Вплив окиснення графену на термічну деструкцію епокси-графенових композитів
The participation of the electronic subsystem of graphene nanoparticles in heat transfer on the interfaphase surface with epoxy polymer, its participation in the thermodestruction processes of epoxy matrix and the concentration interval of the subsystem's influence on the thermal destruction of...
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Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2021
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| author | Сігарьова, Н. В. Горєлов, Б. М. Шульга, С. В. |
| author_facet | Сігарьова, Н. В. Горєлов, Б. М. Шульга, С. В. |
| author_institution_txt_mv | [
{
"author": "Н. В. Сігарьова",
"institution": "Інститут хімії поверхні ім. О.О.Чуйка Національної академії наук України"
},
{
"author": "Б. М. Горєлов",
"institution": "Інститут хімії поверхні ім. О.О.Чуйка Національної академії наук України"
},
{
"author": "С. В. Шульга",
"institution": "Інститут хімії поверхні ім. О.О.Чуйка Національної академії наук України"
}
] |
| author_sort | Сігарьова, Н. В. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2022-02-21T13:55:09Z |
| description | The participation of the electronic subsystem of graphene nanoparticles in heat transfer on the interfaphase surface with epoxy polymer, its participation in the thermodestruction processes of epoxy matrix and the concentration interval of the subsystem's influence on the thermal destruction of the polymer matrix are investigated. For such purpose, epoxy resin composites with oxidized and non-oxidized graphene nanoparticles have been used.The particles were obtained by electrochemical method and those are characterized by the same dispersion and analogical of defect spectra. The particles have the same crystal structure, however in composites with oxidized graphene, the participation of the electronic subsystem in thermophysical processes on the interfacial surface is blocked by the atomic layer of adsorbed oxygen.
Сomposites of epoxy resin filled with the same particles of nonoxidized and oxidized nanoparticles in the filler content 0.0, 1.0, 2.0, and 5.0 wt%. The multilayered graphene particles were studied by X-ray diffraction analysis (XRD) and Raman spectroscopy (RS) methods. It was shown that the graphene particles are the 2D dimensional structures with about of 100 layers. Desorption curves of epoxy and its composites have been obtained using a programmable thermal desorption mass-spectroscopic (TDMS) technique for fragments with 15≤ m/z ≤108 and temperature interval 35 - 800 оС.
The activation energy of desorption was determined from the Wigner-Polanyi equation as 35 - 150 kJ/mol, temperature and mass dependences of the quantity of desorbed atomic fragments have been calculated.
It were established the graphene electron subsystem takes part in polymer structure thermodestruction for epoxy composites with nonoxidized graphene enhancing their heat resistance at graphene content С ≤ 1 wt%. With increasing filler content, the thermodestruction behavior in pristine epoxy and its composites with nonoxidized and oxidized graphene is analogical. The thermodestruction characterizes by the stepwise variations in the desorption intensity of atomic fragments. The electron subsystem of graphene particles does not participate in the heat resistance variations. |
| doi_str_mv | 10.15407/Surface.2021.13.166 |
| first_indexed | 2025-07-22T19:35:23Z |
| format | Article |
| fulltext |
Поверхня. 2021. Вип. 13(28). С. 166–174 166
НАНОМАТЕРИАЛЫ И НАНОТЕХНОЛОГИИ
УДК 536.1; 543.4;543.51; 543.57; 678.686 doi: 10.15407/Surface.2021.13.166
ЕFFECT OF GRAPHENE FILLER OXIDATION
ON THE THERMAL DESTRUCTION OF EPOXY-
GRAPHENE COMPOSITES
N.V. Sigareva, B.M. Gorelov, S.V. Shulga
Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
17 General Naumov Street, Kyiv 03164, Ukraine, microft2@ukr.net
The participation of the electronic subsystem of graphene nanoparticles in heat transfer on
the interfaphase surface with epoxy polymer, its participation in the thermodestruction processes
of epoxy matrix and the concentration interval of the subsystem's influence on the thermal
destruction of the polymer matrix are investigated. For such purpose, epoxy resin composites
with oxidized and non-oxidized graphene nanoparticles have been used.The particles were
obtained by electrochemical method and those are characterized by the same dispersion and
analogical of defect spectra. The particles have the same crystal structure, however in
composites with oxidized graphene, the participation of the electronic subsystem in
thermophysical processes on the interfacial surface is blocked by the atomic layer of adsorbed
oxygen.
