The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II)
Process of formation of ultra disperse iron oxide minerals on steel surface by its contacts with air oxygen and dispersion medium containing ions of cuprum, argentums, aurum, platinum and palladium was studied. The formation of phase’s hydroxysulphate Green Rust, magnetite and lepidocrocite on steel...
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| Published in: | Наноструктурное материаловедение |
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| Date: | 2010 |
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| Format: | Article |
| Language: | English |
| Published: |
Інститут проблем матеріалознавства ім. І.М. Францевича НАН України
2010
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| Online Access: | https://nasplib.isofts.kiev.ua/handle/123456789/62724 |
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| Journal Title: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Cite this: | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) / O. Lavrynenko // Наноструктурное материаловедение. — 2010. — № 3. — С. 3-13. — Бібліогр.: 39 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860079687896662016 |
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| author | Lavrynenko, O. |
| author_facet | Lavrynenko, O. |
| citation_txt | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) / O. Lavrynenko // Наноструктурное материаловедение. — 2010. — № 3. — С. 3-13. — Бібліогр.: 39 назв. — англ. |
| collection | DSpace DC |
| container_title | Наноструктурное материаловедение |
| description | Process of formation of ultra disperse iron oxide minerals on steel surface by its contacts with air oxygen and dispersion medium containing ions of cuprum, argentums, aurum, platinum and palladium was studied. The formation of phase’s hydroxysulphate Green Rust, magnetite and lepidocrocite on steel surface by concentrations of electropositive metals 1–10 mg/dm³ was shown. Mechanism of phase formation occurs by two stages: adsorption of ions from dispersion medium on Green Rust surface with partly reduction of ions and oxidation of GR to magnetite or lepidocrocite and reduction of the rest metal ions on magnetite surface. Interacting iron oxide phases with electropositive ions add colloidal stability to composite particles.
Исследован процесс формирования ультрадисперсных железооксидных минералов на поверхности стали при ее контакте с кислородом воздуха и дисперсионной средой, содержащей ионы меди, серебра, золота, платины и палладия. Показано, что при концентрациях электроположительных металлов 1–10 мг/дм³ на поверхности стали образуются структуры гидроксисульфатного Green Rust, магнетита и лепидокрокита. Фазообразование проходит в две стадии: 1) адсорбция ионов дисперсионной среды на поверхности GR с восстановлением части ионов до металла и окислением GR до магнетита или лепидокрокита; 2) восстановление остаточной концентрации ионов электроположительных металлов на поверхности магнетита. Взаимодействие железооксидных фаз с электроположительными ионами придает частицам коллоидную устойчивость.
Досліджено процес формування ультрадисперсних залізооксидних мінералів на поверхні сталі при її контакті з киснем повітря та дисперсійним середовищем, яке містить іони міді, срібла, золота, платини та паладію. Показано, що за концентрац ій електропозитивних іонів 1–10 мг/дм³ на поверхні сталі утворюються структури гідроксисульфатного Green Rust, магнетиту й лепідокрокіту. Фазоутворення відбувається у дві стадії: 1) адсорбція іонів дисперсійного середовища на поверхні GR з відновленням частини іонів до металу й окисненням GR до магнетиту або лепідокрокіту; 2) відновлення залишкової концентрації іонів електропозитивних металів на поверхні магнетиту. Взаємодія залізооксидних фаз із електропозитивними іонами надає частинкам колоїдної стійкості.
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| first_indexed | 2025-12-07T17:15:44Z |
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ,
ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
O. Lavrynenko
F.D. Ovcharenko Institute of Bio-Colloid Chemistry of NAS of Ukraine
Academic Vernadsky Ave, 42, 03142, Kyiv, Ukraine
THE MECHANISM OF FORMATION
OF THE ULTRA DISPERSE IRON OXIDE MINERALS
ON STEEL SURFACE IN PRESENCE
OF Cu(II), Ag(I), Au(III), Pt (IV), Pd(II)
Key words: ultradisperse iron oxide
minerals, process of phase
formation, precious metals
ÓÄÊ: 544.77 + 549.057
Process of formation of ultra disperse iron oxide minerals on steel surface by its contacts
with air oxygen and dispersion medium containing ions of cuprum, argentums, aurum,
platinum and palladium was studied. The formation of phase’s hydroxysulphate Green
Rust, magnetite and lepidocrocite on steel surface by concentrations of electropositive
metals 1–10 mg/dm3 was shown. Mechanism of phase formation occurs by two stages:
adsorption of ions from dispersion medium on Green Rust surface with partly reduction
of ions and oxidation of GR to magnetite or lepidocrocite and reduction of the rest metal
ions on magnetite surface. Interacting iron oxide phases with electropositive ions add
colloidal stability to composite particles.
