Corrosion Science 43 (2001) 19531961

www.elsevier.com/locate/corsci

EIS comparison on corrosion performance of

PVD TiN and CrN coated mild steel in 0.5 N
NaCl aqueous solution
C. Liu a,b,*, Q. Bi a, A. Matthews a
a

Research Centre in Surface Engineering, Hull University, Hull HU6 7RX, UK

Department of Manufacturing Engineering, Loughborough University, Loughborough LE11 3TU, UK
Received 6 June 2000; accepted 5 December 2000

Abstract
AC electrochemical measurement techniques such as electrochemical impedance spectroscopy (EIS) are nding their usefulness in evaluation of the corrosion behaviour of physical
vapour deposition coated steel systems. In this work, EIS has been employed to study the
corrosion performance of two commercially available hard coatings (TiN and CrN) on mild
steel substrate. In order to improve corrosion resistance, a four-layer deposit of each coating
material was used. EIS data were acquired at the corrosion potential for each coating material
(TiN or CrN) on mild steel in 0.5 N NaCl solution. Interpretation of these spectra reveals the
details of the corrosion process as the coated system is immersed in the solution by correlating
the coating microstructure. Finally, visual inspection as immersion time increases provides the
comparison on pit initiation and progression between TiN and CrN coated systems, as supportive evidence to the EIS analysis. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: EIS; Corrosion; TiN; CrN; PVD coatings

1. Introduction
The improvement of corrosion performance of steels with physical vapour deposition (PVD) hard (e.g. TiN or CrN) coatings is of importance, as increasingly
*
Corresponding author. Address: Department of Manufacturing Engineering, Loughborough University, Loughborough LE11 3TU, UK. Fax: +44-1509-267725.
E-mail address: c.liu@lboro.ac.uk (C. Liu).

0010-938X/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 0 ) 0 0 1 8 8 - 8

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C. Liu et al. / Corrosion Science 43 (2001) 19531961

demands for corrosion resistance from these coatings are required to enhance their
tribological lifetime in an aggressive working environment [110]. PVD coatings
most often exhibit growth related defects, e.g. pores and pinholes, through which a
corrosion attack on the substrate material (usually less noble compared to coating)
takes place [1,57,11,12]. The case is even more severe if the coated systems are
exposed to an aggressive environment, for instance, a Cl -containing corrosive
medium due to the strong eects of Cl in promoting localised corrosion. It has been
considered that the corrosion performance of PVD coated steel systems is related to
the microstructural characteristics. However, the quantitative evaluation of corrosion properties was found to be dicult using the conventional electrochemical
measurements, i.e. potentiostatic, or potentiodynamic techniques. An AC measuring
technique, e.g. electrochemical impedance spectroscopy (EIS) can be expected to be
useful for this application. Particularly, appropriate interpretation of EIS data with
an equivalent circuit can provide detailed information on the corrosion process at
the electrolyte/electrode interface. Furthermore, the EIS testing does not appear to
signicantly accelerate the corrosion reaction, and can also be conducted in situ nondestructively [1316]. The technique is quite sensitive to changes in the resistive
capacitive nature of electrochemical interface, thus more eective for studying the
localised corrosion via small pores. In this study, the EIS spectra were collected from
coated mild steel with four layers of either TiN or CrN as immersion time increased
in 0.5 N NaCl, respectively. The EIS data were interpreted using an equivalent
circuit which was proposed, based on the electrophysical model describing the
electrochemical corrosion at the coated surface. Thus, the quantitative evaluation of
corrosion performance can be realised. In addition, the visual inspection of corrosion
initiation and development as the immersion time increased veried the interpretation of EIS data, such that the comparison of corrosion behaviour of TiN and CrN
coated systems can be made.
2. Preparation of physical vapour deposition coatings
The at substrate samples of mild steel of 30  5 mm2 were ground with a
decreasing grit size of SiC paper, and nally polished with 14 lm liquid diamond
suspension. TiN or CrN coatings were prepared with a Tecvac IP35L electron-beam
plasma-assisted ion plating equipment (a thermionically assisted triode PAPVD
technique). Four multiple plating had been carried out to produce four layers of
either TiN or CrN coatings. Each layer was deposited as a commercial application,
and contained a very thin (100200 nm) pre-deposited Ti or Cr metallic interlayer.
The thickness of the coatings was approximately 910 lm; the deposition parameters
for each layer production are summarised in Table 1.
3. Electrochemical impedance spectroscopy and interpretation
AC impedance data for both TiN and CrN coated systems were derived using a
Solartron 1260 impedance gain-phase analyser with a Solartron 1286 electrochemical

