The observations presented here, summarized in Table
II, show that internal hydrogen strongly influences the development and local structure of deformation bands in forged 304L stainless steel. First, the density of deformation bands increases significantly with internal hydrogen, in contrast to the NC condition, which is characterized by larger gradients in local misorientation and lower density of deformation bands. In addition, internal hydrogen promotes the development of
ε-martensite within the deformation bands. Second, as straining progresses,
α′-martensite more easily nucleates within the hydrogen-precharged material, preferentially forming at the intersections of
ε-martensite-laden bands. The
α′-martensite nuclei grow elongated along the
ε-martensite laths, generally remaining within the deformation bands. In the absence of internal hydrogen, the deformation bands are dominated by deformation twinning and have only negligible quantities of
ε-martensite, with
α′-martensite observed at grain boundary intersections but not at deformation band intersections. We consider the significance of these observations in greater detail in the next sections.
Table II
Summary of Microstructural Observations
As-Forged | dislocation networks | dislocation networks with extended stacking faults |
5 Pct Strain | planar deformation bands composed of austenite deformation twins | planar deformation bands composed of ε-martensite laths and austenite deformation twins |
20 Pct Strain | intersecting deformation bands composed of austenite deformation twins. α′-martensite was found in small amounts at grain boundaries | intersecting deformation bands composed of ε-martensite laths and austenite deformation twins. α’-martensite predominantly located at deformation band intersections |
In FCC materials such as austenite, glide of
\( \frac{1}{6}\left\langle {112} \right\rangle \) dislocations mediates both deformation twinning and the shear-induced transformation to the HCP structure (such as
ε-martensite).[
9,
48,
49] The difference between these structural outcomes is related to the
\( \frac{1}{6}\left\langle {112} \right\rangle \)dislocations and the faults that they produce in the structure. Specifically, a deformation twin is produced by the successive glide of
\( \frac{1}{6}\left\langle {112} \right\rangle \) dislocations on
adjacent \( \left\{ {111} \right\} \) planes, reversing the stacking from ABCABC to CBACBA at the twin plane.[
8,
9] In contrast, the FCC → HCP transformation occurs by glide of
\( \frac{1}{6}\left\langle {112} \right\rangle \) dislocations on every
second \( \left\{ {111} \right\} \) plane, changing the ABCABC stacking to ABABAB type stacking, a transformation that is structurally equivalent to introducing stacking fault on every other plane.[
8,
9]
Although the nucleation mechanisms for such twinning and shear transformation continues to be a question of research focus,[
9,
50‐
53] it seems clear that factors promoting either an energetic or kinetic preference for stacking fault formation will also promote
ε-martensite over twinning as response to shear stress. Thus, our observations showing the formation of extended stacking faults in the as-precharged microstructure, combined with the observed formation of
ε-martensite at planar deformation bands upon deformation of the HC material suggests a mechanistic link between the effect of internal hydrogen, the prevalence of stacking faults within the microstructure, and the observed preference for strain-induced
ε-martensite over deformation twinning.
It is widely thought that hydrogen reduces the stacking fault energy of austenitic stainless steels. Indeed, observations of
ε-martensite in cathodically charged austenitic stainless steels provided key early evidence for such a hydrogen-induced reduction of SFE,[
27,
28] although as noted above, the interpretation of these results is complicated due to the high surface strains imparted by the cathodic charging. As many have noted, such strains may themselves drive the martensitic transformations in the near surface regions of cathodically charged material.[
28,
30,
32,
34,
54] Unfortunately, there are only a few studies for which experimentally measured values of the influence of hydrogen on SFE in the austenitic stainless steels have been reported, either directly, by
in situ and
ex situ TEM[
27,
55‐
57] or indirectly by X-ray diffraction.[
54] These reports suggest hydrogen-induced reduction of stacking fault energy of at most 14 to 50 pct.
Taken on its own, such a reduction of SFE seems insufficient to explain the necessarily wide dissociation of lattice dislocations into extended faults required to produce bands of
ε-martensite. For instance, based on experimental SFE measurements for non-charged 304L stainless steel, one would expect the equilibrium width of stacking fault ribbons at dissociated lattice dislocations to fall within the range of 5 to 24 nm.[
58‐
62] Since the stacking fault width is inversely proportional to SFE, even a 50 pct reduction in SFE due to hydrogen would at most give an equilibrium fault width of 48 nm.
