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N SUS Scripta
N SUS Scripta
c
y
c
l
e
-
1
d
a
d
N
10
-11
10
-10
10
-9
10
-8
10 8 6 4 2
2 . 2 M o - 0 . 0 N
0 . 0 M o - 0 . 2 3 N
2 . 2 M o - 0 . 2 4 N
Figure 1. Fatigue crack propagation properties at room temperature (after Hirukawa et al.).
Scripta materialia, vol. 40, 1999, in press.
developed. Several stacking faults are observed with a thickness fringe contrast. This indicates that nitrogen
addition decreases the stacking fault energy significantly as reported by Stoltz and Vander Sande [5].
Although the stacking fault energy is believe to be low in this specimen, planar array of dislocations is not
evident. In contrast, the microstructure of the 2.2Mo-0.2N alloy shows planar array of dislocations. The
planar structure of dislocations were often reported from the specimens with a low stacking fault energy,
because the cross slip difficulty increases as the stacking fault energy decreases. If the cross slip is difficult,
the dislocations are observed along their slip planes and they do not form bands of tangled dislocations. It
should be noted that extended stacking faults are not observed in the 2.2Mo-0.2N specimen at all, although
many stacking faults are observed in the 0.0Mo-0.2N specimen. This suggests that the planar dislocation
structure may not be explained only by the low stacking fault energy.
Figure 3 shows fatigued microstructures of 2.2Mo-0.0N, 0.0Mo-0.2N and 2.2Mo-0.2N specimens at
ta
=1.25 %. In addition to the nitrogen-free 2.2Mo-0.0N alloy, the microstructure of the 0.0Mo-0.2N
specimen shows the dislocation cell structure. However, the microstructure of the 2.2Mo-0.2N specimen still
shows planar bands of dislocations. These results indicate that the dislocation structure in the fatigued
microstructure of the 2.2Mo-0.2N specimen is completely different from those of the 2.2Mo-0.0N and
0.0Mo-0.2N specimens. This again indicates that the reduction of the stacking fault energy alone cannot
explain the extended fatigue life.
( a ) ( b) ( c )
g
2 0 0
g
2 0 0
g
2 0 0
500nm
Figure 2. Fatigued microstructures of cyclically deformed (a) 2.2Mo-0.0N, (b) 0.0Mo-0.2N and (c) 2.2Mo-0.2N alloy at room
temperature (
ta
= 0.6%).
500nm
(c)
g200
(a)
g200
(b)
g200
Figure 3. Fatigued microstructures of cyclically deformed (a) 2.2Mo-0.0N, (b) 0.0Mo-0.2N and (c) 2.2Mo-0.2N alloy at room
temperature (
ta
= 1.25%).
Scripta materialia, vol. 40, 1999, in press.
In order to examine how Mo and N are dissolved in the austenitic phase, the distributions of atoms
were observed by FIM and APFIM. Figures 4 (a) - (c) show Ne field ion images of 2.2Mo-0.0N, 0.0Mo-0.2N
and 2.2Mo-0.2N specimens. In Figs. 4 (a) and (b), all bright spots exhibit the same imaging feature. This
suggests that major alloying elements protruding on the specimen surface are contributing to the formation of
the bright spots with the same manner. In Fig. 4 (c), diffuse bright spots are observed (indicated by arrows) in
addition to the normal bright spots observed in Fig. 4 (a) and (b). These diffuse bright spots are observed only
in the specimen containing both Mo and N, thus it is believed that the diffuse spots are attributed to Mo-N
pair or clusters. Wada et al. [15] reported the presence of such diffuse spots in Ne field ion images of Cr-Mo-
C steel and concluded that these spots are due to Mo-C clusters. They proposed that the diffuse nature of
these spots is due to the protrusion of Mo-C clusters on the specimen surface, which causes higher electric
field than the best image field of Ne. If the bonding of Mo-N is strong, the evaporation field of Mo-N cluster
will be higher than that of the surrounding atoms, and this would also cause diffuse bright spots as seen in
Fig. 4 (c).
Figures 5 (a) - (c) show atom probe mass spectra obtained from the 2.2Mo-0.0N, 0Mo-0.2 N and
( a ) ( b) ( c )
Figure 4. Ne field ion images of the (a) 2.2Mo-0.0N, (b) 0.0Mo-0.2N and (c) 2.2Mo-0.2N alloy observed at 40 - 60K.The
arrows in photograph (c) indicate the diffused bright spots correspond to the Mo-N pair.
Cr
++
Fe
++
Ni
++
Mo
+++
N
+
MoN
++
Mo
++
(a)
(c)
Mo
++
N
+
(b)
Figure 5. Atom probe mass spectra obtained from the (a) 2.2Mo-0.0N, (b) 0.0Mo-0.2N and (c) 2.2Mo-0.2N alloy.
