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Unusual plate-type iron-carbonitrides development in nitrocarburized

Fe-4 at.% V alloy

A. Kashyap , B. Vishwanadh , A. Chauhan , S.R. Meka

PII: S1359-6454(23)00852-2
DOI: https://doi.org/10.1016/j.actamat.2023.119523
Reference: AM 119523

To appear in: Acta Materialia

Received date: 25 April 2023

Revised date: 13 October 2023
Accepted date: 9 November 2023

Please cite this article as: A. Kashyap , B. Vishwanadh , A. Chauhan , S.R. Meka , Unusual plate-
type iron-carbonitrides development in nitrocarburized Fe-4 at.% V alloy, Acta Materialia (2023), doi:
https://doi.org/10.1016/j.actamat.2023.119523

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Unusual plate-type iron-carbonitrides development in nitrocarburized Fe-4 at.% V alloy

A. Kashyap1, B. Vishwanadh2, A. Chauhan3 and S.R. Meka1

1
Department of Metallurgical and Materials Engineering, Indian Institute of Technology

Roorkee, Roorkee, 247667, India

2
Materials Science Division, Bhabha Atomic Research Centre, Mumbai, 400085, India

3
Department of Materials Engineering, Indian Institute of Science, Bengaluru, 560012,

India

Abstract

The influence of substitutionally dissolved V in ferritic Fe-4 at.% V alloy, on the structure

and morphology of iron-carbonitride ε-Fe3(N, C)1+x and γ'-Fe4(N, C)1-y was investigated

upon salt bath nitrocarburizing. An unusual plate-type morphology of γʹ and ε carbonitrides

development was evidenced during nitrocarburizing of Fe-V alloy as against to the usual

layer-type growth of γʹ and ε nitrides reported for nitrided Fe-V alloys. The ε phase

developed first along ferrite matrix grain boundaries, followed by its formation as plates on

the plates of γʹ within the grains of ferrite matrix and finally as a layer at the surface. In

contrast to ε, γʹ has developed only as plates within the ferrite matrix grains either with

Kurdjumov-Sachs or Pitsch orientation relationship. Initially the inwardly diffusing N gets

consumed for the development of VN precipitates in the ferrite matrix while C gets

enriched at the ferrite-matrix grain boundaries leading to the development of ε carbonitride.

Once all the V precipitates as VN, the development of γʹ occurs as plates within the grains

and upon further increase in the N content lead to the development of ε within grains. This

1
demonstrates that as a consequence of drastically different solubility and diffusivity of C

and N in ferrite, ε and γʹ phases can lead complex microstructural evolution upon

nitrocarburizing of Iron-based alloys.

Keywords: Fe-V alloy, salt bath, nitrocarburizing, iron carbonitrides, nitride-morphology,

vanadium nitride

1. Introduction

It is essential to enhance the life and serviceability of engineering components to reduce the

economic losses which incur from replacing or repairing non-performing components and

also to minimize the adverse changes introduced in the environment as a consequence of

energy spent in components manufacturing and recycling. As surfaces of components

interact with the external environment, most failures are known to initiate from surfaces,

and thus it is of cardinal importance to enhance the resistances of surfaces to wear and

corrosion. In view of this, several dedicated surface treatments were developed for metallic

components to enhance their surface properties. The thermochemical surface treatments,

such as nitriding, carburizing, and nitrocarburizing, which involve the introduction of

interstitial elements like N and/or C into surface regions of steel components lead to a

significant enhancement in surface properties of treated components [1–9]. Although these

thermochemical treatments are quite routinely applied in industries to treat several

engineering components, a complete scientific understanding of the thermodynamic and

kinetic mechanisms of these processes is still lacking. Very recently a new thermodynamic

and kinetic interpretation for the nitriding and carburizing of iron-based alloys is proposed

based on the existence of metastable miscibility gaps in the N supersaturated iron-based

2
solid solutions [10–13]. Most of the fundamental understanding gained in this domain is

largely from the nitriding studies on simple binary [14–22] and ternary iron-based alloys

[23–29] which led to the generation of rich knowledge on how different alloying elements

in steel interact with inwardly diffusing N. During nitrocarburizing, N and C are supplied

simultaneously to the surface of the specimen usually from gaseous or plasma, or salt bath

atmospheres [30–32]. A compound layer developed on the surface after nitrocarburizing

treatment predominantly consists of iron carbonitrides ε-Fe3(N, C)1+x and γ'-Fe4(N, C)

[33,34]. Although nitrocarburizing of pure Fe and Fe-C alloys has been extensively

investigated [32-35], relatively fewer such detailed fundamental investigations on

nitrocarburizing response of model Iron-based alloys exist in the literature [36].

Against this background, binary Fe-V alloy has been chosen to investigate its

nitrocarburizing response. The reason for choosing Fe-V alloy is (i) V is quite commonly

used alloying element in steels and (ii) the existence of extensive literature on nitriding of

Fe-V alloys [18-20,22,37] allows us to compare and contrast the effects of simultaneous

diffusion of C and N on microstructure evolution.

