Всеукраинская конференция с международным участием...
DESCRIPTION
Всеукраинская конференцияс международным участием,посвященная 25-летиюИнститута химии поверхностиим. А.А. Чуйко НАН Украины "АКТУАЛЬНЫЕ ПРОБЛЕМЫХИМИИ И ФИЗИКИПОВЕРХНОСТИ"2011 год стендовые докладыTRANSCRIPT
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POLYMERIC MATERIALS WITH CONTROLLABLE STRUCTURE BASED ON POLYSTYRENE AND
MULTIWALLED CARBON NANOTUBES
POLYMERIC MATERIALS WITH CONTROLLABLE STRUCTURE BASED ON POLYSTYRENE AND
MULTIWALLED CARBON NANOTUBES
ACTUAL PROBLEMS OF CHEMISTRY AND PHYSICS OF SURFACE May 1113 2011 Kyiv Ukraine
Bolbukh Y.1, Gunko G.1, Prikhodko G.1, Tertykh V.1, Maciejewska M.2, Gawdzik B.2, Skubiszewska-Zieba J.2
Bolbukh Y.1, Gunko G.1, Prikhodko G.1, Tertykh V.1, Maciejewska M.2, Gawdzik B.2, Skubiszewska-Zieba J.2
1Chuiko Institute of Surface Chemistry of NAS Ukraine, 17 General Naumov Str., Kyiv 03164; e-mail: [email protected]
2 Maria Curie-Sklodowska University, Lublin, PolandComposites 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.
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.
Objects: 1. Purified MWCNTsThe 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 MWCNTsMWCNTs 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 compositesThe 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%.
Objects: 1. Purified MWCNTsThe 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 MWCNTsMWCNTs 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 nanotubes3. Polymer compositesThe 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%.
Sample description1 Polystyrene (polySt)
2 polySt / purified MWCNTs
3 polySt /MWCNTs, magnetostatic field directed in parallel to the film plane.
5 polySt /purified MWCNTs magnetostatic field directed vertically to the film plane.
6 polySt/oxidized MWCNTs
7 polySt/oxidized MWCNTs, magnetostatic field directed in parallel to the film plane.
8 polySt filled with oxidized MWCNTs. Composite obtained under influence of the magnetostatic field directed vertically to the film plane.
9 polySt filled with purified MWCNTs treated with HCl
10 polySt filled with purified MWCNTs and treated with HCl. magnetostatic field directed in parallel to the film plane.
11 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.
16 polySt filled with purified MWCNTs and treated with NH4 OH.
17 polySt filled with purified MWCNTs and treated with NH4 OH. magnetostatic field directed in parallel to the film plane.
18 polySt filled with purified MWCNTs and treated with NH4 OH. magnetostatic field directed vertically to the film plane.
19 polySt filled with oxidized MWCNTs and treated with NH4 OH
20 polySt filled with oxidized MWCNTs and treated with NH4 OH. magnetostatic field directed in parallel to the film plane.
21 polySt filled with oxidized MWCNTs and treated with NH4 OH. 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.
-0,35
-0,33
-0,31
-0,29
-0,27
-0,25
-0,23
-0,21
-0,19
-0,17
-0,1530 70 110 150 190 230 270
Temperature (oC)
DSC
/(mW
/mg)
1 2
3 555
75
185
170
-0,35
-0,3
-0,25
-0,2
-0,15
-0,130 70 110 150 190 230 270
Temperature (oC)
DSC
/(mW
/mg)
6
7
871
170
160
50
-0,4
-0,35
-0,3
-0,25
-0,2
-0,15
-0,130 70 110 150 190 230 270
Temperature (oC)
DSC
/(mW
/mg)
9
10
1171
157
39
100
206
193
-0,34
-0,3
-0,26
-0,22
-0,1830 70 110 150 190 230 270
Temperature (oC)
DSC
/(mW
/mg)
19
20
21
76
165
104189
218
45129
90
-0,4
-0,36
-0,32
-0,28
-0,24
-0,230 70 110 150 190 230 270
Temperature (oC)
DSC
/(mW
/mg)
13
14
1570
159
85
94 210
-0,4
-0,36
-0,32
-0,28
-0,24
-0,2
-0,16
30 70 110 150 190 230 270
Temperature (oC)
DSC
/(mW
/mg)
16
17
1877
154
96172
217
89
70
80
90
100
110
120
