Highly permeable supported γ-alumina membranes for water ...
Transport properties of anodic alumina membranes
54
Московский государственный университет им. М. В. Ломоносова Факультет наук о материалах Булдаков Дмитрий Алексеевич Транспортные свойства мембран анодного оксида алюминия в жидких средах Магистерская диссертация по специальности 020100 «Химия» (магистерская программа «Химия твердого тела») Научные руководители: асп. 3 г/о Петухов Д.И. к.х.н., доц. Елисеев А.А. Москва 2013
-
Upload
dima-buldakov -
Category
Documents
-
view
34 -
download
8
description
The review giving an outlook at the recent advanced in the research on anodic alumina membranes
Transcript of Transport properties of anodic alumina membranes
-
. . .
020100
( )
:
. 3 / ..
..., . ..
2013
-
2
............................................................................................................................ 2 1. ............................................................................................................................ 4 2. ......................................................................................................... 6
2.1 ......................................................................... 6 2.1.1 ...................................................... 6 2.1.2 ............................ 7 2.2 .................................................... 8
2.3 ..................................................................................................................... 11
2.3.1 ................................................................... 11 2.3.2 ............................................................................. 12 2.3.3 ................................................................................................. 16 2.3.4 ................................................. 17 2.3.5 ............................................................................ 21 2.3.6 ............................ 22 2.3.7 .................. 26
2.4. ........................... 28 2.5
........................................................................................................................ 37 2.5 ............................................ 39
3. ......................................................................................... 46 3.1 .................................................. 46 3.2 .............................................................................................. 49
3.2.1 ............................................................ 49 3.2.2
.............................................................................................................................. 49 3.2.3 ....................................................................................... 49 3.2.4
.............................................................................................................................. 50 3.2.5 ............................................... 50 3.2.6 .............................................. 50 3.2.7 .................................................... 50 3.2.8 -
( ) () ............. 51
-
3
3.2.9 - ............................... 51 3.2.10 .......................................................... 52 3.2.11
.......................................................................... 52 4. ................................................................................................ 54
4.1 ......... 54 4.2 .................... 62 4.3 ............................................ 73 4.4
................................................................................................................................................... 79 4.5 ... 83 4.6 . 93
5. ............................................................................................................................ 97 6. ................................................................................................................. 99 7. ....................................................................................................... 100
-
4
1.
,
.
. ,
,
. ,
,
.
,
. -
. :
,
;
, ,
(
).
, ,
,
,
, , , -
.
,
.
,
( ,
).
. ,
,
. ,
-
5
,
. ,
. ,
.
(
).
,
.
, (
)
. ,
.
,
.
/
1 .
-
6
2.
2.1
2.1.1
,
( 10 ),
. ,
,
[1].
. (pH=5-7)
, .
, , , ,
[2]; [3]. ,
, ,
[4]. ,
(pH
-
7
[13]. ,
,
.
2.1.
2.1.
,
, . 2.1. ,
,
,
.
[14].
.
.
2.1.2
,
.
: (d),
-
8
(dint), (d), (L),
(L) (. 2.2). , ,
, (),
:
! = !! (2.1) ,
:
! = !! (2.2)
:
! = !!! !!!"# ! (2.3) , ,
( , N).
:
! = !!!"#!! !! (2.4)
2.2
,
. . 2.3.
,
( 1 . 2.3). 2
, 3 ,
( 4) [15,16].
. 2.2.
-
9
jp,
,
,
jb,
jhp (jhp = jp jb),
. jb
, jhp
,
,
. ,
:
(mild
anodization -
-
10
( = 1010 - 1012 [18]) ,
jp ( 1 . 2.3 2.4).
.
,
( 2 . 2.4),
,
( 3 . 2.4). j(t)
.
.
, ( 4 . 2.4).
jp ,
( 4 . 2.3).
.
