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Journal of Materials Science and Engineering B 7 (11-12) (2017) 272-277 doi: 10.17265/2161-6221/2017.11-12.005
Influence of Modification on the ABS Plastics Using
Atmospheric UV Irradiation as Plating Pretreatment
Yuki Nakabayashi1,2, Yasushi Umeda2,3, Katsuhiko Tashiro2,3, Hideo Honma2 and Hiroaki Kozai3,4
1. Graduate School of Engineering, Kanto Gakuin University, Mutsurahigashi 1-50-1, Kanazawa-ku, Yokohama, Kanagawa, Japan
2. Materials and Surface Engineering Research Institute, Kanto Gakuin University, Ogikubo 1162-2, Odawara, Kanagawa, Japan
3. Kanto Gakuin University Research Advancement and Management Organization, Mutsurahigashi 1-50-1, Kanazawa-ku,
Yokohama, Kanagawa, Japan
4. College of Science and Engineering, Kanto Gakuin University, Mutsurahigashi 1-50-1, Kanazawa-ku, Yokohama, Kanagawa,
Japan
Abstract: Plating on the plastic is one of the important technologies to decorate exterior automotive parts and electronic devices. Conventionally, etching solution contained carcinogen hexavalent chromium obtained high adhesion strength between metal film and plastic surface to decorative the plating. On the other hand, health damage and environmental pollution from waste etching solution are occurring. For the above reasons, development of chromium free pretreatment is an urgent problem to solve this issue. In this study, we concentrated the environmentally friendly surface modification process in which atmospheric UV treatment was used to investigate effect of surface morphology and state on the ABS (acrylonitrile butadiene styrene) plastic. As a result, morphology of ABS surface was kept smooth after UV irradiation treatment. The conversion from hydrophobic to hydrophilic on the ABS surface state was confirmed by contact angle test and FT-IR spectra. Moreover, it was confirmed that appropriate amount of oxidation was necessary for metal plating on the ABS plastic, in order to obtain high adhesion strength between metal film and plastics surface.
Key words: Atmospheric UV treatment, surface modification, ABS plastic, plating pretreatment.
1. Introduction
ABS plastics have been widely used in various
fields because it has excellent properties such as
workability, impact resistance and dimensional
stability. Deposited metal plating on ABS plastics
surface is utilized to increase the weather resistance
and impart metallic luster. By conventionally plating
method, chromic acid-sulfuric acid mixed solutions
are applied to improve the high adhesion strength
between metal plating layer and plastic surface [1, 2].
However, heavy risk of environmental pollution
occurs because of the including carcinogen hexavalent
chromium in plating process. Therefore, it should
remove the hexavalent chromium from plating process
[3, 4].
Corresponding author: Yuki Nakabayashi, Ph.D. student,
research fields: plating and surface modification.
In recent years, there were many reports about the
substitute methods of etching without chromic acid to
the plating pretreatment on plastic materials [5-8].
Previously, we achieved the possibility to high
adhesion strength between metal plating and smooth
surface on the plastic materials using atmospheric UV
treatment [9, 10]. This process was the formation of
surface modification layer on the plastics surface for
plating pretreatment. The moderate modification layer
was effective to achieve the result of high adhesion
strength between metal plating and plastics surface.
In this study, atmospheric UV treatment was
applied as a pretreatment on ABS plastics for metal
plating. We confirmed that the effect of surface
modification layer on the ABS plating achieved the
high adhesion strength of metal plating. In addition,
we were comparing the surface condition on the
different type ABS plastic materials modified by
D DAVID PUBLISHING
Influence of Modification on the ABS Plastics Using Atmospheric UV Irradiation as Plating Pretreatment
273
atmospheric UV treatment method.
2. Experimental Methods
2.1 Substrates
The samples used commercial type ABS plastics
that were SUNLOID EAR003 (ABS-S, Sumitomo
Bakelite Co., Ltd. Japan), HISHIPLATE Y-268
(ABS-H, Mitsubishi Chemical, Inc., Japan), and UMG
3001M (ABS-U, UMG ABS, Ltd. Japan).
2.2 Surface Modification and Plating Procedures
The equipment used for surface modification was
low pressure mercury vapor lamp (KOL1-300S, Koto
Electric Co., Ltd. Japan) that emitted with a
wavelength of 185 nm and 254 nm. The distance
between UV lamp and ABS surface was set to 30 mm.
Table 1 shows the plating procedure of the ABS
plastics. Heat treatment was performed before and
after UV irradiation. Moreover, alkaline treatment
and conditioning were immersed to improve the
absorption amount of catalyst. Palladium ion
performed absorption on the surface as the catalyst
for electroless plating. After the accelerating step,
ABS plastics were immersed to electroless Ni-P
plating bath for 5 min. The thickness of Ni-P plating
film was deposited about 0.2 µm on the surface.
