METAL 2006 23.-25.5.

2006, Hradec nad Moravicí

___________________________________________________________________________
STRUCTURE AND FATIGUE FAILURE ANALYSIS
OF NITRIDED NODULAR CAST IRON

Radomila Konečnáa
Gianni Nicolettob
Viera Majerováa
a
Department of Materials Engineering, University of Žilina, Univerzitná 1, 01026 Žilina
Slovakia, radomila.konecna@fstroj.utc.sk
b
Department of Industrial Engineering, University of Parma, Viale G.P. Usberti, 181/A,
43100 Parma, Italy, gianni.nicoletto@unipr.it

Abstract
This paper presents and discusses the influence of a nitriding treatment by the patented
Nitreg Controlled Potential process on the case material structure, the fatigue response and
the fatigue fracture mechanisms of the ferritic nodular cast iron EN - GJS 400. The structural
analysis of the nitrided layer was performed and microhardness 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 nitrided depth. A standard procedure for fatigue curve and fatigue limit
determination at 50 % probability of survival using a limited number of specimens was
adopted. 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. 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.

1. INTRODUCTION
Nodular cast irons (NCI) 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. Three main surface modification factors
are identified: i) control of surface roughness, ii) changes in the mechanical properties of the
metal surface, and iii) changes in the residual stress condition near the surface.
Thermo chemical surface treatments, such as nitriding, are frequently applied to ferrous
materials because they promote the formation of a hard and strong surface layer and of a
system of compressive residual stress that simultaneously improve the fatigue endurance and
the wear resistance, [1, 2]. Since the properties of the nitrided layers depend on the material
and its original pre-process hardness, the part must be given proper preliminary heat treatment
to develop the right kind of structure of the base material. The relative low treatment
temperatures involved in nitriding (i.e. 510 – 590°C) eliminates the need for a final finishing
operation because no phase transformation and part distortion occur upon cooling. Only
proper allowance for material growth should be accounted for.
In nitriding, residual stresses are generated by the distortion of the crystalline lattice due to
diffusion of carbon and nitrogen from the surface and by the specific volume change
following a phase change [2, 3]. Atomic nitrogen is diffused into the metal surface and such

1
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________
diffusion continues as long as the temperature is high enough (usually between 500 °C and
590 °C [4]), and there is a fresh supply of nascent nitrogen. The diffused nitrogen interacts
with the substitutional alloying elements to form an interstitial solid solution. The thin
nitrided layer that forms is usually subdivided into a compound (or white) layer near the
surface (i.e. ε phase: Fe2-3N) usually less than 25 µm thick and a diffusion zone beneath the
compound layer (i.e. phase γ´: Fe4N) [4].
In traditional nitriding, the atmosphere flow rate and the resultant dissociation rate of NH3
are controlled but none of these parameters is directly related to the properties of the nitrided
layer. Recently, a controlled gas nitriding, i.e. patented Nitreg Controlled Potential process
by Nitrex, USA, has been developed based on constant monitoring and maintenance of the
nitriding potential by a computer controlled and fully automated gas nitriding system,
according to the modified Lehrer phase diagram (i.e. plot of nitriding potential vs.
temperature) [4]. The nitriding potential corresponds to the equilibrium concentration of
nitrogen in ferrite for a given temperature and gives the nitriding capacity of the atmosphere.
The nitrided surface, particularly the white layer, obtained with this process is more resilient
with a higher toughness than the traditional process.
This paper presents and discusses the influence of the Nitreg treatment on the hardened
layer structure, the fatigue response and the fatigue fracture mechanisms of a ferritic nodular
cast iron EN - GJS 400.

2. MATERIAL AND EXPERIMENTAL PROCEDURES

The test material was a ferritic nodular cast iron EN - GJS 400 with chemical composition
presented according to the norm EN 1564 in Table1.

Chemical composition of EN - GJS 400 Table 1

Material Chemical composition [%]

C Si Mn S P Mg Cr Cu Sn Ni Mo
GJS 400
3.609 2.684 0.131 0.009 0.033 0.047 0.034 0.037 0.013 0.021 0.016

The following basic mechanical properties of untreated ferritic NCI EN - GJS 400 were
obtained: Rm = 450 MPa, A = 19 %, E = 168 GPa. 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).
The structural analysis was performed on polished and etched specimen cross-sections in
the optical metallographic microscope according to the norm and by 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 nitrided layer were performed by EDS analysis
at TU of Brno.
Microhardness (HV 0.2) was measured on metallographic specimens at different distances
starting from the surface to the base material at TU of Brno. The hardness profile
characterizes the effectiveness of the nitriding treatment and is used to define an effective
nitrided depth. A second method of hardness profile characterization consisted in direct
surface microhardness measurement followed by sequential layer removal until the untreated
substrate is 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.
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

2
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________
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].
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 stress level and
showing very different fatigue lives were selected to identify possible sources of weakness.

