(PDF) Surface modification of ABS by photocatalytic

treatment for electroless copper plating

DOI: 10.1080/01694243.2013.845356
Cite this publication

Abstract
Surface roughness of acrylonitrile–butadiene–styrene (ABS) resin prior to metallization is treated
generally with sulphuric/chromic acid system. However, the presence of chrominum (VI) ion imposes
serious environmental problems. In this work, TiO2 photocatalytic treatment was used to enhance the
adhesion strength between the ABS surface and the electroless copper film. Effects of the TiO2
content, irradiation time and UV power upon the surface topography, surface characterization and the
adhesion strength were investigated. The results indicated that the surface hydrophilicity of ABS resin
and the adhesion strength between the electroless copper film and ABS surface increased with an
increase in the UV power and a prolongation in irradiation time, and did not increase linearly with an
increase of TiO2 content. Though the surface topography of ABS changed little, the adhesion
strength reached 1.25 kN/m, which was higher than that in the optimal H2SO4–MnO2 colloid. The
surface chemistry results indicated that –COOH and –OH groups formed with the photocatalytic
treatment and the absorption strengths increased with the UV power. XPS analysis results further
demonstrated that the contents of C=O and –COOH reached 6.4 and 4.9% with the photocatalytic
treatment, which was much higher than that of the H2SO4–MnO2 colloid (3.9 and 3.1%). The high
contents of C=O and –COOH groups enhanced the surface hydrophilicity of the ABS resin and
improved the adhesion strength between the electroless copper film and ABS resin. The results
indicated that the photocatalytic treatment was an environment-friendly and effective method to
replace the commercial wet chemical process for ABS surface modification.
Figures - uploaded by Zenglin Wang
Author content

Content uploaded by Zenglin Wang

Author content
This article was downloaded by: [Northwestern Polytechnical University]
On: 13 December 2013, At: 00:48
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Adhesion Science and
Technology
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/tast20
Surface modification of ABS by
photocatalytic treatment for
electroless copper plating
Wenxia Zhaoab, Qian Maa, Lisha Lia, Xirong Lia & Zenglin Wanga
a Key Laboratory of Applied Surface and Colloid Chemistry, School
of Chemistry and Chemical Engineering, Ministry of Education,
Shaanxi Normal University, Xi’an, 710062, China.
b School of Chemistry and Chemical Engineering, Ningxia Teachers
University, Guyuan, 756000, China.
Published online: 11 Oct 2013.
To cite this article: Wenxia Zhao, Qian Ma, Lisha Li, Xirong Li & Zenglin Wang (2014) Surface
modification of ABS by photocatalytic treatment for electroless copper plating, Journal of Adhesion
Science and Technology, 28:5, 499-511, DOI: 10.1080/01694243.2013.845356
To link to this article: http://dx.doi.org/10.1080/01694243.2013.845356
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
Surface modication of ABS by photocatalytic treatment for
electroless copper plating
Wenxia Zhao
a,b
, Qian Ma
a
, Lisha Li
a
, Xirong Li
a
and Zenglin Wang
a
*
a
Key Laboratory of Applied Surface and Colloid Chemistry, School of Chemistry and Chemical
Engineering, Ministry of Education, Shaanxi Normal University, Xi’an 710062, China;
b
School of
Chemistry and Chemical Engineering, Ningxia Teachers University, Guyuan 756000, China
(Received 19 March 2013; nal version received 9 June 2013; accepted 13 September 2013)
Surface roughness of acrylonitrile–butadiene–styrene (ABS) resin prior to
metallization is treated generally with sulphuric/chromic acid system. However, the
presence of chrominum (VI) ion imposes serious environmental problems. In this
work, TiO
2
photocatalytic treatment was used to enhance the adhesion strength
between the ABS surface and the electroless copper lm. Effects of the TiO
2
content,
irradiation time and UV power upon the surface topography, surface characterization
and the adhesion strength were investigated. The results indicated that the surface
hydrophilicity of ABS resin and the adhesion strength between the electroless copper
lm and ABS surface increased with an increase in the UV power and a prolongation
in irradiation time, and did not increase linearly with an increase of TiO
2
content.