Finally, copper film 20 µm thickness was deposited
on the Ni-P film using electro copper sulfate acid bath
as the current density 3 A/dm2 under room
temperature.
Composition of copper sulfate acid bath contained
0.3 mol/L of copper sulfate and 1.8 mol/L of sulfuric
acid. Moreover, plating additives used commercial
type CUBRITE-21 and STB (JCU Co., Japan).
2.3 Evaluation of Adhesion Strength
The copper plating film was cut with 10 mm width
for peeling tests. In order to investigate the adhesion
strength of plating film on the ABS surface, universal
testing machine (Strograph E2-L05 Toyo Seiki
Seisaku-sho, Ltd. Japan) was used. In addition, the
average of adhesion strength was calculated from 3
times measurement in each sample.
2.4 Characterization
Before and after the atmospheric UV treatment, the
surfaces were observed by SEM (Scanning Electron
Microscopy, Quanta 3D 200i, FEI Inc., USA) and
SPM (Scanning Probe Microscopy, E-sweep, Seiko
Instruments Inc. Japan) to examine the surface
morphologies of the each sample. To obtain
topographic images of the ABS plastics, SPM was
operated in AFM (Atomic Force Microscopy) mode.
In addition, the arithmetic average roughness (Ra)
and 10 points average roughness (Rzjis) were
measured in an area of 10 µm square. The AFM
cantilever used a standard contact mode type
(SI-AF-01, Seiko Instruments Inc. Japan).
Table 1 Experimental procedure.
Heat treatment, 75 °C, 60 min
↓
Atmospheric UV treatment
↓
Heat treatment, 75 °C, 60 min
↓
Alkaline treatment,65 °C, 3 min
(NaOH 50 g/dm3)
▽
Conditioning, 45 °C, 2 min
(CC-231 10 vol%, ROHM and HAAS)
▽
Catalyzing, 45 °C, 5 min
(PdCl2 0.3 g/dm3)
▽
Accelerating, 45 °C, 1 min
(NaH2PO2・H2O 35 g/dm3)
▽
Electroless Ni-P plating, 0.2 μmt
▽
Heat treatment, 75 °C, 60 min
↓
Electro Cu plating, 20 μmt
▽
Heat treatment, 75 °C, 60 min
▽: Rinsing ↓: No rinse
Influenc
274
The surfa
the water co
measured
(DMe-201, K
with fixed
functional
Transform I
JASCO Co
diamond pr
JASCO Co.
number wa
Moreover, f
production,
carbonyl in
carbonyl ban
2,240 cm-1 r
Oxidation
and analyzed
The CL
Chemilumin
Electronics
continuously
3. Results
3.1 Influence
Treatment
In order to
between the
quantitativel
effect of UV
with the co
Electroless
untreated AB
adhesion str
be measured
after sulfuric
that untreate
to obtain ad
plastics, it w
between me
three types
ce of Modifica
ace analysis o
ontact angle m
by automa
Kyowa Interf
water dropl
groups wer
Infrared Spec
o., Japan) e
rism (PKS-D
, Japan). The
as defined 4
for comparis
carbonyl in
ndex was cal
nd at 1,715 c
respectively [
n states amon
d by CL (che
L intensity
nescence an
Industry C
y under N2 at
and Discus
e of Adhesion
o quantitative
e metal plat
ly, peel test
V treatment t
opper film o
Ni-P plating
BS plastics co
rength of untr
d because dep
c copper plat
ed surface did
dhesion stren
was possible
etal film and
of commer
ation on the A
of wettability
measurement
tic contact
face Science
let size of
re analyzed
ctroscopy (FT
equipment fi
D 470 with A
e measuremen
4,000 cm-1
on with amo
ndex value
lculated as
cm-1 and nitri
11].
ng the sample
emical lumine
y measur
nalyzer (CL
Co., Ltd.,
t 160 °C in a s
ssion
n Strength by
ely evaluate a
ting layer an
was used. F
time on the a
n the variou
g film was d
onfirmed by
reated ABS p
posited metal
ting. This rea
d not have m
ngth. When U
to measure a
d plastic surf
rcial materia
ABS Plastics
y was applied
t in which it
angle me
Co., Ltd. Jap
1.0 µL. Sur
using Fou
T-IR, FT/IR4
itted with A
ATR PRO45
nt range of w
to 1,000 c
ount of carb
was used.
