Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах
The work is devoted to elucidation of a general mechanism of action of exomodified carbon nanospheres (CNOs – Brn nanoonions) on different physicochemical and chemmotological properties of ethanol motor fuels. The formation of supramolecular solvate groups in organic media is explained by the partic...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
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Catalysis and petrochemistry| _version_ | 1872008956983902208 |
|---|---|
| author | Polunkin, E.A. Pyliavskyi, V.S. Gaidai, O.O. Melnykova, S.L. Spaska, O.A. Matveeva, I. V. |
| author_facet | Polunkin, E.A. Pyliavskyi, V.S. Gaidai, O.O. Melnykova, S.L. Spaska, O.A. Matveeva, I. V. |
| author_institution_txt_mv | [
{
"author": "E.A. Polunkin",
"institution": "Department of Homogeneous Catalysis and Additives to Petroleum Products, V P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, 50 Kharkivske shosse, Kyiv 02160, Ukraine"
},
{
"author": "V.S. Pyliavskyi",
"institution": "Department of Homogeneous Catalysis and Additives to Petroleum Products, V P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, 50 Kharkivske shosse, Kyiv 02160, Ukraine"
},
{
"author": "O.O. Gaidai",
"institution": "Department of Homogeneous Catalysis and Additives to Petroleum Products, V P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, 50 Kharkivske shosse, Kyiv 02160, Ukraine"
},
{
"author": "S.L. Melnykova",
"institution": "Department of Homogeneous Catalysis and Additives to Petroleum Products, V P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, 50 Kharkivske shosse, Kyiv 02160, Ukraine"
},
{
"author": "O.A. Spaska",
"institution": "Department of Chemistry and Chemical technology, National Aviation University"
},
{
"author": "I. V. Matveeva",
"institution": "Department of Ecology, National Aviation University, 1 Liubomyra Huzara ave., Kyiv, 03058, Ukraine"
}
] |
| author_sort | Polunkin, E.A. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2021-12-10T12:36:41Z |
| description | The work is devoted to elucidation of a general mechanism of action of exomodified carbon nanospheres (CNOs – Brn nanoonions) on different physicochemical and chemmotological properties of ethanol motor fuels. The formation of supramolecular solvate groups in organic media is explained by the participation of different forces of intermolecular interaction, the main of which are polarization and orientation, as well as donor-acceptor forces of interaction of nanospheres with the environment.The concept of creation in an organic medium of solvation formations - domains, the size of which, determined by the method of photon correlation laser spectroscopy, varies from 21 to 1000 nm, depending on the chemical nature of the solvent - is proposed and substantiated. For ethanol, the size of such formations was ~ 400 nm, which significantly exceeds the size of individual particles of the additive. It is established that to improve the operational characteristics of ethanol fuel it is enough to introduce low concentrations (10-3 - 10-2 %, wt.) of synthesized brominated nanoparticles.It is shown that the change of the microheterogeneous structure of fuels affects the change of its physicochemical and operational characteristics: the dielectric constant and hydrophobicity of the medium decrease, the saturated vapor pressure increases, which improves the starting properties of the fuel; hydrophobization of the environment helps to reduce the corrosive properties of ethanol fuel per unit, as a result of which additional introduction of a corrosion inhibitor is not required; the bearing capacity of the fuel in the presence of brominated nanoparticles increases by 1.5 times compared to the base fuel with a corresponding decrease in damage to the metal surface of the friction pairs.It is the rearrangement of the secondary supramolecular structure of fuels in the presence of brominated carbon nanospheres that explains the multifunctionality of their influence on the physicochemical and chemmotological properties of ethanol motor fuels. |
| doi_str_mv | 10.15407/kataliz2021.31.062 |
| first_indexed | 2026-03-12T15:49:45Z |
