Journal of Materials Research and Technology 33 (2024) 5075–5087

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Journal of Materials Research and Technology

journal homepage: www.elsevier.com/locate/jmrt

Ultra-fine grained EUROFER97 steel for nuclear fusion applications

Giulia Stornelli a,* , Andrea Di Schino a , Roberto Montanari b , Mirko Sgambetterra c ,
Claudio Testani d , Alessandra Varone b
a
Engineering Department, University of Perugia, Via G. Duranti 93, 06125 Perugia, Italy
b
Industrial Engineering Department, University of Rome Tor Vergata, Via del Politecnico 1, 00133, Rome, Italy
c
Aeronautical and Space Test Division, Italian Air Force, Via Pratica di Mare 45, 00040, Pomezia, Italy
d
CALEF-ENEA CR-Casaccia, Via Anguillarese 301, S. Maria di Galeria, 00123, Rome, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: EUROFER97 is the european Reduced Activation Ferritic-Martensitic (RAFM) steel, candidate to be used as a
EUROFER97 structural material in fusion energy systems. One of its operational limits is due to the excessive ductility loss
RAFM steels following neutron irradiation below 350 ◦ C. To overcome this drawback, a Thermo-Mechanical Treatment (TMT)
Thermo-mechanical treatments
has been developed for improving mechanical properties through microstructure refinement without ductility
Microstructure
Recrystallization
loss. It consists in cold rolling followed by heat treatment of EUROFER97 steel plates preliminary subjected to the
Mechanical properties standard process. The combination of five cold rolling (CR) ratios (20 %, 40 %, 50 %, 60 %, 80 %) and eight
Strengthening mechanism treatment temperatures in the range 400–750 ◦ C (steps of 50 ◦ C) with a soaking time of 1 h has been considered.
The samples were investigated through microstructural examinations and mechanical tests (hardness and tensile
tests). After heat treatments, recrystallization takes place for each CR ratio with different kinetics depending on
both treatment temperature and CR ratio. The results show that the TMT corresponding to cold rolling with CR of
80 % and treatment at 650 ◦ C leads to a remarkable improvement of mechanical properties: in comparison to
standard EUROFER97 Yield Stress (YS) increases of ~18 %, Ultimate Tensile Strength (UTS) of ~5 % while the
uniform elongation (AU) is more than double. The excellent characteristics, promising for nuclear fusion ap-
plications, are related to the ultra-fine size of grains, their equiaxed shape, the prevalence of High Angle Grain
Boundaries (HAGBs) and the fine dispersion of carbides.

1. Introduction min [18]. The final microstructure consists of tempered lath martensite.
Henceforth, this treatment condition will be referred as “standard’’ in
Reduced Activation Ferritic-Martensitic (RAFM) steels are materials comparison to the variants tested during present research activity.
of great interest for manufacturing high-loaded components in the In DEMO reactor the foreseen operating temperature range is be-
future nuclear fusion reactor DEMO [1–5] and, in recent years, a lot of tween 280–300 ◦ C and 600–650 ◦ C [19]. Recently, results about the
achievements have been made on the microstructural tailoring of these microstructural evolution of EUROFER97 after exposure at temperature
materials (e.g., see Refs. [6,7]). EUROFER97 is the european reference ranging from 450 ◦ C to 650 ◦ C for up to 122.000 h have been published
RAFM steel. Its chemical composition was developed to simplify the by Klimenkov et al. [20]. Since this steel exhibits good resistance under
storage of radioactive waste after the service life of reactor [8,9] by irradiation between 350 ◦ C and 550 ◦ C [21–23], many efforts have been
keeping the concentration of radiologically undesired impurity elements devoted to extend this temperature range.
in the appm range [10]. Elements with long decay times such as Ni, Mo The upper limit can be increased up to 650 ◦ C through Oxide
and Nb, commonly present in commercial Cr–Mo ferritic-martensitic Dispersion Strengthening (ODS), namely by adding nanometric Y2O3
steels [11–13], were replaced with W, Ta and small amounts of V [3, particles which inhibit grain boundary sliding at high temperature [21,
14–17]. EUROFER97 steel plates (14 mm thick) are usually produced 24,25].
through hot-rolling followed by a heat treatment consisting of austeni- The reduction of the lower limit depends on several factors including
tization at 980 ◦ C for 30 min, air-cooling, and tempering at 760 ◦ C for 90 embrittlement, ductility loss and shift of Ductile to Brittle Transition

* Corresponding author.
E-mail addresses: [email protected] (G. Stornelli), [email protected] (A. Di Schino), [email protected] (R. Montanari), mirko.
[email protected] (M. Sgambetterra), [email protected] (C. Testani), [email protected] (A. Varone).