Novadays the ferromagnetic nanosized particles with different
physical-chemical, colloidal-chemical and crystallographic properties are
widely used for medical and biological aims [1, 2]. At first, the use of
such structures is connected with the creation of range of medicals and
new means of diagnostics of oncological diseases [3, 4]. Nanosized
particles with magnetic properties have particular biological activity
dependent on their nature and could be used to investigate the processes
in organism [5, 6] and to create new functional materials of medico-
biological purpose [7, 8]. At present the undisputed leaders which are
used in medico-biological researches are most common ultra disperse
iron oxides of maghemite γ-Fe2O3 or magnetite Fe3O4 because of their
biocompatibility [9]. They are formed by co-precipitation of ferric and
ferrous salts in alkalescent dispersion medium [10], by high-temperature
synthesis [11], by mechanochemistry [12], by sol-gel synthesis [13], by
red-ox potential method [14, 15], by a reverse micelle method [16] and a
range of other methods including addition of stabilizing substance [17,O. LAVRYNENKO, 2010©
4
Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
18]. At the same time, a lot of publications are
devoted to the use in medicine and biology of
composites and composition materials that consist
of maghemite or magnetite particles covered with
precious metal, for example, aurum [19–22]. Such
structures are used for separation of biological
objects, for example, proteins or other [23, 24],
immunoassay, imaging of magnetic resonance,
contrast enhancement, drug delivery [25] et al. The
aim of the investigation is the studying the process
of nanosized iron oxide particles formation on steel
surface by its contact with water solutions
containing cuprum cations and ions of precious
metals.
Objects and methods
The formation of the particles was carried out
on the surface of the steel electrode (St-3) that
contacted by rotation alternately with air oxygen
and dispersion medium [26]. As dispersion medium
has been chosen the solutions of cuprum sulphate
with concentrations from 1 to 100 mg/dm3 at value
of pH in range from 2.5 to 12.0 and solution of
precious metals: argentums, aurum, platinum,
palladium, with initial concentrations 1 and
10 mg/dm3. The process of phase formation was
carried out until stationary condition, when in the
system the content of dispersion medium
(composition of ferrous, ferric, cuprum, precious
metals) and value of pH was stabilized. The
chemical analysis was carried out by the standard
methodics [27]. Phase compositions of ultra disperse
iron oxide structures was determined by X-ray
diffraction (XRD), transmission electron microscopy
(TEM), electronography [28].
Results and discussion
The investigation of the process of formation of
the ultra disperse iron oxides on the steel surface in
the presence of cuprum ions
Studying the process of the formation of the ultra
disperse iron oxides minerals on steel surface was
carried out depending on value of pH of the
dispersion medium and the concentration of cuprum
ions in it.
The Fig. 1 represents the result of the chemical
analysis, that by initial concentration of Cu(II) =
= 100 mg/dm3, shows the occurrence of the
classical reaction of cementation, when because of
the difference of standard electrode potentials
cuprum ions are reduced on steel surface and iron-
constituent is desolated with entering ferrous-ions
in dispersion medium.
Process of phase formation depends on pH value
and can continue from 2 to 3 hours at pH = 3.0 to
24 hours at pH = 6.0, when the maximum amount
of cuprum-ions (~85%) is bond from dispersion
medium of steel surface. It is accompanied by
changing of pH value to sub acid.
For example, the final value of pH at initial pH =
= 3.0 grows to pH = 5.0 and at initial pH = 6.0 it
went down to pH = 5.2.
The access of air oxygen in system leads to
oxidation of ferrous-ions and phase formation on
steel surface, as well as in dispersion medium. The
residual concentration of Fe(III) does not exceed
the 4.2 mg/dm3. The decrease of initial
concentration of Cu(II) to 1–10 mg/dm3 changes
of mechanisms of the process of phase formation:
cations of cuprum practically are not reduced on
steel surface and they participate in formation of
iron oxide phases.