130
140
150
MW
CN
Ts p
urifi
ed
MW
CN
Ts o
xidi
sed
MW
CN
Ts p
urifi
ed (H
Cl)
MW
CN
Ts o
xidi
sed
(HC
l)M
WC
NTs
pur
ified
(NH
4OH
)M
WC
NTs
oxi
dise
d(N
H4O
H)
1 2 3
Har
dnes
s (M
Pa)
polySt
60
70
80
90
100
110
120
130
140
Har
dnes
s (M
Pa)
CN
Tpur
e(vi
nyl.P
hys
)
CN
Toxi
(vin
yl.P
hys)
CN
Toxi
(vin
yl.C
hem
)
1 2 3polySt
-0,42
-0,32
-0,22
-0,12
-0,02
0,08
35 85 135 185 235 285
Temperature (oC)
DSC
(mW
/mg)
222324
61
243
190
170
227 260
274
-2,2
-1,8
-1,4
-1
-0,6
-0,2
0,2
0,6
1
300 350 400 450
Temperature (oC)
DSC
(mW
/mg)
222324
396
420
401
428 -0,4
-0,35
-0,3
-0,25
-0,2
-0,15
-0,1
-0,05 35 85 135 185 235 285
Temperature (oC)
DSC
(mW
/mg)
252627
59
172
170
239
190
274
65
180
174218
-0,85
-0,65
-0,45
-0,25
-0,05
0,15
0,35
0,55
300 350 400 450
Temperature (oC)
DSC
(mW
/mg)
252627
326
415
448
400
392
-0,42
-0,37
-0,32
-0,27
-0,22
-0,17
-0,12 30 80 130 180 230 280
Temperature (oC)
DSC
(mW
/mg)
1282930
75
96
181
166
-4,5
-3,5
-2,5
-1,5
-0,5
0,5
300 350 400 450 500
Temperature (oC)
DSC
(mW
/mg)
1282930
424
Hardness values of the filled with MWCNTs polystyrene composites which were obtained without (1) and under influence (2, 3) of the magnetostatic field directed in parallel (2) or vertically (3) to the film plane
Hardness values of the filled with MWCNTs polystyrene composites which were obtained without (1) and under influence (2, 3) of the magnetostatic field directed in parallel (2) or vertically (3) to the film plane
DSC analysisDSC analysis
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.
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-GA- 2008-230790.
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.
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Evgenii Sergeyevich Brikov
- docent of the department of the micro- and nano-technologies
Tyumen state universityE_mail: [email protected]
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 ( nmD 70 when OeH 5940= ), 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.
:
, , , , , , , , ,
1
-
, .
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].
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, : H 50 .
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j
aBBAA SSrJSIASIAHSgHSgH 2 2100 +++= , (2)
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(2): A B 0H , . A B . - , AS , BS . 0H 0Hg , , . ( , ) [6].
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5
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1. , Fe3O4 (FeOFe2O3). (I) 2: 20o - 33o (7) [3]. V/V1 %, V1 .
H,
I, /
2, o|I, /
V/V1, %
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755
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7
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.
17, 03164, -164, e-mail: [email protected]
,
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NaCl
(100).
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,
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[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.
[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.
. 5.
AM1
NaCl(100)
CO ()
CO () (
).
() ()
() ()
. 6.
AM1
NaCl(100)
CO2
()
CO2
() (
).
. 3. C
CO/NaCl
(100)
(p -
s ).
. 2. (2x1)-
CO2
NaCl(100).. 1. (2x1)-
CO/
NaCl(100)
.
-
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CeO2-ZrO2 (Ce/Zr-1/4) 3,60 1,2 1 -
YOOH 3,00 3,9 35 -
ZnO 0,35 2,1 40 -
AlOOH 3,00 2,2 6 -
LaOOH (100 oC) 0,50 2,6 5 20
LaOOH (20 oC) 0,85 1,9 4 30
CuO 0,18 2,3 4 21
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-
RAMAN SPECTRA OF NANODISPERSED CARBONRAMAN SPECTRA OF NANODISPERSED CARBON IIN CERAMICS OFN CERAMICS OF SYSTEMSSYSTEMS TIB2TIB2--CCKazo I. F., Naumenko A. P., Mavlanova O. D.