Though the surface topography of ABS changed little, the adhesion strength reached
1.25 kN/m, which was higher than that in the optimal H
2
SO
4
–MnO
2
colloid. The sur-
face chemistry results indicated that –COOH and –OH groups formed with the photo-
catalytic treatment and the absorption strengths increased with the UV power. XPS
analysis results further demonstrated that the contents of C=O and –COOH reached
6.4 and 4.9% with the photocatalytic treatment, which was much higher than that of
the H
2
SO
4
–MnO
2
colloid (3.9 and 3.1%). The high contents of C=O and –COOH
groups enhanced the surface hydrophilicity of the ABS resin and improved the adhe-
sion strength between the electroless copper lm and ABS resin. The results indicated
that the photocatalytic treatment was an environment-friendly and effective method to
replace the commercial wet chemical process for ABS surface modication.
Keywords: photocatalytic treatment; electroless plating copper; adhesion strength;
ABS resin
1. Introduction
Acrylonitrile–butadiene–styrene (ABS) is the most commonly used polymer because of
its excellent properties.[1] Through metallization, the application range of polymers is
widened by the addition of properties such as reectivity, abrasion resistance, electrical
conductivity and a variety of decorative effects usually associated with metals.[2] How-
ever, non-conductive materials need an electroless plating process to create an autocata-
lytic conductive metallic thin lm that allows the subsequent electrolytic deposition.
Therefore, surface modication processes are necessary to improve the adhesion
*Corresponding author. Email: wangzl@snnu.edu.cn
Journal of Adhesion Science and Technology, 2014
Vol. 28, No. 5, 499–511, http://dx.doi.org/10.1080/01694243.2013.845356
Ó2013 Taylor & Francis
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
strength and the surface seeding of an electroless catalyst. The sulpho-chromic admix-
ture is the most widely used etchant for this purpose due to its high oxidative power.
[3–6] Because the carcinogen chrominum (VI) ion could impose serious operating prob-
lems, the interest towards a more environment-friendly surface modication process has
increased and the research for a replacement to the conventional chromic acid etching
solutions has gained importance.
Bessho et al. reported ABS surface etching by ozonated water as an etchant, but the
adhesion strength was poor.[7] Wang et al. [8–10] reported the investigation of ABS
resin etched by H
2
SO
4
–H
2
O–MnO
2
colloids, and good etching performance was
obtained when the etching temperature was 70 °C. However, MnO
2
does not dissolve in
H
2
SO
4
colloid and the soluble Mn(IV) ion concentration was very low, which affected
the etching performance of the ABS resin. Wet chemical pretreatment methods may
result in morphological changes and the removal of weakly cohesive surface materials,
which lead to an exceedingly rough and uneven surface morphology.[11] Methods of
plasma or laser need the assistance of special equipment, which increase the cost of
investment.[12]
Although Sugimoto et al. [13,14], Kim et al. [15,16] and Magallón-Cacho et al.
[17] reported a surface modication of ABS by the photocatalytic reaction in titanium
dioxide (TiO
2
) solution, respectively, the adhesion strength was only 1.0 kN/m, and the
effects of UV power, TiO
2
content and irradiation time upon the modication perfor-
mance have not been reported. In addition, changes in surface chemistry and surface
hydrophilicity have not been investigated before and after the surface modication.
In this paper, effects of the TiO
2
content, UV light power and irradiation time upon
surface topography, surface roughness, adhesion strength and surface chemistry of the
ABS resins were investigated. The surface topography and the surface chemistry were
evaluated by scanning electron microscopy (SEM), atomic force microscope (AFM),
X-ray photoelectron spectroscopy (XPS) spectra, FT-IR spectra and surface contact
angle measurements, respectively.
2. Experimental
The ABS substrates with a thickness of 1.0 mm and an area of 40 25 mm were used
in all of the experiments. The photocatalytic experiments were conducted with a TiO
2
suspension over the ABS surface. The anatase phase TiO
2
powder with an average par-
ticle size of 10 nm (JR05, Xuancheng Jing Rui New Material Co. Ltd) dispersed from
0.5 to 10 g in 1 L of distilled water. Surface modication was conducted with a high
pressure mercury vapour lamp, which provides the maximum energy at 365 nm. The
ABS substrates were rst pretreated by the degreasing process,[18] and then were
immersed into a TiO
2
dispersed solution. The distance between the substrate surface
and the lamp was xed at 5 cm. The effects of TiO
2
content (0.5, 1.0, 2.5 and 10 g/L),
irradiated time (10, 20, 30 and 40 min) and UV power (100, 300 and 500 W) upon sur-
face modication performance were investigated. The ABS substrate etched at 70 °C for
20 min in the MnO
2
–H
2
SO
4
colloid (12.3 mol/L H
2
SO
4
and 30 g/L MnO
2
) was used as
a reference.
