Journal of Alloys and Compounds 824 (2020) 153849

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Effects of rare-earth micro-alloying on microstructures, carbides, and

internal friction of 51CrV4 steels
RongChun Chen a, ZhiGang Wang a, b, *, FuSheng Zhu b, Hongjin Zhao a, Jing Qin a,
Lingqiang Zhong a
a
School of Material Science and Engineering, Jiangxi University of Science and Technology, Ganzhou, 341000, China
b
Longnan Longyi Heavy Rare Earths Technology Co., Ltd, Ganzhou, 341700, China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of rare-earth (RE) micro-alloying on the microstructures, mechanical properties, and internal
Received 24 October 2019 friction (IF) of 51CrV4 steels after quenching and tempering were investigated. The addition of RE ele-
Received in revised form ments was beneficial for refining the size of the martensite and increasing the fraction of twins in the
4 January 2020
51CrV4 steels. The RE-51CrV4 steel possessed a high dislocation density and a large fraction of low-angle
Accepted 13 January 2020
Available online 15 January 2020
grain boundaries after quenching. Cr7C3 carbides of RE-51CrV4 steel tended to precipitate along the lath
martensite interfaces and were easily spheroidized during tempering. With the addition of RE elements,
the SnoekeKo €stereKe
^ (SKK) peak was increased after quenching but decreased after different tempering
Keywords:
51CrV4 steels
times. The results of the IF and high-resolution transmission electron microscopy analyses indicated that
RE micro-alloying RE atoms formed micro-segregations at the lath martensite interfaces and resulted in a pinning effect on
Internal friction the carbon atoms. Therefore, the hardenability of the RE-51CrV4 steel was reduced, whereas its elon-
Microstructure gation improved significantly due to the presence of high-density twins and spheroidized carbides.
Cr7C3 carbides © 2020 Elsevier B.V. All rights reserved.

1. Introduction
Due to their high strengths, high impact toughness, and excel-
lent fatigue performances, 51CrV4 steels are widely used as die
steels, spring steels and high-speed steels [1e3]. The morphologies
and distribution of Cr-based carbides during quenching and
tempering influence the mechanical properties of Cr-modified
steels. The addition of strong or medium-strong carbide-forming
elements (Nb, Ti, and V) profoundly affects the precipitation
behaviour of Cr-based carbides and influences the diffusion and
partition of carbon (C) atoms [4e7]. In recent years, RE elements
have been extensively applied for the purification and deoxi-
dization of steels. RE elements react with O and S atoms during the
solidification of metals and form complex compounds with high
melting temperatures (RExOy, RExSy, and RExOySz). In addition, RE
elements can improve the morphologies (from long strips to
spheres) of inclusions (MnS and Al2O3) to yield micro-alloyed steels
with enhanced impact toughness, fatigue lives, and ductilities
[8e11]. Compared to iron atoms, RE atoms have much larger radii
with very little solid solution in the matrix. Hence, it is difficult to
study whether RE elements play similar micro-alloying roles to Nb,
V, and Ti in steels, and the mechanisms of micro-alloying lack
strong evidence.
The precipitation behaviors of RE micro-alloyed steels and their
substructures (dislocations and twins) are greatly affected by so-
lutions and the interactions between RE elements and other
alloying elements. A small quantity of RE elements generally dis-
solves in micro-alloyed steels by occupying lattice section points
through vacancy diffusion [12]. Moreover, significant changes in
the plastic deformation behaviors of RE micro-alloyed steels are
often noticed due to lattice distortion. Due to the reduction of the
stacking fault energy (SFE) in RE-microalloying steels [13e16], RE
elements cause an increase in the dislocation density and promote
the formation of twins. Furthermore, RE elements are beneficial for
Table 1
Chemical compositions of 51CrV4 and RE-51CrV4 steels.

