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Electroplated+Zn Ni Sio2+Composite+Coatings+Treated+With+a+Silane+Coupling+Agent+to+Replace+Chromating
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ACTA
METALLURGI
CA
SINI
CA(
ENGLI
SH
LETTERS)
Vo1
.18
No.3
PP
416-
422 June
2005
ELECTROPLATED Zn.
Ni.
SiO2
COMPOSI
TE COATI
NGS TREATED
WI
TH
A SI
LANE COUPLI
NG
AGENT
TO REPLACE CHROMATI
NG
M .Hi
no,M .Hi
ramat
su and K.M urakam
I
ndust
rial
Technol
ogy Res
earch I
nst
it e of
ut Okayama Pre ̄ct
ure,Haga,Okayama—
shi
Oka
yama 701
—129
6,Ja
pan
A.Sai
io
Hori
Met
al Fi
nis
hing Indus
try Co.,
Ltd.
,Abe,Ochi
ai・
cho,Takaha
shi
shi,Okayama 716・
0061
Ja
pan
Kanadan
Graduat
e School
of Okayama Uni
vers
ity of
Sci
enc
e,Ri
dai・
cho,Okayama・
shi,Okayama
7
00・
0005,
Jap
n
a
Ma
n us
cri
pt recei
ved 13 Dec
ember
2004
T
hef
ixi
ng
ofa
si
lane
co
upl
i
ng
age
nt
to
Zn-
Ni—
si
li
ca(
SiOe
)co
mpos
it
e c
oat
i
ngs
wa
s s
tudi
edf
or
f
^P
pur
pos
e o
fde
vel
opi
ng
a c
oat
i
ng
proc
ess
s
a an
al
te
rnat
iv
e o
t c
hro
mat
i
ng.Th
e c
orr
osi
on
re—
s
is
tan
ce
ofZn
-Ni
—s
il
ic
a c
ompos
it
e c
oat
i
ngs
Wa
s r
emar
kab
ly
impr
ove
d b
y t
he
si
li
ca
nano
par
ti
cl
es
i
n t
he
compos
it
e.wh
ich
wer
e di
s
per
sed t
he
sur
fac
e o
fthi
sf
il
m. Th
e s
il
ane
cou
pli
ng
age
nt
f
owa
ed
chemi
cal
bon
ds
wit
h t
e
h i
nor
gani
c s
il
ic
a par
ti
cl
es
dur
ing
te
h s
il
ane
cou
pli
ng
tre
atme
nt
o
n t
es
h e
co
mpo
sit
e c
oat
in
gs.T
he
tre
atme
nt
suppr
ess
ed
tef
h o
rmat
io
n o
f whi
te
coro
sion
pr
od-
ct
s t
o t
he s
ame e
xtent
a
s chr
om
a t
ing,
as measure
d i
n s
alt
spr
ay t
est
s.
It
is
concl
uded t
hat
t
reat
ing Zn—
Ni—
sil
ica composi
te
coat
ings wi
th
sil
ane
coupl
ing agent
s i
s a vi
abl
e al
ter
nat
ive t
ech—
ni
que
o chrom
t a t
ing.
KE Y W O RD S el
ect
rodepos
iti
on,Zn.