Upon nitriding of Fe-V alloy, equilibrium VN development occurs with prior phase

separation of N supersaturated Fe-V-N ferritic solid solution due to existence of metastable

miscibility gap in the Fe-V-N ferritic solid solution [10]. Initially almost all the V

precipitates as VN in ferrite matrix, due to negligible solubility of VN in ferrite. After that

the successive development of γʹ and ε iron-nitride compound layers occur at the surface of

the specimen [20,37,38]. As often nitriding steels contain both V and C and

nitrocarburization of V alloyed steel involves inward diffusion of C and N, necessitates the

3
need for fundamental investigations on nitrocarburizing of model Fe-V alloys. Objective of

this study is to understand the microstructure evolution during nitrocarburizing of Fe-V

alloy. Main focus is to understand the consequences of (i) V having affinity towards both C

and N and (ii) ε and γʹ iron-nitrides having respectively significant and negligible solubility

for C [39,40], on overall nitride-microstructure evolution. Preliminary work on this topic is

presented recently in the proceedings of a conference [41].

2. Experimental

2.1. Sample preparation

The investigated Fe-4 at. % V alloy casts were produced at Max Planck Institute for

Intelligent Systems, Stuttgart, Germany, by induction melting of the pure elemental metals

in a protective argon atmosphere. Cast alloy was cold-rolled into sheets of a thickness of

approximately 1 mm. From these sheets, rectangular specimens were cut with lateral

dimensions of 15 mm x 10 mm. These rectangular specimens were subjected to

recrystallization in a tubular furnace at 973K (700°C) for 2 h in an argon atmosphere. Then,

the specimens were ground, polished, and ultrasonically cleaned with ethanol.

2.2. Salt bath nitrocarburizing treatment

Salt bath nitrocarburizing was carried using a cyanate-based salt bath [42]. The

composition of the salt bath used and the details of nitrocarburizing treatment carried are

shown in table 1. Salt bath was prepared in an alumina crucible which was heated to the

required temperature in a muffle furnace. After the nitrocarburizing experiment, samples

were quenched in water.

4
 Table 1: Conditions of salt bath nitrocarburizing employed in this study.

Composition of Temperature Nitriding Cooling

salt bath time

88 wt.% KOCN Quenching in

6 wt. % Na2CO3 water after

500℃ 4 h and 10 h
3 wt.% K2CO3 nitrocarburizing.
560°C 4h
3 wt.% CO(NH2)2

2.3. Specimen characterization

2.3.1. Optical and scanning electron microscopy

Cross-sections of the salt bath nitrocarburized specimens were prepared for metallographic

analysis. For this, the nitrocarburized specimens were cut perpendicular to the treated

surface and embedded using electrically conductive powder (ProbeMet). The mounted

specimen cross-sections were then ground and polished finishing with alumina suspension

(particle size of 0.024 μm) followed by etching using 2 vol.% Nital. Such prepared cross-

sections were investigated by light optical microscopy (Leica DMI5000 M) and scanning

electron microscopy. A Zeiss EVO18 SEM equipped with LaB6 filament operated at 20 kV

with 8–10 mm working distance was used.

2.3.2. Electron back scattered diffraction (EBSD)

For EBSD investigation, cross-sections were prepared as detailed above with additional

final polishing using OPS colloidal silica suspension (0.04 μm). EBSD measurements were

5
carried out using Oxford Electron Backscattered Diffraction detector attached with Carl

Zeiss Field Emission Electron Microscope operating at 20 kV. The EBSD data was

analyzed using HKL software. For extracting the crystallographic orientation relationships

between different phases, pole figures were made using TSL OIM 7 software. EBSD

measurements were carried with step sizes of either 0.8 µm or 0.1 µm.

2.3.3. X-ray diffraction (XRD)

For identifying the phases developed on the surface after the nitrocarburizing treatment, X-

ray diffraction (XRD) patterns were recorded from the surfaces of nitrocarburized and un-

nitrocarburized samples. For obtaining the information on phase constitution of the nitrided

layer as a function of depth below the surface, the nitrided surface was ground to a defined

depth and XRD patterns were recorded. A Rigaku SmartLab X-ray diffractometer operating

in Bragg-Brentano geometry equipped with Cu target was used. Measurements were made

with a step size of 0.02° and a scan rate of 1°/min. For Fe-4 at.%V-20at.%N alloy the

estimated penetration depth of Cu-Kα X-ray is between 3 µm to 7 µm in the 2θ range of 30

to 100°.

2.3.4. Electron Probe Micro Analysis (EPMA) and Transmission electron microscopy

(TEM)

For the determination of elemental (Fe, N, C, V) concentrations in the nitrocarburized zone,

EPMA measurements were made on the polished cross sections of salt bath nitrocarburized

specimens employing a JEOL JXA 8230 electron microprobe operating with a tungsten

filament. Measurements were performed with an accelerating voltage of 15 kV and probe

6
current of 50 nA. The Fe-Kα, V-Kα, C-Kα and N-Kα characteristic X-ray peak intensities

were measured using pure Fe, V, C and BN as standards, respectively. Quantification was

carried while applying ZAF correction [43]. ZAF correction method considers the effects of

atomic number (Z), absorption (A), and fluorescence excitation (F) on the intensities of

characteristic X-ray emissions. Site-specific TEM samples from the nitrocarburized

specimens were prepared using the Focused Ion Beam (FIB) system attached with Carl

Zeiss crossbeam Field Emission Scanning Electron Microscope (FESEM) instrument. The

transmission electron microscopy was performed using a Tecnai T20 microscope with an

accelerating voltage of 200 kV.