Elements (wt%) C Si Mn P S Cr V RE
* Corresponding author. School of Material Science and Engineering, Jiangxi
51CrV4 0.49 0.36 0.81 0.026 0.003 1.00 0.13 e
University of Science and Technology, Ganzhou, 341000, China.
RE-51CrV4 0.51 0.47 0.81 0.026 0.0016 1.03 0.16 0.014
E-mail address: wzgang2008cn@163.com (Z. Wang).

https://doi.org/10.1016/j.jallcom.2020.153849
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849

Fig. 1. SEM micrographs of the specimens after quenching: (a) 51CrV4 steel and (b) RE-51CrV4 steel. EBSD phase images of martensite: (c) 51CrV4 steel, and (d) RE-51CrV4 steel. (e)
Statistical graph of the low-angle grain boundaries. (f) Statistical graph of the packet diameter. Red and black lines in the boundary maps denote low-angle grain boundaries (LAGBS;
2
 q  15
) and high-angle grain boundaries (HAGBs; q  15
). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this
article.)
 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849
Fig. 2. Local orientation misorientation (LOM) analysis results of 51CrV4 and RE-51CrV4 steels after quenching: (a) RE-51CrV4 steel-LOM and (b) 51CrV4 steel-LOM.
homogenization and refining the twin distances in twinning
induced plasticity (TWIP) steels [17]. In addition to solid solutions,
RE elements have a certain effect on the C atoms. In CeMn steels, RE
elements interact with C atoms to affect the phase transformation
and the precipitation of carbides. The results of a first-principles
study revealed that lanthanum (La) atoms have strong affinities
with C atoms in four and five nearest-neighbor coordination shells
[18]. RE elements can also affect the distribution of carbides in
high-alloy steels (MCH13 and H13) during quenching and
tempering. In die steels, RE elements refine the eutectic structure,
spheroidize annealed carbides, and inhibit crack propagation [19].
RE atoms tend to segregate at the interface between ferrite and
cementite due to their large diameters and high aberration en-
ergies. However, there have been few studies on the mechanism
through which RE elements affect the C in the CreV steel heat-
treatment process, especially for carbide precipitation. Therefore,
it is necessary to focus on the interactions between RE elements
and C to study the microalloying of the RE elements in medium-
carbon micro-alloying steels.
The micro-segregation of RE elements is generally observed by
high-resolution transmission electron microscopy (HRTEM) or
atom probe tomography (APT) techniques [20], and the solid so-
lution of C atoms can be indirectly analyzed by the IF peaks (Snoek
and SnoekeKo € stereKe
^) [21,22]. Therefore, in this study, the mi-
crostructures, mechanical properties, and IF of 51CrV4 and RE-
51CrV4 steels were investigated in detail. The effects of RE ele-
ments on the morphologies and distribution of Cr-based carbides
were investigated by HRTEM, and the interactions of the RE ele-
ments with C were further proven. This study lays the foundation
for broadening the application of heavy rare earth micro-alloying in
high-alloy-modified special steels.
2. Experimental procedure
2.1. Experimental materials and process
The 51CrV4 and RE-51CrV4 steels were designed [2,11,17], the
whose chemical compositions of steels are presented in Table 1. The
chemical compositions in the hot-rolled plate were measured by
inductively coupled plasma mass spectroscopy (ICPMS, PE
ELAN9000). The RE elements were added into the molten steel
3
under a vacuum atmosphere when the oxygen content of the steel
was reduced to a low level (lower than 10 ppm). RE was added to
the melt, secondary refinement and ladle-bottom argon blowing
technology (about 10 min) were employed to ensure the homo-
geneity of materials. Melting and hot-rolled raw materials with
thicknesses of 18 mm were obtained. The heat treatment process of
the hot-rolled plate was subsequently carried out in laboratory. The
samples were heated to 1133 K for 40 min in a furnace under an
argon gas atmosphere and oil quenched down to room tempera-
ture. The effects of RE elements on the carbide evolution in samples
that were tempered for 20 and 80 min at 723 K and air cooled to
ambient temperature were examined.
2.2. Methods of microstructure characterization
The effects of the RE elements on the microstructures, me-
chanical properties, and IF of the examined steel were revealed by
field-emission scanning electron microscopy (FE-SEM), electron
back-scattered diffraction (EBSD), and transmission electron mi-
croscopy (TEM). In addition, the properties of the Cr-based carbides
were investigated by HRTEM.
The specimens were mechanically polished and etched with a
4% Nital solution for microstructural examination. The martensite
and carbide morphologies were examined using FE-SEM (Zeiss-
SIGMA) operated at an accelerating voltage of 20 kV.
The samples for EBSD were prepared by a standard electrolytic
polishing technique in an electrolyte solution (ratio of alcohol,
glycerin, and perchloric acid ¼ 7:2:1) at ambient temperature.
Surface crystallographic orientation data were analyzed in an HKL-
Technology EBSD system attached to the Zeiss-SIGMA field-emis-
sion scanning electron microscope using the HKL-Channel 5 soft-
ware. Grain boundaries with misorientation angles ranging from 2