Ni—
SiO2
compos
ite
coat
ing,s
ilane
coupl
ing
t
re
atment
,chr
om
e-f
ree
,env
iro
nm
e nt
alf
rie
dl
n i
nes
s
Zi
nc and
zinc—
base
d al
loy pl
ati
ng have be
en a
ppl
ied as
low cos
t cor
ros
ion pr
otect
ion t
reat
ment
t
echni
ques
for
ir
on
and
steel
in
many
indus
tri
al
fiel
ds[
12】
.Recent
ly,t
he
requi
rement
s of
such
thi
ngs
as
cor
ros
ion
res
ist
ance,a
dhes
ive
prope
rty
or
f
organi
c mat
er
ial
s,wel
dabi
li
ty,f
ormabi
li
ty
and
envi
ronm ent
al
f
rie
ndl
ines
s or
f
zinc
plat
ing
have
become
seve
re.To
sat
isf
y t
hes
e r
equi
rement
s,zi
nc—
bas
ed
all
oy
plat
ing
has
deve
lope
d f
rom
zinc
pl
ati
ng,s
uch
as
Zn—
Fe,Zn-
Ni,Zn—
Co
and
Zn—
Mn
plti
a ng,as
wel
l as
Zn—
com—
pos
ite
pl
ati
ng
and
zinc—
bas
ed
all
oy
compos
ite
pl
ati
ng
蜊.
Recent
ly,c
hromat
ing
of
zi
nc
plat
ing
was
found
to
caus
e s
er
ious
pr
obl
ems
due
to
all
ergeni
c and
tox—
i
c a
cti
ons
of
he
xaval
ent
chr
omi
um
ion
in
the
chr
omat
e coa
tings
[51
.Ther
efor
e,much
efor
t has
bee
n made
t
o ind
f alt
ernat
ive
coat
ings
,wi
thout
chr
omat
ing.However
,chr
omi
um—
ree
f process
es
have
st
ill
not
bee
n
devel
oped.
I
n t
his
st
udy
we
inve
sti
gat
e t
he
ixi
f ng
of
sil
ane
coupl
ing
agent
s on
zinc
elect
rodepos
its
and
zinc—
sil
ica
composi
tes
to
impr
ove
coros
ion
prot
ect
ion
and
rubbe
r a
dhe
sion
as
a hi
gh—
funct
ional
, envi
ron
m ent
all
y
维普资讯 http://www.cqvip.com
417
f
riendl
y a
lter
nat
ive
to
chr
omat
ing [
61
. The
i i
dea s
bas
ed
on
the
fac
t t
hat
cer
tai
n s
ila
ne
coupl
ing
agent
s
p
oss
ess
bot
h s
ila
nol(
Si-
OH)g
roup
s,whi
ch
wil
l
fr
om
che
mical
bonds
wi
th
zinc
oxi
de,a
nd
organof
unc-
t
ional
gr
oups
ca
pabl
e of
re
act
ing
wit
h pol
ymer
s. Organof
unct
ional
roups
g can
be
expect
ed
to
provi
de
a
hy
drop
hobi
c l
aye
r o
n z
inc
el
ect
rode
pos
its
.In
add
iti
on,i
nor
gani
c s
il
ica(
SiO2
)pa
rti
cle
s we
re
code
pos
it
ed
wi
th
zinc
el
ect
rodepos
its
to
sre
t ngt
hen
the
int
era
cti
ons
bet
wee
n t
he
sil
ane
coupl
ing
agent
s and
zinc
el
ec。
t
rodepos
its.
2.Expe
rime
ntal
Zn.
Ni.
sil
ica
compos
ites
wi
th
a t
hickness
of
9 m
on
col
d r
oll
st
eel
sheet
s wer
e obt
ained
rom s
f ul-
f
ate
bat
hs.Tabl
e 1
shows
the
ba
th
compos
iti
ons
and
plat
ing
condi
tions.A
cyl
indr
ical
gl
ass
cel
l was
us
ed,
cont
aini
ng
2L
of
elec
trol
yte,whi
ch
was
st
irr
ed
cons
ant
t ly.Pr
ior
to
plat
ing,t
he
steel
cat
hode
wa
s s
olve
nt
deg
reas
ed, el
ect
rocl
eaned
cat
hodi
cal
ly
for
l
min
in
an
alkal
ine
sol
uti
on, pi
ckl
ed
by 1
0% hydr
ochl
or
ic
aci
d f
or
10s
,and
was
hed.
