ACTUAL PROBLEMS OF CHEMISTRY AND PHYSICS OF SURFACE May 1113 2011 Kyiv Ukraine

POLYMERIC MATERIALS WITH CONTROLLABLE

STRUCTURE BASED ON POLYSTYRENE AND
MULTIWALLED CARBON NANOTUBES
Bolbukh Y.11, Gunko G.11, Prikhodko G.11, Tertykh V.11, Maciejewska M.22,
Gawdzik B.22, Skubiszewska-Zieba J.22
1Chuiko

Institute of Surface Chemistry of NAS Ukraine, 17 General Naumov Str., Kyiv 03164;
e-mail: yu_bolbukh@yahoo.com
2 Maria Curie-Sklodowska University, Lublin, Poland

Composites with nanofibers oriented in the proper way are of a great interest. In our opinion, it is possible to form such oriented structures inside of
polymer using CNTs as filler. For solving of this task different approaches could be applied, in particular with using of the magnetostatic field. But the
inherent insolubility in the most organic and aqueous solvents, poor chemical compatibility and tendency to aggregation that leads to nonuniform spatial
distribution of CNTs in the organic matrix are the major limitation to the processability of these structures, greatly hindering the wide application of carbon
nanotubes in the polymeric composites. Dispersability of nanotubes in the polymer is enhanced significantly after covalent or noncovalent
functionalization that can improve their compatibility.
DSC analysis
30

This presentation is directed to investigation of the structures

features of the filled with MWCNTs polymeric composites which
were obtained without and under influence of the magnetostatic
field by DSC methods and hardness measurements. Hardness of
the polystyrene films was measured at the applied load of 28.55
kPa.

70

110

150

190

230

270

30

-0,15

70

110

150

-0,17

-0,25

185

-0,27
-0,29

55

160
-0,2

-0,25

170

30

70

110

150

190

230

polySt /MWCNTs, magnetostatic field directed in parallel to the film plane.

polySt /purified MWCNTs magnetostatic field directed vertically to the film plane.

polySt/oxidized MWCNTs, magnetostatic field directed in parallel to the film plane.

polySt filled with oxidized MWCNTs. Composite obtained under influence of the magnetostatic field directed
vertically to the film plane.

10

30

70

110

150

190

Temperature ( C)

230

270

30

70

10

polySt filled with purified MWCNTs and treated with HCl. magnetostatic field directed in parallel to the film
plane.

217

polySt filled with purified MWCNTs and treated with HCl. magnetostatic field directed vertically to the film plane.

13

polySt filled with oxidized MWCNTs and treated with HCl.

14

polySt filled with oxidized MWCNTs and treated with HCl. magnetostatic field directed in parallel to the film
plane.

15

polySt filled with oxidized MWCNTs and treated with HCl. magnetostatic field directed vertically to the film
plane.

150

159

-0,32

13

85
-0,36

-0,24
-0,28

96

16

172

14

-0,32

15

-0,36

89

230

270

104
189
-0,26

45

17

-0,4

90

19
20

-0,3

21
76

-0,34

Temperature ( C)

Temperature ( C)

Temperature ( C)

0,08

25

260

22

185

235

285
274

-0,05 35

23

0,6

135

24
0,2

-0,22
190

-0,2300

350

400

DSC (mW/mg)

DSC (mW/mg)

170

135

235

450
420

-0,6
401
-1

0,55

285

26
27

0,35

218

448

174

-0,15

274

-0,2

172
190

-0,25

396

0,15
326
-0,05
300

350

400

-0,3

-1,4

-0,45

180

25

-0,35

-1,8

415

26

-0,65

27

24
-2,2

-0,4

428

65

80

130

180

230

280

0,5

300
-0,5

166

-0,22

-0,27

392
Temperature (oC)

Temperature ( C)

Temperature ( C)

-0,12 30

400
-0,85

Temperature ( C)

450

-0,25

170

22
23

185

239
59

243
-0,12

85

-0,1

DSC (mW/mg)

227

61

129

77

-0,4

85

218

18

70

DSC (mW/mg)

190

-0,22

154
DSC/(mW/mg)

210

DSC/(mW/mg)

DSC/(mW/mg)

-0,2

94
-0,28

181

350

400

450

500

-1,5

-2,5

96
28

-0,37

1
-3,5

28
29

29
30
-0,42

75

30
-4,5

424
o
Temperature ( C)

11

110

165

polySt filled with purified MWCNTs treated with HCl

11
o

Temperature (oC)

-0,24

-0,32

157

-0,18

DSC (mW/mg)

polySt/oxidized MWCNTs

100
71

-0,16

-0,17

270

39

-0,2

-0,02 35

230

193
-0,3

-0,4

DSC (mW/mg)

270

190

-0,25

-0,35

150

-0,2

-0,35

71

75

110

-0,3

-0,33

-0,42

polySt / purified MWCNTs

50

-0,31

DSC/(mW/mg)

DSC/(mW/mg)

DSC/(mW/mg)

-0,23

70

206

-0,21

-0,32

Polystyrene (polySt)

30
-0,1

-0,15

-0,19

Sample description
2

270

-0,15

Temperature ( C)

230

170

-0,35

Objects:
1. Purified MWCNTs
The MWCNTs used in this study were synthesized by pyrolysis of propylene on ferric
catalyst and purified by mix of HCl and HF for removing the residual catalyst and
amorphous carbon with following washing from acids by water.
2. Oxidised MWCNTs
MWCNTs were dispersed in water. and then the hydrogen peroxide was added to
suspension. Mixture was heating at 80 C under stirring for 47 h. The concentration of
H2O2 was 30%. The solid was filtered under vacuum and dried at 150 C obtaining the
oxidized nanotubes
3. Polymer composites
The composites were obtained by mixing of purified or oxidized MWCNTs with toluene
solution of polystyrene. The surface treating of MWCNTs was performed with hydrochloric
acid, liquid ammonia, and vinyltrialkoxysilane (a noncovalent and a covalent attaching) as
additives. The introducing of the filler into the polymer was performed via ultrasonic
dispersion of MWCNTs in polystyrene solution in toluene during 10 minutes. Then the
mixtures were formed in films on glass plates orientated parallel or normal to the magnetic
line of constant magnet with average induction 0.039 Tesla. The filling degree of
composites obtained was 0.1 wt%.

190

-0,1

Temperature ( C)

Hardness
Hardness values
values of
of the
the filled
filled with
with MWCNTs
MWCNTs polystyrene
polystyrene composites
composites which
which were obtained
obtained without
without (1)
(1) and
and
under
under influence
influence (2,
(2, 3)
3) of
of the
the magnetostatic
magnetostatic field
field directed
directed in
in parallel
parallel (2)
(2) or
or vertically
vertically (3)
(3) to
to the
the film
film plane
plane

140

polySt filled with oxidized MWCNTs and treated with NH4OH. magnetostatic field directed in parallel to the film
plane.

21

polySt filled with oxidized MWCNTs and treated with NH4OH. magnetostatic field directed vertically to the film
plane.

22

polySt filled with purified MWCNTs and treated with vinylalkoxysilane.

23

polySt filled with purified MWCNTs and treated with vinylalkoxysilane. magnetostatic field directed in parallel to
the film plane.

24

polySt filled with purified MWCNTs and treated with vinylalkoxysilane. magnetostatic field directed vertically to
the film plane.

25

polySt filled with oxidized MWCNTs and treated with vinylalkoxysilane.

26

polySt filled with oxidized MWCNTs and treated with vinylalkoxysilane. magnetostatic field directed in parallel to
the film plane.

27

polySt filled with oxidized MWCNTs and treated with vinylalkoxysilane. magnetostatic field directed vertically to
the film plane.

28

polySt filled with oxidized MWCNTs and covalently modified with vinylalkoxysilane.

29

polySt filled with oxidized MWCNTs and covalently modified with vinylalkoxysilane. magnetostatic field directed
in parallel to the film plane.

30

polySt filled with oxidized MWCNTs and covalently modified with vinylalkoxysilane. magnetostatic field directed
vertically to the film plane.

90
80
70
polySt

120
110
100
90
80
70
60

polySt

CNToxi(vinyl.Chem)

20

100

MWCNTs oxidised
(HCl)
MWCNTs purified
(NH4OH)
MWCNTs oxidised
(NH4OH)

polySt filled with oxidized MWCNTs and treated with NH4OH

110

MWCNTs oxidised

19

120

MWCNTs purified (HCl)

polySt filled with purified MWCNTs and treated with NH4OH. magnetostatic field directed vertically to the film
plane.

130

MWCNTs purified

18

130

CNToxi(vinyl.Phys)

140

CNTpure(vinyl.Phys
)

150
Hardness (MPa)

polySt filled with purified MWCNTs and treated with NH4OH.

polySt filled with purified MWCNTs and treated with NH4OH. magnetostatic field directed in parallel to the film
plane.

Hardness (MPa)

16
17

Carbon nanotubes pre-treatment with NH4OH was found to result in an increase of

the composite hardness. Treatment of MWCNTs with HCl provides the material
flexibility with sensitivity to influence of the magnetostatic field. Introducing nanotubes
modified with vinyltriethoxysilane leads to increase both the hardness and the thermal
resistance of the filled polymeric composite. The degradation enthalpy of this
composite is 757 J/g that exceeds enthalpy of another samples studied.
This work was partly supported by FP7 Marie Curie Actions People Project Hybrid
nanocomposites and their applications - Compositum, Grant Agreement Number PIRSES-GA2008-230790.




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2. Schmidt M.W., Baldridge K.K., Boatz J.A. et al. General atomic and molecular electronic-structure system: a review // J. Comput.
Chem. 1993. V. 14, N 11. P.1347-1363.

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3) 0,9 x 0,95 0,55; b 3,2

: i=2, 3, 4

4) 0,95 x 0,98 0,084; b 3,2 1010

, (3), (5), (6), (7) .

Davisil (.1).
3

V, /

.2

60

100

(R)

700

0,12

600

0,10

500

0,08

400

0,06

300
200

0,04

100

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() ()

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();

2 IR Specord 400;

;

N2 Quantachrome NovaWin2.

O
O

-
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S,
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3

Wmeso,
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950

0,33

0,18

0,51

0,67

0,95

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855

0,29

0,17

0,46

0,85

0,67

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600

0,17

0,18

0,35

2,84

1,08

--

830

0,25

0,20

0,45

1,12

4,02

--

630

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:
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2,42 Ma.
180 .

m,
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m,

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3
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0,6

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0,00

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0,5

0.3
0,4
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0.2

-0.04

0,3

2
0.1

-0.08

0.0
200

400

600

800

0,1

-0,10

0,0
-0,15

0,2

-0.06

1000

200

400

T, C

600

T, C

800

1000

(1), 2 (2) (3) () -- ().

(m)
()*

m,

c, /
(%)

290

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m,

c, /
(%)

0,21
27,6

405

280

0,44
34,4

-HNO3

270

--

m,

c, /
(%)

m,

c, /
(%)

0,08
10,6

545

0,15
19,7

735

0,32
42,1

400

0,09
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530

0,37
28,9

735

0,38
29,7

1,35
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400

1,50
35,7

525

0,78
18,5

680

0,57
13,6

400

1,21
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0,50
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725

0,30
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--

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 DETAMoO3

. . , . . , . . ,
. . , . .
. ..
. 17, 03164, , e-mail: nmo@online.ua
DETAMoO3

m/z
17
28
30

, . .

H2N-CH2-CH2-NH-CH2-CH2NH2MoO3 (DETAMoO3) SiO2

( ) .
DETAMoO3
MoCl5, MoOCl4, 2(acac)2, Mo(3-C3H5), Mo2(3-C3H5)
Mo(CO)6, MoO3
SiO2.

100

200

300

400

500

SiO2 (Silica Gel Davisil, 300 2/),

. 4. [NH3]+ m/z=17, [NHCH]+
DETAMoO3 (DETAMoO3/SiO2)
2
2.4 / , 0.12
(m/z=28) [NH2=CH 2]+ m/z=30 DETAMoO3
DETAMoO3.
DETAMoO3
DETA. DETA

DETAMoO3 250-390
NH=CH2
c
([NHCH]+ m/z=28) CH3NHCH3 ([CH3NHCH3 ]+
DETA DETAMoO3
m/z=45, [CH2 = NH CH3 ]+ m/z=44) (. 4).

H2N

H
N

NH2
m/z
18
28
30
44
56
73

NH4+ / H2O+
NH=CH+ / CH2=CH2+
NH2+=CH2
NH3+-CH=CH2
CH2=CH-NH+=CH2
NH2-CH2-CH2-NH+=CH2

. 1. - DETA
D E TA
D E TA M oO 3

120

M oO 3

80

NH

OH2

NH

NH2

+NH
+NH

OH2
+NH
3

Mo

O
O

+NH
3

NH

Mo
NH2

O
Mo

H2O

II

III

OH2

H2 O
+NH

H2 O

O
Mo
O
O

IV

1. DETAMoO3 ()
(- V).
MoO3
DETA, MoN
II-V ( 1)
100-240 . DETA II-V
-
N, ([NH3]+
m/z=17) ([NH2=CH2]+ m/z=30) (. 4).

DETAMoO3 SiO2

60
40
20
0
4000 3500 3000 2500 2000 1500 1000

cm

500

-1

. 2. DETA, MoO3, DETAMoO3

DETA SiO2
, . .

28
30
44
56
73

100

200

300
0

. 3. DET/SiO2 m/z 28, 30, 44, 56, 73

DETA SiO2
60-130 0C .

m /z
17
28
30

, . .

100

+NH

NH2

100

200

300

400

500

, C

. 5. [NH3]+ m/z=17, [NHCH]+ (m/z=28)

[NH2=CH2]+ m/z=30 DETAMoO3/SiO2
DETAMoO3 SiO2
. ,

II-V,
(50-100 )
(. 5). , -
DETAMoO3 SiO2
20-100
.




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100

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0
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2000

2500

3000

3500

4000
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,

1 -300 2 . 400 1. 600 ; 2

1 .; 3 1 . 200 ; 4 1 . 200 .

100

200

300
400

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119991 , -1, , 31
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,

,
(Purolite Rohm and Haas).
.
.

PFA 600/4740

PFA 460/4783

A 500U/4994

Ambersep 920UCl

Amberlite 910UCl

S-950

S-957

A100/2412

A 140

S 984

104

107/150

, /
400
350
300
PFA-600/4740

250

Ambe rlite 910UCl

200

S-950
S-957

150

A100/2412

100
50
0
0,00

0,05

0,10

0,15

0,20

0,25

0,30

0,35

CSO4,

. 1.
- .
Em, /
450
400
350
300
250
200
150
100
50
0
0,00

PFA-600/4740

S-957
Ambersep 920UCl
S984

0,10

0,20

0,30

0,40

CCl , .

. 2.
- .
/0
1,0
0,9
0,8
0,7
0,6

(=1,5-2,0),
0,8-0,9 /.
- 0,01-0,32 -/.

S-957.
()
400 /.
4-5
. - -
. 1 2.
(.3)

,
,
,
S-957 340 / (88 /),
2-3,5 ,
.

0,5
0,4
PFA 600/4740

0,3

S-957

0,2

0,1
0,0
0

100

200

300

400

500

600

700

800

900

V, ..

. 3.
PFA600/4740 , S-957.
, S-957
-

S-957

,
,
, .

 (II) :
,
.., .., ..
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, 65026, , . , 2.
, (, , )
, ,
,
, (C, PH3, SO2) (O3, NO)
.
1


, .%

SiO2
Al2O3
Fe2O3
TiO2
CaO
MgO
K2O-Na2O
(-)
-
71,5
13,1
0,9
0,5
3,44
0,68
3,03
(-)

80,0
4,0
3,0
5,00
2,00

63,6
19,6
10,5
1,8
(-(1))

(.1) SiO2/Al2O3; -(20)>-(5,5)>(1)*(3,2). , . ,

(80-85%), -, . - -, -
; ( = 49) , ,
(.1).

I/I 100

100

100

75

75

75

50

50

50

25

25

25

0
5

10

15

20

25

30

35

40

45

10

15

20

25

30

35

40

45

10

15

20

25

30

35

40

45

.1
) -; ) MnCl2/- ( ); ) MnCl2/- ( ) -; SiO2; MOR; MnCl2xH2O; MnxOy.

, ,
.
(. 2) ( ) -(100)>-
(120)>-(1)* (140) .
2

,
(m
,
/)
,
, %
H2O
110

25-110
25-500
25-110 m1
25-500 m2
/
/
-(1)*

140
3,2
2,5
6,4
0,025
0,064
0,039
2,16
-

120
2,0
1,6
7,6
0,016
0,076
0,060
3,30
-

100
1,6
1,8
4,0
0,018
0,040
0,022
0,012
- ,
- . 0,93 1,89
/ . (II)
, ..
/s. . ,
, (.2).

, /

100

.2 ( C 3 )

80

()

MnCl2/: 1 - (CMnCl2 = 1,210-6 /);

60

-; 3 -(1)*; 4 - (CMnCl2 = 1,210-4 /) ( C 3 =

40

100 /3; = 20 )

20
0
0

100

200

300

400

500

600

. (%) MnCl2/-
(73) > MnCl2/-(1)* (44) > MnCl2/- (28). ,
MnO2. , , , ,
Mn2O3 MnO2.


:
.. 1, .. 1, .. 2, .. 2
1

.
. .. ,
, . ;
;
.
. .. ,
, .

,

.
,
, ,
, 5-10
(~1,5 ), .
,
,
,
.
, 1-10 ~98 %
,
, .
, Ag8,
5 (. 1).
, ,
.

Ag8[] Ag8
Ag8(OH)2
24 /,
.
Ag8(OH),
Ag8(OH)3 Ag8(OH)4.


.

(. 3).
Ag8,
- .
Ag8 Ag8(OH)4 . 4
5.
-

15

15

22

24

. 3. Ag8 ()
Ag8()2 ()
[].
Ag8

Ag8OH

Ag8(OH)2

Ag8(OH)3

Ag8(OH)4
. 4.

Ag8

.
22 /.

. 1. Ag8
.
,
()
().

6-7.

() - B3LYP SBKJC
, Ag8

(. 2). -
,
-- .
. 5.

Ag8()4


.
6 /.

. 2.
Ag8 . 15 /.

,
, Ag8,
Ag8(OH), Ag8(OH)3, Ag8(OH)4

.

,
0,35. ,
,

.


Evgenii Sergeyevich Brikov
-
docent of the department of the micro- and nano-technologies

Tyumen state university
E_mail: brikov@mail.ru
544

.
UDC 544

Influence of a magnetostatic field with middle value on the formation of the

magnetite nanoparticles in the aqueous ion-exchange precipitation reaction
with the surplus of the alkali.

. :
. :
. ,
, ( D 70 H = 5940 ),

.
, :
,
.
Abstract
In report is presented results of experiments about influence of magnetostatic field with middle
value on the aqueous ion-exchange reaction of magnetite precipitation in alkaline environment. Shape
and size nanoparticles is investigated by methods of probe atomic and magnetic microscopy. Diffraction
and diffusion X-rays on synthesized powders are investigated. It is revealed that when field is being
increased, then deflection of sizes from average is being decreased and shapes are being approached to
forms of disks ( D 70nm when H = 5940Oe ), on curves of diffraction at small angles a diffusion
background is being increased and structural peaks is being disappear. Some preliminary explanations of
physical mechanisms of possible influence of a magnetic field on forming of nanoparticles are
represented; in particular: influence of a magnetostatic field on ions recombination in reaction and
characteristic properties of condensation stages are analyzed.
:
, ,
, , ,
, ,
, ,

 , .
Keywords:
magnetostatic field with middle value, aqueous ion-exchange reaction, magnetite precipitation, alkaline
environment, probe atomic investigation, probe magnetic investigation, diffraction and diffusion X-rays
on nanopowders of magnetite, sizes and shapes of magnetite nanoparticles, mechanisms of nanoparticle
forming, ions recombination in a magnetostatic fields, condensation stages.

, ,
[1,2,4].
2-
Fe3O4

)
[3]:

2 Fe( NO3 ) 3 + FeSO4 + 8 NH 4 OH = Fe3 O4 + 6 NH 4 NO3 + ( NH 4 ) SO4 + 4 H 2 O

(1)

,
: 5940 49,4070 44,0
PH8-9, 80 90 C . , :
CuK (-7);
(, ) CoCr :
NSG01/Co/15 (NTEGRA AURA),
( P = 160 ) ,
().

Fe3O4 ()
, , , 20 < 2 < 33
130 168 cps H ,
CuK Fe,
[3]. ,
, , H = 5940 49Oe
(. . 1, .:1).
(. .1):
1:0,75:0,5 ( ; : V H = 0 = 1 ).
, ,

(, h = 6 , D = 69,8 , D = 4,3

H = 5940 49 ), . . 2 . 2,3,5,6,8,9,11 [3].

(. .4,7,10) [3].
, H = 5940 49
()
[3].

Vereda F.,
() , [2].


:
,
, ( 10 )

- , ,
( ).

, , 1- (1)
, 2- (1).


,
.


[3,5,6] :
Fe( OH ) 2 Fe( OH ) 3 [7,9]; - [7,8,9]; -
( -
) [10, 11];
[12] ( ).
,
,
.
:
.
1- ()
.

.
2- .
, .
,

.

, ,
[7, 8, 9].


(
).
( ).
, ,

.
(), ,
, .

[10, 11].
( OH-)
.
,
OH-
[12].
, ,
,
.
2- (1), ,

 .
.
,
, , PH
: (..
);
(
OH-),
(, ,
).

[5,6]. ,

( )
:
g - : H 3 10 3 .
()
, : H 50 .
,
( H 0
, ):

H = g A S A H 0 + g B SB H 0 +

A j I aj S A +

Ak I bk SB J ( r ) 12 2 S A SB ,

(2)

g A g B - g - () A B , = e 2me c - , A j , Ak j- A k- B , S , J (r ) - .
(2): A B H 0
,
.
A B . - ,

S A , S B . H 0
g H 0 , ,
.
( ,
) [6].
,
( g).
,
( ). 2- (1) :

[7,8].
OH-,
(
),
( ). ,
,
,
. ,
.
[10, 11] Ph
, ,
, () . :

 ( )
,
,
( , ), , ,
.
[12]
Ph ( [2]),
(
, :
):
Ph ,
, ..
, , (. . 12 [4]).
:
: ..
( ,
).

H = 5940 49 - :
[4],

. ,

, ..
[3, 4].
, , :
.

(1)
,
[2,3].
,
.

, [5, 5-2],
,
, ; ;
, , .

: .. , .. , .. , .. , ..
.. .

1. .., , (1971);
2. F. Vereda F., J. de Vicente, R. Hidalgo-Alvarez, Langmuir, 23, 3581 (2007);
3. .. , .. , .. , .. , .. ,
:
- , . .. . : , 67 (2010);
4. .. , .. , .. , .. , , 74(6), 539 (2005);
5. .. , .. , .. ,
, (1978);
6. .., .. , .. , , 155 (1), 1988;
7. .. , ,
(2003);

8. .. , .. , , 113 (6), 2193 (1998);

9. .. , , 12 (11-12), 525 (1942);
10. .. , .. , , 35, 479 (1958);
11. .. , .. , , (1970), . 509;
12. .. , . . . ., 3, 355 (1937);
1. ,
Fe3O4 (FeOFe2O3). (I)
2: 20o - 33o (7) [3]. V/V1
%, V1 .