to 15
were regarded as low-angle boundaries, and the percentage
of boundaries was expressed in terms of their length fractions.
Microstructures and carbides were identified using a FEI Tecnai
G2 F20 transmission electron microscope operated at 200 kV with a
point-to-point resolution of 0.24 nm. TEM samples were first me-
chanically polished to thicknesses of approximately 50 mm, fol-
lowed by ion-beam milling in a Gatan 691 precision ion polishing
system (PIPS) at 5 kV with a final polishing step of 1 kV.
IF can be used to analyse the change in the solute carbon atom
4 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849

Fig. 3. SEM micrographs of the investigated steels after 20 min of tempering: (a) 51CrV4 steel and (b) RE-51CrV4 steel. SEM micrographs of the investigated steels after 80 min of
tempering: (c) and (e) 51CrV4 steel and (d) and (f) RE-51CrV4 steel.

concentration in a solid solution. In this paper, the IF in the
quenched and tempered samples was investigated. The IF was
measured using an MFP-1000 multifunction IF meter in free-decay-
of-oscillation mode [23]. The IF specimens had widths of 2 mm,
lengths of 45 mm, and thicknesses of 1 mm. The specimens were
heated from 30 to 300
C in a vacuum infrared furnace at a heating
rate of 1
C/min. The obtained IF spectra (Q1) were comprised of
Debye peaks and a background. The main peak of the IF spectrum
for martensites was the SKK relaxation peak. The background was
subtracted based on the following equation [24]:
 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849 5

Fig. 4. (a) SKK peaks of the investigated steels in all the heat treatment states (the background was subtracted based on the theory of internal friction) and (b) results of hard-
enability experiments.

! according to the GB/T 228.1e2010 standard with gage lengths of

C
Q 1
b ¼ A þ B exp
kT
The values of parameters A, B, and C were determined after
optimization of the c2 function. Moreover, the special background
fitting software “Damping GaussV2” was employed to eliminate the
IF background.
2.3. Mechanical tests
Hardenability tests (specimen dimension ¼ Ø25 mm  100 mm)
of the hot-rolled samples were carried out on Jominy hardenability
equipment according to the ASTM A255-2010 (2014) standard. The
tensile properties of the investigated steels after tempering for 20
and 80 min were also evaluated at room temperature. Round bar
tensile samples were prepared along their rolling directions
25 mm. They were then tested on a UTM5105X electronic universal
testing machine at a strain rate of 2 mm/min. The tensile properties
were tested at room temperature. To obtain accurate test data, the
tensile samples for each heat treatment state were tested twice. The
hardness values of the samples were determined using a 200HVS-5
Vickers hardness tester under a load of 3 kg with a loading time of
15 s. The mean of five hardness values (measured at five different
points) was considered to be the Vickers hardness.
3. Results
3.1. Microstructural characterization
3.1.1. Effects of RE elements on quenched microstructures
Fig. 1(a) and (b) shows SEM micrographs of the martensites in
the investigated steels after quenching. Each primary austenite

Fig. 5. (a) Hardness of the investigated steels in all heat treatment states. (b) Engineering stressestrain curves in the tempering state.

