COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES
The chemical composition, current efficiency and some properties of galvanic binary CoMo and CoW alloys, deposited from both alkaline citrate and citrate-pyrophosphate electrolytes, were studied. It is shown that the main difference between mono- and polyligand electrolytes is the mechanism of the e...
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Ukrainian Chemistry Journal| _version_ | 1871465901481525248 |
|---|---|
| author | Yapontseva, Yuliya Kublanovsky, Valeriy Maltseva, Tetiana |
| author_facet | Yapontseva, Yuliya Kublanovsky, Valeriy Maltseva, Tetiana |
| author_institution_txt_mv | [
{
"author": "Yuliya Yapontseva",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine, Palladin av., 32-34, 03680, Kiyev, Ukraine"
},
{
"author": "Valeriy Kublanovsky",
"institution": "V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, 32\/34, Academic Palladin Avenue, Kiev, 03142, Ukraine"
},
{
"author": "Tetiana Maltseva",
"institution": "V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, 32\/34, Academic Palladin Avenue, Kiev, 03142, Ukraine"
}
] |
| author_sort | Yapontseva, Yuliya |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:51Z |
| description | The chemical composition, current efficiency and some properties of galvanic binary CoMo and CoW alloys, deposited from both alkaline citrate and citrate-pyrophosphate electrolytes, were studied. It is shown that the main difference between mono- and polyligand electrolytes is the mechanism of the electrodeposition process and the rate of passage of limiting stages preceding the formation of an electrochemically active complex. During electrolysis in a citrate solution, the limiting step is the mass transfer of [CoCit2]4– complexes, while in the citrate-pyrophosphate one, the process proceeds with kinetic control, and the hydrodynamic regime does not significantly affect the content of metals and the rate of their deposition. The use of a polyligand electrolyte makes it possible to increase the current efficiency for CoW alloys from 32.1 to 45.5% in the convective mass transfer mode and from 5.9 to 35.7% in the diffusion transfer mode. During electrodeposition from citrate-pyrophosphate electrolytes of the same composition of alloys of two different refractory metals, it was found that the current efficiency of the CoMo alloy is on average 20% higher than that of CoW. It has been found that at a close value of the content of the refractory component in X-ray amorphous alloys, the differences in the magnetic and corrosion properties of the coatings are determined by the nature of the refractory metal. Thus, during electrodeposition from a polyligand electrolyte, CoMo alloys have Ms 300–380 emu·cm-3 and Hc 60–72 Oe, while CoW alloys have Ms 22–45 emu·cm-3 and Hc 50–70 Oe. Both types of alloys are characterized by Mr/Ms – 0.2-0.3. The properties of CoW alloys deposited from a monoligand citrate electrolyte approach hard magnetic materials with Mr/Ms – 0.6–0.7. |
| doi_str_mv | 10.33609/2708-129X.89.01.2023.34-45 |
| first_indexed | 2025-09-24T17:43:48Z |
| format | Article |
| fulltext |
34 ISSN 2708-129X. Укр. хім. журн., 2023
УДК 544.654.2 doi: 10.33609/2708-129X.89.01.2023.34-45
COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS
DEPOSITED BOTH FROM ALKALINE CITRATE AND
CITRATE-PYROPHOSPHATE ELECTROLYTES
Yu. S. Yapontseva*, T. V. Maltseva, V. S. Kublanovsky
Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine,
32/34 Aсad. Palladin аvе., 03142 Kyiv, Ukraine
*е-mail: juliya_yap@ukr.net
The chemical composition, current efficiency and some properties of galvanic binary CoMo
and CoW alloys, deposited from both alkaline citrate and citrate-pyrophosphate electrolytes,
were studied. It is shown that the main difference between mono- and polyligand electrolytes
is the mechanism of the electrodeposition process and the rate of passage of limiting stages
preceding the formation of an electrochemically active complex. During electrolysis in a citrate
solution, the limiting step is the mass transfer of [CoCit2]
4– complexes, while in the citrate-py-
rophosphate one, the process proceeds with kinetic control, and the hydrodynamic regime does
not significantly affect the content of metals and the rate of their deposition. The use of a polyli-
gand electrolyte makes it possible to increase the current efficiency for CoW alloys from 32.1
to 45.5% in the convective mass transfer mode and from 5.9 to 35.7% in the diffusion transfer
mode. During electrodeposition from citrate-pyrophosphate electrolytes of the same compo-
sition of alloys of two different refractory metals, it was found that the current efficiency of
the CoMo alloy is on average 20% higher than that of CoW. It has been found that at a close
value of the content of the refractory component in X-ray amorphous alloys, the differences in
the magnetic and corrosion properties of the coatings are determined by the nature of the re-
fractory metal. Thus, during electrodeposition from a polyligand electrolyte, CoMo alloys have
Ms 300–380 emu·cm-3 and Hc 60–72 Oe, while CoW alloys have Ms 22–45 emu·cm-3 and
Hc 50–70 Oe. Both types of alloys are characterized by Mr/Ms – 0.2-0.3. The properties of CoW
alloys deposited from a monoligand citrate electrolyte approach hard magnetic materials with
Mr/Ms – 0.6–0.7.