However, this simple interpretation neglects the response of a dislocation to loading conditions. As Byun
et al., have discussed and modeled,[
63] because the leading and trailing partial dislocations in a dissociated lattice dislocation possess different Burgers vectors, the partial dislocations, will in general, experience different Peach–Koehler forces under load. As a result, above a critical shear stress, the leading partial can break away leaving an extended stacking fault that is bounded only by the distance to a blocking obstacle, such as a grain boundary. The critical stress for the fault divergence falls with decreasing stacking fault energy. Drawing on Byun’s model, Talonen and Hänninen[
7] evaluated the formation of shear bands containing
ε- and α’-martensite in several metastable austenitic stainless steels of differing stacking fault energy, concluding that the model predicted well the critical stresses required for shear band formation by stacking fault divergence.
This notion of stacking fault divergence under load has been further developed by considering the barriers for the nucleation of martensite and deformation twin nuclei[
53,
64] which are also sensitive to stacking fault energy.[
20] The theoretical development by Galindo-Nava
et al.[
53] predicts a progressive change of the deformation microstructure and phase distribution as the stacking fault energy is reduced. For materials with high SFE, the deformation occurs through lattice dislocation slip, but in materials with low SFE there is an increased predominance of deformation twinning, followed by
ε-martensite, and eventually α’-martensite. The transitions between these deformation modes are fairly narrow and very sensitive to SFE and loading conditions. Based on this framework, it seems reasonable to anticipate that even small SFE reductions due to the presence of hydrogen may be sufficient to drive a transition from deformation twinning to shear-banding dominated by
ε-martensite.
Regardless of the underlying mechanism by which hydrogen promotes
ε-martensite, the resulting
ε-martensite does influence the subsequent development of
α′-martensite with further straining. In particular, deformation band intersections, particularly those dominated by
ε-martensite, are known to serve as effective nucleation sites for
α′-martensite. This HCP → BCC (or BCT) transformation behavior has also been observed previously in a variety of austenitic steels and has been thoroughly examined by Olson and Cohen.[
17‐
20] Within the Olson–Cohen model, an intersection between a lath of
ε-martensite and a lath of “faulted”
ε-martensite, provides the proper atomic arrangement for nucleation of
α′-martensite, with a secondary shear provided by
\( \frac{1}{6}\left\langle {112} \right\rangle \) dislocations distributed one to every three
\( \left\{ {111} \right\} \) planes. Prior observations of
α′-martensite nucleation at
ε-martensite intersections for a variety of hydrogen-free systems,[
7,
11,
18,
65‐
67] as well as the observations presented here, are consistent with the preferential nucleation of
α′-martensite at such intersections. Molecular Dynamics simulations by Sinclair and Hoagland[
68] further support the Olson-Cohen mechanism, with the caveat that the generally observed KS orientation relationship, the same one observed in the HC specimen, is not observed in the MD simulations, likely as a result of the high levels of strain required for
α′-martensite to form.
These previous observations are relevant in considering our results since the
α′-martensite is most readily observed under conditions where
ε-martensite laths are well developed, as in the HC material with 20 pct strain. Previous magnetic measurements on the same material by San Marchi
et al., detected more than 1 pct
α′-martensite in the absence of hydrogen only after 20 pct tensile strain at room temperature.[
69] The lack of
ε-martensite laths intersecting other
ε-martensite laths in NC material at 20 pct strain explains the absence of
α′-martensite in the NC samples; greater strain is required to generate these
ε-martensite intersections and induce the
α′-martensite transformation (based on ferritoscope measurements).[
69] Our observations, which link internal hydrogen to the enhanced formation of densely packed
ε-martensite laths, suggest that the
α′-martensite formation is thus a secondary effect of the hydrogen-induced deformation structures and not a direct result of internal hydrogen.
It is important to note that increased formation of
α′-martensite in the presence of hydrogen cannot be inferred for all austenitic stainless steels. For instance, Macadre
et al. observed a reduction of strain-induced
α′-martensite with hydrogen (introduced through thermal precharging) for a metastable Fe-16Cr-10Ni alloy, despite observations of increased localized shear.[
70,
71] This result indicates that although shear localization is a clear effect of hydrogen in stainless steels, increased
α′-martensite formation is not always the result of deformation in the presence of hydrogen and requires a fundamental change in the deformation behavior to occur. Similarly, magnetic measurements on these materials when deformed at low temperature also suggest a reduction in the amount of
α′-martensite transformation, which is attributed to the accommodation of the deformation structures (and presumably the required intersections) when the volume fraction of
α′-martensite transformation exceeds about 20 pct.[
69] It is also important to note that hydrogen-induced shear localization (and
ε-martensite)[
72] can also arise in stable austenitic stainless steels, such as 21Cr-6Ni-9Mn, that do not form
α′-martensite phases and yet still suffer from hydrogen embrittlement.[
73‐
75] Nevertheless, the results presented here illuminate the character of hydrogen-induced deformation structures for the important 304L alloy system and motivate future work to better understand fundamental mechanism by which hydrogen influences the formation of
ε-martensite and the subsequent evolution of hydrogen-induced damage.