Polymer 235 (2021) 124243

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Self-assembly behavior of ultra-high molecular weight in-situ anionically

synthesized polymer matrix composite materials “grafted from” single- or
multi-wall CNTs
Evangelos Kasapis a, Konstantina Tsitoni a, Gkreti-Maria Manesi a, Ioannis Moutsios a,
Dimitrios Moschovas a, b, Dmitry V. Vashurkin b, c, Denis S. Kotlyarskiy b, c, Dimitri A. Ivanov b, c, d,
Apostolos Avgeropoulos a, b, *
a
Department of Materials Science Engineering, University of Ioannina, University Campus-Dourouti, 45110, Ioannina, Greece
b
Faculty of Chemistry, Lomonosov Moscow State University (MSU), GSP-1, 1-3 Leninskiye Gory, 119991, Moscow, Russia
c
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432, Moscow, Russia
d
Institut de Sciences des Matériaux de Mulhouse – IS2M, CNRS UMR7361, 15 Jean Starcky, Mulhouse, 68057, France

A R T I C L E I N F O A B S T R A C T

Keywords: A pioneering synthetic approach for the design of novel composite materials is reported. The final products are
Nanocomposites consisting of high number average molecular weight diblock copolymers which are surface initiated (“grafting
SWCNTs & MWCNTs from” approach) from either single or multi-wall carbon nanotubes (SWCNTs or MWCNTs respectively). In-situ
in-situ anionic polymerization
anionic polymerization results in nanocomposites, exhibiting narrow dispersity indices which are in accordance
“Grafting from”
HR-TEM
with anionic polymerization standards, able to self-assemble when studied in bulk. The polymer matrices are
Raman spectroscopy diblock copolymers of the PS-b-PI type [PS: polystyrene and PI: poly(isoprene)]. The successful “grafting from” the
XPS corresponding CNTs is verified by Raman and Х-Ray Photoelectron spectroscopy, while the structure/properties
relationship of the composites is determined employing High Resolution Transmission Electron Microscopy (HR-
TEM). HR-TEM characterization is very important for the successful identification of the MWCNTs as well as for
the justified conformation of the polymeric chains grafted from the CNTs.

1. Introduction
Carbon nanotubes (CNTs) such as single (SWCNTs), double
(DWCNTs) or multi wall (MWCNTs) are considered as promising
nanofiller materials due to their inherent physical [1–3], mechanical
[4], electrical [4–7] and optical [8–11] properties derived from their
coaxially assembled layers of graphene sheets, bearing sp2 hybridiza­
tion. The specific carbon atoms conformation results in relatively high
electric and thermal conductance [7,12,13], low density [14,15], high
mechanical tensile strength [16–18], high tip surface area [19–21], high
chemical stability [22,23], selective absorption [24,25] and photo­
luminescence [26–28]. Despite their potential in various fields, the
insolubility of CNTs in any organic or inorganic solvents, due to the
overspread van der Waals interactions on their sidewalls, renders their
use rather challenging. To overcome this major drawback, but simul­
taneously exploit the aforementioned benefits, nanoscale composite
materials consisted of polymer/CNTs [29–31], have attracted great
scientific and industrial interest due to their improved properties [32].
In order to exploit the exceptional stiffness, strength and resilience of
CNTs, strong interfacial bonding is critical [33,34]. However, the fact
that the scale of the reinforcement phase is in nanometers, instead of
micrometers, poses several challenges. To optimize this property cova­
lent attachment is preferred over non-covalent attachment due to the
more stable character of covalent bonding [34]. It has been established
that the binding energies and frictional forces are critical in determining
the strength of the interface, whereas adopting a helical conformation of
the polymer around the nanotube was found to hold a key role [35].
