Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons
The crystal and electronic structures of SiO₂/α-Fe₂O₃ mixtures are analysed using X-ray diffraction and ultra-soft X-ray emission spectroscopy. The energy redistributions of the Fesрd, Sisp, and Op valence electrons due to changes in the mass ratio (20/80, 50/50, 80/20) of SiO₂ and α-Fe₂O₃ in the mi...
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Інститут металофізики ім. Г.В. Курдюмова НАН України
2015
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| Cite this: | Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons / Ya. V. Zaulychnyy, V. M. Gun’ko, Y. V. Yavorskyi, V. I. Zarko, S. S. Piotrowska, and V. M. Mishchenko // Металлофизика и новейшие технологии. — 2015. — Т. 37, № 8. — С. 1063-1075. — Бібліогр.: 27 назв. — англ. |
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Zaulychnyy, Ya.V. Gun’ko, V.M. Yavorskyi, Y.V. Zarko, V.I. Piotrowska, S.S. Mishchenko, V.M. 2017-01-19T10:57:30Z 2017-01-19T10:57:30Z 2015 Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons / Ya. V. Zaulychnyy, V. M. Gun’ko, Y. V. Yavorskyi, V. I. Zarko, S. S. Piotrowska, and V. M. Mishchenko // Металлофизика и новейшие технологии. — 2015. — Т. 37, № 8. — С. 1063-1075. — Бібліогр.: 27 назв. — англ. 1024-1809 PACS: 61.43.Gt, 71.20.Ps, 71.23.-k, 73.20.At, 78.70.En, 81.20.Wk, 82.80.Ej https://nasplib.isofts.kiev.ua/handle/123456789/112276 The crystal and electronic structures of SiO₂/α-Fe₂O₃ mixtures are analysed using X-ray diffraction and ultra-soft X-ray emission spectroscopy. The energy redistributions of the Fesрd, Sisp, and Op valence electrons due to changes in the mass ratio (20/80, 50/50, 80/20) of SiO₂ and α-Fe₂O₃ in the mixtures are studied. The ultra-soft FeLα, SiLα, and OKα X-ray emission spectra of SiO₂/α-Fe₂O₃ mixtures are compared with those of individual iron oxide and silica powders. Interatomic interactions of surface atoms of adjacent particles occur owing to high local pressures and temperatures under mechanical treatment of the composition. Electrons’ transfer from silicon cations to oxygen anions is observed as a result of the mechanical activation of SiO₂/α-Fe₂O₃ mixtures. Енергетичний перерозподіл Fesрd-, Sisp- та Op-валентних електронів через зміну масового співвідношення (20/80, 50/50, 80/20) вхідних прекурсорів SiO₂ та α-Fe₂O₃ у сумішах досліджували, порівнюючи одержані від них Рентґенівські емісійні спектри FeLα-, SiLα- та OKα-смуг із спектрами порошкового, чистого оксиду заліза та чистого діоксиду кремнію. Аналіза спектрів показала, що міжатомова взаємодія між поверхневими атомами відбувається внаслідок високих локальних тисків і температур при нашаруванні наночастинок діоксиду кремнію на частинки оксиду заліза. Внаслідок механоактивації відбувається перенесення електронів від катіонів Силіцію до аніонів Оксиґену досліджуваної суміші. Энергетическое перераспределение Fespd-, Sisp- и Op-валентных электронов за счёт изменения массового соотношения (20/80, 50/50, 80/20) входных прекурсоров SiO₂ и α-Fe₂O₃ в смесях исследовали, сравнивая полученные от них рентгеновские эмиссионные спектры FeLα-, SiLα- и OKα-полос со спектрами порошкового, чистого оксида железа и чистого диоксида кремния. Анализ спектров показал, что межатомное взаимодействие между поверхностными атомами происходит вследствие высоких локальных давлений и температур при наслоении наночастиц диоксида кремния на частицы оксида железа. В результате механоактивации происходит перенос электронов от катионов кремния к анионам кислорода исследуемой смеси. en Інститут металофізики ім. Г.В. Курдюмова НАН України Металлофизика и новейшие технологии Строение и свойства наноразмерных и мезоскопических материалов Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons Вплив механоактивації сумішей SiO₂/α-Fe₂O₃ на розподіл валентних елетронів Влияние механоактивации смесей SiO₂/α-Fe₂O₃ на распределение валентных электронов Article published earlier |
| institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| collection |
DSpace DC |
| title |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons |
| spellingShingle |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons Zaulychnyy, Ya.V. Gun’ko, V.M. Yavorskyi, Y.V. Zarko, V.I. Piotrowska, S.S. Mishchenko, V.M. Строение и свойства наноразмерных и мезоскопических материалов |
| title_short |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons |
| title_full |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons |
| title_fullStr |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons |
| title_full_unstemmed |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons |
| title_sort |
effect of mechanical activation of highly disperse sio₂/α-fe₂o₃ mixtures on distribution of valence electrons |
| author |
Zaulychnyy, Ya.V. Gun’ko, V.M. Yavorskyi, Y.V. Zarko, V.I. Piotrowska, S.S. Mishchenko, V.M. |
| author_facet |
Zaulychnyy, Ya.V. Gun’ko, V.M. Yavorskyi, Y.V. Zarko, V.I. Piotrowska, S.S. Mishchenko, V.M. |
| topic |
Строение и свойства наноразмерных и мезоскопических материалов |
| topic_facet |
Строение и свойства наноразмерных и мезоскопических материалов |
| publishDate |
2015 |
| language |
English |
| container_title |
Металлофизика и новейшие технологии |
| publisher |
Інститут металофізики ім. Г.В. Курдюмова НАН України |
| format |
Article |
| title_alt |
Вплив механоактивації сумішей SiO₂/α-Fe₂O₃ на розподіл валентних елетронів Влияние механоактивации смесей SiO₂/α-Fe₂O₃ на распределение валентных электронов |
| description |
The crystal and electronic structures of SiO₂/α-Fe₂O₃ mixtures are analysed using X-ray diffraction and ultra-soft X-ray emission spectroscopy. The energy redistributions of the Fesрd, Sisp, and Op valence electrons due to changes in the mass ratio (20/80, 50/50, 80/20) of SiO₂ and α-Fe₂O₃ in the mixtures are studied. The ultra-soft FeLα, SiLα, and OKα X-ray emission spectra of SiO₂/α-Fe₂O₃ mixtures are compared with those of individual iron oxide and silica powders. Interatomic interactions of surface atoms of adjacent particles occur owing to high local pressures and temperatures under mechanical treatment of the composition. Electrons’ transfer from silicon cations to oxygen anions is observed as a result of the mechanical activation of SiO₂/α-Fe₂O₃ mixtures.
Енергетичний перерозподіл Fesрd-, Sisp- та Op-валентних електронів через зміну масового співвідношення (20/80, 50/50, 80/20) вхідних прекурсорів SiO₂ та α-Fe₂O₃ у сумішах досліджували, порівнюючи одержані від них Рентґенівські емісійні спектри FeLα-, SiLα- та OKα-смуг із спектрами порошкового, чистого оксиду заліза та чистого діоксиду кремнію. Аналіза спектрів показала, що міжатомова взаємодія між поверхневими атомами відбувається внаслідок високих локальних тисків і температур при нашаруванні наночастинок діоксиду кремнію на частинки оксиду заліза. Внаслідок механоактивації відбувається перенесення електронів від катіонів Силіцію до аніонів Оксиґену досліджуваної суміші.
Энергетическое перераспределение Fespd-, Sisp- и Op-валентных электронов за счёт изменения массового соотношения (20/80, 50/50, 80/20) входных прекурсоров SiO₂ и α-Fe₂O₃ в смесях исследовали, сравнивая полученные от них рентгеновские эмиссионные спектры FeLα-, SiLα- и OKα-полос со спектрами порошкового, чистого оксида железа и чистого диоксида кремния. Анализ спектров показал, что межатомное взаимодействие между поверхностными атомами происходит вследствие высоких локальных давлений и температур при наслоении наночастиц диоксида кремния на частицы оксида железа. В результате механоактивации происходит перенос электронов от катионов кремния к анионам кислорода исследуемой смеси.
