Sol-Gel - CHERIC · by Sol-Gel Method Dong-Il Lee, Sang-Hong Jang* and Ki-Chang Song † Department...
Transcript of Sol-Gel - CHERIC · by Sol-Gel Method Dong-Il Lee, Sang-Hong Jang* and Ki-Chang Song † Department...
HWAHAK KONGHAK Vol. 41, No. 6, December, 2003, pp. 768-772
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(2003� 7� 30� ��, 2003� 9� 6� ��)
Preparation of Hydrophilic Inorganic-Organic Hybrid Coating Solutions by Sol-Gel Method
Dong-Il Lee, Sang-Hong Jang* and Ki-Chang Song†
Department of Chemical Engineering, Konyang University, 26, Nae-dong, Nonsan, Chungnam 320-711, Korea*Uri-Tech, 88-1, Pyungchon-dong, Seo-gu, Daejeon 302-070, Korea
(Received 30 July 2003; accepted 6 September 2003)
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��%&. ��� ' �() *#�+ ,-. � (Ludox)/ �� 0�� 1�� 2$() APS(3-aminopropyl
triethoxysilane)3 45�� 60�%&. ,7 89:6) APS� *#�+ ,-.; <= >?@A) ��� ��(PET)/
BB C� D$� E��� F G H# &I (J� C�K LD�� D$6 MN� �&. O�P Q�) 0R/H(pH 2,
7) APS5 45ST 60U V�/� WX�"# � ' Y� ST ��� �� �/ �� N � Z[&. \] ^�� 0R
/H(pH 9, 11) _`Ta �� ��� "# ��� �� �/ ��� V�/� �� �� b]� c de� Z� fg
h03 ��i, j' klB� �� ��� ���� mno[&.
Abstract − In order to improve the anti-fogging property of hydrophobic polymer films, inorganic-organic hybrid coating
solutions with a good hydrophilic property were synthesized by the sol-gel method. The coating solutions were prepared byadding 3-aminopropyl triethoxysilane (APS) to a colloidal silica solution(Ludox). APS as a silane coupling agent forms strong
bonds to the colloidal silica and surrounding polymer matrix (PET), and links two different materials together. Solutions pre-
pared by the addition of APS at acidic and neutral conditions (pH 2, 7) resulted in gels which can not be used as coating solu-tions. On the other hand, those at basic conditions (pH 9, 11) resulted in coatings that were less prone to cracking and showed a
good hydrophilic property.
Key words: Aminopropyl Triethoxysilane, Hydrophilic, Sol-Gel Method, Inorganic-Organic, Silane Coupling Agent, CoatingSolution, Silica
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?.]9 Nb� � ��� QRZ PET(polyethylene terephthalate) G
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.+¸7. $ /â� 12 nm ãD� ��3 EJ½, 30 wt%� SiO2E r
�'6 «ä$7. a� h(µ¶·N�� Aldrich Chemical-� 3-aminopropyl
triethoxysilane[APS, H2N-(CH2)3-Si-(OC2H5)3]9 -.+¸7.
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Fig. 1. An illustration of the structure of hydrolyzed APS when it cou-ples a PET film to a silica surface. Fig. 2. Flow chart for preparation of hybrid coating film.
HWAHAK KONGHAK Vol. 41, No. 6, December, 2003
770 �����������
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�³ "å](Ludox) ¥EO ï APS c� ethoxyD� r �� E�
�� 67. E��� 6 APSE .] c� h�³ �� G �Á,�
l� .]� pH ã� ��+� 67. Table 1 �� �ØÙ� R(APS/
silica <Ù��)ç9 EJ� @Ó pHbí � Nb6 >?.]� #ä
3 ÞßXà7. APSE ¥E,D j� � .]� #ä�(R=0) � #ä
3 \J+¸��, pHE ')� c)Z bí(pH 2, 7) �� APSE ¥E
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6o)9 X@�% :�)9 ���9 � � �7.
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E ¥E,% Nb6 >? QR ��� Û �b3 3,000ü� ü�� º
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h�³ ���� �Á�A$ ��,½, Ò }� :�)9 §� h�³
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GPS� ���� .] � � E��� 6 APSE ²�$� h�³ G
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c) bí �� APS5�� Be, )1$ ��,% .]� _Çm
�$ 67� !Ø,½, D)� �� � APS� h�³ �� �� G
� �Á$ ��67� - 67.
3-2. APS ���� ��� ��� ��� ��
� è �� �Ø pHbí(pH 11) + � APSM\Ù� �iE >?
QR� r) ÛÜ� ÝÄ9 ÞßXà7. Fig. 5� pH 11 bí + �
APS� ¥EÙ9 "�+@ Nb6 .]�� >? 6 PETQR� r
þ� Àòó �i3 Þß � Ò!$7. APSE j# ¥E,J Í=�(R=0),
ÛÙ� APSE ¥E ,ñ9 ��(R=0.05) � Ò! �� �$ óó �
� Àòó(18.3o, 19.7o)9 X¸�� APS3 �ØÙ �� +¸9 ��
(R=0.1, 0.15) � óó �� Àòó(7o, 6o)9 X¸7. $� QR� :�
)$ APS� ¥EÙ ã� ��M9 �Û�7.