Taras Shevchenko National University of Kyiv, Faculty of Physics,60, Volodymyrs'ka Str., 01601 Kyiv, Ukraine
[email protected], [email protected], [email protected]
1. IntroductionFormation carbon clusters and fullerenes can occur in many processes at which fixed carbon is allocated in a separate solid phase [1]. Carbon atomspossess unique ability to form bond of various types (sp1, sp2 and sp3) under constraints which the carbon atom can be connected to two, three andfour 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 presentclasses of compounds of products of reaction is important ording to the physical characteristics along with high hardness, wear resistance, arecharacterized corrosive and chemical stability [2-4]. From this point of view, the consideration of phases of carbon which are allocated in ceramics atsolid synthesis titanium boride from the titanium carbide and boron carbide is interesting. The purpose of the given work is research and the analysis ofRaman spectra of ceramics of system TiB2-C; in particular, establishing the presence of predetermined carbon clusters.
2.ExperimentalManufacturing of initial samples of ceramics, which containing carbon, carried out similarly to a way described in work [8, 9]. Manufacturing of sampleswas made by methods of sintering and hot pressing (HP) on installation with resistive heating, without a protective atmosphere with temperature modesfrom 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 ofcooled 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 asubstrate 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 doublespectrometer DFS-24 (LOMO, Russia), equipped with a cooled photo multiplier and registration system working in a photon counting mode. Particularlyseveral lines ofAr+ 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 acylindrical lens was used to focus light in a 100.1 mm2 spot.
3.Results and discussion
The total spectrum, received from several samples, is shown on fig.1.
5 0 0 1 0 0 0 1 5 0 0
1 0 0 0
*
Inte
nsity
, st.
um.
F r e q u e n c y sh i f t , s m -1
4 6 24 9 4
7 4 5 7 9 2
9 4 8
1 3 7 0
1 6 0 1
1 4 6 51 5 3 3
1 1 1 7
4 0 0 8 0 0 1 2 0 0 1 6 0 0
C 2 0 ( C H 3 ) 2
C 2 0 H 2 0
C 2 0 H 1 0 b
C 2 0 H 1 0 a
C 2 0
Inte
nsity
, st.
um.
F r e q u e n c y s h i f t , s m - 1
a b c
20206386368.
2010124212477.
2010117411766.
2010706.46708.315.
20135813444.
20775773.563.
20464459.92.
209479481.
A clusterspectrum
Raman peakscalculatedtheoretically (cm-1)
Raman peaksreceived fromexperiment (cm-1)
Figure 1. Total, received from several samples a Raman spectrum of ceramics systemsT2- at room temperature is shown. The cut line (*) corresponds to the laser compellingradiation, and by virtue of high intensity cannot be submitted in figure.
Figure 2. Theoretically calculated Raman spectra for carbon clusters areshown
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.
Table 1. Theoretical and experimental frequencies of Raman spectra.
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 carbonpolyhedrons spectra possessing a hydrogen atmosphere (like 2010, 2020) and retrace influence of this atmosphere on shift of frequencies of the basicclusters vibrations.For geometrical construction of clusters and calculation of their oscillatory spectra software package Gaussian 03 (by method RB3LYP/6-31G) has beenused for calculation of vibration clusters spectra. Raman spectra of some possible carbon clusters n, where n amount of atoms in clusters, have beencomputer simulated in work. Raman spectra of clusters 20, 2010, 2020 which represent only carbon cluster, and also cluster in a hydrogen cloud and ararefied 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, theyhave 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.
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 isconcentrated by a radial part of dodecahedron, and in the second - in polar positions. In theoretical spectra of the given models the following divergenceswere 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 toexplain formation tube-like cluster in which the breathing mode is considerably simplified, and oscillation hydrogen cloud is forced concerning carbon to acore, in the second case the hydrogen cloud fixes a radial part bonds interfering with oscillation. Despite of these features spectra contain all basic groupsof 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 clusterspresence in samples, which based on chemically active 20.
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 thiscluster 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 incluster two opposite atoms are rigidly fixed, that leads to similar shift of frequency of vibrations. Tangential modes are deformed, and for them shift offrequencies 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 strongreasons to assume existence in ceramics hydrogen-carbonic clusters such as 20n, where n = 10, 20.
References . . , . , . . - . : , (2001) 180 .: . / . . , . . . .: , (2005). 688 . . . -// , 2002, .71, 6, - . 507-532. .., .., .., .. // . 2, (1998),- .5-14.Kazo I.F., Popov A.Yu., Mechanical properties of TiB2 TiC C* ceramic materials // Functional Materials, 3. (2002) p.503 506. .., . ., . ., . . TiB2-. -, (2007) .219.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.