| format | Article |
| fulltext |
62 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
UDC 662.758.2:665.7.038
https://doi.org/10.15407/kataliz2021.31.062
Influence of addition of exomodified carbon nanospheres on the
structuration in ethanol motor fuels
E.V. Polunkin1, V.S. Pyliavskyi1, O.O. Gaidai1, S.L. Melnykova1, O.A. Spaska2, I. V. Matveeva3
1 Department of Homogeneous Catalysis and Additives to Petroleum Products, V P Kukhar Institute of Bioorganic Chemistry and
Petrochemistry of the National Academy of Sciences of Ukraine, 50 Kharkivske shosse, Kyiv 02160, Ukraine, gaidaj@ukr.net
2 Department of Chemistry and Chemical technology, National Aviation University, 3 Department of Ecology, National
Aviation University, 1 Liubomyra Huzara ave., Kyiv, 03058, Ukraine
The work is devoted to elucidation of a general mechanism of action of exomodified carbon nanospheres (CNOs
– Brn nanoonions) on different physicochemical and chemmotological properties of ethanol motor fuels. The
formation of supramolecular solvate groups in organic media is explained by the participation of different forces of
intermolecular interaction, the main of which are polarization and orientation, as well as donor-acceptor forces of
interaction of nanospheres with the environment.
The concept of creation in an organic medium of solvation formations - domains, the size of which, determined
by the method of photon correlation laser spectroscopy, varies from 21 to 1000 nm, depending on the chemical nature
of the solvent - is proposed and substantiated. For ethanol, the size of such formations was ~ 400 nm, which
significantly exceeds the size of individual particles of the additive. It is established that to improve the operational
characteristics of ethanol fuel it is enough to introduce low concentrations (10-3 - 10-2 %, wt.) of synthesized
brominated nanoparticles.
It is shown that the change of the microheterogeneous structure of fuels affects the change of its
physicochemical and operational characteristics: the dielectric constant and hydrophobicity of the medium decrease,
the saturated vapor pressure increases, which improves the starting properties of the fuel; hydrophobization of the
environment helps to reduce the corrosive properties of ethanol fuel per unit, as a result of which additional
introduction of a corrosion inhibitor is not required; the bearing capacity of the fuel in the presence of brominated
nanoparticles increases by 1.5 times compared to the base fuel with a corresponding decrease in damage to the metal
surface of the friction pairs.
It is the rearrangement of the secondary supramolecular structure of fuels in the presence of brominated carbon
nanospheres that explains the multifunctionality of their influence on the physicochemical and chemmotological
properties of ethanol motor fuels.
Keywords: ethanol fuel, carbon nanoscale spheroidal clusters; physico-chemical, performance and ecological
properties of the fuel.
Introduction
In recent decades, ethanol fuels with an ethanol
content of 75–85 % have become widespread in the
world. Their advantages, in addition to environmental
friendliness, are high anti-knock properties, ease of
disposal in contact with soil or water. In addition, the use
of alternative ethanol fuels helps to reduce the
consumption of petroleum gasoline. The availability of
different raw materials for ethanol production in Ukraine
makes it possible to consider high-ethanol fuels as
promising substitutes for petroleum gasoline. Until
recently, blended alcohol-based fuels were not
competitors to pure petroleum motor fuels due to a
number of shortcomings, including unsatisfactory starting,
anti-corrosion, lubricating properties, as well as reduced
calorific value, which lead to increased fuel consumption.
Overcoming these shortcomings and creating a fuel that
meets the requirements of modern standards is an urgent
scientific and applied task.
As we found [1-3], the chemmotological properties
of liquid motor fuels can be significantly changed by adding
carbon nanospheres, which are effective at concentrations of
0.01–0.001 %, wt. - 10-100 times lower than the
concentration of marketable additives of traditional action.
