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. . .

020100
( )

:
. 3 / ..
..., . ..

2013


............................................................................................................................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
2

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

1.

,
.

. ,
,
. ,

,
.
,

. -

. :
,
;
, ,
(
).
, ,
,
,
, , , -
.
,
.
,
( ,
).
. ,
,
. ,
4

,
. ,

.
(
).

,
.
, (
)
. ,
.

,
.
/
1 .

2.
2.1
2.1.1
,
( 10 ),
. ,

,
[1].

. (pH=5-7)
, .

, , , ,
[2]; [3]. ,
, ,
[4]. ,
(pH<5)
, , [5]; [6]
[7]. ,
[8]; [9], [9],
[10]; [11], [11]
[11].
, ,

,

,
. 2.1. ,

[12]

[13]. ,

,
.
2.1.
2.1.


,
, . 2.1. ,
,

.

[14].

.

.
2.1.2

,
.
: (d),
7

(dint), (d), (L),


(L) (. 2.2). , ,
, (),
:
!=!

(2.1)

,

:
!=!

(2.2)


:
!

! = !!

! !

(2.3)

!!"#

, ,
( , N).

:
! =

!
!!!"#

!!

(2.4)

. 2.2.
2.2

. . 2.3.
,
( 1 . 2.3). 2
, 3 ,
( 4) [15,16].
8

jp,

jb,

jhp (jhp = jp jb),

. 2.3.
. jb

. jp
. jhp
,

jp jb.

. jb

, jhp

. ,

(mild

anodization - <10
/2)

(hard

anodization - 30300 /2) [17].

. 2.4.
. 1
; 2

; 3
;
4 .

2.4.

(. 2.3).
9


( = 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+ + 3e2Al3+ + 3H2O Al2O3 + 6H+ + 6e2Al + 3O2- Al2O3 + 6e2H2O O2 + 4H+ + 4e ,
:
SO42- S2O82- + 2e- [14].

10


, .
/
-
/. ,
Al3+ .
, /

/:
3+
+
2Al + 3H2 O Al2 O3 + 6H
/:
3+
+
2Al + 3H2 O Al2 O3 + 6H

(.

.
2.5)

/:
3+
+
2Al + 3H2 O Al2 O3 + 6H

/:
22Al + 3O Al2O3 + 6e

. 2.5.
,
/ /

, (
) [19].

2.3

2.3.1
(dint) (U),
(. 2.6).
k 2,2 2,8 / [17]:
dint = kU

(2.5)

,
, ().
[20] ,
.
,
11

D in t,

650
600
550
500
450
400
350
300
250
200
150
100
50
0


0,3 (C O O H ) 2

[21]

0,3 M (C O O H ) 2 + 3,5 M E tO H

[22].

0,3 H 2 S O 4
0,1 H 3 P O 4

Dint=4,9+2,3*U


.
0

50

100

150

200

250

2.3.2

300

U ,

.
2.6.

,
.
[23]
,
, (Jessensky O.) [24].
,
,

10%.


:
! =

! !!
!

!!

(2.6)

P , k
,
(U).

. 1.7 pH
: n - (COOH)2;
- (COOH)2
+ NaOH; - (COOH)2 + C6H15NO3

, ,
,
12


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),


. 2.8.

45

20C.

45

20C

0,05 0,5.

() -
().
13

.
, ,

,
,
.
, .
.
,

[31].

[32].
,
in-situ .
,
( 1 ) .

)
c

. 2.9. () ()
, ,
[33,34,35]
(re-anodization technique).
, , 0,5 H3BO3 + 0,05 Na2B4O7,
14


.
[7]
,
(, , ) 2
40 (. 2.9). , 10

. 2.10. ,
5% . H3PO4 35C
, 0,1
0,2. 10
, .
,
,


. ,

. 2.11.

5% . H3PO4
35C. - ;
- ,



ImageJ, .

. ,

: 20C
1,5 H2SO4; 30C
0,3 H2C2O4; 40C 0,3 H2CrO4
25C 0,4 H3PO4.

,
15

,
[36,37].
, .
. 2.10
, 40 0,3 H2C2O4,
5% . H3PO4 35C.
34 75
17 50% (. 2.11).
2.3.3
,
,
.
[38,39]
2 .
,
.

(. 2.12)
[40].
, ,
,

,

,
.

. 2.12. ,
CVD
Al2O3 .

16

2.3.4


.
,
,


, .

. 2.13.

,

1,3-1,4 /

1,15 /

. ,

,
/ . . 2.13

.
. 2.14.




17


.

(wet chemical etching) [41,42,43,44], [45],
[46]. , [47]
, ,
.
, HClO4 (72% .)
(CH3CO)2 1:1, 15 ,
,

1-3


. 2.14.
,
,
. (. 2.15)
, ,

. 2.15. ,
. ) 0
; ) 50 ; ) 100
.

