Surface and Coatings Technology 180 – 181 (2004) 290–296

Preparation, characterization, and corrosion behavior of protective

coatings on stainless steel samples deposited by plasma detonation
techniques
P. Misaelidesa,*, A. Hatzidimitrioua , F. Nolia, A.D. Pogrebnjakb, Y.N. Tyurinc, S. Kosionidisd
a
Department of Chemistry, Aristotle University, GR-54124 Thessaloniki, Greece
b
Sumy Institute for Surface Modification, P.O. Box 163, Av. T. Shevchenko, 40030 Sumy, Ukraine
c
Paton Institute for Electric Welding, 252163 Kiev, Ukraine
d
Nuclear Physics Institute, NRCPS Demokritos, GR-15310 Aghia Paraskevi, Attiki, Greece

Abstract

Plasma detonation techniques have been used to modify the surface of austenitic stainless steel samples in order to improve
their corrosion resistance. Deposition of Al2 O3 coatings in combination with high current electron beam treatment and deposition
of titanium nitride (TiN) were applied for this purpose. The characterization of the samples was performed using nuclear reaction
analysis and Rutherford backscattering spectroscopy. The corrosion behavior of the samples was investigated in 1N H2SO4 using
electrochemical techniques (cyclovoltammetry and potentiodynamic polarization). The values of the critical and passivation
current density as well as of the corrosion, passivation and repassivation potentials, showed a considerable increase of the
corrosion resistance of the coated steel samples. This improvement is connected with the properties of the coating (e.g. thickness,
adhesion). The surface morphology and microstructure of the specimens, before and after the corrosion experiments, were
investigated by X-ray diffraction, scanning and transmission electron microscopy.
䊚 2003 Elsevier B.V. All rights reserved.

Keywords: Protective coatings; Stainless steel; Corrosion; Plasma detonation; Alumina coatings

1. Introduction regime of partial melting allows the ablation of surface

impurities (e.g. carbon-, oxygen- and nitrogen-com-
Ceramic coatings are widely used to improve the pounds) and the activation of the surface. The melting
mechanical properties as well as the corrosion and of the surface and its high rate cooling result in the
oxidation resistance of metals and metallic alloys w1– formation of nano-dispersed and metastable phases as
3x. The applied ceramic layers of controlled thickness well as amorphous layers. The further deposition of a
must show high adhesion and low porosity. Their pro- TiN-coating, also showing high melting temperature,
tective action is due both to physical and chemical hardness and corrosion resistance, additionally allows
effects. The application of double or triple surface the decrease the surface porosity of the oxide coating
treatment combined with an electron beam melting can w9,10x.
additionally improve the action of the individual com- The aim of this work was the characterization and
ponents (e.g. TiN and Al2O3) by formation of metasta- the investigation of the corrosion resistance of steel
ble, nano- as well as quasi-disperse phases w4–6x. samples modified by deposition of Al2O3- and TiN-
Aluminum oxide coatings deposited using the plasma coatings and by high current electron beam treatment.
detonation technique find wide applications because of
their technologically interesting properties and their 2. Experimental
enhanced wear, corrosion, heat and electro-erosion resis-
tance w7,8x. The additional treatment of the aluminum 2.1. The preparation of the samples
oxide coatings using high-current electron beams in the
*Corresponding author. Tel.yfax: q30-2310-997753. The investigated samples were prepared by deposition
E-mail address: [email protected] (P. Misaelides). of thin Al2O3 and TiN films on mechanically polished

0257-8972/04/$ - see front matter 䊚 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.10.073
 P. Misaelides et al. / Surface and Coatings Technology 180 – 181 (2004) 290–296 291