H,

V/V1, %

2, o|I, /
I, /
1.
0
130
32.9|175;32.2|172;30.75|178;30.2|173;
100
28|217;27.1|184;
26.9|186
2.
407044
160
30.1|206;30.75|210;28.75|227;
755
28.1|240; 21.5|181
3.
594049
168
30.25|177;30.75|170
505

2. Fe3O4 (FeOFe2O3),
(Ntegra Aura).
H,
2-

;

3-
<d1/d2>; ( , N).
,
d1xd2xd3,
1.
0
( )
60x50x20
; 1.700.45; (25)
2.
407044
( )
50x40x2
; 1.720.28; (14)
3.
594049
( )
100x100x5,5
; 1.360.28; (30)

 1. 2 () I (/) CuK Fe3O4 (FeOFe2O3), (1)

: ). H=0A/ (0) ). H=324000/ (4070);
). H=473000/ (5940). 7 [3].

2. d ()
Fe3O4 (FeOFe2O3) ( 2- ),
(1) [3].

 3. 2- ,
() ,
H=473000/ (5940) [3].

4. ,
() ,
H=473000/ (5940) [3].

 5. 3- ,
() , H=473000/
(5940) [3].

6. 2- ,
() ,
H=324000/ (4070) [3].

 7. ,
() ,
H=324000/ (4070) [3].

8. 3- ,
() , H=324000/
(4070) [3].

10

 9. 2- ,
() ,
[3].

10. ,
() , [3].

11

 11. 3- ,
() , [3].

12. Hc (
) [4]: 1 , 2- , 3
, 4 . 5 (
) [4].

12

 ,
2,
NaCl(100).
.. , ..
. ..
. 17, 03164, -164, e-mail: snigur@isc.gov.ua
,
. -
, ,
(. 1-2) [1].

. 1. (2x1)- CO / NaCl(100)
.

. 3. C
CO/NaCl (100)
(p s ).

. 2. (2x1)-
CO2 NaCl(100).

,
2 NaCl (100).
, ( .. ,
) [2] ,
CO ,
(. 5).
- ,
, ,
(. 5) [3].
. CO2/NaCl (100)
. 2
, , ,
(. 6). ,
, Heidberg
Ewing (. [4]).

. 4. C
CO2/NaCl (100)
(p s ).

[5],
/NaCl (100), s-
, (. 3).
,
CO
(. 1). ..
.
(. 5).
CO2/NaCl (100) (. 2), ..
CO2 ,
( - . 4).

12 (. 5, . c 5).

. [6]

- ,
.

2x1 /NaCl (100) [7].
, ,
,
, s- - ,

.
[1] V. M. Rozenbaum and S. H. Lin, Spectroscopy and Dynamics of Orientationally Structured Adsorbates (World
Scientific Publishing Co. Pte. Ltd., Singapore, 2002).
[2] A.V. Snigur, M.L. Dekhtyar, V.M. Rozenbaum. Orientational surface structures of simple molecular quadrupoles. //
International symposium devoted to the 80th anniversary of academician O.O. Chuiko Modern problems of surface
chemistry and physics. Book of Abstracts. Kyiv, Ukraine, 18-21 May 2010, p. 245-246.
[3] A.V. Snigur. Spectroscopic manifestation of peculiarities of orientational ordering in adsorbate monolayer under low
temperature.
Orientational phase transition in CO/NaCl(100) monolayer. // X International Conference on Nanostructured Materials
NANO 2010. Book of Abstracts. Rome, Italy, 13-17 September, 2010, p. 169.

. 5.
AM1

NaCl(100)
CO
() CO
() ( ).

()

()

. 6.
AM1

NaCl(100)
CO2
()
CO2 () (
).

()

()

[4] A.V. Snigur, V.M. Rozenbaum. Spectroscopic manifestations of orientational phase transition in adsorbate monolayer
// Mol. Phys. 2009. 107, No 22. P. 2367-2372.
[5]. .. , .. . //
. 2003. 95, 5. . 734-738.
[6] .. , .. .
// ,
. . , 20-22 , 2009, .
91-92.
[7] J. Heidberg et al. Fourier-transform infrared spectra of CO adsorbed on NaCl(100): structural changes at low
temperatures // Surf. Sci. 1992. 269/270. P. 128134.

Y_O_V@yahoo.com

-
.., ..
- . ..



, - :
, , ..

/
(d < 100 ).

(S<10 2/, d>(100-200) ):

- ;
- ;
- ;
- ..

, .%

/3

( ),

( ),

CeO2
ZrO2
CeO2-ZrO2 (Ce/Zr-4/1)
CeO2-ZrO2 (Ce/Zr-1/4)

4,0
1,5
2,1
1,2
3,9
2,1
2,2
2,6

YOOH
ZnO
AlOOH
LaOOH (100 oC)

0,60
6,00
6,00
3,60
3,00
0,35
3,00
0,50

2
1
2
1
35
40
6
5

20

LaOOH (20 oC)

CuO
Ag-SiO2
Ag
SiO2

0,85
0,18
0,051/0,19
0,025
35,00

1,9
2,3
4,2
15,0
1,3

4
4
10
2
7

30
21
-

(1),

(
,
,
)

hs

hw,

.

(2),

(
,
)

(3),
(4),


, ,

( ,
(, ) .)

- . CuO ( )
, .

.

CuO

CuO
Al2O3

( 10 )

RAMAN SPECTRA OF NANODISPERSED CARBON IN CERAMICS OF SYSTEMS TIB2TIB2-C

Kazo I. F., Naumenko A. P., Mavlanova O. D.
Taras Shevchenko National University of Kyiv, Faculty of Physics,
60, Volodymyrs'ka Str., 01601 Kyiv, Ukraine
kazo@ukr.net, a_naumenko@univ.kiev.ua, anaskor@i.ua

1. Introduction
Formation carbon clusters and fullerenes can occur in many processes at which fixed carbon is allocated in a separate solid phase [1]. Carbon atoms
possess unique ability to form bond of various types (sp1, sp2 and sp3) under constraints which the carbon atom can be connected to two, three and
four neighbor carbon atoms accordingly. Owing to this existence of various spatial carbon structures graphite, diamond, nanotubes, etc. is possible.
The different structures are probable in a material, because of all types of carbon bonds and a ratio of their quantity, atomic arrangement. The present
classes of compounds of products of reaction is important ording to the physical characteristics along with high hardness, wear resistance, are
characterized corrosive and chemical stability [2-4]. From this point of view, the consideration of phases of carbon which are allocated in ceramics at
solid synthesis titanium boride from the titanium carbide and boron carbide is interesting. The purpose of the given work is research and the analysis of
Raman spectra of ceramics of system TiB2-C; in particular, establishing the presence of predetermined carbon clusters.
2.Experimental
Manufacturing of initial samples of ceramics, which containing carbon, carried out similarly to a way described in work [8, 9]. Manufacturing of samples
was made by methods of sintering and hot pressing (HP) on installation with resistive heating, without a protective atmosphere with temperature modes
from 1100 to 1800, external pressure from 0 to 30 MPa and soaking time with from 60 to 2400 s in graphite crucible. The mechanical treatment of
cooled samples on a abrasive paper was provided for deleting 0.5 mm of a superficial layer, then they were crushed up to medium-sized grains 1 micron.
Then liquid extraction carbon clusters of a powder were carried out in toluene during 7-14 days at a room temperature. A solution precipitated on a
substrate of monocrystal silicon of orientation (100). Toluene drove away under vacuum at pressure 13.3 Pa, consequently the film samples were formed.
The received film and powder samples were investigated by a Raman spectroscopy method (RS). The spectra were detected by an automated double
spectrometer DFS-24 (LOMO, Russia), equipped with a cooled photo multiplier and registration system working in a photon counting mode. Particularly
several lines of
Ar+ laser with the wavelength of 514.5, 488 and 476.5 nm and power of ~50mW were selected with a pricm located outside of laser resonator and a
cylindrical lens was used to focus light in a 100.1 mm2 spot.

The earlier mass-spectroscopy researches [6,8] have shown evidence in similar samples presumably hydrogen-carbon clusters 20n, where n=10, 20.
For this reason, from our point of view, it is expedient to carry out theoretical modeling of cmall carbon polyhedrons (like 20) spectra and carbon
polyhedrons spectra possessing a hydrogen atmosphere (like 2010, 2020) and retrace influence of this atmosphere on shift of frequencies of the basic
clusters vibrations.
For geometrical construction of clusters and calculation of their oscillatory spectra software package Gaussian 03 (by method RB3LYP/6-31G) has been
used for calculation of vibration clusters spectra. Raman spectra of some possible carbon clusters n, where n amount of atoms in clusters, have been
computer simulated in work. Raman spectra of clusters 20, 2010, 2020 which represent only carbon cluster, and also cluster in a hydrogen cloud and a
rarefied hydrogen cloud, accordingly; they have the following features. We got such results using technique described in [18-19].
a) All three spectra contain two frequency bends: up to 900 cm-1 and from 1100 up to 1600 cm-1, except that clusters, which have a hydrogen cloud, they
have high-frequency area in a range about 3000 cm-1, that corresponds hydrogen cloud oscillation, at which carbon core almost immovable (Fig.2);
b) The breathing mode is observed in all three spectra - 789, 716, 643 cm-1 with shift in low-frequency area with growth of amount of atoms.

3.Results and discussion

The total spectrum, received from several samples, is shown on fig.1.

Some facts follow from our more detailed analysis of spectrum:

researched spectra of samples contain bends which correspond
to a graphite phase which intensity insignificantly grows from film up
to powder samples;

Intensity, st. um.

*
462
494

948

1 0 00

in the average frequencies area of a spectrum bends of high

intensity (462, 494, 745, 792, 948 cm-1) are found out, their
unequivocal interpretation is complicated. For an establishment of
the nature of bends of high intensity it is necessary to carry out
additional researches.

1 60 1
1 3 70
745 792

5 00

1533
1465

1117

10 0 0

1500

F req u en cy sh ift, s m

-1

Figure 1. Total, received from several samples a Raman spectrum of ceramics systems
T2- at room temperature is shown. The cut line (*) corresponds to the laser compelling
radiation, and by virtue of high intensity cannot be submitted in figure.

20

Intensity, st. um.

800

12 00

1600
-1

Figure 2. Theoretically calculated Raman spectra for carbon clusters are

shown

20

20

10

20

10

F re q u e n c y s h if t, s m

(C H 3)2

20

20

Raman peaks
received from
experiment (cm-1)

Raman peaks
calculated
theoretically (cm-1)

Fig. 3. Modeling representations of clusters geometry 2010(), 2010(b) and 20(3)2 are shown,
dark spheres - atoms of carbon, light - atoms of hydrogen.

The cluster 2010 modeling was carried out by two geometrical representations: 2010 (a) and 2010 (b) (see fig. 3); in the first case hydrogen cloud is
concentrated by a radial part of dodecahedron, and in the second - in polar positions. In theoretical spectra of the given models the following divergences
were observed:
) in b-cluster occurs one of tangential mode degeneration (~200 cm-1), that associated with increase of rigidity bonds in radial area;
) shift of a breathing mode in a-cluster case to cluster 20 come to 73 cm-1, and for b- cluster - 371 cm-1; that following from a picture, it is possible to
explain formation tube-like cluster in which the breathing mode is considerably simplified, and oscillation hydrogen cloud is forced concerning carbon to a
core, in the second case the hydrogen cloud fixes a radial part bonds interfering with oscillation. Despite of these features spectra contain all basic groups
of tangential oscillation, with insignificant shift of frequencies and activities, oscillation hydrogen clouds almost identical.

Thus, from the submitted results we can assume, that those observable Raman bends quite can be explained by heterogeneous hydrogen-carbon clusters
presence in samples, which based on chemically active 20.

Table 1. Theoretical and experimental frequencies of Raman spectra

400

in film samples, as well as in powder, peaks of low intensity are

registered in area which corresponded tofullerene 60 that is
evidence of clusters synthesis during topochemical reaction;

A cluster
spectrum

1.

948

947

20

2.

459.9

464

20

3.

773.56

775

20

4.

1344

1358

20

5.

708.31

706.46

2010

6.

1176

1174

2010

7.

1247

1242

2010

8.

636

638

2020

The cluster kind as 20(3)2 was also considered (see fig. 2), that production by connection of two methyl groups to cluster 20. The spectrum of this
cluster has similar character to a spectrum of cluster 20, the breathing mode come to 405 cm-1, i.e. at the expense of polar methyl groups connection in
cluster two opposite atoms are rigidly fixed, that leads to similar shift of frequency of vibrations. Tangential modes are deformed, and for them shift of
frequencies about 200 cm-1 in relation to 20 is observed.
Thereby, given Raman spectroscopic researches results not only have confirmed presence in synthesized ceramics fullerenes 60, but also gave strong
reasons to assume existence in ceramics hydrogen-carbonic clusters such as 20n, where n = 10, 20.

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: . / . . , . . . .: , (2005). 688 .
. . -// , 2002, .71, 6, - . 507-532.
.., .., .., .. // . 2, (1998),- .5-14.
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.., . ., . ., . . TiB2-.
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Kazo I. F., Makara V. A., Mavlanova O. D. The Structural status of carbon in solid-state synthesis ceramics.//
2009, 21-23 , (2009), , , .2, . 275 -279.

.., .., .., .., ..
, 03164, . , 17
e-mail: v.slesarenko@mail.ru

() ,
, , [1].
.1.

[2-4].
- 3 ().
( 123) [5], [6],
SBA-15 .
(
870 -1) [6].
- . .2., , ,
, . 1.

1,4

1,2

1,0

V [cc/g]

V [cc/g]

0,8
0,6
0,4

0,8

1,0

. 1.

0,6
0,4
0,2

0,2
0,0
0,0

0,2

0,4

0,6

0,8

0,0

1,0

0,0

p/p0

0,2

0,4

0,6

0,8

.3.
() () -

1,0

p/po

. 2.. -

. 2.. -
-

0,2

0,0

- , ,
. ,
. , ,
, (. 3. , ).
, -. ,
-, .
- . ,
, .
(. 4. , ) ,
.

1.

S. ,

886

2/

V,
1,28

443*

465

3/
0,84*

0,94
443*

0,88*

d,
4,6
7,8
4,6
7,6

. 1,

.

,
: .

.

* , -

-0,2

-0,4

-0,6
100

200

300

400

500

600

700

800

900

1000

. 4..

0,2

0,0

-0,2

-0,4

100

200

300

400

500

600

700

800

900

1000

. 4.. -

.

,

.

1. .. .: , 1985. 32 ..
2. A.Bordoloi, F.Lefebvre, S.B.Halligudi Selective oxidation of anthracene using inorganicorganic hybrid materials based on
molybdovanadophosphoric acids // Journal of Catalysis - 247 2007 - . 166175.
3. Y.Xuemin, L.Jiaheng, L.Dan, G.Liping, W.Yangchun Oxidation Reactivities of Organic Sulfur Compounds in Fuel Oil Using
Immobilized Heteropoly Acid as Catalyst // China Academic Journal - Vol. 22 No.2 . 320-324.
4. N.K. Kala Raj, S.S. Deshpande, Rohit H. Ingle, T. Raja and P. Manikandan Heterogenized molybdovanadophosphoric acid on aminefunctionalized SBA-15 for selective oxidation of alkenes // Catalysis Letters - Vol. 98, No. 4 2004 . 241-246
5. Sujandi, S.Park, D.Han, S.Han, M.Jin, T.Ohsuna Amino-functionalized SBA-15 type mesoporous silica having nanostructured
hexagonal platelet morphology // Chem.Comm. - 2006 - . 4131-4133.
6. .., .., .. //
, ,
20-22 2009, , , . 100-101.

,
25- . ..

11-13 2011
-

 .., .., .., .., ..

. ..
119991 . , , . 31, . 4
- mail: TMSerdyuk@mail.ru 952-00-65

Intens. [a.u.]

-
x10 4

1.2

1.0

.1

172.466

0.6

120.139
0.4

212.677

320.074

0.2

421.361

288.678
92.992

444.375

380.222

264.908

528.677

0.0
100

150

200

250

300

350

400

450

500

550

Intens. [a.u.]

m /z

212.635

8000

.2

6000

147.989

4000

577.302

119.939
320.020
2000

421.287

611.679

252.745

94.820
0
100

200

300

400

500

600

700

m /z

Intens. [a.u.]

- ()
-.
, .
, .
. () / ().
-
, 1,2 . 0,05
1 H2SO4 50 /.
: , ,
, : ITO ( SnO2 In2O3,
), Au, Pt.
, 11 510-3
. 24 .
, , .
- - /
(). - RP Pep Mix Ultraflex Bruker,
330 110 . - .
. - 80 - 95 % .
--4- .
, .
-. .1 - , Au . m/z = 213, 320, 421 529
, , .
. 2 - , ITO .
(m/z = 213), (m/z = 320) (m/z = 421) .
(m/z = 612).
Pt (m/z = 212), (m/z = 320) (.
3). (m/z = 529).
,
, , ,
.
. ,
, . ,
, , .
, -
. - m/z = 213.
. 4 - ,
, .
, , , , (m/z = 213), (m/z = 318)
(m/z = 422).

, .
, , , ,
, , ,
. , Pt Au , , ITO .
, , , ,
.

0.8

x10 4

211.791

1.2

1.0

0.8

320.179

0.6

421.509

299.090
0.4

342.267

146.498

0.2

528.781
172.545
120.092

244.879

393.416

292.043

449.614

507.735

94.906
0.0
50

100

150

200

250

300

350

400

450

500

550

m /z

.4

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11 13 2011
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-mail: borysenko@naverex.kiev.ua
1

, , , , ,
.
- ,
. ,
CeO2 CuO SiO2 -
.
Ce-, Cu-
, . -
Ce-, Cu- . 1. 450 - 650 2/
= 800 , (. 2). CeO2 CuO 1:1.

CeO2/SiO2, CuO/SiO2

S, 2/

700
600
500
400
300
200
100
0

CuO/SiO2
CuO/CeO2/SiO2
CeO2/SiO2

. 1. - Ce-, Cu-
.

200

400
600
T, C

800

1000

. 2.
.

. 3 Ce-, Cu- , . ,
CeO2 (2 .%), CuO (2 .%).
(. 1), -, , CeO2/SiO2 CuO/SiO2 1:0; 1:0,1; 1:0,5; 1:1
0:1. , 60 , 900
() = 1150 (. 3).

. 3. Ce-, Cu- , (1-5)

(6). - 20, 40 , - 2 .
CeO2/SiO2 CuO/SiO2 1:0 (1); 1:0,1 (2); 1:0,5 (3); 1:1
(4); 0:1 (5, 6).

- 3600 -1, O-H (. 4). -

. (1-5) (6).

1
2
3
4
5
6

, %

100
80
60
40
20
0
4000

3500

3000

2500

2000

4,0
3,5
3,0
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2,0
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250
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. Cu-,
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,

=575 .

6
5
3 4
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1
200 300 400 500 600 700 800 900

. 4. - () () Ce-, Cu 2 .

, ,
( 46/11-).

Surface Chemical Oxygen and Nitrogen Functional Groups Modification of CNT

a

O. Stasiukb, N.Kovala, O.Bakalinskaa, N.Kartela

National University of Kyiv-Mohyla Academy, 2 Skovoroda st., Kyiv, 04070, Ukraine
b
Chuiko Institute of Surface Chemistry of NAS of Ukraine,
17 General Naumov st., Kyiv, 03164, Ukraine
e-mail: bakalin2008@ukr.net

INTRODUCTION
The potential of carbon nanotubes (CNTs) in mechanical, electrical,
electronic, thermo-mechanical, optical and sensoring applications is
nowadays undisputable. One of the key factors needed to convert
such a potential into a reality is the achievement of adequate CNT
dispersion. For polymer composites applications, CNT
functionalization is needed to improve dispersion as well as to
promote interfacial bonding and thus CNT-copolymer property
transfer. Wet chemical oxidation and doping of nitrogen
is
recognized as an efficient method for CNT purification, promoting
dispersion and surface activation at the same time. Oxygen
containing functional groups can be introduced on single and multiwalled carbon nanotubes by liquid-phase modification procedures.
Acid treatment is one of the most commonly employed methods for
CNT oxidation, given its versatility, efficiency and potential to scaleup. The most common reagents used for liquid-phase oxidation
treatment are HNO3, H2SO4, and KMnO4. The doping of nitrogen has
received focused attention because significant changes in hardness,
electrical conductivity, and chemical reactivity have been
theoretically predicted and experimentally observed. The CNT can be
treated by plasma gaseous NH3 or N2 ranging from 400 0C to 800 0C
for 2 h or by (NH2)2CO heating to 800 0C for 1 hour [1,6].

MATERIALS AND METHODS

For doping of oxygen atoms to the CNTs, they were oxidized by solution of
HNO3. For the preparation of CNT oxidization form (O-CNT) 1,5 g of CNTs
were boiled during 1, 2, 3, 4 and 5 hours in the HNO3 solution ( = 34 %, V =
200 ml). After cooling of mixture to the room temperature CNTs were washed by
the distilled water to the neutral pH value. As result, oxygen groups bonded to
aromatic rings on CNTs (Fig.1) [2,3].
For doping of nitrogen atoms to the surface layer of carbon nanotubes (N_CNT),
preliminary oxidized CNTs were saturated with solution of urea, dried out, placed
in a quartz reactor through which skip an argon and heated at the temperature of
800 0 during 1 hour. As result, nitrogen groups bonded to aromatic rings on
CNTs (Fig.2) [4].

Fig.1. Simplified schematic of some acidic surface

groups bonded to aromatic rings on CNTs

Fig.2. The nitrogen functional forms possibly

present in carbonaceous materials

RESULTS
ANALYSIS OF SURFACE FUNCTIONAL
GROUPS
The chemical titration method, proposed by Boehm, was used for
analysis of surface functional groups. The amount of oxygencontaining groups (carboxyl, lactonic, and phenol) on the CNTs was
determined by adsorption neutralization with NaHCO3, Na2CO3, and
NaOH solutions, respectively. The basic group content of the CNTs
was determined with 0.05 M HCl. To 0.05 g of CNTs was added 50
ml of 0.05 M reagent solution, dispergated in an ultrasonic bathhouse during 15 min. The suspension was shaken off during 24
hours, filtered solution of reagent from a suspension, for what used
hydrophobic filters ("MF-Millipore", MCE Membrane 0.20 m).
The alkaline reagents were determined by titration of 0.05 M HCl
solution, HCl acid - by 0,05 M NaOH solution [5].

It was shown that the total amount of oxygen-containing groups is proportional to

time of oxidation (Fig. 3). Amount of phenolic groups increases with time oxidation
duration. The amount of lactone and carboxyl groups does not change substantially.
After nitriding of CNTs alkaline groups appear on their surface. The general
tendency of increase of amount of oxygen-containing groups does not change with
time of oxidation, however, in comparing to the O-CNTs, the amount of phenolic
groups diminishes from 2th to 10 times and, accordingly, the total amount of
oxygen-containing groups diminishes (Fig.4). More credible than all, alkaline
groups appear not only at interaction of urea with a surface, and also due to
chemical transformations of phenolic groups on the groups of alkaline character.

