Journal qf Korean Society for Imaging Science & Technology, Volume 12, Number 2, June 2006, pp.

53-60 53

-¥-~ql~r.lil_ %%:§l-~*~--¥-, *~~.:rr~

608-739 !f--;±J-l 'itT %'%% -;± 100 If-7cJLll~_llL -§-%§)-~'6-~!f- 641-772 7cJ'it ~,J-~ ~Pcl% 100l/:!;z1 ~.:2:..31_'iJ

(2006'd 5-%1 11 ~ ~%, 2006'd 6-%1 2~ :'<11 ~)

Characterization of adhesion and preparation of functionalized organic-inorganic hybrid epoxy coatings

Jae Ho Baek, * Jeung Hwan Lee, Min-Gyu Lee, Cha-Soo Suh, Sam Tak Kwak, Myung-Jun Moon t

Faculty of Applied Chemical Engineering, Pukyong National Univ. 100 Yoongdang-Dong, Nam/lu, Pusan, 608-739, South Korea =Hanho Coating co. ltd.

100 Chungang-Dong, Changwon, Kyung Nam. 641-772, South Korea (Received May 11. 2006, accepted for publication june 2. 2006)

Keywords : Adhesion, Organic, Inorganic Hybrid, Epoxy, Coating

Abstract In order to improve adhesion properties and give a toughness of the cured solvent free epoxy system, organic-inorganic hybrid epoxy coatings, which have prepared by adding 3-arninopropyltriethoxysilane (3-APTES) were estimated by UTM test, adhesion test, and the surface hardness test and the physical and chemical behavior of 3-APTES at the interface region was evaluated by XPS and FT-IR-ATR. It was shown that Si atomic ratio of surface without contacting with substrate was higher than the ratio of surface contacted with substrate through the surface analysis. By the addition of 3-APTES Si atomic ratio was totally decreased at both sides of epoxy film and was higher at the contacting surface of substrate than other side. It was found that the free volume and the crosslinking density were simultaneously increased by the silane group of 3-APTES, which has diffused to the inner part of the epoxy film, the flexibility was increased as indicated by the lowering of Tg and adhesion and mechanical strength of film were also improved.

Jl Q} 7cl§)-'f:! "11~J-lsl '1lZl~% 711~:1i5}'i'l},l toughnesssi If-''ii5}71 -'11tH -'f-%Al1~sl °ll~J-l 4';z1"11 3-arnino propyltriethoxysilane(3-APTES){t 1l7}i5}O~ 7cl§)-'f:! %71--'f-71 lij-~ °ll~J-l sot:If91 'i};Z,J-7,J-SOS} 1l3}~, R'i'l7clso {t "'Pai51jl, 'ij3}1l1'i'l"11}'l 3-APTES91 %21§)-~2j -3}%.,g- XPss} FT-IR-ATR"11 91tH 3':},}i519J4. R'i'l~~% %tH 3-APTES7} 1l7}-'9;z1 ~.,g- 7cl-j'-"11-i::c 71~JIj- uI1l3}'i'lsl Si ~5: ~'ll']j17} Ll 3.Y-, 3-APTES{t {l7}i5}711 -"'I 'i'l ~"112j~s_ R'i'l"1iAl Si ~5: ~'ll']jlso ~5:i5}'i'l},l 71~JIj- uI1l3}'i'lsl Si ~5: ~'ll']jl-i::c 71~JIj- 1lZl'i'l°1 _lil_q Ll ,;;!-oH;c1. ol.:;.t.,g- "11~J-l soCIf91 cJ1!f-s.. 3-APTES7} ~--8°1 -"'l'i'l},l silane71"11 Sit]] °ll~J-lsocqsl free volume 'iII 7cl§)-~SO{t %J-I"11 ~7}J-17'j Tg7} '7!0};zljl %<B_J-jol ~7}i5}'i'l},l %J-HI 7cl§)-~SO-i::c ~O}7~ '1l3}~, 'i};zJ7J-SO 7} "'J'2l-"'I5::J,q-i::c .:;.t% ~ 4' ~l5::J,q.