https://doi.org/10.1016/j.jmrt.2024.10.069
Received 19 July 2024; Received in revised form 4 October 2024; Accepted 8 October 2024
Available online 10 October 2024
2238-7854/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Temperature (DBTT) towards higher temperature [26,27]. Owing to Table 2

irradiation damage induced by energetic neutrons, the material un- Thermo-mechanical treatments performed on standard EUROFER97 steel.
dergoes ductility loss and hardness increase [11]; microstructural fea- CR ratio Heat treatment temperature
tures that can affect the process are the clustering of Cr atoms in original (%)
T1 T2 T3 T4 T5 T6 T7 T8
steel [28–31] and He production [32]. (◦ C) (◦ C) (◦ C) (◦ C) (◦ C) (◦ C) (◦ C) (◦ C)
To overcome this problem different types of micro-alloying have
20 400 450 500 550 600 650 700 750
been explored with encouraging results (e.g., see Refs. [33,34]). To date, 40 400 450 500 550 600 650 700 750
grain refinement of EUROFER97 steel represents a valid strategy: a fine 50 400 450 500 550 600 650 700 750
microstructure provides multiple advantages in nuclear applications 60 400 450 500 550 600 650 700 750
[35,36] including the possibility to lower the DBTT without reducing the 80 400 450 500 550 600 650 700 750
mechanical performances [37,38]. In addition, the presence of larger Soaking time of 1 h, in Ar atmosphere.
grain boundary surfaces promotes higher radiation resistance and re-
duces He susceptibility. Indeed, grain boundaries act as sinks for point After mechanical polishing and etching (Vilella reagent for 20 s) of
defects (Frenkel pairs) and He atoms produced by neutron radiation, the surface, the microstructure of the samples was investigated through
ensuring less clustering of defects [39]. FEG-SEM and LM observations. To assess if segregation phenomena
The effect of various Thermo-Mechanical Treatments (TMTs) on the occur in different stages of TMTs the samples were examined by energy
microstructural evolution of ferritic/martensitic steels has been exten- dispersive spectroscopy (EDS - X-Maz, 51-XMX1004, Oxford In-
sively investigated (e.g. Refs. [40–42]) and different approaches for struments, Abingdon, United Kingdom).
grain refinement of EUROFER97 can be found in literature [18,40, XRD patterns were collected in the 2 θ angular range 15–60◦ by using
42–44]. Pilloni et al. [41] and Karthikeyan et al. [45] showed that a the Mo-Kα radiation (λ = 0.070926 nm) with 2 θ steps of 0.05◦ and
double austenitization treatment refines the prior austenitic grain (PAG) counting time for step of 2 s. The comparison between the relative in-
and increases toughness. Eddahbi et al. [46] studied the microstructure tensities of the peaks in each pattern and those reported in the database
refinement of EUROFER97 by means of Equal Channel Angular Pressing JCPDS - file 6-696 [49] of Fe with randomly oriented grains allowed to
(ECAP): after two ECAP passes at 550 ◦ C, a fine microstructure is ach- evaluate the presence of preferred grain orientations. The dislocation
ieved with significant increase of mechanical resistance and still satis- density ρ was determined from the broadening of XRD peak profiles
factory ductility. High-Pressure Torsion testing (HPT) was also used by recorded with 2 θ steps of 0.005◦ and counting time for step of 10 s.
Song et al. [47] but, after irradiation, minor microstructural changes Experimental peak profiles were subtracted from background and fitted
were observed compared to the not deformed material. by Lorentzian curves to eliminate the Kα2 component. The Full Width at
The scope of present work was the development of a TMT suitable to Half Maximum (FWHM) was then corrected from the instrumental
improve the mechanical properties of EUROFER97 without inducing broadening to determine the total broadening (βT ). It is the sum of two
ductility loss. The proposed process consists in cold rolling and subse- contributions, βD due to the size D of coherently diffracting domains and
quent heat treatment leading to a fully recrystallized structure of ultra- βε due to micro-strains ε mainly depending on dislocations:
fine grains. This specific approach (cold rolling + heat treatment) has
been previously proposed by other investigators [41–44], however a 0.89 • λ
βT = βD + βε = + 2 • ε • tan θ (1)
systematic investigation of different TMT parameter combinations is still D • cos θ
lacking. By combining five cold rolling reduction ratios (CR) and eight
where θ is the Bragg’s angle of the XRD peak. The two contributions, βD
treatment temperatures, 40 different TMT conditions were examined to
and βε , were calculated through the Cauchy procedure [50] and from ε
find the optimal condition.
value the dislocation density ρ has been then calculated through the
Williamson-Smallman relationship [51]:
2. Materials and methods
Ξ⋅ε2
ρ= (2)
The nominal chemical composition of EUROFER97 steel (batch 2) is F • b2
reported in Table 1 [1].
A plate of EUROFER97 steel subjected to the standard treatment was In Eq. (2) Ξ = 16.1 is a constant, F ≈ 1 a factor depending on the
cut in six parts. One part was kept as the reference material (standard interaction of dislocations and b = 0.248 nm the modulus of Burgers
EUROFER97) while the other five parts were cold rolled with cold vector.
reduction (CR) ratios of 20, 40, 50, 60 and 80 %. From each of them Electron Back Scattered Diffraction (EBSD) measurements were
eight groups of samples were obtained, heat treated at temperatures performed by means of a FEG-SEM (Ultra-Plus Carl-Zeiss-Oberkochen
from 400 ◦ C to 750 ◦ C (steps of 50 ◦ C), for 1 h in Ar atmosphere, and Germany) equipped with an EBSD detector (C Nano Oxford In-
finally cooled in air. By combining CR ratio and treatment temperature, struments), using a 0.02 μm scanning step size. To determine the
40 different TMT conditions were analyzed (see Table 2). The treatment average grain size, the distribution of grain size, High Angle Grain
temperatures were chosen to operate in the ferritic field [48]. Boundaries (HAGBs), Low Angle Grain Boundaries (LAGBs) and Kernel
The microstructure of the treated samples was examined by high- Average Misorientation (KAM), the image analysis was performed on
resolution field emission gun scanning electron microscopy (FEG-SEM EBSD maps by using a dedicated software (AlexaSoft X-Plus, serial
- Zeiss, Gemini Supra 25, Jena, Germany), light microscopy (LM - Union number: 6308919690486393, Florence, Italy).
Optical Co., Ltd., Tokyo, Japan) and X-ray diffraction (XRD - PW 1729, The mechanical properties were investigated through Vickers hard-
Philips, Eindhoven, The Netherlands). ness and tensile tests. Vickers hardness tests were carried out by means
of a durometer (HV50, REMET, Bologna, Italy) by using a load of 5 kg,
according to ASTM 384 standard. Ten hardness tests were repeated on
Table 1 each sample in the central zone of the longitudinal cross-section.
Nominal chemical composition of EUROFER97 steel (wt. %) (Fe to balance). On the basis of hardness results, tensile tests were performed on
Cr C Mn V W Ta Ti N EUROFER97 steel treated under the conditions considered most rele-
8.93 0.12 0.47 0.20 1.07 0.14 0.009 0.018
vant. The tests were performed on flat samples at room temperature and
with a strain rate of 10− 3 s− 1. The samples were machined along the
P S B Si Nb Mo Ni Cu
transverse cold rolling direction and tested according to ASTM E8
<0.005 0.004 <0.001 0.006 0.002 0.0015 0.002 0.003 standard by using a servo-mechanical tensile machine (MD 100, MAYES,