the ratio of
ile group ban
es were comp
escence) inten
rements u
LA-SF4 Toh
Japan) 5
sample cham
Atmospheric
adhesion stren
nd ABS pla
Fig. 1 shows
adhesion stren
us ABS plas
deposited on
visual. Howe
plastics could
l film was bl
ason was perh
modification l
UV treated A
adhesion stren
face. There w
als, among t
s Using Atmo
d by
was
eters
pan)
rface
urier
100,
ATR
50-S,
wave
cm-1.
onyl
The
f the
nd at
ared
nsity.
used
hoku
min
mber.
c UV
ngth
stics
s the
ngth
stics.
n the
ever,
d not
lister
haps
layer
ABS
ngth
were
them
AB
1.0
sho
kN/
Mo
adh
UV
3.2
F
surf
surf
dim
UV
surf
afte
ima
Fig.stre
Fig.(a) Uof AUV ABS
spheric UV Ir
S-H obtained
kN/m. The o
wed maximu
/m by atmo
reover, we
hesion streng
V treatment tim
Observation
Fig. 2 shows
faces modifie
faces morph
mples were sc
V treatment A
face morphol
er atmospheri
ages. Fig. 3 sh
. 1 Effect oength with the
. 2 SEM imagUntreated of ABABS-U, (d) Aft
treatment 1 minS-U.
rradiation as
d the highes
other two typ
um adhesion
ospheric UV
confirmed t
gth was not
me.
of Surface M
s SEM imag
ed by atmosp
hologies wer
cattered befo
ABS plastics
logy showed
ic UV treatm
hows AFM im
of UV treatmcopper film on
ges of the ABSBS-S, (b) Untreter UV treatmen of ABS-H, (f
Plating Pretr
st adhesion s
pes of ABS-S
n strength o
V treatment
that the cha
constant wit
Morphology
ges before a
pheric UV tre
re confirme
ore and after
s surfaces [1
a little chang
ment observat
mages before
ment time to n the various A
S plastic surfaceated of ABS-Hnt 1 min of AB
f) After UV trea
reatment
strength over
S and ABS-U
of about 0.7
for 1 min.
ange of the
th increasing
and after the
eatment. The
ed that fine
atmospheric
12, 13]. The
ge before and
tion by SEM
and after the
the adhesionABS plastics.
ce. H, (c) UntreatedBS-S, (e) Afteratment 1 min of
r
U
7
.
e
g
e
e
e
c
e
d
M
e
n
d r f
Influenc
surfaces mo
Untreated
topographic
atmospheric
in arithmeti
average roug
-77.2 nm to
nanoscale su
suggested th
obtained w
surface morp
lesser impa
after the UV
almost chan
3.3 Characte
Fig. 4 sh
treatment tim
on the ABS
plastics wer
UV treatmen
ABS-H and
respectively
greatly decr
affected by
samples. Th
properties a
group by us
ABS plastic
at UV 10 m
vicinity 20.0
plastics has
Fig. 5 sh
results on th
treatment tim
IR spectra sh
at 1,715 cm
above func
increasing U
that the oth
similar spec
ce of Modifica
odified by
ABS plasti
images as
c UV treatme
c average ro
ghness (Rzjis
o 10.5 nm, r
urface proper
hat adhesion
without micro
phology by a
ct on adhesi
V treatment, t
ged.
eristic of Surf
hows that it
me to the wat
S plastics. Th
re hydrophob
nt, and the w
d ABS-U w
. The water
reased at U
y atmospheri
hese results sh
arose through
ing atmosphe
cs showed the
min, water c
0°. We confi
lower limit o
hows measur
he ABS-S w
me. After atm
howed adsorp
m-1 and hydro
ctional grou
UV treatmen
her two types
ctra of above
ation on the A
atmospheric
ics surfaces
with SEM
ent, increasing
oughness (Ra
s) were -3.9 n
respectively.
rties were ver
strength of m
o anchor ef
atmospheric U
ion strength
the surface ro
rface State
depends on
ter contact an
he surface sta
bic without
water contact a
ere 82.3°, 8
contact angl
V 1 min an
c UV treatm
howed that su
h the presenc
eric UV treat
e similar resu
ontact angle
rmed that UV
of water conta
rement of th
ith different
mospheric U
ption bands o
xyl group at
ups were
t time [8]. I
s of ABS-H
e result from
ABS Plastics
UV treatm
were smo
M images. A
g and decrea
a) and 10 po
nm to 1.7 nm
The change
ry smooth. It
metal plating
ffect. Theref
UV treatment
and before
oughness was
atmospheric
ngle measurem
ates on the A
the atmosph
angles of AB
85.7° and 86
e of ABS-T
nd it was m
ment than o
urface wettab
ce of hydroph
tment. Moreo
ult of wettab
becomes in
V modified A
act angle.