Сomposites of epoxy resin filled with the same particles of nonoxidized and oxidized
nanoparticles in the filler content 0.0, 1.0, 2.0, and 5.0 wt%. The multilayered graphene
particles were studied by X-ray diffraction analysis (XRD) and Raman spectroscopy (RS)
methods. It was shown that the graphene particles are the 2D dimensional structures with about
of 100 layers. Desorption curves of epoxy and its composites have been obtained using a
programmable thermal desorption mass-spectroscopic (TDMS) technique for fragments with
15≤ m/z ≤108 and temperature interval 35 − 800 оС.
The activation energy of desorption was determined from the Wigner-Polanyi equation as
35 − 150 kJ/mol, temperature and mass dependences of the quantity of desorbed atomic
fragments have been calculated.
It were established the graphene electron subsystem takes part in polymer structure
thermodestruction for epoxy composites with nonoxidized graphene enhancing their heat
resistance at graphene content С ≤ 1 wt%. With increasing filler content, the thermodestruction
behavior in pristine epoxy and its composites with nonoxidized and oxidized graphene is
analogical. The thermodestruction characterizes by the stepwise variations in the desorption
intensity of atomic fragments. The electron subsystem of graphene particles does not participate
in the heat resistance variations.
Keywords: epoxy composite, unoxidized and oxidized graphene, thermal stability, fragment
of destruction.
Introduction
Polymer composites with graphene distinguish the possibility of producing materials
combining excellent mechanical parameters with high electrical and thermal conductivity [1−5].
The enhancement of kinetic parameters and the extent of functionality will make the graphene
composites by the most needed functional materials in many spheres of modern applications. In
particularly, the widening of the operating temperature range, limited by the insufficient thermal
mailto:microft2@ukr.net
167
stability of the most polymer matrixes, is the scientific and technical problems of modern
material science.
The heat resistance of polymer graphene composites can be enhanced due to the fastening
of atoms of polymer chains with active surface sites of unoxidized graphene and the polymer
structure stabilization [6]. Besides, the surface modification of graphene particles with active
functional groups also leads to an enhancement in the composite heat resistance [7]. For the both
cases, the stabilization of polymer structure results increasing thermal stability in graphene
composites, while the heat transfer on the interface in the composites is different. In the first
case, the heat transport realizes from the polymer chains into the graphene where it redistributes
among phonon and electron subsystems. In the second case, the heat from polymer chains
through atomic functional groups transfers into graphene and then divides between the both
subsystems. Thus, in the first case the electron subsystem removes the heat partition on the
interface from polymer chains. In another case, the heat removal occurs from functional groups
at the interface. It is obviously, that the effect of heat transfer to the electron subsystem in the
thermal stability of graphene composites is different.
Note, the heat resistance of composites depends on the many factors. In particular, it
depends on the polymer structure and the polymerization degree of polymer matrix, the size and
shape, and the defectiveness of graphene particles. Therefore, the goal of present study is to
investigate the influence of graphene electron subsystem on the thermal stability of polymer
composites with unoxidized and modified graphene using the same graphene particles and
matrix, and the preparation conditions of composites. The surface modification of graphene
particles was fulfilled using the surface oxidation. It was supposed, that the adsorbed atomic
oxygen layer blocks the direct heat transfer from polymer chains to the graphene electron
subsystem. Epoxy polymer was used as a composite matrix.
Samples and experimental methods
The commercially available CHS-EPOXY 520 (Czech Republic) DGEBA-epoxy resin,
with epoxy group content 5.21−5.50 mol/kg. Epoxy Equivalent Weight 182−192 g/mol was used
as the pure resin. The Polyethylene-polyamine (PEPA) was used as a curing agent. The structural
formulas of the epoxy resin and hardeners can be found elsewhere [8].