The
compos
iti
on of
the
el
ect
rodepos
ited f
ilm was
det
ermi
ned usi
ng a
n X-
・
ray f
luor
esce
nce
spec・
・
t
romet
er. To
obt
ain
inf
or
m a
tion
about
the
sur
face
mor
phol
ogy, depos
ited
sampl
es
wer
e s
tudi
ed
usi
ng
ie
f l
d—e
mis
sio
n s
canni
ng
ele
cron
t mi
cros
copy(
FE—
SEM)a
nd
the
cr
yst
al
s
tru
ctu
re
of
t
he
depos
it
wa
s s
ud-
t
i
ed
wit
h a
n X—
ray
dif
fra
cto
met
er(
50kV,25
0mA)a
nd
by
t
rans
it
ion
ele
cro
t n
mi
cros
cop
y(TEM)o
bse
rva
-
t
ion.
Si
lane
coupl
ing
reat
t ment
was
appl
ied
aft
er
the
elect
rode
pos
its
wer
e ai
r dr
ied
at
378K
or
f
lh. Ea
ch
s
ampl
e
was
di
ppe
d i
n a
so
lut
ion
con
ai
t ni
ng
NH2
(CH2
)3
-Si
(OC2
Hs)
3 一
APS]
,wa
ter
and
et
hanol(
in
a 3:
3:
94
propor
ti
on
by
vo1
.%)f
or
30mi
n,and
air
dr
ied
at
378K
or
f l
h.The
react
ion
of
the
si
lane
coupl
ing
a-
g
ent
wi
t
h he
t
pla
ti
ng
sur
fac
e wa
s e
xami
ned
us
ing
X-
ray
phot
oel
ecro
t n
sp
ecro
t s
cop
y(XPS)
.El
ecrode
t -
p
osi
ts
wi
t
h a
nd
wit
hout
s
il
ane
cou
pli
ng
age
nt
re
t a
tme
nt
wer
e s
ubj
ect
ed
to
sal
t
spr
ay
tes
ts
i
n a
cco
rda
nce
wi
th
the
JI
S Z
237
1.The
ti
me
requi
red
or
f
whi
te
and
red
rus
t occure
nce
for
ea
ch
sampl
e was
me
asured.
Tabl
e 1
Bat
h composi
ti
ons
and
plat
ing
condi
ti
ons
Fi
g.1
sho
ws
the
re
lat
ions
hip
bet
wee
n t
he
cat
hode
cu
ren
t de
nsi
ty
and
he
t
Ni
con
tent
,si
li
ca(
SiO2
)
cont
ent
and
cur
rent
e衔 ci
enc
y i
n de
posi
ts
obt
ained f
or
var
ious
si
lic
a col
loi
d conce
ntra
tions
in
the
bat
h.
The
Ni
cont
ent
in
the
de
pos
its
was
al
mos
t cons
tant
or
f
changes
in
the
cur
rent
dens
ity
and
sil
ica
col
loi
d
concent
rat
ion.Ge
ner
all
y,t
he
compos
iti
on
of
all
oy
elect
rode
pos
its
is
de
pende
nt
on
cure
nt
dens
ity;and
hence
the
super
ior
ity
of
thi
s pl
ati
ng
met
hod
is
shown
in
fact
that
a
cons
tant
compos
iti
on
is
obt
ained
an—
der
di
fer
ent
curent
dens
iti
es. The
si
lica
cont
ent
in
the
de
pos
its
incr
eas
es
wit
h i
ncr
eas
ing
sil
ica
col
loi
d
c
onc
ent
rat
ion
in
the
bat
h.t
hough
the
si
li
ca
cont
ent
is
not
depe
nde
nt
on
cure
nt
dens
iy.The
t curent
ef
矗一
ci
ency
was
in
the
ra
nge
of
80% t
o 90% a
nd
dec
reased
wih
t i
ncr
eas
ing
sil
ica
col
loi
d conce
ntrat
ion
in
the
bat
h.