CONCLUSION
The selected methods of CNTs surface modification allow to carry out their
effective functionalization, correlation is founded between time of CNTs
modification and amount of functional groups.

LIST OF LITERATURE

Fig.3. Distribution of oxygen-containing

functional groups on the surface of O-CNTs.

Fig.4. Distribution of oxygen-containing and

alkaline functional groups on the surface of N-CNTs.

ACKNOWLEDGMENT
Ph.D. Sementcov Yu.I. and Zhuravsky S.V. for CNT.
FP7-PEOPLE-IRSES-230790 COMPOSITUM, Project Hybrid nanocomposites and their applications for supporting.

1. Chemical oxidation of multiwalled carbon

nanotubes / V. Datsyuk, M. Kalyva, K.
Papagelis [etc.] // Carbon. 2008. Vol. 46.
P. 833-840.
2. Controlled oxidative cutting of singlewalled carbon nanotubes / K.J. Ziegler, Z.
Gu, H. Peng [etc.] // JACS. 2005. Vol.
127. P. 1541-1547.
3.Oxidation of multiwalled carbon nanotubes
by nitric acid / I.D. Rosca, F. Watari, M. Uo
[etc.] // Carbon. 2005. Vol. 43. P. 31243131.
4. Maldonado S. Structure, composition, and
chemical reactivity of carbon nanotubes by
selective nitrogen doping / S. Maldonado, S.
Morin, K.J. Stevenson // Carbon. 2006.
Vol.44. P. 1429-1437.
5. Boehm H.P. Surface oxides on carbon and
their analysis: a critical assessment / H.P.
Boehm / Carbon. 2002. Vol. 40. . 145149.
6. Kim H., Sigmund W.M. Modification of
carbon nanotubes // American Science
Publishers. 2004. P. 619631.



.. , .. , ..

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119991 , -1, , 31
/ (495) 335-92-88, nnekrassova@gmail.com
.



PFA 600/4740

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350
300
250
200
150
100
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450
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300
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0,52

195-440

280

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0,25

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285

0,15

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180-405

270

0,21

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100

150

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250

300

350

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20

40

60

80

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,
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100 120 140 160

20

40

60

80

100 120 140 160

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160

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[1] Optical absorption of Ag oligomers dispersed within pores of mesoporous silica. Huijuan Bi, Weiping Cai, Huazhong Shi, Xiong Liu./ Chem. Phys. Lett. 57 (2002) 249254
[2] Ag nanoparticles deposited onto silica, titania, and zirconia mesoporous films synthesized by solgel template method. G. V. Krylova Yu. I. Gnatyuk N. P. Smirnova A. M. Eremenko V. M. Gunko / J
Sol-Gel Sci Technol (Special edition)

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60

80

:
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2000
1000

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60

80

100

120

140

160

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(044)424-35-67, e-mail: t.fesenko@gmail.com

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[1].

.
-,


.

TiO2/SiO2
- .

1. M.A.Henderson The interaction of water with solid surfaces: fundamental aspects revisited/Surface Science Reports 46 (2002) 1-308


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. .11, 2, (2010), . 453-458.

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0,10

0,05

0,02

250

300

350

400

450

0,10
0,08
0,06
0,04

0,00

500 0,00

250

300

350

400

450

kd 105
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300

350

400

450

500

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0,05

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250

300

350

400

450

500

300

400

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.

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[1-2]. ,
.
1.De Ruyck, H.; De Ridder, H.: Van Renterghem, R.; Van Wambeke, F. Food Addit. Contam. 1999, 16(2), 47-56.
2. Zurhelle, G.; Muller-Seitz, E.; Petz, M. J. Chromatogr. B: Biomed. Sci. Appl. 2000, 739(1), 191-203.

 SnO2

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...
. , 17, , 03164,
E-mail: pexim @ukr.net

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, .
, SnCl4. (IV) H2O
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2

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3
4

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5
5

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15

5
6

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30
30

7
8

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15
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10

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261
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6 0 0 2

110
122

6 0 0 2

106
129

6 0 0 2

S, m2/g

S, m2/g

SnO 2 /SiO 2 (A300)

300

110

100

200

300

400

500

600

25

280

700

30

10

15

20

25

0,6

30

C (SnO 2), wt. %

.1. SnO2/SiO2(120) ()
SnO2/SiO2(300) () SnO2.
1 5 w t.%
1
2

SnO 2 on
In i t i a l
0
600 C

30

40

10

70

20

30

40

50

60

70

2Q

2Q

.2. SnO2/SiO2(120) ()
SnO2/SiO.2(300) () SnO2=15.%
20

Zeta Potential, mV

10
0

20

300
5% SnO2 on SiO2
15% SnO2 on SiO2
30% SnO2 on SiO2

-10
-20
-30
-40

-50
2

6
pH

10

o
5% SnO2 on 300, 600 C
o
15% SnO2 on 300, 600 C
o
30% SnO2 on 300, 600 C

12

0
-10
-20
-30
-40

-50
2

100

200

300

400

500

600

700

800

900 1000

100

200

300

400

500

600

700

800

900 1000

D, nm

1
2

120
1 5 w t.% S n O 2 o n A 1 2 0

1 5 w t.% S n O 2 o n A 1 2 0
600

2,0
Si-O H

300 initial

15 wt.% SnO 2

15 wt.% SnO 2
0
after 600 C

Si-OH

1,5

Si-O -Si

0,4

1
2

0,2

1,0

H 2O
Si-O-Si

0,5

3
0,0
1600 2000 2400 2800 3200 3600 4000

-1
cm

,
SnO2/SiO2(300), SnO2=15 30 .%,
(10-15 ) SnO2. ,
(),
SnO2/SiO2(120) SnO2/SiO2(300) -
, (D)
SnO2 SiO2.
D , ,

600 .

300

10
Z eta Potential, mV

pH(PZC)

(3750 -1)
300, Si-OH
,
Si-O-Sn (.5). ,
15 30 %. SnO2 , 120,

(IV) (.5).

60

.5. - SnO2/SiO2 (-120) () SnO2/SiO2 (-300) ().

50

1600 2000 2400 2800 3200 3600 4000

In itia l
o
600 C

20

0,0

1 5 w t.% S n O 2 o n 3 0 0

10

900

cm -1

120

800

0,8

C (SnO 2), wt. %

Initial
600 0 C

Absorbance

20

D, nm

H 2O

15

SiO2 pH
(pH()) SnO2/SiO2
pH()SiO2=2,2 pH()SnO2=5.
(.3),
SnO2 SiO2 (
SnO2=15 .% ),
D
SnO2/SiO2(A300) (.4).

260
10

10

10

a fte r

D ef = 194,2 nm

12

0,2 % susp. H2O

.4. ,

, SnO2/SiO2 (300) : A - 5% SnO2 , B- 15% SnO2 , C - 30%
SnO2

130

D ef =192,1 nm

SnSil 30-600, 30 % SnO2;

14

0,2 % susp. H2O

12

D, nm

SiO2
( SiO2). (S)
SnO2/SiO2 .1, .

120

SnSil 15-600, 15 % SnO2;

14

0,2 % susp. H2O

D ef =173,4 nm

* -

6 0 0 2

255
279

Initial
0
600 C

SnSil5-600, 5 % SnO2;

1 0 -1 5


1 0 -1 5
120

SnO 2 /SiO 2 (A120)

16

16

V, %

[?SiO]nSn(Cl)4-n + (4-n)H2O [?SiO]nSn(OH)4-n + (4-n)HCl (2)

n=1, 2
, 40 ,
450 3-4 .
1 . 1,5 ,
100 1,5 . (~ 0,5 )
HCl. .
2 100-105
. 2 600 .
, - .

Absorbance

[?SiOH]n + Sn(Cl)4

V, %

()
. .
SnO2/SiO2 SnCl4 (

2
100 ) 120 300 /
( 120 300).

V, %

600 SnO2/SiO2(120) (SnO2=15 30 .%)

SnO2/SiO2(300), SnO2=5 .%,
SnO2 (.2) , SnO2/SiO2(300),
SnO2=15 30 .%, (10-15 )
SnO2 (.2).
, (),
SnO2/SiO2(120) SnO2/SiO2(300) -
, (D)
SnO2 SiO2. D
, , 600.
SnO2 120 300
- SnO2/SiO2(120) SnO2/SiO2(300).

10

pH

.3. - SnO2/SiO2(300)

() 600 ().

12

Acknowledgment: This work was supported by the European Community

under a Marie Curie International Research Staff Exchange Scheme
(IRSES), Project No 230790.

.. , .. , .. , ..
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500
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400
300
200
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.%

,%

80
60
40
20
0

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50

85

0,4
280

3
300

3,6
350

8
390

40

20,6
20

16,5

15
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30
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20,8

190

250

280

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0,8

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59

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35

25
20

30

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35
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10

400

45
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100

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40

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60

10

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0
73

87

133

147

191

207

18

-5
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28

32

45

0,2

0,2

59

72

0,5
73

147

207

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-5

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220

CH3-CO-CH2OH + H2 CH3-CH(OH)-CH2OH

165

: - - 100%;

- - (< 8 ) ; (> 50 );
- - Cu/Al2O3 ( 1- ) Cu/Al2O3-Cr2O3 ( 2- );
- 1,2-
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. 1,2-
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1,2-, %

Pt/Al2O3
Ni/SiO2
Ni/Cr2O3-Al2O3

, %
34
37
39

26
30
32

1,2, %
78
81
84

Cu-Pt/Al2O3
Cu/Al2O3
Cu/Al2O3-Cr2O3

46
76
86

36
66
84

78
87
97

100

100

, , %

, , %

a
90

80

90

80

70

70
2

10

12

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40

50

60

70

80

90

1 00

2 : C 3H 8O 3, /

Cu/Cr2O3-Al2O3 () :
: () (
(),
(), 1,2 ())



.., .., .., ..,
.., ..
-
. ..
,
ZnO

ZnO

Zn(NO3)2

(NH32O)

(Zn(OH)2)

,

(Zn(NO3)2) ,

.
0
100

ZnO

t .,

,
.%

1
2
3
4

30
50
70
100

0,360
0,545
0 400
0,400
0,530

0,15
0,18
0 18
0,18
0,26

99
63
39

,
.%

1
2
3
4
5
6

4,0
45
4,5
5,0
5,5
6,0
6,3

0,360
0 381
0,381
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0,510
0,610
0,855

0,27
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0,29
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0,28
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95
41
39
53
64
79

2009 -2011 ( 2.1.1/9317)

r 30 120

 CuO
CuSO4

.., .., ., ..
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[1] CuSO452

.
.
.
.
CuSO4 -300 (S = 300 2/,

Si =0,8 /). () -
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.

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1
(. 2),
2
1

3
2
(. 3)
4
300
5
3
- - (. 1 2)
4
6
,

10
20
30
40
50
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600
800
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2400
3200
4000
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2

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. 2. -
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(4), 4 (5) 5 (6) .

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5 ).

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.
-
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,

1 550 (. 5, . 1-3).
4
2 - -.
[2],
3
3 :
2
2CuSO4 2CuO + 2SO2 + O2,
650 C.

,
10
20
30
40
50 60
2400
3200
4000

650-1
,
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)
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40 , -300.

,
,
,

,
, CuSO4
800 CuO.
CuO.
1. . ., . ., . ., . ., . . CuSO4
. ", 2010, 10, .109-113.
2. . . . .: , 1973. . 1. 656 .

6.22.7.21 -
" "

-
C/MXOY/SiO2
-
.. 1, .. 1, .. 1, . 2,
. -2
1- . . .
. 17, 03164 -164 bogatyrov@isc.gov.ua
2-Faculty of Chemistry, Maria Curie-Skodowska University, 20031 Lublin, Poland

- C/MxOy/SiO2 ,
- () MxOy/SiO2, Cu,
Mg, Mn, Ni Zn.
in situ ,
1:2:1. 3 / SiO2.
800 2 .
.
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- /MxOy/SiO2


50-200 .


250-350 ,
,

.

-
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MxOy/SiO2 C/MxOy/SiO2

,
, .
36-48 % ., .
-
.
PIRSES-GA-2008-230790.

 Gd-

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chemind@ukr.net
. ..
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,
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.

5000
2

10

20

30

40

50

60

70

80

90

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.

.

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3+

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135

140

145

150

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Fe

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130

155

160

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704 706 708 710 712 714 716 718 720

T=1000 C
INT

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704 706 708 710 712 714 716 718 720

0
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T=20 C

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135

140

145

150

155

160

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.
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Fe3O4/Gd,
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1, 2)
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704 706 708 710 712 714 716 718 720

E,

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Fe3O4/Gd,

( 1, 2)
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M r/M s= 0,47

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-3

()

Fe3O4/ 2Gd

H ,

()

Fe3O4/GdFeO3
3

2
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-1

Mr/Ms=0,26

-10

Hc=-144
T=294 K

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10

()

30

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()
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50

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~ 5,0 .


.
, ,
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-
.

.,

.,

.,

.
, 246746, .

, 48,

, dobrodey2007@yandex.ru

. 1.

T = 1100 , t = 1
.2).

350

300

. 2.
(
):
. = 450
1 YAG: Ce, La;
2 YAG: Ce, La < 2
;
3 YAG: Ce, Gd < 2
;
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.
, T = 1100 , t = 1

250

3
200
150

100

50

.
.

0
475

500

525

550

575

600

625

650

675

700

725

750

Y3Al5O12: Ce3+
-08,
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40-60 .

,
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. 3.).

1
2

;
.

THE ELECTROSTATIC POTENTIAL

IN THE SEMICONDUCTOR - VACUUM - METAL
CONTACT.

L.G. ILCHENKO, V.V. LOBANOV

Chuiko Institute of Surface Chemistry of National Academy of
Science of Ukraine, General Naumov Str. 17, 03164, Kiev-164
V.V. ILCHENKO
Radiophysical Department, Kiev Taras Shevchenko University,
Volodimirska Str. 64, 02033, Kiev-33
e-mail: vai@rpd.univ.kiev.ua , . (044) 424 94 72
The theoretical arguments presented in this article have
shown how the distribution of the electrostatic potential
V j ( x ,U ) in semiconductor - vacuum - metal contact changes in

an applied voltage U . The finiteness and continuity of

V j ( x ,U ) at the surfaces is saved through the formation of the

double electric layer due to the change of the charge densities

on the interfaces according to the contact potential and U .
The obtained distribution of V1 ( x ,U ) in a semiconductor are

compared to the known quadratic law of the Schottky barrier

formation.
In [1,2] in the framework of the dielectric formalism method
for the system of three environments with the spatial dispersion
[1], the semiconductor - vacuum - metal (SVM) system is
considered. The electrostatic potential V j ( x ) is calculated in the
SVM system before contact. It was shown that the presence of a
metal in the distance L LSCR ( LSCR is thickness of the space
charge region (SCR) in a semiconductor) leads to the change of
the charge potential V
j ( x ) , which is related to the presence of
charge with the density 10 and 20 on the surfaces of
semiconductor and metal. At the subsequent diminishing of the
vacuum interval L 10 nm a potential barrier determined by the
image potential V j0 ( x ) between a semiconductor and metal [1-3].

Theory
Continuity V j0 ( x ) and total potential V j ( x ) on the interfaces
is caused by the correct account of the spatial dispersion effects in

the dielectric functions of semiconductor 1( k ) and metal 3 ( k )

(TFA) [3]. Adduction of the SVM system to the contact

(establishment of the general Fermi level) leads to the finite jump
of the potential V j ( x ) , which equals to the contact potential
3 1, where 1 and 3 is work function of the

semiconductor and metal, accordingly.

In [3] it is shown that the continuity of V j ( x ) before contact
can be saved after its adduction in the contact due to the change of
charge potential V
j ( x ) through the double electric layer (DEL)
formation. The DEL arises up as result of the redistribution of the
total densities of charges on the interfaces in contact in accordance
to , which change afterwards in an applied voltage U on the
semiconductor 10 1( U ) and metal 20 2 ( U ) surfaces.

On the basis of theory of the formation of a rectifying

contact [3] we defined the analytical equations which determine
the distribution of the total electrostatic potential V j ( x ,U ) in all
SVM system after the contact and its change in forward U and
reverse U voltage.
Results of calculations
In the present work the distribution of V j ( x ,U ) is analysed
on an example n -SivacuumAu system with the well-known
parameters.
The potential V j ( x ) for n -SivacuumAu structure before
contact (dotted curves 1-3) and the shape of the total potential
V j ( x ,U 0 ) after contact (solid curves 1-3) are shown in Fig. 1

[3].
As we can see, the correctly account of the space dispersion
effects in the semiconductor and metal (see [3]) provides
finiteness and continuity of the potential V j ( x ) at the interfaces
before contact and keep it for the potential V j ( x ,U 0 ) after
contact if the DEL is formed.

Fig.1.Shape of the potential V j ( x ) in n -SivacuumAu structure

before contact with 10 3.4 1012 e 2 and 20 1014 e 2
for L 0.2; 0.4; 0.6 nm (dotted curves 1-3, respectively). The solid
curves 1-3 is shape of V j ( x ,U 0 ) in n -SivacuumAu contact.
Eca is the position of the conduction band edge in n Si , when

x , and E Fa is the position of the Fermi energy after the

contact.

The calculations of V
j ( x ,U ) for an any given thickness
L , but L LSCR , in n Si - vacuum - Au contact are shown in

Fig. 2 (Reverse bias) and Fig.e 3 (Forward bias) by the

appropriate solid curves.

Fig.2. Distributions of V
j ( x , ,U ) in n Si - vacuum - Au
contact (U 0 ) in applied reverse bias U 0.5; 1; 1.5 V for the
any gap thickness L , when the condition L LSCR are satisfied.
The broken curves are calculated by the quadratic law of the
Schottky barrier formation.

Fig.3. Distributions of V
j ( x , ,U ) in n -SivacuumAu
contact (U 0 ) in applied forward bias U 0.5 V ; ; 1; 1.25; 1.5 V
for the any gap thickness L , when the condition L LSCR are
satisfied.

Distribution

of

the

total

potential

V1( x , ,U )

in

semiconductor are shown in Fig. 4 (Reverse bias) and Fig. 5

(Forward bias) by the appropriate solid curves.

Fig.4. Distributions of V1( x , ,U ) in n -Si for n -SivacuumAu

contact (U 0 ) in applied reverse bias U 0.5; 1; 1.5 V .

The dotted curves curves in Fig. 2 and Fig. 4 show the

distribution of the potential in n Si , which determine the known
quadratic law of the Schottky barrier formation and its change in
reverse bias U , is calculated by the following equation [4]

Vcl ( x ,U ) Ec ( eU ) 1 1 x Dcl ( U ) ,
2

1/ 2

where

2
eU

Dcl ( U )

3 2
1
.
347
10
n

Fig.5. Distributions of V1( x , ,U ) in n -Si for n -SivacuumAu

contact (U 0 ) in applied forward bias U 0.5 V ; ; 1; 1.25; 1.5 V .
The calculated ideality factor N [5] for n -SivacuumAu
contact with used parameters for a non-degenerate semiconductor
of n -Si: dielectric constant is 1 11.9 , temperature is T 293 K ,

10

concentration is n1 6 1015 cm 3 , 1 Ec 4.05 eB is the

position of bottom of area of conductivity in the volume of
semiconductor, and an any thickness L ,

but

L LSCR , is

N 1.004 .
Conclusions
The origin of the strong interconnection between a
semiconductor and metal, separated by the vacuum gap
L LSCR , before contact there is the necessary condition of

the DEL origin and, as a result, the rectifying contact.

The continuity of the total potential V j ( x ,U ) is saved after
contact due to the correct account of the spatial dispersion

effects in 1( k ) (1) and 3 ( k ) and the redistribution of the

total charge on their surfaces in accordance with L , and
U.
The

barrier

height

h( U ) V1( 0 ,U ) on

the

semiconductor/vacuum interface ( x 0 ) in the contact

(height of the depletion layer) always less than the contact

11

potential h( 0 ) because of the screening properties of

a metal and slowly changes in an applied bias U .
The barrier height V2 ( x ,U ) in the vacuum interval (inside
of the DEL) decreases with the decrease L according to the
image potential distribution of V20 ( x ) .
References
1. L.G.Ilchenko, E.A.Pashitskii, Yu.A.Romanov. Fiz. Tverd. Tela,
22, 2700 (1980).
2. L.G.Il'chenko, E.A. Pashitskii and Yu.A. Romanov, Surf. Sci.
121, 375 (1982).
3. L.G.Ilchenko, V.V.Ilchenko, V.V.Lobanov. Radiophysics and
electronics, Visnyk of Taras Shevchenko National University of
Kiev 11, 29 (2008), 3, 237 (2009), 1, 174 (2010).
4. G.P.Peka, V.I.Stricha. Surfaces and contact phenomena in
semiconductors. (Kiev, Libid, 1992).
5. E.H.Rhoderick and R.H.Williams, Metal-Semiconductor
Contacs, Clarendon Press, Oxford, (1988), p.250.


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1) A.Bagreev, J.A.Menendez, S.Kopyl, I.Dukhno, Yu. Zitsev Yu. Tarasenko, T.J.Bandosz. Bituminous coal based activated carbons modified with nitrogen as adsorbents of hydrogen sulphide//Carbon 42 (2004), 469-476.
2) .., .., .., ... - //, . 2003, .9, .64-70.
3)

V.D.Khavryuchenko, Y.A.Tarasenko, V.V.Strelko, O.V. Khavryuchenko, V.V.Lisnyak. Quantum Chemical Study of Polyaromatic Hydrocarbons in High Multiplicity States//Int.J.Modern Physics.B. Vol.21, 26(2007), 4507-4515.


/
.., .., .., ..
..
. , 17, , 03164, , dvdrusik@ukr.net
()
. , ,
- .
. ,
, .
. ,
.
,
, -, .

(/CuI) .

20000
1

15000

2
3

10000

5000

0
10 14 18

22 26 30

34 38 42

46 50 54

58 62 66

.1.
. CuI (% ): 1 - 100; 2 - 5,2; 3 - 55.

1
70 2

-4-07 (CuK
- ,
). (. 1)
-
.
.
CuI
d=k/cos ~ 30 .

. 2. /CuI
( CuI % (.)): 5; 10.
CuI
.
,

. 10% uI
(. 2),

.

. 3. ' (), '' () ()

9 (, ) 100 () (=295)
-CuI (1) /CuI (2).

/CuI '
10 75 %,

(. 3).
CuI .
( 5 2/),
CuI
. ,
, ,
CuI .


(-CuI, 1 ).
' '

CuI,
.


Br-, S- N-
, , , ,
,
01601, , . , 64; e-mail: lyuda-grischenko@yandex.ru
()
.

,
.

:
Br-
C S- N- .

-0,05

-1

-0,10

0,00

-0,05
2

-2

-0,10

-3

-0,15

-0,15
-4

-0,20

-0,20

-5

200

400

-2
-3
-4
-5
-6

800 t, C

600

-1

-7

dm/dT 10 , / C

m,

dm/dT 10 , / C

m,

0,00

200

400

o
800 t, C

600

(1)
(2) , 1 2.
,

:


-

I, ..

m/z

79
80
81
82

7
6

5
4

200

300

400

79
80
81
82

100

m/z

I, ..