Multilayered graphene particles have been obtained from thermal-expanded graphite flakes
Ukrainian production by using the electrochemical technique described by Xia et al [9].
The so-prepared low-dimension particles to be multilayered graphene nanoplatelets of
about 5×5 µm in-plane dimensions and 50 nm in thickness. The both surfaces of graphene
particles have complicated morphology. On the basal surface, there are the edge defects, surface
curvatures, waviness and mesovoids. The lateral surface contains about hundred graphene layers
and characterizes with disordered structure and roughness.
The specific surface value Sf ≈ 740 m2/g have been determined for multilayered graphene
nanoplatelets by measuring an amount of physically adsorbed nitrogen from adsorption–
desorption isotherms according to the standard Brunauer, Emmett, and Teller (BET) method
[10].
The X-ray diffraction analysis shows that the multilayered nanoplatelets contain graphene
sheets (Fig. 1).
The X-ray diffraction analysis shows that the multilayered nanoplatelets contain 2D
graphene sheets (Fig. 2). Raman spectra of nonoxidized multilayer graphene particles indicate
that graphene particles constructed with loosely bound graphene flakes (Fig. 2). Raman spectra
were recorded using the”DFS-52” double monochromator, CCD camera of Andor company and
microscope. The emission of solid-state laser with wavelength of 457 nm was applied to excite
Raman spectra. The reflection geometry applying the same lens to register the exciting and
scattered radiations was used in the experimental setup. Obtained graphene Raman spectra
168
evince the 2D dimension of graphene flakes. Graphene Raman spectra characterize by а presence
G (∼1582 см-1) band related to exhibition of tensile vibrations for all sp2 hybridized atomic pairs
of carbon atoms located in the benzene rings and as well as the D (∼1350 см-1) band indicating
defect presence within graphene layers. In addition, in the Raman spectra the G (∼1582 см-1)
band whose intensity exceeds that for D band is recorded. The latter is distinctive peculiarity of
graphene spectra [11-13]. Note, the Raman spectra of one layer graphene particles (Fig. 2,
spectrum 3) and multilayered graphene particles are identical. Thus, X-ray and Raman
spectroscopies show the structural identity among one and multilayered graphene particles.
Fig. 1. X-ray diffraction analysis of graphene
particles
Fig. 2. Raman spectra of multilayer graphene
particles are recorded with spectrometer
slit width 70 (1) and 200 μm (2).
Spectrum of one-layer graphene (3)
was taken from [11]
Epoxy composites with non-oxidized graphene nanoplatelets have been prepared by
pouring a suspension of particles in ethanol into an uncured resin, to avoid an oxidation of
graphene in air. The filler-mass-loading C in the nanocomposites was 1, 2, and 5 wt% for
thermophysical studies. As-prepared liquid composites were manually mixed until homogeneous
suspensions were obtained and their further polymerization occurred at a room temperature
during 72 hours with following heat treatment at ~ 60 °C for 1.5 hours. As a curing agent, 16%
by weight of polyethylene polyamine was used.
The oxidization of graphene particles have been performed using Hammer method with
subsequent purification from admixtures and in accordance with [14]. Epoxy composited with
non-oxidized and oxidized graphene were obtained using analogical preparation method. The
graphene content in epoxy matrix was of 1, 2, and 5 % wt.
An influence of graphene filler on the resin thermal stability have been determined using a
programmable thermal desorption technique combined with a mass-spectroscopic detection via
the single-pole mass-analyzer МХ 7304А. Mass spectrometric analysis of positive charged
atomic products was performed in the range 10−200 m/z (m is the mass, z is charge of the
169
fragment), within a temperature range of 25−800 ºC, at a pressure 0.1 Pa, and the heating rate 8
ºC/min [15].
Results and discussion
Тhermodestruction data
The typical of desorption curves characterizing thermal destruction of epoxy chains in the
composites with unoxidized and oxidized graphene is shown in Fig. 3.