Block copolymers (BCPs) properties can be severely enhanced by
adding CNTs even in low concentration levels concluding to immediate
improvement in the materials characteristics as well as ordered two- and
three-dimensional structures can be obtained [36,37]. BCPs exhibiting
low dispersity indices, high Flory-Huggins interaction parameter χ and
specific molecular characteristics are able to self-assemble in various
nanostructures. The self-assembly behavior of polymer-based

* Corresponding author. Department of Materials Science Engineering, University of Ioannina, University Campus-Dourouti, 45110, Ioannina, Greece.
E-mail address: aavger@uoi.gr (A. Avgeropoulos).

https://doi.org/10.1016/j.polymer.2021.124243
Received 2 July 2021; Received in revised form 17 September 2021; Accepted 2 October 2021
Available online 8 October 2021
0032-3861/© 2021 Elsevier Ltd. All rights reserved.
E. Kasapis et al.
nanocomposites constitutes an important scientific field in order to
determine the impact on the adopted morphology after the preparation
of polymer/CNTs composites using “grafting from” and/or “grafting to”
methods [38–44].
A crucial parameter such as the processing of polymer/CNTs nano­
composites, strongly affects the dispersion and the loading percentage of
the nanotubes in the polymeric matrix.
Two general categories of combining CNTs and polymers, namely
blending and in-situ polymerization have been utilized leading to com­
posites with different properties [45].
Although the blending method has been extensively utilized, the
instinctive agglomeration of the CNTs [46] necessitates the use of
ultrasonication in order to achieve homogeneous dispersion in the
polymeric matrix, resulting in reduced CNTs length scale. High nano­
tube loading and good miscibility can be achieved using in-situ poly­
merization techniques where BCPs can be covalently and non-covalently
“grafted to” or “grafted from” CNTs’ walls [45].
Controlled radical polymerization techniques [47–50] have been
widely employed for the preparation of nanocomposites, due to the
facile synthesis of multiple segments exhibiting different properties. The
lack of absolute control over the molecular characteristics of the grafted
polymer constitutes a drawback of the specific polymerization tech­
niques. On the other hand, anionic polymerization and especially
“grafting to” method provides control on the total number average mo­
lecular weight and molecular weight distributions. The “grafting from”
method has been proven to be quite challenging, especially when
anionic polymerization is conducted, due to the exploitation of orga­
nolithium initiators [51] that are susceptible to any volatile compounds
resulting in decreased polymerization control.
The main purpose of this research work was to synthesize composite
materials constituted by well-dispersed SWCNTs or MWCNTs in diblock
copolymers in order to study the effect of the CNTs presence in the
polymeric matrices on the self-assembled morphologies. We report the
synthesis of nanocomposites via in-situ anionic polymerization consist­
ing of linear diblock copolymers of polystyrene-b-poly(isoprene) or (PS-
b-PI) type, “grafted from” either SWCNTs or MWCNTs. To the best of our
knowledge it is the first time that such an approach has been applied for
the preparation of the specific nanocomposites.
All samples were characterized through size exclusion chromatog­
raphy (SEC) in order to verify the successful polymerization using the
“grafting from” method as well as to calculate the total number average
molecular weights and dispersity indices. Raman spectroscopy was
employed in order to determine the electron and phonon properties, the
chirality and also to estimate the CNTs’ purity level. X-Ray photoelec­
tron spectroscopy (XPS) measurements were carried out in order to
verify the successful diblock copolymers “grafting from” the CNTs
through the estimation of sp2 and sp3 hybridisms as well as the
conformation of polymeric chains within the CNTs. High resolution
transmission electron microscopy (HR-TEM) studies were performed in
order to determine the ability of the final composite materials to self-
assemble in well-ordered nanodomains, to determine the MWCNTs
sidewalls number and verify the configuration of the macromolecular
chains “grafted from” the graphitic lattices.
2. Experimental section
Monomers (styrene, isoprene), initiator (sec-BuLi) and solvents
(cyclohexane and methanol) were purchased from Sigma-Aldrich and
purified in accordance with the anionic polymerization standards [52].