500

600 t ,C

0
100

200

300

400

500

600

t ,C

- , 1 2.

1
KBr
2 -
S-

120 15
S .
N-

0,00

-0,05 -2
-3

1.

Br- .
~0.5 /.
2.
- . S- N
~0.5 /.
3. N-
. ,
(
, ).
4. S-
. ,
.

0,00

-0,02

-1

0,5

-0,04

0,4

-5

-0,06

r 10 , /.

0,10

0,08

-2

0,06

-3

-0,08

0,3

-6
-0,15 -7
-8
-0,20 -9
-10

200

400

600

800

-4

0,1

-0,14

-6

-0,16

-7

c(H2O2), /

0,02
0,00

t, C

200

400

800 T, C

600

(1) (2)
SO2 (3)
, .

3,5

0,30

0,04

-5

-0,12

0,0
0

-0,10

0,2

(1) (2)
SO2 (3)
, .

dm/dT 10 , / C

m,

0,6

-4

-11

120 15 .

0,7

-1

-0,10

r 10 , /.

dm/dT 10 , / C

m,

r 10 , /
2

3,0
2,5

0,25

2,0
0,20

1,5
1,0

0,15
0,10
0

50

0,5
0,0
100

150

200

250

50

100

150

200

250 T, C

(1) S- (2) .


,

.. 1, .. 1, .. 1, . . 3, .. 2, .. 1
1
2

. .. , 03680, -164, . , 17, e-mail v_turov@ukr.net

, . .. , 03022 -022, . , 45
3 , 01601 , . , 64

, , . ,
,
.

()

,
,
.

, (
), ,
= 3750 -1.
, . ,
6,1 %,

-300, , ,

,
.
- (-300), (-SiO2)

-
()

()

-
(SAW). ,
()
= 260 , () 270 .

1 SiO2-,
8 % : () ; () .

-SiO2

SAW ()
. - SAW ()

s
, /
Cuw

w
, /
Cuw

Gs, /

Gw,/

S, /

80

-3

18

62

-3

-0,5

1,8

SAW SiO2- 0,6 - 2,2

, 80 % 0,9, 1,5 2,2 .

R = 6,3 .
R < 2,5 . SAW
, .

.
, , ,
.
0,05%
.
, SiO2,
,
SiO2--
, .
, 25- . ..

 -

Pd-Cu-
.., .., ..
.. , , 65026, TLR@ onu.edu.ua
(-) ( ,
, , , -, ),
( --1, --1*; --2). (.),
Pd()-Cu()- [1, 2].

-(1)
-(1)-6
-(1)*
-(1)*-6
-(2)
-(2)-6

, . %

SiO2
Al2O3
Fe2O3
MnO
TiO2
Al2O3/Fe2O3
SiO2/Al2O3
II
68,44
12,82
10,14
0,17
1,98
1,3
5,3
( .) H = 50-70
70,56
11,93
9,02
1,30
1,3
5,9
II
63,62
19,60
10,49
0,12
1,82
1,9
3,2
( .) H = 20-30
73,20
9,42
8,50
0,09
1,24
1,1
7,8

58,79
18,51
7,90
0,52
1,34
2,3
3,2
( .)
72,30
10,10
6,4
0,92
1,6
7,2

S,
2/
17
30
18
54
25
40

- ,
Pd()-Cu()-
. ,
, -
Pd() Cu() , .
, ,
(HCl, HNO3), HNO3
(3 12), (20 , 100 )
. -:
; -
; SiO2/Al2O3 14
Al2O3 /Fe2O3; -, L. 1. ; [3].
:
1 ,
(1); 2 -(1)*; 3-(2).
--1 > --1* > --2,
( 15 ) -
Pd(II) Cu(II) , CLI MOR.
Mont 9- - - (.1).
110
K2PdCl4-Cu(NO3)2-KBr/-. -.
(. 2), (
) Pd(II) Cu(II)
C, /3
,
. 2. C

300
1

:
,

2PdCl4-Cu(NO3)2-KBr250

H2O/(1)

3 HNO3 6, 9
200
: 1
( 2, 3) 6 HNO3 3
50
100
150
60 0
; 2 (1) 6
( 4)
; 3 9

3 HNO3; 4 (1) 3
40
5,0.
6 HNO3 (Pd () = 1,3610-5 ; u() =

2,910-5 ; Br = 1,0210-4 /; C = 300 /3.
( 1), ,
20
2,4
3
Pd(II) Cu(II),
-(1),
0
.
,

0
50
100
150

1.
/ .. , .. , .. , .. // . . 2009. 6. .1823.
2. - (II) (II)
(II) / .. , .. , .. , [ .] // . . . 2010. .83, 7. .
10791084.
3. Pd(II)-Cu(II)- / .., .., .. [ .] // . . -.
. . 2010. .6. . 128134.


TiO2, Co, Ni, Mn, Cu
1..

, 2.. (*), 1.. , 2.. , 1..

1 . . ,
2 . .. , ,
*karpenko_s.v@mail.ru

,
. .
2, C, Ni,
Mn Cu, .
: Ni/TiO2, Co/TiO2 u/TiO2 Mn/TiO2 , , -
(IV), Ni(HCOO)22H2O, Co(CH3COO)24H2O, MnCl24H2O, CuSO45H2O, 25, 2 NO3.
Pluronic F68 , - .
130 , 300 400 .
1%, 5% 30%.

TiO2/Mn+-
0,45

0,40

0,40

0,35

0,35

0,30

0,30

0,45

0,25

0,50

0,50

0,25

0,20

0,20

0,15

0,15

0,10

0,10

0,05
400

500

600

700

800

900 1000 1100

0,05

400

. 1. 2
(1), 2/u2+ (0,025 % u) (2), 2/u2+
(0,25 % u) (3), 2/u2+ (5,5 % u) (4)
.

2
500

600

700

800

900 1000 1100

, nm

. 2.
2/2+ (3 % ) (1), 2/Mnn+
(7 % Mn) (2)
.

1,1
1,0
0,9
0,8
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0,0

3
1

4
2
300

400

500

600

, nm

700

800

900

. 3.
2/Ni2+ (0.1 % Ni) (1),
2/Ni2+ (3 % Ni) (2), 2/Ni2+
(5 % Ni) (3) 2/Ni2+ (7 % Ni) (4)
.

% n+

Egdir,

Egindir,

TiO2

3,87

3,60

TiO2+Cu2+

3,81

3,65

TiO2+Mnn+

3.98

3.64

TiO2+o2+

3.95

3.07

TiO2+Ni2+

0.1

3.97

3.75

.
1.

TiO2-

0 -1.5. NaCl
-0,5 -0,8 (. ..)
TiO2, Co (1-5% ), Ni (1-5% Ni), Mn (1-5%
Mn) Cu (1-5% Cu), ,
.
(~1%)
TiO2
,
2
(. 4., 2,3; . 2., 2,4,6).
(>5%)
(

TiO2 (. 2., 3,5,7)).

. ,

.

. ,
I=f()0.5 (. 5.), ,
,

( 2
).
I, A
0,35
0,3
0,25
0,2
0,15
0,1
0,05
0
0

4
v

E1/2,
B

1,2

TiO2

-0.58

I,. -2

0. 5

. 5.
Ni/TiO2(1%) 0,5.

I,. -2

I,

1,2

0,2

0,16

Co/TiO2(1%)

-0.46

0,8

1
0,12

0,6

0,8
T iO2
Ni-1

0,6

Co/TiO2(5%)

-0.76

Ni/TiO2(1%)

-0.52

Co-1

0,2

0,4
2

0
0

0,2

0,4

0,04

0
0

0,2
3

2
0,08

0,4

1
0,6

0,8

1,2

-,

. 4.
0,9% NaCl : 1 - TO2; 2
C/TO2(1%); 3 Ni/TO2(1%). =10 -1

1,4

Ni/TiO2(5%)

-0.67

Mn/TiO2(1%)

-0.52

Mn/TiO2(5%)

-0.60

Cu/TiO2(1%)

-0.55

Cu/TiO2(5%)

-0.78

10

Cu/TiO2(30%)

. 2.

0,2

0,4

0,6

0,8

-E,

1,2

0
0

0,2

0,4

0,6

0,8

-,
7.

.
6.

.
0,9% NaCl 0,9% NaCl
Cu/TO2 (30%)
Cu/TO2 (1%). =10 -1.
: (1- 3- , 2 5-
). =10 -1.

TiO2, (30% u),

u/TiO2 (1-5% u)
(. 6.),
(. 7.),
, ,
.

1,2

-
-
.. , .. , .. , ..
. ..

. - -
.
.

1.

SiO2

30,46-51,0

CaO

0,12-0,14

Al2O3

4,05-5,05

MnO

0,12-0,14

Fe2O3

1,23-1,53

P2O5

0,03-0,08

MgO

0,56-0,75

26,26-30,05

TiO2

0,24-0,32

H2O

1,40-3,09

FeO

0,32-0,48

7,37

1.
-
,
120 10%
: 1 18 .. (2+); 2 16 ...
(4+); 3 - 64 ... (SO2+); 4 - 48 ... (SO+).

2.

500

31,0

( %)
SiO2 Al2O3 MgO MnO K2O TiO2
54,5 4,62
2.04
1,50 0,66 0,02

31,0

54,5

4,62

0,66

0,02

1,15 0,22

2. ,
10% : 1 18 .. (2+);
2 16 ... (4+); 3 - 64 ... (SO2+); 4 - 48 ... (SO+).

1. (, )
( 120 500) (5, 10 15%).
2. ,
, :
- 120 ,
100, 350 500, 500 100.
- , 120, 300, ,
300 .
- , 500 ( 620),
120 , 400.
-
, 500 , 120.
3.
, 350-500,
, , 500.


LVV -
.., ..
.
. .. .
. ,
, 17, 03164 ,
,
E-mail:
mail: terebinska@isc.gov.ua

,
,
.

.
, , ' .
,
, -.
- ()

,

.

. 1
2 (111) .
, ,
, , (
95%) . ,
(111) 1800 100 ,
, (1112) (111) 27
28 500
100% 1s .
1s
2 (-524,96 ).

,
, 95 %

. 1 , :
) (111) ; )
2 (1112); )
(111).

(1112)

(111-)
23

1s

23

-1799,76

19

1s

28

-1798,72

19

1s

26

-1799,40

21

1s

23

-1799,61

51

1s

27

-519,18

1s

26

-1798,64

52

1s

28

-518,92

51

1s

28

-523,46

14

55

-100,45

52

1s

27

-523,43

63

-100,06

64

-100,06

10

64

-100,04

63

-100,07

68

-99,71

61

-100,15

13

70

-99,70

14

62

-100,10

, 27 28
,
, (5,3
), - LVV (1112) . 2.

2 (111). -
(111) , ,
, ,
27 28 ,
(1112), .

, . .

,
505

525

. 2 - LVV (1112),
1s
, -


,
.

 TiO2,
Co, Ni, Mn, Cu: , A

.. (*), .. , .. , .. ,
..
. . , ,
*
12drummer@mail.ru
(IV)

- , , ,
,
. TiO2

, ,

. 2
, d ,
,
.
Cr(VI)
Cr(III).
Ni/TiO2, Co/TiO2 u/TiO2
Mn/TiO2, , -

,
Ni(HCOO)22H2O,
Co(CH3COO)24H2O, MnCl24H2O, CuSO45H2O, 25, 2 NO3.
Pluronic F68
, -
. 0,1%, 1%, 3% 5%.
, 450
TiO2, Mn/TiO2 u/TiO2
. CoO
NiO.
- Mn/TiO2,
87 2/ 0,1% 224 2/ 5%
. ,
.
Cr(VI) Cr(III) .
Co- Mn-
3%, 5% Ni- 0,1% .

,
- ,

. 1, ., A. 1, T. 2, . 2, M. 2
1

. .. , . , 17, ,
e-mail: nvityuk@gmail.com
2K , , ,
2

,
N-, C-, S- .
- TiO2
- .
C:TiO2 (0.83, 1.66, 2.49)
(2000, 2500, 3000 5000). ,
, - ,
,
.

: -
TiO2 -
,
(2000, 2500, 3000 5000) C:TiO2 (0.83, 1.66,
2.49).
C:TiO2
.
(200).
TiO2
-
Na2 ().

C:TiO2 . ,
2 17, 8, 11 C:TiO2 0,83, 1,66, 2,49.
250

250
I, ..

Si

200

, ..

200

Si

10000

150

100

8000

25

30

35

2,

40

I, ..

50

150

45

100

3 1

50

25

30

35

40

2,

45
0

50

55

T=5000C

Si
144

Si

6000
4000

144
2000

60

144

Si

296 396 637

2
946 978

0
0

500

1000
-1

1500

2000

.2. 2:: 0,83 (1),

1,66 (2), 2,49 (3)
5000.

.1. 2:: 0,83 (1),

1,66 (2), 2,49 (3)
5000.

.2
C:TiO2
5000 .
,
2 .
C:TiO2
2000 151 -1,
2
2
5000.
1604 -1
. .2
,
2.

C:TiO2
(.3)
() (.1). 2000 3 eV, 2
.
.
.1. () - 2 :
C:TiO2

0.83

0.83

1.66

1.66

2.49

2.49

T, 0C

200

500

200

500

200

500

E, eV

2.98

3.56

3.10

3.56

3.11

2.79;
3.8

0,90

200 C

1,00

0,95

I/I0

I/I0

I/I0

4
2

0,80

0,85

1,00

1
2

0,95

0,90
0,85

1,00

1
3
2

0,90

0,85

0,95

I/I0

0,95

1,00

C:TiO2 5000
2
.
5000 ,
. ,
2 .

0,80

0,75

0,90

0,80

0,75

0,70

3
0

20

40

60

t, min

80

100

120

3
0,85

0,65

0,75

0,70

20

40

60

80

100

120

t, min

. 3. Cr(VI) Cr(III)
C:TiO2, 2000C -(a) Vis-
(), C:TiO2: 1- ; 2 0.83; 3 1.66; 4 2.49.

20

40

60

80

100

120

20

40

60

80

100

120

t, min
t,min
.4. Cr(VI) Cr(III)
C:TiO2,
5000C -(a) Vis- (), C:TiO2: 1-
; 2 0.83; 3 1.66; 4 2.49.

, C:TiO2 TiO2 . -
. 5000 10 , 3000 - 4 2000 - < 2 .
- C:TiO2 - .
0,83, (C:TiO2=2)
2.




.., .., ..
,
( ), ilyapanenko@mail.ru

.

96% 86%.

,


,
.
.
,
, ( 1) ( 2)
.




Saccharomyces cerevisiae
.., .., .., ..
. ..
, 03164, , . , 17
oksana.garkusha@gmail.com
,
. , ,
, .
, , .
()
Saccharomyces cerevisiae
39
49 06%. ,
.

. 0,2 10 10%
, .
(50 )
.



, ,
0 6%

.
,
30% 6%.
. 1.
. 2.

Saccharomyces cerevisiae

:
1 ;

2
.
3%.


47,5
. , ,
40 47,5 3%,
3% .
.
. 3.
. 4.

:
3%
1

;
:
1 ;
2
2

47,5 .
3%.
, ,
( 6%) .
( 3%), ,
.


,

.., ..
, -
( ), .
anna.srstu@gmail.com

, , ,

.
, ,
, , ( 1);
( 1)
1

. %
. %
20,18
45,31
20,89
35,22
10,87
05,25
03,31
01,52
00,71
00,33
44,04
12,38

.

.
x 1000
1 -

P. Klonos, A. Kyritsis, P. Pissis

Department of Physics National Technical University of Athens, Zografou Campus, 15780, Athens, Greece

Molecular dynamics and interfacial relaxation phenomena in polymer nanocomposite materials were studied through
Differential Scanning Calorimetry (DSC), Dielectric Relaxation Spectroscopy (DRS) and Thermally Stimulated
Depolarization Currents (TSDC). Materials consisted of crosslinked PDMS and nanoparticles. The particles were
used in order to improve some of the polymer properties (mainly mechanical) and to make functional systems mainly
for industrial applications (i.e. car tyres). Through these techniques, important conclusions were extracted for the
particles distribution, thermal transitions (crystallization, melting, glass transition) and polymer-filler interactions. [1-2]

Materials are based on two types of in situ synthesized

nanoparticles: silica (SiO2) and titania (TiO2), with
diameters of about 5 and 20-40 nm respectively. The
unfilled PDMS network was prepared from
hydroxylterminated PDMS (Gelest, Mw ~ 18000) by
end-linking reactions using tetraethoxysilane (TEOS)
as cross-linking agent. TEOS and TBO was used as
precursor for the sol-gel silica and titania synthesis. [1]
9 wt% silica

11 wt% titania

Fig.1 TEM images

for PDMS/titania
nanocomposites [1]

5 wt% TiO2

15 wt% TiO2

Fig.2 SEM images for PDMS/titania nanocomposites

filler addition

cooling

2 types of
crystal regions
in PDMS [3]

Fig.4 Representative TSDC thermograms for

PDMS and PDMS/titania nanocomposites, in the
temperature region of segmental dynamics (glass
transition).

Fig.3 DSC measurements (center) and

respective Composition diagrams (edges)
for PDMS and its
nanocomposites.

Nanoparticles depress crystallinity and amorphous mobility.

Changes on the temperature development of Segmental Dynamics [4]
Three types of -relaxation(related to glass transition):
relaxation: Amorphous unbound polymer (bulk)
C relaxation: Restricted mobility within the Crystals (RAFCRYST)
relaxation: Interfacial bound polymer, reduced mobility (RAFfiller) [4]
Calorimetry (DSC): No significant variation of Rigid Amorphous Phase (RAF), due
to filler (RAFFILLER) and crystallinity (RAFCRYST)
The mobile amorphous fraction (MAF) seems to be constant, in the
nanocomposites (in agreement with previous results on semicrystalline polymer
nanocomposites)
Dielectric Spectroscopy (DS): Variation of unbound polymer with filler content.
Interactions between polymer-titania is stronger than for silica.
Results agree and supplement other techniques (FTIR, DMA, Swelling).[1]

Fig.5 Interfacial (bound) polymer

fraction, as calculated from the
additive contribution ( relaxation) to
the segmental dynamics relaxations.

REFERENCES
[1] Bokobza L, Diop AL. Express Polym Lett 2010;4:355-63.
[2] Klonos P, Panagopoulou A, Bokobza L, Kyritsis A, Peoglos V, Pissis P. Polymer 2010;51:5490-99.
[3] Sundararajan PR. Polymer 2002;43:1691-3.
[4] Fragiadakis D, Pissis P. J Non-Cryst Solids 2007;353:4344-52.
CONTACT (P. Klonos). e-mail: pklonos@central.ntua.gr

tel. +30 210 772 2974

Fig.6 Activation diagram (Arrhenius Plots) for the

three segmental (, C and ) relaxations of PDMS
and its nanocomposites. Respective DSC and TSDC
points are included. Lines are guides for the eyes.

.. , .. , ..

..

: Q
(, ): M
K
: M Q MQ
:
:
1

{c 0 (M) [M]} V
f ([M])
m

[ MQ ]
f ([M] )
[ Q ] [ MQ ]
0

[M], /

, 25- . ..
11-13 2011 .


p(K)

p(K ) 0

p(K ) dK 1

1918

p(K)j

p(K ) j 0

p(K ) j
j

Kj
, 25- . ..
11-13 2011 .

-
:
- SiO2
-
+ SiO2

:
-
-
-
-

:
-
-
- -
:
-

- , , ,

, 25- . ..
11-13 2011 .



( , )?

: ,
,
, ,
.
:
, ,
/

, 25- . ..
11-13 2011 .

 p(K) c f([M])
1918

f ([M])

local

([M], K ) p( K ) dK

local

K [M]
([M], K )
1 K [M]

: .. (1935), .. (1948),
M. Nederlof, .. (1990),
~
f([M]) f ([M])
~
f ([M]) p( K ) : . .
(1975-1985), Guiochon G., .. (1991)
- .. (1963) : W.A.
House (1978), B.M. Leunberger , . (1986), Nederlof ., .. (1990),
.. . (1999).
, 25- . ..
11-13 2011 .


p(K),
N

k 1

f kcalculated

measured 2
fk

( p )

d p( K )
dK
( p) q j

j
d
K

0 j 0
j

p p ( K ) d K
2

0
, 25- . ..
11-13 2011 .

 .
?

p(K)

2 > 1
2

K
, 25- . ..
11-13 2011 .

 p(K)
Piotr Gauden, Piotr Kowalczyk, Artur Terzyk

, .
(Phys. Rev., 1957)
J

j 1

p( K j ) ln p( K j ) max

p( K j ) 1
j

1
p( K j )
J

, 25- . ..
11-13 2011 .

 p(Kj)
J
K j [ M ]k
~
f k p( K j )
f k , k 1, 2, ..., N
1 K j [ M ]k
j 1

J
K j [ M ]k
~
f k p( K j )
f k , k 1, 2, ..., N
1 K j [ M ]k
j 1

p( K j ) 1

j 1

p( K j ) 0

j 1

, 25- . ..
11-13 2011 .


p(lg K = 2) = p(lg K = 5) = p(lg K = 6) = 1/3
p(lg K)
p(lg K)

0.4

0.3
0.2
0.1
0

lg K
, 25- . ..
11-13 2011 .

 p(lg K),
-
p (lg K)
0.4
0.3
0.2

0.1
0

lg K
, 25- . ..
11-13 2011 .

p(lg K)

H 5.6-5.8

0,6
0,4
0,2
0,0

Cu(II)

4,48

4,50

4,52

4,54

0,4

4,56

= 0.07

4,58

Zn(II)

4,60
= 0.09

0,2
0,0
0,4

4,30

4,35

4,40

4,45

4,50

4,55
= 0.06

Pb(II)

0,2
0,0
4,20

4,25

4,30 4,50

4,55

lg K

4,60

4,65

,
3--

TEOS + HCl

(MeO)3Si(CH)3Cl

, 25- . ..
11-13 2011 .

,
3-- .

p(lg K)
1,5
1,0
0,5
0,0

FeCl3
2,7

3,0

3,3

3,6

3,9

4,2

0,6
0,3
0,0
0,9
0,6
0,3
0,0

CuCl2
3,6

3,8

4,0

CoCl2
3,46

3,48

3,50

3,52

lg K
, 25- . ..
11-13 2011 .



..
..
..

Prof. Yoshitaka Gushikem
Prof. Herica Magosso
Prof. Edilson Benvenutti

 -
.. , .. , .. , .. , ..
. ..
03164, . , . , 17
e-mail:kvoitko@gmail.com

()
.

-
, ,
, ,
. ,
. ,

'
.

(- - [1],
[2]) (
[3]) .

-

( ),


, [4].

1. [2]
CVD: CH2Cl2 2 500 60
Al, Fe, Mo . ,
(. 1), ,
. 50-62 , 10-15 ,
(35-40) ,
.
2.

:
o

3.
- MX-7304A .
10 ,

.1. .
~510-5 .
0.15 / ~750.
5.4
-, .
-,
- -6. -
. -
1-210 ..., - ~240 .

-
-,

().