Key words: alloy, cobalt, tungsten, molybdenum, electrodeposition.
INTRODUCTION. The study of the pro-
cesses occurring during the formation of elect
rolytic alloys of refractory metals with metals
of the iron subgroup receives much attention
from researchers. First of all, that is to obtain
information about the composition and struc-
ture of coatings those are deposited from solu-
tions of various complex compositions, as well
35https://ucj.org.ua
Yu. S. Yapontseva, T. V. Maltseva, V. S. Kublanovsky UCJ № 01 / Vol. 89
as to determine the dependence of functional
properties of the alloys on electrodeposition
conditions. The functional properties of such
coatings are very diverse [1, 2], but the most
demanded for industry are heat resistance,
hardness, and corrosion resistance [3–5].
It is known that for the formation of alloys,
it is necessary to bring the precipitation po-
tentials of two metals closer, i.e., in our case,
to increase the overvoltage of cobalt precipi-
tation due to the formation of a strong com-
plex compound in the solution [6]. The search
for new and better complexing agents for this
process is associated with the impossibility of
foreseeing the impact that a previously unused
complexing agent or a mixture of already stu
died coatings will have on the composition and
quality of coatings, since no correlation has
yet been found between the parameters of the
metal complex of the iron subgroup (size, spa-
tial configuration, stability constant) and alloy
parameters (composition, crystal structure
and physicochemical properties).
The conditions for electrodeposition of bi-
nary alloys of refractory metals with metals
of the iron subgroup are considered in detail
by the authors of [7]. Among the electrolytes
that are considered promising for the deposi-
tion of alloys with tungsten and molybdenum,
one can single out citrate [8], pyrophosphate
[9, 10], and alkaline polyligand electrolytes
containing organic complex polyhydroxy acids
(salts) with carboxyl groups; indicated by the
authors of [7], alkalization of the solution with
ammonia also leads to a change in the com-
plex composition of the electrolyte. An impor-
tant feature of multicomponent complex elec-
trolytes is the possibility of the formation of
polymetallic and/or polyligand complexes in
the bulk of the solution, which can also signi
ficantly affect the kinetics of alloy deposition.
The citrate-pyrophosphate electrolyte pro-
posed by us combines the advantages of citrate
and pyrophosphate electrolytes and makes it
possible to obtain functional coatings of the
required quality with a high deposition rate.
Coatings are deposited with a rather high con-
tent of refractory metal and higher values of
current output compared to citrate electrolyte
[11, 12]. The authors of works on the electro-
deposition of binary alloys of metals of the
iron subgroup with tungsten [13] showed that
coatings containing 17–24 at.% tungsten have
the highest corrosion resistance. This ratio of
components approximately corresponds to the
composition of the Co3W intermetallic phase.
Also important is the transition from the poly-
crystalline to the amorphous structure of the
coatings, which occurs when exactly this con-
centration of tungsten is reached in the binary
alloy.
The purpose of the work is electrochemical
synthesis, study of the composition, structure
and physicochemical properties of binary al-
loys of cobalt with tungsten and molybdenum,
depending on the complex composition of the
electrolytes and the hydrodynamic regime.
EXPERIMENT AND DISCUSSION OF
THE RESULT. CoW alloys were deposited from
both alkaline electrolytes (solution pH 9.0): cit-
rate (Cit) and citrate pyrophosphate (Cit-PPi),
CoMo alloys were deposited from alkaline
Cit-PPi electrolyte. Coatings were obtained in
a thermostated cell in a galvanostatic mode us-
ing a direct current source LIPS-35 under nat-
ural convection conditions, as well as with stir-
ring (magnetic stirrer rotation speed 300 rpm).
A copper plate with an area of 1 cm2 was used
as the working electrode; platinum was the an-
ode.
36 ISSN 2708-129X. Укр. хім. журн., 2023
COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH
FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTESPHISICAL CHEMISTRY
Table 1.
Composition of electrolytes for electrodeposition of alloys, mol∙l-1
For alloy CoSO4 Na2WO3 Na2MoO4 Na3Cit K2PO4 Na2SO4
CoW 0.1 0.2 – 0.2 – 0.3
CoW 0.1 0.2 – 0.2 0.2 0.3
CoMo 0.1 – 0.02 0.2 0.2 0.3
The citrate-pyrophosphate electrolyte was
prepared by adding a solution of potassium
pyrophosphate to an already prepared citrate
electrolyte at a temperature of 70 ºC. Then the
pH was adjusted to a value of 9.0.
The morphology and chemical composition
of samples were studied by using a JSM-6700F
field emission scanning electron microscope
equipped with a JED-2300 energy-dispersive
spectrometer (JEOL). The operating condi-
tions were as follows: 20 kV accelerating vol
tage, 0.75 nA beam current, 1 μm beam size.