, ,
, :
2Al + 3H2O Al2O3 + 3H2
, , :
2H+ + 2e- H2
:
Al Al3+ + 3e-
2Al3+ + 3H2O Al2O3 + 6H+ + 6e-
2Al + 3O2- Al2O3 + 6e-
2H2O O2 + 4H+ + 4e-
,
:
SO42- S2O82- + 2e- [14].
-
11
, .
/
-
/. ,
Al3+ .
, /
.
(. 2.5)
(
)
,
/
, (
) [19].
2.3
2.3.1
(dint) (U),
(. 2.6).
k 2,2 2,8 / [17]:
dint = kU (2.5)
,
, ().
[20] ,
.
,
/: 2Al
3+ + 3H2O Al2O3 + 6H
+
/: 2Al
3+ + 3H2O Al2O3 + 6H
+
/: 2Al
3+ + 3H2O Al2O3 + 6H
+
/: 2Al + 3O
2- Al2O3 + 6e
-
. 2.5. , / /
-
12
[21]
[22].
,
,
.
2.3.2
,
,
.
[23]
,
, (Jessensky O.) [24].
,
,
,
10%.
:
! = ! !!! ! ! (2.6) P , k
,
(U).
,
.
, ,
,
. 2.6. .
. 1.7 pH : n - (COOH)2; - (COOH)2 + NaOH; - (COOH)2 + C6H15NO3
0 50 100 150 200 250 3000
50100150200250300350400450500550600650
0 ,3 (C O OH )2
0,3 M (C O OH )2 + 3,5 M E tO H
0,3 H2S O
4
0,1 H3P O
4
Din
t,
U ,
Dint=4,9+2,3*U
-
13
10% ( 35%) [25], (
3,3%) [26]. [27] ,
0,9 /
. , 1.4,
.
pH. pH
, ,
. [28] ,
3 . % 20 . %
12,5 19,91,9 13,77,8 .
pH [29] pH
.
, ,
,
.
, [30]
,
(. 2.8),
.
45
20C
0,05 0,5.
() -
().
. 2.8. , 45 20C.
-
14
.
, ,
. ,
,
,
.
, .
.
,
[31].
[32].
,
in-situ .
,
( 1 ) .
[33,34,35]
(re-anodization technique).
, , 0,5 H3BO3 + 0,05 Na2B4O7,
. 2.9. () () , ,
)c
)
-
15
.
[7]
,
(, , ) 2
40 (. 2.9). , 10
, 0,1
0,2. 10
, .
,
,
. ,
. ,
: 20C
1,5 H2SO4; 30C
0,3 H2C2O4; 40C 0,3 H2CrO4
25C 0,4 H3PO4.
,
. 2.11. 5% . H3PO4 35C. - ; - , ImageJ, .
. 2.10. , 5% . H3PO4 35C
-
16
,
[36,37].
, .
. 2.10
, 40 0,3 H2C2O4,
5% . H3PO4 35C.
34 75
17 50% (. 2.11).
2.3.3
,
,
.
[38,39]
2 .
,
.
c
(. 2.12)
[40].
, ,
,
,
,
,
.
,
.
. 2.12. , CVD Al2O3 .
-
17
2.3.4
.
,
,
.
,
, .
1,3-1,4 /
1,15 /
. ,
,
/ . . 2.13
.
,
.
. 2.13. ,
. 2.14.
-
18
.
(wet chemical etching) [41,42,43,44], [45],
[46]. , [47]
, ,
.
, HClO4 (72% .)
(CH3CO)2 1:1, 15 ,
, , 1-3 .
. 2.14.
,
,
. (. 2.15)
, ,
.
,
.
,
H3PO4 CrO3 H2CrO4.
,
,
. 2.15. , . ) 0 ; ) 50 ; ) 100
-
19
.
,
.
[43],
. . 2.16
, .
; ,
, 5% .
0,2 KCl.
(1,5-2) .
. ,
,
. 2.17. ,
,
.
. 2.16.
. 2.17. , ,
-
20
[42,41].