At the same time, the agglomeration of ferrous-
ions in dispersion medium does not occur; the final
ferric concentration there is in the range 0.6–
1.7 mg/dm3, and concentration of ferric-ions does
not exceed 0.3 mg/dm3. The final value of pH
changes less than one.
Whereas, in such conditions the binding of the
cuprum-ions hardly occurs; for example, at the value
pH = 6.5 and the initial concentration of Cu(II) =
1 mg/dm3 the final concentration decreased of
= 0.95 mg/dm3. At the initial concentration of 10 mg/dm3
in the dispersion medium remains 8.25 mg/dm3 of
cuprum-ions.
Analysis of the ultra disperse iron oxide phases
shows the formation in the system of iron
oxyhydroxides – goethite α-FeOOH and
lepidocrocite γ-FeOOH with addition of spinel ferrites,
admittedly magnetite Fe3O4, which (pre)dominates
in the content of the sediments at the initial
concentration of Cu(II) = 100 mg/dm3 (Fig. 2).
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
5
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ЛО
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
Fig. 1. Kinetic of the concentration of cations of ferrous (a) and cuprum (b) by the process of phase formation on
steel surface at its contact with cuprum sulphate solution with initial concentration of Cu(II) 100 mg/dm3 and at pH
value: 1 and 4 at pH = 3.0; 2 and 5 at pH = 4.5; 3 and 6 at pH = 6.0
à b
à b
ñ d
Fig. 2. XRD-data of iron oxide phases formed in the near surface layer of the steel electrode at the concentration of
Cu(II) 100 mg/dm3 at pH values: 1 – 3.0; 2 – 4.5; 3 – 6.0 and in dispersion medium. Numbers correspond to the phases:
1 – lepidocrocite γ-FeOOH, 2 – goethite α-FeOOH, 3 – magnetite Fe3O4
50
40
30
20
10
0,0 1,5 2,5 3,5 4,5 5,5 6,5 7,5 8,5
lg τ
Ñ, mg/dm3
1
2
3
100
80
60
40
20
4
5
6
0,0 1,5 2,5 3,5 4,5 5,5 6,5 7,5 8,5
lg τ
Ñ, mg/dm3
900
700
500
300
0 20 40 60 80
2Θ
– 1
– 2
– 3
(0
20
)
(1
11
) (1
10
) (1
20
)
(2
20
)
(0
21
)
(2
22
) (3
11
)
(1
11
)
(1
21
)
(4
00
)
(3
31
)
(2
20
)
(4
22
)
(5
11
)
(0
02
) (4
40
)
(3
30
)
(1
70
)
– 1
– 2
– 3
(0
20
)
(1
11
)
(1
10
)
(1
20
) (2
20
)
(3
11
)
(2
22
)
(1
11
)
(4
00
)
(3
31
)
(2
20
)
(4
22
) (5
11
)
(0
02
)
(4
40
)
1000
800
600
400
0
20 40 60 80
2Θ
– 1
– 2
– 3
(0
20
)
(1
11
)
(1
10
)
(1
20
)
(2
20
)
(3
11
)
(1
21
)
(1
11
) (1
31
, 0
60
)
(3
31
)
(2
20
) (1
51
)
(5
11
)
(0
02
)
(4
40
)
(0
21
)
(0
31
)
(1
51
)
(1
71
)
(3
30
)
(1
70
)
1000
800
600
400
200
0
20 40 60 80
2Θ
– 1
– 2(0
20
)
(1
11
)
(1
10
)
(1
20
)
(0
51
, 2
00
)
(1
21
)
(1
31
, 0
60
)
(2
20
)
(1
51
)
(5
11
) (0
02
)
(0
21
)
(0
31
)
(1
80
)
(1
71
)
(3
30
)
(1
70
)
500
400
300
200
0
20 40 60 80
2Θ
6
Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
Fig. 4. Magnetite particles formed on the steel surface
by its contact with solution of cuprum sulphate
Fig. 3. XRD-data of iron oxide phases formed in the near surface layer of the steel electrode (a) and its surface layer (b)
at the initial concentration of cuprum-ions 1 mg/dm3 and pH value 6.5. Numbers correspond to the phases:
1 – lepidocrocite γ-FeOOH, 2 – magnetite Fe3O4
– 1
– 2
(0
20
) (4
00
)
(1
11
)
(1
20
)
(4
22
)
(2
20
)
(4
40
)
(5
11
)
(3
11
)
(2
22
)
(3
31
)
2000
1600
1200
800
400
0 20 40 60 80
2Θ
à
– 1
– 2
(0
20
)
(1
11
)
(1
20
)
(4
22
)
(2
20
)
(4
40
)
(5
11
)
(3
11
)
(1
00
)
(3
31
)
1800
1400
1000
600
200
0 20 40 60 80
2Θ
b
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
At the intensity of XRD-reflexes it is possible to
make an assumption that the most intensively the
formation of lepidocrocite γ-FeOOH occurs at
neutral medium and spinel ferrites – at value of pH =
= 4.5.
