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Influence of nitriding on the fatigue behavior and fracture

micromechanisms of nodular cast iron

Article  in  Strength of Materials · January 2008

DOI: 10.1007/s11223-008-0020-1

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Proceedings of the Conference FRACTOGRAPHY 2006 156
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

INFLUENCE OF NITRIDING ON FATIGUE BEHAVIOR AND

FRACTURE MECHANISMS OF NODULAR CAST IRON
V. Majerová1, R. Konečná1, G. Nicoletto2
1
University of Žilina, Faculty of Mechanical Engineering, Department of Materials
Engineering, Žilina, Slovak Republic
2
University of Parma, Department of Industrial Engineering, Parma, Italy

Abstract
The paper presents and discusses the influence of a nitriding by the
patented Nitreg® Controlled Potential process on the structure of ferritic
nodular cast iron EN - GJS 400 and the fatigue response and fracture
mechanisms. The structural analysis of the nitrided layer was performed
and microhardness was measured on tested specimens. The hardness
profile characterizes the effectiveness of the nitriding treatment and is
used to define an effective nitrided depth. Special attention was given to
the correlation between the structure and fatigue improvement of the
nodular cast iron. Rotary bending fatigue testing shows a significant
increase in fatigue limit of nitrided nodular cast iron and a dual trend in
the S/N curve. Fracture surfaces were selected to investigate and
determine of fracture micromechanisms associated to the increased and
different fatigue lives. Factors such as structure of nodular cast iron,
content of carbides, penetration depth and concentration of nitrogen on
the boundaries of ferritic grains below the white layer were found
relevant.
Keywords: nodular cast iron, nitriding, fatigue, fracture
micromechanisms

INTRODUCTION
Nodular cast irons are construction materials with a wide range of applications in
engineering practice [1]. For their optimal application it is important to know their basic
mechanical properties and the available methods to improve them. Since fatigue resistance
is sensitive to surface conditions, any phenomenon that changes the surface characteristics
of a material will greatly affect its fatigue performance. Thermo chemical surface
treatments are frequently adopted with ferrous materials because they promote the
formation of a hard and strong surface layer and of a system of compressive residual stress.
Therefore, treatments, such as nitriding, simultaneously improve the fatigue endurance and
the wear resistance [1, 2]. In nitriding, nitrogen is diffused into the metal and such
diffusion, once individual atoms of nitrogen have penetrated the surface, continues as long
as the temperature is high enough, and there is a fresh supply of nascent nitrogen on the
surface. A surface exposed to a nitriding medium will generally form two distinct layers.
The outside layer is called compound layer (or white layer) and its thickness generally
ranges between zero and 25 μm (i.e. phases: ε - Fe2-3N) [3]. Phase γ´- Fe4N is known to
have a good ductility particularly in comparison with microstructure containing both ε + γ´
phases, which is brittle. Compound layer of an adequate thickness improves a quality of the
Proceedings of the Conference FRACTOGRAPHY 2006 157
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

surface [4]. Underneath the compound layer is a diffusion zone (i.e. phase: γ´- Fe4N) [3].
The properties of these layers depend on the material and its original pre-process hardness.
This paper presents and discusses the influence of a nitriding treatment by the
patented Nitreg® Controlled Potential process (Nitrex, USA) on the case material structure,
the fatigue response and the fatigue fracture mechanisms of a ferritic nodular cast iron
(NCI).

MATERIALS AND EXPERIMENTAL PROCEDURES

Experimental material was a ferritic nodular cast iron (GJS 400 according to the
norm EN 1564). The chemical composition is presented in Tab.1.

Tab.1. Chemical composition of GJS 400 according to EN norm.