Table 2
Summary of tensile properties of tempered samples.

Tempered samples 20e51CrV4 20eREe51CrV4 80e51CrV4 80eREe51CrV4

Reduction of area (%) 21.15 ± 0.35 33.68 ± 0.21 24.79 ± 0.22 41.3 ± 0.33
UTS (MPa) 1649 ± 6 1764 ± 4 1465 ± 3 1467 ± 5
6 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849
Fig. 6. SEM micrographs of the tensile specimen fractured after tempering: (a) 20e51CrV4, (b) and (c) 20eREe51CrV4, (d) the EDS of inclusion A in (c), (e) 80e51CrV4, (f) and (g)
80eREe51CrV4, and (h) the EDS of inclusion B in (g).
transformed into several packets, each packet consisted of several
blocks, and each block was composed of several laths [25].
Compared to the martensites in the white region, the sizes of the
packets in the primary austenite grain boundaries were slightly
refined by the RE elements. Fig. 1(c) and (d) shows the EBSD mi-
crographs of the steels after oil quenching. The sizes of blocks were
slightly refined by the addition of RE elements. Furthermore, sta-
tistical analyses were carried out on the LAGBs, and the obtained
histograms revealed that the fraction of LAGBs in the RE-51CrV4
steel increased due to the thinning of blocks. To further verify
this result, the sizes of the blocks were determined in Fig. 1(f). The
number of small-sized blocks (diameters ranging from 0.6 to
1.1 mm) increased in the RE-51CrV4 steel.
Fig. 2(a) and (b) shows the EBSD-measured orientation distri-
butions with average local orientation misorientation (LOM) values
of 0.3464
and 0.2903
, respectively, obtained for the samples
quenched at 1133 K. The value of the RE-51CrV4 steel was signifi-
cantly higher than that of the 51CrV4 steel. The LOM is directly
proportional to the change of the dislocation density [26]. There-
fore, the dislocation density of RE-51CrV4 steel was higher with the
addition of RE elements.
3.1.2. Effects of RE elements on tempered microstructures
Fig. 3(a) displays SEM images of the microstructures and pre-
cipitates in the 51CrV4 steel after 20 min of tempering. The mar-
tensites were mostly decomposed, and the carbides were
distributed through primary austenite grains in the 51CrV4 steel.
However, the white areas in Fig. 3(b) show that there was a slight
decomposition of the martensites in the RE-51CrV4 steel. Further-
more, the precipitation phase of the 51CrV4 steel manifested as a
partially parallel distribution (white areas in Fig. 3(a)), whereas the
precipitation phase of the RE-51CrV4 steel showed mainly a
disordered distribution. After 80 min of tempering, the majority of
the martensites decomposed into supersaturated ferrite matrices
and carbides. The morphologies of the carbides in the 51CrV4 steel
are shown in Fig. 3(c), and the distribution pattern of the carbides
(banded and locally parallel) shown in the white area of Fig. 3(d)
was similar to that observed after 20 min of tempering. The local
amplification of carbide precipitation was evident in 51CrV4 steel
(Fig. 3(e)), which appeared as lamellae and bars. Fig. 3(f) reveals
that the carbides are ellipsoidal and evenly distributed in the RE-
51CrV4 steel.
3.2. Internal friction and hardenability
Based on the different distributions of carbides and the micro-
structures, the diffusion of C was affected by the RE elements. The
behaviour of the solid solution C atoms was indirectly characterized
by the IF. The IF spectra evolved from the diffusion of various
interstitial atoms and the background inherent to the solid and the
measurement assembly. The Snoek and SKK peaks both appeared in
the proposed temperature range in low-carbon steels [27]. Due to
the presence of high-density dislocations in the quenching state,
the tested steels excited only the SKK peak. According to Schoeck’s
“string model” [28], SKK peaks appeared due to the movement of
dislocations [29,30]. As shown in Fig. 4(a), the SKK peak value of the
 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849 7

Fig. 7. TEM micrographs of the investigated steels after quenching: (a) and (c) 51CrV4 steel and (b) and (d) RE-51CrV4 steel.