|
| issn |
1024-1809 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/112276 |
| citation_txt |
Effect of Mechanical Activation of Highly Disperse SiO₂/α-Fe₂O₃ Mixtures on Distribution of Valence Electrons / Ya. V. Zaulychnyy, V. M. Gun’ko, Y. V. Yavorskyi, V. I. Zarko, S. S. Piotrowska, and V. M. Mishchenko // Металлофизика и новейшие технологии. — 2015. — Т. 37, № 8. — С. 1063-1075. — Бібліогр.: 27 назв. — англ. |
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1063
СТРОЕНИЕ И СВОЙСТВА НАНОРАЗМЕРНЫХ
И МЕЗОСКОПИЧЕСКИХ МАТЕРИАЛОВ
PACS numbers:61.43.Gt, 71.20.Ps,71.23.-k,73.20.At,78.70.En,81.20.Wk, 82.80.Ej
Effect of Mechanical Activation of Highly Disperse
SiO2/-Fe2O3 Mixtures on Distribution of Valence Electrons
Ya. V. Zaulychnyy, V. M. Gun’ko*, Yu. V. Yavorskyi, V. I. Zarko*,
S. S. Piotrowska**, and V. M. Mishchenko*
National Technical University of Ukraine ‘Kyiv Polytechnic Institute’,
Physical Engineering Faculty,
35 Politekhnichna Str.,
03056 Kyiv, Ukraine
*O. O. Chuiko Institute of Surface Chemistry, N.A.S. of Ukraine,
17 General Naumov Str.,
03164 Kyiv, Ukraine
**I. M. Frantsevich Institute for Problems of Materials Science, N.A.S. of Ukraine,
3 Krzhizhanovsky Str.,
03680 Kyiv-142, Ukraine
The crystal and electronic structures of SiO2/-Fe2O3 mixtures are analysed
using X-ray diffraction and ultra-soft X-ray emission spectroscopy. The en-
ergy redistributions of the Fesрd, Sisp, and Op valence electrons due to
changes in the mass ratio (20/80, 50/50, 80/20) of SiO2 and -Fe2O3 in the
mixtures are studied. The ultra-soft FeL, SiL, and OK X-ray emission
spectra of SiO2/-Fe2O3 mixtures are compared with those of individual iron
oxide and silica powders. Interatomic interactions of surface atoms of adja-
cent particles occur owing to high local pressures and temperatures under
mechanical treatment of the composition. Electrons’ transfer from silicon
cations to oxygen anions is observed as a result of the mechanical activation
of SiO2/-Fe2O3 mixtures.
Енергетичний перерозподіл Fesрd-, Sisp- та Op-валентних електронів че-
рез зміну масового співвідношення (20/80, 50/50, 80/20) вхідних прекур-
сорів SiO2 та -Fe2O3 у сумішах досліджували, порівнюючи одержані від
них Рентґенівські емісійні спектри FeL-, SiL- та OK-смуг із спектрами
порошкового, чистого оксиду заліза та чистого діоксиду кремнію. Аналіза
спектрів показала, що міжатомова взаємодія між поверхневими атомами
відбувається внаслідок високих локальних тисків і температур при наша-
руванні наночастинок діоксиду кремнію на частинки оксиду заліза. Вна-
слідок механоактивації відбувається перенесення електронів від катіонів
Металлофиз. новейшие технол. / Metallofiz. Noveishie Tekhnol.
2015, т. 37, № 8, сс. 1063—1075
Оттиски доступны непосредственно от издателя
Фотокопирование разрешено только
в соответствии с лицензией
2015 ИМФ (Институт металлофизики
им. Г. В. Курдюмова НАН Украины)
Напечатано в Украине.
1064 Ya. V. ZAULYCHNYY, V. M. GUN’KO, Yu. V. YAVORSKYI et al.
Силіцію до аніонів Оксиґену досліджуваної суміші.
Энергетическое перераспределение Fespd-, Sisp- и Op-валентных электро-
нов за счёт изменения массового соотношения (20/80, 50/50, 80/20) вход-
ных прекурсоров SiO2 и -Fe2O3 в смесях исследовали, сравнивая полу-
ченные от них рентгеновские эмиссионные спектры FeL-, SiL- и OK-
полос со спектрами порошкового, чистого оксида железа и чистого диок-
сида кремния. Анализ спектров показал, что межатомное взаимодействие
между поверхностными атомами происходит вследствие высоких ло-
кальных давлений и температур при наслоении наночастиц диоксида
кремния на частицы оксида железа. В результате механоактивации про-
исходит перенос электронов от катионов кремния к анионам кислорода
исследуемой смеси.
Key words: hematite, nanosilica, electronic structure, ultra-soft X-ray emis-
sion spectroscopy, X-ray diffraction.