Mat. Chemical composition [weight %]
GJS C Si Mn S P Mg Cr Cu Ni Mo
400 3.609 2.684 0.131 0.009 0.033 0.047 0.034 0.037 0.021 0.016

The basic mechanical properties of untreated GJS 400 were: Rm = 450 MPa,
A = 19%, E = 168 MPa. Two sets of smooth fatigue specimens were prepared by
machining from castings. Then, one set of specimens was subjected to a nitriding treatment
by the patented Nitreg® Controlled Potential process (Nitrex, USA). This process is
basically a gas nitriding treatment using ammonia (NH3) but it differs for the strict control
of the properties of the nitrided surface, particularly with regard to the white layer, which is
more resilient with high toughness than is conventional processes.
The structural analysis was performed on polished and etched specimen cross-
sections on the optical metallographic microscope according to the norm and by methods of
quantitative metallography [5]. The nitrided layer was analyzed using methods of color
etching because a high chemical heterogeneity characterized this region [6]. The analysis of
carbides found in the structure and the distribution of nitrogen in the nitrided layer (below
the white layer) were performed by EDS analysis. The EDS analysis was performed on
EDS counter tube and microscope REM Philips XL 30; conditions were 15 KV and 100 s.
The fatigue S/N curves for the untreated and the nitrided NCI were obtained using
smooth 6-mm-dia specimens on a rotating-bending testing machine operating at 50 Hz (i.e.
load ratio R = -1). A standard procedure for fatigue curve and fatigue limit determination at
50% probability of survival using a limited number of specimens was adopted [7]. Tests
were interrupted at 107 cycles if the specimen did not fail. The fatigue limit σc was
determined according to a reduced staircase method [7].
Microhardness (HV 0.2) was measured on these specimens at different distances
starting from the surface down to the basic material. The hardness profile characterizes the
effectiveness of the nitriding treatment and is used to define an effective nitriding depth. A
second method of hardness profile characterization consisted in direct surface
microhardness measurement followed by sequential layer removal until the untreated
substrate was reached. In this laborious method a greater volume of material is available
under the indenter and a more reliable hardness indication is obtained, especially near the
surface.
Special attention was finally given to the investigation of the fatigue fracture
surfaces using the SEM on selected specimens. The fatigue initiation location and the
mechanisms of stable crack propagation were sought. Nitrided specimens tested at the same
Proceedings of the Conference FRACTOGRAPHY 2006 158
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

stress level and showing very different fatigue lives were selected to identify possible
sources of weakness.

STRUCTURAL CHARACTERIZATION
The NCI considered in this study has a ferritic matrix and a regular distribution of
graphite spherical nodules (Fig.1a) with size ranging from 15 to 30 µm and a nodule count
of 197 nodules / mm2. A discontinuous network of carbides on the boundaries of eutectic
cells in the ferrite matrix was observed, see Fig.1b.

a b

Fig.1. EN GJS 400 - a) microstructure, b) discontinuous network of carbides on

boundaries of eutectic cells - specimen 4, SEM; etched with 3% nitric acid.

A significant presence of micro shrinkages was also identified on these

boundaries. Carbides are undesirable in NCI because they negatively affect the material
strength and the different amount of carbides could be responsible of fatigue scatter.
Nonetheless, they significantly increase the wear resistance. The carbides were analyzed in
the SEM using EDS analysis as shown Fig.2. Many different types of carbides were found
depending of the other elements present in the material according to the chemical
composition.

a b
Fig.2. Carbides in the matrix of EN GJS 400 - a) detail of Fig.1b, SEM; b) EDS analysis.
Proceedings of the Conference FRACTOGRAPHY 2006 159
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

The EDS analysis confirmed an unusual high content of Mg, which, together
with elements like Ce, La and Nd, favors the development of micro
shrinkage cavities. The presence of Mg in the micro shrinkages may probably be due to
inappropriate temperature of modification.
A nitrided layer (i.e. case) (Fig.3a) is formed by a thin white (compound) layer (A)
on the specimens surface, a diffused zone (B) and a sub diffused zone (C).The ferrite grain
size (dm = 44 μm) was not influenced by nitriding. The white layer is continuous with
thickness from 10 to 28 μm and the local presence of graphite particles. Thicker nitrided
layer and diffused zone were identified in areas where graphite particles presence was
observed.

a b
A

Fig.3. Structure of the nitrided layer - a) etched with 5% molybdenum acid, b) nitrides
on the boundaries of ferrite grains, specimen 4, SEM, etched with nitric acid.