The counting time for EDS analyses was 60 s.
Pure Co and Re were used as standards. The
raw counts (Co,Kα; W,Lα; Mo,Lα) were cor-
rected for matrix effects with a ZAF algorithm
implemented by JEOL. Three to five spots per
each sample were analyzed.
X-ray patterns were recorded on a diffrac-
tometer (DRON-3.0) with the Bragg-Bren-
tano geometry and using Cu-K radiation
(= 1.54183A˚) operating at 30 kV and 30 mA
at a constant scan rate of 0.02–2 s–1. The study
of corrosion was carried out by voltammetry.
These measurements were carried out using
an MTech PGP-550F potentiostat-galvanostat
[13] in a 1M KOH solution at a temperature
of 20 ± 1 °C in a cell assembled by a working
copper electrode, a silver reference electrode,
and an auxiliary electrode, which is a plati-
num grid. Voltammetric studies of corrosion
included of obtaining cathodic and anodic po-
larization curves with a potential sweep rate of
1.0 mV s-1. As a result of the analysis of polari
zation measurements in the region of station-
ary potential (±100 mV), the corrosion resis
tance was calculated.
Magnetic properties of the obtained de-
posits were determined using a magnetometer
with a vibrating sample in magnetic fields up
to 2 T in SI units (20 kG in Gaussian-cgs units)
at room temperature.
Fig. 1 shows the results of studying the
chemical composition and current efficien-
cy for CoW alloys and its components dur-
ing electrodeposition from Cit and Cit-PPi
electrolytes at a deposition current density of
10 mA∙cm-2 both in the mode of convective
mass transfer (with intensive stirring) and
under conditions of natural diffusion, as well
as the composition and current efficiency
during the electrodeposition of CoMo alloys
from Cit-PPi-electrolyte under different hy-
drodynamic conditions. Based on previous
studies on the electrodeposition of CoW al-
loys from a polyligand Cit-PPi electrolyte
under conditions of intensive mixing, it is
known that CoW alloys contain 22–25 at. %
tungsten over the entire range of deposition
current densities studied [15].
37https://ucj.org.ua
Yu. S. Yapontseva, T. V. Maltseva, V. S. Kublanovsky UCJ № 01 / Vol. 89
Fig. 1. Dependence of the chemical composition (a), current efficiency of the CoW and CoMo alloys,
as well as their components (b) on the deposition conditions.
4
4
Magnetic properties of the obtained deposits were determined using a magnetometer with a
vibrating sample in magnetic fields up to 2 T in SI units (20 kG in Gaussian-cgs units) at room
temperature.
Fig. 1 shows the results of studying the chemical composition and current efficiency for
CoW alloys and its components during electrodeposition from (Cit) and (Cit-PPi) electrolytes at a
deposition current density of 10 mA∙cm-2 both in the mode of convective mass transfer (with
intensive stirring) and under conditions of natural diffusion, as well as the composition and current
efficiency during the electrodeposition of CoMo alloys from (Cit-PPi)-electrolyte under different
hydrodynamic conditions. Based on previous studies on the electrodeposition of CoW alloys from a
polyligand (Cit-PPi) electrolyte under conditions of intensive mixing, it is known that CoW alloys
contain 22–25 at. % tungsten over the entire range of deposition current densities studied [15].
Fig. 1. Dependence of the chemical composition (a), current efficiency of the CoW and CoMo
alloys, as well as their components (b) on the deposition conditions.
Let us consider the effect of intense mechanical mixing on the chemical composition and
current efficiency of CoW alloys at deposition from these electrolytes. A comparison of mono- and
polyligand electrolytes was carried out to demonstrate the key role of the composition of cobalt
complexes on the formation of an electrolytic alloy. It is known that [CoCit2]4– complexes
predominate in an alkaline (pH 9.0) citrate electrolyte with a twofold excess of the ligand [16, 17].
When electrolysis is carried out in such an electrolyte, the overvoltage of cobalt evolution becomes
greater than the overvoltage of hydrogen [18] so that it is not possible to obtain a coating of metallic
cobalt in an amount sufficient for gravimetric determination of the current efficiency, while the
deposit turns out to be loose. Probably, in an alkaline citrate electrolyte, not only tungsten, but also
cobalt can’t be individually reduced to metal. These metals are capable of being reduced only
simultaneously with the formation of an electrolytic alloy. Since cobalt is in solution in the form of
very strong complex compounds with citrate, the formation of bimetallic complexes in the volume
Let us consider the effect of intense me-
chanical mixing on the chemical composition
and current efficiency of CoW alloys at depo-
sition from these electrolytes. A comparison of
mono- and polyligand electrolytes was carried
out to demonstrate the key role of the compo-
sition of cobalt complexes on the formation of
an electrolytic alloy. It is known that [CoCit2]
4–
complexes predominate in an alkaline (pH 9.0)
citrate electrolyte with a twofold excess of the
ligand [16, 17]. When electrolysis is carried out
in such an electrolyte, the overvoltage of cobalt
evolution becomes greater than the overvolt-
age of hydrogen [18] so that it is not possible
to obtain a coating of metallic cobalt in an
amount sufficient for gravimetric determina-
tion of the current efficiency, while the deposit
turns out to be loose. Probably, in an alkaline
citrate electrolyte, not only tungsten, but also
cobalt can’t be individually reduced to metal.