,
.
,
H3PO4 CrO3 H2CrO4.
,

,

18


[43],

. 2.16.

2.16

; ,

, 5% .
0,2 KCl.
(1,5-2) .

. ,
,

. 2.17. ,

.
. 2.17. ,



19

[42,41].

25C 46C
,

3% . (COOH)2
30, 3 .
.

2.18

.
2.18.

.
.
, 0,4 H3PO4 0,2M H2CrO4.
, ,
. ,
, 42 /.
,
.
[42]
5% . H3PO4
30C (. 2.19).
40 90

,
1,3 /,

0,5
/, ,
,
. 2.19.
(
-
) ()

5% . H3PO4
30C

,
.

20

. ,
.
, , ( 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)

!! !"! !! - , !! !"! !! - .
21

, , (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
,
22

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

. 2.20.
,
)
; ) )

; II ;
III

SO32- O2- + SO2


C2O42- CO2 + CO + O2HC2O4- CO2 + CO + OH900 < T < 1100 C:
-Al2O3 -Al2O3
1300 < T < 140 0 C:
-Al2O3 -Al2O3

. 2.21.

.

, , . 2.21.
23

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],
, , ,
).
24

. 2.22. , 8% . H3PO4 ()
(b); (); (d)
[65,66]
pH .
[66]
Whatman
Anodisc 47 100 (. 2.23).
,
pH, 8.
[65]

,

. -

. 2.23. -
Whatman Anodisc 47
pH.

.
,

pH

6,5

5,5

,
25

, . ,
C2O42- HPO42-
.
, ,
,
, ,
,
.
2.3.7

.
, ,
( 2.3).
2.3. ,

, ,

0,3M H2SO4

10

25

1,8M H2SO4

70

6M H2SO4

20

18

0,3M H2C2O4

160

0,3M H2C2O4

0-5

40

0,3M H2C2O4

120-150

0,1M H3PO4

0-5

195

0,1M H3PO4

235

,
, .
.
,
(Jessensky O.).
, -
,
. ,

.
,

26

10%.
,


,
, 3-4%.


, [67,68]. [68]

,


,

.

: , ,

.
2.24.

.
,

, [67],

in-situ
. ,
, ,
. . 2.24
.
.

[69,70],
.
27

,
: , . ,
,
, , .

2.4.
,
-
[71,72,73].
-
:
! = !!

(2.12)

k , (,
,

),

100

1E-3

0,1
1E-4

10

0,01

0,1

10

100

. 2.25.

!=

!
!!

!"#!

!!
!

; L .
(2.13)
(2.4)
P :
!=

!!
!!

!! !

= !"!!"!
! =
!"#

!
!!

!"!"

(2.14)

(2.14)

,
.
28

. 2.25
.
- . , ,
, 0,1
10 .
(, ), ,

(),

(,

) .
, (, , Al2O3, ZrO2, TiO2).
1 100
.

.
(,
, ) .

( , ),
- (, -Al2O3). ,

: ,
,
. ,

:

[74].
-
,
, ,
.

29

. 2.26. : ) ; )

, ,
,
, .
; :
, , ,
(. 2.26).
,
.

(screen

filter),

,
),

(depth

filter),

,
,
(
. 2.27.
() () ,

30

). . 2.27
, ,
[75]. [76]

(.

2.28).

4 /,

(Anopore),
. 2.28.
,

.
,
(Anopore, ),
.
Anopore. ,
, ,


.

,
,

. 2.29. ,
,
. .

31


(,
[77]).

[78].
,
, 10 (. 2.29).
2 150 ,
1,355 150
0,946 42,8 .
:

Rob = 1

Cp
Cf

, f , p

.

, ,
, 10
3,6% 10 .
5

L = 5 9 , d= 5 0 , = 2 1 %
L = 6 5 , d= 1 0 , = 4 .8 %

200

4
3

150

50

100

150

50

100

200

1/,

250

300

1
0
350

-1

. 2.30.
10 50 c

, /( )

250

, /( )

[71,72].
,


(. 2.30).
[72] ,
32

, ,
2 5
.

,
:
Al2O3 + H2O 2AlOOH

. ,
[71]

200

100

L ,
66,7

50

40

)
, /( )

A A o 40
A A o 80

300

6000

100

50

L ,

33,3

25

20

30000

40000

50000

A A p 150

5000
4000

, /( )

) 400

200

100

5000

10000
15000
-1
-1
L ,

20000

25000

3000
2000
1000
0

10000

20000
-1

L ,

-1

. 2.31. ()
() .
(. 2.31).
, 40
( 529 ; c 349) 80 (
12516 ; c 9215)
150 ( 23947 ; c 40180).
. ,
,
- (2.14).