Figure depicts that the behavior of thermal stability for both composites is significantly
different. Thermal stability of composites with unoxidized graphene reveals a sharp increase, by
more than 11 times, at low filling C ≤ 1.0% and the weak nonmonotonic variations in the
desorption intensity with rising graphene content (Fig. 3 a). Thermal destruction of composites
with oxidized graphene shows a weak increase in the thermal stability of about 1.13 times at low
filler content and a gradual reduction in the desorption intensity of volatile products with
increasing filling (Fig. 3 b).
Fig. 3. Desorption curves of atomic fragments with m/z 44 (-COO-) for destruction of neat resin
(0) and its composites with 1.0 (1), 2.0 (2) and 5.0 (5) % of unoxidized (a) and oxidized
(b) graphene particles
Abrupt variations of the total release of desorbed atomic fragments Qi of composites with
nonoxidized and oxidized graphene at low filling occurs in temperature range 300 – 400 oC (Fig.
4). Loading with the low content of nonoxidized graphene particles essentially enhances the heat
resistance of polymer matrix. Successive growth of graphene content upon 1 < C≤ 5% renders
practically the same action on the thermal destruction of composites with nonoxidized and
oxidized graphene. Thus, the maximal effect on the thermal stability reveals at low content C ≤
1% of unoxidized graphene. In composites with oxidized graphene, the changing of filler content
weakly influences their thermal stability. Note that the loading effect with unoxidized graphene
particles at 1 ≤ C ≤ 5 wt% and oxidized those at 0<C ≤ 1.0 wt% is practically the same (Fig. 4).
The latter indicates that the interface structure, and the reactivity, the surface layer disordering in
graphene particles and the surface distortions of graphene energy bands in such composites is
similar.
Note, the total amount of desorbed destruction products Qi in the investigated temperature
range was determined from the following expression:
Qi(Т) = (1)
where Ii(T) is the temperature dependence of thermal desorption intensity of i-th product, and T1
and T2 are the temperature limits of integration.
170
.
Fig. 4. Temperature dependences of the amount of desorbed atomic fragments with m/z 44 for
destruction of pure resin (0) and its composites with 1.0 (1), 2.0 (2) and 5.0 (5) wt% of
unoxidized (a) and oxidized (b) graphene particles
Sharp reduction in the thermodesorption intensity of polymer structure can be attributed to
increasing destruction activation energy of polymer chains due to enhancing interatomic
interaction in the composite matrix upon chemical bonding of atoms of polymer chains and
cross-links with graphene surface sites. However, in the composites with nonoxidized and
oxidized graphene the calculations of destruction activation energy Ed for atomic fragments with
17 ≤ m/z ≤ 108, using the Polanyi – Wigner formula [16]:
Еd = ln (Θ1/Θ2)RT1T2/(T1 – T2), (2)
where T1 and T2 are the temperature range of desorption peak width in the half-height, Θ1 and Θ2
are the areas under desorption curves corresponding to the amount of remaining substance after
reaching T1 and T2 temperatures, gives the Ed values in the same range 55−150 kJ/mol.
Thus, the matrix’s heat resistance behavior upon loading with graphene particles does not
depend on the polymer structure rearrangement and the interatomic interaction in epoxy
composites. The variations in the heat resistance behavior of polymer matrix in graphene
composites can be attributed to the different structure of interphase border and heat processes at
the interface. The destruction features of atomic fragments of polymer structure reveal in
concentration dependences of the amount of desorbed destruction fragments (Fig. 5).
Fig. 5. Concentration dependences of total
quantity of desorbed destruction
products for epoxy resin (0) and its
composites with 1 (1), 2 (2) and 5 %
(5) nonoxidized (a) and oxidized
graphene particles (b) in the range 17 ≤
m/z ≤ 108
171
Fig. 5 shows the two features in the polymer structure destruction reveals in graphene
composites. Firstly, the abrupt enhancement in the thermal stability of atomic fragments with 17
≤ m/z <77 in composites with nonoxidized graphene at low filling C ≤ 1%, and secondly, the
analogical stepwise behavior of polymer structure destruction in composites with nonoxidized
graphene at filling C >1 % and for the neat epoxy and its composites with oxidized graphene.
