Surface & Coatings Technology 200 (2006) 5220 – 5228

www.elsevier.com/locate/surfcoat

Enhancement of adhesion strength between two AISI 316 L stainless steel

plates through atmospheric pressure plasma treatment
Shen Tang, Na Lu, Sung-Woon Myung, Ho-Suk Choi *
Department of Chemical Engineering, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejeon 305-764, Korea

Received 10 April 2005; accepted in revised form 16 June 2005

Available online 31 August 2005

Abstract

The adhesion between AISI 316 L stainless steel plates was studied using a poly(pyromellitic dianhydride-co-4,4V-oxydianiline), amic acid
as adhesive. The surfaces of two 316 L stainless steel plates were pre-treated using an atmospheric pressure plasma to improve the surface
properties before adhesion tests. The surface free energies of the stainless steel plates were improved with plasma treatment and the optimum
plasma treatment conditions such as plasma treatment time, plasma treatment power, gas flow rate, gap distance between power source and
substrates and aging time after plasma treatment were investigated. When the mixed gas (Ar and O2) plasma was used, the surface free energy
of the stainless steel was more enhanced. The surface compositions of the stainless steel were examined by X-ray Photoelectron Spectroscopy
(XPS) after plasma treatment and it was proved that new oxygen-containing groups were generated after plasma treatment. Finally, tensile
tests confirmed that new oxygen-containing groups formed through plasma treatment improved the adhesion strength between two stainless
steel plates.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Atmospheric pressure plasma; 316 L stainless steel plate; Surface free energy; Oxygen-containing strength; Adhesion strength