3. RESULTS AND DISCUSSION

The objectives of this paper are: i) the presentation of the improvement in fatigue response
of NCI obtained by the nitriding treatment and ii) the search for a structural explanation of
this improvement and of the observed scatter in the nitrided test data. The hardness profile
provides a traditional means to assess the effect of the treatment (peak hardness and effective
hardened depth). The structural analysis of selected fatigue specimens and the fracture surface
investigation provides further insight into the explanation of the observed behavior.

3.1 Fatigue properties

The S/N curves of the untreated and nitrided NCI are shown in Fig.1. The fatigue limit is
σc = 169 MPa in the untreated NCI and σc = 381 MPa for the nitrided NCI. Therefore, 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 [1].

Fig.1. Fatigue data and fatigue curves of NCI at 50 % probability of failure

Inspection of Fig. 1, however, shows also that the scatter in fatigue life is much less in the
untreated condition than in the nitrided condition. For example specimens denoted as number
3 and 4 were subjected to the same applied stress amplitude but their fatigue lives differed by
more than two orders of magnitude. The following part of this contribution will seek a
structural explanation of this different behavior.

3.2 Hardness profiles

Vickers microhardness profiles of the nitrided layer for two fatigue specimens (No. 3 and
4 in Fig. 1) tested at the same stress level are presented in Fig. 2. The hardness decreases with

3
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________
distance from the surface due to decreasing nitrogen penetration but with some differences
between specimens. The peak value for both specimens is about 600 HV 0.2 and it is found at
0.05 mm from the surface. A microhardness of 178 HV 0.2 (measured in distance 0.6 mm
from surface) corresponds with the hardness of the untreated ferritic NCI.
Fig. 2 shows that the trend of the measurements on the cross sections of different
specimens is compatible with reference data obtained by the layer removal technique. The
peak value is slightly lower (HV 0.2 = 555) than the cross-section measurements and the
hardness gradient is steeper than in the case of cross sectional measurements.

b)

Fig. 2. Vickers microhardness measurements Fig. 3. Nitrogen content across the surface
across the surface hardened layer hardened layer

The origin of the local differences in microhardness profiles of the different specimens of
Fig. 2 was investigated by determining the nitrogen distribution in the diffusion zone by EDS
analysis. Fig. 3 shows the content of N in the nitrided layer of the specimens 3 and 4, where
the highest content was measured in the thin white layer. With increasing distance from
surface the content of N decreases more rapidly in specimen 3 compared to the specimen 4.
On the interface of sub-diffused zone and basic material (from 130 to 200 µm) higher
nitrogen content was also found in specimen 3.

3.3 Structural characterization

Therefore, the next step was a structural characterization of the base material and of the
nitrided layer of the two NCI specimens. A metallographic analysis provided insight into the
characteristics of the local microstructural inhomogeneities of NCI in base and nitrided
conditions. The base microstructure is characterized by a ferritic matrix with a regular
distribution of graphite spherical nodules, see Fig. 4a with size ranging from 15 to 30 µm and
a nodule count of N = 197 nodules/mm2. A discontinuous network of carbides on the
boundaries of eutectic cells in the ferrite matrix was also observed, see Fig. 4b. Carbides in
the structure are not eliminated by the surface treatment process and could be responsible of
fatigue scatter.
The carbides were analyzed in the SEM using EDS analysis as shown in Fig. 5. Many
different types of carbides were found depending of the other compositional elements in the
material.

4
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________

a
b

Fig. 4. EN GJS 400 - a) microstructure, etched with 3 % nitric acid, b) discontinuous network
of carbides - specimen 4, SEM

If the basic core microstructure of specimen 3 and 4 (i.e. defined in Fig. 1) is compared, it
is found that the carbide network of specimen 3 (i.e. long fatigue life) was less visible
compared to specimen 4. Significant micro shrinkages were also identified on the boundaries
of eutectic cells and predominately in carbides areas (Fig. 4, 5a).
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 be due to inappropriate
temperature of modification.

a) b)

Fig. 5. Carbides in the matrix of NCI - a) detail of Fig.4b, SEM; b) EDS analysis

5
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________
Inspection of the nitrided layers (see Fig. 6a) showed a thin white (compound) layer (A) on
the surface, a diffusion zone (B) and a sub - diffusion zone (C) [1]. The average ferrite grain
size (dm = 17.6 µm) in nitrided region was not influenced by the nitriding process. The white
layer was continuous with variable thickness from 10 to 28 µm and with local presence of
graphite particles. A local porosity in the white layer of specimen 4 (i.e. short fatigue life) was
found. Thicker nitrided layer and diffusion zone were identified in areas where graphite
particles presence was observed. The carbide localities were observed in diffusion zone (i.e.
Fig 6b). The nitrided layer in specimen 3 was without presence of cracks. In the white layer of
pecimen 4, short cracks initiated on the surface of specimen were observed and a long crack
initiated in the white layer propagated along the boundaries of ferrite grains in diffusion zone.

ba A

carbides
C

Fig. 6. Structure of the nitrided layer – a) etched with 5 % molybdenum acid, b) nitrides on
the boundaries of ferrite grains, specimen 4, etched with Klemm I

Therefore, from these local structural and chemical analyses it appears that the specimen 4,
in comparison with specimen 3, has a non-uniform distribution of N with a high nitride
concentration on the ferrite grain boundaries (see Fig. 6b) that result in a negative influence
on fatigue crack initiation and a short fatigue life.