Table 1
Electrochemical corrosion data

No Sample E icorr ipas Epas Erep

(mV) (mA) (mA) (mV) (mV)
1. Steel y445 4.5 1.3 1022 1023
2. Series I (Al2O3) (with HCEB) y385 0.1 0.11 968 950
3. Series II (Al2O3qTiN with HCEB) y273 1.1 0.7 979 1014
4. Series II (Al2O3qTiN without HCEB) y330 0.62 1.2 986 1022

austenitic stainless steel AISI 321 (FeyCr18yNi8yTi) nuclear reaction analysis was applied for the determi-
samples of 2 mm thickness (supplied by Goodfellows nation of the nitrogen and aluminum distribution on the
Ltd) at the Paton Institute of Electric Welding of the electrochemically treated and untreated samples. The
14
National Academy of Sciences (Kiev, Ukraine) and the N(d,a)12C-nuclear reaction using projectiles energy of
Sumy Institute of Surface Modification. Two series of 1.350 MeV was applied for the determination of the N
samples were prepared for this work (Table 1). Series I depth distribution on the samples whereas the narrow
consisted of samples coated by an approximately 45 mm resonance at 991 keV of the 27Al(p,g)28Si was used for
Al2O3 layer and treated by plasma detonation (Hs50 the determination of the aluminum distribution. In the
mm, frequencys4 Hz, jet speeds6.5 kmys, power second case, the proton beam energy was varied between
densitys5.8=106 Wycm2). The energy density was 980 and 1100 keV in steps of 20 keV in order to obtain
high enough to melt totally the layer of Al2O3 and the depth information.
partially the substrate (voltage 30 kV, beam current 30
mA). 2.3. Investigation of the corrosion behavior using elec-
Series II samples consisted of Al2O3-coated steel trochemical techniques
samples additionally covered by a 1.2–2.0 mm TiN
layer (double coating). A Cr-layer of approximately The corrosion resistance of the prepared coatings was
0.2–0.5 mm was deposited on the Al2O3 substrate in investigated using electrochemical techniques. A Bank-
order to improve the adhesion of the TiN coating. The Wenking Potentio-Galvanostat PGS 81R interfaced to a
surface treatment by a high current electron beam PC via a National Instruments data acquisition card (Lab
(HCEB) followed the deposition of the protective coat- PCq) and Princeton Applied Research corrosion testing
ings. The description of plasma-detonation equipment cell were used for the electrochemical measurements,
can be found in Refs. w4–7x. which were performed in the potential region y1000 to
Uncoated steel samples were also investigated for 1500 mV using a 0.5 M H2SO4 solution (ambient
comparison reasons. temperature). A saturated calomel electrode used as a
reference electrode and a graphite one as an auxiliary
2.2. Characterization of the coatings electrode for all measurements. Five rapid scans (scan
rates25 mVys) followed by one slow scan (scan rates
Besides the microhardness, adhesion and thermal 0.25 mVys) were performed on each specimen. The
conductivity tests, the phase composition and the struc- rapid scans allow investigations under constant condi-
ture of the coatings were investigated at the Sumy tions of the material surface and corroding medium,
Institute for Surface Modification using X-ray diffraction whereas slow scans lead to predictions of the general
(XRD) and transmission electron microscopy (TEM). corrosion behavior of the material. In all cases the
For the TEM examinations an EM-125 K electron sample surface exposed to the corroding medium was 1
microscope (Electron, Sumy, Ukraine) with an acceler- cm2 w11–13x.
ation voltage of 125 kV was used. The investigation of
the microstructure and surface morphology of the coat- 3. Results and discussion
ings was performed by scanning electron microscopy
(SEM) in Sumy using a REMMA-102 electron micro- The aluminum oxide coating had an average density
scope and in Thessaloniki by means of a JEOL JSM of 3.9 gycm3, a value close to the theoretical one of a-
840A equipped with a LINK 10000 AN EDS micro-12) Al2O3 (rs3.98 gycm3). The adhesion without HCEB
The elemental distribution in the coatings, before and treatment reached 40–60 MPa. However, after HCEB
after the corrosion treatment, was determined by Ruth- treatment, the adhesion increased to 140–165 MPa. The
erford backscattering spectroscopy (RBS) at the 5.5 MV microhardness of some regions of the coating reached
Tandem Accelerator of the NRCPS DEMOKRITOSy the 1.3=104 Nymm2 and after the HCEB treatment
Athens using proton- (1.5 and 1.75 MeV), deuteron- increased to 1.6–1.78=104 Nymm2. The thermal con-
(1.5 MeV) and 12C3q- (10 MeV) ion beams. The ductivity of the Al2O3 coating was found to be 38 Wy
292 P. Misaelides et al. / Surface and Coatings Technology 180 – 181 (2004) 290–296