2.3.5. Hardness measurement

Microhardness measurements were carried out on the cross-sections of nitrided specimens

by use of a Vickers microhardness tester (UHL-VMH). A load of 20 g (0.2 N), an

indentation speed of 50 mm/s and a loading time of 20 s were applied.

3. Results & Discussion

3.1. Microstructure

Light optical micrographs (LOMs) recorded from the cross-sections of salt bath

nitrocarburized Fe-4 at. % V alloy specimens are shown in Fig. 1 (a) and (c). The nitrided

region is distinguishable due to etching contrast generated between nitrided and unnitrided

core (ferrite matrix grain boundaries are more clearly visible in the nitrided region than in

unnitrided core). Nitrided region of thickness 150 μm and 180 μm is visible after

nitrocarburizing at 500oC for 10 h and 560oC for 4 h, respectively. Higher magnification

7
images recorded from the near surface regions indicated an unusual plate-type features

growing within grains and a layer of phase growing along grain boundaries (see magnified

images in Fig. 1 b and d). These plate and layer-type phases were not etched with Nital and

thus appear white in LOMs. This etching effect together with later presented EBSD and

XRD evidences suggest that these plate-type and layer-type phases belong to Iron-

carbonitride compounds. Absence of features in cross-sections representing the cross-

sections of needles, and visibility of same carbonitride plates even after polishing to 5µm

depth suggests that the observed features are of plate-type rather than needle-type.

However, at the nucleation stage the morphology could be starting as needle which later

grows into a plate.

8
Figure 1: Light optical micrographs recorded from cross-sections of Fe-4 at.% V alloy specimens salt bath
nitrocarburized at 500°C for 10 h (a) & (b) 560°C for 4 h (c) & (d). High magnification images in (b) & (d)
show the unusual plate type morphology of carbonitrides.

The crack parallel to the specimen surface visible in Fig.1a (indicated with arrows) appears

to develop as a consequence of the huge volumetric expansion of the nitrided region

leading to the development of residual stresses parallel to the specimen surface.

Precipitation of V dissolved in ferrite (BCC crystal structure with a = 2.866 Å) as VN

(cubic, NaCl type structure with a = 4.139 Å) results in a huge positive volume-misfit of

about 50% and the transformation of ferrite to cubic γ′-Fe4N (a = 3.795 Å) results in

positive volume-misfit of about 16%. In these estimations, small changes in volumes of

9
unit cells due to dissolved V and N in ferrite are neglected which is justified considering

that dissolved N increases the ferrite lattice parameter while dissolved V decreases the

lattice parameter of ferrite [44]. As this cracking phenomenon was not reported in both

internal and external nitrided Fe-4 at.% V alloy [18,20], the abnormal growth of plate-type

iron-carbonitride developed in the current nitrocarburizing experiments appears to be

responsible for the development of cracks parallel to the specimen surface.

Further high magnification SEM images recorded from cross-sections reveal that, in

addition to thicker plates, very fine secondary plates/needles growing from both the

primary plates (figure 2b) and grain boundary layers (figure 2c). In the surface adjacent

compound layer dark appearing nearly spherical regions are of iron-oxide and/or porosity

(later presented XRD results confirm the presence of Iron-oxide within outer layer).

10
Figure 2: SEM micrographs recorded from the etched cross sections of Fe-4 at.% V alloy specimens salt bath
nitrocarburized at 500°C for 10 h. Micrographs shown in (b) and (c) were recorded at higher magnifications
from the regions shown with black and yellow rectangles in (a). In addition to the thicker carbonitride plates
there are also sub-branches growing from the main plates as shown by black arrows in (b) and also some finer
plates grew along grain boundaries as shown with yellow arrows in (c).

3.2. Structure and Morphology of developed phases as a function of depth

In order to identify the crystal structures of different phases developed after

nitrocarburizing, EBSD measurements were carried on the nitrocarburized region. After

nitrocarburizing of an Iron-based alloy, the phases belonging to hexagonal ε-Fe3(N, C)1+x,

face centered cubic γ'-Fe4(N, C)1 and body centered cubic ferrite (α-Fe) are expected in the

nitrided region [30,32]. BSE (backscattered electron diffraction) image shown in Figure 3a

1
Note that the Bravais lattice of γ'-Fe4(N, C) is simple cubic with ordered occupation of N atoms on
octahedral interstitial sublattice [65]. As the superlattice Kikuchi lines will be very weak owing to low atomic
scattering factor for light element N, in EBSD this phase will be indexed as FCC phase.