To date, no final explanation has been found for
the experimental fact of improving the wear, starting and
corrosion properties of fuels and fuel mixtures in the
presence of nanosized additives. For the most part, the
effect of such additives on the anti-wear properties of
fuels and lubricants is explained by changes in the
mechanical properties of hard metal contact surfaces due
to their chemical interaction with additive molecules and
the creation of the so-called intermediate (third) phase
[4-6]. In liquid fuels, nanocarbon additives have a
multifunctional effect and, unlike commercial additives,
do not increase, but, on the contrary, significantly reduce
the content of toxic substances in the emissions of
engines during combustion. This paper is devoted to
mailto:gaidaj@ukr.net
Каталіз та нафтохімія, 2021, № 31 63
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
elucidating the reasons for the multifunctional action of
exomodified carbon nanospheres on the properties of
ethanol motor fuels.
Materials and Methods
Carbon nanospheres of the fulleroid type - nano
onions (CNOs) [7] - were obtained by using high-
frequency discharge-pulse method [8] on the installation
of plasma chemical synthesis at an output voltage of 4 kV
in the frequency range of 20 - 25 kHz using electrodes
made of pure tungsten and propane-butane mixture as a
raw material.
Increasing the solubility of the synthesized carbon
nanostructures in organic solvents was achieved by
bromination in the presence of excess liquid bromine.
Selection of brominated nano onions from the synthesis
products was carried out by extraction with organic
solvents followed by drying.
The electrical capacity of the capacitor with
ethanolic solutions of brominated carbon nanospheres
between the covers (distance 1 cm) was measured using an
AC bridge under the following conditions: generator
frequency 1000 Hz, electrical resistance in stores 500 Ohm,
store capacity C0 = 0, voltmeter measurement limit - 10 V.
The refractive index was determined on an IRF-
454 B2M refractometer at a temperature of 20 oC at the
operating wavelength of the sodium atom spectrum line
λ = 589.3 nm.
The method of dynamic coherent scattering of laser
light (Malvern Zetasizer Nano S light scattering analyzer)
was used to experimentally estimate the size of the
domains formed by the molecules of the dispersion
medium around the brominated carbon nanospheres.
To assess the corrosion effects of ethanol fuel E-85,
a test method on a copper plate according to GOST 6321
(ISO 2160-85) was used. The essence of the method is to
keep the copper plate in the tested fuel at elevated
temperature and record the change in its appearance,
which characterizes the corrosive effect of the fuel.
Evaluation of test results is performed visually depending
on the degree of copper plate damage.
Indicator of the critical load of the solution to the
scuffering, which is the maximum value of the load at
which there is no metal contact (scuff) by friction in the
test liquid of standardized metal balls made of high-
strength low alloy steel for bearings (microhardness
64-66 HRC, roughness parameter Ra <0, 25 μm), was
evaluated on a four-ball friction machine according to the
method described in ASTM D 2266-01.
Results and discussion
The modern idea of the structure of substances in
the liquid state is based on the assertion of the existence
in the structure of various hierarchical structures that are
not characteristic of the gaseous and solid states. Such
spatially ordered objects in liquids include solid or
localized in some objects hydrogen skeletons from fires,
stable associative molecules and short-lived groupings
of molecules [9-11].
A
B
Fig. 1. Three-dimensional dynamic secondary
structure in the liquid phase of ethanol (A) and the
main elements of the secondary structure of ethanol
due to intermolecular hydrogen bonds (B) [11]: I -
linear associate; II - cyclic dimer; III - cyclic trimmer;
IV— cyclic tetramer.
Dissolution of brominated carbon nanospheres
CNOs – Brn in organic solvents is accompanied by
solvation of added molecules by molecules of the
medium with the participation of different forces of
intermolecular interaction, which are based on Coulomb
interaction forces between electrons and nuclei of
solvent and solute molecules. To describe the
intermolecular interaction between the components of
dilute solutions, the general equation of Van der Waals
is acceptable [12]:
Е = - 1/r6 {2/3٠ μ1
2 μ2
2
/kT + (μ1
2α2
+ μ2
2α1) +
+3α1α2 ٠ І1 І2 / (І1 + І2)} (1)
where E is the energy of intermolecular interaction
solvent (1) - solute (2);
r is the distance between the centres of the interacting
molecules;
μ1 and μ2 are dipole moments,
α1and α2 are polarization,
I1 and I2 are the ionization potentials of solvent and
solute molecules, respectively.
