Surface and Coatings Technology 114 (1999) 94–100

A study of the interfacial structure between the TiN film and the iron
nitride layer in a duplex plasma surface treatment k
Woon-Seung Baek a, *, Sik-Chol Kwon a, Sang-Ro Lee a, Jong-Joo Rha a,
Kee-Seok Nam a, Jai-Young Lee b
a Korea Institute of Machinery and Materials (KIMM), Changwon, Kyungnam 641-010, South Korea
b Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), Taejon 305-701, South Korea

Accepted 26 January 1999

Abstract

The so-called ‘black’ layer between PVD TiN coating and an ion nitrided surface was observed by SEM and TEM to investigate
the detailed microstructure of the interface and the delamination mechanism of the TiN film. Two distinct sublayers were observed
in the black layer. The upper sublayer was of very fine grains and the lower region of 10 times larger grains. The fine grains were
irregular and around 50 nm in size. The larger grains of the lower sublayer were similar to the compound layer underneath. A
Ti-based film was deposited on the surface of the black layer during Ti ion bombardment in a cathodic arc ion plating method
and identified as TiN and Ti phase. The TiN film deposited during Ti ion bombardment was of a very fine grain size and had a
strong preferential arrangement of (200) plane perpendicular to the surface. A lot of pores were observed along the interface
between the TiN film and the upper sublayer. It is suggested that the cracking and delamination of the TiN film be initiated at
these pores during the scratch adhesion test, which thereby decreased the adhesion strength of the TiN film. © 1999 Elsevier
Science S.A. All rights reserved.

Keywords: Adhesion; Black layer; Duplex treatment; Microstructure

1. Introduction formed when Ar ions bombarded the surface of the iron

The duplex surface treatment consisting of ion nitrid-
ing and hard film deposition by plasma-assisted coating
processes has been studied by many researchers [1–8].
The microstructure of the transition interface between
the TiN film and the iron nitride has been shown to be
influenced by experimental conditions and affects the
adhesion strength of the TiN film [9–11]. Quaeyhaegens
et al. studied an effect of the transition treatment
between the ion nitriding and the TiN coating process
on the interfacial structure and adhesion strength [11].
They characterized the interface by using a variety of
physical analysis techniques. A significant change in
nitrogen and titanium content was observed at the
interface depending upon the experimental conditions.
Their results showed that the adhesion strength of the
TiN film decreased with nitrogen content at the interface.
The most distinct transition was the black layer
k
Presented at the AEPSE’97 Conference, Seoul, Asia.
* Corresponding author. Fax: +82 551-80-3599.
E-mail address: bws@kmail.kimm.re.kr ( W.-S. Baek)
nitride of low alloy steel [12]. Sun and Bell stated that
the black layer was so soft, and accordingly weak against
shear, that it may influence badly the adhesion of the
TiN film. Dingremont et al. [13] observed that the main
constituent of the black layer was a-Fe(ferrite) and their
observations about the physical properties of the black
layer were the same as those of Sun and Bell. The
reasons, however, why the ferritic black layer was etched
chemically faster than other regions and appeared black
have not yet been explained.
In this study, the black layer was observed by SEM
and TEM in order to investigate its detailed microstruc-
ture and the interface between the TiN film and the
layer. From the observation of the interfacial microstruc-
ture, a delamination mechanism of the TiN film was
proposed.
2. Experimental
The substrate used for this study was AISI 4140
series low alloy steel (0.4 wt.% C, 0.25 wt.% Si,