The thermal stability enhancement of polymer structure in composites with nonoxidized
graphene depends on the participation of graphene electron subsystem in the redistribution of
heat fluxes at the interphase border. In this case, the electron subsystem removes the heat flux
partition from the graphene phonon subsystem. In result of the heat removal, the vibrational
energy of atoms fastened with graphene surface sites reduces and the heat resistance of atomic
fragments bounded with surface atoms rises.
In the concentration range of graphene filling C >1 % during epoxy polymerization the
chemical bounding of macromolecule atoms with graphene surface sites takes place. Since the
fastening of polymer chains and cross-links is the stochastic process, the disordering structure of
fixed atomic fragments arranges on the surface of graphene particles. The affect of disordered
electrostatic potential of charged surface sites lead to the surface amorphization of graphene
particles and distortion their electron bands. Formation of disordered electron states in the
surface layer of graphene particles blocks the heat removal in the graphene electron subsystem at
the interface. Therefore, in composites with unoxidized graphene at C >1 wt% the electron
subsystem of particles does not participate in the heat transport due to disordering electron bands
in the interface region.
The identity of polymer structure destruction in the pristine epoxy and its composites with
oxidized graphene and nonoxidized graphene at C > 1 wt% evinces the electron subsystem of
graphene particles does not participate in the thermal decomposition of epoxy composites. The
variations of destruction intensity depend on the heat dissipation at the interface. Note, that the
effect of surface oxidation is analogical to the influence of surface modification of graphene
particles due to fastening of polymer chains and cross-links during epoxy condensation. The both
types of surface modification leads to the blocking of graphene electron subsystem due to
disordering electron bands in the surface layer of graphene particles.
The stepwise behavior of polymer structure destruction shows that in composites with
nonoxidized graphene at filling C >1 wt% and in the neat epoxy and its composites with
oxidized graphene the destruction intensity of atomic fragments with m/z 28 (–CO), 42 (–
CH2OC–) and 94 (C6H5OH –) exceeds that of fragment with m/z 17 (–OH), 30 (–CH2O–), 77
(C6H5 –) and 108 (C6H5CH2OH–) (Fig. 5). Step variations in the thermal stability of polymer
structure atomic fragments may indicate the inhomogeneous temperature distribution in polymer
chains during heat transport.
Heat transport
Phenomenological model of local thermal processes at the interface with participation of
graphene electron subsystem is following. The heat flux q entering into the unfilled polymer
from an external source propagates as the phonon flux qph
ep through the polymer chains and
cross-links into the polymer bulk. Neglecting heat dissipation on the surface, defects and
phonons, we can write:
q = qph
ep , (3)
In epoxy composite, the heat transport realizes through polymer chains attached to surface
active sites of graphene particles. Heat flux along each epoxy polymer chain to the interface is
transported by propagating flux of local phonons qph
ep in accordance with the Fourier equation
qph
ep = ‒ кph∇Тph , (4)
172
where кph is the thermal conductivity coefficient of epoxy polymer chains, ∇Тph is temperature
gradient in the polymer chain.
The heat transfer from local phonons to the electronic and phonon subsystems of graphene
particles occurs at the interphase boundary in the places of fastening chain atomic fragments,
having different atomic compositions, to the graphene surface sites in accordance with the laws
of energy and momentum conservation. In the local approximation, at the interphase boundary
for temperature T, heat transfer from the polymer to the graphene particle can be described by
expression
qph
ep = Θ(qph
gr + qe
gr) (5)
where Θ is the heat transfer efficiency at the interface, qpi
g and qei
g are the phonon and electron
heat fluxes in graphene particles. At high temperatures close to destruction temperatures of
polymer chains, the heat transfer occurs in the anharmonic mode of phonon generation, when
backscattering local phonons at the interface is unlikely and the transfer efficiency is high and
probably about to unity Θ ≈1. The obtained heat by the graphene electronic subsystem does not
return to the phonon subsystem of polymer due to absence of electron transport in the polymer.