RESULTS AND DISCUSSION

Fatigue properties. The S/N curves of the untreated and nitrided NCI are shown in
Fig 4a. The fatigue limit is σc = 169 MPa in the untreated NCI and σc = 381 MPa for the
nitrided NCI. The nitriding treatment is demonstrated to give a very significant
improvement of the fatigue response, confirming the range of improvement determined by
previous tests on steels [7].
The high fatigue strength is not due exclusively to the formation of the hardened
surface layer, because favorable compressive residual stresses are also produced in the
surface layers by nitriding. Residual stresses are generated by the distortion of the
crystalline lattice due to diffusion of carbon and nitrogen from the surface and a change in
the specific volume following a phase change [2, 8].
The scatter in fatigue life of the nitrided NCI data can be rationalized using two
distinct parallel trend lines (A, B) (see Fig.4b). For example, specimens denoted as number
3 (from trend line B) and 4 (trend line A) were subjected to the same applied stress
amplitude but their fatigue lives differed by more than two orders of magnitude. A possible
explanation is advanced in the next section.
Proceedings of the Conference FRACTOGRAPHY 2006 160
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

a b
Fig.4. Fatigue data and fatigue curves of EN GJS 400 at 50% probability of failure.

Hardness analysis. Vickers microhardness profiles of the nitrided layers are

presented. The hardness decreases with distance from the surface, following the decreasing
nitrogen diffusion in the diffused and sub diffused zone to the basic material. Fig.5 shows
that the trend of the measurements on the cross sections of different specimens is similar to
the reference data obtained by the layer removal technique. The two methods of
measurements find reasonably close maximum hardness. The highest value of HV 0.2 =
555 was found in the distance 0.05 mm from the specimen surface, and compares to about
600 HV 0.2 of the cross-section measurements. The values of microhardness decreases with
increasing distance from surface and 178 HV 0.2 (measured in distance 0.6 mm from
surface) corresponds with the hardness of the ferritic NCI.

Fig.5. Vickers microhardness measurements across the surface hardened layer.

A difference between the two methods is found in the hardness gradient: in the
case of cross sectional measurements the gradient is less steep. Local drops in hardness are
also found due to local microstructure inhomogeneities, which are not eliminated by the
hardening process.
Proceedings of the Conference FRACTOGRAPHY 2006 161
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

Figure5 shows that microhardness profiles for long fatigue life specimen 3 and
short fatigue life specimen 4 tested at the same stress level (see Fig.4) are different. A
structural analysis demonstrated when the microstructure of specimen 3 and 4 was
compared, it was found that the carbide network on the boundaries of eutectic cells of
specimen 3 (i.e. long fatigue life) was less visible compared to specimen 4. Significant
micro shrinkages were also identified in the same places and predominately near carbides
areas (Fig.1a, 2a).
The nitrided layer in specimen 3 was without presence of cracks. In the white layer
of specimen 4, short cracks initiated on the surface of specimen were observed. A long
crack initiated in the white layer propagated along the boundaries of ferrite grains in
diffusion zone was found too. Therefore, from these local structural and chemical analyses
it appears that the specimen 4, in comparison with specimen 3, has a high nitride
concentration on the ferrite grain boundaries (Fig.3b), that result in a negative influence on
fatigue crack initiation and a short fatigue life.
Microfractographic analysis. In all fatigue fracture surfaces in untreated and
nitrided specimens, two regions were found: i) the fatigue region and ii) region of final
static fracture (Fig.6a). Stable propagation of fatigue crack occurs in the first region, while
the second correspond to unstable crack propagation at fracture.

a b

fatigue final static

region fracture

Fig.6. Fracture surfaces of nitrided EN GJS 400 - a) character of fatigue fracture - macro
view, b) radial stairs, SEM.

