Sol-Gel Nanoporous Alumina Membrane Alumina Sol...
Transcript of Sol-Gel Nanoporous Alumina Membrane Alumina Sol...
Korean Chem. Eng. Res., Vol. 42, No. 1, February, 2004, pp. 96-101
Sol-Gel�� �� Nanoporous Alumina Membrane� Alumina Sol ��
�������*��*��� †
����� �����320-711 �� �� 26
*���������� ��� �����305-343 �� ��� � 71-2
(2003! 9" 22# $%, 2003! 12" 12# &')
Preparation of Alumina Sol for Nanoporous Alumina Membrane by Sol-Gel Method
Ja-Lyong Park, Tae-Hwan Kim*, Jae-Suk Sung* and Ki-Chang Song†
Department of Chemical Engineering, Konyang University, 26, Nae-dong, Nonsan, Chungnam 320-711, Korea*Energy System Division, Korea Institute of Energy Research, 71-2, Jang-dong, Yuseong-gu, Daejeon 305-343, Korea
(Received 22 September 2003; accepted 12 December 2003)
� �
Sol-Gel�� �� ���� aluminum isopropoxide(AIP) �� �, ���� � ����� �� alumina(boehmite)
�� �� ��. �� �� !�"#�$ !�%&, �'� ��� ( )*+,-� ./ �' 0�1� �2� 345
2� �� ��. 100oC�$ )*+ � ��6 �'7 boehmite1� 89:;<8, 500oC�$ γ-alumina 1= >;�.
HCl/AIP=0.10� �!< ��6 ( 600oC )*+6 �'7 4 nm� ?@34 A3 89:;�. �� ��% B�6
HClC D�E� .F 34� A3G HI� JK )*+ ,-� D�E� .F ?@34� A3G D� ��.
Abstract − Alumina (boehmite) sol was prepared by the sol-gel method from aluminum isopropoxide (AIP) through hydrol-
ysis and peptization processes. Powders were obtained by drying the sol in drying oven, and the powder properties, such as
crystalline phase composition and pore structure, were studied as a function of heat-treatment temperatures. The powders
showed boehmite phase at 100oC, and transformed to γ-alumina at 500oC. The powders, heat-treated at 600oC after being
peptized at HCl/AIP=0.10, had 4 nm in average pore diameter. The average pore diameter of the powders decreased with
increasing HCl concentrations added during peptization process, but increased with increasing heat-treatment temperatures.
Key words: γ-Alumina, Alumina Sol, Aluminum Isopropoxide, Boehmite, Hydrolysis, Pore Diameter, Peptization, Sol-Gel Method
1. � �
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[4]. DDb �� (A�3 x��� ��0�� WX�6�(CVD)[5],
(?wI|�(electroless plating)[6], �( L�9�(spray pyrolysis)[7],
Sol-Gel�[3] )$ �a. $ � Sol-Gel�c x��IJ K� x���
$ f�U �r�Z, �� A�* �3 x�� i �� $�$ �.
^c ��J _`-. /a.
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� �* �c ¡O )3 $8¢0�£ D|¤D ~8-. � �¥¦
�N�� §A .¨© aª "z« � x�� i �� J¬O3 �†To whom correspondence should be addressed.E-mail: [email protected]
96
Sol-Gel�� �� Alumina Sol �� 97
,
� �a[8-10]. Sol-Gel�� * alumina�* x�� �sI, ��O,
��gO )* ��$ �0Z �t nanoporous �* gO$ J¬�
E� �� $ �* ��J ®¯t _`-� �a. Nanoporous�c 1
°k± dA* A�3 JD� a�O �3 ² a[11]. $ �c �A/(
A 1°=g�³� ´2 µ �A ��+* 56 � d�¶·�¥¸�
$8 �� )* ¹�Uº ¡8O µ»� ^c ��J $C.Q /a.
IUPAC(international union of pure and applied chemistry)* N*� ¼
½¾ a�O ��c A�* dA� ¼z " JD� 1h i �a[12].
¿� micropore� A�* Àm$ 2 nm$�$�, ÁÂ� mesopore� A
�* dAJ 2-50 nm$Z, ¶D�0� macropore� 50 nm$� dA*
Ã�� �� A�3 1ÄÅa. 1 nm�� 100 nm~$* A�dA� J
D� nanopore� A�* Àm ƾ�� S¾ micropore, mesopore ��
� macropore� ÇÈ É¢ a. � U0� mesoporous��c ?ÊU
º nanoporous��$a. �� ;�U0� (A �� � ��* Ë�
O$ �È-� ���, nanoporous �c � �ÌD Íf �/A, �/Î
* �� ) Ïm, ¦Ð� Ñ !Òz Ó ¡ ) NÔWX ;�* Í
��I ®8Õ i �a.
