Applied Surface Science 156 Ž2000.

47–64
www.elsevier.nlrlocaterapsusc

Effect of chromium nitride coating on the corrosion and wear

resistance of stainless steel
Jacek Jagielski a , A.S. Khanna b,) , Jacek Kucinski c , D.S. Mishra d , P. Racolta e,
Piran Sioshansi f , Eric Tobin g , J. Thereska h , Vladimir Uglov i , T. Vilaithong j,
J. Viviente k , Si-Ze Yang l , Anton Zalar m
a
Department of Microstructural Research, Institute of Electronic Materials Technology, Warsaw, Poland
b
Department of Corrosion Science and Engineering, Indian Institute of Technology, Powai, Mumbai 400 076, India
c
Material Research Laboratory, Institute of Atomic Energy, Swierk, Poland
d
Department of Physics, Indian Institute of Technology, Powai, Mumbai 400 076, India
e
Cyclotron Laboratory, National Institute of Physics and Nuclear Engineering, Bucharest, Romania
f
Radio-Med, Belford, MA, USA
g
Spire, Belford, MA, USA
h
Industrial Application and Chemistry Section, DiÕision of Physical and Chemical Science, Vienna, Austria
i
Physics of Ion Plasma Modification of Solids Research Laboratory, Department of Solid State Physics, Belarussian State UniÕersity,
Minsk, Belarus
j
Department of Physics, Faculty of Science, Chiang Mai UniÕersity, Chiang Mai, Thailand
k
Surface Technology Department, INASMET-Centro Technologico Materials, Camino de Portuetxe, San Sebastian, Spain
l
Institute of Physics, Chinese Academy of Sciences, Beijing, People’s Republic of China
m
Department of Surface and Thin Film Analysis, Institute of Surface Engineering and Optoelectronics, TesloÕa, SloÕenia
Received 9 February 1999; accepted 18 August 1999

Abstract

Ion beam-assisted deposition ŽIBAD. technique has been used to deposit chromium nitride on the stainless steel
substrates. Characterization and performance of this coating was carried out by a round-robin test at various laboratories.
About 300 samples, prepared at Spire, USA, were distributed to 10 different laboratories. Characterization of coated
materials, carried out using Rutherford backscattering ŽRBS., X-ray diffraction ŽXRD., glancing X-ray diffraction, Auger
electron spectroscopy ŽAES. and X-ray photoelectron spectroscopy ŽXPS., confirmed a well-adherent layer of chromium
nitride with composition and thickness of Cr0.8 N0.2 and 1.2 mm, respectively. The performance of the coating was tested by
tribological tests: dynamic micro-indentation, micro-hardness, wear and friction, and corrosion tests. The coating was found
to be hard with good wear resistance and had enhanced resistance to corrosion in acid media. q 2000 Elsevier Science B.V.
All rights reserved.

Keywords: Chromium nitride; Corrosion; Wear

)
Corresponding author. Tel.: q91-22-576-7891; fax: q91-22-578-3480.
E-mail address: khanna@cc.iitb.ernet.in ŽA.S. Khanna..