(Received March 3, 2015)
1. INTRODUCTION
Micro- and nanoparticles play an important role in various industrial
processes and natural phenomena. Nanooxides and nanocomposite ma-
terials are used in photocatalysis [1], thermophotoelectric [2], as well
as fillers of polymers, pigments, etc. These materials can be used in the
fabrication of photon crystals [3] and have a highly promising poten-
tial in electrochemistry [4], as they are highly stable and nontoxic in
tough conditions. Therefore, synthesis and investigation of new na-
nooxides and nanocomposite materials is of importance from practical
point of view.
Among a variety of new materials [5—11], it is worth to mark out
nanomaterials, which sorption, photocatalytic, photoelectric and elec-
trochemical properties along with their structure—morphology charac-
teristics are determined by the energy and charge states of atoms or
ions. The energy and charge states of ions depend on energy redistribu-
tion of valence electrons of atoms of surface layers of nanoparticles
with developed surface area as in nanosize SiO2 and -Fe2O3 [12—23].
Properties of such materials in nanocomposites are reciprocally sup-
plemented [24—27]. Thus, it is important to investigate the electronic
structure depending on composition of such nanomaterials and synthe-
sis method.
One of widely used methods of processing of nanocomposite materi-
als is mechanoactivation. Therefore, the aim of this work is to study
the mechanoactivation effect on the energy distribution of the valence
electrons and charge state of constituent atoms after treatment of
highly disperse iron oxide and silica mixed in different ratios.
EFFECT OF MECHANICAL ACTIVATION OF DISPERSE SiO2/-Fe2O3 MIXTURES 1065
2. MATERIALS AND METHODS
2.1. Materials
Studied amorphous highly dispersed silica (HDS) had the specific sur-
face area SBET 300 m
2/g (PS300) and average particle diameter d 9.2
nm. Pyrogenic silica (pilot plant of the O. O. Chuiko Institute of Sur-
face Chemistry, Kalush, Ukraine) was synthesized using SiCl4 as a pre-
cursor burned in the О2/Н2 flame resulting in hydrolysis/oxidation and
formation of nanoparticles of silica.
Hematite -Fe2O3 (O. O. Chuiko Institute of Surface Chemistry,
Ukraine) was synthesized by thermal decomposition of hydrated iron
(III) oxalate (Fe2(C2O4)35H2O) at 350—370С in air. The yield of -Fe2O3
is approximately 35%. Crystalline -Fe2O3 had SBET 7 m
2/g and co-
herent-scattering region size dCSR 92 nm. This value is much smaller
than the particle size determined from the specific surface area d
6/(SBET0) 163 nm, where 0 is the true density of hematite (5.26
g/cm3), assuming a spherical shape of particles. This suggests that
primary hematite particles are not monocrystalline.
Mechanically activated (MA) systems x-SiO2 y-Fe2O3 were prepared
using a microbreaker (stainless steel sphere of 10 cm
3
in volume with a
stainless steel ball of 0.8 cm in diameter, 30 W, and frequency 50 Hz).
Treatment time was 5 minutes for all samples. Non-activated mechani-
cal mixtures of x-SiO2 y-Fe2O3 were prepared by simple stirring of ox-
ides (without strong mechanical loading) during 5 minutes and then
with very short (3 s) mixing in the microbreaker. Atomic composition
of SiO2, -Fe2O3 and mechanical mixtures at various mass ratios are
shown in Table 1.
2.2. Methods
X-ray diffraction (XRD) investigation was carried out using a DRON-
TABLE 1. Mass and atomic composition of x-SiO2 y-Fe2O3 mixtures.
Mass composition
Relative contribution of atoms
Si O(Si) Fe O(Fe) O (total)
SiO2 0.33333 0.66667 — — 0.66667
Fe2O3 — — 0.40000 0.60000 0.60000
0.2SiO2 0.8Fe2O3 0.13307 0.26613 0.24032 0.36048 0.62661
0.5SiO2 0.5Fe2O3 0.24220 0.48441 0.10935 0.16403 0.64844
0.8SiO2 0.2Fe2O3 0.30467 0.60935 0.03439 0.05158 0.66093
1066 Ya. V. ZAULYCHNYY, V. M. GUN’KO, Yu. V. YAVORSKYI et al.
UM1 diffractometer (‘Burevestnik’, St.-Petersburg, Russia) with mon-
ochromatic CuK-radiation. Graphite single crystal mounted on dif-
fracted beam is used as a monochromator. The diffractograms are rec-
orded at 2 10—90 with a scan step angle of 0.05 and exposure time
in each point of 3—7 s. The XRD data processing is carried out using
Powder Cell 2.4 program for full-contour analysis of a mixture of poly-
crystalline components. Analysis of diffraction maxima broadening
connected with coherent-scattering region sizes (which can be consid-
ered as the average size of crystallites) and lattice strain is carried out
using the Wіllіamson—Hall method. The crystallinity is determined by
normalization of integral intensity of amorphous halo in a sample to
intensity of amorphous halo in completely amorphous matter.