These metals are capable of being reduced only
simultaneously with the formation of an elec-
trolytic alloy. Since cobalt is in solution in the
form of very strong complex compounds with
citrate, the formation of bimetallic complexes
in the volume of the solution is unlikely, but
the result obtained indirectly confirms the hy-
pothesis that reduction occurs from complex
compounds formed precisely on the electrode
surface [19].
During the deposition of the CoW alloy
from a citrate electrolyte, the mass transfer
regime has a significant effect on the compo-
sition of the resulting alloys: the tungsten con-
tent in the coating (9 at.%) and the current
efficiency of the alloy (6 at.%) in the absence
of forced convection are much lower than
when the electrolyte is stirred (23 and 33 at.%,
respectively). Based on the mechanism of in-
duced co-deposition of the metals presented
in [19], the necessary condition for the forma-
tion of electroactive complexes on the surface
is the presence of [CoCit]- particles, which can
be formed as a result of dissociation of the ad-
sorbed [CoCit2]4- complex on the cathode sur-
face according to equation (1):
[CoCit2]
4- → [CoCit]-
ads + [Cit]3- (1)
38 ISSN 2708-129X. Укр. хім. журн., 2023
COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH
FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTESPHISICAL CHEMISTRY
During electrodeposition from a citrate-py-
rophosphate electrolyte, convection in the elec-
trolyte has practically no effect on its chemical
composition, but contributes to an increase in
the current efficiency of the alloy up to 35.7%.
A feature of the polyligand electrolyte is the
formation of a cobalt complex [Co(PPi)(Cit)]5–,
as was shown in [20]. Thus, for the formation
of the [CoCit]- complex, it is necessary to dis-
sociate the adsorbed complex on the electrode
surface according to reaction (2):
[Co(PPi)(Cit)]5– → [CoCit]-
ads
+ [PPi]4- (2)
After that, in both cases, it becomes possible
to form an electroactive complex according to
reaction (3):
WO4
2- + [CoCit]-
ads + 2H20 + 2ē →
→ [CoCitWO2]
-
ads + 4OH- (3)
Taking into account the fact that the [WO4]
2-
concentration is high, and [CoCit]- is formed
directly on the surface (1), the low current ef-
ficiency in the citrate electrolyte in the natural
convection mode can be explained with the dif-
fusion of cobalt citrate complexes [CoCit2]
4- ,
with the rate of reaction (1), or with a large
number and insufficiently fast removal of the
formed bubbles of gaseous hydrogen, blocking
the active centers of the surface.
When comparing alloys of two refractory
metals, it should also be noted that the cur-
rent efficiency of the CoW alloy is lower than
that of the CoMo alloy during convective mass
transfer in a polyligand electrolyte and even
lower at deposition in a monoligand electro-
lyte. Such a difference may be due to the nature
of the refractory metal, its concentration in the
electrolyte, and its electrocatalytic activity in
the hydrogen evolution reaction. It was shown
in [21] for the electrodeposition of CoMo al-
loys that an increase in the concentration of
molybdate ions in a solution and a change
in the ratio of metal concentrations from
Co: Mo = 5:1 to Co: Mo =1:1 leads to a signi
ficant decrease in the current efficiency of the
alloy. Therefore, based on the analogy of the
properties and deposition processes of these
metals, it can be assumed that with a 10-fold
excess of tungstate ions compared to the con-
tent of molybdate ions (in deposition electro-
lytes), a decrease in the current efficiency of
the CoW alloy is also possible.
On fig. 2 shown that the CoW coating de-
posited from the Cit electrolyte under natural
convection conditions is smoother and has al-
most no spherulites. Coatings deposited from
a polyligand electrolyte are more stressed and
cracked.
The main problem of electrolytic alloys of
molybdenum is significant internal stresses in
coatings, which lead to cracking [22, 23]. To
solve this problem, several options have been
proposed: the addition of surfactants [24, 25],
the usage of pulsed electrolysis [26], the se-
lection of fundamentally different deposition
electrolytes [27], and the use of a constant
magnetic field [28, 29].
Comparing the cracking of CoMo coatings
deposited at a current density of 10 mA∙cm-2 in
natural and forced convection, we can draw a
similar conclusion that a coating growing at a
slower rate is less stressed. On the diffraction
patterns shown in Fig. 3, it is shown that, re-
gardless of the mass transfer regime and the
complex composition of electrolytes (for the
CoW alloy), all coatings are X-ray amorphous.