0169-4332r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 Ž 9 9 . 0 0 3 5 0 - 5
48 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64
1. Introduction
Surface modification by coatings has become an
essential step to improve the surface properties such
as wear, corrosion and oxidation. Various conven-
tional techniques are utilized for depositing the de-
sired material on to the substrate to achieve the
surface modification. Ion beam-based techniques,
such as ion implantation, ion plating, etc., are known
for a long time. Ion implantation results in a very
thin modified layer, not fully adequate for demand-
ing tribological environments. To get around this
problem, ion beam-assisted deposition ŽIBAD. has
been developed. In this paper, results from inter-
laboratory tests, carried out to characterize and eval-
uate the performance of chromium nitride coatings
deposited on stainless steel using IBAD, are pre-
sented. This technique has been reviewed by Smidt
w1x for the purpose of understanding the role of
adding energetic ions in the conventional physical
vapor deposition ŽPVD. processes. IBAD, also called
ion beam-enhanced deposition, or dynamic ion beam
mixing or ion vapor deposition w2–5x, is presently
being introduced to the industry w6–8x. It has been
recognized that the presence of energetic ion has a
synergistic effect on thin film growth. There are
several aspects of film growth that can be benefi-
cially influenced by ion bombardment during thin
film deposition, including: Ži. film nucleation and
growth; Žii. adhesion w9x; Žiii. internal stress w10x; Živ.
surface morphology; Žv. density; and Žvi. composi-
tion.
Ion bombardment during deposition has also been
shown to produce quite drastic changes. For exam-
ple, Bunshah w11x has reported that ion bombardment
changes a normally columnar morphology of metal
coatings into a denser isotropic structure.
IBAD consists of depositing simultaneously the
desired material using vacuum evaporation and bom-
bardment of energetic ion beam. This technique
combines the advantages of a vacuum coating
method, electron beam evaporation and ion implanta-
tion. In contrast to plasma-based physical vapor de-
position techniques, the actual coating process is
de-coupled from the energy-input process. This
makes IBAD highly versatile and flexible. IBAD has
two basic parameters, the evaporation rate and inten-
sity of the energetic ions, which are independent
from each other and can be varied over a wide range.
As a result, it is highly controllable and reproducible.
Due to these features, IBAD constitutes an excellent
addition to other PVD methods and provides coating
systems with special features, which, in some cases,
cannot be obtained by other techniques. For instance,
a comparison of IBAD and other PVD techniques for
depositing corrosion protection layers on tempera-
ture-sensitive substrates under very low process tem-
peratures showed that the IBAD films generally had
a higher structural density and adhesion to the sub-
strate than the corresponding PVD films. This re-
sulted in a superior corrosion–protection perfor-
mance w12x. The ion beam provides the energy,
which is necessary to grow films with suitable struc-
tures and sufficient adhesion. For a flexible IBAD
system, a very wide range of ion intensities Žcurrent.
and energies should be available. The energies, which
are suitable for optical thin films, are quite different
from those useful for tribologically protective coat-
ings.
2. Experimental
Stainless steel coupons of 20-mm diameter and
2-mm thickness were cut from a controlled lot of an
AISI type 304 stainless steel bar. These samples
were then polished up to a mirror finish using a
series of standard metallurgical polishing steps. Dia-
mond paste was used as a last step. A total of 300
polished samples were then loaded into a planetary
system for rotation and translation to receive a uni-
form chromium nitride coating.
IBAD system of Spire, USA was used for this
purpose. Experimental set-up and mechanism of the
process is shown in Fig. 1. The equipment consists
of a chamber with two independent systems, one for
deposition of Cr by electron beam evaporation and
the other for bombarding the sample surface with
intense beam of N ions at an operating voltage of 1
V. The base pressure of the chamber was maintained
at 5 = 10y7 Torr. Nitrogen pressure was maintained
at 10y5 Torr. The temperature of the substrate was
controlled at 1508C, to obtain the best coating perfor-
mance. Ion current density used was 0.06 mArcm2
and the evaporation rate of Cr was 3–5 Ars, which
was deposited at an angle of 908.
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 49

Fig. 1. Experimental set-up and mechanism of IBAD technique.

The chromium nitride-coated samples, prepared
by IBAD were distributed among the participating
laboratories sponsored by the International Atomic
Energy Agency ‘‘Coordinated Research Programme’’
on ‘‘Modification of Materials by Ion Treatment for
Industrial Applications’’. Each participant was en-
couraged to use the available analytical technique to
characterize the coating and to use appropriate test-
ing method to evaluate the performance of the coat-
ing. The motivation was to provide standard samples
for inter-laboratory tests to validate the characteriza-
tion techniques and provide identical samples for
comparison of performance testing at each labora-
tory.
Chromium nitride was chosen as the coating of
choice for several reasons:
1. It is a fully developed and optimized coating
offered by Spire with extensive laboratory testing
behind it.
2. It is a hard, wear-resistant coating for challenging
industrial applications.

Fig. 2. Backscattered proton spectrum of IB-assisted CrN film on Fig. 3. RBS spectrum of ion beam-assisted CrN film on SS
SS Ž Ep s1.711 MeV.. Ž EA s 3 MeV..
50 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64

3. It is chemically inert and is an ideal coating for

corrosion testing.

The samples were characterized by Rutherford

backscattering ŽRBS., Auger electron spectroscopy
ŽAES., atomic force microscopy ŽAFM., X-ray
photoelectron spectroscopy ŽXPS., X-ray diffraction
ŽXRD. and glancing XRD methods and their perfor-
mance was evaluated by tribological tests, such as
micro-hardness, dynamic micro-indentation, impact,
scratch, dry sliding, wear and friction, and corrosion
tests.