1. Introduction Polyimides are widely used as dielectrics, adhesives in

The surface functionalities and morphologies of a
substance can be dramatically modified using plasma
treatment [1 –8]. Many materials, including organic materi-
als, inorganic materials and metals, can be readily surface-
modified using plasma treatments [9 – 18]. Especially
atmospheric pressure plasmas have shown many advantages
[19]. Compared with other plasma systems, such as corona
and vacuum plasmas, atmospheric pressure plasma treat-
ment gives higher electric field uniformity, versatility, and
easy controllability without the need for a vacuum system.
Moreover, it is suitable for both continuous and batch
processes, and a stable discharge can be formed for various
gases (air, N2, He, Ar, etc.) [20].
* Corresponding author. Tel.: +82 42 821 5689; fax: +82 42 822 8995.
E-mail address: hchoi@cnu.ac.kr (H.-S. Choi).
0257-8972/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.06.020
microelectronics and matrix materials due to their excellent
thermal stability, chemical resistance and low electrical
constants [21]. Much research has been conducted to
enhance the adhesion between the polyimides and metals
such as Cr, Ni, Cu, Al, and Ag [22 –24]. Among these
metals, Cu is the most widely studied since it shows very
good dielectric properties.
Stainless steel is a familiar metal with excellent corrosion
resistance and thermal stability which facilitate it in a wide
range of application. In the micro-channel reactor industry,
stainless steel plates are used as the main frame of the
micro-channel reactors [25], and in this field, surface
properties are very important when the substrates are
combined with each other. Until now, however, there are
few papers concerning stainless steel in the application of
adhesion enhancement with plasma treatment. Based on the
surface properties, such as surface morphology and func-
tionality, some researchers once reported the surface
modification of stainless steel using plasmas. Abd El-
 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228
Rahman et al. [26] discussed the effect of N2 to C2H2 ratio
on r.f. plasma surface treatment of austenitic stainless steel
(ASS), and they verified that both nitriding and carburizing
could be realized on AISI 304 with r.f. plasma by addition
of N2 and C2H2. The surface oxide layer did not play a
crucial role during r.f. plasma carburizing and carbonitriding
of the stainless steel. Kim et al. [27] utilized an atmospheric
plasma jet to modify the surface of Al, Cu, and stainless
steel and demonstrated the etching and oxidation effect of
plasma jet generated by N2 and O2 gas, and also indicated
that all of the surfaces contained oxygen and carbon without
nitrogen after plasma treatment. Kim et al. [28] also
discussed the effect of a N2 and O2 plasma jet on the
surface properties of stainless steel and proved that the
surface of stainless steel became more hydrophilic because
new functional groups appeared after N2 and O2 plasma jet
treatment.
In this study, one atmospheric pressure plasma treatment
was conducted to improve the adhesion properties on the
AISI 316 L stainless steel plates, where poly(amic acid) was
used as the adhesive. To investigate the appropriate
parameters of plasma treatment in detail, the static contact
angles with two liquids were measured and subsequently the
surface free energy of plasma-treated surface was obtained.
The plasma treatment using mixed gas (Ar and O2) was also
conducted to compare its effect with that of the pure Ar
plasma treatment. Surface compositions on the stainless
steel were examined using XPS. The adhesion strength was
measured with tensile test.
2. Experimental
2.1. Materials
The AISI 316 L stainless steel plates (60 mm  20
mm  0.5 mm) were purchased from Duwon Company in
Daejeon, Korea. The ultra pure Argon gas and nitrogen gas
were provided by Praxair Korea Co. Ltd. The poly(pyr-
omellitic dianhydride-co-4,4V-oxydianiline), amic acid,
(PAA), 15 wt.% solution in N-methyl-pyrrolidone (NMP)
was purchased from Aldrich Chemical Co.
2.2. Surface modification of stainless steel plates with
atmospheric pressure plasma
The stainless steel plates were cleaned in 1% hydro-
chloric acid solution for 1 h in ultrasonic bath, and then
rinsed with distilled water and acetone, followed by drying
with a stream of nitrogen gas. The surface modification of
the stainless steel was carried out on the atmospheric
pressure plasma (Model ATMOS, Plasmart Inc. Korea) [11].
Both Ar and mixed gas (Ar + O2) plasma treatments were
attempted. The plasma treatment time, plasma treatment
power, flow rate of the Ar and O2, gap distance between
plasma discharge source and substrate, and the aging time
5221
were systematically studied in a view point of surface free
energy enhancement, respectively.
2.3. The contact angle test and the calculation of surface
free energy
The contact angle test was performed on the FACE
contact angle meter made by Kyowa Interface Science Co.
Ltd., Japan. Deionized water (DW) and diiodomethane (DI),
which were used as polar and non-polar components,
respectively, were dropped onto the surface of the plasma-
treated stainless steel plate. Then, after a certain exposure
time in air (aging time), the angles were read through the
lens. In this experiment, 8-point measurements on each
sample were performed at positions selected randomly, and
the average value of the 8-point measurements was regarded
as the contact angle of the sample.
The surface free energy (c s), the free energy of polar
components (c ps ) and non-polar components (c ds ) of the
stainless steel after plasma treatment were all calculated
from the results of the contact angle test through Owen’s
method [29,30].
2.4. XPS test on the surface of the plasma-treated stainless
steel
After plasma treatment, the stainless steel plates were
exposed to air not over than 10 h and the XPS (ESCALAB
MK II, V.G Scientific Ltd.) characterization was conducted
to study the surface chemical compositions of the plasma-
treated stainless steel. The base pressure was 5  10 10 Torr
and the photoelectron takeoff angle was held at 45-.
2.5. The spin coating of adhesive on the stainless steel
plates
The PAA was spin coated on the plasma-treated stainless
steel plates with a spin coater/200 (Made in Korea) (shown
in Fig. 1). The spin speed was controllable.
Adhesion section
2cm
2cm
Stainless steel plates
Console
Tensile test machine
Fig. 1. Tensile test scheme for the measurement of adhesion strength.
5222 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228

Table 1
The effect of plasma treatment time on the contact angles on the stainless steel
Plasma treatment time (s) 0 3 5 10 30 50 60 80 120 180
Contact angles of DW (degree [-]) 72.7 34.6 27.7 25.4 16.9 11.3 8.7 11.8 11.9 11.8
Contact angles of DI (degree [-]) 50.3 39.7 31.9 27.6 25.8 23.5 21.1 24.1 25.3 25.5
Plasma treatment power: 100 W.
Flow rate: 5 L/min.
Aging time: 3 min.
Gap distance: 5 mm.

2.6. Curing and binding
Two stainless steel plates coated with the PAA were first
pre-cured at 70 -C for 14 min. Then, the coated surfaces of
the two stainless steel plates were tightly jointed, followed
by curing at 350 -C in air for 1.5 h with a temperature
increasing rate of 10 -C/min.
2.7. The measurement of adhesion strength
The measurement of adhesion strength was conducted on
a tensile test machine (Lloyd Instruments Ltd.) (Fig. 1). A
small hole at the end of each side of the stainless steel plate
was made, through which the steel ring was threaded. The
steel ring was able to fix the steel plate between jaws
without local torsion.
3. Results and discussion
stainless steel after plasma treatment. In this study, the
changes in contact angles and surface free energies were
also ascribed to the changes of surface functionalities, and
this is discussed later in this paper.
In Table 1 and Fig. 2, it was observed that contact angle
and surface free energy could be dramatically changed
within only short time (3 s) plasma treatment, especially the
contact angle of deionized water. This phenomenon proved
that the plasma treatment could quickly form the surface
functionality within a short time. However, once the surface
functionality was fully formed (at 60 s), long time plasma
treatment had nearly no effect on the change of contact
angle and surface free energy.
It was also found that plasma treatment time and power
mainly influenced polar component rather than non-polar
component (in Figs. 2 and 3), which meant that the change
of surface free energy was mainly caused by polar
component. This fact is consistent with the discussion in
aforementioned paper [11].