The surface activation and the surface sensitization processes of the ABS substrates
were the same as the literature.[10] Distilled water was used to wash the substrates after
each procedure. The chemicals of the electroless copper plating solution were the same
as mentioned in an earlier report,[19] and the contents of the various components are
shown in Table 1. The pH of the solution was adjusted to 12.5 using NaOH and the
500 W. Zhao et al.
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
bath temperature was 70 °C. The electroless copper plating and the electroplating pro-
cesses were carried out according to an earlier report.[10] After the annealing was car-
ried out at 110 °C for 120 min, the copper-coated ABS substrates were cut into
10 40 mm strips, and the adhesion strength was measured by a 90° peel test at a peel
rate of 25 mm/min.[20] The experiment was repeated four times, and the adhesion
strength was reported as an average value of these four times.
The surface topographies of the ABS substrates were observed by SEM
(Philips-FEI Quanta-200 electron microscope). And the surface roughness of the ABS
substrates was measured by AFM (WETSPM-9500-J3, Shimazu Co. Ltd), which was
reported as an average roughness (R
a
) and the root mean square roughness (R
ms
).
Besides, the surface contact angles of the ABS substrates were determined as quick as
possible after the photocatalytic treatment by a video-based contact angle measurement
instrument. The volume of the water drop used in the measurements was 2 μL, at least
ve positions on the surface of the treated samples were measured and averaged. The
reection IR spectra were measured by Brucher-EQUINX55 FT-IR. The surface compo-
sition and chemistry of the ABS substrates were determined by XPS measurements
using a JPS90-MXV spectrometer from JEOL with a non-monochromatized Mg Ka
X-ray source. The elemental binding energies were corrected using the C1s binding
energy at 285 eV.[21]
3. Results and discussion
3.1. Effects of the UV power and irradiation time upon the surface topography and
surface roughness of ABS substrates
The effects of UV power and irradiation time upon the ABS surface topography and
surface roughness were investigated when the TiO
2
content was 1.0 g/L, and the results
are shown in Figures 1 and 2 and Tables 2 and 3. Before the photocatalytic treatment,
the ABS resin was smooth, and R
a
and R
ms
were 10 and 16 nm, respectively.
When the UV power was 100 W, only a few small cavities appeared on the ABS
surface (see Figure 1) irrespective of the irradiation time (10 or 40 min), and the density
and depth of the cavities slowly increased with the irradiation time prolongation. R
a
and
R
ms
were 13 and 18 nm with the irradiation time of 10 min, and then increased to 28
and 36 nm when the irradiation time was prolonged to 40 min. The inconspicuous
increase of R
a
and R
ms
might be attributed to the low UV power.
When the UV power was 300 W, some small cavities appeared on the ABS surface,
and the density and the depth of the cavities increased with an increase in the irradia-
tion time from 10 to 30 min, R
a
and R
ms
reached the maximum of 30 and 42 nm,
respectively. When the irradiation time was prolonged to 40 min, the density and depth
of the cavities became shallow, and R
a
and R
ms
of the treated ABS substrates decreased
Table 1. The chemicals of the electroless copper plating bath.
Chemicals Contents
Copper sulphate (CuSO
4
·5H
2
O) 10 g/L
Ethylenediaminetetraacetic acid disodium salt (EDTA·2Na) 30 g/L
Formaldehyde (HCHO, 37%) 3 ml/L
2,2′-dipyridyl 15 mg/L
Poly(ethylene glycol) (PEG 1000) 0.5 g/L
Journal of Adhesion Science and Technology 501
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
to about 25 and 35 nm, respectively. It was indicated that the intensity of 300 W UV
light was suitable for ABS resins’surface modication.
When the UV power was 500 W, the change in surface topography and the change
tendency of surface topography with the irradiation time were the same as that modied
at 300 W UV light. When the irradiation time was 30 min, the surface R
a
and R
ms
reached the maximum of 33 and 46 nm, respectively. The results indicated that there
was no substantial change in the surface topography with the UV power increase.
ABS polymers consist of two phases, acrylonitrile styrene and butadiene phases.