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Fig. 1. SEM micrographs of standard EUROFER97 steel (a–b). The carbides indicated in (b) have been analyzed by EDS (Table 3).

Table 3
Composition (wt.%) of carbides indicated in Fig. 1 (b) determined by EDS.
Point Fe C Cr W Mn Ta V

A 76.9 ± 0.2 5.7 ± 0.2 13.5 ± 0.1 2.4 ± 0.1 0.6 ± 0.1 0.4 ± 0.1 0.5 ± 0.1
B 75.6 ± 0.2 3.6 ± 0.2 15.3 ± 0.1 3.8 ± 0.1 0.6 ± 0.1 0.4 ± 0.1 0.7 ± 0.1
C 77.2 ± 0.2 3.7 ± 0.2 15.5 ± 0.1 1.6 ± 0.1 0.4 ± 0.1 1.1 ± 0.1 0.5 ± 0.1
D 81.7 ± 0.2 3.2 ± 0.2 9.5 ± 0.1 1.4 ± 0.1 0.6 ± 0.1 1.7 ± 0.1 1.9 ± 0.1
E 74.9 ± 0.2 4.7 ± 0.2 9.3 ± 0.1 1.6 ± 0.1 0.5 ± 0.1 6.1 ± 0.1 2.9 ± 0.1

China). Three tests were carried out for each TMT condition and the The carbo-nitrides of Ta and V, finely dispersed inside the lath structure
obtained curves showed high reproducibility. Data from mechanical [18,53,56], pin dislocations retarding their annihilation at high tem-
tests were compared with those of the standard EUROFER97 steel to perature [18,57].
assess the effectiveness of the different treatments. An EBSD orientation map, acquired on the cross-section longitudinal
to the hot rolling direction is displayed in Fig. 2. The Inverse Pole Fig-
3. Results ures (IPF) of the same map are shown in Fig. 3. The map describes, for
each scanned pixel (spot size), the orientations of the crystallographic
The results of microstructural examinations and mechanical tests directions with respect to the rolling direction; in this representation at
made on the standard, cold rolled and heat treated EUROFER97 steel are each pixel is attributed a color depending on the crystallographic di-
reported in the following three sections. rection. Standard EUROFER97 steel exhibits a nearly random grain
orientation, as shown from the variety of colors in the map of Fig. 2 and
3.1. Standard EUROFER97 steel the predominant green shading in Fig. 3. The green color, corresponding
to 1 on the graduate scale on the right side of Fig. 3, indicates a random
The microstructure of EUROFER97 plate in standard conditions is orientation, therefore along the hot rolling direction (X), there is a weak
shown in Fig. 1 (a). It consists of tempered martensite with carbides [101] preferred grain orientation approximately 1.2 times higher than
decorating the Prior Austenitic Grains (PAGs) and laths. Fig. 1 (b) shows the random one. On the other hand, along the directions orthogonal to
at higher magnification carbides of different size and morphology. EDS the rolling direction (Y and Z), there is a slight prevalence of the [111]
analyses of some of them (Table 3) show that carbides rich of Cr (A-B-C) orientation. The distribution of grain misorientation angles, referred to
are aligned along PAGs while those with greater content of V and Ta are the map in Fig. 2, is shown in Fig. 4. The distribution shows three
of smaller size (D-E) and dispersed in the matrix. These results are in distinct peaks at ∿ 6◦ , ∿ 54◦ , and ∿ 60◦ . This result, already reported in
substantial agreement with literature data (e.g., see Refs. [10,52]). The literature for tempered martensite [58], indicates that the misorienta-
M23C6 (M = Fe, Cr, W) carbides, aligned along the boundaries of PAGs, tion is 6◦ in the packets forming the blocks while the misorientation
packets and laths of martensite [52–54], stabilize the microstructure in angles between adjacent blocks are 54◦ and 60◦ .
order to guarantee an increased creep strength at high temperature [55]. The dislocation density ρ obtained by XRD measurement and

Fig. 2. Schematic view of the area on the steel plate analyzed by EBSD (a). EBSD orientation map of standard EUROFER97 steel (b).