1,8

0,9

0,9

28

(a)

0,8

18

28

0,7
28

0,7
31

0,6

81

0,5
100

0,4
0,3

18

44

17

N-+1% H2O2 (-1)

18

1,6

N- ()

0,8

1,0

0,6
0,5

1,4
1,2

(-2)
1,0
0,8

28

0,4

28

0,6

0,3

18

50

0,4

18

0,2

0,2
36

0,1

30
69

16

17

0,0

44

17

0,1

100

200

300

400

500

600

700

36

48
41

43
67

100

200

300

0,0

39

400

500

600

44

64

0,2

27

0,0

41

100

200

43

300 T, oC
400

700

500

600

700

T, C

() H2O (m\z 18,

17; 50 350), 2 (300-550), CO (550 >700), (m\z 30,50,69,81,100),
500-550.
450-550.
: n=1, E=240 /, k0=6,86x1015 c-1, dS=12,2 *-1-1, R2=0,956.
,
.
m\z 16,
4. m\z 36 (HCl)
(0.18%) C-Cl [2].
N- () , ,
[5]. ' ,
, : m\z 67 (C4H5N+),
4H5N+C2NH3+(m\z 41)+C2H2 4H5N+C3H3+(m\z 39)+CH2N.
m\z 27 (HCN). m\z 43 (HNCO)
, CO2, NH3, HNCO H2.

. ,
. N- (-1),
22 . ,
HCl (m\z 38, 36, 35) SO2, SO (m\z 64, 48). , 22 ,
, .
. , (m\z 27,41,67) (m\z 43) (-2) ,
m\z 16 N- 22.

N-+1% H2O2 (-2)

0,25

64

0,20
36

HNO3 , 70 C
,800 C , Ar
70
%

0,15
48

0,10
43

16

41

27

0,05
67

0,00
0

100

200

300

400

500

600

700

T, C

, -,
, . , N-
, .
1. Catalysis activity, stability and structure of multi-walled carbon nanotubes in the wet air oxidation of phenol / S. Yang, X. Li, W. Zhu [etc.] // Carbon 2008. Vol. 46. P. 445-452.
2. Synthesis of carbon nanotubes from chlorine-containing precursor and their properties / S.Ya. Brichka, G.P. Prikhodko, Yu.I. Sementcov [etc.] // Carbon. 2004. Vol. 42. P. 2581-2587.
3. Characterization of surface chemistry of carbon materials by potentiometric and temperature-programmed desorption / H.F. Gorgulho, J.P. Mesquita, F. Goncalves [etc.] // Carbon. 2008. Vol. 46. P. 1544-1555.
4. Pokrovskiy V.A., Galagan N.P., Kulik T.V. // Chemistry, Physics and Technology of surface / Ed. by A.A. Chuiko. Kyiv: Institute of Surface chemistry. 2001. V. 46. P. 332.
5. Reactivity of different kinds of carbon during oxidative purification of catalytically prepared carbon nanotubes / K. Hernadi, A. Siska, L. Thien-Nga [etc.] // Solid State Ionics. 2001. Vol. 203-209. P.141142.

.. .. ;
- FP7-PEOPLE-IRSES-230790 COMPOSITUM, Project Hybrid nanocomposites and their applications.



..1, ..1, ..2, ..3, ..3
1

. .. 03164, , . , 17; e-mail: fyong@ukr.net

01033, , . , 64
3 - 49005, . , ., 8
2

, .
, ,
.


(-).
:
Cl
OC2H5

+ (H5C2O)3SiRNH2
Si OH

Si

- C2H5OH

Si

+
Cl

NH2

N
N

Cl

- HCl

OC2H5

. 1.

- :
1 V(V) (. ); 2 Mo(VI) (. ); 3 Cr(VI) (=1.7);
4 W(VI) (=8.0).

OC2H5
OC2H5
Si

Si

Cl
N
NH

OC2H5

Si

Si

OC2H5

+-
N

NH
(CH2)6

Cl
HO

+
NH2

N CH2 COOH
n

-
-.
.
55 / .

. 1,
,
,
.

, -
V(V), Cr(VI), W(V) Mo(V)
. 1.
: 0.1 ,
25 , W 5 , Mo 100 ,
V 300 , Cr 104 .
1
V VI

-
pH

. 3.
Cr(VI)

- (pH=1.7)

, %

W(VI)

Mo(VI)

K2Cr2O7

(NH4)2Cr2O7

V(V)

1.0
( )

50

16

70

65

18

1.7
(
)

45

97

100

47

[Cr2O7]2-

[Cr2O7]2-

4.0
(
)

66

82,5

23

52

6.9
(
)

59

49

91

8.0
(
)

[H2W12O40]6WO42-

9.2
(
)

. 2.
Mo(VI)

- (. )

W(VI)

Mo(VI)

Cr(VI)

V(V)

0.32

0.41

0.42

45

,
/

38

7,5

75

90

80

83

65

82

57

59

16

MoO42-

100

37

2

: 0.1 , 25

,
Cr(VI) W(VI) (=1.7)
(=8.0) ,
91% Mo(VI) 80% V(V).
Cr(VI) ,
,
.
.

1.

.
55 / .
2. Cr(VI)
W(VI) (=1.7) (=8.0)
, 91% Mo(VI)
80% V(V).
3.
- .
4.
,

.


NaAu
.. , ..
. .. , 26, 194021, C
E-mail:Lapushkin@ms.ioffe.rssi.ru

NaxAuy

-
NaxAuy
:

NaAu ,
[2].
-
:
.
[3]. .

99.99 0.052.550 3.
. 10
=1100 30 210-6 rr.
950<<1200
I=1012 1014 1/cm2s.
110-7
210-7 rr. 110-6 210-5 rr.
-
- .

NaxAuy

(1)
(2)

Na+

2.0

I+, ..

1.5

1.0

K+

(M-H)+

0.5

0.0
300

400

NaxAuy
- Na

600
700
,

800

900

-



Na NaxAuy

I+, ..

Na+
0.5

.., .., .., , 75,

19(2005)
2. .., .., .., , 74,
99(2004)
3. .., .., .., , 68, 104(1998)
1.

1. Na
NaxAuy
2. Na
NaxAuy-Au
3.

1.0

0.0
22.6

22.8

23.0

23.2

23.4

m/e

0
15

20

25

30

m/e
(2) (M-H)+(1)

+h

-h

0.6

0.5

0.5

+E

0.4

0.4
0.3

+h

0.2

current, arb.un.

current, arb.un.

Intensity, arb.un.

500

NaxAuy. ~ 2.8
, ,

NaxAuy.

NaxAuy

NaxAuy.
,
NaxAuy
.

+E

0.3

0.2

0.1

0.1

-E

0.0

0.0
0

200

400

600

time, s

800

1000

1200

200

400

600

time, s

800

1000

1200

1400

-

NaxAuy
T=1270 K



.. 1, .. 1 , .. 1,2
, . 13, 03164, E mail
khain@ispe.kiev.u
2 , . . 38,
03142, E mail kir@i.kiev.ua
1

V1,2

3/
%

S 1 2/

V1
3/

V2
3/

480

0,4029

0,380

110 0

500
536

0,4053
0,4201

0,267
0,229

0,1383
0,191

400 0

0.05

1,68

1,77

34,1
45,5

1,61
1,57

1,71
1,72

16
12
,/

0.03

10
8
6

0.02

0.01

14

0.04

6
2

4
2

2
0.00
1

r,

0
0
4 5 0 1 2 3 4 5 6 7 8 9 10 0
pH

14

2
-25-20 -15 -10 -5
HCl,

(4)
(5)

8
6

8
pH

10 12 14

5 10 15 20 25 25 20 15 10 5
NaOH HCl,

10

10

12

8
(4)
(5)

30

14

10

9
8
7
6
5
4
3
2
1
0

25

10
6

10
15
20
Na2HPO4,

14

(1)
(2)
12
(3)

(1)
(2)
12
(3)

. 2. 110
(1) 400 (2). =5,6 /.

. 1.
( DFT)

dV(r)

R2

10

1 BET ; 2 BJH-

0
110
0
400

, /

0.06

R1

10

12

pH

5 10 15 20 25
NaOH,

. 3. pH- Hl NaOH (1)

(2) (3) C110
() t 400(). A pH
(4) (5) 110 () 400
().

10 15 20
C Na2HPO4, /

25

30

. 4. - 400 (a) 4 (1) 8

(2), 110 () 4 (1) 8
(2).

 - ..., , .
,
.
,
20
/ , ,

1000 .

.

/
(Cu, Ni, o, Fe)
.
, .

/
: ,
.

, ,

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

 / ?
/
,
.
.
.

,
,
,
, , , .


,

.

,
/3

Cu/C

1,15

25

,

, .

Ni/C

1,04

11

Co/C

1,16

10

Fe/C

1,09

17

Cu/C

Ni/C

Co/C

Fe/C

(Cu(I) ) 21.05.10
25
20
15
10
5
0
5

10 15 20 25 30 35 40 45 50 55 60 65 70

(Cu(II) ) 21.05.10
30
25
20
15
10
5
0
5

10

15

20

25

30

35

40

45

50

55

60

65

(Fe )21.05.10
25
20
15
10
5
0
5

10

15

20

25

30

35

40

45

50

60

( )
21.05.10
60
50
40
30
20
10
0
5

10

15

20

25

30

35

40

45

50

55

60

 /
-
(Ni )
06.05.10
70
60
50
40
30
20
10
0
5

10

15

20

25

30



/







/
,
/

,
.. (
- )

,
(B )

,
(B )

Ni/C

0,6

2,5

Co/C

1,7

2,5

Cu/C

0,3



.
(
) 2,0 0,001-0,0033%
.

/



75 100
,

.



, .


, .
/
/


,
.

50 %
80 %,
/
0,0001-0,0003%.


0,0001% /

 /




. ,
0,01% /

( 1,5 )
.
400
500
560760.

 (
-
, . )

/
,



.

,
( 8721-027-00302480-04).

13 %
.

/





.



.



.




,
:


,

426033,
, . ,
. , 3

:

E-mail:
itc2003@rambler.ru,
techpro-ur@mail.ru.
: (3412) 90-3068, 90-32-32

..1, ..1,
..1, .. 2
1

,
. , 6, 79005, . , o_hertsyk@yahoo.com
2
,. , 76, 79015, .
35

d,

25
0,6

10

10

-1

-1

20

40

80

100

300
250
S*10 ,

60

. 2.
, -1
: 0,5 / (1); 2,5 / (2);
5,0 / (3) .

200

20
2

35

35

35

35

19,34

15,03

85,9

110,5

30,12

9,03

550,2

184,0

6,02

15,06

275,9

110,3

3,01

48,90

551,9

34,0

9,04

30,76

183,8

54,0

3,62

29,95

458,9

55,5

14,47

36,14

114,8

46,0

16,32

54,20

101,8

30,6

150
100
50
0
0,0

1,25
-2

t,

.
1.

Fe78,5Ni1,0Mo0,5B6,0Si14.0
(1)

Fe73.1Cu1.0Nb3.0Si6.5B7.4 (2) 5 /
-1

0,2

20
15

0,4

1.
() (S) -1 -2 ()
35 () - -
.107,
S.1020,
.107,
S.1020,
10 ,
/

30

0,8

-E ,

()
~ 2000
, 2--2--5-3- (1) , 3--3-
(-2).

.

() Fe78,5Ni1,0Mo0,5B6,0Si14,0

Fe73,1Cu1,0Nb3,0Si6,5B7,4.

-
,
(
).

()
,
(S).

.

1
0,2

0,4

0,6
, %

0,8

1,0

. 3.
-1 (1) -2 (2)
.

0,50
-2

2.
2

( E A ) ( EA )

104,
/

-1

-2

E 1A ,

E A2 ,

E 1A ,

EA2 ,

5,0

/
8,5

/
62,3

/
12,4

/
84,3

2,5

6,2

42,0

11,2

102,0

0,5

5,4

56,0

8,6

33,2

,
(. 2).
E 1A E A2 .
, .
, E 1A
.

. 4. -1
() -2 ().



. .1, ..2, ..1, ..1, ..2
1

. .. , -mail: ryash@i.ua
2

. -, 2, 01011, , , -mail: mfibers@ukr.net

Ag/SiO2 .
308 420 ,
10 .
- : :
, 150 .
. 1.
,

1.
,
, =7

146

154; 164; 170

186

40

118

113

104

14

+0,1 % Ag/SiO2

150

162; 174

192

42

124

120

110

14

+0,5 % Ag/SiO2

147

157; 174

192

45

125

121

112

13

+1,0 % Ag/SiO2

145

152; 174

190

45

122

116

106

16

1 ,3
, 2 ,4

2.
, =7

,%

E, M

,%

, %

4,0

400

8,9

5300

0,20

11,0

+0,1 % Ag/SiO2

4,1

540

14,5

7500

0,20

8,7

+0,5 % Ag/SiO2

5,0

510

14,6

6400

0,25

8,4

+1,0 % Ag/SiO2

4,8

410

11,1

6200

0,30

8,3

, , , ,

3. , 0,5 . % Ag/SiO2
, (n=6)
St.aureus
ATCC
25923

St.aureus
ATCC
6538

E.coli
ATCC
225922

P.vulgaris
ATCC
4636

Ps.aeurog.
ATCC
27853

Ps.aeurog.
ATCC
9027

C.albicans
ATCC
855/653

11,2+1,2

11,2+0,8

11,1+0,9

9,5+0,9

10,0+0,9

10,1+0,8

7,8+0,8



.. , .. , ..
. ..
e-mail: nasiedkindm@gmail.com
: C1s, O1s S2p
.

( 26 2/)

( ~12/) H2SO4
H2O2
()
900 10 .

35 , 100
.

6000
4000

RO

2000

C
O

0
296

14.0
13.6
13.2
12.8
12.4
12.0
11.6
11.2
10.8
176

C O
O C O

292
288
284
',

280

S2p1/2, S2p3/2
O S
S OH

O
O

O S

OOH

172 168 164 160

',

160

150
O S
S2p1/2, S2p3/2
140
130
120
S OH
110
100 S
90
80
70
60
50
176 172 168 164 160
',

S2p (175-160 )


,
,
(S, S(OH)),
,
(S(O), S(O)2), ,
(HSO3, HSO4).

, ..

C C
RO C C H

C1s
O1s (296-280 540-526 , )



(),
(=), (),
(=)
, ,
(, ).

820
800
780
760
740
720
700
680
540

, ..

8000

C1s

, ..

, ..

, ..

12.8
12.4
12.0
11.6
11.2
10.8
10.4
10.0
9.6
176

O1s

O
C

OR

RO

C
O

OH
HO C

O C

537 534 531 528

',

S2p1/2, S2p3/2
O S
S OH

O
O

S
O S

O-

O-

O
O

OH

OH

172 168 164 160

',

C C, O S

H2SO4
1,49 13,21 . %, 0,02 0,61 . %.

1,08 0,03 . %, .
,
,
.

 .., .., .., .., * ..

. .. ,
. 41, . e-mail: pavlovich.inga@mail.ru
* ,
. 1, .
1

8 .
HBr.
. % H2O2 HBr.
8 .% H2O2 HBr

lnC

23

20,67

10,61

n-(Bi2Te3)0,9(Sb2Te3)0,05(Sb2Se3)0,05

28,95

14,05

-(Bi2Te3)0,25(Sb2Te3)0,72(Sb2Se3)0,03

11,93

7,14

25

20

V, /

:
1 ;
2 ;
3 ;
4 ;
5 ;
6 -

15

10

3
1
2

30

60

90

120

150

180

23 (1),
n-(Bi2Te3)0,9(Sb2Te3)0,05(Sb2Se3)0,05 (2)
p-(Bi2Te3)0,25(Sb2Te3)0,72(Sb2Se3)0,03 (3)
,

8 . % H2O2 HBr (=291 , =86 1).

210

25

V, /

20

15

10

p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 ();
10 5 () ,
8 .
. % H2O2 : 92 .%
.% HBr ().

10

12

14

16

18

20

c, .% H 2O 2

23 (1), n-(Bi2Te3)0,9(Sb2Te3)0,05(Sb2Se3)0,05 (2),
p-(Bi2Te3)0,25(Sb2Te3)0,72(Sb2Se3)0,03 (3)
H2O2HBr ( = 291 , = 86 -1).
0,4

0,2

3
1
2

0,1

0,0
0,08

0,10

0,12

-1/2
1/2
,

0,14

0,16

ln V, [V,/]

-1
v , /

0,3

3
1
2

3,25

3,30

3,35

3,40

3,45

3,50

3,55

103/,

23 (1),
n-(Bi2Te3)0,9(Sb2Te3)0,05(Sb2Se3)0,05 (2)
p-(Bi2Te3)0,25(Sb2Te3)0,72(Sb2Se3)0,03 (3)
(=291 ) ()
(=86 1) () ,
8 . % H2O2 HBr.



.
.., .., .., ..
. ..
17, . , 17 -164, 03164,
sprokop@yandex.ru
(Ag2S) .
, , , ,
.

(). Ag2S.
(Ag2S)
Ag2S. (SiO2/Ag2S) Ag2S -300.
(/Ag2S)
Ag2S.
log
1

log

0
-1
-2
-3
-4

1
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
0,0

5
4
3
2
1

-5

0
30 60 90 120 150 180 210 t C
. 1.
/Ag2S
' Ag2S: 1 - 0,105, 2 - 0,154, 3
- 0,215, 4 - 0,5, 5 - 0,65.

3
5

4
6

0,1

0,2

0,3

0,4

0,5

0,6

0,7

. 2.
/Ag2S (1, 2), SiO2/Ag2S (3, 4), Ag2S (5, 6)
Ag2S: 1, 3, 5 - 200, 2, 4, 6 - 30.

(0,1; 1 10 ) 7-14,
(', '') () 9 .
Ag2S
, , -Ag2S,
35 55 .
''

'

12

16

12

2
3

0,1

0,2

0,3

0,4

0,5

0,1

0,7

0,6

'

50
40

180

0,2

0,3

0,4

0,5

0,6

0,7

''

150

. 4.
' () '' ()

/Ag2S 9 '
Ag2S: 1 - 0,154, 2 - 0,215, 3 - 0,29.

120

30

90

20

2
1

60

10
0

. 3. ' ()
'' ()

Ag2S 1 /Ag2S, 2 - Ag2S/SiO2, 3 Ag2S.

10

10

14

30

30

60

90

120 150 180 210 t, C

0
0

30

60

90

120 150 180 210 t, C

1 /Ag2S, Ag2S/SiO2, Ag2S.

/Ag2S (. 1) t=176C
Ag2S .
(. 2) ,
. Ag2S/SO2 Ag2S 0,12 0,2 ' .
/Ag2S 0.1.
. 3 ' ''
Ag2S. Ag2S Ag2S
. Ag2S SO2 , ' '.
Ag2S SO2
. , ' '' /Ag2S.
' '' /Ag2S .4. Ag2S 0,154 0,215
' ''
. Ag2S 0,29 ' '
'' . .

ACTUAL PROBLEMS OF CHEMISTRY AND PHYSICS OF SURFACE May 1113 2011 Kyiv Ukraine

EFFECT OF SALT AND DISPERSION CONCENTRATION

ON ZETA-POTENTIAL OF PRISTINE AND OXIDIZED
MULTIWALLED CARBON NANOTUBES
Bolbukh Y.11, Gunko G.11, Prikhodko G.11, Tertykh V.11, Laszlo K.22, Toth A.22,
Koczka B.22
1Chuiko

Institute of Surface Chemistry of NAS Ukraine, 17 General Naumov Str., Kyiv 03164;
e-mail: yu_bolbukh@yahoo.com
2 Budapest University of Technology and Economics, Budapest, Hungary

Among other carbon materials carbon nanotubes are characterized by the ability to accumulate charge, fast cycle of
charge/discharge and these properties are important for creation of devices operating on the principle of an electric
double layer (EDL). The rapid development of technology of preparation of ionistors based on application of nanotubes
determines the relevance of studies of EDL formation on nanotubes with different functionality in the electrolyte
medium.
ICP results

This presentation is directed to investigation of the structures features

of the MWCNTs by zeta-potential mesuarment
Objects:
1. Purified MWCNTs
The MWCNTs used in this study were synthesized by pyrolysis of propylene on ferric
catalyst and purified by mix of HCl and HF for removing the residual catalyst and
amorphous carbon with following washing from acids by water.
2. Oxidised MWCNTs
MWCNTs were dispersed in water. and then the hydrogen peroxide was added to
suspension. Mixture was heating at 80 C under stirring for 47 h. The concentration of
H2O2 was 30%. The solid was filtered under vacuum and dried at 150 C obtaining the
oxidized nanotubes. The bordered layers of the nanotubes obtained mainly contain
hydroxyl groups. In addition, for fulvic acid removal the pristine and oxidized nanotubes
were treated with sodium hydroxide solution followed by washing the samples with
hydrochloric acid.

The zeta-potential values of pure and functionalized carbon

nanotubes were determined at the different concentrations of
nanotubes dispersion in sodium chloride aqueous solution (0.01 M
and 0.1 M) using a Zeta-analyzer (Zetaplus, Brookhaven, USA).
A value of zeta potential on the nanotubes is determined by defects in the
structure of walls, nature and concentration of active sites, nanotubes
morphology, and degree of dispergation. The electrolyte availability
improves the dispersability of nanotubes in aqueous medium, while the
electrolyte solvating action is more noticeable at the less concentrations. As
expected, values of the zeta potential are decreased with increasing in KCl
concentration, it results in rapid coagulation of the suspension. During
aggregation a compensation of charge or change of the counterions charge
in the diffusion layer takes place. Sedimentation of the enlarged aggregates
complicates the measurement of zeta potential in these systems.
pristine MWCNT

15

5
0
0

10

pH
12

-10

Zeta potential

Zeta potential

MWCNT
oxidized

mg/kg

mg/kg

Ag

Al

14

12

As

13

12

Ba

1.1

0.9

Be

0.18

0.16

Bi

20

17

Ca

25

22

Cd

1.9

1.6

Co

Cr

Cu

Fe

47

150

Hg

0.7

0.6

Li

10

Mg

6.48

5.98

Mn

0.9

0.8

Mo

319

243

Na

60

90

Ni

10

13

14

Pb

30

20

15

46

Sb

30

30

Se

50

40

Sn

17

14

Sr

0.3

0.2

Ti

20

17

Zn

2.2

Zr

oxidized MWCNT

10

-5

10

MWCNT
purified
Element

0
-5
-10

10

pH
12

-15
-20

Dependences of zeta potential of purified or oxidized MWCNTs on medium pH at initial concentration

of the nanotubes suspension of 0.5 mg/ml in 0.1 (1) or 0.01 mol/l KCl solution (2).
An
An increase
increase of
of initial
initial concentration
concentration of
of the
the dispersion
dispersion
was
was found
found do
do not
not change
change the
the value
value and
and the
the
character
character of
of zeta
zeta potential
potential dependence
dependence on
on the
the
medium
medium pH
pH also.
also. The
The curves
curves obtained
obtained at
at the
the initial
initial
concentration
concentration of
of the
the nanotubes
nanotubes dispersion
dispersion of
of
0.5
0.5 mg/ml
mg/ml (Figure)
(Figure) have
have an
an extremum
extremum in
in the
the zetazetapotential
potential value
value at
at pH
pH 5.
5. Earlier
Earlier this
this effect
effect was
was
observed
observed for
for dispersion
dispersion of
of nanotubes
nanotubes with
with
concentration
concentration of
of 0.4
0.4 mg/ml.
mg/ml.