0257-8972/99/$ – see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0 2 5 7- 8 9 7 2 ( 9 9 ) 0 0 02 9 - 8
 W.-S. Baek et al. / Surface and Coatings Technology 114 (1999) 94–100
0.75 wt.% Mn, 0.8 wt.% Cr, 0.15 wt.% Mo). The sub-
strate, 22 mm in diameter and 5 mm thick, was heat-
treated and the hardness was HRC 52. The substrate
was ground mechanically with emery paper and then
mechanically polished until the average surface rough-
ness R of 0.02 mm was obtained. The ion nitriding
a
process was carried out in a conventional d.c. plasma
and then the cathodic arc ion plating method was used
to coat TiN film. For the ion nitriding of low alloy steel,
an experimental condition of the total pressure, nitrogen
concentration with hydrogen and substrate temperature
was 2.5 Torr, 70%, and 590°C respectively. The 15
samples were nitrided for 15 h with a bias voltage of
−560 V and a current density of 1.44 mA cm−2. The
nitrided samples were taken out to the atmospheric
environment and reserved in the desiccator. After insert-
ing the nitrided substrate into the ion plating holder
and facing with the arc source of Ti target, the chamber
Fig. 1. Cross-sectional micrographs of the duplex treated low alloy
steel. (a) Optical micrograph showing the black layer with thickness
of around 5 mm. (b) SEM close-up of the black layer. The black layer
consisted of two distinct sublayers. (c) Detailed microstructure show-
ing the etched grain boundaries. (a) and (b) were etched for 20 s and
(c) for 5 s in 3% nital solution.
95
was evacuated down to 5×10−6 Torr while the substrate
was heated to 250°C with a graphite-heating element.
The substrate was bombarded with Ti ions which were
evaporated from the arc source, at a substrate bias
voltage of −1000 V for 30 min, which was used to
modify the substrate surface and increase the adhesion
of TiN film. Thereafter, the TiN film was deposited with
a bias voltage of −100 V and a pressure of
5×10−4 Torr with nitrogen for 2 h.
The cross-sectional surface was polished with Al O
2 3
powder of 0.3 mm, etched with 3% nital solution for 5–
20 s, rinsed with water and dried. The cross-sectional
morphology was observed by optical and scanning
microscopy. The microstructure of the transition layer
Fig. 2. (a) Cross-sectional bright field TEM micrograph of the black
layer. (b) Magnified image of the fine grains and (c) larger grains. The
two sublayers were observed.
96 W.-S. Baek et al. / Surface and Coatings Technology 114 (1999) 94–100
was observed in detail with TEM. The sample for TEM
was prepared by ‘Tripod’ polisher which was well estab-
lished by Southbay Co. [14]. The sample was thinned
finally using an ion miller with two guns for 20 to
60 min depending on the thickness of the cross-sectional
layer. The ion milling conditions were 4 keV, 0.3 mA
per ion gun. The cross-sectional and planar view of
TEM was observed for the microstructural analysis of
grain size, defect and phase between the TiN film and
the nitrided layer.
3. Results and discussion
Fig. 1(a) is an optical micrograph of the cross-section
chemically etched with 3% nital solution for 20 s. It
shows the uppermost TiN film, the black layer 5 mm
thick and the iron nitride compound layer underneath.
The black layer was observed in detail with SEM as
Fig. 3. TEM micrograph of the substrate matrix. The micrograph and
diffraction pattern illustrate that the matrix was mainly of the martens-
itic a∞ phase.
shown in Fig. 1(b). Two distinct sublayers were
observed. The upper sublayer was of fine grains and
darker than the lower sublayer, the grains of which were
about 10 times larger in size. To investigate the etching
behavior of the black layer, the specimen was slightly
etched for 5 s. As shown in Fig. 1(c), the chemical
etching took place mostly along the grain boundaries.
The black layer was observed in more detail by TEM.
Fig. 2 is the bright field image of the layer. It is clear
that the black layer consisted of the two distinct sublay-
ers as observed in the SEM micrograph [Fig. 1(b)].
Fig. 2(a) shows the fine grains of the upper sublayer of
the black layer, the size of which was around 50 nm.
Fig. 2(b) shows the coarse grains of the lower sublayer
of the black layer, the size of which was around 500 nm,
around 10 times larger than those of the upper one.
Fig. 2(c) shows a selected area diffraction pattern
(SADP) taken from the image in Fig. 2(b), which shows
the phase of the black layer was bcc a-Fe. The fine
grains of the upper sublayer are considered to have
resulted from the energetic Ti ion bombardment induc-
ing a higher nucleation density for transformation from
Fig. 4. (a) Cross-sectional bright field TEM micrograph of the black
layer and (b) microbeam electron diffraction of a particle indicated
with a circle in (a), indicating (311) direction of Cr C from the analysis
3
of the diffraction pattern. The chromium carbide was surrounded with
a ferritic a-Fe.
 W.-S. Baek et al. / Surface and Coatings Technology 114 (1999) 94–100