t E-mail: mjmoon@pknu.ac.kr

54

1. Ai -E-

011~Al'TA1~ 7cj·W~ u]1 ~l;!Pa ~~91 ~A~ 01LJ- 1f-3I191 'T~01 31_2_oj, 7111131 Aa~olLJ;;~171 ~ '?:Fa 01 !?I ~ L.} oj, Ll1 §} "§:j-Aa 01 -'i'-'T-8"}.Jl, ~g~~~~u]1~~~~%~~~~%£~ ~~L}. 7cj§j-711~ Llo}'i'l, EejO}'i'l, 0lulq~fr, ::E~ II~{}1f-'T~JIj- ~,'"'_ {} 1f-'T~g {l7}-8"} oj 7}~-8"}li'! 3~}~ LilE.!f~~ TSc~ ~Aa~ ¥ o} y t} silane, silanol % silicon §j- ~~ Jl} 91 ~ g Aa £ ~o} £.fi_ L.} ii-:<;- JIj- %ej 1l3)-711, %ej {l%LJ- ~5:{l%011 II2-1~ejuj %Qlj g ~{J-8"} = 7cj§j-A1Zl ~A}71% 31~J,It, ""J~717BS>J- r:j:>:: ~Gl101LJ-z)-% ~A} AJtll91 1l3)-711~ ficol A}% .!r].Jl 9) q.[l]

~~ ~~~ 'T~91 1l3)-~% %~~li'!~ toughness-a 7l-;-i-8"}71 ~~ ~.g_ '?::lT7} ~i5].!r] ~ 3,k.Jl, epoxy oligomer s] ':iF;:] 01 LJ- urethanes] 91 ~~;'.(11 ~Aa ~ 01 ]xl_.Jl :sol.Jl s:J_q.[2-4l -=:lej.Jl

%2-1 {l % 5>} .Jl1f- matrix ~ 91 §j-"§:j- ~ ~ g % £ -8"} ~ {l7}711~ silane7Hl -OR, -Cl, -NH2, -SH 5>} ~,'"'_ 71%01 ~;:z} 0J~ ~011 91~ silane 111 coupling7117} ~01 J..}%.!r].Jl 9Jr:.J-.[5l i":- '?::lT01]J..i ~ 1"l.:3f711 ~711~ ~01 J..}%.!r]~ 1f-%711~sl 011 ~Al 'TAl 011 {l7}711~ silane coupling agent'i'l 3-aminopropyltriethoxysilane(3- APTES)~ ~ 7} ~_2_~-Y.l 011~Al'TAl91 7cj§}011 ~I£l °a""Jg n] .:.<.1.Jl 3-APTES91 ~~01 ~7}~011 uJ-t} 7cj§}:sol ~~ 011~Al £~91 'i'lAJ7J£5>} 1"lzf~, 7cj£ % sl ~A;:]0l ~'@1l1 ~§j--8"}~Al ScJ..}-8"}.Jl, J11li'!011 J..i 3-APTES7} ~I£l ~ej§j-"§:j-31 Z)-%g -8"}~Al ScJ..}-8"}~q.

2. ~ ~

2.1 Al Q}

~711~ 1f-%711~91 ~2.j{" ~Aa 011~Al'TA1~ J..i -;:;-£§j-~·91 KSR-177(EEW 190-220) g J..}% -8"}~.Jl, 7cj§}711~ ~/.a Al~~ o}'i'l'i'l -;:;-£§j-"§:j-

91 KH-818B(amine7} 540± 30mgKOH/g, ~/.a 'T5:~~ 60g/eq)~ J..}%-8"}9;Jq. -=:l2.j.Jl 1"l3)-~ ~ 7}~ ~ ~ 7'}~ ~ 711 s. -Y.l 3-aminopropyltrietho xysilane(3-APTES, Aldrich) ~ J..}%-8"}~ r:.J-. 3- APTES91 §}"§:j-TSc~ 0}~5>} ~q.

2.2 Al~All~

'TAl ~ Table 191 uB ~011 uJ-t} ~711 'i'l KSR-177JIj- {l7}711 3-APTES ~ 1ii;:zi 11 A 'ill tll 017',1011 ~.Jl, 300rpm_2_~ 5~~ .ill ~~ .!?l, 7cj§}711 KH-818B~ ~.Jl r:.J-Al 300rpm_2_~ 5 ~~ .ill ~-8"}oj 711 Sc-8"}~ r:.J-. 7cj §j- ~ 80'C 011 J..i 30~~ 7cj§j-Al5J.q. 3-APTES91 {l7}~,'"'_ ~ 711~ 71~_2_~ 0, 1, 3, 5, 7, 10wt%~ L}~lll -8"}~ r:.J-.