Some facts follow from our more detailed analysis of spectrum:
researched spectra of samples contain bends which correspondto a graphite phase which intensity insignificantly grows from film upto powder samples;
in film samples, as well as in powder, peaks of low intensity areregistered in area which corresponded tofullerene 60 that isevidence of clusters synthesis during topochemical reaction;
in the average frequencies area of a spectrum bends of highintensity (462, 494, 745, 792, 948 cm-1) are found out, theirunequivocal interpretation is complicated. For an establishment ofthe nature of bends of high intensity it is necessary to carry outadditional researches.
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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 amine-
functionalized 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.
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. . 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).
4000 3500 3000 2500 20000
20406080
100
65432
, %
, 1
1
a
200 300 400 500 600 700 800 9000,00,51,01,52,02,53,03,54,0
6
53 421
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,
. 4. -
() -
() Ce-, Cu
2 .
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1 2 3 4 5 6
-
Surface Chemical Oxygen and Nitrogen Functional Groups Modification of CNTO. Stasiukb, N.Kovala, O.Bakalinskaa, N.Kartela
a 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, Ukrainee-mail: [email protected]
INTRODUCTIONThe 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 multi-walled 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 scale-up. 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 METHODSFor 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
ANALYSIS OF SURFACE FUNCTIONAL GROUPS
The chemical titration method, proposed by Boehm, was used for analysis of surface functional groups. The amount of oxygen-containing 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 bath-house 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].
RESULTS 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.
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.
CONCLUSIONThe 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 LITERATURE1. 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 single-walled 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. 3124-3131.4. 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. . 145-149.6. Kim H., Sigmund W.M. Modification of carbon nanotubes // American Science Publishers. 2004. P. 619631.
ACKNOWLEDGMENTPh.D. Sementcov Yu.I. and Zhuravsky S.V. for CNT.FP7-PEOPLE-IRSES-230790 COMPOSITUM, Project Hybrid nanocomposites and their applications for supporting.
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()
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(AgSiO2) - - . 3 10% (v:v). =400C 380 nm (.1.) 380430 nm [1]. , =450C, 400 nm. , 400C 2 5 nm, >400C 6 11 nm [2].
350 400 450 500 5500,02
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, AgSiO2, , - /. . 25 nm , / , .
[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 / JSol-Gel Sci Technol (Special edition)
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44, 53.3, 57.4, 62.8 2.96, 2.52, 2.05, 1.71,
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19-629) 2 = 22,4; 23,8; 25,3; 39,3; 42,7; 45,3; 46,5,
3,96; 3,73; 3,5; 2,29; 2,12; 2,0; 1,95 ,
AgI (JCPDS 9-374). :
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364 368 372 376 380
0
1000
2000
3000
4000
5000
6000
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3/2
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Int
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SET, 2/
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TS10 430 490
TiO2 120 120
FT-IR TiO2/SiO2 , 1640 cm-1 , , 3600-3300cm-1, TiO2 SiO2 . , Ti Si-O , , , .
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1. .
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TiO2/SiO2 - .
1. M.A.Henderson The interaction of water with solid surfaces: fundamental aspects revisited/Surface Science Reports 46 (2002) 1-308
.1. .
Ti4+ . TiO2, , 1 10 % (.1), TiO2 . , 270 220 , .
. TiO2 , SiO2 .
-
TiB2 - C
..
, ,c , 2/1, , 03680, [email protected].
: , , .
[1,2] - , , , , . :
2Ti + 4 = 2TiB2 + 3C .
, .
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, . , . .
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( , , , n (n = 20 70)) .
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2. .., .. Ti2-C*. . .11, 2, (2010), . 453-458.
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TiO2
5
50 .
(
10 )
TiO2
100
60-80 ,
130 .
.
TiO2
,
,
240-700 .
TiO2
-
250 300 350 400 450 5000,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
, .
.
, 250 300 350 400 450 5000,00
0,05
0,10
0,15
, .
.
, 300 400 500
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
, .
.
,
TiO2 (), Au/TiO2 (),
(3)
Au/TiO2(),
(1,5 ).
250 300 350 400 450 5000,00
0,05
0,10
0,15
, .
.
, 250 300 350 400 450 500
0,00
0,05
0,10
0,15
0,20
, ..
, 300 400 500
0,00
0,05
0,10
0,15
0,20
, ..