Fig. 8. (a) Hierarchical microstructure of a martensitic steel system and schematic of the carbon solid solution with and without RE elements. (b) Traditional BCC microstructure
with many free C atoms locking the dislocations. (c) RE-modified solid solution in the BCC microstructure with few free C atoms locking the dislocations.
8 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849
Fig. 9. (a) Bright field and (b) dark field micrographs of carbides in 51CrV4 steel after 20 min of tempering. (c) bright field and (d) dark field micrographs of carbides in RE-51CrV4
steel.
RE-51CrV4 in the quenching state began to decrease and then
increased significantly during tempering. This shows that the in-
teractions between the interstitial C atoms and dislocations became
stronger after the RE addition in the quenching state. During
tempering, the interactions between the C atoms and dislocations
gradually weakened due to the RE micro-alloying. To verify the
interactions of the RE elements and C, the hardenability properties
of the steels were tested. The results in Fig. 4(b) show that the
hardenability of the RE-51CrV4 (black line) steel was lower than
that of the 51CrV4 steel (red line). This further indicated that RE
elements inhibited the diffusion of C atoms in austenite, thereby
increasing the stability of the austenite and decreasing its
hardenability.
3.3. Mechanical properties
The mechanical properties of the investigated steels are pre-
sented in Fig. 5. As shown in Fig. 5(a), the hardness values of the
samples increased significantly with the addition of RE elements.
Fig. 5(b) shows the engineering stressestrain curves of the
tempered specimens. As indicated by the arrows, RE-51CrV4 steel
exhibited a better necking phenomenon in the tempering state. The
ultimate tensile strength (UTS) of the samples after 20 min of
tempering were found to be much higher than those after 80 min of
tempering with much lower elongation. Moreover, the UTS of the
RE-51CrV4 steel after 20 min of tempering was slightly higher than
that of the 51CrV4 steel, and the UTS of the RE-51CrV4 steel
increased by 6% after 20 min of tempering. However, no significant
improvement was noted after 80 min of tempering. The reduction
of area and UTS values of the different specimens are summarized
in Table 2. The addition of RE elements led to increases of 12.53%
and 16.51% in the reduction of area after 20 and 80 min of
tempering, respectively.
The fractured micrographs of the tensile specimens are shown
in Fig. 6(a)e(h). In Fig. 6(a)e(d), the fracture micrographs of the
51CrV4 and RE-51CrV4 steels showed mixed modes of cleavage
fracture and ductile-dimpled fracture after tempering for 20 min.
The number and depths of the dimples increased with the addition
of RE elements. As the tempering time increased to 80 min, the
fracture of the 51CrV4 steel retained the original fracture mode
(Fig. 6(e)). The fracture micrographs of the REe51CrV4 steel mainly
showed the ductile-dimpled fracture mode, which implied that
there was an improvement of the plastic properties. This is
consistent with the results of the mechanical properties (Table 2).
In addition, the spherical inclusions rich in Y and Ce were observed
in the dimples of the RE-51CrV4 steel (Fig. 6 (c) and (g)), which may
have also been a factor in improving the plasticity, because it could
inhibit the propagation of cracks during the tensile process [31].
4. Discussion
4.1. Microalloying mechanism during quenching
During quenching, no diffusion of C atoms was evident, and only