11
indicates that the plate-type and layer-type features are visible with relatively dark contrast

as compared to ferrite matrix grains which are in agreement with the low average atomic

number for iron-carbonitrides as compared to ferrite. The corresponding band contrast

image also shows contrast for the plate-type and layer-type regions indicating that these

regions are either differently oriented than the surrounding ferrite matrix and/or having

different crystal structure (Figure 3b). EBSD phase map (Figure 3c) indicates that the phase

which is growing along ferrite-matrix grain boundaries is of mostly ε (HCP) and plate-type

phase within ferrite grains is of mostly γʹ with small number of ε plates at the γʹ-plate/ferrite

matrix interface. Location of ferrite-matrix grain boundaries can be identified by comparing

the orientation map (Figure 3d) with phase map (Figure 3c). Orientation map indicates that

all parallel set of plates within ferrite grain have same orientation which implies the

existence of a specific crystallographic orientation relationship (OR) between ferrite matrix

and iron-carbonitride plates (Figure 3d). Close to the surface a layer of ε is present.

12
Figure 3: (a) BSE image (b) Band contrast image (c) EBSD phase map (d) corresponding orientation map
recorded from the cross-section of Fe-4 at.% V alloy specimen salt bath nitrocarburized at 560°C (833K) for 4
h. The phase map indicates the presence of ε phase (green color) at the surface and along the ferrite-matrix
grain boundaries and γʹ phase (yellow color) present as plates within the ferrite grain. Band contrast image,
EBSD phase map and corresponding orientation map of the area shown by black rectangle in (c) has been
shown in (e), (f) and (g), respectively. EBSD phase map in (f) shows the presence of ε phase along ferrite-
matrix grain boundaries (see, dashed black rectangle in (f)) and corresponding orientation map (g) shows that
this grain boundary ε is having nearly equiaxed grain morphology. Within the ε layer (marked with a circle in
(f) and (g) both plate-type and equiaxed-type morphology of ε grains are present.

The grain boundary ε phase (see dashed rectangles in Figure 3f) is of fine grained with

nearly equiaxed morphology and appears to have multiple orientations (see the regions

within dashed rectangles in Figure 3g). Early development of ε along grain boundaries is

possibly due to the C enrichment at grain boundaries in addition to N which leads to ε

development as it can take up both C and N in significant amounts (ε can take up 15 to 33

at. % N and up to about 8 at. % C [32,33,39,40,45]. The ε region marked with black dashed

13
circle in Figure 3f contains two types of morphology with some having plate-type and

others nearly equiaxed (Figure 3g). These two types of morphology for ε grains within ε

layer can be understood as follows. The ε phase growing from grain boundaries of ferrite

matrix are of equiaxed morphology whereas the ε developed on γʹ plate is of plate-type

morphology. With the time, existing γʹ plates and the remaining ferrite matrix are

transforming to ε which results in the two types of morphology for ε in the final ε layer, i.e.,

initially developed plates of ε in ferrite remain with same plate-type morphology in the

final ε layer.

The phases identified by EBSD were also confirmed by X-ray diffraction measurements.

X-ray diffractograms recorded from the surfaces of unnitrocarburized and after polishing

the nitrocarburized surface to different depths are shown in Figure 4. Nitrocarburized

specimen surface evidenced the presence of iron-oxide (Fe3O4) together with the ε

carbonitride. Iron-oxide is possibly developed as a consequence of reactions within the salt

bath which changes the salt bath composition with treatment time. After polishing the

nitrided surface to about 6 μm depth, XRD evidenced the presence of ferrite, ε and γʹ. Upon

further polishing the nitrided surface to a total depth of 25 μm and 28 μm, XRD evidenced

the presence of ε and ferrite and only ferrite, respectively. This sequence of phases present

as a function of depth agrees with the phases as a function of depth observed in EBSD

analysis. In comparison to the peaks of γʹ, ε diffraction peaks are broader which is

attributed to the large non-stoichiometry for interstitials (N and C) in ε than in γʹ which

leads to larger composition gradients in the ε phase [46].

14
Figure 4: XRD patterns recorded from Fe-4 at.% V alloy specimen salt bath nitrocarburized at 500°C for 4 h.
XRD patterns from different depths below the surface of the samples were recorded after mechanically
grinding/polishing of the surfaces to defined depths.

3.3. Vanadium nitrides development in ferrite matrix

The measured elemental concentration depth profile of the nitrocarburized Fe-4 at.% V

specimen is presented in Figure 5a. The measured N content is much above the N solubility

of ferrite (≈ 0.4 at. %) and is also higher than the V content of the alloy suggesting entire V

being precipitated as VN [18,19,22]. The depth of diffusion zone where all V has

precipitated as VN is much larger than the depth up to which plate-type iron-carbonitrides

15
have developed. This suggests that the iron-carbonitrides are growing into the ferrite matrix

containing VN precipitates. An EPMA elemental line scan performed parallel to specimen

surface crossing iron-carbonitride plates is presented in Figure 5b with an overlay of the

corresponding region backscattered electron image. Some iron-carbonitrides showed

relatively higher enrichment of C while others showed lesser C enrichment. This suggests

that some of the plates are of ε which can take up significant amounts of both C and N

while others are γʹ which takes up smaller amount of C [40,47].

Figure 5: (a) Elemental (N, C, V and Fe) concentrations-depth profile of the Fe-4 at.% V alloy specimen salt
bath nitrocarburized at 500°C for 10 h. (b) EPMA line scan parallel to the nitrided specimen surface together
with the overlay of corresponding BSE image. The white dashed line indicates the location of EPMA
measurement.