C. Liu et al. / Corrosion Science 43 (2001) 19531961

1955

Table 1
Deposition conditions of PAPVD TiN and CrN coatings
Substrate temperature (C)
Deposition time per run (min)
Evaporation rate (g/min)
Coating thickness per run (lm)

TiN

CrN

400480
90
0.3
22.5

330470
60
0.86
22.5

interface. Measurements were performed in 0.5 N NaCl solution in the three-electrode (potentiostatic) mode using a saturated calomel reference electrode (SCE). A
sinusoidal AC perturbation of 10 mV amplitude (rms) was applied to the electrode at
its corrosion potential via the 1286 EIC over the frequency range 10 mHz to 100
kHz. The impedance spectra at the corrosion potential were collected with increasing
exposure time. Each collection was started when the corrosion potential did not
change by more than 1 mV/min in 20 min. The EIS data collection for each system was conducted at regular intervals from initial immersion up to several weeks
of exposure. Finally, the acquired data were curve tted and analysed using
EQUIVCRT program (version 3.96) written by Bernard A. Boukamp of Twente
University [17].
From SEM cross-sectional micrograph in Fig. 1(a) and (b), TiN coatings have
coarse columnar structure, whilst CrN has denser (lower porosity) equiaxed structure. The metallic Ti or Cr interlayers can be hardly observed, as they are very thin
200 nm. It is very likely for TiN coatings to form through coating defects, and the
grain boundaries can provide the direct diusion passes for corrosion medium.
However, CrN is denser and gives no direct diusion path.
Fig. 2 gives the Nyquist plot of EIS spectra from TiN coated mild steel systems as
the immersion time increased. Impedance data at high frequencies usually represents
the responses of coating, thus exhibits the coatings characteristics and performance
in the solution. A plot zoomed at 500 X cm2 (ZRe and ZIm ) of impedance range was

Fig. 1. SEM cross-sectional micrographs of four layer PVD: (a) TiN, and (b) CrN coating.

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C. Liu et al. / Corrosion Science 43 (2001) 19531961

Fig. 2. Nyquist plots of EIS data obtained from four layer TiN coated mild steel at dierent times of
exposure to 0.5 N NaCl solution. Zoom shows the impedance at high frequency region.

selected highlighting EIS data in the high frequency region. It is evident that, after
0.5 and 2 h exposure, EIS spectrum showed only one semi-circle, corresponding to
the time constant from TiN coating. In fact, as such a short period of exposure time
was not sucient to reveal any degradation of the substrate [1,5,7,8]. According to
Rudenja et al. [18], Ti interlayer may prevent pitting corrosion to the stainless steel
by forming a protective titanium oxide atop the Ti interlayer at coating defects. In
this work the typical of capacitive response gained at the initial exposure (less than 2
h) may also be due to the passivity of the TiN coating, in particular, anodic oxidation of TiN and Ti interlayers at structure defects. The second time constant related to the electrolyte/steel interface via pinholes had been resolved after 1.5 days of
exposure. This suggests that the solution had penetrated the coating through defects
(i.e. pinholes). Thereby, the galvanic corrosion cells had established, and the localised corrosion dominated the corrosion processes. In such a case, the electrochemical interface can be subdivided into two sub-interfaces: electrolyte/coating and
electrolyte/steel [7,8]. Interestingly, the impedance increased slightly at seven days.
This characteristic of EIS evolution can be interpreted as the ``blocking'' of the
pinholes by corrosion products (e.g. rust) from coating/steel interface. After certain
period of exposure, the rust generated from coating/steel interface had plugged
through pinholes. As the electric resistance of rust is greater than the solution, a
slightly increase of impedance was induced at seven days. The evidence from visual
inspection had also conrmed this nding.
As shown in Fig. 3, AC impedance from CrN coated system decreases as immersion time increases. Nevertheless, CrN coated system did not show any drastic
decrease of impedance as increasing the immersion time for the rst few days. This
suggests that CrN coatings degraded more slowly than TiN. The impedance showed
slightly increase after exposed for 35 days, indicating the ``plugging'' of the rust via
defects. This period is about ve times longer than that for TiN (seven days).

C. Liu et al. / Corrosion Science 43 (2001) 19531961

1957

Fig. 3. Nyquist plots of EIS data obtained from four layer CrN coated mild steel at dierent times of
exposure to 0.5 N NaCl solution. Zoom shows the impedance evolution at high frequency region.