,
25C 46C
,
,
3% . (COOH)2
30, 3 .
. 2.18
.
, 0,4 H3PO4 0,2M H2CrO4.
, ,
. ,
, 42 /.
,
.
[42]
5% . H3PO4
30C (. 2.19).
40 90
,
,
1,3 /,
0,5
/, ,
,
,
.
. 2.18. .
. 2.19. ( - ) () 5% . H3PO4 30C
-
21
. ,
.
, , ( 10
60 ) 0,93 /,
0,17 /,
. , ,
,
-.
2.3.5
,
,
.
,
. [48,49,50]
, [51]
160 0,3 H3PO4.
, ,
:
2Al + 3H2O Al2O3 + 3H2
: !! !"!!! = !!!"!!!!/(!") (2.7)
mt(Al2O3) , !!"!!! - Al2O3, Q , , z ,
, F (96485 -1),
( , ,
).
,
!! !"!!! = !! !"!!! !! !"!!! (2.8) !! !"!!! - , !! !"!!! - .
-
22
, , (mAl)
: (!!")! = 2!!!"!/(!") (2.9) (!!")! . (!!")!
!! !"!!! = (!!")! +!! !"!!! !! !" (2.10) !! !" !! !"!!! .
! = (!!")!/(!!")!!!""% (2.11) (!!")! (2.10) !! !"!!! , !! !"!!! !! !" , (!!")!!!""% (2.9).
, ,
.
, [48],
. 0,4 H3PO4
5 /2 67%, 12 /2
93%. , , [51]
.
100%.
, ,
/ O2- OH-
. /
,
O2- OH-, .
,
,
[51].
[49]. ,
0,3 H3PO4 160 1
1,924 /2.
2.3.6
,
-
23
Al(OH)3, -
AlOOH () Al2O3xH2O [52,53,54].
,
[55]. (
) ,
, [56]. [52]
-
, .
[57], [58,53,59]
[53].
,
, . 2.20.
[60,53]:
25 < T < 100 C:
Al(OH)3 + H2O() Al(OH)3 + H2O()
100 < T < 400 C:
Al(OH)3 AlOOH + H2O
550 < T < 800 C:
2AlOOH -Al2O3 + H2O
800 < T < 900 C:
-Al2O3 -Al2O3
SO42- SO32- + O2
SO32- O2- + SO2
C2O42- CO2 + CO + O2-
HC2O4- CO2 + CO + OH-
900 < T < 1100 C:
-Al2O3 -Al2O3
1300 < T < 140 0 C:
-Al2O3 -Al2O3
, , . 2.21.
. 2.20. , ) ; ) ) . I ; II ; III
. 2.21. .
-
24
830-840,
-Al2O3 -Al2O3.
-Al2O3 -Al2O3. 1080
-Al2O3 -Al2O3,
. , ,
, 1500
.
AlPO4. C
, ,
[60,59] 4 . %.
2.2 ,
,
.
2.2. ,
, ,
, % , %
25-400 400-700 700-1400
0,3 H2SO4 5,68 (H2O) 1,19 (OH) 9,84 (SO2) 83,29 (Al2O2,77)100(SO4)19(OH)839H2O
0,3M H2C2O4 4,17 (H2O) 0,60 (OH) 4,92 (CO2) 92,45 (Al2O2,92)100(C2O4)6(OH)426H2O
0,4M H3PO4 1,15 (H2O) 0,09 (OH) - 98,76 (Al2O2,88)100(PO4)8(OH)0,1H2O
[61,62] ,
: ,
. [57]
,
,
(. 2.22). ,
,
Al2O30,24AlPO4x1H2O;
Al2O3H2O.
[63,64],
, , ,
).
-
25
[65,66]
pH .
[66]
Whatman
Anodisc 47 100 (. 2.23).
,
pH, 8.
[65]
,
. -
pH 6,5 5,5
.