he FT-IR spe
atmospheric
UV treatment,
of carbonyl gr
3,300 cm-1.
increased w
It was confir
and ABS-U
0 min to 5
s Using Atmo
ment.
ooth
After
asing
oints
m and
es of
was
was
fore,
t had
and
s not
UV
ment
ABS
heric
S-S,
6.2°,
was
more
other
bility
hilic
over,
bility
n the
ABS
ectra
UV
, the
roup
The
with
rmed
had
min
trea
tim
grou
calc
each
Fig.(a) Uof AUV ABS
Fig.the
Fig.afte
spheric UV Ir
ated. Howeve
e of 10 min
up. For the
culated from
h sample.
. 3 AFM imaUntreated of ABABS-U, (d) Aft
treatment 1 minS-U.
. 4 Dependenwater contact
. 5 FT-IR sper UV treatmen
rradiation as
er, FT-IR spe
had the diff
above reas
m FT-IR spec
ges of the ABSBS-S, (b) Untreter UV treatmen of ABS-H, (f
nce of atmosphangle measure
pectra of the nt.
Plating Pretr
ectra from U
ferent result
on, carbonyl
ctra and com
S plastic surfaceated of ABS-Hnt 1 min of AB
f) After UV trea
heric UV treatement on the A
ABS-S surfac
reatment 275
UV treatment
for carbonyl
l index was
mpared with
ce. H, (c) UntreatedBS-S, (e) Afteratment 1 min of
tment time onABS plastic.
ce before and
5
t
l
s
h
d r f
n
d
Influence of Modification on the ABS Plastics Using Atmospheric UV Irradiation as Plating Pretreatment
276
Fig. 6 shows relation between the atmospheric UV
treatment time and the carbonyl index. The values of
the carbonyl index on the ABS-S were maximum
value after UV treated 5 min and it was decreased
when UV treated 10 min. For that reasons, carbonyl
group at 1715 cm-1 was shifted to the low wave
number in ABS-S. Moreover, there was the difference
in the value of the adhesion strength in each sample,
but the increase rate of the carbonyl index was almost
the same. Therefore, surface hydrophilic groups were
necessary for plating on the ABS plastics and it was
uncertain to correlate with the density of adhesion
strength.
Fig. 7 shows relation between the total CL intensity
on the various ABS plastics. The amount of chemical
luminescence was emitted from degraded peroxide
and it was arranged by descending order ABS-S,
ABS-H and ABS-U respectively. As the above results,
amount of carbonyl index was not too much difference,
but we confirmed that each sample had obvious
difference for CL intensity. We considered that
oxidized butadiene component and amount of
oxidation inhibitor of additives in ABS plastics
influenced chemical luminescence species. For above
reasons, ABS-S was susceptible to oxidation and
ABS-U was insusceptible to oxidation in these three
materials. It was suggested that for ABS-U there
existed less butadiene on the surface or contained
more oxidation inhibitor of additives than other
samples [14].
On the other hand, amount of chemical
luminescence intensity of ABS-H was intermediate
value between ABS-U and ABS-T. At the same time,
it was suggested that surface state was becoming
sufficient oxidation for modification by using
atmospheric UV treatment. Therefore, for the above
results, ABS-H was suitable for UV surface
modification process and it obtained high adhesion
strength between metal plating and plastic. Moreover,
it was possible that appropriate amount of oxidation
was necessary for metallization on the ABS plastics.
Fig. 6 Relation between the atmospheric UV treatment time and the carbonyl index.
Fig. 7 Relation between the total CL intensity and the various ABS plastics.
4. Conclusions
The surface roughness of ABS plastics was changed
by nanometer scale before and after UV treatment. For
this reason, surface morphology by atmospheric UV
treatment has lesser impact on adhesion strength
between plating metal film and ABS plastics.
Carbonyl group of all samples was increased with
increasing atmospheric UV treatment time. Therefore,
the change in surface state from hydrophobic to
hydrophilic was attributed to appear of polar
functional groups. However, approximately there was
not too much difference in increasing rate of carbonyl
index each sample after atmospheric UV treatment.
We considered that oxidized butadiene component
and amount of oxidation inhibitor of additives in ABS
plastics were influenced to oxidation degree of
deterioration. Moreover, in order to form high
adhesion strength plating on the ABS plastics, it was
necessary to have appropriate amount of oxidation
state. For above reasons, while maintaining the
Influence of Modification on the ABS Plastics Using Atmospheric UV Irradiation as Plating Pretreatment
277
performance of the materials, it is desired
development of ABS plastics suitable for atmospheric
UV treatment.
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