Fig. 5. Cross-sectional bright field TEM micrograph of TiN (a), magnified micrograph of the film near the interface between TiN and the black
layer (b). Electron diffraction pattern illustrates TiN phase (c).
the iron nitride to the ferritic a-phase. The figure shows
a strain field that may come from defects such as high
density of dislocations or point defects inside the grains.
The high etching rate of the black layer may also have
resulted from the high strain field inside the grains [15].
Fig. 3(a) shows the micrograph of the substrate
matrix. Fig. 3(b) shows a selected area diffraction
pattern (SADP) taken from the image indicated A in
Fig. 3(a). The structure appeared lath-shape, that is,
typical morphology of a martensitic phase, and analysis
of the SADP showed that there was a (111) orientation
of the bcc a-Fe phase. From the analysis of the image
and the diffraction pattern, the microstructure of the
substrate matrix was identified as quenched martensite
and the size of grains was much larger than that of the
black layer and the iron nitride.
The behavior of alloying elements such as Cr and
Mo during the ion nitriding process and the formation
of the black layer has not yet been mentioned. Fig. 4(a)
shows the cross-sectional bright field TEM image of the
black layer. Chromium carbide particles were sur-
rounded by grains of the a phase. In Fig. 4(b), micro-
beam electron diffraction was taken from the particle
97
indicated with a circle in Fig. 4(a). From the analysis of
the electron diffraction pattern, the particle was iden-
tified as chromium carbide having a zone axis of (311)
of Cr C. This result demonstrated that the carbide of
3
the alloying element was stable during ion nitriding and
the modification of the iron nitride by energetic Ti ions.
Dingremont et al. suggested that Ar ion bombard-
ment destabilized the iron nitride to form the black
layer [13]. It was observed in this study that the Ti ion
bombardment also modified the iron nitride. After Ti
ion bombarding treatment, TEM analysis was conducted
to investigate how it would modify the surface. Fig. 5(a)
is the cross-sectional TEM micrograph of TiN film
which was deposited for 2 h after Ti ion bombarding
treatment for 30 min; Fig. 5(b) is the magnified view of
the image near the interface and Fig. 5(c) is the diffrac-
tion pattern of the film, indicated with A in the micro-
graph of Fig. 5(b), which was deposited during the Ti
ion bombardment. The main TiN film, deposited with
the experimental condition mentioned earlier, showed a
columnar structure. A film was deposited during the Ti
ion bombarding treatment which also had a columnar
structure and the size of the grains was smaller than
98 W.-S. Baek et al. / Surface and Coatings Technology 114 (1999) 94–100
Fig. 6. Planar bright field TEM micrograph of the film deposited
during Ti ion bombardment (a), SADP of the planar view (b). The
film was identified as TiN and Ti phase. The TiN film was deposited
during the process of the Ti ion bombardment. The incoming Ti ions
reacted with nitrogens dissociated from the ion nitride to form a
TiN layer.
those formed in the condition for TiN deposition. The
diffraction rings agreed well with the lattice indices of
the TiN phase.
Fig. 6(a) is the bright field TEM image of planar
view of the film which was deposited during Ti ion
bombarding treatment for 30 min, without coating TiN
film; Fig. 6(b) is the SADP of the image indicated with
A in the micrograph of Fig. 6(a). Most of the diffraction
rings agreed well with the lattice indices of the TiN
phase as observed at the cross-sectional diffraction
Fig. 7. Cross-sectional TEM micrograph of the interface between TiN
and the black layer. Many pores were found along the interface
between TiN and the black layer. The crack would be initiated and
propagated along the pores.
pattern shown in Fig. 5(c). The diffraction ring of the
Ti phase was also observed, while large particles such
as the Ti droplet were not reacted with the nitrogen
atom decomposed from the iron nitride during Ti ion
bombardment. The diffraction rings obtained from the
image of the planar view were more continuous and
denser than those of the cross-sectional view, which
consisted of many spots. It means that the TiN film
deposited during Ti ion bombardment was of columnar
microstructure. If the film consisted of columnar micro-
structure, the column should be cut perpendicular to
the column during the preparation of planar TEM
sample. The final size of the grain should be so fine that
the diffraction pattern is continuous as shown in Fig. 6.
When the diffraction rings of the planar image were
viewed in detail, the (200) diffraction ring of the TiN
phase was brighter than the others. This means that the
film deposited during Ti ion bombardment had a strong
preferential arrangement of (200) plane perpendicular
to the plane of the surface. From Figs. 5 and 6, we
could reach the conclusion that a bombarding Ti com-