3. Results

3.1. Characterization of chromium nitride coatings

3.1.1. RBS analysis

The composition and thickness of the chromium
nitride film on stainless steel samples were analysed
by RBS method. The experiments were carried out
using a 3-MV TANDETRON at the Surface and
Profile Measurement Laboratory, Hyderabad, India.
The ion beam of a-particle and protons were gener-
ated using the duoplasmatron and sputter ion sources,
respectively. Ion beams of high energy, collimated to
2-mm diameter, were impinged normally on the
targets, placed inside a scattering chamber. A silicon
surface barrier detector Žwith a resolution of ; 11
keV for 5.5 MeV a-particles. mounted at a backward Fig. 5. Photoelectron spectra of Ža. Cr 2p, Žb. N 1s, Žc. O 1s, and
angle of 1688 was used to detect the backscattered Žd. C 1s measured in the CrN coating after 60 min ion sputtering
time in depth of about 70 nm.

Fig. 4. AES sputter depth profile of the CrN-coated SS. Fig. 6. XRD of CrN coated SS.
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 51

Fig. 7. XRD analysis of Ža. AISI 304 and Žb. CrN-coated AISI
304.

particles. Backscattered spectra were acquired by

PC-based multi-channel analyser.
The backscattered spectrum of the chromium ni-
tride film acquired using 14 N Žp,p. 14 N resonance
reaction at 1.74 MeV is shown in Fig. 2. The first
step in this spectrum is due to Cr in the chromium
nitride film, the second due to Fe in the backing
material, whereas, the peak corresponds to N in the
film.
Fig. 9. Scanning electron micrographs of CrN-coated SS 304.
The cross-section of the resonance reaction at
1.74 MeV has been reported to be 145 mbrsr. In
order to estimate the thickness, the film was profiled
by increasing the energy of the beam from 1.74 MeV
onwards in steps of 20 keV.
The width of this resonance reaction is about 4–6
keV. Thus, the reaction yield at the resonance is
sensitive to detector resolution, ion energy and thick-
ness of the film. Therefore, this energy was not
considered suitable for determining the composition.

Table 1
Chemical composition of various elements present in coating
Element Wt.% At.% %S.E.
Fe 5.47 5.11 2.1
Cr 94.53 94.89 0.32
Fig. 8. Glancing X-ray analysis of CrN coated SS.
52 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64
Fig. 10. AFM of polycrystalline CrN coating at two different scan
areas: Ža. 5=5 mm2 and Žb. 2.5=2.5 mm2 .
However, the cross-section of the resonance reaction
is almost constant Ž; 95 mbrsr. in the energy re-
gion of 1.6–1.7 MeV. Hence, 14 N Žp,p. 14 N reso-
nance reaction at different proton energies in this
region was utilized to estimate the composition of
the film. The composition of the film ŽCrrN. ratio,
estimated using the formula:
YCr rYN s NCr sCrrNN s N
where Y s counts under the N peak or Cr step, and
s s respective scattering cross-section.
The composition of the chromium nitride film
was found to be Cr0.75 N0.25 .
The backscattered spectrum of the chromium ni-
tride film obtained using 3 MeV a-particles is shown
in Fig. 3. The step observed at the high energy and
corresponds to Cr in the chromium nitride film
whereas the peak can be attributed to the presence of
an interfacial thin film of Cr. However, the backscat-
tered signal due to N is not discernible.
Table 2
Process parameters for sample preparation
Ball material Ball diameter Applied load Track radius
AISI 52100 steel 10.0 mm 100 g 9 mm
Fig. 11. Friction curves obtained from CrN-coated samples.
The thickness of the film calculated by taking into
consideration the energy separation between the front
and rear edges of the Cr step in the spectrum de-
picted in Fig. 3 is ; 1.3 mm. The stopping power
required for estimating the thickness has been calcu-
lated using TRIM’95. The thickness of the film as
determined by profiling using 14 N Žp,p. 14 N reaction
is in close agreement with this value.
The interfacial chromium is not clearly distin-
guishable while using proton beam ŽFig. 2.. This
film calculated to be ; 1000 A is deposited to
enhance the adhesion of chromium nitride. This study
shows that while 14 N Žp,p. 14 N is suitable for deter-
mining composition of films containing low z ele-
ments, RBS provides valuable information regarding
the film thickness and interfacial regions.
3.1.2. AES
AES was used to determine the composition and
depth profile of chromium nitride coating. The sam-
ple was analysed using a PHI 545A scanning Auger
microprobe with a base pressure in the vacuum
chamber below 1.3 = 10y7 Pa. Static primary elec-
tron beam of 3 keV with 1 mA ion current density
Speed Linear speed Temperature Relative humidity
53 rpm 5.0 cmrs 258C 60%
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 53