It is known that nanosized cubic NaCl-type VN platelets develop in the ferrite matrix of

nitrided Fe-V alloys [18]. It is also proposed that prior to VN platelets development, ferrite

matrix can undergo isothermal spinodal phase separation [10,11]. Other well established

evidences for the development of VN platelets in ferrite matrix are expansion of ferrite

16
lattice (which results in shifting of ferrite XRD peaks to lower diffraction angles [44]) and

about 5 fold increase in the Vickers Microhardness2 [18]. In the current work when we

polish off the top compound layer and measured XRD patterns from the underlying ferrite

matrix (i.e., diffusion zone), the measured ferrite diffraction peaks clearly got shifted

towards lower diffraction angles as compared to corresponding peaks of unnitrocarburized

specimens (Figure 6a) suggesting the occurrence of expansion of ferrite lattice of diffusion

zone. The Vickers hardness depth profiles measured on nitrided cross-sections revealed the

6-fold increase in the hardness of ferrite matrix (Figure 6b & 6c). These two evidences

together with the EPMA measurements indicating N content of diffusion zone above the V

content of the alloy suggest the development of VN platelets in ferrite matrix before the

development of iron-carbonitrides.

2
The maximum solubility of N in ferrite is less than 0.4 at.% and this amount of N can only increase the
hardness of ferrite by a maximum of 200 HV [65-67]

17
Figure 6: (a) 200 ferrite matrix reflection recorded from the surface of unnitrocarburized and salt bath
nitrocarburized Fe-4 at.% V alloy for 500°C, 10 h at a depth 36 μm below the surface. Clearly diffraction
peak broadened and shifted to lower 2θ is evidenced. Vickers microhardness-depth profile for specimens
nitrocarburized for (b) 10 h at 500oC and (c) and 4 h at 560oC.

3.4 Crystallographic Orientation Relationships

TEM and EBSD investigations indicated that the γʹ plates have grown with either Pitsch,

and or Kurdjumov-Sachs (KS),

and , orientation relationship with the

18
surrounding ferrite matrix (Figures 7 and 8). Development of ε together with the γ‵ in ferrite

matrix evidenced in XRD and EBSD is also evidenced in TEM characterization (Figure 9).

The SADPs (Selected area diffraction pattern) clearly evidenced the weak diffraction spots

expected for ordered occupation of N atoms on octahedral interstitial sublattice of

substitutional FCC lattice (see, white arrows in SADP in Figure 7). These superlattice

reflections are not evidenced in measured X-ray diffractograms due to very low values of

X-ray atomic scattering factor of N and the increased background intensity associated with

the fluorescence from iron-matrix for Cu-kα X-ray beam. Literature information on the

orientation relationships (ORs) between ferrite and γʹ reported are summarized in Table 2.

The occurrence of both Pitsch and KS ORs between ferrite and γʹ could be due to the

development of γʹ directly in the ferrite and some γʹ developing on ε nitride plates. A

detailed further measurements and investigation of these ORs is essential to clarify the

origins of different ORs. Recently [21,48,49], the crystallography of γʹ developed in ferrite

matrix during nitriding was thoroughly investigated and it has been shown that the

observed crystallography (habit planes and ORs) are as expected from Phenomenological

Theory of Martensitic Crystallography (PTMC). In the current situation due to

simultaneous/sequential development of different nitrides like VN in ferrite matrix and the

γʹ with different crystallographic variants of different ORs alters the course of

transformation crystallography due to evolving composition and misfit strain gradients in

the matrix.

19
Figure 7: TEM BF image and the SADPs from plate-type γʹ (zone axis [ 0] γʹ) and its surrounding ferrite
matrix (zone axis [11̅1] α-Fe). Key diagram after superimposing both the SADPs indicating the existence of K-
S OR between γʹ and ferrite-matrix. Miller Indices for diffraction spots of α-Ferrite and γʹ are indicated
without and with underline, respectively.

20
Figure 8: EBSD phase map (a), orientation map (b), 011 and 111 pole figures of α-Fe (c) and 001 and 110
pole figures of γʹ-Fe4N indicating the existence of Pitsch OR between ferrite matrix and γʹ plates.

21
Figure 9: TEM BF image and the corresponding SADP (zone axis [11̅1] α-Fe and [ֿ123] ε) recorded from salt
bath nitrocarburized (560°C, 4h) Fe-4 at.% V alloy specimen. Key diagram for the measured SADP indicating
the presence of ε in ferrite matrix. Low intensity spots marked with arrows belong to 100 of γ‵. Miller Indices
for diffraction spots of α-Ferrite and ε are indicated without and with underline, respectively.