Scripta materialia, vol. 40, 1999, in press.
2.2Mo-0.2N specimens. From the nitrogen-free specimen, all metallic ions are detected as doubly-charged
single metallic ions. All Mo atoms are detected as Mo
++
. When nitrogen is added in the Mo-free specimen,
nitrogen atoms are exclusively detected as N
+
. Although Cr has a strong affinity with N, no CrN compound
ions are detected. On the other hand, in the 2.2Mo-0.2N alloy, nitrogen atoms are detected as MoN
++
ions as
well as N
+
ions. In this specimen, approximately 30 % of N atoms are detected as MoN
++
ions. CrN
compound ions are not detected in this alloy as well. However, it should be noted that this does not rule out
the possibility of the presence of Cr-N pairs in the specimen, since they may be detected as separate Cr and N
ions. In other words, the detection of MoN
++
ion indicates that there is a very strong interaction between Mo
and N, because Mo-N pairs are preserved as molecular ions even after the field evaporation process.
Therefore, it is concluded that the Mo and N form strong I-S atomic pairs in the alloy. From this atom probe
result, the diffuse bright spots in the FIM image can be attributed to Mo-N pairs. Detection of MoN
++
ions
was also reported by Lundin et al. [16] in an 9Cr-1Mo martensitic steel, and they also interpreted this as
evidence for Mo-N clusters.
In order to investigate whether or not these Mo-N pairs form clusters in the austenite phase, the
distributions of the alloying elements were examined by 3DAP. Figure 6 shows 3DAP elemental maps of N,
Mo, Ni and Cr in the 2.2Mo-0.2N alloy. In these maps, each dot corresponds to the positions of the individual
atoms. The uniformly distributed N atoms indicate that nitrogen does not form their own clusters. In addition,
the uniformly distributed Mo, Cr and Ni atoms suggest that austenite phase is a uniform solid solution. It is
known that the affinity between nitrogen and chromium is high. Douglass et al. [10] and Oda et al. [11]
reported the presence of Cr-N clusters and they proposed that these clusters influence the dislocation
structure, thereby changing the cycling deformation mode. Since Cr concentration in the alloy is high (~20
at.%), there is no doubt that many nitrogen atoms have Cr as the nearest neighbor atoms. Assuming that N
atoms occupy octahedral sites, 1.2 Cr atoms are around a nitrogen atom in average. Therefore, N atoms can
move freely throughout the lattice maintaining the contact with at least one Cr atom. Thus, Cr-N clusters, if
present, may not work effectively as obstacles of dislocation motion. In the atom probe analysis, no nitrogen
atoms were detected as CrN molecular ion, suggesting that their bonding is not strong as that of Mo-N.
On the other hand, approximately 30% of nitrogen atoms are detected as Mo-N pairs in the atom probe
mass spectrum obtained from the 2.2Mo-0.2N specimen, Fig. 5 (c). 3DAP results suggest that these Mo-N
pairs are uniformly distributed in the austenite phase. In this case, the densities of Mo-N atom pairs in the
matrix is estimated to be ~ 0.2 nm
-3
. This means the average separation distance between the adjacent Mo-N
pairs is 2.28 nm, which roughly corresponds to 7.9 Burgers vectors. Dislocations moving through the lattice
would have to destroy the strong Mo-N bonding and this would work as strong obstacle for the dislocation
motion. This is in line with the proposal that short range order (SRO) or precipitate particles is more
important factor for the formation of planar dislocation structures rather than the stacking fault energy [12].
Summary
The mechanism of the improved fatigue crack growth properties of SUS316 austenitic stainless steels
by nitrogen addition has been investigated by comparing the fatigue properties of the modified SUS316
N
Mo
N i
C r
~ 2 5 n m
~
1
0
n
m
Figure 6. 3DAP elemental mapping of N, Mo, Cr and Ni obtained from the 2.2Mo-0.2N alloy.
Scripta materialia, vol. 40, 1999, in press.
based steels with and without Mo and N. TEM observations of the dislocation structures and APFIM analysis
results suggest that this effect is not only due to the single addition of nitrogen, but also is due to the
interactions between Mo and N atoms. FIM and atom probe results strongly suggest that there are Mo-N pairs
in the nitrogen containing SUS316 stainless steel, and TEM observation results show the planar array of
dislocations only in the Mo-N containing specimens. These results suggest that the stacking fault energy
alone cannot explain the change in the fatigue properties, but the presence of Mo-N atomic pairs would also
influence the dislocation microstructure.
Acknowledgements
The authors wish to thank Dr. O. Umezawa at NRIM and Prof. W. T. Reynolds Jr. at Virginia
Polytechnic Institute and State University for valuable discussions. This work was supported by the Frontier
Research Center for Structural Materials, NRIM.
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