and a diameter of about 40 mm was used. The

sample was ion sputtered with 3 keV Arq ion beam,
rastered across an area larger than 5 = 5 mm, with a
sputtering rate of about 5 nmrmin. The Auger peak-
to-peak heights of C Ž272 eV., N Ž379 eV., O Ž510
eV., Cr Ž529 eV., Fe Ž703 eV. and Ni Ž848 eV. as a
function of the sputtering time were quantified by
applying the following relative elemental sensitivity
factors: S N s 0.32, SO s 0.50, SCr s 0.32, SFe s 0.2,1
and S Ni s 0.29. The sensitivity factors were gained
from the measurements of standards.
Fig. 4 shows the AES depth profile of the as-de-
posited chromium nitride coating on the stainless
steel. The elemental composition of the coating by
design does not correspond to the stoichiometric CrN
Fig. 12. Friction curves obtained from AISI 52100 steel, CrN
with the atomic ratio CrrN s 1r1. The maximum Žsample 1., TINALOX and Ti-DLC-coated samples.
concentration of the N at the coatingrsubstrate inter-
face is about 27 at.% and is gradually decreased up
to the coating’s surface where the concentration is
acquisition was performed by an Apollo workstation
about 22 at.%. The chromium rich chromium nitride
interfaced with the spectrometer. The peak areas of
coating with this composition has excellent proper-
Cr 2p, N 1s, O 1s and C 1s were registered and the
ties and has been developed based on many years of
atomic concentration was calculated through a proper
research. The average concentration of C in the
area calculation and using correspondent sensitivity
coating was about 1 at.% and the surface of the
factors.
chromium nitride film was slightly oxidized.
Contrary to the AES results, the XPS analysis
also showed presence of oxygen besides carbon in
3.1.3. XPS
the coating ŽFig. 5.. In the XPS spectra, the corre-
XPS analysis on chromium nitride-coated stain-
sponding peaks of Cr 2p at 574.2 eV, N 1s at 396.6
less steel substrate was carried out on a Perkin-Elmer
eV ŽFig. 5b. O 1s at 529.5 eV ŽFig. 5c. and C 1s at
5300 spectrometer with a hemispherical electron en-
281.9 eV ŽFig. 5d. are characteristics for chromium
ergy analyser using Mg K a irradiation. The CrN
nitride, oxide and carbide, respectively. XPS sputter
coating was sputtered using a differentially pumped
depth profiling also revealed the following composi-
3 keV Ar ion gun at an incidence angle of 458C. The
tion of the coating: 75 at.% Cr, 16.0 at.% N, 5 at.%
sample was ion sputtered over an area of 5 = 5 mm,
O and 4 at.% C.
with a sputtering rate of about 1.2 nmrmin. The size
of an analysed area was about 1 mm2 . The data
3.1.4. XRD analysis
The XRD of chromium nitride-coated SS 304 is
given in Fig. 6. The amorphous pattern can be
Table 3
Wear areas obtained by optical laser profilometry from worn
chromium nitride coatings
Chromium nitride coatings Wear tracks area Žmm2 . Table 4
Worn areas measured by optical profilometry
Sample 1 0.0000225
Sample 2 0.0000225 MaterialsrCoatings Wear track areas Žmm2 .
Sample 3 0.0000500 AISI 52100 steel 0.0001025
Sample 4 0.0000500 Chromium nitride Žsample 1. 0.0000225
Sample 5 0.0000525 TINALOX 0.0000475
Sample 6 0.0000525 TI-DLC 0.0000275
54 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64

Table 5
Dynamic micro-indentation results for chromium nitride and its substrate material
Chromium nitride coating Steel substrate
Vickers hardness at 10 mN 16749 Nrmm2 3728 Nrmm2
Relative elastic recovery 35.96% 8.48%
Total work ŽJ. 0.75 1.51
Elastic work Ž%. 46.59 10.35
Plastic work Ž%. 53.41 89.65
Young modulus ŽGPa. 201 165
Plastic hardness ŽNrmm2 . 14373 Nrmm2 2549 Nrmm2