Analysis of phase composition of samples after mechanical activa-
tion shows that phase composition of samples before and after treat-
ment is practically the same within the experimental error range. How-
ever, the values of dCSR decreased for hematite crystallites (Table 2).
X-ray emission spectra of atoms of x-SiO2 y-Fe2O3 were obtained
using ultra-soft X-ray emission spectrometry (USXES) method [4] ap-
plying RSM-500 (SCBXA, ‘Burevestnik’, St.-Petersburg, Russia) X-
ray spectrometer-monochromator. Energy of electron beam was Е 5
keV and intensity was I 51017
electroncm2
for the OK and Е 7
keV, I 51017
electroncm2
for FeL and Е 4 keV, and I 21017
electroncm2
for the SiL band. The excitation mode used does not lead
TABLE 2. Phase composition, coherent-scattering region size (dCSR) and
change of coherent-scattering region size (dCSR) in x-SiO2 y-Fe2O3 samples
depending on mass ratio of initial precursors.
Sample Phase composition, % dCSR, nm dCSR, nm
-Fe2O3 -Fe2O3– 100 92
2
MA -Fe2O3 -Fe2O3– 100 90
0.2SiO2 0.8Fe2O3
-Fe2O3– 80
Am. SiO2– 20
94
8
MA 0.2SiO2 0.8Fe2O3
-Fe2O3– 80
Am. SiO2– 20
86
0.5SiO2 + 0.5Fe2O3
-Fe2O3– 50
Am. SiO2– 50
93
15
MA 0.5SiO2 0.5Fe2O3
-Fe2O3– 50
Am. SiO2– 50
78
0.8SiO2 0.2Fe2O3
-Fe2O3– 20
Am. SiO2– 80
82
22
MA 0.8SiO2 0.2Fe2O3
-Fe2O3– 20
Am. SiO2– 80
60
EFFECT OF MECHANICAL ACTIVATION OF DISPERSE SiO2/-Fe2O3 MIXTURES 1067
to the formation of radiation defects in the materials.
Residual pressure in an X-ray tube and a spectrometer detector was
2.6710—4
Nm2. Samples were rubbed into copper anode (etched and
rinsed in ethanol) cooled by running water to prevent oxygen thermo-
desorption and sintering of SiO2 and -Fe2O3 nanoparticles during
measurements. Intensity of X-ray quanta in the energy region h
510—535 eV corresponding to OK band was measured to persuade in
absence of overlap of CuO OK spectra and OK bands of the studied
samples. The repeated measurements after sample investigation
showed that intensity of quanta generated by copper anode in men-
tioned energy region did not exceed background intensity. The forth—
eighth spectra were analysed to obtain reliable results.
Diffraction grating with groove density of 600 mm
1
and curvature
radius of 6 m (OK), and 2 m (AlL and FeL) is used. In the first case,
filtering mirror with gold and, in the second case, filtering mirror
with polystyrene are used to screen the CK line. Instrumental distor-
tions measured by comparison of theoretical and measured widths of
the TiLl line at Imax at the wave length 3.1nm are smaller than 0.2 eV
that converting to the wave length 2.36 nm, where the OK localiz-
es, is 0.3 eV. X-ray photons are registered using secondary electron
multiplier with primary CsJ photocathode.
3. RESULTS AND DISCUSSION
In order to analyse the effect of mechanical activation on interatomic
interactions, namely on a character of electron distributions in oxy-
gen, silicon, and iron atoms, it is necessary to determine the energy
regions, where Op, Sisd, and Fesd valence electrons localize for the
studied materials. The energy distributions of valence electrons in var-
ious silicas were analysed in detail elsewhere [24—26]. It is shown [24—
26], that lower subband corresponds to covalent-binding states in sili-
ca, and the high-energy OK band describes non-binding electronic
states occupied by electrons transferred from silicon to oxygen.