Similarly, the metallic Cr layers may have further enhanced the passivity of the
coatings at structure defects, so that they protect the substrate from rapid degradation at defects [18].
For EIS data simulation, a general equivalent circuit model in Fig. 4 was proposed to ascribe two sub-electrochemical interfaces. A pair of elements of CPE-c
(c means coating) and Rpore in parallel replaces the dielectric properties of the coating.
Another pair of CPE-s and Rs (s means substrate) in parallel was adopted to describe
the charge transfer process at coating/steel interface at pinholes. Constant phase
element (CPE), is commonly used to replace capacitance, because it hardly has pure
capacitance in real electrochemical process. In EQUIVCRT program (version 3.96),
Q stands for CPE in circuit description code (CDC), and it is dened by admittance
n
Y and power index number n, given by Y Y0 jx . This is a general dispersion
formula, for n 0 it stands for resistance, while it is capacitance if n 1. In all cases
of this study, n is close to 1, represents capacitive characteristic of the interfaces.
However, the general model has to be modied in order to realise the best tting
to EIS data from TiN or CrN coating systems. As seen in Fig. 1(a), TiN coatings had
a columnar structure that made the direct passes for diusion. Warburg (W) impedance is readily an appropriate diusion element to describe this as a semi-innite
length diusion. However, CrN coatings had denser and equiaxed structure (Fig.
1(b)) which may signicantly conne the diusion inward to steel substrate.
Therefore, the cotangent diusion element (O) should be adopted for CrN systems in
the intermediate frequency region to describe the nite length diusion behavior.
Therefore, in Fig. 4, the CDC codes are R(Q(R(Q(RW)))), and R(Q(RO(QR))) for
TiN and CrN systems respectively. Warburg (W) is a well known diusional element
1=2
as the semi-innite transmission line. The general formula is Y W Y0 jx . The
cotangent diusional element (O) is usually used to simulate nite length diusion

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C. Liu et al. / Corrosion Science 43 (2001) 19531961

Fig. 4. General model of equivalent circuit and modied models proposed to carry out curve tting for the
EIS data from TiN and CrN coated systems exposed to 0.5 N NaCl solution.

with the case where one boundary imposes a xed concentration for diusion
species, given by Y O Y0 jx1=2 coth Bjx1=2 .
Using the equivalent circuits in Fig. 4(a) and (b), curve tting performed for both
TiN and CrN systems yields the values of parameters for circuit elements (Tables 2
and 3). Fitting errors were less than 10% for both real and imaginary parts of impedance. From Tables 2 and 3, the Ecorr decreased with immersion time, indicating
that potential became more negative as the solution reached the steel substrate. Ecorr
of CrN coatings was more positive than that of TiN after exposed for 1.5 days and
onwards. This suggests that the CrN coated system is more noble than TiN. The
parameter Y0 Qc and Y0 Qs reected the dielectric behaviour of electrolyte/coating
and electrolyte/steel (via defects) interfaces, Y0 Qc and Y0 Qs become Cc and Cs , for
n 1 (the power (n) of CPE-c and CPE-s), respectively. According to Tsai and
Mansfeld [19], Cc Cc0 A, Cs Cs0 Ad , where Cc0 , Cs0 , A, Ad are normalised capacitance
of coating and steel, the exposed coating area and degraded area, respectively. The
reason for n 6 1 when using CPEs to carry out curve tting can be various, for
instance, the fractal nature (e.g. special geometry of the roughness) of the interface
[20].
For TiN coatings, Y0 Qc increased with time for rst 3.5 days, indicating that the
exposed coating area (A) increased due to uncovering of porosity. However, Y0 Qc
decreased after seven days, when the rust started to block the pinholes. At initial
immersion (e.g. 30 min) n 0:913, this is close to 1, suggests a strong capacitive

31
250
590
585
650

Ecorr
(mV (SCE))

4.56
5.55
5.05
3.77
4.55

Re (X cm2 )
52.58
96.95
267.7
449.1
314.7

Y0 Qc (l/
cm2 X sn )
0.913
0.854
0.798
0.742
0.779

nQc

36

375

453

549

585

2h

1.5 days

3.5 days

7 days

Ecorr (mV
(SCE))

30 min

Exposure
time

4.44

7.52

3.29

7.91

5.21

Re (X)

64.09

46.99

18.27

3.47

2.45

Y0 Qc (l/
cm2 X sn )