Ö ����� aluminum isopropoxide(AIP)� ׯ��� �B $�
�Øi� Ji�9 � �Nª* Ù;(HCl)3 J9 9��Ú,
nanoporous�0� ~8Õ i �� FÛ�� MN alumina�3 x�
�Üa. D|¤D ^c ��+2$ Sol-Gel�3 $8�B alumina��
~8-� alumina�3 ݯ�Üa� ¯Þ�ÜD´ gOGN � HCl/
AIP* ßf àWJ x�á �* A� �O� k�� âã3 äåSD
æ�Üa. ¼z� Ö ç»��� Sol-Gel�3 $8�B x� alumina
�* ;ª� ¼è A� dA � fÞ¾U àWé lc A� �O3 ä
åSêa.
2. � �
Ö ����� ׯ ��� aluminum isopropoxide(AIP, 98%, Al
(OC3H7)3, Aldrich)� ~8�Ü0Z 9���� Ù;(35.0%, HCl,
Dongyang Chemical)3 ~8�Üa. ¡A ë� Uìu* �Øi(H2O/
AIP* ßf 100)� íJ�� heating mantle3 ~8�B �I(90oC)�
�N�e �D�î �, ¡�º AIP� íJ�B 1�� oM � �Ú
Ji�9 ¡3 _`�ïa. $µ ¡0� ðOá ñ¯O ��* �
¯� º ò&3 �A ��B ¡óA� �6�ïa. � � jô~$õ
� � Ù;* ßf� �ö�B $ 8Î� íJ � 90oC�� 24�
� oM � 3 VH�B �* 9�J T?t �.1I� �B alumina
�3 x��Üa. $÷e x�á �3 80oC* ø� �ù�� 48��o
M ø��Ú �bW�Ü�, $ �b �³� �+~¯3 $8�B �²
��� ´2úa. 7 ø� �²3 Bû �I(100-600oC)�� 1��
oM �Í�B \ü alumina�²3 x��Üa. $µ Lý� �øc
2 oC/min* HI� þ��Ü0Z, 5oC/min* HI� ÿ��Üa. $�*
&�ö�� Fig. 1� 1Äëúa. � � x�á alumina�²* �O3
XRD(D/Max-IIIC, Rigaku), BET(ASAP 2400, Micromeritics), FT-IR(FTS155
Bio-Rad), TEM(CM30, Philips), TG-DTA(THERMOFLEX, Rigaku) )*
��AA� $8�B �~�Üa.
3. �� �
3-1. FT-IR ��
HCl/AIP=0.10* �ø0� 9�á alumina�* TEM��� Fig. 2�
1Äëúa. � ë* �+� ��Ǫ$Z � 40 nmNI* dA� 1
Äëú0Z �+2$ �� ¡,-D �� �;-. �� MN �*
Ê�� 1Äëúa. $� 9�� íJá HCl�* H+ $�$ �+* Þ
¾� 56-. �+��* N?AU ¯3 ¥�A µ»0� ~³
áa[13-14]. x�á �3 80oC* ø��ù�� ø��Ú �²W �
Bû �I�� Lý��Üa. $µ §._ �²2* WX ��� Lý
��IJ k�� âã3 äåSA �9 Fig. 3� FT-IR �� RG� 1
Äëúa. 100oCé 300oC�� �4U0� ¯�-� 3,200-3,600 cm−1
* �� �c 5i�� H2O �+* OH �ó_o� �V-� �$
�, 1,640 cm−1 �]��* 5i¸d� H-O-H ��_o� * �$Z,
1,070 cm−1é 770 cm−1 �]��* 5i ¸d� boehmiteRNë* Al-
OH* �� _o� * �0� ~³áa[15-16]. $ ��0��±
100oCé 300oC* �²2c boehmite��� S�3 j i �a. ¾
500oC $�0� Lý�á �²* FT-IR RG� S¾ 100oCé 300oC
�� 1Ä1� H2O �+� * 3,200-3,600 cm−1é 1,640 cm−1* 5
i�J �Í�Z boehmiteRN ë* Al-OH* ��_o� * 1,070
cm−1é 770 cm−1* 5i� ¸dJ ~z�3 j i ��� $�c Fig.
6* XRD���� :º� i ��$ γ-alumina* ðO µ»0� ~³
áa.
Fig. 1. Flow diagram for preparation of alumina powder. Fig. 2. TEM photomicrograph of alumina sol (HCl/AIP=0.10).
Korean Chem. Eng. Res., Vol. 42, No. 1, February, 2004
98 ���� ������
Fig. 4� 9� � HCl* ª3 @��B gOá �3 80oC�� 48�
� oM ø��î � � �³� a� 600oC�� 1�� oM �Í�B
x�á �²* FT-IR �� RG$a. $ ����� Ç� m� �.