22
 Table 2: Orientation relationships reported in literature between α-ferrite and γʹ.

Alloy Treatment temperature and method Observed orientation Ref.

nitrided/nitrocarburized relationship

Pure Fe Gas Nitriding [50]

840°C, 2 h, furnace cooled Nishiyama-Wassermann

Fe-4.75 at.% Al Gas Nitriding (011)α-Fe ‖ (111) γʹ [51]

550°C, 20 h, water quenched [100]α-Fe ‖ [1 0] γʹ

[0 1]α-Fe ‖ [ 2] γ

Fe-3 wt.% Si Gas Nitriding [49]

540°C, 1, 4, 16, 48 h, Pitsch

furnace cooled (0 1)α-Fe ‖ (001) γʹ

Single crystal α-Fe Gas Nitriding [111]α-Fe ‖ [110] γʹ [52]

whiskers
550°C, 20 min, furnace cooled [ 11]α-Fe ‖ [ 10] γʹ

Pure Fe Single crystals N ion implantation [53]

Pure Fe Plasma carbonitriding, Kurdjumov-Sachs [54]

600°C, slow cooled & quenched (1 0) α-Fe || (1 1) γ’

Low carbon steel Plasma nitrocarburizing, [ ] α-Fe || [ 0] γ’ [55]

0.08C-0.36Mn-0.032Cr) 560-580°C, 5 h, furnace cooled [ ]α-Fe ‖ [ ] γʹ

Martensitic steel Plasma nitriding, [56]

500°C, 4,8 & 20 min

23
4. Thermodynamic predictions

Equilibrium phases expected during isothermal nitriding and nitrocarburizing of Fe-4 at.

%V alloy was calculated using Thermo-Calc software and TCFE11 thermodynamic

database. For getting an idea of phase evolution during nitrocarburizing, a C content of 0.1

at. % is considered in the alloy while N content is varied. This way the equilibrium phases

evolution with addition of N in Fe-4 at. %V alloy and Fe-4 at. %V-0.1at. % C at 500°C are

presented in Figure 10 and Figure 11, respectively. Thermo-Calc predictions indicated the

development of cementite at smaller N contents (Fig. 11a). As we have observed no

evidence for the cementite development in the samples, we have performed the Thermo-

Calc calculations with suppressing the cementite formation (see Figure 11b). When we

suppress the cementite formation, we expect the formation of epsilon carbonitride at lower

N contents as observed in this study (this study has evidence for initial development of

epsilon along ferrite matrix grain boundaries, Ref. Fig. 3). Note that the Fe-N system was

assessed up to 20 at. %N only in the used thermodynamic database of TCFE11 and thus the

predictions presented beyond 20 at. %N are based on extrapolations and thus needs

precaution in interpretation. During nitriding (Figure 10) inwardly diffusing N is expected

to be consumed for the development of VN precipitates in ferrite matrix and only after all V

is precipitated, the development of γʹ iron-nitride starts followed by the development of ε

iron-nitride. This way the microstructure expected as a function of depth is layer of ε

followed by a layer of γʹ and diffusion zone is reported [20][37]. In contrast to this, an

interesting sequence of phase evolution is expected during nitrocarburizing (Figure 11 b)

where even before all V precipitates as VN, development of ε iron-carbonitride occurs

24
followed by γʹ and again the development of ε. Initially developed ε (i.e., at low N content

of 6 at. %) is stabilized by significant amount of C in addition to N while the later

developed ε iron nitride (i.e., at total N content of 25at. %) is stabilized dominantly by N

(see the composition of phases presented in Table. 3). Even the C content of γʹ is also

initially high as compared to the later developed one. At all stages, VN is stable with

negligible solubility in ferrite and both iron-carbonitrides. The thermodynamic predictions

while suppressing the cementite development indicates the phase sequence as the VN

precipitation in ferrite followed by ε phase development and γʹ and finally a layer of ε at the

surface. In the following section the details on the cementite development is presented.

Figure 10: Equilibrium phase factions as a function of N addition into Fe-4 at. % V alloy at 500°C (situation
which occur during nitriding of Fe-4 at. % V alloy).

25
26
Figure 11: Equilibrium phase factions as a function of N addition into Fe-4V-0.1C at.% alloy at 500°C
(situation which occur during nitrocarburizing of Fe-4 at. % V alloy). (a) when cementite is allowed (b) when
cementite is not allowed. Composition for different phases for alloys (A) and (B) in (b) are presented in Table
3.

Table 3: Showing composition of equilibrium phases for overall alloy compositions marked at (A) and (B) in
figure 11 b.

Overall Alloy Phases ε-Fe3(N,C) γʹ-Fe4(N,C) VN α-

Composition Ferrite
(at. %)
elements
(at. %)
C 7 2 ≈ 0.015
Fe-4V-0.1C-6N
(A) N 13 17 49 0.1
V ≈ 0 33 ≈
C 0.13 0.05 ≈ NA
Fe-4V-0.1C-
25N (B) N 25.26 19.88 48.80 NA
V ≈ ≈ 26.61 NA

4.1 Cementite precipitation during nitrocarburizing

As literature studies evidenced the cementite development in nitrocarburized Iron [32-34],

and also Thermo-Calc predictions also indicate its development (Fig. 11a), we have

investigated in detail about its formation in this study. The smaller step size EBSD scans

carried showed no evidence for cementite even at the grain boundaries of ferrite deep into

the diffusion zone (Fig. 12). All grain boundary phase was indexed as epsilon carbonitride.

The EPMA, XRD and EBSD measurements indicated the absence of cementite in treated

specimens.