The study of fatigue fracture of nitrided specimens started with analysis of places
of crack initiation. Multiple sites of fatigue crack initiation were confirmed by the presence
of radial stairs on the fracture surface (Fig.6b). The cracks initiated at casting defects
(micro shrinkages) found below the white layer (Fig.7a). In the case of untreated
specimens, the fatigue cracks were initiated in the places of micro shrinkages located in the
subsurface areas. From these places the fatigue cracks progressively propagated generating
striations in the ferrite matrix.
Proceedings of the Conference FRACTOGRAPHY 2006 162
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

a b

Fig.7. Fracture surface of nitrided EN GJS 400 - a) nitrided layer - micro shrinkage shown
by arrow, plastic deformation of ferrite around graphite nodule in square, specimen 3; b)
intergranular cleavage in diffusion zone, specimen 4; SEM.

A detailed study of fracture surface of nitrided layer based on metallographic

study and EDS analyses (Figs.2 and 3) showed the presence of carbides in white layer and
in diffusion zone (Fig.8b). In these places the cracks can easily initiate because the carbides
could be also responsible of crack creation. The initiated cracks propagated in two
directions: the growth through the white layer to the surface of specimen was characterized
by transcrystalline cleavage (Fig.7a) and the fatigue cracks propagation into the material
(from micro shrinkage below the white layer) was characterized initially by local plastic
deformation of ferrite around graphite nodule (see square detail in Fig.7a).

a b

Fig.8. Fracture surface of a) nitrided layer, b) diffusion zone with carbides, SEM.

In diffusion and sub – diffusion zone cracks continued predominately by

intercrystalline cleavage along ferrite grain boundaries (Fig.7b) and partly by formation of
fine striations with more multiple localization in sub – diffusion zone (Fig.9a). The
presence of striations supports plastic deformation mechanisms in ferrite. The fatigue
cracks propagated mainly through the ferrite grains by transcrystalline cleavage and only
rarely along the ferrite/graphite interface.
Proceedings of the Conference FRACTOGRAPHY 2006 163
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

a b

Fig.9. Fracture surface of nitrided EN GJS 400, specimen 3 - a) striations in the fatigue
region, b) region of final static fracture, SEM.

In the region of final static fracture of both untreated and nitrided specimens, the
crack propagated by transcrystalline ductile fracture of ferrite with dimple morphology
(Fig.9b).

CONCLUSIONS
This study has investigated the influence of a nitriding treatment by the patented
Nitreg® Controlled Potential process (Nitrex, USA) on the material structure and on the
fatigue response of EN GJS 400 nodular cast iron. The following conclusions are reached:
• The nitriding treatment generates a hardened layer with a top surface hardness of 600
HV 0.2.
• Tests on smooth specimens of untreated and nitrided ferritic nodular cast iron
demonstrated a very significant increase in the fatigue limit. Therefore, the hardened
surface layer and the residual stress system greatly increase the fatigue resistance of
nodular cast iron.
• Content of carbides was higher for specimens in trend line A with the comparison to
the specimens in trend line B.
• Fatigue fracture mechanisms were investigated in the SEM demonstrating subsurface
fatigue initiation in the nitrided specimens at micro shrinkages located below the white
layer.
• Fatigue cracks propagated in the diffused zone along ferrite grain boundaries where the
high content of nitrogen was found.

Acknowledgments
This work was done as a part of the SK/IT project No10/NT and a part of SK/CZ
project No SK36/CZ 37 and of the Scientific Grant Agency of Ministry of Education of
Slovak Republic and Slovak Academy of Sciences grant No.1/3194/06 It is also consistent
with the objectives of MATMEC, one of Emilia-Romagna newly established regional net-
laboratories (http://www.diem.ing.unibo.it/matmec/). The authors thank to Ing. Drahomíra
Janová (TU of Brno) for performance of the EDS analysis.
 Proceedings of the Conference FRACTOGRAPHY 2006 164
Editor: Ľ. Parilák, Stará Lesná, October 15 - 18, 2006, IMR SAS Košice, Slovak Republic

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