observed very clearly from the XRD spectrum. The tric drives. AFM provides a topography image and
first peak that appeared at about 438 Ž2 u . is g-Fe quantitative topography information ŽFig. 10.. The
Ž111.. The second peak at about 50.58 is g-Fe Ž200.. most frequently used roughness parameter is R a ,
The third peak at about 748 is g-Fe Ž220.. The fourth which is the arithmetic mean of the deviations in
peak at about 908 is g-Fe Ž222.. The amorphous height from the profile mean value. The root mean
peak at about 428 is of CrN peak. square ŽRMS. roughness values based on the power
XRD of AISI 304 SS and CrN-coated AISI 304 spectral density, which is defined as the square
SS are also shown in Fig. 7a and b, which reveal that magnitude of the Fourier transform of the surface
chromium nitride coating consists mainly of Cr2 N profile. The values of the roughness parameters de-
phase Ž28 at.% 0f N. with some quantity of pure Cr. termined are: R a s 5.91 nm and RMS s 7.53 nm.
The presence of CrN phase cannot be determined
unambiguously because CrN diffraction lines coin- 3.2. Performance of chromium nitride coating
cide with diffraction lines of Cr2 N and substrate
g-ŽFe, Cr, Ni..
3.2.1. Tribological and dynamic micro-indentation
test
3.1.5. Glancing X-ray analysis
Tribological and micro-indentation tests were per-
The results of glancing X-ray analysis of
formed on chromium nitride-coated SS substrate.
chromium nitride-coated stainless steel samples are
given in Fig. 8. These results confirm the coating as
Cr2 N with grain size of 5 " 2 nm in Ž002. plane.
Grain size was calculated using XRD by means of
the Scherrer formula w13x. It also confirms that the
thickness of the coating is equal to around 1.2 mm,
which is also confirmed by RBS method.

3.1.6. SEM r EDAXr AFM

Surface of chromium nitride-coated SS 304 was
analysed by scanning electron microscopy. The coat-
ing was found uniform and dense. Some voids were
also present in the coating ŽFig. 9.. The composition
of the chromium nitride layer as measured by EDAX
is given in Table 1.
The AFM measurements were performed on a
Topo-Metrix TMX 2000 Explorer in ambient condi-
tions. In this equipment, the cantilever with the tip Fig. 13. Loading and unloading curves from substrate and CrN
scans over the fixed sample by means of piezoelec- coating after micro-indentation experiments.
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 55

Fig. 16. Wear trend for SS and CrN coating. Žloads1.5 kg,
Õ s 0.5 mrs, sliding distances 250 m..

Fig. 14. Dry sliding analysis for CrN-coated and uncoated AISI
SS304.
information, is an ultra-hard coating, specially devel-
oped for metals with a hardness of 3300 HV0.05.
The coating withstands temperatures up to 8008C
The ball-on-disk friction and wear tests were per-
and, as a result of its low thermal conductivity,
formed on a TRIBOMETEER FALEX ISC 320. The
protects the tool against damage due to high temper-
samples were identically prepared. General condi-
atures. The results are presented in Fig. 12 and Table
tions of the test for all the samples are specified in
4.
Table 2.
Dynamic micro-indentation tests were carried out
The friction curves for all chromium nitride sam-
with the FISHERSCOPE H100 MICROHARDNESS
ples are presented in Fig. 11, where a dispersion of
TEST SYSTEM with load increments until a maxi-
results can be observed.
mum load of 10 mN was achieved and finally de-
The wear tracks after an UBM OPTICAL PRO-
creasing the load. At each loading and unloading
FILOMETRY SYSTEM examined the tests, and the
sequence, the vertical displacement Žindentation
worn area was calculated for all the samples. The
depth. of the indentor into the material is recorded.
results are indicated in Table 3. For comparison,
The results obtained are given in Table 5. The
results from a set of coatings, including TINALOX
loading and unloading curves for both the CrN coat-
and a Ti-doped DLC coating are also given.
ing Žlower curves. and the corresponding substrate
TINALOX is a trade name of CemeCon for a coat-
material Župper curves. are presented in Fig. 13. In
ing produced by magnetron sputtering with a compo-
this figure, it is clearly seen that the elastic recovery
sition of TiAlN. This coating, according to CemeCon
and hardness values for the coating are significantly
higher than the base material.
Dry sliding test on chromium nitride-coated and
uncoated AISI 304 steel samples is presented in Fig.
14. In this figure, it is clearly seen that the friction
coefficient of chromium nitride coating Ž m s 0.4. is

Table 6
Wear rate and coefficient of friction for SS and CrN coated SS
Sample Coefficient of Wear rate
friction Žmmrmin.
Stainless steel 0.54 2.24
Fig. 15. Wear trend for SS and CrN coating. Žloads 0.5 kg, CrN-coated SS 0.47 1.75
Õ s 0.5 mrs, sliding distances 250 m..
56 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64

1.5 times less than that of AISI 304 steel substrate at
the load of 0.7 N.
Wear and Friction tests were carried out on pin-
on-disk wear machine, as per ASTM standard G
99-90. The apparatus consist of a cylindrical pin,
which is pressed vertically against a rotating disk. A
desired load is applied to the pin while it is sliding.
The bottom surface of the pin and the face of the
disk together from a wear couple. En 32 steel is the
disc material. The CrN-coated stainless steel sample
cut into a size of 0.5 mm2 was mounted horizontally
on the cylindrical pin. The experiment is carried out
for a particular duration for which a time setter is
provided. A linear variable differential transducer