At the initial concentrations of cuprum-ions 1–
10 mg/dm3 in the composition of the surface
structures there dominate the phases of spinel
ferrites and lepidocrocite γ-FeOOH (Fig. 3). As a
rule, on the steel surface two layers of iron oxide
phases are formed where the outer (near surface)
layer (Fig. 3a) is characterized the more intensive
reflexes of oxyhydroxides than phases of the inner
(surface) layer (Fig. 3b).
The absence of cuprum containing phase in
sediment composition, for example, cuprum ferrite,
makes us think about the binding of cuprum ions by
sorption on surface of iron oxyhydroxides or
replacing ferric-cations in the structure of magnetite
Fe3O4.
Fig. 4 shows TEM image of magnetite Fe3O4
formed on steel surface by its contact with cuprum
sulphate solution by concentration Cu(II) 1 mg/dm3.
Thus, our investigation shows that the formation
of ultra disperse iron oxide minerals on the steel
surface in the presence of cuprum ions in water
medium is possible by two mechanisms: oxidation-
reduction with reduction of cuprum-ions and
oxidation of iron and oxidation of ferrous-ions with
7
М
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ЛО
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
Fig. 5. Kinetic of changing the concentration of ferric and ferrous ions in the process of phase formation on steel
surface in the presence of precious metals: platinum (1) – Fe total, 2 – Fe(III); palladium (3) – Fe total, 4 – Fe(III),
argentums (5) – Fe total, 6 – Fe(III)
4,5
4,0
3,5
3,0
2,5
2,0
1,5
1,0
0,5
0,0
-0,5
-1,0
-1,5
1,5 2,5 3,5 4,5 5,5 6,5 7,5 8,5
lg τ
lg C
1
2
3
4
5
6
Fig. 6. Kinetic of binding of ions of precious metals: a –
platinum, b – palladium, c – aurum, d – argentums
10
8
6
4
2
0 1,5 2,5 3,5 4,5 5,5 6,5 7,5
lg τ
1
2
3
4
Ñ, mg/dm3formation of iron oxyhydroxides and magnetite
phases.
The investigation of the process of formation
of the ultra disperse iron oxide minerals on the
steel surface in the presence of the precious
metals
The process of phase formation on the steel
surface was carried out by its contact with solution
containing precious metals, there were argentums,
aurum and palladium with the concentration of metal
ions of 1 mg/dm3; argentums and platinum with the
concentration of metals 10 mg/dm3.
According to the data of chemical analysis the
presence of precious metals in dispersion medium
activates the anodic solution of the iron with
agglomeration of ferric and ferrous ions in the
dispersion medium. The final concentrations of total
ferric and ferrous ions by addition of platinum were
8
Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
1800
1400
1000
600
0 20 40 60 80
2Θ
(0
20
)
(1
11
)
(1
10
)
(1
20
)
(2
20
)
(1
11
)
(0
31
)
(3
11
)
(1
21
)
(4
00
)
(1
31
, 0
60
)
(0
51
, 2
00
)
(2
20
)
(1
51
) (3
33
, 5
11
)
(2
31
) (4
40
)
(2
51
)
– 1
– 2
– 3
– 4
à
(0
20
)
(1
11
)
(1
10
)
(1
20
)
(2
20
)
(1
11
)
(1
30
)
(3
11
)
(4
00
)
(0
51
, 2
00
)
(4
22
) (5
11
)
(0
80
)
(4
40
)
– 1
– 2
– 3
– 5
900
700
500
300
0
20 40 60 80
2Θ
c
(0
20
)
(1
11
)
(1
10
)
(1
20
)
(2
20
)
(1
11
)
(0
31
)
(3
11
)
(1
71
)
(4
00
)
(1
31
, 0
60
)
(0
51
, 2
00
)
(2
20
)
(1
51
) (3
33
, 5
11
)
(2
31
) (4
40
)
(2
51
)
– 1
– 2
– 3