~<':j g ~ ~ Al ~ ~,'"'_ 2f-7J11 200,um91 applicator ~ 15x7cm ~7191 ~ Al~JIj- 15x7cm ~71s1 % 2.jJ,It011 Z)-Z)- s=.~-8"}oj ~tll-8"}9J.r:.J-.

Table 1. Form ulation of sam pies

Sample KSR-177(g) KH-818B 3-APTES(g)
Names (g)
SO 0
Sl 1
S2 3
100 55
S3 5
S4 7
S5 10 2.3 ~~

3-APTES91 {l7}~011 uJ-~ %2-1 ~ 01.g.£ (Tg) ~§j-~ ~71 ~""B DSC(Pyris 1, PERKINELMER(US.A))~-Y.l ~Acl-8"}~q. DSC ~Acl,'"'_ N2 ~.!f171011J..i ~.g.:<;-£~ lOoC/min_2_~ -30~

100°ClJ}7:1Qj 'fI-'f1"1P'l "';-/Z~t"}'1Xq. 3-APTESQj {l7}7} '(l:AJ7J5:."11 <>1r;i °cJ'8'J% ul5<H:07:1 ~ "';/Z~ t"}71-'f1"8'] 'i'!'-'g-J..1 ~ AB.~U1(Universal Testing Machine(uTM), SHIMADZU)% J..}-§-t"}oj '(l:AJ

(~P~t"}711 %7:1t"}oj :sttJIl1lJI} llBo1 J..1~~ ujJ lJ}7:1 ~~-c- J..1Zl'g "';-/Z~t"}'1Xq.[6J

"8'B ASTM D4366 "11 Qj 'fiB 7cJ §},g- 5:. "11 rr:}~ 7cJ 5:. Qj 1(1 §} ~ pendulum hardness tester(BYK, Gennany)~ J..}%t"}oj "';-/Z~t"}~J.L}. ~7:}~ Konig 'il % ~ ~ t"} j1. -'f-711 ~ 200g± 0,2, ~?-J 7cJ 2 5mm/0,2in, J,i1'8'J5:.-c- "'l~ol 6° ~01 3°'(l -5i g A}%t"}~l q.[7]

1lzV~% ~0}_lil_71 -'f1t"}oj UTMg 01%t"} oj ASTM Dl002"11 Qj"8'B "';- /Z~ t"Hl q. 1l Zf "'1 J,i1 "11 A}%-'8 ii-4f }Ij ZfA11 £ -c- SUS304 ~ f11 '(l ~ ~ e: ~ % A}%t"}'1X_2_uj, "'1 J,i12 Figure lJI} 7,,{.g_ .5'_0JJI} 5<ly(B-'f1 mml.s'. A11~t"}'1Xq, ~ -t,LAJrB(76 mmHg)"11Al 71~-'4 ~l~P~~g A11 7Hl- J):- 1lZfrB."11 5:.~~ J):- ~/Z~~ t"Hs"g 7} ~ AJrB£ 80°C"11Al 1"'1Zl' 7cJ§}"'171 "'1J,i1% A11 s.t"}~l q,[8]

8$1: mm

c========§~~r=========i~ 1.8

Figure 1. Typical geometry of specimens used in the adhesion tests.

5:. ~ R rB. "11 Al2-1 §}~ S.A~ 1(1§} ~ ~o} _lil_71 -'f1"8'B Mg Ka(1253.6 eV)Qj x-~ g A}%t"}~ XPS(MultiLab2000, THERMO VG SCIENTIFIC (UK))£ 5:.~ RrB.% "';-/Z~t"}'1Xq.[9.10)

{l_ it} 71 w'lS A11Qj RrB. ~ g.g_ FT-IR-ATR (IFS88, Bruker(Gennany))£ ~'(lo}'1Xq.