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Fig. 3. IPF of standard EUROFER97 steel from EBSD measurements.

strengthening: the hardness of standard EUROFER97 (201.6 ± 1.9 HV5)

progressively increases with CR ratio, up to about 298.9 ± 1.1 HV5 in
the case of CR: 80 %.
Moreover, the analysis of the relative intensities of XRD peaks
(Table 4) showed that the nearly random texture with the presence of a
weak [110] component of original material evolves towards a cubic
[100] texture with a secondary [211] component for the highest CR
ratio (80 %).

3.3. Heat treated EUROFER97 steel

SEM observations showed that heat treatments induce recrystalli-

zation in all the cold rolled samples and the typical elongated grain
structure is progressively replaced by equiaxed grains. For example,
Fig. 7 compares the structure of the material cold rolled with CR ratio of
40 % before (a) and after the heat treatment at 700 ◦ C (b). EDS analyses
do not show significant composition variations: data collected on both
the cold rolled and heat treated samples are close to the nominal element
concentration of EUROFER97.
Of course, the fraction of new recrystallized grains depends on the
Fig. 4. Distribution of grain misorientation angles of standard EUROFER97 treatment temperature and original deformation state of the samples
steel determined through EBSD. (CR ratio). As shown by hardness results in Fig. 8, this corresponds to a
different evolution of mechanical properties.
calculated through the Williamson-Smallman relationship (Eq. (2)) Following heat treatments at increasing temperature there is a pro-
resulted to be of 8.0 × 1010 cm− 2. Moreover, the plates treated in gressive reduction of hardness with respect to the work-hardened state:
standard condition, had a hardness of 201.6 ± 1.9 HV5, in substantial the higher the treatment temperature, the greater the decrease. This has
agreement with literature data. been observed in all the samples, independently on the CR they under-
went. The hardness decrease depends on the progressive annihilation of
3.2. Cold rolled EUROFER97 steel dislocations which are present with high density in the cold worked
material (see Table 4). Except for the samples deformed with CR: 20 %,
As shown by SEM images in Fig. 5, cold rolling with increasing hardness drops below the value of standard EUROFER97 above a critical
reduction ratio strongly modifies grain size and shape. The equiaxed temperature. In the case of CR: 60 % and CR: 80 % this temperature is
grains of standard EUROFER97 steel (Fig. 5 (a)) progressively evolve 650 ◦ C. The hardness values of the samples deformed with CR: 60 % and
towards elongated grains of smaller size (Fig. 5 (b-c-d-e-f)) as CR CR: 80 % after the treatment at 650 ◦ C are 236.5 ± 0.2 HV5 and 228.3 ±
increases. 0.3 HV5, respectively. These values are quite lower with respect to those
As shown at higher magnification in Fig. 6, inside some original of cold-rolled state (298.9 ± 1.1 HV5 and 275.2 ± 1.8 HV5) but still 20 %
grains a population of nanometric sub-grains (~200 nm) can be and 15 % higher than the one of standard treatment (201.6 ± 1.9 HV5).
observed, especially near carbides. From the comparison of micrographs The behavior of the samples deformed with CR: 40 % and CR: 50 % is
in Fig. 6 (a-b), this feature seems to be more pronounced and homoge- similar but the critical temperature (700 ◦ C) is higher.
neous in the samples with the lower reduction ratio (CR: 20 %) than in On the basis of hardness data the samples with the best mechanical
those which underwent a more severe deformation (CR: 80 %). This is in performances (CR ratios of 40 %, 50 %, 60 % and 80 % - heating tem-
agreement with results of other investigators on the rearrangement of perature below the critical one) have been subjected to tensile tests. The
dislocations during plastic deformation and their preferred clustering tensile curves are shown in Fig. 9.
around precipitates [59,60]. Yield Stress (YS), Ultimate Tensile Stress (UTS), uniform elongation
The work-hardening in EUROFER97 steel was also studied by XRD (AU) and total elongation (AT) determined from the curves in Fig. 9 are
and Vickers hardness measurements. It is the result of simultaneous reported in Table 5. UTS and YS values decrease as treatment temper-
occurrence of accumulation, rearrangement and annihilation of dislo- ature increases while AU and AT exhibit the opposite behavior. After heat
cations following a plastic deformation process. Table 4 compares the treatments up to 600 ◦ C the YS and UTS values of all the examined
dislocation density obtained by XRD of the cold rolled samples with samples are quite larger than those of standard EUROFER97, however
increasing CR ratios to that of standard EUROFER97 steel. such a strengthening effect is accompanied by a reduced ductility.
Dislocation density increases with CR ratio and after 80 % of Generally, some benefits to ductility are observed if treatment temper-
deformation it is about two orders of magnitude greater than in the ature is higher than 650 ◦ C but YS and UTS drastically drop. The only
standard material (7.2 × 1010 cm− 2 vs. 1.2 × 1012 cm− 2). As expected, samples, which result strengthened and also have better ductility as
such ρ increase appears to be extremely effective in terms of compared to standard EUROFER97, are those deformed with CR ratio of