2500
1500
500
0 20 40 60 80
2Θ
b
(0
20
)
(1
11
)
(1
10
)
(1
20
) (2
20
)
(1
11
)
(1
30
)
(3
11
)
(4
00
)
(0
51
, 2
00
)
(4
22
)
(5
11
)
(4
40
)
(0
80
)
– 1
– 2
– 3
– 5
1000
800
600
400
200
0
20 40 60 80
2Θ
d
(0
20
)
(1
11
)
(1
10
)
(1
20
)
(2
20
)
(0
11
) (0
31
)
(3
11
)
(4
00
)
(0
51
, 2
00
)
(5
11
)
(4
40
)
(4
22
)
– 1
– 2
– 3
– 6
1200
800
400
0
20 40 60 80
2Θ
e
(0
20
)
(1
11
)
(1
20
)
(2
20
)
(3
11
)
(4
00
)
(5
11
)
(4
40
)
(4
22
)
– 1
– 2
– 6
1400
1000
600
0
20 40 60 80
2Θ
f
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
9
М
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ИА
ЛО
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
Fig. 7. XRD-data of structures formed on the steel surface by its contact with solution of: argentums – near surface
layer (à), surface layer (b); aurum – near surface layer (c), – surface layer (d); platinum – near surface layer (e),
surface layer (f); palladium – single layer (g). Numbers correspond to the phases: 1 – lepidocrocite γ-FeOOH; 2 –
magnetite Fe3O4, 3 – goethite α-FeOOH, 4 – silver Ag0, 5 – aurum Au0, 6 – platinum Pt0, 7 – palladium Pd0
g
800
600
400
200
0
20 40 60 80
2Θ
(0
20
)
(1
11
)
(1
10
)
(1
20
)
(2
20
)
(1
11
)
(0
31
) (
31
1)
(4
22
)(4
00
)
(0
51
, 2
00
)
(2
20
)
(1
51
)
– 1
– 2
– 3
– 7
(5
11
)
(0
80
)
(2
31
) (0
22
)
(1
10
)
(1
80
)
(2
51
)
40 mg/dm3 and ferric ions – 1 mg/dm3; by addition
of argentums were 28.5 and 0.17 mg/gm3,
correspondingly; by addition of palladium were 55.0
and 3.36 mg/gm3, correspondingly, and in the presence
of aurum were 70.0 and 5.2 mg/gm3, correspondingly
(Fig. 4). Fig. 5 shows the kinetics of concentrations
of precious metals in dispersion medium on the
formation of the iron oxide minerals process. The
concentration of platinum decreases drastically from
10 to 2 mg/gm3 during 15 minutes and than gradually
decreasing to the final concentration > 0.08 mg/dm3.
On the opposite the content of palladium (1 mg/dm3)
does not change during 24 hours and only after 70
hours decreases to 0.06 mg/dm3. The initial
concentration of aurum (1 mg/dm3) decrease during
several hours to 0.4 mg/dm3, and then slowly
decreases to 0.07 mg/dm3 at the end of phase
formation. The content of argentums decreases from
10 to 0.01 mg/dm3 during 15 minutes. The initial value
of pH = 2.5 in systems with platinum, palladium and
aurum by process of phase formation increases on
average to pH = 5.3 and in systems with argentums
increases from 5.0 to 9.4.
As show the obtained data, the main phases of
iron oxides there are lepidocrocite and magnetite.
The process of phase formation in such a system
goes throws the stages of origin on the steel surface
the phase of hydroxysulphate Green Rust, its
transformation to phase of iron oxyhydroxides and
than to phase of magnetite Fe3O4.
Fig. 8 shows the TEM images of ultra disperse
minerals formed on steel surface in the presence
of the precious metals in dispersion medium.
On the basis of our own data and literature sources
it is possible to make conclusions that the process of
interaction of iron oxides with low concentration of
metals from dispersion medium can go at any stage of
formation and transformation of iron oxide phases.