3.1. Effect of plasma treatment time and power 3.2. Effect of gas flow rate

Plasma treatment time and power are both important Gas flow rate is another important factor that controls
factors in plasma techniques, which have been widely the plasma treatment effect. Table 3 shows the effect of gas
studied by many researchers [31 – 33]. In this experiment, flow rate on the contact angle of deionized water and
the optimum plasma treatment time and power appeared at
60 s and 120 W, respectively. At this plasma treatment
time and power, the contact angles of deionized water and
diiodomethane both decreased to minimums (shown in
Surface free energy (mJ/m2)

Tables 1 and 2) and the surface free energies also reached 60

maximums (shown in Figs. 2 and 3). In aforementioned
paper [11], it was verified that the surface free energies
were closely related to the surface functionalities of 40

Table 2
The effect of plasma treatment power on the contact angles on the stainless 20
steel
Plasma treatment 0 40 60 80 100 120 150 180
power (W)
0[s] 3[s] 5[s] 10[s] 30[s] 50[s] 60[s] 80[s] 120[s] 180[s]
Contact angles of 72.7 55.4 35.6 26.3 16.9 10.9 14.8 15.3 Plasma treatment time (sec)
DW (degree [-])
p d
Contact angles of 50.3 39.1 31.5 26.0 25.8 21.5 23.7 24.8 polar components(rs ) Non-polar components(rs )
DM (degree [-])
Aggregation(rs)
Plasma treatment time: 30 s.
Flow rate: 5 L/min. Fig. 2. Changes of surface free energy with respect to the plasma treatment
Aging time: 3 min. time. Plasma treatment power: 100 W, flow rate: 5 L/min, aging time: 3
Gap distance: 5 mm. min, gap distance: 5 mm.
 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228 5223

Surface free energy (mJ/m2)

Surface free energy (mJ/m2)

60 60

40 40

20 20

0[W] 40[W] 60[W] 80[W] 100[W] 120[W] 150[W] 180[W] 0[l/min] 3[l/min] 5[l/min] 7[l/min] 10[l/min]
Plasma treatment power (W) Gas flow rate (l/min)
p d p d
polar components(rs ) Non-polar components(rs ) polar components(r s ) Non-polar components(rs )
Aggregation(rs) Aggregation(rs)

Fig. 3. Changes of surface free energy with respect to the plasma treatment Fig. 4. Changes of surface free energy with respect to the gas flow rate of
power. Plasma treatment time: 30 s, flow rate: 5 L/min, aging time: 3 min, Argon. Plasma treatment time: 30 s, plasma treatment power: 100 W, aging
gap distance: 5 mm. time: 3 min, gap distance: 5 mm.

diiodomethane on the stainless steel. Fig. 4 shows the
change of the surface free energy of stainless steel with
respect to the gas flow rate of Ar. In Table 3, the contact
angles of deionized water and diiodomethane both
decrease to minimums at Ar flow rate of 5 L/min, which
corresponds to the maximum of surface free energy on the
surface of stainless steel at the same flow rate. Since the
gas was used to initiate the plasma discharge, higher flow
rate meant more excited electrons, ions, and energetic
photons were generated to attack the treated surface. If the
flow rate was low, the excited ions, electrons and photons
were not enough to activate the surface. However, when
the flow rate was too high, although enough excited ions,
electrons and photons are generated, the present plasma
system became more and more unstable and this phenom-
enon is thought to be related to the plasma properties.
Large amount of gas can break the equilibrium between
the loss and the generation of ions. Therefore, as the Ar
flow rate was 5 L/min, the contact angles of deionized
water and diiodomethane both reached minimums, and the
surface free energy reached a maximum. It is not hard to
see that the change of the surface free energy (c s) is quite
related to the polar component, and non-polar component
has nearly no influence on it (c s). This fact indicated that
the plasma gas flow rate mainly influenced polar compo-
nent rather than non-polar component.
3.3. Effect of the distance between plasma source and
substrate
During plasma treatment, plasma discharge kept attack-
ing the surface of stainless steel. The distance between
plasma source and treated sample can accordingly be
another factor affecting the surface free energies of the
treated sample. As shown in Table 4 and Fig. 5, when the
gap distance between plasma source and substrate is 3 mm,
the contact angles of deionized water and diiodomethane
both reach minimums and the surface free energy reaches a
maximum. When the gap distance was too large, the plasma
flame was hardly able to touch the surface of substrate,
which meant that few activated ions, electrons and photons
could arrive at the surface. In the present plasma system, the
possible access of substrate to the plasma source is 2 –3 mm.
Therefore, the contact angles of deionized water and
diiodomethane both reached the minimums at the gap
distance of 3 mm and the surface free energy reached a
maximum at the same gap distance. For stainless steel,
plasma treatment cannot essentially change the surface