,
TiO2
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Al
Au/TiO2
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.
,
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2
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420
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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.
-
SnO 2
.. , .., ..
... . , 17, , 03164,
E-mail: pexim @ukr.net
() . . SnO /SiO SnCl ( 2 2 4
2100 ) 120 300 / ( 120 300). SnO /SiO 5, 15 30 .% SnO 120 300. , 2 2 2 , . , SnCl . (IV) H O 4 2 (1) (2) SnO , 300 2 5, 15 30 %., 120 15 30 %.
[?SiOH] + Sn(Cl) [?SiO] Sn(Cl) + nHCl (1)n 4 n 4-n
[?SiO] Sn(Cl) + (4-n)H O [?SiO] Sn(OH) + (4-n)HCl (2)n 4-n 2 n 4-n n=1, 2 , 40 ,
450 3-4 . 1 . 1,5 , 100 1,5 . (~ 0,5 ) HCl. .
2 100-105 . 2 600 .
, - .
SiO 2( SiO ). (S ) 2 SnO /SiO .1, . 2 2
.5. - (-120) () (-300) ().SnO /SiO SnO /SiO2 2 2 2
, SnO /SiO (300), =15 30 .%, 2 2 SnO2 (10-15 ) SnO . , 2 (), SnO /SiO (120) SnO /SiO (300) - 2 2 2 2 , (D ) SiO . SnO2 2 D , ,
600 .
Acknowledgment: This work was supported by the European Community under a Marie Curie International Research Staff Exchange Scheme (IRSES), Project No 230790.
600 SnO /SiO (120) ( =15 30 .%) 2 2 SnO2SnO /SiO (300), =5 .%, 2 2 SnO2 SnO (.2) , SnO /SiO (300), 2 2 2 =15 30 .%, (10-15 ) SnO2SnO (.2).2
, (), SnO /SiO (120) SnO /SiO (300) - 2 2 2 2 , (D ) SiO . D SnO2 2
, , 600 . SnO 120 300 2 - SnO /SiO (120) SnO /SiO (300). 2 2 2 2
.4. , , SnO /SiO (300) : A - 5% SnO , B- 15% SnO , C - 30% 2 2 2 2SnO2
SiO pH 2 (pH()) SnO /SiO 2 2 pH() =2,2 pH() =5. SiO2 SnO2 (.3), SnO SiO ( 2 2 =15 .% ), SnO2 D SnO /SiO (A300) (.4).2 2
10 20 30 40 50 60 70
2
15 w t.% S nO 2 on 3001 Initia l
2 600 oC
1
2
1 0 2 0 3 0 4 0 5 0 6 0 7 0
2
1 5 w t .% S n O 2 o n 1 2 01 In i t ia l
2 6 0 0 0 C
1
2
.2. SnO /SiO (120) () 2 2SnO /SiO (300) () =152 2 SnO2. .%
a
0 5 10 15 20 25 30
110
120
130
S,m
2 /g
C (SnO2), wt. %
SnO2/SiO2 (A120)
Initial
600 0C
0 5 10 15 20 25 30
260
280
300
SnO2/SiO2 (A300) Initial
600 0C
S,m
2 /g
C (SnO2), wt. %
.1. SnO2/SiO2(120) () SnO2/SiO2(300) () SnO2.
a
* S n O 2 , % .
S n O 2
,
2/
3 0 0 1 S n S il 5 -3 0 0 5 2 5 9 ,5 2 S n S il 5 -6 0 0 5 2 9 6
6 0 0 2 3 S n S il 15 -3 0 0 1 5 2 6 1 4 S n S il 15 -6 0 0 1 5
1 0 -1 5 2 7 7
6 0 0 2 5 S n S il 30 -3 0 0 3 0 2 5 5 6 S n S il 30 -6 0 0 3 0
1 0 -1 5 2 7 9
6 0 0 2 1 2 0
7 S n S il 15 1 5 1 1 0 8 S n S il 15 (6 0 0) 1 5 1 2 2
6 0 0 2 9 S n S il 30 3 0 1 0 6 1 0 S n S il 30 (6 0 0) 3 0 1 2 9
6 0 0 2 * -
2 4 6 8 10 12-50
-40
-30
-20
-10
0
10
20
Zeta
Pote
ntia
l,m
V
pH
300 5% SnO2 on SiO215% SnO2 on SiO230% SnO2 on SiO2
pH(PZC)
2 4 6 8 10 12-50
-40
-30
-20
-10
0
10
20
Zet
aPo
tent
ial,
mV
pH
300
5% SnO2 on 300, 600oC
15% SnO2 on 300, 600oC
30% SnO2 on 300, 600oC
.3. - SnO /SiO (300) 2 2 () 600 ().