3.4 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 failure. Stable propagation of fatigue
crack occurs in the first region, while the second correspond to unstable crack propagation at
failure. 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.

6
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________

b
a

Fig. 7. Fracture surface of nitrided NCI - a) nitrided layer - micro shrinkage shown by arrow,
plastic deformation of ferrite around graphite nodule in square, specimen 3;
b) intercrystalline cleavage in diffusion zone, specimen 4, 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. The cracks initiated at casting defects (micro shrinkages) found
below the white layer (see Fig.7a). A detailed study of fracture surface of nitrided layer based
on metallographic study and EDS analyses (see Fig. 5 and 6) showed the presence of carbides
in white layer and in diffusion zone, see Fig. 8. In these places the cracks can easily initiate
because the carbides are responsible of crack creation.

b
a

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

The initiated cracks then propagated in two directions: the growth through the white layer
to the surface of specimen is characterized by transcrystalline cleavage (see Fig. 7a) and the
fatigue cracks propagation into the material (from micro shrinkage at the interface of white
layer and diffusion zone) was characterized initially by local plastic deformation of ferrite
around graphite nodule (see square detail in Fig. 7a). In diffusion and sub - diffusion zone
cracks continued predominately by intercrystalline cleavage along grain boundaries of ferrite

7
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________
grains (see Fig. 7b) and partly by formation of fine striations with more multiple localization
in sub – diffusion zone (see Fig. 9).

Fig. 9. Fatigue region with striations in Fig. 10. Final static fracture with dimple
nitrided specimen 3, SEM morphology in ferrite, SEM

The presence of striations supports plastic deformation mechanisms in ferrite. The fatigue
cracks propagated mainly through the ferrite grains and only rarely along the ferrite/graphite
interface by transcrystalline cleavage. 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 (see Fig .10).

4. CONCLUSIONS
This study has investigated the influence of a nitriding treatment by the patented Nitreg
Controlled Potential process (Nitrex, USA) on the fatigue response of GJS 400 nodular cast
iron with special attention to the origin of scatter in specimen life. The following conclusions
are reached:
• Tests on smooth specimens of nodular cast iron demonstrated a very significant increase
(more than 100 %) in the fatigue limit after nitriding due to the formation of a hardened
surface layer and a residual stress system.
• Fatigue fracture mechanisms were investigated in the SEM demonstrating subsurface
fatigue initiation in the nitrided specimens at micro shrinkages located below the white
layer.
• A structural and local elemental analysis suggests that the reduction in fatigue life of
nitrided nodular cast iron is due to a high concentration of nitrides at ferrite grain
boundaries favoring early crack initiation.

Acknowledgments
This work was done as a part of the SK/IT project No10/NT and SK/CZ project No144
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 acknowledge the contribution of Ing.
Drahomíra Janová (TU of Brno) to the EDS analysis.

8
METAL 2006 23.-25.5.2006, Hradec nad Moravicí
___________________________________________________________________________

References
1. DAVIS, J. Cast Irons/Metallurgy and Properties of Ductile Cast Irons. ASM Specialty
Handbook, The Materials Information Society, USA 1996.
2. NICOLETTO G., TUCCI A., ESPOSITO L.: Sliding wear behavior of nitrided and
nitrocarburized cast irons, Wear, Vol. 197, 1996, pp.38-44.
3. PLUHAŘ, J., KORITTA, J. Strojírenské materiály. 2. přepracované vyd., SNTL - ALFA,
Praha 1977.
4. SINHA, A. Physical metallurgy handbook, 2003, McGraw-Hill, NY, ISBN 0-07-05 7986
-5.
5. SKOČOVSKÝ, P., MATEJKA, M. Mikroštruktúra liatin. ES VŠDS, Žilina 1994.
6. SKOČOVSKÝ, P., PODRÁBSKÝ, T. Colour metallography of ferrous alloys. Žilina,
EDIS 2001, ISBN 80-7100-911-3.
7. BOKŮVKA, O., NICOLETTO, G., KUNZ, L., PALČEK, P., CHALUPOVÁ, M. Low &
High Frequency Fatigue testing. 1. vyd., CETRA, Žilina, EDIS 2002.