m K, which is close to the value of its purest form (40

Wym K).
The phase composition of the Al2O3-coating was
determined by electron diffraction using TEM. The
following phases were identified in the diffraction pat-
tern: a-Al2O3, b-Al2O3, g-Al2O3, h-Al2O3, AlFe.
The a-Al2O3 was polycrystalline with average crystal
dimensions of 250 nm. The crystallites were regular
without defects (Fig. 1a).
The a-Al2O3, b-Al2O3 and h-Al2O3 were also poly-
crystalline with crystal dimensions between 100 and 300
nm (Fig. 1b,c). A defect structure consisting of dislo-
cations (showed as a contrast) was observed inside the
crystallites. The region of transition, which was contig-
uous with the substrate, consisted of AlFe polycrystals
(Fig. 1c) with average dimensions of approximately 20
nm. This transition layer had a high dislocation density.
Some discrepancies between the parameters of the crys-
tal lattice of the coating and the normal values were
revealed by the electron diffraction. These discrepancies
are due to the high deposition rate and to the high
temperature of the plasma jet incident on the substrate
also inducing stress effects.
The XRD patterns of the aluminum oxide coating
demonstrated good correlation with the TEM results.
Regardless of the fact that the XRD information was
obtained from a thick layer, it is obvious that the a-
phase was the principal component of the coating
(approx. 60%), whereas the g-phase constituted the
approximately 30% of the material. The meta-stable
phases (e.g. b- and h-phases), which could hardly be
observed in the XRD pattern without special thermal
Fig. 1. Phase composition of the Al2O3-coating determined by electron annealing, formed the remainder. Fig. 2 shows the XRD
diffraction (TEM). patterns of the Series II sample (Al2O3 –TiN coating)
with and without HCEB treatment. In the case of the
electron beam treated sample the constitution of the
coating showed an increase of the a-Al2O3 phase

Fig. 2. XRD patterns of the series II samples (Al2O3 –TiN coating) with and without HCEB treatment.
 P. Misaelides et al. / Surface and Coatings Technology 180 – 181 (2004) 290–296 293

Fig. 3 shows the aluminum depth distribution on an

Al2O3-coated steel sample (Series I) determined using
the 27Al(p,g)28Si reaction. It can be observed that the
Al concentration is lower in the upper layers of the
coating and increasing in the depth.
Similar observations can be made in the case of
nitrogen depth distribution on samples belonging to
Series II. As can be seen in Fig. 4a, displaying the
energy spectrum of the particles emitted during the
deuteron bombardment of the TiN-containing coating
(a0- and a1- groups of the 14N(d,a)12C nuclear reac-
tion), the nitrogen distribution is not uniform over the
thickness of the TiN layer. This could be related with
N-diffusion in the layer during the preparation proce-
dure. The carbon distribution in the surface layers shows
a similar trend with nitrogen one, whereas a higher
carbon concentration was found on the HCEB-treated
samples. The diffusion-type distribution of nitrogen in
the titanium nitride layer was also confirmed by the
deuterons backscattering spectrum measured simultane-
Fig. 3. Aluminum depth distribution on a coated with Al2O3 steel
sample (Series I) using the 27Al(p,g)28Si reaction.
ously. Regardless of the varying the N to Ti ratio in the
individual layers used in the simulation procedure, the
overall composition of the titanium nitride coating seems
(;85%). The remainder consisted of b-Al2O3 (;1%), to be very close to the TiN. The presence of Cr is also
g-Al2O3 (;5%), TiN (;4.5%) and Cr (;1%). visible in the obtained spectra.
The investigation of the samples of Series I using The investigation using SEMyEDS revealed infor-
RBS leads to the conclusion that the composition of the mation about the surface morphology and microstruc-
coatings corresponds to Al2O3. The evaluation of the ture. Fig. 5a shows a SEM microphotograph of the
RBS data, obtained using spectra simulation techniques, Al2O3-coating deposited on the steel substrate. The
provided a thickness estimate of approximately 20 mm thickness of the coating was estimated to be approxi-
and the following atomic composition averaged over the mately 25 mm and its composition (obtained using EDS
whole thickness of the coatings: Fe 0.08364, Al 0.26313, data) Al 28.5%, O 59.5%, Fe 9%, Cr 2.2%, Ni 0.8%.
C 0.13286, O 0.61473, H 0.02564. The presence of The surface morphology of coated samples belonging
carbon is due to the sample preparation procedure to Series II without HCEB treatment before and after
(plasma detonation). the corrosion attack is given in Fig. 5b,c, respectively.