SEM images of purified and oxidised

MWCNTs

It should be noted that the nanotubes are

dispersed better in the acidic media. The
isoelectric points (IEP) for the pristine and
oxidized nanotubes were observed at about
pH 4.0 and 3.5, respectively. The largest
value of zeta potential of the samples was
registered at the dispersion concentration of
0.05 mg/ml. Increase in the dispersion
concentration as well as growth of the
concentration of potassium chloride caused a
shift of the IEP values to the lower pH. This
shift was more significant for the oxidized
nanotubes. At the higher dispersion
concentrations the values of zeta-potential
became more positive.

At concentration of 0.1 M the electrolyte caused the greater effect on the pristine nanotubes: for this
sample zeta in the acidic pH range the potential values became positive and were in reasonably
good agreement with the literature data. In contrast, for the oxidized nanotubes with increasing of
the electrolyte concentration the potential values became more negative in the whole pH range.
Change in a character of the foregoing dependence for the systems under study may be connected
with the morphological features of aggregates formed at the high concentrations of the dispersion.
This work was partly supported by FP7 Marie Curie Actions People Project Hybrid nanocomposites and their
applications - Compositum, Grant Agreement Number PIRSES-GA-2008-230790.

.., .., ..
-ml: karvan@ukr.net

,
-
..
. 0,5

l , = 4,5 N- 1 N3 . N3 ,
= 7,5, .
0,51 . , , 1- . . , . 6 ( 300 ) 150 3/. ( , ) 9 (, ), -2.

NaCl (1 2 )
2000

1
1-

(Fe),
()1000,/

1500

1000

NaHCO3
:
, 30, W30, N1/2
2,

40

2-

30

15

15

2-Fe

45
45

1-Fe

20

15 25 20

500

25

20
. .

-1

0
0

100

200

300

400

10

50

15
15

15

15

:
10
-2
, ;
-2
-1
30 ,
30 .. , ;
W30 ( , ), %;
N1/2 ' , 1/2 .

100

20
0

25 30 35
1
2
1,

, %

NaCl i NaHCO3

W
W

, %

W
W

NaCl

89,9

37,5

16,8

NaHCO3

82,0

75,8

25,5

NaCl + NaHC3

98,2

84,9

37,9

C -

.., .., .., .., .., ..
- . ..
n.i.makhova@gmail.com

- 4-6

SnCl2
HCl

C6H12O6

(NH4)6Mo7O244H2O
SnO2

HNO3

HCl

(TEM)

25

30

30
25
20
15
10
5

, %

, %

, %

35
20
15
10
5

10

11

12

25
20
15
10
5
0

10

, %

40

10

11

12

6
4
2
0

13

10

12

14

16

18

-

4
2
1
3
, % .

2,5-3,0

, % .


,
, , 20

6,5-7,0
0.8-1,0

2,2-2,5

1,0-1,2

22,0-27,0
1,7-2,0

926 + 411

2,4-4,0

-
2009-2013 . (.. 1001) 10-03-01002-.

SELF-ORGANIZATION OF N-ALKYLCYANOBIPHENYL
ON RECONSTRUCTED Au(111) SURFACE: STM STUDY
Sergii S1, Senenko A2**, Marchenko A2, Lacaze E4
1 Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, Kyiv, Ukraine
2 Institute of Physics, National Academy of Sciences of Ukraine, Kyiv, Ukraine
3 Institut des Nano-sciences de Paris (INSP), CNRS/Universit Pierre et Marie Curie, Paris, France
* ssnegir@gmail.com ** senenkoanton@gmail.com

Introduction. Liquid crystals (LQ) such as n-alkylcyanobiphenyles (CB) are widely used in different devices especially
in LCD. The remarkable property of LQ is their ability to change bulk structure under the external electric field due to
dipole moment of the molecules. Such field stimulated phase transitions are determined by anchoring of first layer with
the surface of metal electrodes, in particular Au(111) .

STM tip

Piezoceramic

Sample holder
of gold substrate
a)

b)

Figure 1. Image of STM low current head.

Figure 2. a) STM image of reconstructed Au(111) surface; b) Model of reconstructed Au(111) 23x3 surface [1].
Experimental section. The structures of formed monolayers were investigated using a commercial STM equipped by low current head (Veeco, Digital Instruments,
Inc. USA). The STM tip was prepared by mechanical cutting of Pt/Ir (80:20) wire. For each monolayer, several STM-images recorded in constant current mode with
current of about 13 pA and tip bias of 50300 mV were obtained with different samples and tips to check reproducibility and to ensure that results are free from
artifacts. The Au(111) substrates are Neyco gold films (thickness ~150 nm), carefully annealed in a gas flame (propane+air) in order to obtain a reconstructed surface
(Fig.2a,b), as an evidence of chemical purity of a surface.

4-pentyl-4-cyanobiphenyl (5CB)

a
b

60
c)

b)

a)

Figure 3. a) 8.78.7 nm2 and b) 19 19 nm2 STM

images of SAM of 5CB molecules on Au(111), scanning
parameters: It= 2 pA, Ut = 180 mV. Rectangle define
unit cell with basic vector a = 17.34 0.2 and
b = 24.9 0.2 of molecular packing. c) packing
model of 5CB on Au(111).

070

4-octyl-4-cyanobiphenyl (8CB)

b)

a)

Phenyl rings of one molecule.

direction of row jump

Figure 4. a) 1515 nm2 and b) 4.6 4.6 nm2 STM images

of SAM of 8CB molecules on Au(111), scanning parameters:
It= 8.4 pA, Ut = 267 mV. Rectangle define unit cell with basic
vector a = 86 0.2 and b = 10.3 0.2 of molecular
packing. c) packing model of 8CB on Au(111).

c)

CN= group

4-dodecyl-4-cyanobiphenyl (10CB)

a)

[1] Langmuir 2002, 18, 8116-8122

b)

c)

Figure 5. a) 76.576.5 nm2 and b) 9.2 9.2 nm2 STM

images of SAM of 10CB molecules on Au(111), scanning
parameters: It= 11.8 pA, Ut = -160 mV. c) packing model
of 10CB

APLICATION OF CARBON NANOTUBES IN MEDICINE

V. Korolovych1, P. Pour Khosrow2, A.G. Derzhypolskyi1, D.O. Melenevskyi1
1

Department of Physics, Kyiv National Taras Shevchenko University, Kyiv,

Ukraine. E-mail: korolovich@gmail.com
2
Bogomolets National medical University, Peremogy Av. 34, Kyiv, Ukraine

Development of contemporary nanotechology for medicine on the basis of

carbon nanotubes with functionalisation of their surface opens up new
opportunities for the mankind, such as targeted transport of drugs, vaccines and
genes, creation of biosensors, nanomedical-devices, and efficient nanotechnologies
for medical purposes. It will have a significant influence over the length, the
quality and safety of human life in different conditions. But the strong Van der
Waals interactions between nanotubes leads to their aggregation in various
solvents, that much limits their applications. Therefore, it is important to
investigate processes of aggregations of carbon nanotubes as well as the geometry
and stability of such aggregates in solvents.
We have introduced dynamic light scattering (DLS) to measured the optical
inhomogeneties in water system with single-wall carbon nanotubes (SWCNTs),
wich are functionalized with carboxyl groups (-COOH) in the temperature interval
(25 50) C and concentration (0,3 3) g/l.
The DLS spectra were obtained by using an complex of laser correlational
spectroscopy Nano S (Malvern Instruments). The wave-length of laser is 632.5 nm.
The calculation error of globule size is 2%.
By experimental data of distribution the intensity of scattered light on the
size of optical inhomogeneities was calculated bulk distribution (V) of inhomogeneties per their sizes (D) (Fig. 2).
Scattering analysis shows,
that there are inhomogeneties with
two diameters: 300 n, and 5500
nm. For our opinion, 5500 nm
aggregates
(65%
of
all
inhomogeneties) are constructed
by SWCNT, organized by van der
Vaals forces.
It is another inhomogeneity
with diameter 300 nm we
attributed to amorphous carbon.
Fig.2. Distribution of the optical
Geometry of the SWCNT
inhomogeneties in the water-SWCNT
aggregates are stable in the
system. Concentration is 0.3 g/l
temperature interval (25 50) C
and concentration (0,3 3) g/l.

 ,


. . 1 , .. 2 , . . 1 ,
1

. .. , , 03164, . , 17, e-ma il: taiscrust@mail.ru

2
. .. , , 03162, . , 36
, ,
, ,

, , .
,
, (U-=aU+ , U+
V).

U,
,
,

U r :

r (x , t ) = - J (x , t )m
g + r + (x , t ) - g - r - (x , t )
,
t
x
- bU x
bU x
J ( x, t ) = - De ( )
e ( ) r (x , t )
.
x

r (0 , t ) = r (L, t )

[0,L], ,
:

r ( x, t ) = - J ( x, t ) m
g + r + ( x, t )- g - r - ( x, t )
,
t
x
b U ( x)
J ( x, t ) = - De - bU (x )
e
r ( x, t )
.
x

r (0 ) =

gm
gm
r0 , r (L) =
r1
g+ + g g + + g-

D , (x,t) , J (x,t) -- +
-, g -- , b=1/(k BT)

.
3
2
(b V) , (bV) .
a,

. .

( ) a=2/3 ( ) a=-2/3 (
). , .

P. Reimann, Phys. Rep. 361, 57 (2002).

P. Hnggi, F. Marchesoni, Rev. Mod. P hys. 81, 387 (2009).
V. M. Rozenbaum, D.-Y. Yang, S. H. Lin, T.Y. Tsong, J. Phys. Chem. B 108, 15880 (2004).
. . , . . . , ( 11-12), . . . , , , 2006
(436 .), . 29-40.
A. Gomez-Marin, J. M. Sancho, EP L 86, 40002 (2009).
V. M. Rozenbaum, T. Ye. Korochkova, A. A. Chernova and M. L. Dekhtyar, Phys. Rev. E (2011, to be published).

 -

.. , .. , .. *, .. *, ..
. .. ,
. 17, 03164, , okstavinskaya@yahoo.com
* . .. ,
. , 1, 01014, , nbg@nbg.kiev.ua

(M. sieboldi, M. kobus, M. Soulangeana,
Magnolia stellata) . ,
70 %
- .
- .
-
-300 200 2/, Fluka .
- ,
t . ; 2
- 4
.
, , ,
,
.
,
330 , c .

,
, ,
.
.
, .
.

;
. ,
,
, ;
.
, ,
, , .

-

Magnolia
sieboldi

( )

(70 %- )
1 / 100

30

Magnolia
kobus
Magnolia
Soulangeana
Magnolia
stellata

* - **

1
2
3
4

* * ** * *
** **
**
1
2
3

+
+
-

+
+
+

+
+
+

+
+
+

+
+
+

+
-

0,6
m/z

7.4
6.0
8.0
5.6
2.0

0.37
0.30
0.40
0.28
-

1
2
3
4
0.1

D (520 ), . .

162
, =163

0,5

0,4

179
, =180

M2

301 ,
=302

M4
0,3

354
, =354

M1
M3

0,2
0

20

40

60

80

100

- 1-4

120

1-4

1000

0,4

Gel+SiO2+M1

0,3

4 10 8

15

M3
M2

0,50

0,0
250

300

350

0,00

0,0

1 - Gel

2 - Gel+SiO2
4 - Gel+SiO2+M1

5 -Gel+M2

6 - Gel+SiO2+M2

7 -Gel+M3

8 - Gel+SiO2+M3

9 -Gel+M4

10 - Gel+SiO2+M4

30

0,5

1,0

1,5

2,0

0,0

0,5

1,0

1,5

2,0

0,75

Gel+M3

450

500

Gel+SiO2+M3

0,4

0,50

0,00
0,0

0,5

1,0

1,5

2,0

*,

*,

0,144

0,007

0,007

0,106

0,005

0.006

0,169

0,008

0.008

0,129

0,006

0.006

Gel+SiO2+M4

0,25

0,0

1-4 70 %- ,
1:125

,
1-4.
48

Gel+M4

0,6

45

400

0,1

3 - Gel+M1

M4

0,1

Gel+SiO2+M2

0,2

0,75

0,2

0,25

0,0

500

Gel+M2

0,2

D, . .

Gel+M1

, . .

, . .

dM/M(Gel), %

1500

0,5

, . .

, . .

M1

0,3

0,0

0,5

1,0

1,5

2,0

1- 4 -

- M. sieboldi, M. kobus, M. Soulangeana, M. stellata, .

- , . ,
,

EFFECT OF OXYGEN AND WATER ADSORPTION ON THE GAP STATES FOR GeS SINGLE CRYSTALS
Savchenko N.D.1, Shchurova T.N.1, Opachko I.I.1, Panait T.I.1, Popovic K.O.2
1Uzhgorod
2NanoTecCenter

National University, 13 Kapitulna St., 88000 Uzhgorod, Ukraine, fax: +38 03122 30656, email: shchrv@ukr.net
Weiz Forschungsgesellschaft mbH, Franz-Pichler-Strasse 32, A-8160 Weiz, Austria, email: karl.popovic@ntc-weiz.at

Motivation

Computation Results

Application of theoretical approaches to the development of gas sensors

Table 1

Objective
Determination of the surface bending of the energy bands for GeS single
crystals under oxygen and water molecules adsorption in terms
theoretical approach by W.A. Harrison

GeS

Ec =

2
+ pS
Ge
p

where

+ (V2 )2 +(V3 )2 + Es o V1 E pd

(V2 )2 +(V3 )2 + V1

U
,
2

U
,
2

U/2, eV

Es-o, eV

Epd, eV

2.14

4.24

0.06

00.08
Table 2

V3, eV

U/2,
eV

EF, eV

theory, eV

exp, eV

O2

0.120

6.77

7.23

9.54

0.16

0.12

(1)

H2 O

0.153

4.00

1.59

6.02

9.17

-0.21

-0.25

d interatomic distance
V1 metallic bond energy
V2 covalent bond energy
V3 polar bond energy

(2)

h
Ge pS
1
, V3 = p
, Es o = Es o ,
2
md
2
2
p s
V1Ge + V1S
U U Ge + U S
Ge ( S )
V1 =
, V1
=
,
=
,
2
4
2
4
2
E pd
10 15 h 2
E pd =
, with E pd =
rp rd3 .
p d
3 md 4

V3, eV

2.77

V2 = 2.96

Evac
-5.14
Ec
E g =1.76 eV

= E

GeS
F

-5.14

E g =1.76 eV

O , H 2O
F

Fig. 3. Energy band diagram under water adsorption for GeS surface: a) clean
surface; b) water exposed surface

Experimental Results
1

1.5

0.1

0.05

Ec
EF 2
EF 2

-10

Ev

S 3p

, A

Ge 4p

-6

Ev

-5

-5

=-0.21 eV

-6

Ev

(4)

-4
-4.93

EF

=0.16 eV

U
,
2

E, eV

Ec

-5

Results of Modelling

E, eV

O
p

-4
-5.30

EF

O2
F

E vac

E, eV

(3)

Fermi level and work function changes under adsorption:

S

Ge
1
p +p
,
E FGeS = E spGe3 +

2
2

H 2O
H
O

U
s
p
EFH 2O =
,
2
2

U Coulomb intratomic repulsion energy

Es-o Ev shift due to spin-orbital splitting
Epd Ev shift due to pd-coupling
work function shift

0.5
1

p, 10 3 Pa

-0.5

, eV

Ev =

V2, eV

2.53

V2, eV

Computation of the positions of valence band maximum (Ev) and

conduction band minimum (Ec) for GeS:
S
p

V1, eV

d, nm

Computational procedure

Ge
p

d, nm
0.286

p, 10 3 Pa

-0.05
-0.1
-0.15

-1

-1.5

a)

-0.2

b)

-2

U/2
H 1s

Fig. 4. Conductivity (a) and thermoelectronic work function (b) changes versus
pressure for GeS single crystals under oxygen (curve 1) and water (curve 2) adsorption

-15
O 2p

Fig. 1. Energy bands formation from the atomic terms for GeS
and Fermi level formation for H2O and O2 molecules

-5

10

t, min

-0.05

2
0

-0.1

E, eV

-0.15

Ge 4p

II

3.6

0.05

, eV

0.1

2.4

1.2

a)

b)
0

Ge sp3
-10

Ec = 8.52 eV
EF = 9.38 eV
Ev = 10.36 eV

12

16

20

t, min

Fig. 5. Work function (a) and dark current (b) versus time for GeS single crystals
under oxygen (curve 1) and water (curve 2) adsorption.

S 3p

Summary

Fig. 5. Work function (a) and dark current (b) versus time for GeS single

-15

Ge 4s

Fig. 2. Fermi level formation in GeS

Different effect of oxygen and water molecules adsorption on the surface bending of the
oxygen
(curve
1) and
water (curve 2) adsorption
energy crystals
bands for under
GeS single
crystals
has been
found
Applicability of the developed approach to the prediction of work function changes in GeS
single crystals under oxygen and water molecules adsorption has been shown



. . , . .
. . .
, 03164, . , 17, mohican@inbox.ru

( T (t ) = T0 + bt )
,
,
j (T ) , [1-3].

ln j (T ) const U / k BT

,
. ,
. [4]

b = 0.1 1 K / c
w(T ) = exp ( U k BT )

U
= 1010 1011 c-1

(1)

zm = U / k BTm

zm ln[ U /(bk B zm2 )]

[4]

(2)

Tm

( )

U

[4]

Tm* = 100 K

0 = Tm* / b

0 = 1012 1014

, Tm 130, 240, 310 K , [5] ,

-300, 10 %
U = 30, 55, 17 /

0 2
:

U k BTm ln[ 0Tm /(T ln 0 )]

*
m

80

(3)

U Tm 0 = 10 ,
1013, 1012 , .
.

0 (. 3)
14

0 , 10
2.3,
10 %
Tm U
,
.
, ,
, .

U (KJ/mol)

U k BTm ln[ 0 / ln 0 ] (24.3 28.8) k BTm .

60

40

20

0
0

100

200

300

T m (K)

. 1. U Tm 0 = 1014, 1013 , 1012

( ).

[1]. T. Nedetzka, M. Reichle, A. Mayer, H.Vogel, J. Phys. Chem. 74, 2652 (1970).
[2]. S.W.S. McKeever, D.M. Hughes. J. Phys. D: Appl. Phys. 8, 13, 1520-1529 (1975).
[3]. J. Vanderschueren, A. Linkens, J. Gasiot, J. P. Fillard, P. Parot, J Appl. Phys. 51, 4967 (1980).
[4]. . . , . ., . . , 52, 2046 (2010).
[5]. V.M. Gun'ko, V.I. Zarko, E.V. Goncharuk, L.S. Andriyko, V.V. Turov, et al., Adv. Colloid Interface Sci. 131, 1 (2007).


,
-18--6
., .., ..
. ..,
-164, . , 17
lgolovkova@rambler.ru
, , , . -, , .
, - .
, , -, , ,
, .

- ,
.

-18--6
()


.

,
-
.

-.

, /

40
30
20
10
0

H2N

0,4

0,8

1,2
1,6
C ,

2,0

H
N

NH2
H2 H 2 H2
C C C CH2

70
60
, /

50

50
40
30
20
10
0

HO

4
5
,

CH 2CH 2NH 2

NH

15

, /

25

, /

20
15
10

H 2N

0,2

H
N

0,4

0,6 0,8 1,0

,

1,2

-1818--6

1,4

NH

OH

25

1,0
1,5
,

2,0

CH2 CH
+
NH3

20

OH

15
10
5
0

0,5

HO C O
HO

NH2
H2 H2 H2
C C C CH
, /

10

0,4

0,8
1,2
,

1,6

H2N

C
NH

H
N

O
NH2 O
H2 H2 H2
C C C CH C HN

C
H2
CH C

,

()
.

S- .

,
.

lgK
SiO2+DB186
SiO2

+
SiO + HAm SiO HAm (pH=7,3)

2,60
2,51

2,14
1,76
SiO + AaH2+ SiOAaH2+ (pH=4,3)

1,53

1,01

SiO + H2DP+ SiO H2DP+ (pH=5,6)

3,06
2,7

, -
. -,
- -18--6 .

- .

 WO3.

.., .., .., ..

. .. , 03680, -142, . . ,
32/34, . (044) 424-22-80 424-3070, e-mail: kolbasov@ionc.kiev.ua
WO3,
. 0,1 . H2SO4
, 10-20 .

.1 WO3,
=632.8 , ,
: 0,4
(1); 0,2 (2); 0,1 (3); 0,0 (4); -0,1 (5); -0,2 (6)
-0,3 (7) . Ag/AgCl.

.2 =1000
n ( 1,3) k
WO3,
. Ag/AgCl.

.3 WO3,

,
- '
2 4% (1), 30% (2) 100% (3).

- WO3/Pt
.

.4
WO3
- (0,1 H2SO4) =650
0,5 (1) 0,3 (2)

.5
= 1000
n = 1.65
WO3/Pt
: 0% (1); 0,01% (2);
0,05% (3); 0,2% (4); 1% (5); 10% (6).

.6
: 1 ; 2
WO3/Pd ; 3 ; 4 - ; 5
-
Log[H2] ( ).

Au/WO3/Pt.

.7

.

. 8
Au (40 )WO3 (25 ) Pt ,
-
5% 100 % 2.

.9 =650
(n=1,62) Au(54) WO3(310)
(0,1 H2SO4) 0,5
(1), 0,2 (2) 0 (3) . Ag/AgCl.

DIELECTRIC STUDIES OF THE INTERFACIAL AND

CONFINED SEGMENTAL DYNAMICS IN
PDMS/ZrO2/SiO2 NANOCOMPOSITES
K. Kyriakos1, I. Sulym2, P. Klonos1, I. Vangelidis1, A. Kyritsis1, M.V. Borysenko2, V.M. Gunko2, P. Pissis1
1
2

Department of Physics-National Technical University of Athens, Zografou Campus, 15780, Athens Greece
Institute of Surface Chemistry, 17 General Naumov Street, Kiev 03164, Ukraine

Introduction

Materials

The molecular dynamics of composite systems consisting of adsorbed polymer (polydimethylosiloxanePDMS) on the surface of complex nanooxides were studied. The oxides are composite materials of silica
matrix with grafted nanozirconia. The applied methods are Differential Scanning Calorimetry (DSC,
temperature range -150 oC to +40 oC in helium atmosphere), Thermally Stimulated Depolarization Currents
(TSDC, -150 oC to +60 oC) and Dielectric Relaxation Spectroscopy (DRS, -150 oC to +60 oC, frequency range
10-1 to 106 Hz) under two crystallization treatments. The different treatments aim to clarify the effect of the
crystal phase on the general mobility of the amorphous phase. Important results have been obtained about the
effect of the zirconia on the molecular mobility of the polymer and on the strength polymer-silica interactions.
Also some confinement effects on the segmental dynamics of the PDMS have been observed.

Three types of silica matrix were used (fumed silica A-380 [pilot plant of
the Institute of Surface Chemistry, Kalush, Ukraine], fumed silica OX-50
[Merck], silica gel Si-60 [Degussa]) and one to four cycles (repetitions) of
zirconia grafting were applied. The PDMS (linear, Mw=7960) was
adsorbed onto oxides samples in the amounts of 40 wt% and 80 %wt.
Before the adsorption oxide samples were dried at 383 K for 1 h, then the
solution of PDMS in hexane (oxide+PDMS~10 wt%) was added. The
zirconia grafting procedure has been described elsewhere in details[1].