a
0 100 200 300 400 500 600 700 800 900 10000
2
4
6
8
10
12
14
16
V,
%
D, nm
SnSil 15-600, 15 % SnO2; 0,2 % susp. H2O
D ef =192,1 nm
0 100 200 300 400 500 600 700 800 9000
2
4
6
8
V,
%
D, nm
SnSil5-600, 5 % SnO2; 0,2 % susp. H2O
D ef =173,4 nm
0 100 200 300 400 500 600 700 800 900 10000
2
4
6
8
10
12
14
16
D ef = 194,2 nm
V,
%
D, nm
SnSil 30-600, 30 % SnO2; 0,2 % susp. H2OA B C
1600 2000 2400 2800 3200 3600 40000,0
0,2
0,4
0,6
0,8
32
Abso
rban
ce
cm -1
1 120 2 15 w t.% SnO
2 on A120
3 15 w t.% SnO2 on A120
after 600 0 C
1
Si-O H
Si-O -SiH 2O
1600 2000 2400 2800 3200 3600 40000,0
0,5
1,0
1,5
2,0
32
Abso
rban
ce
cm-1
1 300 initial2 15 wt.% SnO23 15 wt.% SnO2
after 600 0 C
Si-OH
Si-O-Si
H2O
1
-1 (3750 ) 300, Si-OH , Si-O-Sn (.5). , 15 30 %. SnO , 120, 2 ( I V ) ( . 5 ) .
-
.. , .. , .. , ..
.
.
.
-
-
..,
..,
..
,
,
()
,
,
,
,
-
() , -
-
.
,
-
.
((33
))33
SS--[[OO--SS((33
))22
--]]nn--SiSi((33
))33
+ + HH22
SOSO44
((33
))33
SS
--[[OO--SS((33
))22
--]]mOHmOH
+ + ++HOSOHOSO22
OO[[--((33
))22
SS--]]mSimSi((33
))33
((mm
-
1,2-
.., .., .., ..
03164 . , . , 13, : 452-54-17, [email protected]
: 1,2-
: ; -
- ( 3 : 1, ); 2 100-300 /
-
, %
1,2-, %
1,2-
, %
Pt/Al2O3 34 26 78
Ni/SiO2 37 30 81
Ni/Cr2O3-Al2O3 39 32 84
Cu-Pt/Al2O3 46 36 78
Cu/Al2O3 76 66 87
Cu/Al2O3-Cr2O3 86 84 97
: - - 100%;
- - (< 8 ) ; -
(> 50 );- - Cu/Al2O3 ( 1- ) Cu/Al2O3-Cr2O3 ( 2- );
- 1,2-
3,5-11,6 / /;
- 11 / ;
- : .
HO-CH2-CH(OH)-CH2OH CH3-CO-CH2OH+H2O
CH3-CO-CH2OH + H2 CH3-CH(OH)-CH2OH
. 1,2- ( 18,5 383 / /, 2 100 /).
2 4 6 8 1 0 1 2
7 0
8 0
9 0
1 0 0
, , %
, C 3 H 8 O 3 / /
a
40 50 60 70 80 90 100
70
80
90
100
, , %
2 : C3H8O3, /
. Cu/Cr2O3-Al2O3 () :
: () (
(), (), 1,2-
())
220
165
-
.., .., .., .., .., .. .., ..
- . ..
ZnO
, ZnO
Zn(NO3)2
(NH32O)
(Zn(OH)2)
(Zn(NO3)2)
, ,
1000
ZnO
.
t .,
, .%
,
1 30 0,360 0,15 -2 50 0,545 0,18 993 70 0 400 0 18 63
r 30 120
3 70 0,400 0,18 634 100 0,530 0,26 39
.
, .%
,
1 4,0 0,360 0,27 952 4 5 0 381 0 29 41
2009 -2011 ( 2.1.1/9317)
2 4,5 0,381 0,29 413 5,0 0,530 0,26 394 5,5 0,510 0,28 535 6,0 0,610 0,25 646 6,3 0,855 0,27 79
-
CuOCuO
CuSOCuSO44
..
, 03164, , .