SWCNTs (average diameter 1.1 nm; length >5 μm) were purchased from
Carbon Nanotechnologies Incorporating (CNI) and were prepared using
the HiPCO method (High Pressure disproportionation of CO), while the
MWCNTs were developed using the CCVD (Catalytic Chemical Vapor
Deposition) method and were supplied by ARKEMA (graphistrength
C100).
The molecular characterization was realized through SEC,
2
Polymer 235 (2021) 124243
employing a PL-GPC 50 Integrated GPC System from Agilent Technol­
ogies and was calibrated with ten PS standards Mp: 1.360 kg/mol to
2000 kg/mol.
Raman spectroscopy studies were accomplished via a micro-Raman
RM 1000 Renishaw system. The power of the laser was 30 mW and a
2 μm focus spot was used.
XPS or electron spectroscopy for chemical analysis (ESCA) was
accomplished using a monochromatic Al Kα X-ray source of 1486 keV
and a Scienta R4000 hemispherical electron analyzer. For the analysis
and deconvolution of the spectra, WinSpec Version 2.09 software was
used.
HR-TEM was conducted with a JEOL 2100 TEM using 200 KeV as the
acceleration voltage. The casted films were cryo-ultramicrotomed in
order to receive ultra-thin sections (~40 nm) in a Leica EM UC7 cryo-
ultramicrotome below the lowest Tg of both segments (− 100 ◦ C) and
the sections were picked up on a loop loaded with an aqueous sucrose
solution and were placed on 600 mesh copper grids for immediate
observation.
Appropriate amount of CNTs’ powder (SWCNTs and MWCNTs) was
placed in a glass apparatus and heated at 200 ◦ C in an oil bath for
approximately 12 h under high vacuum conditions, resulting in the
thermal oxidation of carbon and/or catalytic residues derived from the
different preparation methods (HiPCO and CCVD) and to ensure the
absence of any traces of humidity that would deactivate the living ends
during the polymerization reaction. Approximately 10 ml of purified
cyclohexane were distilled, the mixture was degassed and the apparatus
was removed from the vacuum line after sealing-off.
All composites were synthesized using in-situ anionic sequential
polymerization, utilizing a novel technique [51] in which the initiator
(sec-BuLi) is covalently bound on sidewall defects of the CNTs, pro­
ducing a macroinitiator capable of initiating the polymerization of sty­
rene. It must be mentioned here that both unbound sec-BuLi and the
nanotube carbanions initiate polymerization. The purified CNTs (5 mg),
as mentioned above, had not undergone any further chemical func­
tionalization or modification and the apparatus (cyclohexane + CNTs)
was placed in a sonicator at 25 ◦ C for 2 h resulting in well-dispersed
CNTs bearing higher number of defects. sec-BuLi (0.025 mmol) was
then introduced to the glass apparatus and sonicated for approximately
1 h leading to its covalent addition to the defects of the CNTs walls due
to nucleophilic addition to the sp2 bonds. Appropriate amount of styrene
(5 g, 0.048 mol) was added to the apparatus and left to react for 3 h
employing similar conditions. Finally, isoprene (5 g, 0.07 mol) was
added to the solution and the grafting of the final diblock copolymer
from the CNTs sidewalls was terminated after 8 h in 50 ◦ C.
Based on an already established method [51] in the literature the
SWCNTs-g-PS-b-PI and MWCNTs-g-PS-b-PI were isolated from the pure
copolymer matrix by employing repeating washing cycles with toluene
and vacuum filtration through a 0.2 m Teflon membrane. The final
grafted-copolymer was dried in a vacuum oven and subsequently the
pristine SWNTs and MWNTs loading was estimated approximately to be
equal to 0.05 wt % for all samples.
It should be mentioned that the control over the in-situ anionic
polymerization kinetics utilizing CNTs’ macroinitiators is rather chal­
lenging and meticulous manipulation of all reagents is of paramount
importance. SEC was employed for the determination of the successful
synthesis as well as the total number average molecular weights and
dispersity of the final nanocomposites. Aliquots were taken after
completion of polymerization of styrene in order to estimate the mo­
lecular characteristics of the PS blocks for all composites.