Articles [29, 30] show that limited oxidation in the
system results in formation on steel surface derived
structures of Fe(II)–Fe(III) layered double hydroxides –
Green Rust. The same result was obtained in our
system, where on steel surface by its contact with
water dispersion medium after processing the surface
by solution of sulphuric acid shows the origin of
hydroxysulphate Green Rust particles is observed,
which is proved by the XRD-data in situ [31]. Due to
the presence the ferrous iron the structure of Green
Rust possesses high reducing activity with respect to
the components of the dispersion medium, especially
precious metals. For example, the research [32] shows
that ions of aurum, argentums, cuprum and mercury
by their addition in water suspension of Green Rust
are reduced to metals and structure of Green Rust in
its turn is oxidized to the phases of magnetite or
oxyhygroxides. The distinction of the studying our
10
Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
c d
a b
Fig. 8. The TEM images of iron oxide particles on steel surface that were formed in the presence of ions of precious
metals in dispersion medium: a – argentums, b – aurum, c – platinum, d – palladium
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
system is that red-ox reaction goes as a single process
and not as two separate as it was shown in the previous
case. So, in our research there was made
ferromagnetic composite compound core of
maghemite and shell of argentums [33].
The initial mechanism of such interaction was
sorption. At the same time, the sorption interaction
of hygroxy complexes of cuprum and precious
metals with iron oxide phases could go at the stage
of formation of oxyhydroxides without the process
11
М
АТ
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ЛО
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Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
of phase transformation [34, 35] or with next phase
transformation to phase of the corresponding spinel
ferrite or magnetite and incorporating of cations
from dispersion medium to lattice of iron oxides
minerals [36].
Process of sorption could take place on iron oxide
surface [37, 38]. In this case the metathesis
between adsorbed cations and ferrous iron in lattice
of magnetite is more likely. At that the formation of
nonstoichiometric complicated oxides or solid
solutions is possible.
Having analyzed kinetic of chemical composition
of dispersion medium, XRD-data and TEM images
it is possible to assume that in the system of steel
electrode contacting with water solutions of cuprum
and precious metals the process of bonding the
metals-ions by iron oxides goes by two mechanisms.
In the first process cuprum, aurum, argentums,
platinum, palladium reduction occurs in structure of
Green Rust with its transformation to phase of
magnetite with including of part of ions into the
structure of the iron oxide. That assumption is
proved by the course of kinetic curves, there are
the extremes that depend on sudden decrease of
cation concentrations and contains of surface
structures among which the phase of magnetite
dominates. In the second process the decrease of
cation concentrations slows down after the
formation of magnetite. Obviously, the following
redacting of remains of the metals from dispersion
medium occurs on the surface of magnetite by it’s
partly oxidation to lepidocrocite.
That was confirmed by XRD-data. The curves
simultaneously show the reflexes of oxyhydroxides
and weak reflexes of reduced metals. Low intensity
of peaks of aurum, platinum, palladium and
argentums depends on their small (at the breaking
point of sensitivity (~5%), concentrations.
Decreasing initial pH value to acid medium changes
of phase composition to formation of oxyhydroxides.
The modification of the surface of iron oxide
particles by layer of precious metal gives them of
colloidal stability, which was shown in our articles
[39] by the example of composites maghemite –
argentums, maghemite – platinum. That opens the
possibility of their practical use for investigation of
biological systems.
Conclusions
1. The result of studying the process of formation
of ultra disperse iron oxide minerals on steel surface
by its contact with air and dispersion medium
containing of cuprum, argentums, aurum, platinum,
palladium ions shows that the formation of the
structures of iron-oxides occurs within γ-row: Green
Rust – lepidocrocite – magnetite Fe3O4.
2. The phase composition of iron oxides
depends on concentration of electropositive
metals in dispersion medium. On the example of
cuprum it is shown that by concentration of Cu(II)
100 mg/dm3 in the system there occurs the
classical reaction of cementation including the
ionization of metal iron and redacting of cuprum
ions on steel surface. Decreasing of concentra-
tion of cuprum to 1–10 mg/dm3 changes the
mechanism of phase formation: on steel surface
magnetite formed.
3. In the presence of precious metals the process
of phase formation occurs by two mechanisms. At
first the process of reduction of argentums, aurum,
platinum and palladium take place into GR structure
with its transformation to the phase of magnetite
and possibly including of ions in its lattice. At second
the reduction of remaining ions from dispersion
medium take place on magnetite surface by its partly
oxidizing to lepidocrocite .
4. By addition of precious metals in the system
on stage of iron oxides particles formation their water
sols obtaine the colloidal stability. Their new
properties can be used by investigation of biological
systems.