3,200-3,600 cm−1é 1,640 cm−1* H2O 5i�J de �Í�Ü0Z 1,070
cm−1é 770 cm−1* Al-OH 5i�J ~z�3 � i �úa. $�0� Fig. 3
* 100oCé 300oC* m�� boehmiteRN$ 1Äë� 5i�* ̧ dJ
Fig. 4��� 1Ä1D �0E�, 600oC� Lý�� m� HCl íJu
� ���$ γ-alumina�* �?$J �.��3 �Æ� i �a.
3-2. TG-DTA ��
Fig. 5� HCl/AIP=0.10* �ø0� x�á �* L�� RG$a. TG
p0��± ���* (e�uc ���� 450oC¤D* �IÃ��
� !}t 1Ä" ¾ 450oC$���� (e* �ÍJ #* �.1
D ��3 j i �0Z 450oC¤D* (e�uc 25% NI$a. DTA
p�� 100oC�]* 5L ¸d� � ë 56i* �¯� *9� �
.1Z � 400oC��* 5L ¸d� boehmite� ë* ��iJ P.
Q 1J¾� γ-alumina� �?$ $� *9 ¯ð-� �0� %Náa.
3-3. XRD ��
Fig. 6c 9�� HCl* íJu3 HCl/AIP=0.100� �N�B �3
x� � 80oC�� 48�� oM ø��Ú x� �²3 a� 100oC,
300oC, 500oC, 600oC�� 1��& Lý� �²* XRD �� RG
$a. BA�� 100oC�� Lý�á �²* RN��� fN�*
Al(OH)3(k� bayerite, gibbsite � pseudo-boehmite RN$ '�¢)
z� ~³-Z, 2θ=14o, 28o, 38o, 49o��* ¸d� S! boehmite�$
ðOá �3 j i �a[17]. 300oC� Lý�á �²��� boehmite
¸d2$ ��t �9DZ, 500oC$��� Lý�á m��
boehmite��� 1Ä1� ¸d2$ ~zDZ, 2θ=45o, 68o�� γ-alumina
�* ̧ d� SB γ-alumina�0� �?$J �.��c j i �a[18].
$�* RG� Fig. 3, 4* FT-IRRGé ( ��$3 j i �a.
Fig. 7c 9�GN� ;ª3 àW�Ú x�á �3 80oC�� 48��
oM ø��Ú x� � a� 600oC�� 1�� oM Lý��B ;
ª$ �* RN��� k�� âã3 j!Ö XRD ��RG$a. 9�
� íJ-� ;ª$ �* RN��� âã3 nD� æ)0Z 2θ=45o,
68o�� �4* ¸dJ 1Ä" �0� S! ÇÈ γ-alumina�$ 1Ä"
�3 j i �a.
3-4. ����
Fig. 8c 9�� HCl* íJu3 @��B x�á �23 �²W
Fig. 3. FT-IR spectra of alumina powders heat-treated at different tem-peratures.
Fig. 4. FT-IR spectra of alumina powders heat-treated at 600oC afterbeing peptized at different HCl concentrations.
Fig. 5. TG-DTA curves of alumina powder peptizied at HCl/AIP=0.10condition.
Fig. 6. X-ray diffraction patterns of alumina powders heat-treated atdifferent temperatures after being peptized at HCl/AIP=0.10condition.
���� �42� �1� 2004� 2�
Sol-Gel�� �� Alumina Sol �� 99
� 600oC�� 1�� oM Lý�á �²2* N2 56-<6 )�p2$
a. $ )�p2c BDDT[19]J �Ø 5JD* �ÞUº 56 )�p
� mesopore �O3 1Äë� type** )�p�3 j i �a. 7
$ )�p2c de Bore[20]J xM hysteresis p � type Aé �~
Ê�� JDE�, A�c ‘+,(bottleneck)’ Ê�º �0� %N-Z
r�;(monodisperse)�* -c A� dA �� J�3 j i �a
. � U0� .c �+2$ �;-. �� �$ /ó$� ¼z �
+2 ~$* ¡,$ �.1 �$ ÊO-E� ¡,bë* .c A�G
¡,b ~$* #� A�2� º�B ‘bimodal’Ê* A��É� ���
i �01, &xU0�� ø�é Lý� GN�� Ç"� 0� *�
B $ #� A�2$ 1.DE� r�;Ê* A��É� J_a� j
¨Q �a[17]. íJá HCl* ª$ J� Uc HCl/AIP=0.05 �ø �²
* 56u$ J� ^ê0Z HCl$ J� ^$ íJá HCl/AIP=0.15 �
ø�� x�á �²* 56u$ J� Uúa.