维普资讯 http://www.cqvip.com
418
Fi
g.2 s
hows
FE—
SEM i
mages
of
de—
pos
its
obt
ained f
or var
ious
si
li
ca col
loi
d 20
concent
rat
ions
西en
ther
e was
no
sil
ica
c
oll
oid
in
the
ba
th(
Fig.
2a)
,the
su
rfa
ce 1
5
mor
phol
ogy
of
t
he
il
f m
was
smoot
h.I
n t
he
il
f ms
deposi
ted wi
th si
lica
col
loi
d i
n t
he
1
0
b
ath(
Figs
.2b
,C
and
d)
,it
i
s po
ssi
ble
to
obs
erve
si
lica
nanopar
ticl
es.
5
Fi
g.3 s
hows
X—
ray di
fi'
fact
ion pat
—
t
erns
of
deposi
ts
f
or
vaious
r si
li
ca
col
loi
d
c
onc
ent
rat
ions
in t
he bat
h. Eac
h f
ilm 0
s
truct
ure i
s compos
ed of
the ^
,一phas
e 5
(
Nic
Zn:
l1
or
ien
tat
ed
in
the
4
1
1
pl
ane
.It
was
found
that
the il
f m struc
ur
t e
iS
not
af-
4
0
/0
. 卫C luoo乞 0
/0
一
∞lu
luoo
oI
s 0
/0
oc
l。E
f
ect
ed by the sil
ica content.
It iS
well
known
that
a
Zn—
Ni
all
oy
coa
ting
depos
it—
3
e
d i
n onl
y t
he 一
phas
e s
hows
excel
lent
2
c
orr
osi
on
res
ist
ance[
 ̄.
n or
I der
to cl
ari
fy t
he di
sper
sion of
s
ili
ca par
ticl
es i
n t
hes
e compos
ite
fil
ms.
c
ros
s—s
ect
ional
TE:
M obs
ervat
ion
was
car
-
0
r
ied
out
.Fi
g.4
shows
cr
oss
—sect
ional
TEM
i
mages
of
a Zn—
Ni—
sil
ica
compos
ite
coat
. 1
00
i
ng
and
eleme
ntal
maps
.As
seen
in
Fig.
4,
80
s
ili
con
and
oxyge
n wer
e det
ect
ed
and
zinc
and ni
ckel
wer
e abs
ent
in t
he s
urf
ace
of
60
t
his
il
f m.I
n addi
tion,f
low
dis
char
ge
opt
i.
∞
c
al e
mis
sion
spe
cros
t copy (
GD—
OES
) C
40
∞
anal
ysi
s was
car
ried out
in
order
to con.
ir
f m
thi
s r
esul
t. The
res
ult
s of
GD—
OES o 20
anal
ysi
s wer
e i
n good
agr
eement
wi
th t
he
0
0 2
TEM r
esul
ts.
Fr
om t
hes
e r
esul
ts i
t was
. 5 5
7.
5 1
0
f
ound
that
si
lica
par
ticl
es
are
not
uni
or
f m .
Cur
rent
densi
ty,A/
dm
1
y di
spersed
in
the il
f m, and a
sil
ica ic
r h
l
ayer
is
for
m ed i
n t
he sur
face
Ofthi
s il
f m. |1
g・l
Rel
ati
onshi
p bet
ween c ̄hode cur
rent
densi
ty and
t
he
Ni
cont
ent(
a),Si
O2
cont
ent(
b)a
nd
cur
rent
efi
—
Fi
g.5
shows
the
rel
ati
ons
hip
bet
ween
ci
enc
y(c)i
n depos
it
obt
aine
d f
or
var
ious
Si
O2
col
—
t
he
sil
ica
cont
ent
in
a deposi
t and
the
cor
.
l
oid
concent
rat
ion
in
bat
h s.