In graphene a heated electron gas dissipates the received heat into the phonon subsystem due to
the electron-phonon interaction during relaxation time τr at a distance from the interface
s = vτr (6)
where v is the velocity of heated electrons. In the local approximation оn the interface surface
the temperature of the heat flux of local phonons in the polymer Тph
ep and the heat fluxes of
phonons Tph
gr and electrons Tph
gr in a graphene are the same
Т= Тph
ep = Tph
gr + Te
gr (7)
Hence, the temperature of the phonon flux in graphene qph
gr at the interphase boundary
abruptly decreases by the temperature value of heated electrons
Δ = Te
gr = Тph
ep ‒ Tph
gr (8)
Reduction in the temperature of the graphene phonon subsystem leads to a decrease in the
energy of vibrations of surface site atoms by value kΔ (k is the Boltzmann constant). As a result,
the destruction probability of polymeric atom groups fixed with surface sites decreases, and the
decomposition intensity of the polymer structure located near the interface also reduces.
In composites with oxidized graphene at the border with adsorbed oxygen layer the phonon
flux qph
ep tests the boundary heat resistance (Kapitza resistance) and the temperature step ΔТК.
Values of the boundary heat resistance and the temperature step depend on the bind
character between oxygen sites and the polymer chain atoms. In the case when the binding does
not change the acoustic parameters of polymer chains fastened with oxygen sites Kapitza
resistance has a minimal value and the flux value qph
ep through oxygen layer can be unchanged.
At the interphase border with graphene the heat resistance does not exhibits in the
temperature range close to destruction temperatures since the thermal decomposition of atomic
fragments in the pristine epoxy and its graphene composites is practically the same (Fig. 5 b).
Within graphene particles the phonon flux passes through the amorphous layer where the energy
of localized electrons can be increased in the result of heat loss. However, at the interphase
border the heat removal by the localized electrons does not occurs. In the graphene bulk where
the band structure is undisturbed the heating of band electrons occurs, however it does not effect
at the destruction of polymer matrix.
Note, at the interface due to the complicate morphology of graphene surface the phonon-
phonon interaction is obviously enhanced. Intensive phonon interaction can lead to the local
heating of filler surface and surface sites with fastened atomic fragments enhancing their thermal
173
decomposition [17]. In particular, in the composites with oxidized graphene the intensive
thermal destruction of some atomic fragments exceeding that in the neat epoxy can be attributed
to the enhanced phonon- phonon interaction.
Conclusions
The thermodestruction of epoxy resin and its composites with the same nanoparticles of
nonoxidized and oxidized graphene have been investigated using a programmable thermal
desorption mass-spectroscopic technique in the graphene content range 0 ≤ С ≤ 5 wt% and
temperature interval 35−800 оС.
The thermodesorption curves for atomic fragments with 15≤ m/z ≤108 were obtained. The
activation energy of desorption, temperature and mass dependences of the quantity of desorbed
atomic fragments have been calculated.
It were established the graphene electron subsystem takes part in polymer structure
thermodestruction for epoxy composites with nonoxidized graphene enhancing their heat
resistance at graphene content С ≤ 1%. With increasing filler content, the thermodestruction
behavior in pristine epoxy and its composites with nonoxidized and oxidized graphene is
analogical. The thermodestruction characterizes by the stepwise variations in the desorption
intensity of atomic fragments. The electron subsystem of graphene particles does not participate
in the heat resistance variations.
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ВПЛИВ ОКИСНЕННЯ ГРАФЕНУ НА ТЕРМІЧНУ
ДЕСТРУКЦІЮ ЕПОКСИ-ГРАФЕНОВИХ КОМПОЗИТІВ
Н. В. Сігарьова, Б. М. Горєлов, С. В. Шульга
Інститут хімії поверхні ім. О. О. Чуйка НАН України,
вул. Генерала Наумова, 17, 03164 Київ, Україна, microft2@ukr.net
У роботі досліджена участь електронної підсистеми графенових наночастинок в
теплопереносі на міжфазній поверхні з епоксидним полімером, її участь у процесах
термічної деструкції епоксидної матриці та концентраційний інтервал впливу
підсистеми графену на терморуйнування полімерної матриці. Для цього використано
композити епоксидної смоли з частинками окисненого на неокисненого графену, які
отримані електрохімічним методом. Частинки характеризуються однаковою
дисперсією та аналогічними спектрами дефектів. Частинки мають однакову
кристалічну структуру, але відрізняються тим, що в композитах з окисненим графеном
участь електронної підсистеми у теплофізичних процесах на міжфазній поверхні
блокована атомарним шаром адсорбованого кисню.