,
,
,
. 2.22. , 8% . H3PO4 () (b); (); (d)
. 2.23. - Whatman Anodisc 47 pH.
-
26
, . ,
C2O42- HPO42-
.
, ,
,
, ,
,
.
2.3.7
.
, ,
( 2.3).
2.3. ,
,
,
,
,
0,3M H2SO4 10 25 1,8M H2SO4 0 70
6M H2SO4 20 18 0,3M H2C2O4 3 160
0,3M H2C2O4 0-5 40 0,3M H2C2O4 1 120-150
0,1M H3PO4 0-5 195 0,1M H3PO4 0 235
,
, .
.
,
(Jessensky O.).
, -
,
. ,
.
,
-
27
10%.
,
,
,
, 3-4%.
,
, [67,68]. [68]
,
,
.
: , ,
.
,
, [67],
in-situ
. ,
, ,
. . 2.24
.
.
[69,70],
.
. 2.24. ,
-
28
,
: , . ,
,
, , .
2.4. ,
-
[71,72,73].
-
:
! = !! (2.12) k , (,
,
),
.
,
,
-
:
! = !!!!"#! !!! (2.13) ; L .
(2.13)
(2.4)
P :
! = !!!! = !!!!"!!"!!"#! = !!!!"!" (2.14) (2.14)
,
.
. 2.25.
1E-4 1E-3 0,01 0,1 1 10 1000,1
1
10
100
,
-
,
-
-
-
-
29
. 2.25
.
- . , ,
, 0,1
10 .
(, ), ,
(,
(), , , ,
) .
, (, , -
Al2O3, ZrO2, TiO2).
1 100
.
,
.
(,
, ) .
( , ),
- (, -Al2O3). ,
: ,
,
. ,
:
[74].
-
,
, ,
.
-
30
, ,
,
, .
; :
, , ,
(. 2.26).
,
.
:
(screen filter),
(
,
),
(depth filter),
,
,
(
,
. 2.26. : ) ; )
) )
. 2.27. () () ,
) )
-
31
). . 2.27
, ,
[75]. [76]
(. 2.28).
4 /,
(Anopore),
,
,
,
.
,
(Anopore, ),
.
Anopore. ,
, ,
.
,
,
,
.
,
. 2.28. ,
. 2.29. , , . .
-
32
. ,
(,
[77]).
[78].
,
, 10 (. 2.29).
2 150 ,
1,355 150
0,946 42,8 .
:
, f , p
.
, ,
, 10
3,6% 10 .
,
.
[71,72].
,
,
(. 2.30).
[72] ,
f
pob C
CR =1
0 50 100 150 200 250 300 3500
50
100
150
200
250 L =59 , d=50 , =21%
,
/(
2
)
,
/(
2
)
1/, -1
0
1
2
3
4
5
L =65 , d=10 , =4.8%
. 2.30. 10 50 c
-
33
, ,
2 5
.
,
:
Al2O3 + H2O 2AlOOH
. ,
[71]
(. 2.31).
, 40
( 529 ; c 349) 80 (
12516 ; c 9215)
150 ( 23947 ; c 40180).
. ,
,
- (2.14).
[73].
29
0 10000 20000 30000 40000 500000
1000
2000
3000
4000
5000
6000 AAp 150
25 2033,350
,
/(
2
)
L -1, -1
L , 100
0 5000 10000 15000 20000 250000
100
200
300
400 AAo 40 AAo 80
L , 4066,7 50100
,
/(
2
)
L -1, -1
200
)
)
. 2.31. () () .
-
34
96 ,
-.
, . 2.32
,
,
.
,
-,
.
60
. 60
,
(flow with slip)
.
( )
,
[79].
.
,
,
.
: ! = !!!!! !!,
0 20 40 60 80 1000,000
0,003
0,006
0,009
0,012
0,015
0,018
0,021
,
/(
)
, . 2.32. , 25-80
-
35
Ds
, Ks
, d ,
cs
.