When ABS resins were etched by the 12.3 mol/L H
2
SO
4
–MnO
2
colloid at 70 °C, many
cavities appeared on the ABS surface, and the density and depth of the cavities clearly
increased with the etching time and R
a
and R
ms
of the etched ABS substrates reached
the maximum of 320 and 408 nm with an etching time of 20 min. It was attributed that
Figure 1. SEM images of ABS substrates treated by 1.0 g/L TiO
2
dispersed solution at different
UV light powers.
502 W. Zhao et al.
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
Figure 2. AFM images of ABS substrates treated by 1.0 g/L TiO
2
dispersed solution for 30 min,
UV power: (a) 100 W, (b) 300 W, (c) 500 W.
Table 2. The R
a
value of ABS substrates with UV power and irradiation time (TiO
2
content:
1.0 g/L).
R
a
(nm)
UV power (W) 10 min 20 min 30 min 40 min
100 13 16 24 28
300 14 18 30 25
500 15 22 33 23
Table 3. The R
ms
value of ABS substrates with UV power and irradiation time (TiO
2
content:
1.0 g/L).
R
ms
(nm)
UV power (W) 10 min 20 min 30 min 40 min
100 18 22 33 36
300 18 24 42 35
500 20 32 46 31
Journal of Adhesion Science and Technology 503
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
both the butadiene phase and the acrylonitrile styrene phase were oxidized by the col-
loid, and the oxidation rate of the butadiene phase was much quicker than that of the
acrylonitrile styrene phase.
But with the photocatalytic treatment, the surface topography and the surface rough-
ness of ABS substrate changed little. It was attributed to the fact that only part of the
butadiene phase on the ABS surface was oxidized by the hydroxyl radical (•OH), which
resulted in low surface roughness.
3.2. Effects of the UV power, irradiation time and TiO
2
content upon the surface
contact angle
In the photocatalytic treatment, the photo-generated holes react with the water mole-
cules and hydroxyl ions adsorbed on the surface of the photocatalyst to form hydroxyl
radicals. The resulting hydroxyl radicals, as very strong oxidizing agents, could oxidize
most organic compounds and form the activated oxygen species such as C=O, –OH
and –COOH to increase the surface wettability.[22–24] And so, the surface contact
angles of the ABS substrates were measured to evaluate effects of the UV power, irradi-
ation time and TiO
2
content on the surface modication performance. The ABS surface
was hydrophobic before the photocatalytic treatment, and the contact angle between dis-
tilled water and the ABS surface was 92.1°.
When the UV power was 300 W, the effects of TiO
2
content and irradiation time on
the surface contact angles were investigated, and the results are shown in Figure 3.
Whether the irradiation time was 10 or 40 min, the surface contact angle decreased with
an increase in TiO
2
content, and reached the lowest value when the TiO
2
content was
1.0 g/L. After that, the contact angle increased with a further increase of the TiO
2
con-
tent, which was attributed to agglomeration of TiO
2
particles in the high content TiO
2
dispersed solution decreasing the oxidative capacity of hydroxyl radicals (•OH). And
so, 1.0 g/L TiO
2
content in dispersed solution was used for the following experiments.
Figure 3. Dependence of the surface contact angle upon the TiO
2
content and the irradiation
time at 300 W UV light.
504 W. Zhao et al.
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
When the TiO
2
content was 1.0 g/L, effects of the UV power and the irradiation
time upon the surface contact angle were measured, and the results are shown in
Figure 4. Whether the irradiation time was 10 or 40 min, the surface contact angle
decreased with an increase in the UV power at the same irradiation time, and the
amount of reduction was not obvious when the UV power exceeded 300 W. The surface
contact angle decreased quickly with the irradiation time from 10 to 30 min at the same
UV power.
When the UV power was 100 W, the surface contact angle rst decreased quickly
with the irradiation time from 0 to 10 min. With a further prolongation of the irradiation
time, the surface contact angle decreased continuously, and reached to 36.8° when the
irradiation time was 40 min, which indicated that the ABS surface changed from a
hydrophobic to a hydrophilic surface. This could be attributed to the low UV power.