64 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Equation (1) includes orientational (first term),
polarization (second term) and dispersion (third term)
forces of intermolecular interaction.
Electrostatic interaction forces play a major role in
the formation of the primary solvate shell, which
consists of solvent molecules strongly bound to the
solute molecule [13, 14].
By the method of dynamic coherent scattering of
laser light, we experimentally determined the region of
coherent scattering, which corresponds to the size of
structural groups formed by brominated carbon
nanospheres CNOs – Brn in the environment of
chemically different organic solvents (Table 1) [14-16].
According to the above data, the size of the
domains formed by solvation of the added CNOs – Brn
nanospheres in the investigated solvents is different and
varies from 21 to 1000 nm. For ethanol, this size is ~
400 nm, which is much larger than the size of individual
additive particles (5 - 40 nm) [17]. Table 1 also shows
the reference values of dipole moments (µ), dielectric
constant (ε) and the acceptor number of the investigated
solvents. The parameters ε and µ are related by the
Debye equation [18]:
(ε–1)/(ε+2) = 4πN1/3*(α0+3µ2/3kТ) (2)
where ε is the dielectric constant of the medium,
µ is the intrinsic dipole moment of the molecule,
α0 is the polarization of the molecule,
N1 is the number of molecules in 1 cm3,
k is the Boltzmann constant,
T is absolute temperature.
As can be seen from the above data, a clear
relationship between the size of the domain formed by
the dissolution of CNOs – Brn nanospheres, dielectric
constant and dipole moment is not observed. These
dependences are complex because the dipole moment of
a molecule is a vector sum of the dipole moments of the
groups of which it consists. The corresponding
correlations are more characteristic of systems of simple
molecules with a small content of polar groups.
However, according to the data in table 1, the
determined volume of the domain correlates well with
the acceptor number of the solvent in the series: dioxane
- dimethylformamide - ethanol: the value of the latter
increases in the same direction as the size of the domain
CNOs – Brn - solvent. This dependence suggests that
donor-acceptor interaction forces are involved in the
formation of domains, where the electron donor is a
brominated onion molecule containing a system of
conjugated double bonds and an electronegative
substituent, and the acceptor is a solvent molecule. It is
significant that solvent molecules with high electron
density (benzyl alcohol, dioxane), which are good
electron donors, block the formation of stable bonds
with CNOs – Brn. The low values of the size of the
domains obtained in the latter environments are also
explained by the peculiarities of the geometric
configuration of their molecules, which complicates their
intermolecular interaction with solute molecules.
Table 1. Experimentally determined domain sizes from solvated CNOs – Brn nanospheres in
different media and some physicochemical properties of the corresponding solvents
Solvent
Structural formula Domain size,
nm
Dipole
moment
(µ, D)
Dielectric
constant
(ε)
Acceptor
number
Benzyl alcohol
21
1,71 13,5
Dioxane
28 0,0
2,2 10,8
N, N-dimethylformamide
220 3,8 36,7 16
Ethanol
400 1,68 25,2 37,9
N-methyl-pyrrolidone
950 4,06 34,9 13,3
Каталіз та нафтохімія, 2021, № 31 65
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
The dielectric constant of the medium (equation 2) as
well as the intermolecular interaction of the solvent with the
solute (equation 1) significantly depend on the polarization of
the interacting molecules. Considering the abnormally high
polarization (ε) of fullerene and fulleroid structures [19, 20],
the influence of this indicator on the solvation of CNOs – Brn
nanospheres in polar media is the most important. The
presence of heteroatoms attached to the outer shell of the
framework of the onion molecule causes an increase in the
polarization of the molecule compared to the carbon analogue.