Fig. 17. Surface profiles using 3D Tayler–Hobson Profilometer for Ža. as-deposited and Žb. nitrogen-implanted chromium nitride-coated
stainless steel specimens.
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 57

Table 8
Results of microhardness test of chromium nitride coated and
uncoated 304 SS sample
Av-HK saverage Knoop hardness; Av-HVsaverage Vickers
hardness; Dev sdeviation.
Sample Av-HK Dev Av-HV Dev
surface Žkgrmm2 .
Chromium nitride-coated 1013.6 59.8 988.9 74.4
Uncoated 230.9 8.9 213.4 6.6

Fig. 18. The loading–unloading curves for three indents made
with maximum load of 2 mN.
ŽLVDT. sensor converts the displacement of the pin
into an electronic signal, which, when connected to a
computer terminal through a software, gives a graph-
ical plot of a wear vs. time. The frictional force can
also be obtained through a load cell. The speed of
the rotating disk can be varied when desired.
The results are obtained in the form of a plot of
‘‘Displacement in microns vs. Time in minute’’ and
‘‘Frictional force vs. Time’’. The test was carried
out at a load of 0.5 kg Ž5 N. for the sliding distance
of 250 m at a sliding velocity of 0.5 mrs. The plots
of displacement vs. time are shown in Figs. 15 and
16 for a load of 0.5 and 1.5 kg, respectively. Ini-
tially, some scatter in the data was observed but later
on the overall trends were found to be uniform.
The slope of displacement vs. time gives the wear
rate of the coatings in microns per minute. From the
plots of frictional force vs. time, coefficient of fric-
tion can be calculated as given in Table 6.
Wear and friction tests were also carried out on
nitrogen implanted chromium nitride-coated samples.
The as-deposited chromium nitride layers were nitro-
gen implanted up to a dose of 5 = 10 16 Nq 2
2 rcm ,
17 q 2 17 q 2
1 = 10 N2 rcm , 2 = 10 N2 rcm by 100 keV
molecular nitrogen ion ŽNq 2
. beam. The test was
carried out using a ball-on-flat Tribotester. The 6.5-
mm balls were used as a counter sample. The test
was carried at a load of 5 N in air up to 300
oscillations. The values of friction coefficient were
found to be 0.76 to 0.8 for the as-deposited low- and
medium-dose nitrogen-implanted samples. For the
highest nitrogen implanted dose, the friction coeffi-
cient value dropped down to 0.54.
The extent of wear was determined using a 3D
Taylor–Hobson Profilometer. The typical surface
profiles obtained for as-deposited and high-dose ni-
trogen-implanted samples are shown in Fig. 17. It is
interesting to note that striking reduction of wear
was observed after nitrogen implantation.
3.2.2. Hardness and modulus
The hardness and modulus of the chromium ni-
tride-coated samples were measured using an ultra-
low load depth sensing force transducer for the
Digital Instruments Nanoscope III, developed by
Hysitron. The Hysitron Triboscope has a load resolu-
tion of 100 nN and displacement resolution of 0.2

Table 9
Results of scratch and adhesion tests for SS and CrN coated SS
Table 7 Loading Scratching Adhesion
Result of hardness and modulus test of coated material at different rate speed strength
load Žkgrmin. Žmmrmin. Ž=10 7 Nrm2 .
Load Hardness H ŽGPa. Load modulus E ŽGPa.
4 5 120
2 mN 18.4"1.2 234"12 3 4 130
5 mN 19.6"1.5 198"9.5 4 3 125
58 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64

Fig. 19. Žtop. Microphotographs of the tracks made with diamond stylus in scratch test. The images show the early part of the tracks. Ža.
As-deposited CrN layer, Žb. CrN layer implanted with 140 keV N2 q ions up to a dose of 2 = 10 17 Nq 2 Ž
2 rcm . middle Microphotographs of
.
the tracks made with diamond stylus in scratch test. The images show the middle part of the tracks. Ža. As-deposited CrN layer, Žb. CrN
17 2 Ž
layer implanted with 140 keV Nq 2 ions up to a dose of 2 = 10 Nq
2 rcm . bottom Microphotographs of the tracks made with diamond
.
stylus in scratch test. The images show the end part of the tracks. Ža. As-deposited CrN layer, Žb. CrN layer implanted with 140 keV
17 2
Nq2 ions up to a dose of 2 = 10 Nq2 rcm .
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 59

nm. Indentations were made using a Berkovich dia-

mond tip to a maximum load of 2 and 5 mN. The
loading–unloading behavior was analysed using the
method of Oliver and Pharr w14x The load displace-
ment curves of the 2-mN load for three indents are
shown in Fig. 18. Result of hardness and modulus is
given in Table 7.
While the hardness is approximately the same for
both loads, the modulus is different. The reason is
that the indents made with 5 mN are strongly influ-
enced by the substrate. The measured hardness, how-
ever, seems to be the real hardness of the film.
Microhardness test on chromium nitride-coated
and uncoated SS 304 samples were performed by the
MXT-a Digital Microhardness using a load of 5 g.
The result is shown in Table 8.