3. Results and discussion
Despite the sensitivity of living anionic sites, the final materials
exhibited molecular and compositional homogeneity as indicated by the
obtained narrow dispersity (below 1.1). The synthesis procedure of the
diblock copolymer is given in detail elsewhere [53]. In Fig. 1 the
E. Kasapis et al.
Fig. 1. SEC chromatographs of all final synthesized composite materials corresponding to (as graphs are shown from bottom to top): SWCNTs-g-PS-b-PI_1 (purple
color), SWCNTs-g-PS-b-PI_2 (red color), MWCNTs-g-PS-b-PI_3 (blue color) and MWCNTs-g-PS-b-PI_4 (black color). (For interpretation of the references to color in this
figure legend, the reader is referred to the Web version of this article.)
chromatographs of all synthesized composite materials are presented
and their total number average molecular weights
total
(Mn )
were ranging
from 275 kg/mol to 400 kg/mol as evident in Table 1.
The quality, diameter distribution and purity of the CNTs as well as
the sidewall functionalization degree and the successful grafting can be
validated utilizing Raman spectroscopy [36]. The extensive use of the
aforementioned technique has led to well-established assignment of the
Raman bands which enables the accurate interpretation of the acquired
data. In all cases, pure CNTs alongside with the final nanocomposite
materials spectra are given for comparison reasons as well as for further
verification of the successful synthesis.
As far as pure SWCNTs spectra (Fig. 2a and b corresponding to the
black colored curves) are concerned, the ID/IG ratio was calculated equal
to 0.85 that indicated the existence of structural defects in the graphitic
lattice and therefore the CNTs ability to make covalent bonds. Specif­
ically, at ~1350 cm− 1 the D band, attributed to the overall structural
defects on the SWCNTs sidewalls was evident, while at ~1592 cm− 1 the
G band, indicating the permitted phononic transmittance derived from
sp2 carbon hybridisms was also verified. Furthermore, the nanotubes
diameter could be calculated through the observed peak at ~210 cm− 1,
that emerged due to the radial breathing mode [51] but due to bending
modes of the PS in the same area the results are not trustworthy.
The red colored curve in Fig. 2a corresponds to the final nano­
composite of the SWCNTs-g-PS-b-PI_1 type where the peak emerging at
~1033 cm− 1 is attributed to in plane distortion of monosubstituted
benzene rings, while the vibrations at ~1157 cm− 1 are attributed to the
double carbon-carbon bond of the monosubstituted benzene rings. In
Table 1
Molecular characterization results as calculated directly from SEC (the PS con­
tent or weight fraction was calculated based on the initial aliquot taken prior to
the addition of the second monomer quantity).
sample Mn
total
(kg/mol) Đtotal
SWCNTs-g-PS-b-PI_1 275 1.07
SWCNTs-g-PS-b-PI_2 340 1.08
MWCNTs-g-PS-b-PI_3 350 1.08
MWCNTs-g-PS-b-PI_4 400 1.09
Polymer 235 (2021) 124243
addition, the observed peak at ~1186 cm− 1 is correlated to rocking and
twisting vibrations, while the peaks at ~1206 cm− 1 and ~1450 cm− 1 are
attributed to the vibrations of the aromatic rings of the polystyrene
monomeric units and to –CH3 deformations due to the PI blocks
respectively. Finally, at ~1667 cm− 1 stretching vibrations of the PI1,4
segments double bonds could be observed. D and G bands were shifted at
~1328 cm− 1 and ~1603 cm− 1 respectively, indicating an alternation of
the CNTs electron configuration, attributed to the existence of sp3 bonds
of the graphitic structures and the organolithium initiator.
Accordingly, for the second sample of the SWCNTs-g-PS-b-PI_2 type
(Fig. 2b, red colored curve), the ID/IG ratio was altered (1331 and 1602
cm− 1 respectively) further confirming the successful grafting of the
diblock copolymer from the SWCNT macroinitiator.