The study of solvation of exomodified onions with various
substituents showed that in ethanol the smallest domains (~ 75
nm) are formed on the basis of oxidized nanocarbon spheres,
slightly larger - on the basis of chlorinated (~ 90 nm) and
much larger - on the basis of brominated ones (~ 400 nm)
(Table 2) [17].
The obtained results correlate with the valuesof
electronic polarization and the radius of the substituent
and, to a lesser extent, with the value of the dipole
moment of the Ar-X bond (Ar is an aromatic ring, X is a
substituent) (Table 2). As the electronic polarization of
the substituent increases, the polarization of dissolved
onion molecules increases, the value of which is additive
to the polarization of individual bonds, and the
contribution of the polarization component of the Van
der Waals interaction forces to the medium increases.
This can explain the increase in the size of solvate
structures in ethanol in a number of substituents: ОН-
1(О2-) – Cl ˉ – Br ˉ.
When dissolving CNOs – Brn onions in ethanol,
the scheme shown in Figure 2 gives an idea of the
formation of the primary solvate shell, which consists of
solvent molecules strongly bound to the solute molecule
by electrostatic interaction.
Under the action of the solvent, the C-Br bond,
like the whole onion molecule, is polarized with the
formation of dipoles, which, in turn, polarize the
substrate molecules. The secondary solvate shell is
formed due to the electrostatic interaction of primary
solvated molecules with solvent molecules with the
formation of a bulk supramolecular cluster - domain.
Fig. 2. Orientation ordering of ethanol molecules
under the action of brominated carbon nanospheres.
Hydrogen bonds play a significant role in ethanol
solution. Solvation of dissolved nanoparticles is
accompanied by a change in the electronic structure of
both substances in contact. The formation of similar
structures was observed in the study of the properties of
hydrated C60 fullerenes [21]. In [22] it is noted that the
properties of the boundary water layer formed near
hydrophilic surfaces, which has a thickness of tens and
hundreds of microns, are so different from bulk water that it
can be considered a special aggregate phase of water, whose
unusual properties are due to mobile the state of the electrons
in this phase. The corresponding changes in the properties of
ethanol take place in the solvate shell formed around the
CNOs – Brn nano onion. The scheme of the supramolecular
domain formed in ethanol can be represented as follows
(Figure 3).
The formation of an ordered structure of domains
with the orientation of hydrocarbon fragments of ethanol
molecules outward, and protons - to the center-forming
brominated carbon nanospheres - structures the
environment and significantly changes the
physicochemical and operational characteristics of CNOs
– Brn solutions compared to pure solvent. Considering
the linear relationship [23]:
С = ε ε 0 S/ d (3)
where C is the capacitance of the flat capacitor C,
between the covers of which is placed the test solution;
ε is the dielectric constant of the medium between the
plates of the capacitor;
ε0 is dielectric constant of vacuum;
S is the value of the surface area of the capacitor plate
(smaller if the opposite plates are uneven);
d is the distance between the plates of the capacitor
a b
Fig. 3. Possible secondary supramolecular structure
of the liquid phase of ethanol:
a - dynamic continuous network of hydrogen bonds of
ethanol molecules [9]; b - ordered islet groupings of
ethanol molecules around nanoparticles; -
hydrogen bond; - ethanol; - CNOsBrn.
66 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Table 2. The effect of the substituent in the structure of exomodified carbon nanospheres on the size of
the domain formed in the ethanol medium (additive concentration: 0, 01%, wt.)
Table 3. Anticorrosive properties of ethanol fuel E-85* in the presence of 0.001% wt. of CNOs-Brn
additive in comparison with traditional anticorrosive additives (0.01% wt.)