,
.
[80,81,82]
. [80]
,
.
. [81]
.
, .
20 50 ,
Anodisc 0,02 m ( 20
200 ) Anodisc 0,2 m (
200 ).
,
200 ,
,
8
,
(. 2.33).
. 2.33. , ,
. 2.34. .
-
36
2.4
Merck Millipore,
,
,
, /(2)
MF-Millipore (
)
25 105 0,13
50 105 0,64
100 105 1,3
Hydrophilic PVDF ()
100 102 1600
PCTE
(, ) 100 25 2100
PER (, )
100 23
[82].
1 .
(,
Mr = 66 ) (, Mr = 65 )
0,01, pH
.
. . 2.34.
5,310-8 /(2), 1,2510-9 /(2),
42. , pH = 4,7
, ,
,
pH. ,
,
-
37
.
,
,
Merck Millipore ( 2.4).
.
.
,
- . ,
.
2.5
,
,
, .
,
, ,
, ,
[83]. ,
[84].
-
, [85].
. ,
() [86].
,
,
[87,88,83].
(. 2.35). ,
-
38
.
: ,
, /
, .
SPG (Shirasu Porous Glass),
,
. ,
0,1 14 [89]. ,
-Al2O3
[90],
() [91].
, 5 . [92,93]
(,
) .
.
, ,
1 ,
, [94,95].
,
,
(, ),
1
.
,
,
.
. 2.35.
-
39
,
. [96]
120
500 . [97]
, ,
125 .
,
.
,
( ,
/ )
.
2.5 [73,98,99,100],
[101,102], [103],
[104,105] ,
.
- , -
.
,
- ,
- ,
, (. 2.36).
. 2.36. - () c ()
R
) )
-
40
,
[99] (. 2.36).
,
, -
,
. [106]
. 200
3-, 3-
. ,
. . 2.37
, .
,
-
.
[103]
. 2.37.
. 2.38. , , (); ()
) )
-
41
,
.
200
(TEOS)
(CTAB).
3,40,2
15 (. 2.38).
,
B ( 1 ),
B12 ( - 2,4 ),
( 4
() (
-7,2 ).
0,2 /. ,
,
B12.
( B B12),
,
(. 2.39).
pH-
,
[107].
pH (. 2.40).
, , pH (. 2.41).
pH 3,
. 2.39. B, B12, ,
. 2.40. ,
-
42
. pH
,
.
,
,
-
. ,
.
-
(atomic layer deposition),
,
. . 2.42
,
-
. ,
,
,
.
,
, -
(, ).
,
(. 2.43).
. 2.41. pH ,
. 2.42. , -
-
43
[105]
-
.
(. 2.44).
[108]
,
(IV).
-
,
[109].
,
[105,110,111]. , ,
450-950,
, , , , [112].
( )
[113], [110].
, ,
(. 2.45). ,
,
, , .
,
. 2.43. -
. 2.44. 20 , -
-
44
.
.
,
[114,115].
[113]
, ,
, .
624 ,
433 . ,
,
.
,
OH, -COOH
.
,
,
(electrically-
switchable membranes),
. [114]
(II) [Ru(bpy)3]2+
[Fe(CN)6]3-/4-.
25 ,
CVD, , ,
. ,
,
.
. 2.45. ,
-
45
,
(. 2.46).
,
. ,
-0,5
36%,
29% ,
.
,
,
. ,
.
.
,
.
. 2.46. [Ru(bpy)3]2 , , 25 ,
-
46
3.
3.1
: Al ( 0,5 , Goodfellow, 99,999%
100 , 99,99%), (COOH)2 (Aldrich, 98%), H3PO4,
(...), HCl, . (..), CrO3 (..), CuCl2 (..).
MilliQ (> 18).
.
(CrO3) 185 / (H3PO4) 1480 /
80 .
650 /2 20, 3
, 40 . 50
.