From comparison of the OK and FeL bands with calculations of
partial density of states [27] in a common energy scale, it is clear that
the OK band reflects mainly O2p states of oxygen strongly hybridized
with Fe3d orbitals. Peculiarities of the OK band are observed in the
same energy region as Van Hove singularities are in density of the Op
and Fe3d states.
Shapes of the OK and FeL bands (Fig. 1) are similar with exception
of a low-energy region, where subband ‘а’ appears.
This subband, which according to the calculations of the partial den-
sities of states [27], represents high density of the Fe3d states that is
three times higher than that of the Op states, and it is separated from
the high-energy region by a deep minimum. Such distribution of the
1068 Ya. V. ZAULYCHNYY, V. M. GUN’KO, Yu. V. YAVORSKYI et al.
electron states in -Fe2O3 differs from that in silica. Since the shape of
OK and FeL bands in the energy (7—0) eV are very similar, it indi-
cates that this part of the valence band hybridized strongly confirming
data calculations [27], although these data by content of Fe3d states is
lower than Op orbitals. This indicates the valence-binding character of
the electron states in the whole valence band in contrast to that of SiO2.
Figure 2 shows that the OK bands of -Fe2O3 before and after me-
Fig. 1. The FeL and OK USXES of pure Fe2O3. Spectra are plotted in a com-
mon energy scale. The spectral features are labelled by a and b. All the spectra
of samples have been normalized to the peak b.
Fig. 2. The OK USXES of -Fe2O3 and mechanically activated (MA) -Fe2O3.
The spectral features are labelled by a and b. All the spectra of samples have
been normalized to the peak b.
EFFECT OF MECHANICAL ACTIVATION OF DISPERSE SiO2/-Fe2O3 MIXTURES 1069
chanical activation are almost similar with exception of narrowing of
‘a’ feature in near-peak region of the OK of -Fe2O3 after mechanical
activation by 0.5 eV.
Total width of the OK band of -Fe2O3 after mechanical activation
slightly decreases due to a shift of a low-energy part of the band by 0.2
eV. It is possibly occurred due to partial dehybridization of the Fed
Op states when ion—covalent bonds break during nanoparticles grind-
ing under mechanical activation (Table 2). It is confirmed by dCSR de-
creasing.
Analysis of the OK bands of x-SiO2 y-Fe2O3 mixtures with differ-
ent mass and atomic composition (Table 1) shows narrowing of OK
bands when going from -Fe2O3 to SiO2 and sharpening a maximum
that is typical for SiO2 (Fig. 3). Maximum b shifts toward higher ener-
gy and becomes narrower in a low-energy part of the OK band, when
maintains SiO2 increase in the mechanical mixture. It confirms preva-
lent contribution of SiO2 in a source mixture.
Narrowing OK band of mixture containing 20% SiO2 by 0.3 eV in a
near-peak region is caused by a shift of the long-wave contour c toward
higher energy. Shift of the low-energy contour toward the short-wave
Fig. 3. The OK USXES of x-SiO2 y-Fe2O3 mixtures with different mass rati-
os: a–mechanical mixtures, b–mechanically activated (MA) mixtures. The
spectral features are labelled by a, b, and c. All the spectra of samples have
been normalized to the peak c.
1070 Ya. V. ZAULYCHNYY, V. M. GUN’KO, Yu. V. YAVORSKYI et al.
side is 1.61 and 2.7 eV for 50 and 80% wt. of SiO2 in the mechanical
mixtures, respectively.
Maximal shift of the high-energy contour of the OK band toward
shorter wave by 0.9 eV occurs at minimal content of Fe2O3 at 20% wt.
When content of Fe2O3 increases to 50 and 80% wt., the high-energy
contour of the OK band shifts by 0.7 and 0.3 eV, respectively. Differ-
ence in the energy positions of the high-energy contours of the OK
bands of -Fe2O3 and SiO2 powders is 0.6 eV. Therefore, the shift of the
high-energy contour of the OK band of mixture with 80% wt. of SiO2
is not connected with dominant contribution of the OK of SiO2.
The shift of the long-wave contours of the OK bands of the mechan-
ically activated mixtures is almost similar to that of the mechanical
mixtures (Table 3). The short-wave contours of the OK bands of the
mechanically activated mixtures shift toward higher energy much
greater than that for the mechanical mixtures (see Table 3). Namely,
the high-energy contour of the OK band of the mechanically activated
mixture containing 80% wt. of silica is shifted by 1.46 eV relative to
that of Fe2O3. This value is by 0.5 eV higher than that of the mechani-
cal mixtures.