Additive Corrosion degree
Absent 2a
CNOs-Brn 1a
TEPA (tetramethylene polyamine) 1b
THETA (triethylenetetramine) 1a
Monoethanolamine 1b
Diethanolamine 1b
Triethanolamine 2b
Triethylamine 1a
* E-85 - ethanol fuel (85% ethanol, 15% gasoline A-95)
According to the experimental measurement of C,
the effect of the CNOs – Brn onion concentration not only
on the electrical conductivity but also on the dielectric
constant ε of ethanolic solutions was indirectly estimated.
As can be seen from Figure 4, the addition of brominated
carbon nanospheres to ethanol is accompanied by a
decrease in the electrical capacitance of the capacitor in the
range of CNOs – Brn concentrations from 0 to 0.001 %,
practically does not change from 0.001 to 0.006 % and then
increases
Fig. 4. Concentration change of electric capacitor
capacity with ethanol solution of brominated carbon
nanospheres between covers (curve 1) and critical load
of solution to scuffering (curve 2).
As can be seen from table 3, the introduction of
CNOs – Brn nanospheres into ethanol fuel at a
concentration an order of magnitude lower than
traditional corrosion inhibitors (mono-, di-,
triethanolamine, triethylamine, TEPA, TETA) exceeds
the anticorrosive efficiency of the latter.
The structuring of the solution at low concentrations
of the additive improves its anti-wear properties - the
critical load of ethanol solution to scuffering increases
with increasing concentration of CNOs – Brn from 0 to
0.06 % and with a subsequent increase of the latter to
0.01 %, these values do not change (Figure 4).
Conclusions
Based on the analysis of research results, it can be
stated that the formation of supramolecular solvate groups,
the center of which are nanosized carbon clusters of CNOs
– Brn, in the ethanol medium, occurs with the participation
of different in nature forces of intermolecular interaction.
The basis of intermolecular interaction is the Coulomb
forces of interaction between electrons and nuclei of
ethanol molecules and nanoadditives.
Based on the data obtained, it can be concluded that
when adding onions to ethanol fuel should work in the
range of operating concentrations of 0.001-0.01 wt.%
CNOs - Brn, where there is no agglomeration of the
structures formed in solution.
The influence of microstructural changes in the
studied system on its macrophysical properties is
revealed and the interrelation between physicochemical
Substitute
(Х)
Domain size in ethanol, А
(experiment)
dipole moment of
С6Н5 –Х (µ, D)
The value of the
electronic
polarization of the
ion, А
Ion radius, А
ОН ˉ ~ 750 1,40 2,04 1,36 (for О-2)
Cl ˉ ~ 900 1,69 2,96 1,81
Br ˉ ~ 4000 1,77 4,16 1,96
Каталіз та нафтохімія, 2021, № 31 67
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
and operational properties of ethanol fuels containing
nanocarbon clusters is found [23].
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Надійшла до редакції 09.06.21 р.
http://dx.doi.org/10.15587/2313-8416.2016.71955
http://dx.doi.org/10.21303/2461-4262.2016.00213
68 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Вплив додавання екзомодифікованих вуглецевих наносфер на
структурування в етанольних моторних паливах
Є.В. Полункін1, В.С. Пилявський1, O.O. Гайдай1, С.Л. Мельникова 1, O. A. Спаська2,
І.В. Матвєєва3
1 Відділ гомогенного каталізу та присадок до нафтопродуктів, Інститут біоорганічної хімії та нафтохімії ім. В.П.