MWCNTs Raman spectra are illustrated in Fig. 2c and d (black
colored curves) and the existence of defects on the graphitic lattice lead
to relative D to G band intensity equal to 0.85 as expected. In the spectra
of nanocomposites consisting of the diblock copolymers grafted from
MWCNTs, coherent structural vibrations to the already described
SWCNTs are exhibited. In both final materials of the MWCNTs-g-PS-b-
PI_3 and MWCNTs-g-PS-b-PI_4 type, only trivial differentiations can be
identified regarding the ID/IG ratio but the appearance of the MWCNTs
characteristic peaks verify the successful synthesis of the final nano­
composite materials.
XPS was applied in order to determine the surface stoichiometry and
the nature of the bonds formed by the surface atoms of the hybrid ma­
terials. All spectra of the polymer/CNTs nanocomposites are focused on
the C1s region, fitting by a Shirley background, due to the sensitivity of
the samples and the need for identification of the different nature of the
surface atoms with high content on sp2 and/or sp3 hybridism. Regarding
the SWCNTs-g-PS-b-PI_1, SWCNTs-g-PS-b-PI_2 samples, presented in
Fig. 3a and b, the highest peak at ~282 eV corresponds to the sp2 car­
bons (C– – C bond), while for samples of the MWCNTs-g-PS-b-PI_3 and
MWCNTs-g-PS-b-PI_4 type, as shown in Fig. 3c and d, the peak attributed
fPS to the sp2 carbons is depicted at ~284 eV. In all samples, broad peak
0.54
distributions can be observed, attributed probably to the inadequate
0.69 charge compensation [54], resulting in a non-uniform charging poten­
0.52 tial across the sample surface. It should be mentioned that, potential
0.52 fluctuation abnormalities are frequently encountered on
3
E. Kasapis et al. Polymer 235 (2021) 124243

Fig. 2. Raman spectra of all final synthesized composite materials (red color or upper spectra) in comparison with the respective CNTs (SWCNTS or MWCNTs
respectively, black color or lower spectra): (a) SWCNTs-g-PS-b-PI_1 (red color) and neat SWCNTs (black color), (b) SWCNTs-g-PS-b-PI_2 (red color) and neat SWCNTs
(black color), (c) MWCNTs-g-PS-b-PI_3 (red color) and neat MWCNTs (black color) and (d) MWCNTs-g-PS-b-PI_4 (red color) and neat MWCNTs (black color). (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

polymeric/CNTs materials due to the existence of conductive CNT re­
gions and non-conductive polymeric segments. In all spectra the for­
mation of a satellite peak at the region of 288–290 eV is attributed to a
shake-up process involving the energy of the π⇒π* transition of the
aromatic ring electrons. In Fig. 3b designated to the SWCNTs-g-PS-b-PI_2
sample, where the PS content equals to 69%, small shake-up peaks
around 4–6 eV above the main carbon peak are possibly assigned to the
high content of aromatic groups in the polystyrene segments [54]. In
Fig. 3b–d, the wide mixed Gaussian/Lorentzian [55] asymmetrical tail
and the slightly shifted sp2 carbon peaks, towards higher binding en­
ergies, suggested the lower concentration on sp2, further verifying the
higher grafting content of polymeric chains from the CNTs, while in
Fig. 3a the narrow Gaussian symmetric distribution indicated the lower
incorporation of SWCNTs.
The structure/properties relationship of the synthesized composite
materials, exploiting in-situ anionic polymerization, has not yet been
reported in the literature. The self-assembly behavior of the nano­
composite materials was studied through TEM, using 5% wt solution
casting in toluene for all synthesized nanocomposites (5–7 days), fol­
lowed by thermal annealing (48 h) well-above the glass transition
temperature of the PS segment and subsequently the samples were ultra-
cryomicrotomed in order to obtain thin (~50 nm) sections. Since both
blocks have similar electron densities, selective staining with aqueous
vapors of OsO4 4% was employed [56] for approximately 90 min for the
PI domains exclusively.