, 17, [email protected]
..,
..,
.,
..
CuSOCuSO44
--300300
(S
= 300 2/, Si
=0,8
/).
()
-
(
CuSO4
0,8
1
SiO2
)
,
.
10 20 30 40 50 60
3
4
12
2400 3200 4000
, -1
123456
. 3.
,
(
5 ).
2400 3200 4000
, -11
2
3
4
10 20 30 40 50 60
123
4
CuOCuO..
[1].
,
.
. 3
,
300
.
. ,
800
3
-
,
(. 5, . 4)
,
CuO
(JCPDS
#
80-76).
CuO,
,
40 ,
-300.
,,
, ,
, ,
CuSOCuSO
44
800800
CuOCuO..
. 5.
80 (1),
300 (2), 550 (3)
800
(4).
. 2.
-
CuSO4
-
1
(2), 2 (3), 3 (4), 4 (5)
5 (6) .
. 1.
CuSO4
-
1
(1), 2 (2), 3 (3)
5 (4)
.4.
-
t=80 (1), 300 (2), 550 (3), 800 oC (4).
6.22.7.21
-
"
"
-
3750 -1
(.4).
,
550
(. 5, .
1-3).
-
-.
[2],
:2CuSO2CuSO4 4 2CuO + 2SO2CuO + 2SO22
+ O+ O22
,
650
C.
,
650-
850
(. 3).
,
: )
)
.
1.
.
.,
.
.,
.
.,
.
.,
.
.
CuSO4
.
", 2010, 10, .109-113.2.
.
.
.
.: , 1973.
.
1.
656 .
[[11] ]
CuSOCuSO44
5522
..
..
(. 1)
-
(. 2),
300
(. 3)
-
-
(. 1
2) ,
3
.200 400 600 800 1000
,
mH2O = 24%
-
-
C/MX
OY
/SiO2
-
.. 1, .. 1, .. 1, . 2,
.
-2
PIRSES-GA-2008-230790.
-
C/Mx
Oy
/SiO2
,
-
()
Mx
Oy
/SiO2
,
Cu,
Mg, Mn, Ni
Zn.
in situ
,
1:2:1.
3 /
SiO2
.
800 2 .
.
1-
. . .
.
17, 03164 -164 [email protected] of Chemistry, Maria Curie-Skodowska
University, 20031 Lublin, Poland
,
,
.
36-48 % .,
.
-
.
-
Mx
Oy
/SiO2
-
C/Mx
Oy
/SiO2
Mx
Oy
/SiO2
-
C/Mx
Oy
/SiO2
/Mx
Oy
/SiO2
()
-
/Mx
Oy
/SiO2
(, )
-
/Mx
Oy
/SiO2
50-200
.
250-350 ,
,
.
-
,
,
.
(10B, 157Gd).
,
-
,
.
,
-.
.
1000
.
-1
Gd-
.. , .. , .. , .. , .. , ..
. ..
*
. ..
. 1
. 4.
,
Gd3+: 1 -
= 20
, 2 -
,
1000
.
.
()
-2402
PHOIBOS-
100_SPECS (
ga =1253,6 ;
= 200 ;
= 210-7 ).
0 10 20 30 40 50 60 70 80 900
5000
10000
I, c
- 1
1
2
-4 -2 0 2 4
-50
0
50
*3/
Fe3O
4
Hc=-55
M r/M s=0,20
()
H , -3 0 3
-30
0
30
*3 /
H,
Fe3O 4/Gd
Hc=106,5
M r/M s=0,47
()
130 135 140 145 150 155 160
130 135 140 145 150 155 160
130 135 140 145 150 155 160
3
XPSGd4d
E,
2
Gd-OH
Gd-O-Fe
Gd3+
T=20 0C
T=1000 0C
T=20 0
INT
1
Gd3+
3/2
5/2
704 706 708 710 712 714 716 718 720
704 706 708 710 712 714 716 718 720
704 706 708 710 712 714 716 718 720
3
INT
XPSFe2p3/2
E,
2
T=1000 0C
1
T=20 0C
T=20 0 FeOOH,sat.
subox.
Fe2+Fe3+
sat 2+sat 3+
. 5.
:() , () -
, ()
-
,
() -
~ 1000
.
. 2.
Gd4d-
Fe3
O4
/Gd,
(
1, 2)
Gd3+
(
4,
3).
. 3.
Fe2p-
Fe3
O4
/Gd,
(
1, 2)
Gd3+
(
4,
3).