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Fig. 5. Structure of EUROFER97 steel in standard condition (a) and after cold-rolling with CR ratios of 20 % (b), 40 % (c), 50 % (d), 60 % (e), and 80 % (f).

Fig. 6. SEM micrographs at high magnification of EUROFER97 steel cold rolled with CR 20 % (a) and CR: 80 % (b). Black arrows indicate some new equiaxed
sub-grains.

80 % and treated at 650 ◦ C. In fact, there is an YS and UTS increase of EBSD maps collected at increasing treatment temperature (Fig. 10)
about 18 % and 5 %, respectively, while AT is 23.1 %, a little greater than revealed that the optimal combination of strength and ductility sub-
that of standard steel (21.6 %) but, most important, AU is more than stantially corresponds to a fully recrystallized material before the onset
double (13.4 % vs. 6.5 %). of grain growth.
On these grounds the attention has been focused on the samples cold The fraction of new grains increases with treatment temperature and,
rolled with CR ratio of 80 % and heat treated at 650 ◦ C because of the at 650 ◦ C, the material is fully recrystallized with equiaxed grains of
improvement of both strength and ductility. nanometric size. At higher temperature (700 and 750 ◦ C) the

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Table 4
Relative intensities of XRD peaks, dislocation density ρ and hardness HV5 of samples after increasing deformation by cold rolling are compared to the values of standard
EUROFER97 steel.
Peaks Relative intensities of XRD peaks ρ (cm¡2) HV5

110 200 211 220 310 222

JCPDS- file 6–696 100 20 30 10 12 6 ​ ​

Standard 100 11 20 8 6 – 8.0 × 1010 201.6 ± 1.9
CR 20 % 100 24 27 6 9 5 2.0 × 1011 230.5 ± 1.2
CR 40 % 100 15 38 6 7 4 6.0 × 1011 251.0 ± 3.3
CR 50 % 100 7 12 5 4 – 8.0 × 1011 269.2 ± 3.2
CR 60 % 100 20 30 1 1 1 9.0 × 1011 272.3 ± 1.8
CR 80 % 100 52 63 – 1 1 1.2 × 1012 298.9 ± 1.1

microstructure is inhomogeneous with the presence of grains with

micrometric and sub-micrometric size. For instance, the samples heated
at 750 ◦ C have an average grain size of about 1.6 μm, however some
grains exceed 15 μm. This evidence appears to be in agreement with
what was observed by Oliveira et al. [43]. The synergistic contribution
between the high intrinsic grain boundary mobility and the presence of
local microstructure instabilities such as dislocations and coarsened
M23C6 carbides [62], favors both grain growth and abnormal grain
growth phenomena.
The fractions of HAGBs and LAGBs determined from EBSD data are
reported in Table 6. Even if there are some fluctuations, the fraction of
HAGBs substantially increases with the number of recrystallized grains
and decrease with the onset of grain growth while LAGBs have the
opposite behavior. Indeed, HAGBs exhibit a maximum around 650 ◦ C
corresponding to a minimum of LAGBs.
KAM analysis showed that the cold rolled samples (CR: 80 %) exhibit
stress accumulation areas corresponding to the deformed grains with
high dislocation density (Fig. 11 (a)). The average KAM is 0.62◦ (Fig. 11
(b)). Similar characteristics are found in the not yet completely recrys- Fig. 8. Hardness vs. heat treatment temperature of EUROFER97 samples cold
tallized samples treated at 400 ◦ C (Fig. 11 (c)) with average KAM of rolled with increasing CR ratio. The red line indicates the hardness value of
0.60◦ . As reported in a previous work [63], green zones are strongly standard EUROFER97. (For interpretation of the references to color in this
reduced and more uniformly distributed in the fully recrystallized figure legend, the reader is referred to the Web version of this article.)
sample (Fig. 11 (d)) that has a lower average KAM of 0.32◦ .
The values of mean grain size <D> and dislocation density ρ deter- the distribution of misorientation angles (c) and the distribution of grain
mined from the analysis of XRD peak profiles are reported in Table 7. As size (d).
treatment temperature increases the dislocation density exhibits a Fig. 12 (a) shows an extremely fine microstructure with a population
continuously decreasing trend; the mean grain size has an analogous of equiaxed grain, indicating that the primary recrystallization process
behavior up to 650 ◦ C whereas above 650 ◦ C an increasing trend is has been completed. In agreement with previous XRD results [64] IPFs
observed. These results are in good agreement with EBSD analyses (b) reveal the presence of a [100] texture. Misorientation angle distri-
because dislocation density decrease is the consequence of the formation bution (c) exhibits two peaks at 2◦ and 55◦ corresponding to LAGBs and
of new grains free from defects during recrystallization. Many nucle- HAGBs, respectively.
ation sites and slow growth due to the relatively low temperature pro- The grain size distribution (d) has the typical log-normal shape with
duce a population of grains of small size up to 650 ◦ C while above this an average size of about 600 ± 60 nm. This result is about 3 times
temperature grain growth occurs leading to the increase of <D>. greater than that (206 nm) reported in Table 7 and determined by XRD.
Fig. 12 shows a more detailed analysis, namely an EBSD map However, it is well-known from the literature that the crystallite size
collected at higher magnification (a), the inverse pole figures (IPF) (b), obtained from XRD analysis is generally smaller than the ones