lattice reorganization occurred due to the concerted motion of RE
elements and C atoms in the AISI 304 stainless steel [32]. The
micro-alloying of RE elements in the quenching state was achieved
by the lattice distortion of RE atoms. High-density dislocations and
fine twins were obtained as the major substructures in the inves-
tigated steels after quenching (Fig. 7). This indicated that the
dislocation density of the RE-51CrV4 steel (Fig. 7(b)) was signifi-
cantly higher than that of 51CrV4 steel (Fig. 7(a)), which is
consistent with the EBSD results in Fig. 1(e). Moreover, the twins
became finer and longer with the addition of RE elements (Fig. 7(c)
and (d)), which was attributed to the lattice distortion by RE atoms.
When the strain energy in the local area increased due to lattice
distortion, fine twins were more easily formed to regulate the
generated strain energy.
In addition to the difference in the dislocation density, lattice
distortion caused micro-segregation of C atoms. The radii of the RE
 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849
atoms was nearly 50% larger than that of the iron (Fe) atoms. Hence,
they could not easily form a solid solution. However, the polariza-
tion between RE elements and typical non-metallic elements could
cause significant changes in the atomic radius. The metal covalent
radius of La atoms is 0.1877 nm. However, when the ionization
degree reached 60%, the radius decreased to 0.1277 nm, which is
similar to the covalent radius of an Fe atom [33]. When RE atoms
occupied the Fe matrix or replaced Fe atoms, a RE-modified sub-
stitutional solid solution formed. As shown in Fig. 8(a), the lath
martensites possessed a complex microstructure with a hierarchi-
cal arrangement of laths, blocks, packets, and prior austenite grain
boundaries. The structural characteristics of the RE-modified solid
solution at the lath martensite interfaces are shown in Fig. 8(b) and
(c). Fig. 8(b) shows the CeFe octahedra and different
soluteedislocation interactions in the 51CrV4 steel. Fig. 8(c) shows
the effects of RE atoms on the lattice structure of 51CrV4 steel, and
it was found that RE atoms significantly influenced the SKK peak
through interstitial C atoms. When few interstitial C atoms
Fig. 10. HRTEM micrographs of the carbides in (a) 51CrV4 steel and (b) RE-51CrV4 steel. (c) and (d) SAED patterns. (e) and (f) EDS results for Cr7C3 precipitates after 20 min of
tempering.
9
segregated from the dislocations with the addition of RE elements,
a weaker SKK relaxation occurred after quenching in Fig. 4 (a). As
shown in Fig. 8, the REe51CrV4 steel contained more interstitial C
atoms than the 51CrV4 steel; however, very few of them migrated
and segregated to dislocations due to the lattice distortion of the RE
atoms. Hence, more clusters were formed in the 51CrV4 steel when
a large number of C atoms interacted with dislocations.
4.2. Microalloying mechanism during tempering
To reveal the micro-alloying mechanism during tempering, the
crystal structures and chemical compositions of the carbides were
investigated. As shown in Fig. 3, the distribution of carbides
changed noticeably with the addition of RE elements. Fig. 9 shows
the TEM micrographs of the carbides after 20 min of tempering.
Fig. 9(a) shows that carbides in the 51CrV4 steel and the lath matrix
maintained a certain distribution with an angle of 50
at the
beginning of tempering. Furthermore, carbides in the 51CrV4 steel
10 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849