When the same amount of electricity is passed,
the CoW coatings from the alkaline citrate elec-
trolyte, which are released with a small current
efficiency, are deposited in a small thickness,
39https://ucj.org.ua
Yu. S. Yapontseva, T. V. Maltseva, V. S. Kublanovsky UCJ № 01 / Vol. 89
and therefore, sharp peaks related to copper
can be seen in the diffraction pattern. Only
for the CoMo alloy deposited from the Cit-PPi
electrolyte, a peak of the Co3Mo intermetallic
compound is observed. The broad peak ob-
served for all samples in terms of the diffrac-
tion angle also corresponds to the formation of
Co3Mo and Co3W intermetallic compounds.
Fig. 2. Surface morphology of CoW alloy coatings deposited from Cit (a, d) and Cit-PPi (b, e) electro-
lytes, as well as CoMo alloys (c, f) in the convective mass transfer mode (a, b, c) and without mixing (d, e, f).
6
6
of tungstate ions compared to the content of molybdate ions (in deposition electrolytes), a decrease
in the current efficiency of the CoW alloy is also possible.
On fig. 2 shown that the CoW coating deposited from the Cit electrolyte under natural
convection conditions is smoother and has almost no spherulites. Coatings deposited from a
polyligand electrolyte are more stressed and cracked.
Fig. 2. Surface morphology of CoW alloy coatings deposited from Cit (a, d) and Cit-PPi (b, e)
electrolytes, as well as CoMo alloys (c, f) in the convective mass transfer mode (a, b, c) and without mixing
(d, e, f).
The main problem of electrolytic alloys of molybdenum is significant internal stresses in
coatings, which lead to cracking [22, 23]. To solve this problem, several options have been
proposed: the addition of surfactants [24, 25], the usage of pulsed electrolysis [26], the selection of
fundamentally different deposition electrolytes [27], and the use of a constant magnetic field [28,
29].
Comparing the cracking of CoMo coatings deposited at a current density of 10 mA∙cm-2 in
natural and forced convection, we can draw a similar conclusion that a coating growing at a slower
rate is less stressed. On the diffraction patterns shown in Fig. 3, it is shown that, regardless of the
mass transfer regime and the complex composition of electrolytes (for the CoW alloy), all coatings
are X-ray amorphous. When the same amount of electricity is passed, the CoW coatings from the
alkaline citrate electrolyte, which are released with a small current efficiency, are deposited in a
small thickness, and therefore, sharp peaks related to copper can be seen in the diffraction pattern.
Only for the CoMo alloy deposited from the Cit-PPi electrolyte, a peak of the Co3Mo intermetallic
Fig. 3. X-ray diffraction patterns of CoW and
CoMo alloys coatings deposited from Cit and
Cit-PPi electrolytes under various mass transfer
conditions.
7
7
compound is observed. The broad peak observed for all samples in terms of the diffraction angle
also corresponds to the formation of Co3Mo and Co3W intermetallic compounds.
Fig. 3. X-ray diffraction patterns of CoW (a) and CoMo (b) alloy coatings deposited from Cit and
Cit-PPi electrolytes under various mass transfer conditions.
The dependences obtained in the study of the influence of the mass transfer mode and the
conditions of deposition of coatings by tungsten and molybdenum alloys with cobalt on their
magnetic properties are shown in Fig. 4. It can be seen from the results that, despite the similarity of
the chemical composition and structure, the coatings deposited from electrolytes of different
complex compositions have fundamentally different magnetic properties.
Fig. 4. Magnetic hysteresis loops for CoW(a) and CoMo(b) alloys.
Table 2.
Magnetic hysteresis parameters of CoW and CoMo alloys.
Parameter
CoW-Cit CoW-Cit-PPi CoMo-Cit-PPi
stirring diff. stirring diff. stirring diff.
Ms, emu·cm-3 30 3.8 45 22 380 300
Hc, Oe 85 275 50 70 72 60
40 ISSN 2708-129X. Укр. хім. журн., 2023
COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH
FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTESPHISICAL CHEMISTRY
The dependences obtained in the study of
the influence of the mass transfer mode and the
conditions of deposition of coatings by tung-
sten and molybdenum alloys with cobalt on
their magnetic properties are shown in Fig. 4.
It can be seen from the results that, despite the
similarity of the chemical composition and
structure, the coatings deposited from electro-
lytes of different complex compositions have
fundamentally different magnetic properties.
7
7
compound is observed. The broad peak observed for all samples in terms of the diffraction angle
also corresponds to the formation of Co3Mo and Co3W intermetallic compounds.
Fig. 3. X-ray diffraction patterns of CoW (a) and CoMo (b) alloy coatings deposited from Cit and
Cit-PPi electrolytes under various mass transfer conditions.
The dependences obtained in the study of the influence of the mass transfer mode and the
conditions of deposition of coatings by tungsten and molybdenum alloys with cobalt on their
magnetic properties are shown in Fig. 4. It can be seen from the results that, despite the similarity of
the chemical composition and structure, the coatings deposited from electrolytes of different
complex compositions have fundamentally different magnetic properties.