When the UV power was 300 W, the surface contact angle decreased quickly with the
increase in the irradiation time and reached a minimum of 35.4° with an irradiation time
of 30 min, which was lower than that in the 12.3 mol/L H
2
SO
4
–MnO
2
colloid (about
38.5°). After that, the surface contact angle increased slowly with the increase in the
irradiation time. The results suggested that the modication condition was t. When the
UV power was 500 W, the change of surface contact angle with the irradiation time
was similar to that of 300 W UV powers, which clearly indicated that the 300 W UV
power was enough for surface modication.
Surface contact angle is usually affected by two factors, surface roughness and the
hydrophilic nature of the surface. Surface contact angle decreased with an increase
in surface roughness and also decreased with an increase in the hydrophilic nature of
the surface. Though the surface topography and the surface roughness changed little,
the surface contact angle was lower than that in the H
2
SO
4
–MnO
2
colloid. Therefore, a
lower surface contact angle was attributed to the fact that the density of the hydrophilic
groups formed on the ABS surface after the photocatalytic treatment was much higher
than that of the H
2
SO
4
–MnO
2
colloid.
Figure 4. Dependence of the surface contact angle upon UV power and the irradiation time at
the TiO
2
content of 1.0 g/L.
Journal of Adhesion Science and Technology 505
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
3.3. Effects of the UV power, irradiation time and TiO
2
content upon adhesion
strength
When the UV power was 300 W, the dependence of adhesion strength on the irradi-
ation time and TiO
2
content was investigated and the results are shown in Figure 5.
Whether the irradiation time was 10 or 40 min, the adhesion strength between the
ABS resin and the electroless copper lm increased with an increase of TiO
2
con-
tent, and reached the highest value when the TiO
2
content was 1.0 g/L. After that,
the adhesion strength decreased with a further increase of the TiO
2
content, TiO
2
content higher than 1.0 g/L may reduce the oxidative capacity of hydroxyl radicals
(•OH). At the same TiO
2
content, the adhesion strength rst increased and then
decreased with an increase in the irradiation time from 10 to 40 min. The results
were in agreement with the surface SEM observation and the surface contact angle
measurement.
When the TiO
2
content was 1.0 g/L, effects of the UV power and irradiation time
upon the adhesion strength were investigated and the results are shown in Figure 6. As
seen from Figure 6, the adhesion strength increased with an increase of the UV power
at the same irradiation time, and the increment was relatively smaller when the UV
power was higher than 300 W. These results further demonstrated that the UV power of
300 W was enough for ABS surface modication.
When the UV power was 100 W and the irradiation time was 10 min, the adhesion
strength was 0.66 kN/m. The adhesion strength increased quickly with the irradiation
time and reached about 1.18 kN/m at the irradiation time of 40 min. This was corre-
sponding to the etching by the 12.3 mol/L H
2
SO
4
–MnO
2
colloid (1.19 kN/m) and was
much higher than that required in the PCB process (0.70 kN/m).
When the UV power was 300 W, the adhesion strength initially increased quickly
with an increase in the irradiation time, and reached a maximum of 1.22 kN/m at the
irradiation time of 30 min, which was higher than that in the optimal MnO
2
–H
2
SO
4
col-
loid. After that, the adhesion strength decreased slowly with a further prolongation of
Figure 5. Adhesion strength as the function of the TiO
2
content and the irradiation time at
300 W UV light.
506 W. Zhao et al.
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
the irradiation time. When the UV power was 500 W, the change tendency of the adhe-
sion strength with the irradiation time was the same as mentioned above. The adhesion
strength reached 1.25 kN/m at the irradiation time of 30 min. This result was attributed
to a high UV power.
The adhesion strength between the polymer surface and electroless copper lm was
affected by three factors: surface roughness of the polymer, presence of oxygen and
nitrogen-containing polar groups at the surface, and condition of the electroless copper
plating.[25] When the condition of electroless copper plating was same, the adhesion
strength was dependent not only on the surface roughness, but also on the surface
hydrophilicity or density of the polar groups.
Figure 6. Adhesion strength as the function of UV power and irradiation time at a TiO
2
content
of 1.0 g/L.
Figure 7. FT-IR spectra of ABS substrates with different UV powers in 1.0 g/L TiO
2
dispersed
solution, treatment time: 30 min, (a) before treatment, (b) 100 W, (c) 300 W, (d) 500 W.