Fig. 11. Crystal surface spacings and lattice defects observed through IFFT after 20 min of tempering: (a) HRTEM image of Cr-based carbides in 51CrV4 steel, (e) HRTEM image of Cr-
based carbides in RE-51CrV4 steel, (b) interplanar crystal spacing in the lath matrix in 51CrV4 steel, (f) interplanar crystal spacing in the lath matrix in RE-51CrV4 steel, (c)
interplanar crystal spacing in the precipitated phase in 51CrV4 steel, (g) interplanar crystal spacing in the precipitated phase in RE-51CrV4 steel, (d) lattice distortion in 51CrV4 steel,
and (h) lattice distortion in RE-51CrV4 steel.

parallelly precipitated at a distance of about 75 nm (dark field
micrograph in Fig. 9(b)). On the contrary, carbides in the RE-51CrV4
steel precipitated along the lath interfaces (Fig. 9(c) and (d)).
The HRTEM results in Fig. 10 confirmed the presence of a
stacking fault structure with abundant Cr atoms in both steels, and
EDS and SAED results in Fig. 10 (c)e(f) revealed that Cr7C3 was the
main carbide precipitate. Furthermore, a total dislocation ‘b’ was
decomposed into two Shockley incomplete dislocations ‘b1’ and ‘b2.’
These two incomplete dislocations in the same slip plane tended to
separate, and a layer with a Cr-rich fault area was sandwiched
between these two dislocations. The fault energy was inversely
proportional to the distance. The distances in the 51CrV4 and RE-
51CrV4 steels were measured as 24.15 and 31.87 nm, respectively.
The EDS results in Fig. 10(f) suggest that trace yttrium was present
at the lath martensite interfaces. Therefore, it was inferred that the
addition of RE elements caused a decrease in the stacking fault
energy.
With the addition of RE elements, Cr7C3 carbides began to grow
laterally and became spheroidized. The SKK peak height of the RE-
51CrV4 steel was found to be higher than that of the 51CrV4 steel
after tempering (Fig. 4(a)). This implies that many interstitial C
atoms were present in the RE-51CrV4 steel. Moreover, interstitial C
atoms migrated and segregated to the dislocations due to the RE
solid solution and lattice expansion in RE-51CrV4 steel. During
tempering, the thermal activation energy increased significantly
with the increase in temperature, resulting in the carbon breaking
away from the pinning points with the RE atoms. Consequently, the
SKK peak value and width of RE-51CrV4 steel in the tempering state
increased significantly (Fig. 4(a)). The SKK peak became wider
when a large number of interstitial C atoms accumulated in the
dislocations based on the coupling model [34]. Therefore, in the RE-
51CrV4 steel, carbides precipitated along the grain boundaries and
attained ellipsoidal shapes (changing the original behaviour of
parallel precipitation).
Fig. 11(a) and (e) displays HRTEM micrographs of the carbides
and their adjacent areas in the 51CrV4 and RE-51CrV4 steels,
respectively. In the 51CrV4 steel (Fig. 11(a)), Cr7C3 carbides were
arranged on the (112) plane, and the distance between the planes
(d) was calculated as 0.1994 nm (Fig. 11(b)). However, the matrix
was found on the (111) plane of a-Fe with a d value of 0.2115 nm
(Fig. 11(c)). Hence, the mismatch between the precipitated phase
and the lath matrix was found to be 5.72%, and the Cr7C3 carbides
maintained a semi-coherent relationship with a-Fe in this steel. In
the RE-51CrV4 steel (Fig. 11(e)), Cr7C3 carbides were arranged on
the (022) plane with d ¼ 0.2089 nm (Fig. 11(f)), whereas the matrix
was found on the (111) plane of the a-Fe with d ¼ 0.2057 nm
(Fig. 11(g)). Hence, the mismatch between the precipitated phase
and the matrix was only 1.56%. The addition of RE elements greatly
reduced the mismatch degree and changed the semi-coherent
relationship to a coherent lattice relationship. Inverse fast Fourier
transform (IFFT) was further applied to the junction between the
precipitated phase and the matrix, and the presence of lattice de-
fects at the interface of the lath martensites in the RE-51CrV4 steel
was confirmed (Fig. 11(h)). Combined with the analysis of the SKK
peak (Fig. 4(a)), it can be seen that under tempering conditions, the
number of interactions of the C atoms with the dislocations
increased, providing nucleation sites for the precipitation of Cr7C3.
As RE atoms had strong affinities for the C atoms, C atoms near the
lath boundaries became enriched with RE atoms. Moreover, the
micro-segregation of the RE atoms at the lath martensite interfaces
caused a decrease in the interface energy and facilitated the
nucleation and growth of the carbides [35]. Furthermore, the
addition of RE elements at the beginning of the tempering inhibited