55

3.1 DSC "';-7:J

Figure 2~ _lil_rB. "'lJ,i1Qj Tg~ 30-40°C 'fl-'f1 "11 ~J_2_uj 3-APTES~ {l7}o}71 ~ tr-y~ "11 ~"'1 ~;;Qj Tg-c- 38°C£Ml 3-APTES {l7} J):Qj Tg"11 lll"8'B ~j1., 3-APTES~ {l7}~ J):-Qj Tg~ 35°colt"}~g Y-Etc11j1. ~J~q. .J:f.~ 3-APTES {l7}~"11 rr:}~ TgQj 1(1§}~2 5%lJ} 7:1-c- 71Qj ~:A~t"}711 %7:1 solY-, :J_ 0lAJ {l7}~ 01 ~7}t"}rB. Tg7} ~:ei::.Wg ~ y ~J~q, ol-5i 2 3-APTES2-1 {l7}"11 2-1"8'B "11~"'1 1l1E~~3. '(l- _2_£ siloxane :J_ ~ o 1 5:. ~ .5'1 <>1 A~ Al, 7cJ §} ~ 5:. ~ ~7}"'171-c- :B:_JI}5:. ~J7:1'i'!' u1~% silane (-Si-OR)71"11 2-1"8'] free volumec] ~7}sol<>1 "11 ~"'1 5:.~Qj Tg~ ~:ei::."'171 %ZVd% ~7}"'171 ~ -5i_2_£ ;,~Zf-'8q.

5o,--------------

40

- -.--- - .

~

~ 30

I

~ 20

f-

10

0~0~~~-~~5~~~-~,0 Concentration (wt%)

Figure 2. Tg change of epoxy film after adding 3-APTES.

3.2 UTM ~AJ

Figure 32 UTMg 0l%o}oj :sttJIl51-c-]:ll c -c- ~ (a)JI} :sttJIllJ}Al ~ ~ ~ "'1 Zl'(b), :J_ ~ j1. :stt JIl "'llJ}7:1 ~<>1Y-~ "'lJ,i1Qj ~o1(c)~ "';-:AdO}'1X q. Figure 3(a)-c- 3-APTES {l7}~"11 rr:}2} :stt JIl51-c- ]:ll '=. ~ ~ 2-1 1(1 §} ~ Y- Et \R -5i.Q..£ 3-APTES{l7}~ol ~7}W"11 rr:}2} :sttJIl51<>17:1~ ]:ll '=.-C- ~ol ~7}t"}O:j 3-APTES7} 5:.~Qj 7cJ §}~5:.~ ~7}"'171~ :B:_JI}~ 7}A~%g ~ y ~J ~ L}. Figure 3(b)-c- :stt.llllJ}7:1 ~ ~ -c- "'1 Zl'% "';-

56

Acl~ ~JI}~ 3-APTES ~7}2-Jol %7}WoJl u:j-e} :uJ-jllS:l<>1;zl~Lll ~T.'1~ A1Zl-ol ~7}Wg_ ~ Y ~ls::J_q. ~<>1\::l- 7,J°l~ ~Acl~ ~JI}~~ 3- APTES ~7}~01 {7}WoJl IT}e} :uJ-:cr1 Al7J};zl ~<>1Lj-~ 7,J °17} 7,J<>1J;q. 01 ~ 3-APTES£1 W ~01 %7}WY~ 78:§:}Sl<>1~ y;Zl J..}oloJl 47B£1 3]-%71 ~ 7}~ 3-APTES7} %<>17} 78:§:}~_5=_7} ~7}i5B~W~01 7J:§:}1'lJI} %AloJl 78:§:}\1g oJl % 9il};z1 ~.g_ ul\1%71£1 %7}~ y;Zl1-}loJl free volumes] ~7}~ 7}A~5'} %'?1AcJ g_ 7}A~_2_711 B q.Jl .A~Z1S:1<>1~q.

~~------------------~~

18

i 16 b) ~~~-.

14 • /~

~ 12 //

F 10 .:

~ ~v./

o 1 357

Cmcentratim (%)

3.5 ,-----------------------------,

3 5 7

Conalntratim (%)

Figure 3. (a) Change of crack force, (b) cracking time, and (c) extended length in crack point according to the increase of 3-APTES concentration

420
"E
E
~ 400
s:
0,
c
i" 380
U5
c;
0
'in
Q) 360
.c
"0
«
ro
Q) 340 "
s:
en
320
0 5 10
Concentration (%) Figure 4. Shear adhesion strength increased by the addition of 3-APTES

3.3 ~.3I- -"1 ~

3- APTES ~ 7}2-JoJl u:j-e} {l Zj~,'"'_ ~ 7}il}~; _<;l__Lj- ~7}~01 5%7J};z1~ {l;3f~ 01 -'0-zqill ~7} il}q7} 01-"9=-£1 {l;3f~.g_ (~_lAcJ~ ijroJl Y'8il}~ 78 trJ g_ _J;I_~; q.