Fig. 9� )�p* <6 p0��± � A�dA �É2$a. ;ª
$ J� Uc HCl/AIP=0.05* �ø0� x�á �²* A�2c � 45-
47 ÅNI* A�dA� JD� �a. �û1 ;ª$ ̂ $ íJÕi� A
�* dA� .!DZ �t HCl/AIP=0.15* �ø0� x���� A�
$ 33-40 Å* �É� $C� �a. $ RG��± alumina�3 x��
µ 9��� íJ-� ;ª� ¼z� A�dA* �ö$ J¬�Z, Sol-
Gel�� *9 nanoporous A�* ÊO$ J¬¢3 j i �a.
Fig. 10c 600oC� 1�� Lý�á �²* ;ª� ¼è fÞ¾U à
W� 1ÄÅ RG� �* x�� íJá ;ª$ �J¢� ¼z� fÞ
¾U$ �Í¢3 j i �a.
Fig. 7. X-ray diffraction patterns of alumina powders heat-treated at600oC after being peptized at different HCl/AIP conditions.
Fig. 8. Adsorption-desorption isotherms of N2 of alumina powders heat-treated at 600oC.
Fig. 9. Pore size distributions of alumina powders heat-treated at 600oCafter being peptized at different concentrations of HCl.
Fig. 10. Specific surface areas of alumina powders heat-treated at 600oCafter being peptized at different concentrations of HCl.
Fig. 11. Adsorption-desorption isotherms of N2 of alumina powders heat-treated at different temperatures after being peptized at differ-ent concentrations of HCl.
Korean Chem. Eng. Res., Vol. 42, No. 1, February, 2004
100 ���� ������
f
act
es,
-
u-
J.,
i-
hi,
p-
d
or
Gel
e-
Fig. 11c HCl/AIP=0.10* �ø0� 9�á �3 80oC�� 48��
ø��î � a� 100oC, 300oC, 600oC* �I�� �� 1��& L
ý�� �²* �Í 56-<6 )�p2$a. 100oCé 300oC��
Lý�� �²2c <6 p�� <6u* !} �ÍJ �.1�
0(P/P0)$ fv�E� A�* dA� fv¢3 j i �a. �û1
600oC�� Lý� �²* <6 p3 S¾ <6u$ !} �Í�
�02� 0$ 3 �! 3 [ A�dA� S�3 j i �a. $�
XRD �� RG�� � i ��$ 600oC��� γ-alumina* RN$ ð
O-ú0E� 100oC, 300oC* boehmite�� Sa 3 [ A� dA�
J_a� %N� i �a.
Fig. 12� )�p* <6 p0��± � A�dA �É ��$a.
100oCé 300oC��* 4�A� dA� � 35 Å$1 600oC� Lý�
á �²* 4�A� dA� � 40 ÅNI� 1Äë� �a. $�
boehmite* O��� γ-alumina� �?$�¾� A�* dAJ 5D�
�3 *k a.
Fig. 13c HCl/AIP=0.10� 9�á �²* Lý� �I� ¼è fÞ¾
U RG� 100oC�� 330 m2/g* fÞ¾U$ Lý� �IJ �J¢�
¼z �Í�B, 600oC��� 240 m2/g* fÞ¾U3 1Ä63 j i
�a.
4. � �
Aluminum isopropoxide(AIP)� ׯ��� �B �� Ji�9 �
HCl� 9��� Sol-Gel�3 $8�B nanoporous A�3 ��
alumina�3 x��Üa. $÷e x�á �3 80oC�� 48�� ø��
Ú �²W�� Bû �I�� Lý�á �²3 FT-IR, XRD, TEM, BET
)* ��AA� ~8�B a�G lc R73 §3 i �úa.
(1) HCl/AIP=0.10* ßf� 9�á alumina�3 TEM3 $8�B �
Æ RG � ë* �+� ��Ǫ$Z 40 nmNI* dA� 1Äëúa.
(2) ø� �²* Lý� �I� ¼è aluminaRN �* àW� äå
Ö RG 100oC, 300oC�� Lý�á �²��� boehmite�$ 1Ä1
�, 500oC $��� Lý�á �²c γ-alumina�3 1Äëúa.
(3) 9�� ;ª$ Uc HCl/AIP=0.05* �ø�� x�á alumina�
* A�2c � 45-47 ÅNI* A�dA� JD� �a. �û1 ;ª
$ ��U0� ^c HCl/AIP=0.15* �ø�� x�á �c A�* dA
J .!Q 33-40 Å* A�dA� 1Äëúa. $� � x�� 9�GN
� íJ-� ;ª� *9 A�* dA� �ö� i ��3 *k a.
�
$ ��� GXA8� D�0� i`�� 21"A 97:. ~�($;
W;Í �� � ý� A8ݯ)* �Ï0� i`-ú<Òa.
���
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Fig. 13. Specific surface areas of alumina powders heat-treated at dif-ferent temperatures after being peptized at HCl/AIP=0.10 con-dition.
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