Досліджено композити епоксидної смоли, наповнені однаковими наночастинками
неокисненого і окисненого графену в інтервалі наповнень 0.0, 1.0, 2.0, і 5.0 мас%.
Частинки багатошарового графену характеризувалися методами рентгентгено-
структурного аналізу (РСА) і Рамінівської спектроскопії (СКР) як двомірні структури з
числом шарів близько 100. Десорбційні криві епоксидної смоли і композитів отримано за
результатами досліджень методом термопрограмованої десорбційної мас-спектроскопії
(ТПДМС) фрагментів з 15 ≤ m/z ≤108 в інтервалі температур 35−800 °С.
Визначено енергію активації деструкції атомних фрагментів 35−150 кДж/моль і
отримано температурні і масові залежності десорбції атомних фрагментів.
Встановлено, що в композитах з неокисненим графеном при наповненні С ≤ 1 мас%
електронна підсистема частинок графену бере участь в термодеструкції, підвищуючи
термостійкість композитів. При збільшенні наповнення поведінка термодеструкції в
ненаповненій смолі і її композитах з неокисненим і окисненим графеном аналогічна і
характеризується немонотонною зміною інтенсивності термічної деструкції атомних
фрагментів. Проведено аналіз теплових процесів на міжфазній границі композитів
епоксидної смоли з багатошаровим графеном.
Ключові слова: епоксидний композит, неокиснений та окиснений графен, термічна
стійкість, фрагмент деструкції.
mailto:microft2@ukr.net
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| id | oai:ojs.pkp.sfu.ca:article-731 |
| institution | Surface |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2025-09-24T17:45:56Z |
| publishDate | 2021 |
| publisher | Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | surfacezbircomua/97/5118889de0b349edd0db746a3d6ad697.pdf |
| spelling | oai:ojs.pkp.sfu.ca:article-7312022-02-21T13:55:09Z Еffect of graphene filler oxidation on the thermal destruction of epoxy-graphene composites Вплив окиснення графену на термічну деструкцію епокси-графенових композитів Сігарьова, Н. В. Горєлов, Б. М. Шульга, С. В. epoxy composite unoxidized and oxidized graphene thermal stability fragment of destruction епоксидний композит неокиснений та окиснений графен термічна стійкість фрагмент деструкції The participation of the electronic subsystem of graphene nanoparticles in heat transfer on the interfaphase surface with epoxy polymer, its participation in the thermodestruction processes of epoxy matrix and the concentration interval of the subsystem's influence on the thermal destruction of the polymer matrix are investigated. For such purpose, epoxy resin composites with oxidized and non-oxidized graphene nanoparticles have been used.The particles were obtained by electrochemical method and those are characterized by the same dispersion and analogical of defect spectra. The particles have the same crystal structure, however in composites with oxidized graphene, the participation of the electronic subsystem in thermophysical processes on the interfacial surface is blocked by the atomic layer of adsorbed oxygen. Сomposites of epoxy resin filled with the same particles of nonoxidized and oxidized nanoparticles in the filler content 0.0, 1.0, 2.0, and 5.0 wt%. The multilayered graphene particles were studied by X-ray diffraction analysis (XRD) and Raman spectroscopy (RS) methods. It was shown that the graphene particles are the 2D dimensional structures with about of 100 layers. Desorption curves of epoxy and its composites have been obtained using a programmable thermal desorption mass-spectroscopic (TDMS) technique for fragments with 15≤&nbsp;m/z&nbsp;≤108 and temperature interval 35 - 800 оС. The activation energy of desorption was determined from the Wigner-Polanyi equation as 35 - 150 kJ/mol, temperature and mass dependences of the quantity of desorbed atomic fragments have been calculated. It were established the graphene electron subsystem takes part in polymer structure thermodestruction for epoxy composites with nonoxidized graphene enhancing their heat resistance at graphene content С ≤ 1 wt%. With