bines with a nitrogen atom dissociated from the iron
nitride at the surface to form TiN. The grain of TiN
was of a fine columnar structure and had strong prefe-
rential arrangement of (200) plane perpendicular to
the surface.
The adhesion strength of the duplex treated TiN
coating was decreased with increasing thickness of the
 W.-S. Baek et al. / Surface and Coatings Technology 114 (1999) 94–100
Fig. 8. (a) and (c) are planar SEM micrographs at the edge and center of the scratch channel, and (b) and (d ) show the Ti mapping result by EDS
of (a) and (c), respectively. Deep pores were found at the delaminated area.
black layer, which was increased with increasing time
of Ti ion bombardment [16 ]. The adhesion strength was
closely related to the microstructure of the interface [9–
11]. Fig. 7 shows the interfacial microstructure between
TiN film and the black layer observed by TEM and the
crack observed at the edge of the scratch-channel by
SEM. The TEM micrograph shows that many pores
were found along the interface, as indicated by arrows
in Fig. 7(a). The cross-sectional SEM micrograph shows
the crack lying in the interface between the TiN film
and the black layer. The crack would be initiated at the
pores and propagated along the interface.
Fig. 8(a) and (c) shows the planar SEM micrographs
taken at the edge and center of the scratch-tested surface,
and Fig. 8(b) and (d ) shows the Ti mapping result by
EDS of Fig. 8(a) and (c), respectively. The deep pores
were found at the delaminated area of the edge and
center of the scratch channel. Sun et al. suggested that
a shearing of the black layer resulted from a decrease
in hardness due to the decomposition of hard iron
nitride, causing a delamination of the TiN film [12].
From the observation of the interface between iron
nitride and TiN, it is suggested that the cracks and
delamination of the TiN film during scratch test would
99
be initiated at the pores and that the soft black layer
would also play an important role in crack propagation.
4. Conclusions
Low alloy steel substrates were ion nitrided and
coated with TiN film. The interface was analyzed micro-
scopically in detail. The black layer formed by Ti ion
bombardment after ion nitriding consisted of two dis-
tinct sublayers. While the upper sublayer showed fine
grains which were around 50 nm in size, the lower one
showed the size of those was around 10 times larger
than those of the upper one.
A Ti-based film was deposited during Ti ion bom-
bardment and identified as TiN film which was of a fine
columnar grain and had a strong preferential arrange-
ment of (200) plane perpendicular to the surface. The
TiN layer was considered to result from the formation
mechanism that the incident Ti ions combine with the
nitrogen atoms dissociated from the iron nitride.
The pores were observed at the upper sublayer along
the interface between the TiN film and the sublayer.
The delamination of the TiN film during the scratch
100 W.-S. Baek et al. / Surface and Coatings Technology 114 (1999) 94–100
test was initiated at the pores. The decrease in adhesion
strength of the duplex coating is considered to result
from the pores as well as from the soft black layer.
Acknowledgements
This work was carried out with the financial support
of the Ministry of Science and Technology (MOST ) of
Korea. The authors would like to thank Dr. A.
Matthews for a sincere review and comments.
References
[1] J. Michalski, E. Lunarska, T. Wierzchon, S. AlGhanem, Surf.
Coat. Technol. 72 (1995) 189.
[2] P.C. Twigg, T.F. Page, Surf. Coat. Technol. 68/69 (1994) 453.
[3] B. Buecken, G. Leonhardt, R. Wilberg, K. Hoeck, H.-J. Spies,
Surf. Coat. Technol. 68/69 (1994) 244.
[4] H.-J. Spies, K. Hoeck, E. Broszeit, B. Matthes, W. Herr, Surf.
Coat. Technol. 60 (1993) 441.
[5] J. Kadlec, V. Hruby, M. Novak, Vacuum 41 (7–9) (1990) 2226.
[6 ] H.-J. Spies, B. Larish, K. Hoeck, E. Broszeit, H.-J. Schroder,
Surf. Coat. Technol. 74/75 (1995) 178.
[7] M. Zlatanovic, T. Gredic, N. Popovic, Z. Bogdanov, Vacuum 44
(1993) 83.
[8] M. Van Stappen, B. Malliet, L.M. Stals, L. De Schepper, J.R.
Roos, J.P. Celis, Mater. Sci. Eng. A 140 (1) (1991) 554.
[9] Y. Anjing, L. Yufei, G. Xiang, L. Pengxing, Conference on Heat
Treatment and Surface Engineering, Chicago, IL, 1988, p. 43.
[10] J. D’Hain, C. Quaeyhaegens, G. Knuyt, L. De Schepper, L.M.
Stals, M. Van Steppen, Surf. Coat. Technol. 60 (1993) 468.
[11] C. Quaeyhaegens, M. Van Stappen, L.M. Stals, F. Bodart, G.
Terwagne, R. Vlaemink, Surf. Coat. Technol. 54/55 (1992) 279.
[12] Y. Sun, T. Bell, Mater. Sci. Eng. A 140 (1991) 419.
[13] N. Dingremont, A. Pianelli, E. Bergmann, M. Michel, Surf. Coat.
Technol. 61 (1993) 18.
[14] J.P. Benedict, S.J. Klepeis, W.G. Vandygrift, R. Anderson, EMSA
Bull. 19 (2) (1989) 74.
[15] Metallography and Microstructures, Metals Handbook, 9th edn.,
Vol. 9 , ASM, Metals Park, OH, 1985, p. 62.
[16 ] W.-S. Baek, S.-C. Kwon, S.-R. Lee, J.-J. Rha, K.-S. Nam, J.-Y.
Lee, Thin Solid Films 323 (1998) 146.