Fig. 4. Magnetic hysteresis loops for CoW(a) and CoMo(b) alloys.
Table 2.
Magnetic hysteresis parameters of CoW and CoMo alloys.
Parameter
CoW-Cit CoW-Cit-PPi CoMo-Cit-PPi
stirring diff. stirring diff. stirring diff.
Ms, emu·cm-3 30 3.8 45 22 380 300
Hc, Oe 85 275 50 70 72 60
Fig. 4. Magnetic hysteresis loops for CoW(a) and CoMo(b) alloys.
Table 2.
Magnetic hysteresis parameters of CoW and CoMo alloys.
Parameter
CoW-Cit CoW-Cit-PPi CoMo-Cit-PPi
stirring diff. stirring diff. stirring diff.
Ms, emu·cm-3 30 3.8 45 22 380 300
Hc, Oe 85 275 50 70 72 60
Mr/Ms 0.73 0.61 0.20 0.37 0.25 0.32
First of all, it should be noted that the sa
turation magnetization of molybdenum alloys
Ms (300–380 emu cm-3) is an order of magni-
tude higher than that of tungsten alloys. Such
alloys reach saturation magnetization in low
strength fields, have a relatively low coercive
force (60–72 Oe), and are classified as magne
tically soft materials in terms of their proper-
ties. In addition, the saturation magnetization
of all coatings obtained by mixing is signifi-
cantly higher than for alloys deposited under
natural diffusion conditions. For CoW alloys,
there is also a difference between the proper-
ties of coatings deposited from electrolytes of
different complex compositions. For example,
the coatings obtained in the Cit electrolytes
are distinguished by a significantly higher
coefficient of loop rectangularity, i.e., their
properties are close to those of hard mag-
netic materials. Particularly distinguished is
the alloy deposited under natural convection
and having the lowest tungsten content, the
41https://ucj.org.ua
Yu. S. Yapontseva, T. V. Maltseva, V. S. Kublanovsky UCJ № 01 / Vol. 89
properties of which are closest to those of
pure cobalt.
The magnetic properties of electrolytic co-
balt depend on its crystal structure [30] and,
consequently, on the conditions of deposition
and composition of electrolytes. The coercive
force of cobalt coatings varies over a wide range:
from 15 Oe for amorphous films to 380 Oe for
coatings with an hcp structure and a preferred
(002) orientation. The high coercive force and
the rectangular shape of the hysteresis loop in-
dicate that coatings with the crystal lattice of
hcp are deposited from the citrate electrolyte,
but the size of the crystals (2–3 nm) does not
make it possible to accurately identify and con-
firm this assumption by XRD.
The corrosion resistance of coatings de-
posited at current density of 10 mA∙cm-2 in a
corrosion solution of 1M KOH are presented
in table. 3.
8
8
Mr/Ms 0.73 0.61 0.20 0.37 0.25 0.32
First of all, it should be noted that the saturation magnetization of molybdenum alloys Ms
(300–380 emu cm-3) is an order of magnitude higher than that of tungsten alloys. Such alloys reach
saturation magnetization in low strength fields, have a relatively low coercive force (60–72 Oe), and
are classified as magnetically soft materials in terms of their properties. In addition, the saturation
magnetization of all coatings obtained by mixing is significantly higher than for alloys deposited
under natural diffusion conditions. For CoW alloys, there is also a difference between the properties
of coatings deposited from electrolytes of different complex compositions. For example, the
coatings obtained in the Cit electrolytes are distinguished by a significantly higher coefficient of
loop rectangularity, i.e., their properties are close to those of hard magnetic materials. Particularly
distinguished is the alloy deposited under natural convection and having the lowest tungsten
content, the properties of which are closest to those of pure cobalt.
The magnetic properties of electrolytic cobalt depend on its crystal structure [30] and,
consequently, on the conditions of deposition and composition of electrolytes. The coercive force of
cobalt coatings varies over a wide range: from 15 Oe for amorphous films to 380 Oe for coatings
with an hcp structure and a preferred (002) orientation. The high coercive force and the rectangular
shape of the hysteresis loop indicate that coatings with the crystal lattice of hcp are deposited from
the citrate electrolyte, but the size of the crystals (2–3 nm) does not make it possible to accurately
identify and confirm this assumption by XRD.
Fig. 5. Voltammetric curves of corrosion of alloys in a solution of 1M KOH.
The corrosion resistance of coatings deposited at current density of 10 mA∙cm-2 in a
corrosion solution of 1M KOH are presented in table. 3.
Table 3.
Corrosion resistance of coatings with CoW and CoMo alloys.
Fig. 5. Voltammetric curves of corrosion
of alloys in a solution of 1M KOH.
Table 3.
Corrosion resistance of coatings with CoW and CoMo alloys.