Fig. 7. SEM micrographs of EUROFER97 steel cold-rolled with CR ratio of 40 % in work hardened state (a) and after the heat treatment at 700 ◦ C (b).

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Fig. 9. – Effect of heat treatments on the tensile curves of EUROFER97 steel cold rolled with different CR ratios: 40 % (a), 50 % (b), 60 % (c), and 80 % (d).

determined through other techniques [65]. In fact, XRD gives the

Table 5
average size of the coherently diffracting domains including dislocation
Yield Stress (YS), Ultimate Tensile Stress (UTS), Uniform Elongation (AU) and
cells with a reciprocal misorientation smaller than 1◦ whereas the
Total Elongation (AT) of EUROFER97 samples after different thermo-mechanical
treatments. Data have been determined from tensile tests reported in Fig. 9. The
angular resolution of EBSD technique allows to distinguish only crystals
values of standard EUROFER97 are reported for comparison [61]. with misorientation greater than 2◦ .
As shown by Fig. 13, another relevant feature of the microstructure is
Thermo-mechanical treatment YS (MPa) UTS (MPa) AU (%) A (%)
the fine distribution of precipitates. In comparison to the cold rolled
Standard EUROFER97 547 683 6.5 21.6 steel (Fig. 5 (f)), carbide size is a little greater: from a statistical analysis
CR: 40% - 550 ◦ C 653 738 5.4 16.6
carried out on 30 SEM micrographs taken at high magnification
CR: 40% - 600 ◦ C 637 725 5.0 15.9
CR: 40% - 650 ◦ C 572 667 6.8 17.8 (50,000X) the average particle size is ⁓ 100 nm while the average
CR: 40% - 700 ◦ C 535 655 7.6 21.1 distance between the precipitates is ⁓ 450 nm.
CR: 50% - 500 ◦ C 708 799 4.1 12.6 To assess possible changes of atomic distribution near the surface
CR: 50% - 550 ◦ C 697 783 4.0 12.0 induced by heat treatments, EDS measurements have been carried out
CR: 50% - 600 ◦ C 682 772 4.8 15.2
CR: 50% - 650 ◦ C 605 694 5.8 16.8
on the treated samples. For each sample three measures were made on
CR: 50% - 700 ◦ C 310 538 12.2 20.4 an area of 56 × 42 μm2 and Table 8 reports the average values. The
CR: 60% - 500 ◦ C 751 841 3.8 12.4 obtained data are close to the nominal composition of the steel and do
CR: 60% - 550 ◦ C 722 815 4.1 13.6 not show relevant variations as compared to the not treated sample.
CR: 60% - 600 ◦ C 711 789 3.5 11.9
CR: 60% - 650 ◦ C 611 689 6.7 18.4
CR: 60% - 700 ◦ C 215 467 15.5 22.1 4. Discussion
CR: 80% - 400 ◦ C 870 927 3.6 10.8
CR: 80% - 500 ◦ C 821 878 5.0 12.2 This work examined 40 different TMT conditions by combining CR
CR: 80% - 600 ◦ C 673 739 7.9 15.8
ratio and heat treatment temperature.
CR: 80% - 650 ◦ C 644 714 13.4 23.1
As expected, cold rolling modifies grain size and shape, and conse-
quently the mechanical properties of the material. The population of
equiaxed grains present in the standard EUROFER97 progressively

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Fig. 10. EBSD maps of samples cold rolled (CR 80 %) and heated at increasing temperature. The rolling direction (RD) is indicated.