Journal of Adhesion Science and Technology 507
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
Though the surface topography changed little with the photocatalytic treatment, and
the maximum R
a
was 33 nm, which was much lower than that in the H
2
SO
4
–MnO
2
col-
loid, the maximum adhesion strength reached 1.25 kN/m, which was higher than that in
the optimal H
2
SO
4
–MnO
2
colloid. Due to the formation of abundant hydrophilic
groups, the wettability of the ABS surface improved and the overall increased wettabil-
ity led to more intimate contact between the substrate and the electroless copper lm.
Therefore, the high adhesion strength between the substrate and the electroless copper
lm was caused by improving the hydrophilic property.[26] Hence, the effects of the
photocatalytic treatment on the surface chemical properties of the ABS resins were
investigated.
3.4. The surface chemical properties of ABS substrates before and after photocatalytic
treatment
When the TiO
2
content 1.0 g/L and the irradiation time was 30 min, FT-IR spectra and
XPS analysis of the ABS surface were performed to understand the reason for an
improvement in the hydrophilic property. Figure 7 shows FT-IR spectra for ABS sub-
strates with different UV light powers at the same irradiation time. The two characteris-
tic absorption peaks at 1700 and 3745 cm
1
could be attributed to the absorption
vibrations of the –COOH and –OH groups which appeared with the photocatalytic treat-
ment. Furthermore, the absorption strengths of the peaks at 1700 and 3745 cm
1
increased with the increase of UV power from 100 to 500 W. The results indicated that
–COOH and –OH groups were formed on the ABS surface with the photocatalytic
treatment, and the density of –COOH and –OH groups increased with an increase of
the UV power. The change of the absorption strengths of –COOH and –OH groups
with the UV power was in agreement with that of the surface contact angle with the
UV power.
The elemental contents of carbon, oxygen and nitrogen on the ABS surface with
different UV powers were measured by XPS, and the results are shown in Table 4.
Before the photocatalytic treatment, the contents of carbon, oxygen and nitrogen on the
ABS surface were 91.2, 5.6 and 3.2%, respectively.
From Table 4, it can be seen that the oxygen content on the ABS surface increased
signicantly and the carbon content decreased rapidly with the photocatalytic treatment.
The nitrogen content on the surface remained stable before and after the photocatalytic
treatment. These results meant that the ABS surface was oxidized with the photocata-
lytic treatment, and some polar groups, such as –COOH and –OH, were formed on the
surface. The carbon content on the ABS surface decreased with the UV power and
reached 79.7% when the UV power was 500 W. The change in the oxygen content on
Table 4. Surface elemental contents of ABS substrates before and after the photocatalytic
treatment (irradiation time: 30 min, TiO
2
content: 1.0 g/L).
Content
UV power (W) C (%) O (%) N (%)
0 91.2 5.6 3.2
100 81.9 15.2 2.9
300 80.2 16.8 3.0
500 79.7 17.3 3.0
508 W. Zhao et al.
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
the ABS surface was opposite to that of the carbon content. It increased with the UV
power and reached 17.3% when the UV power was 500 W, which was higher than that
in the H
2
SO
4
–MnO
2
colloid (about 15.1%). This result indicated that the density of
polar groups formed on the ABS surface by the photocatalytic treatment was much lar-
ger than that by H
2
SO
4
–MnO
2
colloid. This result was in agreement with that of the
FT-IR spectra and the surface contact angle with the UV power.
The C1s XPS spectra of the ABS surface with the UV power of 100, 300 and
500 W were measured, and the results are shown in Figure 8. There are two peaks at
285.0 and 286.5 eV in the reference spectrum, which are attributed to C–C, C–H, C=C
and O–C, N≡C species.[9,10,25] Two peaks at 287.6 and 289.0 eV appeared after the
photocatalytic treatment, which could be attributed to C=O and –COOH species,
respectively.[25]
The contents of the four carbon groups on the ABS surface with different UV pow-
ers are shown in Table 5. The content of the hydrophobic groups (C–C, C–H, C=C)
decreased with the photocatalytic treatment, further more, the content decreased with
Figure 8. The C1s XPS spectra of the ABS substrates treated by 1.0 g/L TiO
2
dispersed solution
at 300 W UV light for 30 min.
Table 5. The contents of four carbon groups on ABS surface before and after the photocatalytic
treatment (irradiation time: 30 min, TiO
2
content: 1.0 g/L).