(. 3.1)
AgilentN5751A (V = 0300 , I = 02 ), AgilentN8740A (V =0150 , I =
022 ) GPC-60300 (V = 080, I = 03 A),
,
0,3
H2C2O4.
.
,
,
.
( )Pt
( )Al
V=5-250
. 3.1. .
-
47
,
Heidolph PD5006 ,
Huber K6-CC1 0 .
,
.
.
,
,
, (mild anodization)
. ,
, 20 / CrO3 35 / H3PO4
60,
.
3.1.
3.1 ,
.
(hard anodization)
: 0,5 /
.
0,5
CuCl2 5% HCl.
,
, ,
,
,
0,3 (COOH)2
20 20 48 140 0 1
0,3 (COOH)2
40 20 48 96 0 1
0,3 (OOH)2
140 3 - 0 1
. 3.2.
-
48
,
,
,
(. 3.2).
. ,
, . 3.3.
, ,
.
,
(5%-25% .).
0,2 KCl.
(4), .
(IV) . (IV)
-
, [116].
, 2,5 , 47
0,5 1M HCl, 30 ,
120 4 .
SiO2.
, .
600 4
(15 . %) (85 . %), 150 /.
.
: i-C4H10()4C()+5H2().
, .
. 3.3.
15-25% H PO3 4 0.2M K l
A
C
-
49
3.2
3.2.1
Leo Supra 50VP.
5-20 ; 10000 200 000.
Q150TES (Quorum Technologies).
,
ImageJ.
3.2.2
, . 3.4.
:
5-10 ,
( 3 )
.
100-.
25.
,
,
:
F = !V!P "S " !t , F
/(2), V , (), P
(), S (2), t ().
3.2.3
-
DiamondPyris (PerkinElmer).
. 3.4. - .
-
50
.
15-20 0,1 . 5
/. ,
10 , 1500.
3.2.4
1 HCl. .
-
- - PerkinElmer Elan DRCII.
Al3+ 10 /.
7757-2000
Al3+ 0,1, 1, 3, 10 30 /.
3.2.5
,
,
. Leo
912AB Omega 120 .
, ,
3 NaOH 10 ,
.
3.2.6
,
,
Renishaw InVia
633 (He-Ne, 20 ) 785 (300 ).
( 520,5 1).
3.2.7
FTA1000 Drop Shape Instrument B Frame System.
-
51
. ,
,
.
100 . CCD
640x480 . 1 .
3.2.8 - ( ) ()
- ,
pH
Zeta-analyzer (NanoZS, MalvernInstruments),
- (=633 ).
10
HCl pH=3 .
0.01M NaOH
MPT-2.
- pH
pH=3.
, .
3.2.9 -
, . 3.4.
1
/.
.
-
. , ,
; .
. 3.5. .
-
52
3.2.10
(. 3.5), ,
.
pH,
pH .
.
-
PerkinElmer Lambda 35
190 1100 . 0,5 , 2 .
,
(, Aldrich, 96%) 10 /,
(, Aldrich) 10 /, .
in situ.
.
- OceanOptics QE65000,
HPX-2000.
3.2.11
/ - 2%-
Tween 20
. Tween 20
. 3.6. , () ()
) )
-
53
- ,
.
.
(dead-end)
,
, .
(1-2 ) ,
(. 3.6).
,
. ,
. 3.6.
-
54
4.
4.1
( , , )
. ,
,
.
ImageJ.
,
.
4.1
,
,
.
,
, ,
.
, ,
. ,
, -
. ,
. ,
(120-140)
0,5/ .
,
, . ,
, 120-
140, .
![Preparation of anodic aluminum oxide (AAO) nano-template …electrolytes under appropriate electrochemical conditions [3-5]. The synthesis and application of nanoporous alumina mask](https://static.fdocuments.net/doc/165x107/60c2ff62b7970f410e08e26b/preparation-of-anodic-aluminum-oxide-aao-nano-template-electrolytes-under-appropriate.jpg)