Table 3 Table 4
The effect of plasma gas flow rate on the contact angles on the stainless The effect of gap distance between plasma source and substrate on the
steel contact angles on the stainless steel
Gas flow rate (L/min) 0 3 5 7 10 Gap distance (mm) 3 5 7 10 35
Contact angles of DW (degree [-]) 72.7 19.0 16.9 19.8 55.1 Contact angles of DW (degree [-]) 10.6 16.9 40.4 51.8 71.6
Contact angles of DI (degree [-]) 50.3 27.9 25.8 28.4 44.5 Contact angles of DI (degree [-]) 19.2 25.8 35.2 42.6 49.7
Plasma treatment time: 30 s. Plasma treatment time: 30 s.
Plasma treatment power: 100 W. Plasma treatment power: 100 W.
Aging time: 3 min. Flow rate: 5 L/min.
Gap distance: 5 mm. Aging time: 3 min.
5224 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228

70

Surface free energy (mJ/m2)

Surface free energy (mJ/m )
2

60 60

50
40

40

20 30

20
3[mm] 5[mm] 7[mm] 10[mm] 35[mm] 1[min] 3[min] 5[min] 10[min] 30[min] 60[min] 840[min]1440[min]
Gap distance between the plasma source and substrate (mm) Aging time in air (min)
p d p d
polar components(rs ) Non-polar components(rs ) polar components(rs ) Non-polar components(rs )
Aggregation(rs) Aggregation(rs)

Fig. 5. Changes of surface free energy with respect to the gap distance Fig. 6. Changes of surface free energy with respect to aging time in air after
between the plasma source and substrate. Plasma treatment time: 30 s, plasma treatment. Plasma treatment time: 30 s, plasma treatment power:
plasma treatment power: 100 W, flow rate: 5 L/min, aging time: 3 min. 100 W, flow rate: 5 L/min, gap distance: 5 mm.