3.2.3. Adhesion and scratch test
The adhesion test on chromium nitride-coated SS
304 substrate was carried out by using Scratching
Tester equipped with a diamond tip and sound sen-
sor. The adhesion strength was given by the output
data of the Scratching Tester, and not from calcula-
tion using a formula. The data are shown in Table 9.
The adhesion of the deposited layers on AISI
316L steel coated with chromium nitride, was also
measured using a scratch test apparatus. Diamond
stylus having 120 mm in diameter spherical tip was
used as a counter sample. The stylus was mounted
on the lever having the stiffness of 45.739 mNrmm.
The first part of the test was devoted to the
determination of the critical load, i.e., the load caus-
ing the layer damage. The speed of translation was
set to 0.1 mmrs. The critical force value was deter-
mined from the length of the crack from the track
beginning up to the place in which the first traces of
damage were observed. The tests were done on
untreated samples and chromium nitride layers prior
and after nitrogen implantations. During the tests
performed in increasing load mode, tensile type
Hertzian cracks were observed for loads exceeding
700 mN ŽFig. 19.. This type of damage suggests that
the CrN0.4 layer was not delaminated from the sur-
face of the sample. The final depth of the track
equals to several micrometers Žtypically 3.5–4 mm.
ŽFig. 20.. This value exceeds the total thickness of
the deposited layer. Nevertheless, even at the end of
Fig. 20. Surface micro-topography of the end part of scratch track
for CrN coated SS.
the track the chromium nitride layer remains bonded
to the substrate ŽFig. 19 Žbottom... One can thus
conclude, that the soft austenitic substrate became
contorted, however, due to the strong adhesion, the
chromium nitride layers bends following the sub-
strate deformations. Only slight differences were ob-
served between as-deposited and nitrogen ion-im-
planted chromium nitride layers. At the beginning
ŽFig. 19 Žtop.. and in the middle ŽFig. 19 Žmiddle..,
the cracks seem to be less in numbers and shallower
in the case of nitrogen implanted layers. The differ-
ence disappears at the end of the cracks ŽFig. 19
Žbottom...
The tests in multi-pass mode Žconstant load 700
mN, speed of translation 0.05 mmrs, up to 100
scans over the same area. revealed good adhesion
and low wear of the deposited layers. In all tests
performed on as-deposited CrN layers neither delam-
ination, neither complete wear of the deposited lay-
ers was observed. Typical images of tracks after 1,
10, 100 and 150 passes are shown in Fig. 21.
It is interesting to note that after the constitution
of the wear track occurring during the first few
passes Žless than 10. the tracks remain almost un-
changed during the test. Fig. 22 presents the mi-
 60
J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64
Fig. 21. Microphotographs of the tracks made with diamond stylus in scratch test. The images show the middle part of the tracks. Ža. 1 pass Žb. 10 passes, Žc. 100 passes, Žd. 150
passes.
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64 61

Fig. 22. Microphotographs of the tracks made with diamond stylus in scratch test. The images show the middle part of the tracks. Ža. 10
pass, Žb. 100 passes.

crophotographs taken from the CrN sample used in 3.2.4. Impact testing
multi-pass test after 10 and 100 passes. Both images Impact test of the coated material was carried out
are almost identical, neither width nor the depth of by using Impactor-I. Results of impact test on
the tracks changed significantly. The results of pro- chromium nitride-coated SS 304 samples using 0.035
filometric analysis performed on the CrN samples J impact energy are given by the following.
after 10 and 150 passes are shown in Fig. 23a and b,
respectively. In both cases, the depth of the worn Measuring condition:
track roughly equals 1 mm.
CrN layers revealed very good adhesion to the Impacting energy: 0.035 J for each impacting
substrate. The critical load in scratch test required to Frequency: f s 2.5 timesrs Total impacting
cause layer-cracking equals to about 700 mN in test numbers: 200
using 120-mm-diameter diamond stylus. Frequency: f s 3 timesrs Total impacting
numbers: 3000
62 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64

Fig. 23. Ža. Profilometric analysis of the tracks made in multipass test after 10 passes. Žb. Profilometric analysis of the tracks made in
multipass test after 150 passes.