Кухаря НАН України, Харківське шосе 50, Київ 02160, Україна, gaidaj@ukr.net
2 Кафедра хімії і хімічної технології, Національний авіаційний університет, 3 Кафедра екології, Національний авіаційний
університет, просп. Любомира Гузара 1, Київ 03058, Україна
Робота присвячена з'ясуванню загального механізму дії екзомодифікованих вуглецевих наносфер (CNO - Brn
нано-оніонів) на різні хімічні та фізико-хімічні властивості етанольних моторних палив. Формування
надмолекулярних сольватних груп в органічних середовищах пояснюється участю різних сил міжмолекулярної
взаємодії, основними з яких є поляризаційні та орієнтаційні, а також донорно-акцепторних сил взаємодії наносфер
з навколишнім середовищем. Запропоновано та обґрунтовано концепцію створення в органічному середовищі
сольватаційних утворень - доменів, розміри яких, визначені методом фотонно-кореляційної лазерної спектроскопії,
варіюються від 21 до 1000 нм залежно від хімічної природи розчинника. Для етанолу розмір таких утворень
становив ~ 400 нм, що значно перевищує розмір окремих частинок добавки. Встановлено, що для поліпшення
експлуатаційних характеристик етанолового палива достатньо ввести низькі концентрації (10-3-10-2%, мас.)
cинтезованих бромованих наночастинок.
Показано, що зміна мікрогетерогенної структури палива впливає на зміну його фізико-хімічних та
експлуатаційних характеристик: зменшуються діелектрична проникність та гідрофобність середовища,
збільшується тиск насиченої пари, що покращує вихідні властивості палива; гідрофобізація середовища допомагає
зменшити корозійні властивості етанольного палива на одиницю, внаслідок чого не потрібне додаткове введення
інгібітора корозії; несуча здатність палива в присутності бромованих наночастинок збільшується в 1,5 рази
порівняно з базовим паливом з відповідним зменшенням пошкодження металевої поверхні пар тертя.
Саме перегрупування вторинної надмолекулярної структури палив у присутності бромованих вуглецевих
наносфер пояснює багатофункціональність їх впливу на фізико-хімічні властивості та хіммотологічні
характеристики ета-нольних моторних палив.
Ключові слова: етанольне паливо; карбонові нанорозмірні сферичні кластери; фізико-хімічні,
експлуатаційні та екологічні властивості палива
mailto:gaidaj@ukr.net
|
| id | oai:katalizorgua:article-15 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:49:45Z |
| publishDate | 2021 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/9f/9ac3d94684c8ea04315b1a31d6a9259f.pdf |
| spelling | oai:katalizorgua:article-152021-12-10T12:36:41Z Influence of addition of exomodified carbon nanospheres on the structuration in ethanol motor fuels Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах Polunkin, E.A. Pyliavskyi, V.S. Gaidai, O.O. Melnykova, S.L. Spaska, O.A. Matveeva, I. V. ethanol fuel carbon nanoscale spheroidal clusters performance and ecological properties of the fuel етанольне паливо карбонові нанорозмірні сферичні кластери фізико-хімічні експлуатаційні та екологічні властивості палива The work is devoted to elucidation of a general mechanism of action of exomodified carbon nanospheres (CNOs – Brn nanoonions) on different physicochemical and chemmotological properties of ethanol motor fuels. The formation of supramolecular solvate groups in organic media is explained by the participation of different forces of intermolecular interaction, the main of which are polarization and orientation, as well as donor-acceptor forces of interaction of nanospheres with the environment.The concept of creation in an organic medium of solvation formations - domains, the size of which, determined by the method of photon correlation laser spectroscopy, varies from 21 to 1000 nm, depending on the chemical nature of the solvent - is proposed and substantiated. For ethanol, the size of such formations was ~ 400 nm, which significantly exceeds the size of individual particles of the additive. It is established that to improve the operational characteristics of ethanol fuel it is enough to introduce low concentrations (10-3 - 10-2 %, wt.) of synthesized brominated nanoparticles.It is shown that the change of the microheterogeneous structure of fuels affects the change of its physicochemical and operational characteristics: the dielectric constant and hydrophobicity of the medium decrease, the saturated vapor pressure increases, which