3.4 Pendulum Hardness Tester

Figure 5(a) oJl £1il} Z! R Z! 78 _5=_ ~ 78:§:}..g_ _5=_£1 ~7Hl u:j-4 ~;zlQj ~SlA1Zl-°l %71"8"ljl, 01 ~ 7;S:§:}..g__5=_7} %7}"8"}Z!Al 78:§:}~_5=_7} ~O}A~ RZ! 78_5=_7} ~7}~t1"~ ~% ~ Y 9lL}.

Figure 5(b)oJl Qj"8"}Z! 3-APTES ~7}~oJl u] ~ ~;z}Qj ~SlA1Zl-.g_ ~:§:}7} 'irtg g_ ~Y ~1s::J_ q. °1~ RZ!78_5=_7} 3-APTESQj ~7}oJl u:j-e} free volume.s] ~7}oJl u:j-;::: Tg ~:::i:5'} 7;S:§:}~_5=_ ~7}7} Al~ /-.JsBSl<>1 RZ!78_5=_~ ~7}~011 IT} t} ~:§:}~ _J;I_0l;zl ~ g % ~" Y ~ls::J_L}. RZ!78_5=_~ 3-APTES£1 ~7Pi:l'_J;I_q~ 78:§:}..g_ _5=_ ~7}oJl Qj~ 78:§:}~_5=_ ~7}oJl +5'.. Qj~W

10

10

T.'1 ul{l;3fZ!£1 111,'=17} %T.'1 {lZj"Z!_J;I_L} 1:--1 3.. q. g:_~ 3113..oJl Lj-E}Lj-~ zj-zj-£1 1113..2.1 Z!~ g_ ~~~~Qjz!~~u:j-~q;:::1113..~Qj~~g_ Figure 7011 l..-}E}L]1s::J_q.

3-APTES £1 78-9- Si5'} N -'tl:::i:£1 tl17} 1:1 01 E..~ 01 :§:}W%g_ ~7H:~% rr]1 .A~71~ RZ!oJ1Al

-"i Ad-r:J1~'i'l Al]7] 1(1_:§}~ jj]li':!cj]Al 3-APTES-"i 7-1%% <5~-Jij-t}~[1] o]%w ~ s;J,Sj,t:}.

nittAl 3-APTES~ 1l7}~ 4- 3Jj3.-"i 1(1_:§}~ ~0}~7] -'f1<5~ 7]~:.t4 ~31--'tl 3-APTES7} 1l7} B li':!-"i 31]3.£} 3-APTES~1l7}-t}7] 'i'.Jc.g. ~ Z}li':!-"i 3Jj3.~ Figure 6(b)cj] 1.-}E}1.J19JA. Figure 6(b)cjjAl ~ Y ~l::: 3:1.g. 3-APTES~ -1l7}~ li':!-"i 3Jj3.7} 3-APTES~1l7}-t}7] 'i'.Jc.g. Zl-"i 3Jj3.~t:} 3Jj3.7} ~7}-t}~.Q..1.-}, Si 2s9} Si 2p-"i 3Jj3.~ 1frr:J1s] ~JJ1-7} 4S};Jt:}. ~, 3-APTES~ {l7HH] rr}ij- Sis] 3Jj3.~ Ad-r:J1~ .Q..~ 3)-O}A~ 3-APTES T::Ecj]Al ~~ 31:.t4 ~ 0] 3-APTES"i]~ Si ~~7} ¥.~o] s:]0l ~].Q.. E.~ 3-APTES~ -1l7}~cj] rr}tt cj]~A] ljpi'-~ ~~s:]0l ~t:}~ 3:1% ~ ~ s;J,9JA.