r
osi
on
resi
stance
from
a s
alt
spr
ay
tes
t. I
t
was
found
tha
t corosi
on
res
isance
t impr
oved
wit
h an
incr
eas
e i
n t
he
sil
ica
cont
ent
;the
red
rus
t occur
—
r
ence
ti
me
ros
e rom
f 4000
to
8000h
as
the
sil
ica
cont
ent
incr
eas
ed . At
pr
ese
nt, t
he
reas
on
or
f
the
im—
pr
oveme
nt
in
the
coros
ion
res
isance
t is
not
cl
ear
, howeve
r i
t i
s r
eas
onabl
, e t
o s
pecul
ate
that
the
si
li
ca
ich
r laye
r at
the
surf
ace
si
de
act
s as
a
prot
ect
ive
il
f m .
维普资讯 http://www.cqvip.com
41g
F璀 2
gEM
obs
e1%'
[i
L]
on ol
’Zn—Ni
—Si
C. conl
po ̄J
le
coat
ing(
Cul
Tenl
den
sit
y:I
kAi
m (
al
SiO CO
I
oid
I 】
一:I
b)Si
(/:c
oll
oid
20g,
'
L l
c I
Si
O-c
oll
oid
40
L,l
d}Si
O c
oll
oid
60g
,'
,
I
Si
O 6Og/
L
Si
O。.4Og/L
0
Si
O :
2Og
/L
I
Si
O一091
L
2 deg
Fi
g 3X—
ray
dil
Tract
ion
pat
ter
ns
ofZn—
l_si
O composi
te
coat
ings[
cur
rent
densi
t
y:I
kAl
m )
维普资讯 http://www.cqvip.com
■
●● composi
te coat
ing and
c
2
§
0
8
2
12OO 10(
30 800 600 400 2OO 0
Bi
ndi
ng e
r
 ̄rgy eV
刊=
i
● ●
Fi
g 5
Rel
ali
onshi
p bc
L
vce
c r
l t
he Y
;it
)、eL
ll
llel
ll
ll
_dcp ̄s
● 手
了●●●●
g.
6 XI
’ wi
de specL
ra f
nlr
c at
;deposi
lei
an【
COI
l T,t
) ̄
.1
)n
1℃ L
stancc
cL
In c
b xi
lane
coupl
ing
h'L
'at
nlen1)
I
n el
’
der
to
exa
lll
il
le
the
1
eac
tion
wi
th a
Il
ali
e coupl
ing
agent Zn—
Ni-
si
.
I
ica
compos
ite
coal
ings
wi
th
an
d wi
th
out
t
re
atme
ll
l
wit
h a ̄
,
il
ane
cou
pli
ng
age
nt
wer
e s
ubj
ect
ed
to
XPS
an
alys
is
Fi
g
6 s
hows
t
he
XPS
wi
de
spect
]a Ni
lrogen
1s
11
01
det
ect
ed
wit
hout
si
lanc
coupl
ing
treat
ll
lC[
11 However
.wi
th 1
1Ri
le
coL
.
ipl
in ̄
t
reat
men1
.ni
trogen.whi
ch
der
ive
s F
mn1
II
e
ami
ne
011
一APS i
det
ecl
ed I
.n addi
tion.a
wat
er—
repel
leI
I'
UV
t
est
was
tar
ried(
)Li
t
1(
]conf
irnl
ti
le
fixat
ion
ort
he
sj
J
all
e COUpj
_l】
a ̄enl
Fi
g.7
shows
the
appea
r
ance
01
’a
wat
er
drop
on
coat
ings
wi
th and
wit
hout
the
si
lane
COt
tpl
ing
I cnt
The
cont
act
angl
e el
the
wat
er
drop
wit
h t
he si
lane
coupl
ing I
rcal
mcl
ii
is}
_i
gher
tha
r
l l
ll
at wi
tht
tUI
ti
le
s
ilane c
oupl
ing
irea[
Rlel
l[. The
we
lt
er r
epel
lency i
s i
mpr
oved
duc“)t
he ami
ne deri
ved I
To1
11
—APS .