Content
UV power (W) C–CC–H C=C (%) C≡NC–O (%) C=O (%) –COOH (%)
0 87.5 12.5 0 0
100 80.7 10.0 5.8 3.5
300 77.9 11.4 6.3 4.4
500 76.4 12.3 6.4 4.9
Journal of Adhesion Science and Technology 509
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
the increase in the UV power and reached 76.4% when the UV power was 500 W. The
contents of –COOH and C=O increased with the UV power. And when the UV power
increased from 100 to 500 W, the content of –COOH increased from 3.5 to 4.9%, which
was much higher than that in the H
2
SO
4
–MnO
2
colloid. The high contents of the C=O
and –COOH groups enhanced the surface hydrophilicity of the ABS resin and improved
the adhesion strength between the electroless copper lm and the ABS substrate.
4. Conclusion
Effects of the TiO
2
content, irradiation time and UV power upon the surface topogra-
phy, surface chemical properties and adhesion strength of ABS substrates were investi-
gated by surface SEM observation, AFM and XPS measurements. With the
photocatalytic treatment, the surface hydrophilicity of the ABS substrate and the adhe-
sion strength between the electroless copper lm and the ABS substrate increased with
an increase in the UV power and a prolongation of irradiation time, and did not
increased linearly with an increase in TiO
2
content, as the agglomeration of TiO
2
parti-
cles in the high content-dispersed solution led to the decrease in the oxidative capacity
of hydroxyl radicals (•OH). Though the surface topography and the surface roughness
changed little, the adhesion strength reached 1.25 kN/m, which was higher than that in
the optimal H
2
SO
4
–MnO
2
colloid (1.19 kN/m). This result was attributed to the forma-
tion of abundant polar groups on the ABS surface with the photocatalytic treatment and
the increasing density of the hydrophilic groups with an increase in UV power, which
was further demonstrated by the surface contact angle, FT-IR spectra and XPS measure-
ments. And so, the photocatalytic treatment was an environmental-friendly and effective
method to replace commercial wet chemical process for ABS surface modication. With
the photocatalytic treatment, not only a high adhesion strength was obtained, but also
smoothness of the ABS surface was maintained, which is conducive to the improve-
ment in the attenuation of high-frequency signal.
Funding
The authors would like to thank the Research Fund for the National Natural Science Foundation
of China [Grant No. 21273144]; Doctoral Program of Higher Education of China [Grant No.
20110202110004] and Changjiang Scholars and Innovative Research Team in University of China
[IRT1070] for supporting this research.
References
[1] Kulich DM. ABS resins. In: Kirk O, editor. Encyclopedia of chemical technology, vol. 1.
New York (NY): Wiley; 1993. p. 391–411.
[2] Corp GE. Metallization guide. Pittseld (MA): GE Plastics; 1995.
[3] McCaskie JE. A survey of mechanisms for adhering metal lms to plastic surfaces. Plat.
Plast. 2006;5:31–39.
[4] Wang GX, Li N, Hu HL, Yu YC. Process of direct copper plating on ABS plastics. Appl.
Surf. Sci. 2006;253:480–484.
[5] Charbonnier M, Romand M. Polymer pretreatments for enhanced adhesion of metals depos-
ited by the electroless process. Int. J. Adhes. Adhes. 2003;23:277–285.
[6] Yen PC. Improved ABS plastics activating treatment for electroless copper plating. Polymer.
1995;36:3399–3400.
[7] Bessho T, Yoshinaga F, Inoue K, Koiwa I, Honma H. Pretreatment of nickel plating on
ASA resin using ozonated water as replacement for chromic acid etching. J. Surf. Finish.
Soc. Jpn. 2006;57:659–663.
510 W. Zhao et al.
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
[8] Yang ZF, He Y, Li ZX, Li N, Wang ZL. Adhesion improvement of ABS resin to electroless
copper by H
2
SO
4
–MnO
2
colloid with ultrasound-assisted treatment. J. Adhes. Sci. Technol.
2011;25:1211–1221.
[9] Li ZX, Li N, Yin L, He Y, Wang ZL. An environment-friendly surface pretreatment of ABS
resin prior to electroless plating. Electrochem. Solid-State Lett. 2009;12:D92–D95.
[10] Wang ZL, Li ZX, He Y, Wang ZX. Study of an environmentally friendly surface etching
system of ABS for improving adhesion of electroless Cu lm. J. Electrochem. Soc.
2011;158:D664–D670.
[11] Brewis DM. Adhesion to polymers: how important are weak boundary layers. Int. J. Adhes.
Adhes. 1993;13:251–256.