Parameter
CoW-Cit CoW-Cit-PPi CoMo-Cit-PPi
stirring diff. stirring diff. stirring diff.
-E, B -0.772 -0.801 -0.742 -0.760 -0.627 -0.637
-lgjcorr, A·см-2 4.9 4.1 4.6 4.5 4.7 4.9
R, кОм·см2 3.6 0.9 3.0 2.4 3.3 3.6
It can be noted that during the deposition
of alloys from polyligand electrolytes, the
mass transfer regime has practically no ef-
fect on the corrosion resistance of the alloys.
In terms of their corrosion resistance, alloys
deposited from the same electrolyte, but in
different hydrodynamic conditions, are very
similar to each other. The only exception is
the coating containing the least amount of re-
fractory component and being the least cor-
rosion resistant. It should also be noted that
tungsten alloys are more prone to passivation
in an alkaline solution than molybdenum
alloys.
42 ISSN 2708-129X. Укр. хім. журн., 2023
COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH
FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTESPHISICAL CHEMISTRY
CONCLUSIONS.
− The composition of cobalt complexes
in solution plays a key role in the formation
of electroactive particles on the cathode. In a
polyligand electrolyte, the deposition of me
tals proceeds with kinetic control, regardless of
the presence or absence of mechanical mixing.
The deposition rate of alloys under these con-
ditions is much higher, with a slight increase
in the cracking of the coatings, which is typical
for such alloys.
− In alkaline citrate electrolyte, the hy-
drodynamic regime has the greatest influence
on the chemical composition and current ef-
ficiency of CoW alloys. Thus, the amount of
tungsten in the alloy during stirring increases
3 times, and the current efficiency of the alloy
increases 6 times compared to natural convec-
tion mode.
− All obtained coatings are X-ray amor-
phous and it is not depend on the conditions
of deposition and the content of the refractory
component
− Given the close chemical composition
and structure of the coatings, the differences in
magnetic and corrosion properties can be at-
tributed to the influence of the nature of the
refractory metal: for example, molybdenum al-
loys are magnetically soft materials, and tung-
sten alloys are close to magnetically hard.
ACKNOWLEGEMENT. This work
was performed with the financial
support of the National Academy of
Sciences of Ukraine within the state
budget theme «Finishing processing of mate-
rials in order to give them unique functional
properties» 0123U100650.
ПОРІВНЯННЯ ВЛАСТИВОСТЕЙ СПЛАВІВ
CoW ТА CoMo, ОСАДЖЕНИХ ІЗ ЛУЖНОГО
ЦИТРАТНОГО ТА ЦИТРАТНО-ПІРОФОС
ФАТНОГО ЕЛЕКТРОЛІТІВ
Ю. С. Японцева*, Т. В. Мальцева,
В. С. Кублановський
Інститут загальної та неорганічної хімії
ім. В. І. Вернадського НАН України,
просп. Акад. Палладіна, 32/34, Київ 03142,
Україна
e-mail: juliya_yap@ukr.net
У роботі вивчено хімічний склад, вихід
за струмом, властивості бінарних сплавів
CoMo та CoW, що осаджені з лужного цит
ратного (Cit) та цитратно-пірофосфатного
(Cit-PPi) електролітів. Показано, що ос-
новна відмінність моно- та полілігандних
електролітів полягає у механізмі процесу
та швидкості проходження лімітуючих ста-
дій, що передують утворенню електрохіміч-
но активного комплексу. При електролізі в
цитратному розчині лімітуючою стадією є
масоперенесення комплексів [CoCit2]
4-, а в
цитратно-пірофосфатному – процес прохо-
дить із кінетичним контролем, завдяки чому
гідродинамічний режим незначно впливає
на вміст металів та швидкість їхнього оса-
дження. При цьому покриття сплавами, які
осаджуються з меншою швидкістю, є менш
тріщинуватими та напруженими.
Незалежно від режиму масопереносу та
комплексного складу електролітів покрит-
тя сплавами є рентгеноаморфними. Широ-
кий пік, що спостерігається для всіх зразків
за величиною кута дифракції, відповідає
утворенню інтерметалідів Co3Mo та Co3W.
43https://ucj.org.ua
Yu. S. Yapontseva, T. V. Maltseva, V. S. Kublanovsky UCJ № 01 / Vol. 89
Знайдено, що при близькому значенні
вмісту тугоплавкого компонента в рентге-
ноаморфних сплавах відмінності в магніт-
них та корозійних властивостях покрит-
тів визначаються природою тугоплавкого
металу. Намагніченість насичення сплавів
молібдену Ms (300–380 emu·cm-3) є значно
вищою, ніж сплавів вольфраму. Такі спла-
ви досягають намагніченості насичення в
полях малої напруженості, мають відносно
низьку коерцитивну силу (60–72 Oe) та за
своїми властивостями належать до магніто
м’яких матеріалів. Крім цього, намагніче-
ність насичення всіх покриттів, отриманих
при перемішуванні, є значно вищою, ніж
для сплавів, осаджених за умов природної
дифузії. Для сплавів CoW також спосте-
рігається відмінність між властивостями
покриттів, що осаджені з електролітів різ-
ного комплексного складу. Так, покриття,
отримані в Cit-електроліті, відрізняються
значно більшим коефіцієнтом прямокут-
ності петлі, тобто за своїми властивостями
наближаються до магнітотвердих матері-
алів. Особливо виділяється сплав, що був
осаджений за умов природної конвекції та
має найменший вміст вольфраму, власти-
вості якого найбільш близькі до властивос-
тей чистого кобальту. За своєю корозійною
стійкістю сплави, що осаджені з одного
електроліту, але в різних гідродинаміч-
них режимах, є дуже схожими між собою.