27
Literature studies reported the development of cementite at the surface of specimens only at

early stages of nitrocarburizing treatment, i.e., only appears at shorter treatment times

which later transform into epsilon carbonitride [30,32]. Interestingly upon prolonged

treatment times, neither at the specimen surface nor at the compound-layer/diffusion-zone

interface the cementite formation occurs. In order to see whether cementite develops at

early stages in our salt bath nitrocarburizing conditions, we have treated a pure Fe specimen

and Fe-4 at.% V specimen for short durations of 15 min at 500°C. Interestingly, 15 min

treatment evidenced (from XRD) the development of cementite in Fe-4 at.% V alloy while

no evidence for cementite in pure Fe (see Figure 13). Literature shows that the development

of cementite depends on the relative activities of C and N imposed during nitrocarburizing

[33]. Assuming that similar fluxes of C and N enter the surfaces of specimens of pure iron

and Fe-V during the treatment, due to consumption of inwardly diffusing N for VN

development in Fe-V alloy, enhancement in dissolved C content in ferrite occurs leading to

cementite formation. Whereas in pure Iron, both C and N dissolve in ferrite and thus

reduces the C saturation level which diminishes the chance for cementite nucleation. To

further validate this hypothesis, the surface of the 15 min treated Fe-V specimen was

polished to remove the developed iron-carbonitrides and cementite while retaining the

underlying nitrided ferrite matrix already having V precipitated as VN. Such polished

specimen was salt bath nitrocarburized for another 15min and the recorded XRD patterns

(not presented here) from such doubly treated specimen showed no cementite formation

suggesting the role of consumption of N for VN precipitation on development of cementite

at early stages of treatment. However, the unique plate-type morphology of iron-

28
carbonitrides development is not explainable from the thermodynamic predictions

presented in this section. This aspect is discussed in the following section.

Figure 12: Band contrast image, EBSD phase map and corresponding orientation map recorded from the
cross-section of Fe-4 at.% V alloy specimen salt bath nitrocarburized at 560°C for 4 h. The phase map
indicates the presence of ε phase (blue color) along the ferrite-matrix grain boundaries and γʹ phase (yellow
color) present as plates within the ferrite grains. EBSD showed no evidence for cementite formation.

29
Figure 13: SEM micrographs recorded from cross-sections of (a) Pure Fe (b) Fe-4 at.% V alloy specimens salt
bath nitrocarburized at 500°C for 15 min. (c) X-ray diffraction patterns recorded from the surfaces of 15 min
salt bath nitrocarburized pure iron and Fe-4 at. %V specimens.

5. Plate-type vs layer type growth morphology for Iron carbo-nitrides

Fundamental investigations on the nitriding of model binary Fe-V and Fe-Cr alloys have

reported the early development of VN/CrN in the ferrite matrix followed by the usual layer-

type growth of Iron-nitride with incorporation of existing VN/CrN in ferrite into the layer

[20,37,38,57]. Whereas such kind of nitriding investigations on Fe-Al [51], Fe-Si

[21,49,58] and Fe-Mo [59] reported the unusual plate-type iron-nitrides growth into ferrite

matrix as observed in this study. This contrasting morphology of iron-nitride development

in these two alloy groups (Fe-Cr/V and Fe-Si/Al/Mo) has been attributed to the slow

precipitation of nitrides of Si, Al and Mo in ferrite and/or their low solubility in iron-

nitrides. As Cr and V can precipitate rather quickly as nitrides in ferrite, they do not

interfere in the growth of iron-nitrides and thus a layer-type growth occurs.

Various literature studies on nitrided/nitrocarburized steels evidenced the needle/plate-type

nitrides in the diffusion zone below the compound layer. Lee et. al studied the salt bath

nitriding of IF steel at 650⁰C for 3 h followed by air cooling and reported needle-like

nitrides precipitates of γ´-Fe4N and α̋-Fe16N2 below the compound layer [60]. Blawert et. al

studied the plasma nitriding behavior of various ferritic steels (Fe-0.45%C, Fe-0.3% Al, Fe-

3.% Cr) and observed coarse needle-like iron nitrides close to the surface [61]. P. Jacquet

et. al studied the behavior of low-carbon steel and alloyed steel after salt bath

nitrocarburizing followed by post-oxidation and evidenced the sticks of Fe4N below the

compound layer in the case of low-carbon steel [62]. Plasma nitriding of low carbon

30
alloyed steels showed the development of needle-type iron-nitrides (γ´ and/or α˝) in the

diffusion zone [63]. As after plasma nitriding the specimens usually get cooled in the

furnace, most studies indicate the development of needles in the diffusion zone due to the

establishment of N supersaturation of ferrite matrix with decreasing temperature.

As during nitriding of Fe-4 wt. % V alloy, no plate-type iron-nitrides develop, occurrence

of unusual plate-type morphology in the current nitrocarburizing experiments on Fe-

4wt.%V alloy has been attributed to the C which diffuses inwardly in addition to N.