Fig. 4. RBS-spectra indicating: (a) the nitrogen, and (b) the titanium distribution.
294 P. Misaelides et al. / Surface and Coatings Technology 180 – 181 (2004) 290–296

Fig. 5. SEM microphotographs of an Al2O3-coated steel sample of Series I (upper left), of a steel sample of Series II without HCEB treatment
before (upper right) and after (lower left) the corrosion attack and of a cross-section of HCEB-treated steel sample (lower right).

In the first case the coating seems to be porous and Fig. 6a,b shows the potentiodynamic polarization
consists of irregularities. Cracks are visible over the curves (slow scan) of the uncoated and coated steel
surface and the adhesion of the surface appears to be samples (Series I) whereas some characteristic corrosion
poor. The results of microanalysis lead to the conclusion data are presented in Table 1.
that the elemental composition of the coating varied The decrease of the corrosion potential (E) as well
from point to point. This non-uniformity of the compo- as of the corrosion (icorr) and passivation (ipas) current
sition of the coatings, also indicated by the RBS and density in the case of coated steel samples indicated an
NRA measurements, could eventually be attributed to improvement of its corrosion resistance. This improve-
the high temperature of the plasma used during the ment was even higher in the case of the Series II
deposition procedure w7x. However, the low closed samples, due to the presence of the titanium nitride
porosity and the improved adhesion of the HCEB treated layer and the increased thickness of the coating. The
samples of Series II is an evidence of the highly good quality of the coating in the cases 2 and 3 was
beneficial effect of the HCEB treatment. This effect can confirmed. The sample of the case 4 (without HCEB
also be observed in Fig. 5d showing a cross-sectional irradiation treatment) exhibited poor adhesion during
picture of a HCEB treated Series II sample. the slow scan rate investigation and finally was
Measurements of current–potential relationship under destroyed.
carefully controlled conditions can yield information The qualitative examination of the RBS spectra of
concerning the corrosion resistance and the surface the corroded samples indicated, that the electrochemical
quality of the samples under investigation w1,2x. corrosion process did not create observable deterioration
 P. Misaelides et al. / Surface and Coatings Technology 180 – 181 (2004) 290–296 295

Fig. 6. Potentiodynamic polarization curves (slow scan) (a) uncoated and (b) coated steel samples (Series I).

of the near-surface layers of the coatings. This was reaction analysis and Rutherford backscattering spec-
mainly indicated by the persistence of the chromium troscopy. Transmission and scanning electron microsco-
layer after corrosion, as well as, the well-formed titani- py as well as X-ray diffraction were applied for the
um peak in all RBS spectra. The limited effect of the investigation of the surface morphology and microstruc-
electrochemical corrosion treatment on the surface mor- ture. The measurements indicated, that the composition
phology of the samples was also obvious from the of the investigated Al2O3 and TiN coatings was very
SEMyEDS examinations. close to the theoretical.

4. Conclusions Acknowledgments

Ceramic coatings on austenitic stainless steel samples This work was performed within the frame of the
using plasma detonation techniques exhibited a remark- Project ‘Oxidation and Corrosion Behaviour of Pulsed-
able corrosion resistance. Deposition of Al2O3 coatings Plasma Modified Metallic Alloys’ supported by the
in combination with high current electron beam treat- NATO Collaborative Linkage Grant No PST 978157.
ment and deposition of titanium nitride (TiN) increase
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