influence of modification on the abs plastics using atmospheric...

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

↓


↓

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

▽


↓

Electro Cu plating, 20 μmt

▽


▽: 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


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


277

performance of the materials, it is desired

development of ABS plastics suitable for atmospheric

UV treatment.

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