morphology due to the physical properties of stainless steel,

the exposure to air after plasma treatment [31,34], and this
which was studied in aforementioned paper [11]. In this
change was attributed to reactive radicals formed on the
experiment, it was also thought that, with the change of gap
surface, which were generated by plasma. When these
distance between the substrates and plasma source, the
radicals were exposed to air after plasma treatment, they
surface of stainless steel was not damaged either.
reacted with air and generated more oxides on the surface,
In Fig. 5, similar phenomenon with Fig. 4 was also
which were beneficial for the surface wettability and free
observed. The surface free energy was mainly influenced by
energy. From this perspective, it is affirmed that radicals
polar component during its decreasing process. However,
determine the increase in surface free energy during aging
non-polar component seemed stable during this process.
process. At the outset of aging process, the surface after
From this fact, it is predicted that changing the gap distance
plasma treatment was so activated that the radicals formed
between the plasma source and substrate is merely able to
on the surface reacted rapidly with air. Within a short period,
improve the properties of polar component and has nearly
the surface oxidation would approach a saturated state, at
no effect on non-polar component.
which further increasing the aging time would not contrib-
ute to improve the surface polarity any more. In contrast, the
3.4. Effect of aging time in air after plasma treatment
undesired compounds and impurities may be formed from
the contaminants and stable components in air. They made
Aging property is also a quite important factor for
the surface passive, which was disadvantageous for surface
maintaining high surface energy of materials for prolonged
wettability and surface free energy.
period, which has also been discussed before [11]. In this
In Fig. 6, it is found that the surface free energy does not
experiment, the contact angles of both polar and non-polar
show remarkable decrease within 10 min. In contrast, the
components decrease to minimums within a short exposure
free energy begins to gradually decrease after 10 min.
time to air (5 min), and in this period, the surface free
During the decrease in the surface free energy, the non-polar
energy reaches a maximum (shown in Table 5 and Fig. 6). It
component (c ds ) dominantly contributes its decrease and the
was considered that new oxides were also produced during
polar component (c ps ) remains stable for nearly 12 h after
plasma treatment. This result indicates that, during short
Table 5 period of surface aging in air, surface contamination and
The effect of exposure time in air on the contact angles on the stainless steel
passivation mainly influence the non-polar component
Aging time (min) 1 3 5 10 30 60 840 1440 rather than the polar component.
Contact angles of 18.1 16.9 12.7 18.1 21.5 22.6 28.3 41.2
DW (degree [-]) 3.5. Effect of a mixed gas (argon and oxygen) plasma
Contact angles of 26.6 25.8 20.6 25.3 29.5 33.0 36.8 42.6
DI (degree [-])
Argon and oxygen are both popular gases to initiate
Plasma treatment time: 30 s.
Plasma treatment power: 100 W.
plasma. In this experiment, plasma treatment with mixed gas
Flow rate: 5 L/min. of Ar and O2 was conducted to investigate the plasma effect
Gap distance: 5 mm. with mixed gas (Ar + O2). Table 6 and Fig. 7 show the effect
 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228
Table 6
The effect of the ratio of O2 and Ar on the contact angles on the stainless
steel
Ratio of O2 and Ar (%) 0 0.4 0.8
Contact angles of DM (degree [-]) 16.9 16.6 16.6 11.0 12.7 14.2
Contact angles of DI (degree [-]) 25.8 22.0 22.0 20.5 22.1 23.7
Plasma treatment time: 30 s.
Plasma treatment power: 100 W.
Flow rate: 5 L/min.
Gap distance: 5 mm.
Aging time: 3 min.
of plasma with mixed gas on the contact angles and surface
free energy of stainless steel, respectively. The contact
angles of deionized water and diiodomethane both
decreased to minimums when the content of O2 in the
mixed gas was 1%, and the surface free energy of the
stainless steel slightly increased to a maximum at the same
composition of mixed gas. This result proved that the mixed
gas plasma could further improve the surface free energy of
the stainless steel. During the experiment, it was observed
that, when the mixed gas was utilized, the plasma discharge
became stronger than that of pure Ar. At the outset, when
the ratio of O2 was small (lower than 1%), the plasma effect
with mixed gas was not so appreciable due to the small
portion of O2. As the proportion of O2 reached 1%, the
effect of mixed gas became much more remarkable,
however, the discharge uniformity declined and the system
became more unstable. This phenomenon is ascribed to the
plasma system itself. Since oxygen itself could act as an
electron acceptor, which caused large electron loss, the
injection of large amount of O2 resulted in the loss of large
amount of electrons. When the electron loss was greater
than electron generation, the plasma would extinguish
automatically. However, in contrast, once the oxygen was
Surface free energy (mJ/m2)
60
40
20
0.0 0.2 0.4 0.6 0.8 1.0
Gas flow rate ratio of O2 and Ar (%)
p d
Polar component(rs ) Non-polar component(rs )
Aggregation(rs )
Fig. 7. Changes of surface free energy with respect to ratio of O2 to Ar
during plasma treatment. Plasma treatment time: 30 s, plasma treatment
power: 100 W, flow rate: 5 L/min, gap distance: 5 mm, aging time: 3 min.
5225
added into the plasma system, new oxygen active species
could be formed during plasma treatment, which let plasma
have stronger oxidation ability. Therefore, adding oxygen
1.0 1.2 1.5
into plasma system is a balanceable parameter. In this
experiment, the optimum oxygen percentage is about 1%.
In Fig. 7, it was noticed that the free energy of polar
component (c ps ) slightly increased as the proportion of O2
reached 1%, which proved that plasma with appropriate
amount of O2 further improved the polar component of
stainless steel. However, as to the non-polar component, the
effect of mixed gas was not appreciable.
3.6. Surface chemical compositions of the stainless steel
A very important effect of plasma treatment is the
modification of surface chemical composition. Usually,
after plasma treatment, the surface of substrate is oxidized
and become more hydrophilic. In this study, the surface
components such as carbon (C1s), nitrogen (N1s), oxygen
(O1s), chromium (Cr2p) and iron (Fe2p) on the surface of
the stainless steel were investigated.
Fig. 8 shows the XPS result on the surface of stainless
steel including (A) untreated sample, (B) Ar plasma-treated
sample (at 60 s), and (C) a mixed gas plasma-treated sample
(at 60 s with O2/Ar ratio of 0.01). It is observed from Fig. 8
that, the amount of C1s (282 eV – 292 eV), N1s (390 eV –
410 eV) and Cr2p (571 eV – 581 eV) did not show
remarkable changes. Since in stainless alloy, the element
of Fe occupies the largest proportion, it is imaginable that
the change of other element is not appreciable. Even so, it
can be seen that the peak of C1s in the curve C is the
smallest among other C1s peaks. Usually the carbon
component on the surface of stainless steel was regarded
as the compound of the bulky components of stainless steel
and surface contaminants formed in air. Due to the plasma
120
100
Fe2p
Intensity (arb. unit)
O1s
80 Cr2p
N1s C1s
60
C
40
B
20
A
1.2 1.4 0
1000 900 800 700 600 500 400 300 200 100 0
Binding energy (eV)
Fig. 8. XPS spectra of the surface of stainless steel, (A) original stainless
steel; (B) Ar plasma-treated stainless steel (plasma treatment time: 60 s,
plasma treatment power: 120 W, gas flow rate: 5 L/min, gap distance: 3
mm, aging time: 10 h) (C) mixed gas of plasma-treated stainless steel
(plasma treatment time: 60 s, plasma treatment power: 120 W, gas flow rate:
5 L/min, gap distance: 3 mm, aging time: 10 h, ratio of O2 to Ar at 0.01).
5226 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228