Èññëåäîâàí ïðîöåññ ôîðìèðîâàíèÿ óëüòðàäèñïåðñíûõ
æåëåçîîêñèäíûõ ìèíåðàëîâ íà ïîâåðõíîñòè ñòàëè ïðè åå
êîíòàêòå ñ êèñëîðîäîì âîçäóõà è äèñïåðñèîííîé ñðåäîé,
ñîäåðæàùåé èîíû ìåäè, ñåðåáðà, çîëîòà, ïëàòèíû è ïàëëà-
äèÿ. Ïîêàçàíî, ÷òî ïðè êîíöåíòðàöèÿõ ýëåêòðîïîëîæèòåëü-
íûõ ìåòàëëîâ 1–10 ìã/äì3 íà ïîâåðõíîñòè ñòàëè îáðàçóþò-
ñÿ ñòðóêòóðû ãèäðîêñèñóëüôàòíîãî Green Rust, ìàãíåòè-
òà è ëåïèäîêðîêèòà. Ôàçîîáðàçîâàíèå ïðîõîäèò â äâå
ñòàäèè: 1) àäñîðáöèÿ èîíîâ äèñïåðñèîííîé ñðåäû íà ïî-
âåðõíîñòè GR ñ âîññòàíîâëåíèåì ÷àñòè èîíîâ äî ìåòàëëà è
îêèñëåíèåì GR äî ìàãíåòèòà èëè ëåïèäîêðîêèòà; 2) âîñ-
ñòàíîâëåíèå îñòàòî÷íîé êîíöåíòðàöèè èîíîâ ýëåêòðîïîëî-
æèòåëüíûõ ìåòàëëîâ íà ïîâåðõíîñòè ìàãíåòèòà. Âçàèìî-
äåéñòâèå æåëåçîîêñèäíûõ ôàç ñ ýëåêòðîïîëîæèòåëüíûìè
èîíàìè ïðèäàåò ÷àñòèöàì êîëëîèäíóþ óñòîé÷èâîñòü
12
Íàíîñòðóêòóðíîå ìàòåðèàëîâåäåíèå, 2010, ¹ 3
ÍÀÍÎ×ÀÑÒÈÖÛ, ÍÀÍÎÊËÀÑÒÅÐÛ, ÍÓËÜÌÅÐÍÛÅ ÎÁÚÅÊÒÛ
Êëþ÷åâûå ñëîâà: óëüòðàäèñïåðñíûå æåëåçîîêñèäíûå ìè-
íåðàëû, ôàçîîáðàçîâàíèå, áëàãîðîäíûå ìåòàëëû
Äîñë³äæåíî ïðîöåñ ôîðìóâàííÿ óëüòðàäèñïåðñíèõ çàë³çî-
îêñèäíèõ ì³íåðàë³â íà ïîâåðõí³ ñòàë³ ïðè ¿¿ êîíòàêò³ ç êèñíåì
ïîâ³òðÿ òà äèñïåðñ³éíèì ñåðåäîâèùåì, ÿêå ì³ñòèòü ³îíè ì³ä³,
ñð³áëà, çîëîòà, ïëàòèíè òà ïàëàä³þ. Ïîêàçàíî, ùî çà êîíöåí-
òðàö³é åëåêòðîïîçèòèâíèõ ³îí³â 1–10 ìã/äì3 íà ïîâåðõí³ ñòàë³
óòâîðþþòüñÿ ñòðóêòóðè ã³äðîêñèñóëüôàòíîãî Green Rust,
ìàãíåòèòó é ëåï³äîêðîê³òó. Ôàçîóòâîðåííÿ â³äáóâàºòüñÿ ó
äâ³ ñòà䳿: 1) àäñîðáö³ÿ ³îí³â äèñïåðñ³éíîãî ñåðåäîâèùà íà
ïîâåðõí³ GR ç â³äíîâëåííÿì ÷àñòèíè ³îí³â äî ìåòàëó é îêèñ-
íåííÿì GR äî ìàãíåòèòó àáî ëåï³äîêðîê³òó; 2) â³äíîâëåííÿ
çàëèøêîâî¿ êîíöåíòðàö³¿ ³îí³â åëåêòðîïîçèòèâíèõ ìåòàë³â íà
ïîâåðõí³ ìàãíåòèòó. Âçàºìîä³ÿ çàë³çîîêñèäíèõ ôàç ³ç åëåêò-
ðîïîçèòèâíèìè ³îíàìè íàäຠ÷àñòèíêàì êîëî¿äíî¿ ñò³éêîñò³.