Value of a shift of the OK bands decreases to 1.0 and 0.5 eV with
decreasing SiO2 content to 50 and 20% wt., respectively. Increasing
intensity in the high-energy part of the OK bands due to mechanical
activation of the mixture indicates an increase in the occupation of the
2p states of oxygen near the top of the valence band.
To explain this effect, it is necessary to compare the OK emission
bands of the mechanical and mechanically activated mixtures. Low-
energy contours of the OK bands of mixtures before and after activa-
tion near the bottom of the valence band are absolutely similar (Fig. 4).
This testifies to absence of the effect of mechanical activation on elec-
TABLE 3. Dependence of differences in shifts of contours of the OK bands of
x-SiO2 y-Fe2O3 mixtures relative to the OK band of Fe2O3 on composition
before and after mechanical activation.
Mixture
composition
Mechanical mixture Mechanically activated mixture
E of low-
energy region,
eV
E of high-
energy,
eV
E of low-
energy region,
eV
E of high-
energy,
eV
Fe2O3 0 0 0.20—0.50 0
SiO2 2.70 0.20—1.0 — —
0.2SiO2 0.8Fe2O3 0.20—0.30 0.2—0.40 0.36 0.50
0.5SiO2 0.5Fe2O3 1.61 0.70 1.57 1.02
0.8SiO2 0.2Fe2O3 2.07 0.90 2.09 1.46
EFFECT OF MECHANICAL ACTIVATION OF DISPERSE SiO2/-Fe2O3 MIXTURES 1071
trons in deep covalent-binding states. Electrons from the energy re-
gion corresponding to photon energy h 525.4—257.0 eV redistribute
to the energy region of 527—530 eV (Fig. 4).
Intensity of the low-energy part of the OK emission band decreases
less if content of SiO2 increases. Its value becomes maximal in the OK
bands of the sample with maximal content of SiO2.
Intensity of the SiL band decreased in a photon energy region h
90.6—94.6 eV (Fig. 5) that indicates a decrease in the occupation of
the Sisd states in a central part of the valence band. This decrease of
intensity diminishes if content of SiO2 increases. Thus, the SiL bands
of the mechanical and mechanically activated 0.8SiO2 0.2Fe2O3 sam-
ples almost coincide. The ratio of x-SiO2 and y-Fe2O3 decreases in atom-
ic percents more than in mass percents (Table 1). Therefore, contribu-
Fig. 4. The OK USXES of mechanical and mechanically activated (MA) mix-
tures: 0.2SiO2 0.8Fe2O3 (a), 0.5SiO2 0.5Fe2O3 (b), 0.8SiO2 0.2Fe2O3 (c). All
the spectra of samples have been normalized to the peak c.
1072 Ya. V. ZAULYCHNYY, V. M. GUN’KO, Yu. V. YAVORSKYI et al.
tion of silicon ions into emission of the SiL band and oxygen ions in-
creases, when content of -Fe2O3 decreases. Supposed transfer of elec-
trons to oxygen ions of -Fe2O3 and SiO2 did not occur due to mechani-
cal activation, than a shape of the OK band had to approach to that of
SiO2. However, a shift of the high-energy contour of the OK band to-
ward higher energy is maximal for a sample with the maximal content
of SiO2 due to the mechanical activation of 0.2Fe2O3 0.8SiO2 mixture.
It indicates that electrons transfer to anions of SiO2 and -Fe2O3 is
caused by the mechanical activation.
The increase in the SiO2 content and the decrease in the relative
number of -Fe2O3 anions points out that transfer of charge to -Fe2O3
anions increases due to the mechanical activation. As a result, intensi-
ty of the high-energy contour of the OK band increases with -Fe2O3
Fig. 5. The SiL USXES of mechanical and mechanically activated (MA) mix-
tures: 0.2SiO2 0.8Fe2O3 (a), 0.5SiO2 0.5Fe2O3 (b), 0.8SiO2 0.2 Fe2O3 (c).
All the spectra of samples have been normalized to the peak c.
EFFECT OF MECHANICAL ACTIVATION OF DISPERSE SiO2/-Fe2O3 MIXTURES 1073
content decreasing. It is possible, if the interatomic interactions be-
tween surface atoms of -Fe2O3 and SiO2 nanoparticles rise.