0.827

0.848

0.964

0.886

0.680

nQc

Table 3
EIS data simulations for four layer CrN/MS in 0.5 N NaCl solution

30 min
2h
1.5 days
3.5 days
7 days

Exposed
time

Table 2
EIS data simulations for four layer TiN/MS in 0.5 N NaCl solution

12.4

8.9

2.5

4.05

110.49

Rpore
(kX cm2 )

12.97
7.91
1.19
0.31
0.12

138.3

132.8

125.1

75.02

16.84

Y0 O (l/
p
cm2 X s)

Rpore
(kX cm2 )

2.52

3.99

1.48

0.89

1.5

p
B ( s)

16.39
28.16
99.12
187
484.9

Y0 Qs (l/
cm2 X sn )

881.5

626.3

577

14.72

12.85

Y0 Qs (l/
cm2 X)

0.689
0.999
0.636
0.844
0.775

nQs

0.639

0.750

0.815

0.549

0.789

nQs

331.54
9.99
3.89
2.73
6.02

Rs (kX cm2 )

4.97

3.48

11.141

157.39

8792

Rs (kX cm2 )

660
1625
9921
37,496

Y0 W (l/
p
cm2 X s)
C. Liu et al. / Corrosion Science 43 (2001) 19531961
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C. Liu et al. / Corrosion Science 43 (2001) 19531961

response from electrolyte/coating. The n value decreased as time increases indicated

that the capacitive interface was weakened because the coating became more conductive with the increased number of opening pinholes. Rpore is pore resistance,
Rpore R0pore =Ad . Apparently, Ad will increase as immersion time increases, due to the
more revealed pinholes, and the deliminated area at coating/steel interface. This can
interpret the decrease of Rpore and increase of Y0 Qs with immersion time. Y0 W is a
parameter which contains diusion coecient and characteristic of diusion layer.
Y0 W increase with immersion time can be attributed to the Ad increase, decrease of
Rs (charge transfer resistance) and increase of oxygen near electrode surface.
The parameters such as Y0 Qc , Y0 Qs , Rpore obtained for CrN coatings had shown
the same trend with immersion time as TiN, but no decrease of Y0 Qc was observed
for seven days of exposure. This suggests that the ``plugging'' had not occurred
during immersion of seven days. The nQc from CrN increased to 0.964 before 1.5
days, then decreased and remained at 0.83. The reason for this is unknown at this
stage, and some further work may be needed to gain an insight understanding. In
addition, it has been noticed that Y0 Qc value is much higher for TiN than CrN
coatings. This dierence is determined by the dielectric property of coating materials.
Y0 Qc  Cc Cc0 A ee0 A=d, where e is the dielectric constant of coating, e0 the dielectric constant of free space, and d the thickness of coatings. TiN has much greater
dielectric constant than CrN, this is the reason why Y0 Qc from TiN is much higher.
Finally, visual inspection conducted during immersion has further supported the
EIS and interpretation. The pits were initiated earlier on TiN than on CrN coated
systems. Once the pits was formed, the number of pits on TiN did not signicantly
increase, but the existing pits severely propagated causing ``blocking'' of pinholes. As
for CrN, the pitting corrosion developed far more slowly for the rst few days, and it
was hardly seen that the corrosion products (e.g. rust) plugged through pinholes for
the rst few weeks.
4. Conclusions
EIS has found its usefulness for investigating the corrosion performance of PVD
hard coating steel system without signicant interfering to the ongoing corrosion
processes. In this study, four layer TiN coatings with 200 nm metallic Ti interlayers
have coarse columnar structure, while CrN coatings with Cr interlayers have denser
(lower porosity) and equiaxed structure. In associated with their microstructural
features, and the electro-physical processes of the corrosion processes, the modied
equivalent circuit models were proposed for TiN and CrN coated mild steel systems
respectively. The simulation and interpretation of EIS data with the models had thus
produced various variables (e.g. Y0 Qc , Y0 Qs , Rpore , Y0 W, Y0 O). The variation of
these variables with immersion time had revealed the detailed information with regard to the corrosion behaviour of the coated systems. It has been found that CrN
coatings degraded more slowly than TiN via pinholes. The pits once initiated via
small pinholes in TiN propagated more rapidly, thus severe plugging of corrosion
products occurred on TiN coated systems much earlier than on CrN. These ndings

C. Liu et al. / Corrosion Science 43 (2001) 19531961

1961

were further supported by visual inspection along the exposure of the coated systems. The further work is needed to understand the behaviour of the metallic Ti or
Cr interlayers during corrosion processes.

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