oxidation effect, it is thought that the generation of new

(a) Original sample
oxygen-containing groups on the surface decreased the
carbon component on the surface and the smallest C1s peak
15
on curve C also indicates that mixed gas plasma had
stronger oxidation effect than the Ar plasma. The oxides on
the surface of stainless steel consist of carbon oxides,
Intensity (arb. unit)

10
1 nitrogen oxides, chromium oxides and iron oxides. After
plasma treatment, it is thought that all these oxides were
increased.
Since Fe occupies the largest proportion among all
2
5 components in stainless alloy, the iron oxides are discussed
4
3 in detail. Fig. 9 shows the XPS spectra of iron component,
Fe2p (705 eV –715 eV), with the Ar and mixed gas plasma
treatment. In Fig. 9(a) to (c), the Fe2p peak is deconvolved
0
into four component Gaussian, i.e., peak 1, Fe – Fe (706.8
718 716 714 712 710 708 706 704
eV), peak 2, Fe – O and Fe (OH)2 (708.6 eV), peak 3, Fe2O3
Binding energy (eV)
(710.4 eV) and peak 4, FeOOH (711.6 eV) groups. Table 7
shows the area ratio of the sub-peaks, from which the
(b) Plasma treated sample at 60 sec
change of polar groups with plasma treatment is more
clearly seen. It is found that the proportion of peak 1 (Fe –
15
Fe) increased on Ar plasma-treated sample. However, on
mixed gas plasma-treated sample, the proportion is smaller
Intensity (arb. unit)

than the original sample. This result is related to the plasma

10 cleaning effect [20] and oxidation effect. On the surface of
1 original sample, there are some envelops such as hydro-
carbons and some weakly bonded metal oxides. These
materials could be removed due to strong plasma cleaning
5 effect on the Ar plasma-treated sample. It is thought that the
2
removal of these materials makes more Fe – Fe bonds on the
3
4
surface. On the mixed gas treated sample, since the mixed
gas plasma has stronger oxidation effect which has been
0
discussed before, the surface changes of stainless steel is
718 716 714 712 710 708 706 704
dominantly affected by oxidation effect. It is also found that
Binding energy (eV)
the protoxides (FeO and Fe(OH)2) decrease while the high
oxides (Fe2O3) increase after both plasma treatments. This
(c) Mixed gas plasma treated sample at 60 sec
result indicates that during plasma treatment, the protoxides
could be transferred to high oxides (Fe2O3) and peroxides
15
(FeOOH). Since the mixed gas has stronger oxidation
ability, more protoxides were further oxidized to high oxides
and peroxides. Therefore, in Table 7, peak 2 decreases the
Intensity (arb. unit)