The Op orbitals of -Fe2O3 and SiO2 nanoparticles could overlap un-
der high local pressures during mechanical activation. Hybridized
Fe3d Op states under the top of the valence band could be occupied.
Breakage of the Si—O bonds, when SiO2 nanoparticles are under action
of larger and harder -Fe2O3 particles, can cause increase of the energy
of electrons in non-binding Op states in silica nanoparticles.
This result can explain the charge capacity of cells with cathode
based on mechanical and mechanically activated 0.8SiO2 0.2Fe2O3
mixtures. Anode of electrochemical cell was made of lithium. Lithium
hexafluorophosphate in ethyl carbonate:diethyl carbonate (1:1) LiPF6
is used as an electrolyte.
Increase of occupation of Op states near the top of valence band due
to mechanical activation results in increasing of the charge state of
oxygen in tetrahedral environment of silicon. It promotes increasing
of the degree of intercalation of lithium ions in the channels of struc-
ture of cathode material, resulting in increased charge capacity of
electrochemical cell (Fig. 6).
Figure 6 shows that specific capacity of cell with cathode material
based on mechanically activated 0.8SiO2 0.2Fe2O3 mixture is by 76.88
Ah/kg higher than that based on mechanical mixture. Whereas, power
of cell with cathode material based on MA mixture is 2.75 times higher
than that based on mechanical mixture.
4. CONCLUSIONS
The mechanical activation of the mixtures of amorphous nanosilica
Fig. 6. Discharge curves of cells with cathode material based on mechanical
and mechanically activated 0.8SiO2 0.2Fe2O3 mixtures.
1074 Ya. V. ZAULYCHNYY, V. M. GUN’KO, Yu. V. YAVORSKYI et al.
particles (dav 9.2 nm in average diameter) and crystalline -Fe2O3 par-
ticles (dCSR 92 nm and dav 163 nm) leads to diminution of the values
of dCSR. This diminution enhances with decreasing of hematite parti-
cles content. Interatomic interactions between the surface atoms of
coarse -Fe2O3 and finer SiO2 nanoparticles occur due to high local
pressures and temperatures under the mechanical activation of the
mixtures. Electrons transfer from silicon cations to oxygen anions be-
longing to both -Fe2O3 and SiO2 owing to mechanical activation of x-
SiO2 y-Fe2O3 mixtures. Increase of occupation of Op states near the
top of valence band due to mechanical activation results in increasing
of the charge state of oxygen in tetrahedral environment of silicon. It
promotes and increases the degree of intercalation of lithium ions in
the channels of structure of cathode material, resulting in increased
charge capacity of electrochemical cell.
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/NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken die zijn geoptimaliseerd voor prepress-afdrukken van hoge kwaliteit. De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 5.0 en hoger.)
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/UKR <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>
/ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
>>
/Namespace [
(Adobe)
(Common)
(1.0)
]
/OtherNamespaces [
<<
/AsReaderSpreads false
/CropImagesToFrames true
/ErrorControl /WarnAndContinue
/FlattenerIgnoreSpreadOverrides false
/IncludeGuidesGrids false
/IncludeNonPrinting false
/IncludeSlug false
/Namespace [
(Adobe)
(InDesign)
(4.0)
]
/OmitPlacedBitmaps false
/OmitPlacedEPS false
/OmitPlacedPDF false
/SimulateOverprint /Legacy
>>
<<
/AddBleedMarks false
/AddColorBars false
/AddCropMarks false
/AddPageInfo false
/AddRegMarks false
/ConvertColors /ConvertToCMYK
/DestinationProfileName ()
/DestinationProfileSelector /DocumentCMYK
/Downsample16BitImages true
/FlattenerPreset <<
/PresetSelector /MediumResolution
>>
/FormElements false
/GenerateStructure false
/IncludeBookmarks false
/IncludeHyperlinks false
/IncludeInteractive false
/IncludeLayers false
/IncludeProfiles false
/MultimediaHandling /UseObjectSettings
/Namespace [
(Adobe)
(CreativeSuite)
(2.0)
]
/PDFXOutputIntentProfileSelector /DocumentCMYK
/PreserveEditing true
/UntaggedCMYKHandling /LeaveUntagged
/UntaggedRGBHandling /UseDocumentProfile
/UseDocumentBleed false
>>
]
>> setdistillerparams
<<
/HWResolution [2400 2400]
/PageSize [612.000 792.000]
>> setpagedevice
|