(a)
Fig. 2. Comparative TSDC diagram for samples based on
A-380 with 80 wt% for both crystallization treatments. A
strong dependence of the polymer dynamics on the
zirconia content and the crystallization treatment is
observed. The application of different crystallization
treatment favors the c relaxation which reveals a high
degree of crystallinity. Same result produces the presence
of more zirconia.

Fig. 3. DRS spectra ((f)) for sample based on silica

A-380 with 1 zirconia cycle and 80 %wt PDMS. Three
dielectric relaxations are observed each assigned to the
segmental dynamics of a different section of the
polymer with different molecular mobility: of the
bulk polymer, c of polymer chains constrained from
polymers crystal phases and of a section of the
polymer with modified dynamics due to interactions
with the filler (in increasing temperature)

(b)
Fig. 1. Comparative DSC thermogramms for all samples
with 80 wt% PDMS and (a) 1 cycle and (b) 4 cycles of
zirconia. The degree of crystallinity depends strongly on
the silica oxide type and the zirconia content of the
composite oxide.

Conclusions

The type of the silica matrix used in the composite oxides is strongly affecting the
crystallization of the polymer depending on the specific surface of each silicon oxide
used.
The presence of zirconia acts furnishing the interaction between the silica and the
PDMS for A-380 and OX-50 (e.g. favors the crystal phase) but does not effect the
system based on silica gel Si-60.
Three dielectric relaxations are observed in all systems: , c, relaxations in
increasing temperature; each assigned to a section of the polymer with different
molecular mobility.
An extra relaxation x is observed (by TSDC and DRS) for PDMS adsorbed on
composite oxides based on silica gel Si-60, probably originated from polymer
fragments confined in nanoporous of the silica matrix. The radius and the number of
the porous are not affected by the grafted nanozirconia [1].
References
[1] Sulym I. et al. Applied Surface Science, 225, 2009, 7818-7824
[2] Klonos P. et al. Polymer 51 (23), 2010, 5490-5499
[3] Schoenhals A. et al. Journal of Non-Crystalline solids, 351, 2005, 2668-2677

CONTACT K.K. e-mail: kurkost@hotmail.com

Fig. 2. Comparative Arrhenius diagram (dielectric map) for all samples based on silica
Si-60. The data from TSDC and DSC have been incorporated at the equivalent
frequencies logfTSDC = -2.81 and logfDSC = -2 respectively. An extra relaxation is
observed (x) at low temperature region originated probably from the segmental
dynamics of polymer chains which are confined in nanoporous of the silica matrix.
Solid lines are to guide the eye.

Acknowledgments: The research leading to these results has received funding from NSRF 2007-2013 European Social
Programme Education and Lifelong Learning investing in knowledge society co-financed by Greece and EU and the
European Community's Seventh Framework Programme (FP7/2007-2013) under a Marie Curie International Research
Staff Exchange Scheme, Grant Agreement No PIRSES-GA-2008-230790.



.. , .. , .. , ..
. ..
- ,
, , .

.
, ,
0,2 - 0,3 /, 30 50 1 .
-

:
- ;
- , , -
;
- , ,
.

. , , ,
,
.

, .
,
.

. .
.



.. 1, .. 2 *, .. 2, .. 1, .C.1,
.. 2
1
. . . , 65026, ,
, , 2.
2
-
. . . , 65026, , , 27.
*
. +38 048 7230329, e-mail: v_skobeeva@ukr.net


,

,

( -,

.
Ag
,

, .

().

=405 (.1,
. 1)
Ag 10 , = 420
(.1, . 2, 3) 30 .

. 3,

.


.

. 1. 30 (1),
40 (2), 50 (3) .
(AgNO3)/(Na3C6H5O7) = 1:4, 10-3M
.
.

. 2. ,

. 3.

, :
(1), 24 (2).

Ag
.

RAMAN SPECTRA OF NANODISPERSED CARBON IN CERAMICS OF SYSTEMS TIB2-C

Kazo I. F., Naumenko A. P., Mavlanova O. D.
Taras Shevchenko National University of Kyiv, Faculty of Physics,60, Volodymyrs'ka Str., 01601 Kyiv,
Ukraine, kazo@ukr.net, a_naumenko@univ.kiev.ua, anaskor@i.ua
Keywords: Raman spectroscopy, carbon nanoclusters.
The purpose of the given work is to research and analyse Raman spectra of ceramics of system TiB 2-C.
Nowadays, the Raman spectroscopy method (RS) is one of the most informative and convenient methods of
carbon structures researches. We consider such researches are a next step for verification of presence carbon
clusters in the synthesized ceramics.
Manufacturing of initial samples of ceramics, which containing carbon, carried out similarly to a way
described in work [1]. Manufacturing of samples was made by methods of sintering and hot pressing (HP) on
installation with resistive heating, without a protective atmosphere with temperature modes from 1100 to
1800, external pressure from 0 to 30 MPa and soaking time with from 60 to 2400 s in graphite crucible.
Spectroscopic researches spent by the automated spectral complex which based on diffraction grating
spectrometer DFS-24 (LOMO, Russia). Spectra were excited by radiation of Ar + laser (514.5 nm). The total
spectrum, received from several samples, is shown on fig. 1.

Intensity, st. um.

*
4 6 2
4 9 4

9 4 8

1 0 0 0

1 6 0 1
1 3 7 0
7 4 5 7 9 2

5 0 0

1 5 3 3
1 4 6 5

1 1 1 7

1 0 0 0

F re q u e n c y s h ift, s m

1 5 0 0
-1

Figure 1. Total, received from several samples a Raman spectrum of ceramics systems T2- at room
temperature is shown. The cut line (*) corresponds to the laser compelling radiation, and by virtue of high
intensity cannot be submitted in figure.
The earlier mass-spectroscopy researches [2,3] have shown evidence in similar samples presumably
hydrogen-carbon clusters 20n, where n=10, 20.
For this reason, from our point of view, it is expedient to carry out theoretical modeling of small carbon
polyhedrons spectra possessing a hydrogen atmosphere and retrace influence of this atmosphere on shift of
frequencies of the basic clusters vibrations.
Software package Gaussian 98 was used for calculation the vibration clusters spectra. Raman spectra of
clusters 20, 2010, 2020 which represent only carbon cluster, and also cluster in a hydrogen cloud and a
rarefied hydrogen cloud, accordingly; have the following features:
a) all three spectra contain two frequency bends: up to 900 cm-1 and from 1100 up to 1600 cm-1, except
that clusters, which have a hydrogen cloud, they have high-frequency area in a range about 3000 cm -1, that
corresponds hydrogen cloud oscillation, at which carbon core almost immovable;
b) the breathing mode is observed in all three spectra - 789, 716, 643 cm-1 with shift in low-frequency
area with growth of amount of atoms.
Thus, from the submitted results we can assume, that those observable Raman bends quite can be explained
by heterogeneous hydrogen-carbon clusters presence in samples, which based on chemically active 20.
Thereby, given Raman spectroscopic researches results not only have confirmed presence in synthesized
ceramics fullerenes 60, but also gave strong reasons to assume existence in ceramics hydrogen-carbonic
clusters such as 20n, where n = 10, 20.
1. .., .. 4.
. .11, 3, (2010), . 646-650.
2. .., . ., . ., . .
TiB2-.
-, (2007) .219.
3. .., .. Ti2-C*. .
.11, 2, (2010), . 453-458.


C/MXOY/SiO2
. .1, ..1, ..1, ..1, ..1, ..1,
.2, - .2
1

. . .
. 17, 03164 -164
2Faculty of Chemistry, Maria Curie-Skodowska University, 20031 Lublin, Poland
- C/MxOy/SiO2 ,
(), - () MxOy/SiO2 (
Cu, Mg, Mn, Ni, Zn) Co, Fe Zn.
MxOy/SiO2 in situ,
, SiO2 ,
. 3 / SiO2.
800 .

-
,

V,
S,
, %
2/
3/
.
0,1, 1,0 10 7-, SiO2
A-380-C
299
0,995
0,92
14.
-, SiO2
344
1,567
1,04
2-320-C
,
- ,SiO2, u,
3-Cu-C
239
1,122
5,34
Cu2O
1 48 %.

-, SiO2
167
1,039
2,90
3-Mg-C
-
- ,SiO2,
3-Mn-C
130
0,740
7,42
.
- ,SiO2, Ni
3-Ni-C
255
0,907
2,46

, SiO2,
158
0,834
4,02
3-Zn-C
Cu, Fe, Ni Co .
Zn2SiO4
SiO2.
-, SiO2
Zn-35C
228
0,979
6,53
,
-, SiO2, Fe
Fe-320C
226
0,995
11,97
( 1).
- ,SiO2, Co,
Co-320C
262
1,033
8,03
-
CoSiO4
130 624 2/
-, SiO2
Zn-320C
238
1,175
5,83
..

-, SiO2
RF(SiO2) -2
368
0,741
45,95
.
-, SiO2
RF(Mg)-4
311
0,443
36,33
, ,
- ,SiO2, MnO,
RF(Mn)-5
323
0,532
44,92
.
- ,SiO2, Ni
RF(Ni)-6
443
0,795
47,66
(C) = (C) ,
-, SiO2,
RF(Zn)-7
333
0,638
44,61

Zn2SiO4
:
-
RF-1PUR-C
0.2
0,003
100
= o ( )t , < < 1
(1)
-
RF-2PUR-C
623.3 0,692
100
, o
-
RF-4PUR-C
567.1 0,250
100
, ; t
. ,
2
C
C = * 100%. .
0

-2
.
. . 1
-4
1
lg = ()
2
-6
1 2
(1).
-8
1 %.
(1)
-10

0
20
40
60
80
100
C ,%

-
.
, , SiO2.
. 1 .- 15%,
: 1- 2,28,
; 2- (1).
.
1 - .

lg

, ,
C/MxOy/SiO2 .
.
PIRSES-GA-2008-230790.

 .., .., .., .., ..

. . . , . 17, 03164 . ,
E-mail: nazarkovsky.michael@gmail.com
. [1].
(/ ) ( /)
.
: SiO2 (S = 300 2/) TiO2 (15% .),
Sn (IV) Ni (II). () SnO2 NiO,
SnCl4 Ni(NO3)2 6H2O (100 0 ). , SnO2,
NiO- 600 0. SnO2 (% . TiO2 ):
0,14; 1; 4; 5; 6; 10; 30. NiO : 0,14; 1; 5; 10; 30.
. (). . 1 3. ( ), r - ( ), NT -
NiTiO3.

TiO2
(Rutile). 4.235 /3. 2.7. 2. Hf 298 = -944,75 /
(Anatase). 4.05 /3. 2.55. 4. Hf 298 = -933,03 /

SiO2-TiO2(15%)-SnO2

w(SnO2) =

(30%)
(10%)
(6%)
(5%)
(4%)
(1%)
(0.14%)

(30%)
(10%)
(6%)
(5%)
(4%)
(1%)
(0.14%)

w(SnO2)=

SiO2-TiO2(15%)-SnO2

a
a

SiO2-TiO2(15%)-NiO

NT

a
NT

a
a

a
a

a
a

100

200

300

400

500

600

700

. 1. ,
SnO2

100

200

300

500

600

400

NT

a
a

NT

a
0

w(NiO) :
NT

10

20

30

40

50

a
a

10%
5%

0,14%

a
60

30%

1%

700

NT

70

. 2. 600 0
, SnO2

. 3. 600 0 ,
NiO

:
1. SnO2 4-6% (.1.).
( 5% SnO2). .
2. , 600 0 (.2.) .
5% SnO2.
3. NiO 30% . .
NiTiO3 (. 3.). (w NiO < 30% .) .
4. (TiO2) (SnO2, NiO)

:
1. K. Y. Jung, S. B. Park // Applied Catalysis B: Environmental, 25, p. 249-256, 2000



..1, ..1, ..1, ..1,
..2, ..2
1
.. ,
246746, . , - , 48, , podd-evgen@yandex.ru
2
,
. ,
. .. , ,
( , ), , . 1100-1200 YAG: 3+ . 40-80 .
: PbO-Bi2O3-SiO2, Bi2 O3B2O3, ZnO-CaO-B2O3.
, Bi-B-
,
-- .

YAG: 3+,
. ,
700-750 .

, .

3
2

:
1 ; 2 ; 3 ; 4 GaAlN; 5

YAG
YAG:, , 20-60 .
YAG:, , 1-10 .

Bi2O3-B2O3

ZnO-CaO-B2O3



.., .., ..
. .. , 03164, -164, . , 17,
e-mail LenaYukhymenko@ukr.net
()
, .
. ,
,
. ,
( ).
: .
: MxOy/SiO2, M - Ni, Mg, Mn, Cu, Zn Fe = 0,2 1,0 / SiO2;
( , ; - : 20 %
SiO2 80 % (). .

1. ,
MxOy/SiO2

(),
/ SiO2
NixOy/SiO2
0,2
1,0
MgO/SiO2
0,2
1,0
MnxOy/SiO2
0,2
1,0
CuxOy/SiO2
0,2
1,0
ZnOy/SiO2
0,2
1,0
FexOy/SiO2
0,2
1,0

NiO
NiO

CuO

15
16
20
-

,
2/
360
328
353
262
333
255
369
351
355
273
222
222

,
,

. ,
.
,
, .
2, ,
,
.
5
.


.

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.

.

.
:
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, .
- , ,
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,
.
, 25- . ..


., .., .., .., ..
.... , .. , 17, 03164 , ,
. 422-96-85, :38 (044) 424-35-67,
-mail:nastasienkon@ukr.net
- , , , .
. -
. , (, , ) ,
, .
- .
( ICN , ), () 300 2/
() . : .
.

.
(.1.) 100 170, 1 2, .
200 600.

.1. (1) (2) (),,

(), , () ,
. . , .

112,8
99,8
107

.1 , . (1)/(2)
. , , SiO2.
, ,
.
, (1) (. 1)
, 1 E=(lnI)/(1/RT) lg Ko, Ko=cE/RTexp(E/RT), T
, 0,1/, R = 8,31 /() .

1.
18 ... 1 2 , ,
, 1, 2
, .

(2), .

(2), .

(1)/ (2),
..

1,

2,

0,40

0,13

3,21

101,5

150,5

0,8894

3,28

0,32

4,66

114,4

166,7

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2,9

2,37

1,22

104,9

147,1

0,9954

0,16

0,78

0,21

106,61

168,6

0,9735

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92,0

12,80

104,04

92,1

10,30

104,42

100

11,70

111,17

111

13,30

126,50

10,8

12,15

113,35 14,00

., %

0,163

0,78

0,21

106,61

168,6

0,9993

15

0,529

1,47

0,36

103,21

156,4

0,9989

20

0,52

1,63

0,32

116,6

167,0

0,9987

30

0,24

2,31

0,18

99,9

172,99

0,9990

, ,%

2.
,
1 2, .

, (.=15%)

115

13,8

133,78

15

111

13,3

126,50

20

103

11,7

116,32

30

99

11,8

118,41

7,3

12,65

123,75 7,00

14

0,95

3,42

0,287

91,5

172,4

0,9988

12

0,82

3,24

0,25

90,4

167,5

0,9987

23

0,61

1,79

0,34

87,3

160,5

0,9979

42

0,35

0,98

0,35

93,6

151,6

0,9500

14

112

14

136,85

79

0,21

0,32

0,65

102,3

170,6

0,9970

12

110

13,9

133,34

23

117

14,9

140,80

42

119

14,9

137,83

79

106

13,7

125,29

5,3

14,28

134,82 6,04

, %

,
, (.=15%),

, 1 , .
lg Ko , Ko=kT/h. , 2 (. 2),
2=12/1. , 2, , , , (. 2),
. , ,
. . 1, 2 , 2 1 .
, 1 2, 18 ... , . 1
, 2 - [1] , .

.
, . .
, . , (100 ) , (170 ) ,
(200 600 )- , .
, , .
1. Derbyshire H.M., Feldman Y, Bland C.R., Broadhead J., Smith G. A Study of the Propeties of Water in Hydrated Mannitol // Journal of Pharmaceutical Sciences. - 2002. 91, 4. . 1080 1088.

 Cr(acac)3 Mn(acac)3
SiO2 -
. . , . . , . . , . .
. ..
. 17, 03164 ,
e-mail: davydenko@isc.gov.ua, l.davydenko@yahoo.com

- ( )
Cr(acac)3 Mn(acac)3 SiO2
.

(Aerosil 200, Evonik Degussa AG,
12 nm, 200 2/), (0.25-0.50 ),
400 2 .
Cr(acac)3 (Aldrich) ,
200.
Mn(acac)3 (Aldrich)
.
(10-6 )
30-800, - m/z 12-200
- 7304
(, ).

Cr(acac)3
SiO2 (
acac:r=3).

SiOH + r(acac)3 SiOHacac-Cr(acac)2

Mn(acac)3
SiO2 ( acac:r<3).

SiOH + Mn(acac)3 SiOMn(acac)2

(m/z 85) 115-190

SiO2 ( 1)
Cr(acac)3/SiO2.

42

I, . .

44

58

85
0

200

400

600

200

400

600

190-250

(
2),

Cr(acac)3/SiO2, Mn(acac)3/SiO2.
( 3) 250300 Cr(acac)3/SiO2,

Mn(acac)3/SiO2

( 4).

[O]

M OH + 2

OH
m/z 42
H2O

-
+
+
CH
[H3CCOCH2CO]+
[H3CCOCH2COCH3 ]
CHCOCH
[H3CCO]
2

m/z 100

T,
T,
(m/z 85), (m/z 58), CO2 (m/z
44) 2 (m/z 42) Cr(acac)3/SiO2 () Mn(acac)3/SiO2 ()

150-550
(m/z 85), (m/z
58), CO2 (m/z 44) 2 (m/z 42).

m/z 85

44

85

58

42

I, . .

m/z 43

M OH +

m/z 58

CO2
m/z 44

, CO2 2
270-450 200-550 Cr(acac)3/SiO2
Mn(acac)3/SiO2, .

SiOHacac-(acac)2 SiO(acac)2 + Hacac (m/z 85)

SiOM(acac)2 + H2O SiOM(acac)OH + Hacac (m/z 85)
SiO(acac)OH + H2O SiO(OH)2 + Haca (m/z 85)
=MOCH3CHCOCH3 + [O] =MOCOCH2COCH3 + CO2 (m/z 44)
=MOCOCH2COCH3 + H2O =MOH + CH3COCH3 (m/z 58) + CO2 (m/z 44)
=MOCOCH2COCH3 =MOH + 2 CH2CO (m/z 42)

(1)
(2)
(3)
(4)

Cr(acac)3/SiO2
115-190
190-250

Mn(acac)3/SiO2

190-250

190-300
270-450

200-550

L. Davydenko, B. Mischanchuk, V. Pokrovskiy, I. Babich, Yu. Plyuto TPD-MS and IR studies of Cr(acac)3 binding upon CVD at silica and alumina surface // Chemical Vapor
Deposition (accepted for publication).

11-13 2011, ,


, DMSA
.. , .. , ..
...
,
,
.
.

-2,3 (DMSA)


, ,


. DMSA ,

' .

-:

: = 6-9
-2- 343
- DMSA
-
.


'.

,
-
SS '
.

.. , .. , .. , .. *. ., *
...
* ,
. ..

,
,
.
(), 2000 ()
.
IN VITRO

IN VIVO

(-),

MCF-7

C(Fe3O4) = 0,003 /,
C () = 1/
1
2
3

-
C57Bl/6/21
(6106 ).

.
(, %)
: = (/) 100, x
; y -
.

MCF-7, %

100%
Fe3O4/ Na
99%
Fe3O4/ Na
99%
()
4 Fe3O4/
98%
Na/
5 Fe3O4/
99%
Na/ ()
6

75%
Fe3O4/ Na//

78%Fe
O
/
Na/
73%
3 4

8
Fe3O4/
IC25 6%
67%
Na//

Fe3O4/ Na/.

1
2
3

,%

18,0+2,8
0%
Fe3O4/ Na
18,9+2,0
5%
Fe3O4/
19,8+2,0
10%
Na/
4 Fe3O4/
, Fe3O
4%
18,8+2,6
4/ Na//
Na/

5 Fe3O4/
.
22,0+2,2
22%
Na//



.., .., ..
. ..,
-164, . , 17
natalie.vlasova@gmail.com

H2N

NH2

, PFH+

60
pH 7,0

40
pH 5,7

30

NH2

, ,
2 : (SiOHPFH+)
(SiOPFH+ ).
.
-, -
,
58 64 / .

A, mkmol/g

50

, ,
, .


. ,
. ,
.

O
HO

SiOHPFH

OH

OH

SiO PFH
3

-5-

100

0
2

10

pH

HL
80 H 2L

OH
H

20

(n+1)-

4 9

(Ln)
(HL(n+1))
(H2L(n+2) ).

n-

(n+2)-

60

A, mkmol/g
40

ATP

-5-

pH 5,7

20
ADP

AMP

0
4

A , m k m o l/ g

pH

AMP

6
5
4

2
pH 7,0

1
0
0,00

0,05

0,10

0,20 C eq ,mmol/l

0,15

GRFIT. ,
4
2
:

SiOHPFH LH n SiOHPFH LH n

5,7 7,0

( n 1)

SiOHPFH L

3
2
p H 5 ,7

1
p H 7 ,0

0
4

ADP

5
4

( n 1)

SiOHPFH L

3
2

A,%
80

SiO PFH LH n SiO PFH LH n

ATP

ADP

40

AMP

20

0
4

8 pH

p H 5 ,7

1
p H 7 ,0

SiO PFH L( n 1) SiO PFH L( n 1)

60

n-

- lg [ L ]

, 7,0 ,
5,7, , , -,

, -,
.

,
,
.

n-

- lg [ L ]
ATP

p H 5 ,8

5
4
3
2
1
p H 7 ,0

n-

- lg [ L ]

5,7 7,0

(lgK)
SiOHPFH LH n SiOHPFH LH n

AMP
3,83

ADP
4,50

ATP
5,42

SiOHPFH L( n 1) SiOHPFH L( n 1)

5,05

5,65

6,35

, ,
. ,
. . -,

,
(-).

 Cu


.. 1, .. 2, .. 1, .. 1
1

. .. , . , 17, , 03164, .
E-mail: irinapetrik@online.com.ua
2 . . . 25, 98, . ,
58000, .

NaBH4 CuSO4*52 KI
Cu:=1:1, [1]

, .
,

,
(PEG300),
(SDS)
Pluronic
(P123).

, ,
.
.
,
. ,
,
, ,
. .
, ,
.
- .

CuSO4*5H2O Na4, Cu2-

. , CuO ,
CuSO4*5H2O:=1:1.
Cu, - -
(. 2.). , -, (
, ).
PEG300, P123 SDS ,
PEG300 P123 . SDS
, ,
Cu.
PEG300, P123 SDS -
, 1.
1

Cu

PEG 300

1,53

SDS

1,65

P123

5,62

. 1. .

2,5

2,0

1,5
3

1,0

0,5
6

0,0
300

1. ,

, ( ),
.
.