10 most on the mixed gas plasma-treated sample and peak 3

and peak 4 both increase on it.
1
Table 7
5 3 Relative XPS sub-peak area (%) of Fe2p of stainless steel treated by Ar and
4 mixed gas plasma (peak 1, Fe – Fe (706.8 eV); peak 2, FeO and Fe(OH)2
2
(708.6 eV); peak 3, Fe2O3 (710.4 eV); peak 4, FeOOH (711.6 eV))
Peak 1, Peak 2, Fe – O Peak 3, Peak 4,
0 Fe – Fe and Fe(OH)2 Fe2O3 FeOOH
718 716 714 712 710 708 706 704 (706.8 eV) (708.6 eV) (710.4 eV) (711.6 eV)
Binding energy (eV) [%] [%] [%] [%]
Original sample 28.3 21.0 16.7 34.0
Ar plasma-treated 33.2 19.3 18.8 28.7
Fig. 9. XPS spectra of Fe2p, (a) original stainless steel, (b) Ar plasma-
sample (60 s)
treated stainless steel at 60 s, (c) mixed gas of plasma-treated stainless steel
Mixed gas 24.7 10.8 25.0 39.5
with O2/Ar ratio of 0.01 at 60 s. Peak1, Fe – Fe (706.8 eV); peak 2, FeO and
plasma-treated
Fe(OH)2 (708.6 eV); peak 3, Fe2O3 (710.4 eV); peak 4, FeOOH (711.6 eV).
sample (60 s)
Plasma treatment parameters are same with those in Fig. 8.
 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228
800
Adhesion strength (N/cm2)
750
700
650
600
550
500
Sample 1 Sample 2
Fig. 10. The effect of plasma treatment on the adhesion strength of
conglutinated stainless steel plates. Plasma treatment time: 60 s, plasma
treatment power: 120 W, flow rate: 5 L/min, gap distance: 3 mm, aging
time: 5 min, ratio of O2 to Ar: 0.01. Sample 1, original stainless steel,
sample 2, Ar plasma-treated stainless steel, sample 3, mixed gas plasma-
treated stainless steel.
3.7. Adhesion of the stainless steel plates
The adhesion between two stainless steel plates was
conducted with PAA. The results of adhesion strengths are
shown in Fig. 10. Sample 1 represents the adhesion strength
of the conglutinated stainless steel plates without plasma
treatment using PAA. Samples 2 and 3 represent the
adhesion strength of the conglutinated stainless steel plates
with Ar and mixed gas plasma treatment also using PAA.
The adhesion strengths both increased on the two plasma-
treated samples, which illustrates that plasma treatments
could improve the adhesion strength between stainless steel
plates. As discussed in Section 3.6, the surface of the
stainless steel was oxidized and higher oxides and peroxides
were generated on the stainless steel after plasma treatment.
The enhanced adhesion strengths were thought to be directly
related to these newly generated oxides by plasma. When
the surface of stainless steel plates were covered with the
adhesives, the surface oxygen-containing groups could form
hydrogen and/or covalent bonds with the adhesives, which
makes two stainless steel plates strongly bound together
[22]. Fig. 11 shows the simple adhesion scheme of stainless
steels. In this study, it is believed that chemical (covalent)
O O
OH
HO NH
O O
O OH
Fig. 11. The possible adhesion scheme between stainless steels by poly (amic acid).
5227
and non-chemical (hydrogen) bonds both formed at the
interface between substrate and adhesives. The adhesion
strength was determined by the energy of both chemical and
hydrogen bonds formed at the interface. After plasma
treatment, more oxides appeared on the surface, which
provided more possibility to form hydrogen bond. There-
fore, the adhesion strength was more improved on the
plasma-treated samples. Since more oxygen-containing
groups were generated on the mixed gas plasma-treated
sample, the adhesion strength of sample 3 was larger than
that of sample 2.
Sample 3
4. Conclusions
The 316 L stainless steel was surface modified using
atmospheric pressure plasma. The surface free energy was
improved after plasma treatment and the appropriate plasma
treatment conditions such as plasma treatment time of 60 s,
plasma treatment power of 120 W, gas distance between the
plasma source and substrate of 3 mm, gas flow rate of 5 L/
min and aging time in air of 5 min were obtained. A mixed
gas plasma treatment using O2 and Ar was conducted with
the optimum ratio of 0.01 and it was proved that mixed gas