Solubility of N in ferrite is relatively higher than C solubility [64]. Inwardly diffusing N

and C can dissolve interstitially first followed by the development of equilibrium

carbide/nitride/carbonitride phases. As VN can precipitate rather quickly in ferrite, initially

the N gets consumed for this purpose whereas C which has less solubility in both ferrite

and γʹ-Fe4N, can only be accommodated in the ε-Fe1-x(N, C). Due to this C tries to diffuse

inwardly especially along ferrite matrix grain boundaries and the moment VN precipitation

gets completed then N also gets enriched in ferrite adjacent to grain boundaries leading to

the nucleation of ε carbonitride along grain boundaries. With continued N inward diffusion,

grain centers get enriched in N while grain boundary surroundings get enriched in both C

and N. Due to this situation, γʹ nucleates within ferrite grains as plates. In order to minimize

the misfit (volume misfit between ferrite and γʹ) strain energy and interfacial energy, γʹ

develops with a specific orientation relationship with the ferrite matrix [58]. As

nitrocarburizing proceeds, even within grains too C gets enriched leading to the

development of ε plates within grains. This way the ε growing from grain boundaries into

the grains is of nearly equiaxed morphology without any specific OR with ferrite whereas

31
the γʹ and ε grown directly within the grains show plate-type morphology. The plate-type

growth morphology of Iron-Nitrides reported in nitrided polycrystalline Fe-Al alloy and

single crystalline Fe-Al alloy indicated the less role of grain boundaries on developed plate-

type morphology [51]. Also, nitriding studies on single crystalline Iron-whiskers also

showed the development of plate-type iron-nitrides in ferrite matrix suggesting the role of

grain boundaries. The absence of grain boundaries allows the supersaturation of solutes due

to delayed precipitation of product phases and thus can lead to unusual morphologies of

nitrides development [52]. However, in current study as the development of grain-boundary

epsilon carbonitrides is observed, the finer the ferrite grain size the more amount of the

grain-boundary epsilon development can occur. It could be of interest to carry the

nitrocarburizing studies on single crystalline Fe-V alloys to understand the role of grain

boundaries on the observed plate type iron-carbonitrides development.

In the above discussion, the role of VN platelets in ferrite matrix on the growth of Iron-

nitrides is not considered. It is also likely that the existing VN platelets which have cubic

rock-salt type crystal structure could favor the nucleation of cubic γʹ plates. In order to

understand and verify such possibilities high resolution TEM characterization together with

Atom Probe Tomography measurement (APT) are required. The understanding developed

in this study on the microstructure evolution with time during nitrocarburizing of Fe-4 wt.

% V alloy is schematically depicted in the graphical abstract of this paper. Initially the

development starts with the precipitation of VN in ferrite matrix followed by the

development of ε-carbonitride along grain boundaries. Later the γʹ and ε carbonitrides

develop as plates within the ferrite grains with finally leading to the transformation of

32
developed γʹ and remaining ferrite matrix into a ε-iron-carbonitride layer. The schematic

illustration of the evolution of the microstructure as a function of treatment time is

presented in Fig. 14.

Figure 14: Schematic illustration of the evolution of the nitrocarburized microstructure as a function of

treatment time.

Conclusions

In this study, Fe-at.% V alloy was subjected to salt bath nitrocarburizing treatments and the

obtained nitrided zone microstructure was characterized. Based on the experimental

evidences gathered, the following conclusions were drawn;

1. An unusual plate-type γʹ and ε carbonitrides growing within the ferrite grains was

evidenced in addition to growth of ε along grain boundaries. From the primary

33
 plates, fine secondary plates have also grown leading to division of ferrite grain into

compartments enclosed by plates of carbonitrides.

2. The developed plates seem to maintain a specific crystallographic OR with the

ferrite matrix. The ε growing along ferrite-matrix grain boundaries has a nearly

equiaxed morphology. Due to this the finally developed ε layer at the surface

contained grains with plate-type and nearly globular morphology.

3. Ferrite matrix of diffusion zone got expanded and showed 6-fold increase in

hardness suggesting the development of VN platelets in the ferrite matrix. Plate-

type iron-carbonitrides grew into ferrite grains which contained VN precipitates.

4. The occurrence of this unique microstructure has been related to the simultaneous

diffusion of both C and N into alloy and their solubility in different phases.

Solubility of C in ferrite and γʹ is low while significant C solubility exists in ε.

Because of this C gets enriched along grain boundaries which leads to the formation

of ε. This way grain-boundary surrounded ferrite gets enriched with C and thus γʹ

(which has low solubility for C) develops within grains as a plate.

5. It is expected that the developed VN platelets in ferrite matrix can obstruct or

promote the γʹ development based on whether or not the VN/ferrite interface acts as

heterogeneous nucleation site.

6. Under similar short nitrocarburizing times, cementite formation occurs only at the

surface of Fe-V alloy with no cementite formation in pure iron. This has been

attributed to the consumption of N for VN development in Fe-V alloy leading to

34
 enhanced C solubility in the ferrite matrix which promotes the cementite

development.

Acknowledgements

Authors are grateful to Max Planck Society, Germany for financial support to the Max-

Planck Partner Group of the Department of Microstructure Physics and Alloy Design,

Max Planck Institute for Iron Research, Dusseldorf, Germany at Indian Institute of

Technology Roorkee, Roorkee, India and Science and Engineering Research Board

(SERB) DST, India for financial support under CRG scheme CRG/2020/004661.

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Graphical Abstract

44
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:

45