improves the starting properties of the fuel; hydrophobization of the environment helps to reduce the corrosive properties of ethanol fuel per unit, as a result of which additional introduction of a corrosion inhibitor is not required; the bearing capacity of the fuel in the presence of brominated nanoparticles increases by 1.5 times compared to the base fuel with a corresponding decrease in damage to the metal surface of the friction pairs.It is the rearrangement of the secondary supramolecular structure of fuels in the presence of brominated carbon nanospheres that explains the multifunctionality of their influence on the physicochemical and chemmotological properties of ethanol motor fuels. Робота присвячена з'ясуванню загального механізму дії екзомодифікованих вуглецевих наносфер (CNO - Brn нано-оніонів) на різні хімічні та фізико-хімічні властивості етанольних моторних палив. Формування надмолекулярних сольватних груп в органічних середовищах пояснюється участю різних сил міжмолекулярної взаємодії, основними з яких є поляризаційні та орієнтаційні, а також донорно-акцепторних сил взаємодії наносфер з навколишнім середовищем. Запропоновано та обґрунтовано концепцію створення в органічному середовищі сольватаційних утворень - доменів, розміри яких, визначені методом фотонно-кореляційної лазерної спектроскопії, варіюються від 21 до 1000 нм залежно від хімічної природи розчинника. Для етанолу розмір таких утворень становив ~ 400 нм, що значно перевищує розмір окремих частинок добавки. Встановлено, що для поліпшення експлуатаційних характеристик етанолового палива достатньо ввести низькі концентрації (10-3 -10-2%, мас.) cинтезованих бромованих наночастинок. Показано, що зміна мікрогетерогенної структури палива впливає на зміну його фізико-хімічних та експлуатаційних характеристик: зменшуються діелектрична проникність та гідрофобність середовища, збільшується тиск насиченої пари, що покращує вихідні властивості палива; гідрофобізація середовища допомагає зменшити корозійні властивості етанольного палива на одиницю, внаслідок чого не потрібне додаткове введення інгібітора корозії; несуча здатність палива в присутності бромованих наночастинок збільшується в 1,5 рази порівняно з базовим паливом з відповідним зменшенням пошкодження металевої поверхні пар тертя. Саме перегрупування вторинної надмолекулярної структури палив у присутності бромованих вуглецевих наносфер пояснює багатофункціональність їх впливу на фізико-хімічні властивості та хіммотологічні характеристики ета-нольних моторних палив. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2021-11-07 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/15 10.15407/kataliz2021.31.062 Catalysis and petrochemistry; No. 31 (2021): Catalysis and petrochemistry; 62-68 Каталіз та нафтохімія; № 31 (2021): Каталіз та нафтохімія; 62-68 2707-5796 2412-4176 10.15407/kataliz2021.31 en https://kataliz.org.ua/index.php/journal/article/view/15/6 Copyright (c) 2021 Catalysis and petrochemistry |
| spellingShingle | етанольне паливо карбонові нанорозмірні сферичні кластери фізико-хімічні експлуатаційні та екологічні властивості палива Polunkin, E.A. Pyliavskyi, V.S. Gaidai, O.O. Melnykova, S.L. Spaska, O.A. Matveeva, I. V. Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| title | Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| title_alt | Influence of addition of exomodified carbon nanospheres on the structuration in ethanol motor fuels |
| title_full | Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| title_fullStr | Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| title_full_unstemmed | Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| title_short | Вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| title_sort | вплив додавання екзомодифікованих вуглецевих наносфер на структурування в етанольних моторних паливах |
| topic | етанольне паливо карбонові нанорозмірні сферичні кластери фізико-хімічні експлуатаційні та екологічні властивості палива |
| topic_facet | ethanol fuel carbon nanoscale spheroidal clusters performance and ecological properties of the fuel етанольне паливо карбонові нанорозмірні сферичні кластери фізико-хімічні експлуатаційні та екологічні властивості палива |
| url | https://kataliz.org.ua/index.php/journal/article/view/15 |
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