Êëþ÷îâ³ ñëîâà: óëüòðàäèñïåðñí³ çàë³çîîêñèäí³ ì³íåðàëè,
ôàçîóòâîðåííÿ, áëàãîðîäí³ ìåòàëè
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âîäíîìó ñåðåäîâèù³: Àâòîðåô. äèñ. … êàíä. õ³ì. íàóê:
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|
| id | nasplib_isofts_kiev_ua-123456789-62724 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1996-9988 |
| language | English |
| last_indexed | 2025-12-07T17:15:44Z |
| publishDate | 2010 |
| publisher | Інститут проблем матеріалознавства ім. І.М. Францевича НАН України |
| record_format | dspace |
| spelling | Lavrynenko, O. 2014-05-25T08:00:21Z 2014-05-25T08:00:21Z 2010 The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) / O. Lavrynenko // Наноструктурное материаловедение. — 2010. — № 3. — С. 3-13. — Бібліогр.: 39 назв. — англ. 1996-9988 https://nasplib.isofts.kiev.ua/handle/123456789/62724 544.77 + 549.057 Process of formation of ultra disperse iron oxide minerals on steel surface by its contacts with air oxygen and dispersion medium containing ions of cuprum, argentums, aurum, platinum and palladium was studied. The formation of phase’s hydroxysulphate Green Rust, magnetite and lepidocrocite on steel surface by concentrations of electropositive metals 1–10 mg/dm³ was shown. Mechanism of phase formation occurs by two stages: adsorption of ions from dispersion medium on Green Rust surface with partly reduction of ions and oxidation of GR to magnetite or lepidocrocite and reduction of the rest metal ions on magnetite surface. Interacting iron oxide phases with electropositive ions add colloidal stability to composite particles. Исследован процесс формирования ультрадисперсных железооксидных минералов на поверхности стали при ее контакте с кислородом воздуха и дисперсионной средой, содержащей ионы меди, серебра, золота, платины и палладия. Показано, что при концентрациях электроположительных металлов 1–10 мг/дм³ на поверхности стали образуются структуры гидроксисульфатного Green Rust, магнетита и лепидокрокита. Фазообразование проходит в две стадии: 1) адсорбция ионов дисперсионной среды на поверхности GR с восстановлением части ионов до металла и окислением GR до магнетита или лепидокрокита; 2) восстановление остаточной концентрации ионов электроположительных металлов на поверхности магнетита. Взаимодействие железооксидных фаз с электроположительными ионами придает частицам коллоидную устойчивость. Досліджено процес формування ультрадисперсних залізооксидних мінералів на поверхні сталі при її контакті з киснем повітря та дисперсійним середовищем, яке містить іони міді, срібла, золота, платини та паладію. Показано, що за концентрац ій електропозитивних іонів 1–10 мг/дм³ на поверхні сталі утворюються структури гідроксисульфатного Green Rust, магнетиту й лепідокрокіту. Фазоутворення відбувається у дві стадії: 1) адсорбція іонів дисперсійного середовища на поверхні GR з відновленням частини іонів до металу й окисненням GR до магнетиту або лепідокрокіту; 2) відновлення залишкової концентрації іонів електропозитивних металів на поверхні магнетиту. Взаємодія залізооксидних фаз із електропозитивними іонами надає частинкам колоїдної стійкості. en Інститут проблем матеріалознавства ім. І.М. Францевича НАН України Наноструктурное материаловедение Наночастицы, нанокластеры, нульмерные объекты The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) Article published earlier |
| spellingShingle | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) Lavrynenko, O. Наночастицы, нанокластеры, нульмерные объекты |
| title | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) |
| title_full | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) |
| title_fullStr | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) |
| title_full_unstemmed | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) |
| title_short | The mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of Cu(II), Ag(I), Au(III), Pt (IV), Pd(II) |
| title_sort | mechanism of formation of the ultra disperse iron oxide minerals on steel surface in presence of cu(ii), ag(i), au(iii), pt (iv), pd(ii) |
| topic | Наночастицы, нанокластеры, нульмерные объекты |
| topic_facet | Наночастицы, нанокластеры, нульмерные объекты |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/62724 |
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