Виняток становить лише покриття, що
містить найменшу кількість тугоплавкого
компонента та є найменш корозійностій-
ким. Слід зазначити, що сплави вольфраму
більше схильні до пасивації в лужному роз-
чині, ніж сплави молібдену.
Ключові слова: сплав, кобальт, воль-
фрам, молібден, електроосадження.
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Стаття надійшла 13. 02. 2023.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-516 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:09:24Z |
| publishDate | 2023 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/92/0db6b27f715783edb4a7f35d2b457492.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5162026-07-22T08:23:51Z COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES Yapontseva, Yuliya Kublanovsky, Valeriy Maltseva, Tetiana alloy, cobalt, tungsten, molybdenum, electrodeposition The chemical composition, current efficiency and some properties of galvanic binary CoMo and CoW alloys, deposited from both alkaline citrate and citrate-pyrophosphate electrolytes, were studied. It is shown that the main difference between mono- and polyligand electrolytes is the mechanism of the electrodeposition process and the rate of passage of limiting stages preceding the formation of an electrochemically active complex. During electrolysis in a citrate solution, the limiting step is the mass transfer of [CoCit2]4– complexes, while in the citrate-pyrophosphate one, the process proceeds with kinetic control, and the hydrodynamic regime does not significantly affect the content of metals and the rate of their deposition. The use of a polyligand electrolyte makes it possible to increase the current efficiency for CoW alloys from 32.1 to 45.5% in the convective mass transfer mode and from 5.9 to 35.7% in the diffusion transfer mode. During electrodeposition from citrate-pyrophosphate electrolytes of the same composition of alloys of two different refractory metals, it was found that the current efficiency of the CoMo alloy is on average 20% higher than that of CoW. It has been found that at a close value of the content of the refractory component in X-ray amorphous alloys, the differences in the magnetic and corrosion properties of the coatings are determined by the nature of the refractory metal. Thus, during electrodeposition from a polyligand electrolyte, CoMo alloys have Ms 300–380 emu·cm-3 and Hc 60–72 Oe, while CoW alloys have Ms 22–45 emu·cm-3 and Hc 50–70 Oe. Both types of alloys are characterized by Mr/Ms – 0.2-0.3. The properties of CoW alloys deposited from a monoligand citrate electrolyte approach hard magnetic materials with Mr/Ms – 0.6–0.7. V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-02-24 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/516 10.33609/2708-129X.89.01.2023.34-45 Ukrainian Chemistry Journal; Vol. 89 No. 1 (2023): Ukrainian Chemistry Journal; 34-45 Украинский химический журнал; ##issue.vol## 89 ##issue.no## 1 (2023): Ukrainian Chemistry Journal; 34-45 Український хімічний журнал; Том 89 № 1 (2023): Український хімічний журнал; 34-45 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/516/263 Copyright (c) 2023 Yuliya Yapontseva, Valeriy Kublanovsky, Tetiana Maltseva https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Yapontseva, Yuliya Kublanovsky, Valeriy Maltseva, Tetiana COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES |
| title | COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES |
| title_full | COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES |
| title_fullStr | COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES |
| title_full_unstemmed | COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES |
| title_short | COMPARISON OF THE PROPERTIES OF CoW AND CoMo ALLOYS DEPOSITED BOTH FROM ALKALINE CITRATE AND CITRATE-PYROPHOSPHATE ELECTROLYTES |
| title_sort | comparison of the properties of cow and como alloys deposited both from alkaline citrate and citrate-pyrophosphate electrolytes |
| topic_facet | alloy cobalt tungsten molybdenum electrodeposition |
| url | https://ucj.org.ua/index.php/journal/article/view/516 |
| work_keys_str_mv | AT yapontsevayuliya comparisonofthepropertiesofcowandcomoalloysdepositedbothfromalkalinecitrateandcitratepyrophosphateelectrolytes AT kublanovskyvaleriy comparisonofthepropertiesofcowandcomoalloysdepositedbothfromalkalinecitrateandcitratepyrophosphateelectrolytes AT maltsevatetiana comparisonofthepropertiesofcowandcomoalloysdepositedbothfromalkalinecitrateandcitratepyrophosphateelectrolytes |