Fig. 6� pH 11� �Ø� bí + � APS� ¥EÙ �i Ö� N
b6 QR��� Û �b3 3,000ü� ü�� ºú� SEM�� }�
$7. APSE j# ¥E,J Í� ��(R=0)� ��� kÙ ¥E6 �
� � (R=0.05) QR� Û �b� p�$ T$ �+¸Jo, APSE
�$Ù $# ¥E6 QR(R=0.10, 0.15)� Û �b� p�$ �,J
Í� Ü%� �b3 X@�� �7. $Ó� }�� .] � �� APS
� Æ©9 &�� �� l�� APSE ¥E,� QR G >?,% �
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³ �� -$� }e9 '�¤ ��v� íb Ú �i ðØ �� ]F
Fig. 4. SEM photomicrographs of the surfaces of coating films preparedwith APS(R=0.15) added at different pH; (a) pH 9 and (b) pH 11.
Fig. 3. Photographs of contact angles with water for coating films pre-pared with APS(R=0.15) added at different pH; (a) pH 9 and (b)pH 11.
Fig. 5. Photographs of contact angles with water of the coating filmsprepared with different amounts of APS at pH 11; (a) R=0, (b)R=0.05, (c) R=0.1 and (d) R=0.15.
Table 1. The state of coating solutions prepared from different conditions.R is the weight ratio of APS to silica.
R=0 R=0.05 R=0.1 R=0.15 R=0.2
pH2 Sol Gel Gel Gel GelpH7 Sol Gel Gel Gel GelpH9 Sol Sol Sol Sol GelpH11 Sol Sol Sol Sol Gel
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9 UJ+� 67[11, 13].
Fig. 7� �Ø� pHbí(pH 11) � Nb6 >? .]� TEM-´�
� APSE ¥E,J Í� .](R=0) �� h�³ ��� ãD(12 nm)
X7� APSE ¥E6 .](R=0.15) �� h�³ ��� ãD(14 nm)
E ê µ´ l9 � � �7. $� D) bí � APSE ¥E6 �
� � APSE .] c� h�³ �� �� �Á,� l9 �Û�7.
Fig. 8� pH 11� bí � �ØÙ� APS(R=0.15)3 ¥E+@ Nb
6 �D-\D d) .]�� PETQR G >?� � >?Ì� ®�3
�ËXD G� >? ^�9 ôØ� SEM-´$7. >? ®�E þ(
430 nm� p�+½ ®)° *$ «),% �+9 � � �7. $� �
D-\D d) >? .]� 1~9 ���� l�� Sol-GelV �� D
�� �D 'ir >?]� >? ®�� 100-200 nm ØK� HË, �
µm >? ®�� �*9 Nb+D G��� �, -� �ª >?$ Q
.� ��, �D-\D d) >? .]� >? ®�� 1/ >? ®�E
430 nm ØK� ®)0 � µm ®�� �*9 ¨�� Nb© � �7�
l9 �Û�7.
4. � �
²�$� h�³ �� �� � h(µ¶·NZ APS� �Á "#9
$.+@ ¯�° �D-\D d) >? .]9 Sol-GelV �� e)+
¸7. Ò � >?.]9 DPZ PETQR G ×� >?(dip-coating)+
@ ±%´ >? QR� :�) Ú ��� Û �b3 b-+@ 7+�
�� }19 ±ñ7.
(1) ²�$� h�³ "å] APS3 ¥E/ ')� c)� bí
�� �$ ,% >? .]9 Nb© � Õñ�, D)� bí �� >
? .]$ �$ ,% >? .]9 Nb© � �ñ7. D) bí �
Nb6 >? QR� r þ� �� Àòó9(6-7o) X@ ��� :�
)9 X¸�, >?6 QR ��� Û �bK p�$ Õ� ��� Û
�b3 X¸7.
(2) D) bí � (pH 11) >?6 QR� Àòó� APS� ÿ ã
� ��+¸7. APSE ¥E,J Í=� kÙ� ÿ$ ¥E,ñ9 ��
(R=0, 0.05) � r þ� �� Àòó9(18-20o) X¸�, APSE �Ø
Ù ¥E,ñ9 ��(R=0.1, 0.15) � r þ� �� Àòó9(6-7o) X
¸7. a� D) bí � APS� ¥EÙ �i Ö» QR� Û �
b3 ºú� }� APSE ¥E,J Í� �� � �� Û p�$ �
+¸Jo, APSE ¥E6 QR� Û �b� p�$ �,J Í�
Ü%� �b3 X@�ñ7. $� APSE ¥E,� ²�$� h�³ �
� G �Á$ �%� DPZ PET QR� h�³ �� -$� }e9
'�¤ �29 �Û�7.
(3) TEM �� }� D) bí � ²�$� � APSE ¥E,�
APSE h�³ �� G �Á$ �%� h�³ ��� ãDE ê3 µ
�9 � � �ñ7.
�
$ 45� 20026K �789´:P^� Jæ �+@ ��,ñ;
�7(KRF-2002-002-D00057).
���
1. Lim, J. U., “Coating Method and the Equipment of Anti-fogging Age
Fig. 6. SEM photomicrographs of the surfaces of coating films preparedwith different amounts of APS at pH 11; (a) R=0, (b) R=0.05, (c)R=0.1 and (d) R=0.15.
Fig. 7. TEM photomicrographs of colloidal silica suspensions withoutAPS (R=0) and with APS (R=0.15).
Fig. 8. SEM photomicrograph of the cross section of coating film pre-pared from APS (R=0.15) added at pH 11.
HWAHAK KONGHAK Vol. 41, No. 6, December, 2003
772 �����������
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���� �41� �6� 2003� 12