190

a)

185

III III

:g 180 "0

ffi 175 J:

~ 170 :;

-g 165 Q)

0.. 160

80

120 Temperature (OC)

160

500

_aD
b) C=:J 120
_160 400

III III Q) C

"C 300

~ J:

§ 200 :;

"C

5i 100 0..

o

50

S2 53

Sample Name

55

54

51

Figure 5. Ternperatureta) and concentrationib) dependence of pendulum hardness of epoxy film on glass according to the addition of 3-APTES

57

C~~~~~.Q..~~t:}~~~~-"i ~%~ 1[:rr1 ~~t:}. Figure 7 ~ ~ li':!, 3- APTES7} {l7} ,£]7] ?J"~ 78-'H] %ij ~31-ZlJI} p]~z}Zlo] 0 9} Ncj]Al~ ~~ ~~ll]7} lllj.:-t}t:}~ 31 ~ ~ 'i'l~ Y ~]t:} . .:::Ic11.-} Si~ Pl~ZfZl 0] ~z}Zl_l;l_ r:.} ~~ ~~ll]7} r:-l 3.t:} . .:::Ic14, 3-APTES~ 1l7}-t}71] S:]Zl, O~ lll%ol .:tl-~-t}71] .£12, N.g. ~7}-t}71] S:]~, Si~ ~~-t}71] Br:.}~ 31 ~ ~'i'l w = ~]t:}. O-"i 7cl-9-, 3-APTES7} ~0l7}71 'i'.Jc .g. 7cl-9-~r:.} 3-APTES *s:.7} 5% 7as:.7J}71~ O-"i ~-;:zrol ~~~ -t}71'i'!, .:::I *s:. °lAd-°l s:]li':! '2f:n ~7}-t}~ 31% i't ~ s;J,t:}. Nsj 7cl-9-cjl~, 3-APTES-"i {l7FJol~7}wY~ N-"i ~~ol 71 % _l;I_t:} s:. t:l %,7}s:] Ol ~ t:}~ -3l ~ ~ ~ s;J, ct. .:::It..12, Si-"i 7cl-9-~ 1[:rr~~Zl, 3-APTES7} ~

[UP]

i::.U')

c Q)

C

I-~.A.' -.JJ...._ _

c is

r-J01'

N ,.

Si 2s Si 2p

600 500 400 300 200 100 Binding energy (eV)

a

z'e;; c Q)

C

[DOWN] 1:-50d
-53d
I 55d
- -- -
J

c "
01.
W N 1,
Si2s Si2p 600

400 300 200 Binding energy (eV)

a

100

500

Figure 6. XPS spectra of upperta) and bottom (b) surface of epoxy films prepared by adding 3- APTES

58

-o-~ ~0-]7};:z1 eJ-2 ~_lil_T1- ~:Ail '5 £ 7J};:z1 iI-Zj-o-} 711 si21 W~ol ~o-]~Jl, :J_ oP'J21 '5 £7} Sl ;1, r:pl ~7}-o-}~ ~% ~ 'T'- ~~4, 3-APTES ~A~ T:5::011Al _lil_-c ~J1} :Q-ol 3-APTES011-c SiS'} Nol ~WSlo-] 9J_Q_E__iiO_ 3-APTES~ ~7} -o-}Jl, 01~01 711;1011 ~AB-o-};1 si21 W~ol ~7} W ~_Q__iiO_ ojj/'Jol '84. :J_GlY- ~J1}7} ~~-o-}-c ~ 2 3-APTES011 9J-c -Si(OClliC!I:J)3-C 011~ Al S'} %t121 711;1 011 llB'~ :sol-c ~ 01 o} Li4 ~:Ail '5 £7J};:z1-c 011 ~Al 1-1Pr- _iiO_ ~{!-o 1 :solOl o1PPl 4PJl-011Al free volumes] ~::&~£~ ~7}A1Zl4 -c ~-g_- ~ 'T'- 9J~4, :J_GlY- '5£7} 5% °lAJol Sl;1, L1l-¥-_iiO_ ~{!-Sl ~ ~ 01 ~::&Sl;1Al y-uj;:zl ~7}'8 3-APTES-c 711;1_Q__iiO_ AB~{!-Sl;1Al ~ 3]-;1 J1} 1fl- g -o}~ ~_Q__iiO_ ;.& Zj-Sl 0-] ~ 4.

