermo-Calc were used for the formulation of basic
expectations on the high temperature behaviour of the investigated steels (Fig. 4). Simulations of the
diffusional processes were performed in DICTRA module afterwards.
Fig. 4. Temperature dependence of carbon activity of the investigated steels (Thermo-Calc calculation)

The P24/P22 joint
Higher carbon activity in the P24 steel compared to steel P22 can be derived from the computed
dependences of carbon activity on temperature (Fig. 4.). Diffusion of carbon from the P24 steel to the P22
steel causes formation of CDZ and CEZ by which the joint can be gradually weakened. This presumption
was confirmed by simulation in DICTRA software and by examination of the annealed samples.
Changes of microstructure were found at 575 and 500°C. At 575°C (sample 8) the precipitates partly
dissolved on the side of P24 and the amount of precipitates was increased on the site of P22. Maximum
value of carbon concentration profile measured in the CEZ in P22 steel was 0,15 mass %. This
concentration declined steeply with the distance from weld interface and at 200 μm from weld interface,
original concentration of carbon was measured again. The P24 half of the joint was partially recrystallised
and intensive precipitation occurred in the steel P22 in 10 μm thick zone from the interface.
The average decrease of hardness in CDZ of P24 steel was 15 – 30 HV 0,1, growth of hardness in CEZ of
P22 steel were 20 – 35 HV 0,1, 60 HV 0,1 in case of sample “9”.
The P22/P91 joint
The carbon activity values in the P22 steel are two orders of magnitude higher when compared to the P91
steel (Fig. 4.). Therefore strong redistribution of carbon by diffusion at elevated temperatures can be
expected. Also distinctive zones of changed microstructure are formed (CEZ and CDZ). Again, this was
confirmed by combination of DICTRA simulations and experimental evaluation of the samples.
The highest gradient of carbon activity across the weld interface correspons to temperature of 575°C
(sample 3). Considerable carbon redistribution was also well observed on samples annealed at 625°C. In
these cases, almost complete decarburisation of the P22 steel was measured in a zone 140 μm wide from
P22 P24
    18. ‐ 20. 5. 2010, Rožnov pod Radhoštěm, Česká Republika 

Fig. 7. Microhardness values profile across weld
interface of P22/P91 joint
the weld interface. Simultaneously, the P91 steel was carburised in the width of 140 μm from interface. The
changes were very distinctive even after relatively short time of annealing, which in this case was 320 hours.
The maximum concentration of carbon measured in the CEZ was 0,91 mass % (Fig. 5.).
The carbon redistribution was followed by
microhardness changes in the vicinity of the weld. The decarburizing of P22 steel led in all cases to
dissolution of carbides, hence lower dispersion hardening of the matrix. Dissolution of carbides in P22 also
enabled grain coarsening at 575°C and at 625°C re-crystallisation of main part of the bainitic ferrite. These
microstructural changes had direct effect on the reduction of hardness in CDZ (by 30 – 50 HV 0,1). The
fraction of carbidic phases increased dramatically in the P91 steel as result of carburizing. At 625°C the
carbides underwent marked coarsening, whereas at 575°C stayed the particles size remained small and the
carbides were finely dispersed in the matrix. The coarsening of the carbidic particles strongly suppresses the
effect of dispersion strengthening, thus no intensive increase of hardness was measured at 625°C in the
CEZ, even though considerable carburising was identified. On the other hand at temperature 575°C, where
the carbides did not coarsen, the hardness was increased due to carburizing for 60 HV 0,1 in CEZ (Fig. 7.).
The values of chemical profiles of carbon
content across the weld interface measured by
WDX corresponded to calculations results from
DICTRA software and also compared to
previous published results [8 – 11] with good
agreement. One exception in this is the
comparison of calculated chemical composition
of MX phases compared to published data. MX
composition show inaccuracies larger than the
measurement error usually is [12],[13]. The
reason lies within the fact that MX carbo-
nitrides do not have stoichiometric composition,
since they contain a large amount of vacancies
[14]. The proportion of metallic elements to
carbon and nitrogen can be larger than
expected for that reason.
Fig. 5. Carbon redistribution in the P22/P91 weld
joint after annealing 575°C/320h.
P22 P91
Fig. 6. Weld interface in P22/P91 joint after
annealing 575°C/320h.
    18. ‐ 20. 5. 2010, Rožnov pod Radhoštěm, Česká Republika 

The dissimilar weld joints P24/P22 and P22/P91 are unstable at temperature 500 – 900°C from
microstructural point of view. During their high-temperature long-term exposition, carbon diffuses in the
direction of its chemical potential gradient and CDZ and CEZ are formed in the weld interface area (usually
"up hill" diffusion occurs). The steel with larger Cr amount is carburised. Microstructural instability of the
examined joints reaches a critical point at temperatures near 575°C, when mechanical properties of the
materials forming the weld joints are significantly degraded.
This work was supported by GP106/07/P198 funded by GAČR and FSI-J-10-51 funded by FSI VUT
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