the diffusion of C atoms and the decomposition of martensites.
 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849
Fig. 12. (a) and (b) TEM micrographs of Cr-based carbides in 51CrV4 steel (the upper left inset shows the SAED patterns). (c) and (d) EDS analysis of M7C3 precipitates after 80 min
of tempering.
Hence, the hardness and the UTS of the matrix increased signifi-
cantly, as shown in Fig. 5.
Fig. 12 shows that the effect of RE addition on the Cr7C3 carbides
after 80 min of tempering was similar to that after 20 min of
tempering. With the increase in the tempering time, the lath
martensites gradually disappeared, and the number of carbides
decreased greatly due to re-solubility. When the tempering time
increased to 80 min, the strengthening effects of RE disappeared.
This was because the density of dislocations in 51CrV4 and RE-
51CrV4 steels were almost equivalent after sufficient tempering
time, and the strengthening effects of the secondary phase or the
dislocations were not significantly different. Therefore, the UTS was
not increased in RE-51CrV4 spring steel. Moreover, the SKK peak
intensity after 80 min of tempering was found to be much higher
than that obtained after 20 min of tempering (Fig. 4(a)). This
indicated that the solid solution of RE atoms formed when the steel
was tempered for 80 min. Consequently, more interstitial C atoms
interacted with dislocations in the RE-51CrV4 steel. Hence, the
reduction of area was improved significantly.
Interstitial C atoms escaped from the BCC structure and diffused
into the alloying elements during tempering. To explain this un-
usual behaviour of the Cr7C3 carbides in the 51CrV4 steels, the
concentration lines of RE elements and C atoms are shown in
Fig. 13. Fig. 13(b) shows the distributions of these elements at two
locations of the lath martensite interface, and the Cr7C3 carbides
precipitated along the grain boundaries. Furthermore, lines 1 and 2
evince the micro-segregation of RE elements at the lath martensite
11
interface (marked by triangles in Fig. 13(d) and (e)), and it is evident
that the micro-segregation of C and RE atoms occurred at nearly the
same distance. This indirectly reflects the strong affinities of the RE
atoms for C atoms. Consequently, more interstitial C atoms were
found at the lath interfaces.
5. Conclusions
(1) After quenching, the addition of RE elements into the 51CrV4
spring steel caused an increase in the dislocation density and
reduced the spacing of twins in the martensites. RE micro-
alloying refined the sizes of the blocks and packets and
promoted the fraction of low-angle grain boundaries in the
RE-51CrV4 steel.
(2) In comparison to the 51CrV4 steel, RE atoms were prone to
segregate at the lath martensite interfaces during tempering,
and the SFE was reduced in the RE-51CrV4 steel. Hence, the
distortion of the interface was intensified, and globular car-
bides Cr7C3 were distributed along the lath interfaces.
Moreover, the spheroidization of carbides contributed to the
improvement of the elongation.
(3) The addition of RE elements decreased the SKK internal
friction peak in the quenching state of 51CrV4 steel, whereas
an increase in the SKK peak intensity was noted during
tempering. This was attributed to the high affinity between
the RE and C atoms, resulting in pinning of the C atoms and
the reduction of the hardenability in the RE-51CrV4 steel.
12 R. Chen et al. / Journal of Alloys and Compounds 824 (2020) 153849

Fig. 13. (a) Micrograph of line 1. (b) TEM micrograph of carbides in RE-51CrV4 steel after 80 min of tempering (upper left inset shows the SAED patterns). (c) Micrograph of line 2.
(d) Interactions between C and RE atoms in line 1. (e) Interactions between C and RE atoms in line 2.

Declaration of competing interest Acknowledgments

Conflict of interest statement: All the authors listed have
approved the manuscript that is enclosed. We declare that we have
no financial and personal relationships with other people or or-
ganizations that can inappropriately influence our work, there is no
professional or other personal interest of any nature or kind in any
product.
This work was supported by the National Natural Science
Foundation of China (Grant No. 51704132) and the Key Research
and Development Program of Jiangxi Province (Grant Nos.
20192ACB50010, 20192BBEL50016, and 20161BBE50065). The au-
thors acknowledge the Fangda Special Steel Co., Ltd and Longyi
Heavy Rare Earths Co., Ltd for their support of raw materials and RE
alloys, respectively.

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