Tabl
e 2
shows
the
efect
s of
si
lica
composi
ting
and
sil
aie
L coupl
ing
tr
eat
mer
it
ol
l CO
r
TOsi
on
prot
ecl
i0『
] I
t
维普资讯 http://www.cqvip.com
421
F‘
?App
eal
ante(
1I
I
hc、
:
I【
cl
dr
opl
et
:ca}a
dep
osi
lc
d an
d I
b}s
il
anc
coupl
mg[
ICal
l
lle
ll
[『 一
APs
]
rabl
e 2
W I
li
le
i1
1u.
I
re
d r
LLM
LlcL
'ur
rcnce i
.
bml
d by
sal
t
spr
a y
tes
t
Ⅶas
Ibml
d t
hai
a
an—
Ni—
sil
ica
compos
ite
coat
ing
wi
th
sil
ane
coupl
ing
treat
mcnt
had
a hi
gh
cor
ros
ion
pr
o —
L
eet
ien
I‘
1 bot
h whi
1c
and
red
rust
It
i
s cons
ider
ed
tha
t t
he
imp
rev
enl
enl
oft
he
eor
ros
l。I
]resi
stance
i due
1
0 t
he
v,'
atcr
-repel
lenc
y(r
ein
til
e si
lane
coupl
ing
tlc
atmenl
4.Concl
usions
I
he
pres
ent
st
ud)
'
. i
Is
car
rie
d OUt
to
exam h
le
the
ti
xing
oi
’a si
lane
coupl
ing
agent
On
Zn Ni
.si
lic
a —
omposi
te
coat
ings
l0r
ti
le
p L
lrpos
e Or
dc,
,el
opi
ng
a c‘
・aI
ing
l1H
ccs
s I
tS
an
al
temat
ive
to
chr
oma
ting The
(
11"
OS]
Oll
reSl
stancc
el
n—
Ni—
siI
lea
coml
?ost
le eo ̄
itl
ngs
was
renl
arkabl
y i
mpr
oved
due
lo t
he s
ili
ca
nanopal
licl
e,,di
spel
cd
I)
1
ti
le … l
aec
nr
the
ihn 5
f ;il
ane
eO
L
Ipl
ing
agen
Ls
lbnn
chemi
cal
bonds
wi
th t
he
…or
gani
c R
III
Ca
pal
’
tide
,
.,dur
ing
the
sIl
ane
coupl
ing
treat
nlet
l[el
thes
e C'
1l
ll
posi
lc
coat
. ings
The
tr
eaml
ent
suppr
esse
s t
ile
lor
lll
all
on
ot
wh1
1c C
Ol̈
ru 1
011[
;r
edact
s n I
]10
sL
lnl
e cx【
cI1
1
as
ch
romal
ing . as
rneasur
ed
1n
sai
l s
pray
tes
ts rhi
. s hybr
id
COal
ing
I “vi
abl
e al
tenl
ali
vc
techni
que
1‘
)chr
omat
in
REFERENCES
^Sl
l
ibt
b.
a・H ¨¨ Ⅶ }
… ,tⅢ… {
t
、h n!
、
ll【
fI
{c
、
c
t[s
K Ya
mak
awa
an
d F
I F
uii
kawa
IThe
S【
el
M at
eri
als
Sci.J
apan I
j
9^)n I
! M Hi
no,N Ni
hi
da-M Hi
mn1
at u ,
M.r
stt
i
ikawa
an
d M.Ka
wal
ll
C,
Lo
,"t
, 3
40-
2)r
I
99g
)81
维普资讯 http://www.cqvip.com
422
3
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ama
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ama
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200
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ive
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a oft
he
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ember
2000 on
end
ofLi
fe
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cles.
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su,
H.Kawas
aki
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Naka
yama
andT.
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ati
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nd
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r c
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