400

500

600

700

800

900

1000

. 2.
CuSO4*5H2O+KI (1:1)
NaBH4 2 (1), 8 (2), 17
(3), 39 (4), 56 (5) 75 (6).

-, - PEG 300, - SDS, - P123 3.

300
0,01, 0,05, 0,1, 0,5, 1 % ,
450 1 .
300+0,5 %u . 4.
200
.
(. 5) ,
CuO
300. ,
Cu2O. ,
3 .

. 4. -
300+0,5% Cu.

. 3. , - (), - PEG 300 (), - SDS (), - P123 () ().

20

-3

2,7x10

-3

1,8x10

1
3

K-M

,
PEG300, SDS P123 -. ,
: -,
, PEG300, SDS P123
.
5,6 .
:
u:I=1:1, Cu:PEG300=1:370, Cu:SDS=1:2, Cu:P123=10:8.
300
450 Cu2O 300
2 5 .

.

-4

9,0x10

0,0
500 510 520 530 540 550 560 570 580 590 600

. 5.

Cu
300/Cu 0,01%. 1
,
,
2 ,
4-
(3, 4, 5, 6).

1. S. Kapoor, R. Joshi, T. Mukherjee Influence of I- anions on the

formation and stabilization of copper nanoparticles. // Chemical
Physics Letters 354 (2002) 443448.

.., .., .., .., ..

,
. 100- , 159, 690022, , ., 7(4232) 312590, 311889, 313801,
e-mail: zemskova@ich.dvo.ru
: ,
,
, .

, ,
,
. (, )


() .

.

c :
,
NaCl;

/ *
*. 2281160 . /
.. .; . 09.11.2004; . 10.08.2006, 22.

,
pH- .

(Ni, Cu) /CHIT /

**

, *
/CHIT/

: CHIT H+ + OH CHIT + H2O

,
.

219

Ni(OH)2 40 1 ,
2.5 . = 900 . .
100 6 .
(Ni) = 290 /, = 0.078 %

4.08 % Ni .
().
Ni(OH)2

()

224

70 5 1.5 % Ni .
20 . = 700 . . 100- Ni(OH)2

120 4 . (Ni) = 230 /, = 0.05 %

()

227

3.36 % Ni . Ni(OH)2
(-900). = 700 . . 100
3 . (Ni) = 310 /
()

264

(II) .
0.77 % u
= 940 25 3 . .
(u) = 17.1 /, = 0.022 %

258

(II) .
= 700 25O 3 . .
(Cu) = 17,1 /, = 0,022 %

0,77 % Cu
uO, u2O, Cu ()
u(I), u(II) ()

263

(II)
(-900) 25O 3 . = 700 . .
(u) = 17.1 /, = 0.022%

1.11 % Cu
u(I), u(II) ()

266

(-900) ( ). (u) = 22,8 /

: = 1: 1000

1.18 % u
CHIT + Cu(II)

/CHIT/

() ()

,

(ELD)

(EPD)

(,
)

,
. ,
.
,
//

, E
22O + 2e = H2 + 2OH
u2O + H2O + 2e = 2Cu + 2OH
Cu(OH)2 + 2e = Cu + 2OH
2Cu(OH)2 + 2e = Cu2O + 2OH + H2O
CuCl2 + 2e = Cu + 2Cl
CuCl32 + e = Cu + 3Cl
Cu + Cu2+ Cu2O ()

*C
, ()
** (AAC).
C1s

Ni, Cu.

Ni2p3/2

Cu2p3/2

C1s

1
3
CO32-

Cu(I)

227

Cu(II)

0.828
0.361
0.22
0.08
0.190
0.178

1. / CHIT /
/ CHIT / .
2.
-
,
:
Ni(OH)2 [Ni, Ni] /
Cu2O [CuO, Cu-CHIT, Cu] /

263

282

286

288

290

292

930

935

940

945

950

,
282

284

219 2
280

284

286

288

290

292

294

296

850

855

860

865

870

- C1s- Ni2p3/2- 219, 227 C1s- Cu2p3/2- 263.

sp2- sp3- * ;
1 - CHOH, CHO ; 2 - CHNH2, CHNH3+ ;
3 - CO , OHRCO (R - CHNH2, CHNH3+ ).

- C1s , .
/CHIT/
(+2).
Ni23/2 Ni(OH)2. Ni2p 227
(), C1s = 291,40,1 ,
.
Cu2p /CHIT/ ,
Cu2O. Cu2
, .
Cu2p(II) Cu(II) .




.., ..

.
. ..

,
,

E-mail:
mail: filonenko_ov@ukr.net

,
.
-
B3LYP 6-31G**

() (SiO2)N (N = 20, 24, 28, 60) (. 1).

, .
-
B3LYP 6-31G**

PC
GAMESS

"-". ,
,

""
.

(SiO2)60
. ,
,
.
1,346, 1,151 1,623 .
,
"" . 60,
Si (SiO2)60
, .
0,548, 0,492
. , ,
"",
,
( 0,356 )
"" "".
"" H2O, CH4 CH3NH2.
(H2O),
(CH4) , ,
(CH3NH2).
. 2.

(SiO2)60@H2O, (SiO2)60@4 (SiO2)60@CH3NH2 ,
- .
""
. ,
,
. ""

(. ),
-
.
, ,
+

.
. 3 , + 1
1,00 0,75
( +
0 160 /),
. ,
, , ,

.
(S2)60

[ (r) = grad (r)] .

. 3 ,
~ 0,75 ~ 108 /.
,

"-".

. 1. (Si2)N.

. 2. "": ) (SiO2)60@H2O; ) (SiO2)60@4; ) (SiO2)60@CH3NH2

2, 4, H3NH2


R(O)

(SiO2)60+H2O

0,096

0,096

103,76
4

103,69
(SiO2)60+ 4

R()

0,109
109,47

0,109
109,47

R(CN)

H3NH2
0,146

(SiO2)60+H3NH2
0,146

R(CH)
R(NH)

0,110
0,102

0,110
0,102

CNH
HNH

109,72
105,88

109,70
105,86

* , .

. 3. ()
()
(SiO2)60. l

 -
(III)
..1, .. 1,.. 1, .. 1,
..A1, .. 1, .. 1,2
1

, . 13, -03164
2
,
. . 38-, 03142, E-mail kir@i.kiev.ua

dV/d(logR)

1.2

12

pH

10

0.8

4.0
3.5

3.0
2.5

0.4

1.5
1.0

3
1

0.0
1

10

0.5
0.0
4

10

12

pH

100

R,

2.0

-20

-10

10

20

30
-

OH

-2

x10

HNO3 NaOH
0,1 NaNO3 ()
(): FeOOH();
()

:FeOOH - (1),
- FeOOH (2), FeOOH (3),
2.2

pH=3.2-3.6

2.0

1.8

S 2-1

FeOOH

90

FeOOH

151

FeOOH

344

1.6
1.4

pH=11

1.2
1.0
0.8
0.6
0.4
0.2
0.0
0

20

40

60

80

100

120

140

160

C0

11,37
6,94
2,05
8,68
6,95
2,58
11,44
7,03
3,04

9,01
7,03
2,11
8,83
7,31
2,71
9,47
7,23
6,33

, -1
0,5
0,1
0,3
0,5
0
0,6
1,1
0,4
2,2

- FeOOH
=3,2 3,6 (1) ~11 (2)
1.0

1.0

0.8

0.8

0.6

0.6

0.8

2
3

0.6

0.4

0.4

0.2

0.0
0.0

0.0

-0.2
2000

2500

, cm

3000

-1

3500

0.4

0.2
0.2

200 0

250 0

3000

-1

, cm

3500

2000

2500

3000
-1

3500

, cm

FeOOH
: 0=50 / (); 0=150 / () (). 1-
FeOOH; 2- FeOOH ;=2-1; 3 FeOOH
, c0=50 /. pH =2.8-3.7

 -
. ..
. , 42, , , e-mail: olgasavchenko@mail.ru

.., .., .., .., ..

V, 3 /
48

36
28

44

Birm

40

Purolax

12

-
.

10

24

12

16

12

0,2

0,4

0,6

0,8

Greensand
-

P/P0

20

V, 3 /

28

16

14

32

24
20

V, 3/

48

36

32

(Quantachrome Instruments 2.01)

;

(JSM-6060LA)

-

V, 3 /

44
40

( ., );
-
() ( ., );
,
.
-
.

0,0
0

0,2

0,4

0,6

0,8

0,2

0,4

0,6

0,8

1
P/P0

P/P0

1,0

0,2

0,4

0,6

0,8

1
P/P0

1. -
dV (r)

dV(r)
3

//

0,0008

0,0016

dV(r),

0,0002

//

Pyrolax

0,0006

-

Birm

//

0,00015

0,0012

dV(r)

0,0003

//

-

Greensand

0,00025

M TM
0,0002

0,0008

0,0001

0,0004

0,00005

0,0004

0,0002

0,00015

0,0001

0,00005

0
15

30

45

60

75

90

105

10

25

40

55

70

85

100

0
10

25

40

55

r,

r, A

70

85

100

0
10

20

30

40

50

60

70

80

r,

Birm

Greensand

100

r,

2.

90

Pyrolax

3.
:

;
- .
.
- , ,
.

 -
, ,
.., .., ..
,
. , . 13-, man@bstu.unibel.by
1

S, 2/

1
SiO2 ()
Sil4
120
175
2
SiO2
SiO2 H2SiF6
120
381
120
262
3
4
300
259
5
400
230
TiO2
TiCl4, (NH4)2CO3
6
500
219
7
600
66
120
264
8
9 SiO TiO TiO TiCl ,
300
408
10
11

SiO2

50/50

400

142

500

118

12

600

95

13
14
15
16
17
18
19
20
21

120
300
400
500
600
500
600
700
800

246
214
197

120

249

400

264

600

283

22
23
24

SiO2TiO2

TiCl4,
50/50
, (NH4)2CO3

MgO

MgC2O4

MgOSiO2

0,45:1

MgCl2, SiO2
H2SiF6

189
182
284
196
65
12

2 -

1
2
3
4
5
6
7
8
9

C27H34O4N2S
20H20N3Cl*4H2O
C14H14N3O3SNa
C19H10Br4O5S

, /
482
409,5
327
670

1,3
2,1
3,46
4,1

,
630
555
477
439

C15H14O2N3Na

291

430

C21H15O5Br2SNa
C27H28Br2O5S
C19H14O5S
C20H14O4

562
624
354
318

6,4
7,3
8
9,6

431
431
431
553

TiO2/SiO2 ,
SiO2 TiO2 [1], MgO/SiO2 ,
, .
, , , ( 1).

- . 9
( 2), .
175 2/ , MgO/SiO2.
- 1.
- [2].
[3], TiO2SiO2
, , ,
,
. SiO2 TiO2
,
, Si
OTi., - .
MgOSiO2
, 120
, 400 600
.
MgOSiO2 .
TiO2SiO2 -
,
, ,
SiOTi.
SiO2 TiO2
, -
.
,
[4].
- MgOSiO2
( ) , =1,3 2535 /.
, ,
- ,
-
, ,
: -
, .

1. . ., . ., . ., . . // . 2009.
10. C. 1-7.
2. . ., . . // . 1985. .55. . 244 253.
3. . ., . ., . ., . . . . // :
. . . 6. , 2010. . 48 55.
4. . ., . ., . . // -
, ,
-, 22 24 2010. . 199.

1 - -
20

25

., /

SiO2 (T=120 C): (),

SiO2 2SiF6 ()

16

TiO2

20

25

120
300
400
500
600

., /

15

15

10

10

0
1,3
40

2,1

3,46

4,1

6,4

7,3

8 9,6

0
1,3

2,1

3,46

4,1

6,4

7,3

35

500
600
700
800

MgO

30

25

., /
25

1,3

8 9,6

30
., /

SiO2 TiO2

20

12

120
300
400
500
600

., /

120
400
600

MgOSiO2

2,1

3,46

4,1

6,4

7,3

., /

SiO2 - TiO2

20

8 9,6
120
300
400
500
600

20
25

15
15

20

10

15

10

10
5

5
0

0
1,3

2,1

3,46

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8 9,6

1,3

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3,46

4,1

6,4

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9,6

1,3

2,1

3,46

4,1

6,4

7,3

8 9,6

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.

. () 40 . %; (, ) 10 .%.
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90% TiO2
50% TiO2

. , / 0

T, . .

0,8

10% TiO2

0,6

0,4

0,2

200

400

600

800

t, 0

SiO2/TiO2.

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.

40

80

120

160

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: e-mail: masalov@issp.ac.ru, ./.: 8(496) 522-46-93
, 70 2200
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.

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.

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SiO2:315(),1000().

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~400.

(1)(2).

()

a
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b
(a)

(b).

350

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-- .

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.
,

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., ., ., .
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,
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A MOLECULAR PHOTOMOTOR BASED ON FLUCTUATING CHARGE DENSITY DISTRIBUTIONS

T. Ye. Korochkova1, M. L. Dekhtyar2, V. . Rozenbaum1
Institute of Surface Chemistry of NAS of Ukraine, 17 General Naumov Str., Kiev, 03164, Ukraine, e-mail: taiscrust@mail.ru
2Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya Str. 5, Kiev-02094, Ukraine. E-mail address: mdekh@mail.ru
1Chuiko

Background and Motivation Much current interest is focused on the Brownian

motor models in which directed motion is induced by a spatially periodic time-changing
potential energy [1,2]. As an example, the previously suggested [3,4] dipole photomotor
involves switching on/off the resonance laser radiation, i.e., fluctuations of the potential
energy of a molecule by changing its dipole moment on photoexcitation/de-excitation. To
generalize this approach, here we develop a straightforward theory for the photoexcited
Brownian motor in which potential energy changes due to the interaction of the fluctuating
charge density distribution in the dynamic motor part (a quasilinear molecule) with the
constant charge density distribution in the static part (a periodic substrate) [5]. Importantly,
the photomotor based on this mechanism (as well as its predecessor, the dipole photomotor,
provides unrestricted translational motion, in contrast to a diversity of light-driven molecular
devices generating, as a rule, unidirectional rotations [6] or restricted-path translations [7].
Thus, we aim to fill a gap in the functionalities of existing molecular photomachines.

Example 1 A model system of a triatomic molecule and a periodic

substrate with three potential-generating atoms in the unit cell (p0 is the net
charge of the molecule; Qs, ps and Qa, pa respectively denote the symmetric
and antisymmetric contributions to the atomic charges of the substrate and
the molecule).

Objects and Methodology As a simple model of a polar substrate involved in the

photomotor concerned, we consider a 1D chain with the linear density (x) of periodically
distributed charge. At the distance z from the chain, it generates the electrostatic potential

( x)dx

2 q K 0 k q z e

p0( ) p0( ) 0 ,

where K0(z) is the Macdonald

function and kq = 2q/L (q is an

integer, L is a spatial period of

charge distribution), and q is the Fourier component of the charge density:

( x, z )

q L

( x x) 2 z 2

dx ( x)e

ikq x

q0

ikq x

If

V ( x , z ) p j ( x x j , z z j ) 2 q e

ikq x

p K k (z z ) e
j

q 0

ikq x j

ps( ) ps( ) 0

ps( ) ps( ) 0
Qs 0, Qa 0 , p

, Vq ( z ) 2 q Rq K 0 kq z

then W 1
(no stopping points arise on varying Z ).

If
( )
s

()
s

pa( ) pa( ) 0

the molecular conformation described by the xj set; it represents a generating function of

the multipole expansion. Then the expression for the potential energy is simplified:
ikq x

pa( ) pa( ) 0

then directed motion is possible only if

Qs 0, Qa 0 , pa( ) pa( ) 0

V ( x, z ) Vq ( z )e

Qs 0, Qa 0

Qs 0, Qa 0

For a quasi-1D molecule, with its axis parallel to the chain axis and |zj| << z, we introduce
ik x
a single parameter R
p e q j sensitive to the fluctuations of atomic charges pj and

Then the potential energy of the molecule is written as:

Qa 0

ps( ) pa( ) 0

The motion direction is also governed by the ratio of the molecular length
r to the substrate period L.

(Vq(z) is the Fourier component of

q 0
the potential energy, with its
fluctuations governed by the fluctuations of the quantity Rq).

The curves are built with D 109 m 2 / s , T 300 K , L z 1nm , l / L 0.3 , Z 0.2 , and
0 . The charges (in electron units) are as follows: Qs 0.5, Qa 0 , ps( ) 0 , pa( ) 0.15 ,

pa( ) 0.33 (dash-dotted line); Qs 0, Qa 0.5 , pa( ) 0 , ps( ) 0.25 , ps( ) 0.38 (dashed

,
.

line); Qs 0.1, Qa 0.5 , ps( ) 0.2 , ps( ) 0.35 , pa( ) 0.4 , pa( ) 0.2 (solid line).

Results The average velocity of the motor concerned along the longitudinal x
axis of the system (coinciding with the molecular axis) appears as

0.5

D
16 (1 2 ) Z
v
Im (1 4Z )u1w1w2* 2(1 Z ) w12u2* 6 Zw12 w2*
L (k BT )3 (1 4Z ) 2 (1 Z )
Here D k BT / is the diffusion coefficient (with kB denoting the Boltzmann constant, T the
equilibrium absolute temperature, and the friction coefficient); L is a spatial period of the

Rq p j e

ikq x j

()
q

Rq( ) and wq q K 0 kq z

()
q

Rq( )

(with

1,

0.2

0.4

0.6

0.8

-0.5

dark, , phases) and temperature (through the diffusion coefficient D); ( ) / ;

uq q K 0 kq z

<v> m/s

charge distribution; Z L2 (4 ) 2 D is a dimensionless parameter depending on the laser

operating regime (through 1 1 determined by the durations of the light, + and
and

referring to the + and phases).

-1

r /L

Stopping points The stopping points (and, accordingly, motion reversals) of the motor are
dictated by the vanishing condition for the imaginary part of the bracketed expression. In the
cases when only the potential energy amplitude fluctuates, this condition is fulfilled only with
the temporal asymmetry of the motor cycle (different + and phase durations). In the
general case when the potential energy fluctuates both in amplitude and shape, stopping points
can occur even in the absence of temporal asymmetry, at certain Z = Z0 = (1+2W)/[2(2+W)],
provided the parameter W = Im(w12u2*)/Im(u1w1w2*) specified by the electron density
distributions in the molecule and the substrate belongs to the interval (2, 1/2).

Example 2

T 300 K , L z 0.66 nm , 0 , l / L 0.3 , Qs 0.5, Qa 0 . (AM1 method).

0.1

Conclusions

0
0.001

0.01

0.1

0.3

-0.2

References

[1]. P. Reimann, Phys. Rep. 361, 57 (2002). [2]. P. Hnggi, F. Marchesoni,

Rev. Mod. Phys. 81, 387 (2009). [3]. M. L. Dekhtyar, A. A. Ishchenko, V. M. Rozenbaum, J.
Phys. Chem. B 110, 20111 (2006). [4]. M. L. Dekhtyar, T. Ye. Korochkova, V. M.
Rozenbaum, Int. J. Quantum Chem. 110, 67 (2010). [5]. V. M. Rozenbaum, T. Ye.
Korochkova, A. A. Chernova, M. L. Dekhtyar, Phys. Rev. E (2011, to be publ.). [6]. M. Liu, T.
Zentgraf, Y. Liu, G. Bartal, X. Zhang, Nat. Nanotechnol. 5, 570 (2010). [7]. A. Coskun, D. C.
Friedman, H. Li, K. Patel, H. A. Khatib, J. F. Stoddart, J. Am. Chem. Soc. 131, 2493 (2009).

10

-0.1

V (x )/k B T

<v > m/s

A special feature promising much for the practical implementation of the

new mechanism is that the substrate-generated periodic potential need not necessarily be
asymmetric (contrary to what is assumed for most of Brownian motors) since asymmetry can
emerge dynamically. As another distinction, a fluctuating resonant laser beam is used for
excitation, with the combined effect of the laser regime and the molecular structure on the
motion direction. In this context, the range of instrumental and structural controllability of
light-driven nanodevices can be largely extended.

1-[3,4-di(methoxycarbonyl)phenyl]pyrene molecule.

The average velocity versus the parameter Z depending on the laser operating
regime and temperature. The coordinate dependences of the potential energies
V ( x) (in k BT units) are presented in the framed insert. As assumed, D 109 m 2 /s ,

-0.3

0
0

0.5

-0.3

x /L

-0.4
Z

Though the potential

profiles V+(x) and
differ very
V-(x)
100 slightly
both
in
amplitude and in
shape, these small
fluctuations
prove
sufficient to provide
relatively
large
1
average
motor
velocities: <v>~ 340
nm/s at Z=0.16 and
<v>~ 30 nm/s at Z=4.

 ,
TiO2
.. , .., .., ..,. . , ..
1 . .. ,
. , 17, , 03164, . E-mail: smirnat@i.com.ua
(),
, 69,3C,
,
, ,
, ,
.

:
h TiO2
C17H35COOH + 26O2

18CO2 + 18H2O

104 .
FT-IR
2957,5 cm1 ,
CH3 , 2922,8 cm1 and 2853,4 cm1
CH2 , .

,
TiO2 .
(. 1).

(m/z=284)
+Na ( m/z=306) +K (m/z= 322).
m/z =910 m/z=1184,
( 3 a,b). 15
,
. m/z 428, 656, 911,
1186 ,
TiO2.
TiO2 (. 1).

0,
.
( 75 )
`
m/z=197, 102, 86, 62 35,
CH CH2
FT-IR.

a) 400oC, 23
) 450oC, 17
) 500oC, 5-7 ) 400oC (15),
~ 0 .1 30
TiO2: 400oC (a), 450oC (), 500oC ()
, 400oC, 15 . ()

, . .

,

2 ,
,
. , , ,
1520.

, 72 Wang et al. 33.3
Sakai et al. 15 Watanabe et al.
. Zn (< 5%)
TiO2
0.

530
380
320
260
200
140
80
50
20
0

1,0
0,9
0,8
0,7
3100

3000
2900
-1
, c

2800

2700

. 2 FT-IR c

.3 0, 15 75
TiO2. (a) () .
,
-
:
,
,
,
2
.


,

.., .., ..
. .., .

:
(. . 3, 4) (. . 1, 2)
(1)
= ET + + + IR,
U.
ET (ET = 1.229 25),
, IR . (1),
.

.

Co-Mo

Co-W

W ( Na2WO4)
Co ( CSO4)
NH4Cl

70 /
28 /
50 /
125 /
1 /100

, i = 100 /2,
t = 55C, = 10-15
W 12 %

Mo ( Na2MoO4) 15 /
Co ( CoSO4)
3 /
(NH4)SO4
100 /
25 %
50 /

1 /100

, i = 25-30 /2,
t = 60C, = 20-40
Mo 86 %

. 2.
Co-W,

1810

. 1. 30 %
KOH (25)
1810, (1) Co-Mo (2) Co-W (3).

. 3.
Co-W,

1810,

(. . 1) (. . 2, 3)
.

= 47.2 /
= 830

b = 113.7 139.1

. 4.
1810 30 % KOH , : 1 25,
2 40, 3 55, 4 70.
,
, = 830 .

= 48.4 /
= 250

b = 29.0 44.2

. 5.
1810, Co-W,
30 % KOH , : 1 25, 2 40, 3 55,
4 70.
,
, = 250 .