increasing filler content, the thermodestruction behavior in pristine epoxy and its composites with nonoxidized and oxidized graphene is analogical. The thermodestruction characterizes by the stepwise variations in the desorption intensity of atomic fragments. The electron subsystem of graphene particles does not participate in the heat resistance variations. У роботі досліджена участь електронної підсистеми графенових наночастинок в теплопереносі на міжфазній поверхні з епоксидним полімером, її участь у процесах термічної деструкції епоксидної матриці та концентраційний інтервал впливу підсистеми графену на терморуйнування полімерної матриці. Для цього використано композити епоксидної смоли з частинками окисненого на неокисненого графену, які отримані електрохімічним методом. Частинки характеризуються однаковою дисперсією та аналогічними спектрами дефектів. Частинки мають однакову кристалічну структуру, але відрізняються тим, що в композитах з окисненим графеном участь електронної підсистеми у теплофізичних процесах на міжфазній поверхні блокована атомарним шаром адсорбованого кисню. Досліджено композити епоксидної смоли, наповнені однаковими наночастинками неокисненого і окисненого графену в інтервалі наповнень 0.0, 1.0, 2.0, і 5.0 мас%. Частинки багатошарового графену характеризувалися методами рентгентгено-структурного аналізу (РСА) і Рамінівської спектроскопії (СКР) як двомірні структури з числом шарів близько 100. Десорбційні криві епоксидної смоли і композитів отримано за результатами досліджень методом термопрограмованої десорбційної мас-спектроскопії (ТПДМС) фрагментів з 15&nbsp;≤&nbsp;m/z&nbsp;≤108 в інтервалі температур 35-800 °С. Визначено енергію активації деструкції атомних фрагментів 35-150 кДж/моль і отримано температурні і масові залежності десорбції атомних фрагментів. Встановлено, що в композитах з неокисненим графеном при наповненні С&nbsp;≤&nbsp;1&nbsp;мас% електронна підсистема частинок графену бере участь в термодеструкції, підвищуючи термостійкість композитів. При збільшенні наповнення поведінка термодеструкції в ненаповненій смолі і її композитах з неокисненим і окисненим графеном аналогічна і характеризується немонотонною зміною інтенсивності термічної деструкції атомних фрагментів. Проведено аналіз теплових процесів на міжфазній границі композитів епоксидної смоли з багатошаровим графеном. Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2021-11-28 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/731 10.15407/Surface.2021.13.166 Surface; No. 13(28) (2021): Surface; 166-174 Поверхность; № 13(28) (2021): Поверхня; 166-174 Поверхня; № 13(28) (2021): Поверхня; 166-174 3154-8091 3154-8083 10.15407/Surface.2021.13 en https://surfacezbir.com.ua/index.php/surface/article/view/731/728 Авторське право (c) 2021 Н. В. Сігарьова, Б. М. Горєлов, С. В. Шульга |
| spellingShingle | епоксидний композит неокиснений та окиснений графен термічна стійкість фрагмент деструкції Сігарьова, Н. В. Горєлов, Б. М. Шульга, С. В. Вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| title | Вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| title_alt | Еffect of graphene filler oxidation on the thermal destruction of epoxy-graphene composites |
| title_full | Вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| title_fullStr | Вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| title_full_unstemmed | Вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| title_short | Вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| title_sort | вплив окиснення графену на термічну деструкцію епокси-графенових композитів |
| topic | епоксидний композит неокиснений та окиснений графен термічна стійкість фрагмент деструкції |
| topic_facet | epoxy composite unoxidized and oxidized graphene thermal stability fragment of destruction епоксидний композит неокиснений та окиснений графен термічна стійкість фрагмент деструкції |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/731 |
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