Q'4

[O/Cll-·-UP I

, -.-DOWN

~:-------- -:

2 3 ~

til 2 i!! « 1 L.__..L._ _ _'_ _ __L_---'- __ L----l

50

53 Sample name

55

c: 5 o

x -4

Q'

[N/Cll-·-UP -'l>--DOWN

3

o

1il 2 0::

m 1 L.__..L._ _ _'_ _ __L_---'- __ L----l <

so

S3 Sample name

S5

~ 5

x

[Si/Cl -·-Up ---61-- DOWN

_Q 3

~ ______________-@

~2l--..L.---'--~'~@-==~==~L---j

SO S3 S5

Sample name

Figure 7. Atomic area ratio of XPS spectra of up and down surface.

3.6 FT-IR-ATR ~-1J

Figure 821 FT-IR-ATR21 ~~E401Vl -NH71S'} -OH71~ 2rz]- 3400J1} 1611cm-1oJ1Al :c;%21 7J~ !'T'- 3113.~ L-}E} \li 4. :J_t1Jl1600, 1248, 1180, 1036, 3400cm-1011 Al21 -%'T'- II13.-C ZjA 011~Al 'T'-;:z121 Aromatic C=C, Si-CH'l, Si -O-C, Si -0- Si, C - NH :J_;; _Q__iiO_ ~:Ail:SOl 0-] ~ 4. Aromatic C=C II13.~ 71~_Q__iiO_ !'T'-A1171~ tll.J:il-OlH 3-APTES21 ~7}~oJl u}t1- %t1011 ~ 3]-Sl-c ;1J1} pl~3]-;121 Si ~%71S'} -NH 7121 J:ili::&~ L-}E}\li ~01 Figure golL}. Figure g~ _lil_;1 ~;(f3:j_Q__iiO_ Si-CH3, Si-O-C _:::I-,§-01 ~.7il '5£7J};:z1-c 7-121 J:ili::&7} 'fdL}7} (~Pil '5£ °VJ 01 Sl;1 ~o-] -'=--c ~ g ~'d W 'T'- 9J 4. 01 ~ 2 ~:Ail '5 £7J}.71-C :ill;1 011Al2-1 ~ 'W"i'@ Et17} Si-CI-l,

a)

- SOup

----- S3up

S5up

4000 3500 3000 2500 2000 1500 1000 Wavenumber (ern")

b)

- SOdn

----- S3dn

S5dn

4000 3500 3000 2500 2000 1500 1000 Wavenumber (ern")

Figure 8. ATR spectra anti-adhesion surface (a) and adhesion surtacetb) of epoxy film prepared by adding 3-APTES

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References

[1] J H. Kim, H. J joo, J H. Kim, F. L.

Jin, and S. J Park, Elastomer, 41(1), 19 (2006).

[2J T. Okamatsu and M. Ochi, Polymer, 43, 721(2002).

60

[3J M. Ochi, R Takahashi, and A.

Terauchi, Polymer, 42, 5151(2001).

[4J A. A. prabu and M. Alagar, Progress in Organic Coatings, 49, 236(2004).

[5J K. ]. Kim, ]. S. Kim, B. K. Ahn, H.

J. Choi, and Y. J. Chang, Journal of the Korea Institute of Rubber Industry, 25(4), 280(1990).

[6J ~~7t <5pJ~, JI.!t!-7.f .cJL35!2f {f/;}', I11 ~ A} (1990).

[7J Y. H. Kim, K. W. Lee, and Y. C.

Kwak, Elastomer, 35(1), 12(2000).

[8J ]. H. Kim, K. Y. Choi, H. ]. joo, F.

L. Jin, and S. ]. Park, Elastomer, 40(3), 166(2005).

[ 9 J ]. H. Baek, ]. H. Lee, H. W. Lee, M. ].

Moon, and S. T. Kwak, J Korean Socity for Imaging Science & Technology, 12(1), 10(2006).

[10 J ]. H. Baek, ]. H. Lee, M. ]. Moon, and S.

T. Kwak, J Korean Socity for Imaging Science & Technology, 12(1), 37(2006).

[11] G. Ertl., Low Energy Electrons and Surface Oiemisry, VCH, (1985).

[12 J S. Hufner, Photoelectron Spectroscopy, Springer-Verlag Berlin Heidelberg (1998).

[13J ]. C. Fiviere, Handbook of Surface

and Interface Analysis, Marcel

Dekker (1997).

[14] D. Brune, Surface Characterization,

WILEY - VCH(1997).