[73].
29

33

,
/( )

0,021

0,018

0,015

0,012


-.

0,009

0,006

0,003

, . 2.32

0,000
0

20

40

60

80

100

. 2.32.

,
25-80

96

-,
.
60
. 60
,
(flow with slip)
.
( )
,
[79].

.
,

,
.

:
! =

!! !!
!

!! ,

34

Ds

Ks

, d ,
cs

,
.
2.33.

[80,81,82]
. [80]
,
.

. [81]

.
, .
20 50 ,
Anodisc 0,02 m ( 20
200 ) Anodisc 0,2 m (

200

).

,
200 ,
,
8
,

(. 2.33).

. 2.34.
.



35

2.4
Merck Millipore,

MF-Millipore
(
)

Hydrophilic PVDF
()

PCTE
(, )
PER
(, )

,
,

25
105

,
/(2)
0,13

50

105

0,64

100

105

1,3

100

102

1600

100

25

2100

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. ,
,
36


.
,
,
Merck Millipore ( 2.4).
.
.
,
- . ,

.

2.5

,
, .
,
, ,
, ,
[83]. ,

[84].

, [85].


. ,

() [86].
,
,

[87,88,83].

(. 2.35). ,
37


.
: ,
, /
, .

SPG (Shirasu Porous Glass),

. ,

0,1 14 [89]. ,

-Al2O3
[90],
() [91].

. 2.35.

, 5 . [92,93]
(,
) .
.
, ,
1 ,

, [94,95].
,

,
(, ),

1
.

,
.
38

,
. [96]
120
500 . [97]
, ,

125 .
,
.
,
( ,
/ )

2.5
[73,98,99,100],
[101,102], [103],

[104,105] ,
.
- , -
.
,
- ,
-

, (. 2.36).
)

)
R

. 2.36.
- ()
c ()

39

[99] (. 2.36).
,

, ,

. [106]
.
2.37.


. 200

3-,

3-

. ,

. . 2.37
, .
,
-

. 2.38. ,
,
();
()

[103]

40

,
.
200

(TEOS)

(CTAB).

3,40,2
15 (. 2.38).
. 2.39.
B,
B12,

,
B ( 1 ),
B12 ( - 2,4 ),
( 4

()

-7,2 ).
0,2 /. ,


B12.

. 2.40.


( B B12),

,
(. 2.39).
pH ,
[107].
pH (. 2.40).

, , pH (. 2.41).
pH 3,
41

pH


.
,

. ,

(atomic layer deposition),


2.42

. 2.41.
pH

,

. ,


,
, -

.
2.42.

,

-

(, ).
,

(. 2.43).
42

[105]

. 2.43.


-

(. 2.44).

[108]

(IV).

-
,

. 2.44.

20
,

[109].

[105,110,111]. , ,
450-950,
, , , , [112].
( )
[113], [110].
, ,
(. 2.45). ,
,
, , .
,
43



.
.

,

[114,115].
[113]

. 2.45.

, ,
, .

624 ,

433 . ,
,

.
,
OH, -COOH
.
,
,
(electricallyswitchable membranes),
. [114]
(II) [Ru(bpy)3]2+
[Fe(CN)6]3-/4-.
25 ,
CVD, , ,
. ,

.
44

,

(. 2.46).
,
. ,
-0,5
36%,
29% ,
.
,

. 2.46.
[Ru(bpy)3]2

,

, 25 ,

45

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 =

(Pt)

022 ) GPC-60300 (V = 080, I = 03 A),


,
0,3

V=5-250

H2C2O4.

(Al)
. 3.1.

46

Heidolph PD5006 ,
Huber K6-CC1 0 .
,

.
.
,
,
, (mild anodization)
. ,
, 20 / CrO3 35 / H3PO4
60,
.
3.1.

0,3
(COOH)2
0,3
(COOH)2
0,3
(OOH)2

20

20

48 140

01

40

20

48 96

01

140

01

3.1 ,
.

(hard anodization)

: 0,5 /


.
. 3.2.

0,5
CuCl2 5% HCl.

47

,
15-25% H3 PO4

0.2M KCl


(. 3.2).
. 3.3.

, . 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().
, .
48

3.2
3.2.1

Leo Supra 50VP.
5-20 ; 10000 200 000.

Q150TES

(Quorum

Technologies).

,
ImageJ.
3.2.2

, . 3.4.
:
5-10 ,


100-.
25.

. 3.4.

,
,

F=

!V
, F
!P " S " !t

/(2), V , (), P
(), S (2), t ().
3.2.3
-

DiamondPyris

(PerkinElmer).

49

.
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
,
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