plasma had even stronger oxidation ability than the Ar
plasma. In contrast, the plasma treatment mainly influenced
the polar components on the surface of stainless steel.
However, the effect on the non-polar components was
subordinate. XPS results revealed that the surface of
stainless steel was oxidized after plasma treatment, and
the mixed gas plasma has more ability to increase high
oxides on the surface. The adhesion strength on the stainless
steel using PAA showed that the oxygen-containing groups
generated by plasma made great contributions on forming
both hydrogen and covalent bonds at the interface of PAA
and stainless steel plates.
Acknowledgements
This research was a project for the Graduate Research
Resource Development for Special Regional Industries
Pyromellitic diahydride -co-4, 4'-oxydianiline
HO O O O O
NH O NH OH
OH HO
O NH
O O O O
n
O O OH Stainless steel plate
Hydrogen bonds
Chemical bonds
5228 S. Tang et al. / Surface & Coatings Technology 200 (2006) 5220 – 5228
supported by the Korean Ministry of Commerce, Industry
and Energy. The authors would like to thank the various
people involved in this project for their support.
References
[1] M. Tatoulian, M. Bouloussa, F. Moriere, F. Arefi-Khonsari, J.
Amouroux, F. Rondelez, Langmuir 20 (2004) 10481.
[2] M.L. Steen, W.C. Flory, N.E. Capps, E.R. Fisher, Chem. Mater. 13
(2001) 2749.
[3] J. Kuppers, Surf. Sci. Rep. 22 (1995) 249.
[4] B.T. Ginn, O. Steinbock, Langmuir 19 (2003) 8117.
[5] T.G. Ruardy, J.M. Schakenraad, H.C. Van der Mei, H.J. Busscher,
Surf. Sci. Rep. 29 (1997) 1.
[6] C.M. Chan, T.M. Ko, Surf. Sci. Rep. 24 (1996) 1.
[7] Ch.C. Dupont-Gillain, Y. Adriaensen, S. Derclaye, P.G. Rouxhet,
Langmuir 16 (2000) 8194.
[8] H. Kaczmarek, J. Kowalonek, A. Szalla, A. Sionkowska, Surf. Sci.
507 – 510 (2002) 883.
[9] S.J. Park, B.J. Kim, J. Colloid Interface Sci. 275 (2004) 590.
[10] Q.D. Chen, L.M. Dai, M. Gao, S.M. Huang, A. Mau, J. Phys. Chem.,
B 105 (2001) 618.
[11] S. Tang, O.J. Kwon, N. Lu, H.S. Choi, Surf. Coat. Technol. 195 (2005)
298.
[12] O.J. Kwon, S. Tang, S.W. Myung, N. Lu, H.S. Choi, Surf. Coat.
Technol. 192 (2005) 1.
[13] J.P. Boudou, J.I. Paredes, A. Cuesta, A. Martinez-Alonso, J.M.D.
Tascon, Carbon 41 (2003) 41.
[14] J.N. Chai, F.Z. Lu, B.M. Li, D.Y. Kwok, Langmuir 20 (2004) 10919.
[15] M.K. Seo, S.J. Park, S.K. Lee, J. Colloid Interface Sci. 285 (2005)
306.
[16] D. Zhang, S.M. Dougal, M.S. Yeganeh, Langmuir 16 (2000) 4528.
[17] R.V. Dabhade, D.S. Bodas, S.A. Gangal, Sens. Actuators, B, Chem.
98 (2004) 37.
[18] J.S. Kim, Y.E. Kim, K.H. Lee, J. Colloid Interface Sci. 271 (2004)
187.
[19] J.B. Lynch, P.D. Spence, D.E. Baker, T.A. Postlethwaite, J. Appl.
Polym. Sci. 71 (1999) 319.
[20] M.J. Shenton, G.C. Stevens, N.P. Wright, X. Duan, J. Polym. Sci., A,
Polym. Chem. 40 (2002) 95.
[21] M.K. Ghosh, K.L. Mittal, Polyimides Fundamentals and Applications,
Marcel Dekker, Inc., 1996.
[22] J.H. Kang, K. Cho, C.E. Park, J. Adhes. Sci. Technol. 15 (2001) 913.
[23] F.D. Buyl, J. Comyn, N.E. Shephard, N.P. Subramaniam, J. Adhes.
Sci. Technol. 16 (2002) 1055.
[24] J. Jang, H. Kim, J. Appl. Polym. Sci. 56 (1995) 1495.
[25] U. Benz, L. Haug, W. Kleinekathoefer, P. Waitkat, Patent 2001 US
6220497 B1.
[26] A.M. Abd El-Rahman, F.M. El-Hossary, T. Fitz, N.Z. Negm, F.
Prokert, T.M. Pham, E. Richter, W. Möller, Surf. Coat. Technol. 183
(2004) 268.
[27] M.C. Kim, S.H. Yang, J.H. Boo, J.G. Han, Surf. Coat. Technol. 174 –
175 (2003) 839.
[28] M.C. Kim, D.K. Song, H.S. Shin, S.H. Baeg, G.S. Kim, J.H. Boob,
J.G. Han, S.H. Yang, Surf. Coat. Technol. 171 (2003) 312.
[29] M. Zenkiewicz, J. Adhes. Sci. Technol. 15 (2001) 1769.
[30] D.K. Owens, R.C. Wendt, J. Appl. Polym. Sci. 13 (1969) 1741.
[31] M. Suzuki, A. Kishida, H. Iwata, Y. Hata, Y. Ikada, Macromolecules
19 (1986) 1804.
[32] Y. Ito, M. Inaba, D.J. Chung, Y. Imanishi, Macromolecules 25 (1992)
7313.
[33] H. Yasuda, Plasma Polymerization, Academic Press, Inc., 1985.
[34] G. Kühn, St. Weidner, R. Decker, A. Ghode, J. Friedrich, Surf. Coat.
Technol. 116 – 119 (1999) 796.