deformed in various conditions lead to different microstructural evolu-

Table 6 tion: partial recrystallization, complete recrystallization, grain growth
Fractions of HAGBs and LAGBs determined from EBSD data collected on
and abnormal grain growth. The results of tensile tests and micro-
EUROFER97 samples cold rolled (CR 80 %) after heat treatments at increasing
structural examinations showed that, when recrystallization has not yet
temperature.
completed, the material exhibit greater hardness, YS and UTS than
Heat treatment temperature (◦ C) HAGBs LAGBs
standard EUROFER97 due the presence of grains with dislocations in
Standard EUROFER97 38.7 61.3 high density induced by cold rolling. In this condition the material is
Cold rolled CR 80 % 50.7 49.3 inhomogeneous consisting of zones with high and low dislocation den-
400 45.4 54.6
450 57.8 42.2
sity with stress gradients, as evidenced by KAM map in Fig. 11 (a).
500 48.5 51.5 Therefore, the improved strengthening is obtained to detriment of
550 65.0 35.0 ductility that results to be lower. On the other hand, the onset of grain
600 59.6 40.4 growth following high temperature annealing leads to a drastic drop of
650 63.8 36.2
mechanical properties.
700 56.1 43.9
750 30.1 69.9 The best trade-off is obtained through cold rolling with CR ratio 80%
and annealing at 650 ◦ C. Such TMT gives rise to a fully recrystallized
material with equiaxed nanometric grains and induces an improvement
evolves towards elongated grains of smaller size. Some of them result of both strength and ductility in comparison to standard EUROFER97. It
fragmented in nanometric sub-grains which are observed especially near is noteworthy that the grain size is ≈ 600 nm, not far from the size of 1
carbides. Fragmentation is due to the original fine structure of μm, value corresponding to the optimal strength-ductility combination
martensite: blocks and packets with HAGBs represent constraints to calculated through the theoretical approach of Wang et al. [66]. More-
plastic deformation enhancing heterogeneous deformation, grain sub- over, as evidenced by the comparison of grain size values obtained by
division and rotation. Indeed, a cubic [100] texture with a secondary XRD and EBSD, inside the grains there is a mosaic cell structure with
[211] component develops substituting the original near random boundary misorientations lower than 2◦ .
orientation of grains. The dislocations density increases leading to an To understand the mechanical properties behavior of EUROFER97
enhancement of hardness. These effects are more pronounced with steel after this treatment, the contributions of different strengthening
greater reduction ratios. mechanisms affecting YS have been considered: (i) solid solution (σSS ),
Heat treatments at increasing temperature carried out on samples (ii) Bailey-Hirsch (σBH ) due to dislocations, (iii) Hall-Petch (σ HP ) related

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Fig. 11. KAM map (a) and KAM angle distribution (b) of a sample cold rolled (CR: 80 %). KAM maps of samples cold rolled (CR 80%) and heated at 400 ◦ C (c) and
650 ◦ C (d).

where M = 2.9 is the Taylor factor for b.c.c. metals, the parameter α =
Table 7
0.24 [68], G = 81 GPa the shear modulus, b = 0.248 nm the modulus of
Dislocation density ρ and average grain size <D> determined from XRD peak
Burgers vector and ρ = 1 × 109 cm− 2 the dislocation density determined
profile analyses of EUROFER97 samples deformed with CR 80 % and heat
treated at different temperature (T.T.).
by XRD (Table 7). Therefore, the calculated value of σ BH is 45 MPa.
Hall-Petch strengthening σ HP = 410 MPa has been obtained by the
T.T. (◦ C) <D> (nm) ρ (cm¡2)
relationship:
Not treated 400 1.2 × 1012
1
400 380 5.1 × 1011 σ HP = σ 0 + K • D− 2 (6)
450 330 2.9 × 1011
500 275 2.8 × 1011
being σ 0 = 13 MPa [69] the friction stress, i.e., the matrix yield stress for
550 260 2.1 × 1011
600 250 1.3 × 1010 a grain of theoretically infinite size, K = 0.18 MPa•m1/2 and D = 206 nm
650 206 1.0 × 109 the average crystallite size (Table 7).
700 218 4.0 × 108 The Orowan critical stress σ K = 113 MPa has been determined
750 350 3.1 × 108
through the relationship of Kocks [70]:
[ ( )]3 [ ]
2
to the grain size and (iv) Orowan (σK ) connected to the precipitates. 0.9 • M • ln πb•d G•b
4•π•(1− υ)

YS = σ SS + σ BH + σ HP + σK (3) σK = [ ( )]1 •[ ( )] (7)

2 L− π •d
The four contributions in equation (3) have been calculated on the ln Lb 4

basis of the data from microstructural examinations.

Solid solution strengthening σ SS mainly depends on the amounts of where υ = 0.3 is the Poisson’s ratio, L = 450 nm and d = 100 nm are the
Cr and W [24] and the contribution of each element is given by: mean spacing between particles and particle size, respectively, deter-
mined from SEM observations. The results of these calculations are
σ SS = 0.00689 • k • C • n (4)
displayed in Fig. 14.
being C the concentration (at. %) of the elements, n = 0.75, the coeffi- The sum of the four contributions is 652 MPa, close to the YS value
cient k is 1400 for Cr and 11,000 for W [67]. Since the atomic concen- (611 MPa) determined through tensile tests (Table 5). From these results
trations of Cr and W are 9.56 and 0.32, respectively, their specific it is apparent that the major contribution to strengthening comes from
contributions result to be about 53 MPa for Cr and 32 MPa for W, thus the sub-micrometric size of grains and the contribution σ HP mainly
the total value of σSS is 85 MPa. controls the yield stress.
The Bailey-Hirsch stress σBH is expressed by the relationship: Generally, materials which exhibit high strength have poor ductility
and viceversa: the trade-off between strength and ductility of metals is
1 typically represented by the ‘‘banana curve’‘. Of particular relevance for
σ BH = M • α • G • b • ρ • (5)
2 ductility is the energy stored in the material per unit volume before the
localization of strain (necking) that corresponds to the area enclosed by

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Fig. 12. EUROFER97 cold rolled with CR ratio of 80 % and heat treated 1 h at 650 ◦ C: EBSD map (a), inverse pole figures (b), misorientation angle distribution (c)
and grain size distribution.