.
11,9 .
Gd(OH)3
Fe3
O4
~ 1,9 ,
~ 5,0 .
.
, ,
~ 1000
~ 4-
5%,
.
-
.
-4 -2 0 2 4-5
0
5
Hc=-144
Mr/Ms=0,44
H,
* -1
*3
T=294 K
Fe3O4/GdFeO3()
-3 0 3
-10
0
10
*3 /
H,
Fe3O4/ 2Gd
2Hc=-227,9
Mr/Ms=0,26
()
,
(. 4,
1).
= 900
1000
(. 4,
2)
,
GdFeO3
-
? ? ?
???????????????????????????????????????????????????????????????????????????????????????????
??????????????????????
????????????., ???????????????., ?????????., ????????????.
???????????????????????????????????????????????????????????????????, 246746, ?.??????, ????????????, 48, ????????, [email protected]
???????????? ???????????????????? ???????? ??????? ?? ???????????? ?????????? ???????????????????????????? ??????????????????????????????????????????, ??????????????????????????? ??????? ????????????. ???????????????????????????????????????-?????????????????????????????????????????????????????? T = 1100 ?, t = 1 ????????????-???? (???.2).
0
50
100
150
200
250
300
350
475 500 525 550 575 600 625 650 675 700 725 750
???????????, ??
???????????????????????????
, ???
.
2
34
1
???. 1. ????????????????? ?????? ?????-????? ?????????? ??????? ??????????? ???????????????????:? ??????????, ? ??????, ? ?????.
???. 2. ???????? ??????????-??? (?????. = 450 ??):1 YAG: Ce, La;2 YAG: Ce, La < 2 ????;3 YAG: Ce, Gd < 2 ????;4 YAG: Ce, Gd, ???. ???. ???????, T = 1100 ?, t = 1 ???.
???. 3. ??????????????????????????-???????????????????????????????:1 ????????????????????????????;2 ????????????????????.
????????? ?????????? ??????????????????????????????????????????????? ??????-??? ???????????????????? ????????? ?? ????? ???-??????????????? Y3Al5O12: Ce3+????????????-???????????????????-08, ?????????????????-??????? ???????????? ??????????????? ???????-???? ????????? ?????? ???????? 20-50 ???? ??????? ???? ??????????? 40-60 ?. ?? ????????????????????????????????????????????????,?????????? ??? ???????????? ??????????? ????-??????? ?? ????????? ????????????. ?????????????????????????????????????????????????????????? ?????????????? ?? ?????? ????? ?????-?????, ???????????????????????????????????,????????????????????????????????? (???. 3.).
-
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: [email protected] , . (044) 424 94 72 The theoretical arguments presented in this article have
shown how the distribution of the electrostatic potential
in semiconductor - vacuum - metal contact changes in
an applied voltage
)U,x(V j
U . The finiteness and continuity of )U,x(V j 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 )U,x(V1 in a semiconductor are
-
2
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 is calculated in the
SVM system before contact. It was shown that the presence of a
metal in the distance ( is thickness of the space
charge region (SCR) in a semiconductor) leads to the change of
the charge potential
)x(V j
SCRLL
)x(V j
SCRL
x
, which is related to the presence of
charge with the density and on the surfaces of
semiconductor and metal. At the subsequent diminishing of the
vacuum interval a potential barrier determined by the
image potential V between a semiconductor and metal [1-3].
01
nm10
)
02
L
(j0
-
3
Theory
Continuity and total potential )x(V j0 )x(V j
)k(
on the interfaces
is caused by the correct account of the spatial dispersion effects in
the dielectric functions of semiconductor
1 and metal )k(
3 (TFA) [3]. Adduction of the SVM system to the contact
(establishment of the general Fermi level) leads to the finite jump
of the potential )x(V j , which equals to the contact potential
13 , where 1 and 3 is work function of the semiconductor and metal, accordingly.
In [3] it is shown that the continuity of before contact
can be saved after its adduction in the contact due to the change of
charge potential
)x(V j
)x(V j 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 and metal surfaces. )U(101 )U02 (2
-
4
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 in all
SVM system after the contact and its change in forward
)U,x(V j
U and
reverse U voltage. Results of calculations
In the present work the distribution of )U,x(V j is analysed
on an example n -SivacuumAu system with the well-known
parameters.
The potential )x(V j for -SivacuumAu structure before
contact (d