After impacting, the chromium nitride coatings of 3.2.5. Corrosion test

two samples were not broken or peeled off, confirm- Corrosion tests were carried out in 1 N H 2 SO4
ing a good impact resistance of the coating. solution for the base SS 304 and chromium nitride-
 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64
Fig. 24. Anodic polarization curve of Ža. SS 304, and Žb. CrN
coated SS 304.
coated SS samples by Potentiodynamic scan. Both
samples were scanned from y0.2 to 1 V with a scan
rate of 1 mVrs. A standard three-electrode set-up
was used for corrosion test of coated and uncoated
material. Coated material was used as a working
electrode and platinum strip was used as a counter
electrode. Saturated calomel electrode ŽSCE. was
used as a reference electrode for measuring the
potential of coated material. The anodic polarization
curves are given in Fig. 24a and b. Icorr value was
measured by extrapolating tafel plots and corrosion
rate ŽCR in mryr. was calculated from the following
formula.
CR in mryr s 0.471 Icorr .
Table 10
Results of anodic polarization tests of SS 304 and chromium nitride SS 304 in 1 N H 2 SO4 on SS specimen
Sample Eocp ŽV. Area Žcm2 .
SS 304 y0.527 1 508.4
Chromium nitride-coated 0.245 0.42
63
The following inference can be obtained about the
corrosion behavior of the coated and uncoated speci-
mens ŽTable 10..
It is clear that Ecorr and Icorr values are much
lower for chromium nitride-coated stainless steel
specimen. These analyses confirm that chromium
nitride-coated SS shows lower corrosion rate than
the base SS 304.
4. Discussion
Scanning electron micrographs of chromium ni-
tride-coated stainless steel substrate showed that the
chromium nitride coating is uniform and dense. The
thickness of the chromium nitride coating on SS
specimens was calculated to be 1.2 mm by RBS
method, which was also confirmed by glancing X-ray
method.
The XPS analysis of the chromium nitride coating
on stainless steel sample showed that the chromium
nitride coating was composed mostly of Cr2 N, and
potentially CrN in an elemental Cr matrix, and small
quantities of chromium carbide and oxide. The over-
all ratio of Cr to N was 75 " 5% Cr to 25 " 5% N.
AES and XPS sputter depth profile analyses of the
chromium nitride coating on stainless steel has shown
that the average atomic composition was close to
Cr0.80 N0.20 Žalso confirmed by RBS method. in the
sub-surface region; and close to Cr0.73 N0.27 near the
substratercoating interface. The coating also con-
tained small quantities of carbide and oxide. The
roughness parameters of the coated specimens mea-
sured with the AFM method are: R a s 5.91 nm and
RMSs 7.53 nm. The hardness of the coated sample
obtained using a maximum load of 2 mN is 18.4 "
1.2 GPa and the modulus is 234 " 12 GPa. The
chromium nitride coating consists mainly of Cr2 N
phase as confirmed by glancing XRD analysis, with
grain size of 5 " 2 mm. The low grain size is a result
of low temperature coating deposition process which
characterizes the IBAD process.
Ecorr ŽmV. Icorr ŽArcm2 . Corrosion rate Žmryr.
y4
3.51 = 10 4.084
150.1 1.0 = 10y7 0.001
64 J. Jagielski et al.r Applied Surface Science 156 (2000) 47–64
Stainless steel specimens coated with chromium
nitride were also subjected to various performance
tests. Several mechanical tests were carried out on
chromium nitride-coated and uncoated AISI 304 steel
sample. Chromium nitride coatings are not known
for low friction; however, dry sliding wear test
showed that the friction coefficient of stainless steel
improves by 1.5 times by chromium nitride coating.
Other tests such as hardness, scratch and impact and
corrosion test also showed significant improvement
on tribological properties. Knoop hardness and Vick-
ers hardness of the coated material are higher than
the base material. It is interesting to note that corro-
sion rate was 4000 times less than the base alloy.
The adhesion of the coating to the substrate proved
to be excellent as tested in various indentation tests
and scratch tests, which shows that layer composi-
tion corresponds to CrN0.4 in all analysed layers
within 10% accuracy.
Acknowledgements
The authors thank IAEA for creating a coordina-
tion group to carry out these studies. Thanks are due
to Spire USA for preparing chromium nitride-coated
samples. Also, thanks are due to Dr. K.G. Prasad,
co-investigator of the project from the Indian side,
who carried out detailed RBS work at surface and
profile measurements laboratory at Hyderabad.
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