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

Fig. 13. Precipitates in EUROFER97 steel after cold rolling with CR of 80 %

and heat treatment at 650 ◦ C.

Fig. 14. Calculated strengthening contributions to yield stress of EUROFER97

the ascending branch of tensile engineering stress-strain curve. From cold rolled with CR ratio of 80 % and heat treated 1 h at 650 ◦ C: solid solution
Fig. 9 the energy value of these samples is ≈ 90 mJ/mm3, namely about (σSS ), Bailey-Hirsch (σ BH ), Hall-Petch (σ HP ) and Orowan (σK ).
three times that of standard EUROFER97 (≈ 33 mJ/mm3).
In order to improve the ductility of metals, it is necessary to retard
the plastic instability (necking) and the most effective approach consists
deformation produced a homogeneous dispersion of fine precipitates
in increasing their strain hardening rate (Considère criterion), namely in
which undergo only a little coarsening following the heat treatment at
activating efficient mechanisms to block and accumulate dislocations. In
650 ◦ C (Fig. 13) thus they may play an important role in the pinning of
the present case some microstructural features play this role: (i) the
dislocations.
small size of grains, (ii) their equiaxed shape, (iii) the type of grain
In addition to mechanical performance, an aspect which may impact
boundaries, and (iv) the fine dispersion of precipitates.
a fusion-relevant property such as sputtering yield regards potential
The size of grains is very small but still above the critical value Dc ≈
changes in atomic distribution induced by heat treatments. Previous
100 nm [71], where deviations from the Hall-Petch relationship (inverse
studies of Strӧm and Primetzhofer [73] have shown that annealing in
effect) are observed because the grain boundary area per unit volume is
vacuum can result in W-surface segregation with maximum enrichment
so large to suppress the generation of dislocations in the grain interior
at 650–700 ◦ C. EDS measurements carried out in present work on the
and the grain boundaries act themselves as sources of dislocations [72].
samples deformed with CR: 80% and heated at different temperature did
The equiaxed shape favors the rotation of grains during plastic defor-
not show significant segregation phenomena (see Table 8). Since the
mation avoiding the localization of stresses which leads to crack for-
information provided by EDS regards a surface layer of about 0.5 μm, it
mation. Moreover, as shown in Table 6, there is a strong prevalence of
is not possible to rule out that composition changes may occur in a
HAGBs (63.8 %) which are more effective than LAGBs in hindering
thinner layer near the surface. Therefore, X-ray photoelectron spec-
dislocation motion because there is greater crystallographic misalign-
troscopy (XPS) analyses with depth profiling will be made in future
ment across the grain boundary. Finally, the relevant plastic
activity.

5. Conclusions

Table 8
The main results of this work can be summarized as follows.
EDS analyses of EUROFER97 samples deformed with CR 80 % and heat treated
at different temperature (T.T.). The chemical composition measured in not
treated sample is reported for comparison. (i) Following cold rolling the grains become flat and elongated along
the rolling direction, the nearly random grain orientation of
Samples CR: Fe C Cr W Mn Ta V
standard EUROFER97 evolves towards a [100] cubic one and,
80%
after 80 % of deformation, the dislocation density increases up to
Not treated 87.5 0.3 9.6 1.3 0.6 0.3 0.4
reach a value about two orders of magnitude greater than that of
± 0.2 ± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1
400 ◦ C 87.6 0.3 9.5 1.3 0.6 0.3 0.4 the standard condition. Mechanical properties increase with CR
± 0.2 ± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ratio.
450 ◦ C 87.8 0.2 9.4 1.2 0.7 0.4 0.3 (ii) In all the examined samples heat treatments induce recrystalli-
± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 zation with kinetics depending on both treatment temperature
500 ◦ C 88.0 0.1 9.4 1.2 0.6 0.4 0.3
± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1
and CR ratio.
550 ◦ C 87.4 0.3 9.5 1.4 0.6 0.4 0.4 (iii) The thermo-mechanical treatment consisting of cold rolling with
± 0.2 ± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 CR of 80 % followed by annealing at 650 ◦ C gives rise to a fully
600 ◦ C 87.7 0.2 9.3 1.4 0.6 0.4 0.4 recrystallized microstructure with a population of equiaxed
± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1
grains with sub-micrometer size (600 ± 60 nm) and prevalent
650 ◦ C 87.8 0.2 9.3 1.4 0.6 0.4 0.3
± 0.2 ± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 HAGBs. Inside the grains there is a sub-structure of cells (⁓ 200
700 ◦ C 87.6 0.3 9.4 1.3 0.6 0.4 0.4 nm) separated by LAGBs. Moreover, there is a fine dispersion of
± 0.2 ± 0.1 ± 0.1 ± 0.2 ± 0.1 ± 0.1 ± 0.1 precipitates with average size of ⁓ 100 nm.
750 ◦ C 87.5 0.2 9.5 1.4 0.6 0.4 0.4
± 0.2 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1 ± 0.1

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G. Stornelli et al. Journal of Materials Research and Technology 33 (2024) 5075–5087

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