[12] Abenojar J, Torregrosa-Coque R, Martínez MA, Martín-Martínez JM. Surface modications
of polycarbonate (PC) and acrylonitrile butadiene styrene (ABS) copolymer by treatment
with atmospheric plasma. Surf. Coat. Technol. 2009;203:2173–2180.
[13] Sugimoto M, Tashiro K, Bessho T, Koiwa I, Honma H. Surface reforming of ABS resin
using TiO
2
under UV light irradiation. Surf. Finish. Soc. Jpn. 2006;57:162–166.
[14] Bessho T, Inoue K, Ishikawa K, Koiwa I, Honma H. Electroless copper plating on the insu-
lating resin for build-up process using TiO
2
as a photocatalyst. J. Surf. Finish. Soc. Jpn.
2006;57:157–161.
[15] Kim GG, Kang JA, Kim JH, Lee KY, Kim SJ, Kim SJ, Shin SH. Improved adhesion to
ABS plastics by a photocatalytic reaction. Mater. Sci. Forum. 2007;75:544–545.
[16] Kim GG, Kang JA, Kim JH, Lee KY, Kim SJ, Kim SJ. Photocatalytic pretreatment of acry-
lonitrile–butadiene–styrene polymer for electroless plating. Scripta Mater. 2007;56:349–351.
[17] Magallón-Cacho L, Pérez-Bueno JJ, Meas-Vong Y, Stremsdoerfer G, Espinoza-Beltrán FJ.
Surface modication of acrylonitrile–butadiene–styrene (ABS) with heterogeneous photoca-
talysis (TiO
2
) for the substitution of the etching stage in the electroless process. Surf. Coat.
Technol. 2011;206:1410–1415.
[18] Jiang HY, Liu ZJ, Wang XW, Wang ZL. Effect of triethanolamine on deposition rate of elec-
troless copper plating. Trans. Inst. Met. Finish. 2007;85:103–106.
[19] Wang ZL, Furaya A, Yasuda K, Ikeda H, Baba T, Hagiwara M, Toki S, Shigubara S,
Kubota H, Ohmi T. Adhesion improvement of electroless copper to a polyimide lm
substrate by combining surface microroughening and imide ring cleavage. J. Adhes. Sci.
Technol. 2002;16:1027–1040.
[20] Wang ZL, Yaegashi O, Sakaue H, Takahagi T, Shingubara S. Suppression of native oxide
growth in sputtered TaN lms and its application to Cu electroless plating. J. Appl. Phys.
2003;7:4697–4701.
[21] Chastain J, editor. Handbook of X-ray photoelectron spectroscopy. Eden Prairie (MN): Per-
kin–Elmer Corporation, Physical Electronics Division; 1992. p. 182–261.
[22] Sakkas VA, Arabatzis IM, Konstantinou IK, Dimou AD, Albanis TA, Falaras P. Metolachlor
photocatalytic degradation using TiO
2
photocatalysts. Appl. Catal. B. 2004;49:195–205.
[23] Carp O, Huisman CL, Reller A. Photoinduced reactivity of titanium dioxide. Prog. Solid
State Chem. 2004;32:33–177.
[24] Mathieson I, Bradley RH. Improved adhesion to polymers by UV/ozone surface oxidation.
Int. J. Adhes. Adhes. 1996;16:29–31.
[25] Siau S, Vervaet A, Vaeck L, Schacht E, Demeter U, Calster AV. Adhesion strength of the
epoxy polymer/copper interface for use in microelectronics. J. Electrochem. Soc. 2005;152:
C442–C455.
[26] Mittal KL, Pizzi A. Adhesion promotion techniques: techno. applications. New York: Marcel
Dekker; 1999.
Journal of Adhesion Science and Technology 511
Downloaded by [Northwestern Polytechnical University] at 00:48 13 December 2013
Show abstract
... The TiO 2 photocatalytic treatment has received extensive attention in recent years because of
its high good stability, high catalytic activity, and environment-friendly sys- tem.[8] Zhao et al. [9],
Magallón-Cacho et al. [10], and Kim et al. [11] investigated the surface modification of acrylonitrile–
butadiene–styrene (ABS) substrates in photocatalytic TiO 2 solution. The surface hydrophilicity of
ABS was improved and the adhesion strength between the ABS film and the electroless copper film
was enhanced though the surface roughness increased a little. ...