In Fig. 4a the final nanocomposite of the SWCNTs-g-PS-b-PI_1 type is
presented, exhibiting alternating lamellar morphology, where the white
domains correspond to the PS segments and the black regions to PI
blocks. Also, an incorporated SWCNT can be observed within the well-
organized alternating lamellar layers (clearly indicated in the image),
forming a local discontinuity on the adopted morphology (grey color)
possibly assigned to the direct attachment of the PS chains onto the
carbon nanotube sidewalls or one may suggest the observation of a grain
boundary defect between alternating lamellae orientation. The fact that
the specific “defect” is so rigid (which is extremely rare in grain
boundary defects of alternating lamellae as has been reported already in
the literature by Gido et al. [57]) it cannot be assigned as a grain
boundary. Furthermore, our assumption is well justified by the “blurry”
grey area surrounding the rigid line which may be attributed to the fact
that the copolymer is surrounding the CNT due to the covalent
attachment.
Regarding the SWCNTs-g-PS-b-PI_2 sample a different morphology
was obtained, namely hexagonally close packed cylinders where the
matrix corresponds to the white PS domains and the black to the PI
cylinders (Fig. 4b). In Fig. 4b a well-defined morphology of hexagonally
close packed PI dark cylinders in a white PS matrix is evident, without
identifying any SWCNT, while in Fig. 4c the presence of SWCNTs leads
to not periodic cylindrical domains. Randomly oriented exfoliated
bundles of SWCNTs are observed by indicating no specific orientation
(different angles, horizontal or vertical orientations are evident), and
cannot be assigned as grain boundaries, which can be attributed to the
“grafting from” approach used for the synthesis of the studied nano­
composites. Furthermore, it is also evident in Fig. 4c (as in Fig. 4a) that
within the close viscinity of the SWCNTs there is a slight “blurry” grey
area attributed to the copolymer. This fact strongly suggests the differ­
entiation on structure/properties relationship of these composite ma­
terials when compared to the regions constituted exclusively by the
pristine diblock copolymer domains (Fig. 4b vs. Fig. 4c).
In the case of nanocomposite materials consisted by diblock co­
polymers “grafted from” MWCNTs, namely the MWCNTs-g-PS-b-PI_3

4
E. Kasapis et al.
Fig. 3. XPS spectra of all final synthesized composite materials corresponding to: (a) SWCNTs-g-PS-b-PI_1, (b) SWCNTs-g-PS-b-PI_2, (c) MWCNTs-g-PS-b-PI_3 and (d)
MWCNTs-g-PS-b-PI_4.
type nanocomposites, lamellar morphology was obtained, as depicted in
Fig. 4d, where white PS and black PI domains can be clearly observed
along with a dark region attributed to a single MWCNT arranged
vertically to the obtained lamellar sheets. In Fig. 4e the presence of
various MWCNTs is evident in both vertical and perpendicular orien­
tations, although horizontal alignment induces discontinuity on the
obtained morphology, further confirming the inability of the composite
to microphase separate in the vicinity of MWCNTs. Specifically, as
evident in Fig. 4e, white PS and dark PI layers are observed, together
with MWCNTs either vertically or horizontally aligned.
Furthermore, the HR-TEM studies on the hybrid material of the
MWCNTs-g-PS-b-PI_4 type revealed again, as in the previous sample,
alternating lamellae where the white domains are attributed to the PS
segments and the black correspond to the PI domains (Fig. 4f). In
addition, a vertically oriented MWCNT is observed in dark color with an
estimated diameter of approximately 20 nm.
5
Polymer 235 (2021) 124243
Finally, HR-TEM experiments were also conducted exclusively on the
pristine MWCNTs in order to verify the excessive number of the side­
walls as described by the purchasing Company. The number of the
sidewalls could be estimated, resulting in approximately 15 distinct
consecutive sidewalls (Fig. 4g).
4. Conclusion
In this study we report the synthesis of composite materials
comprising of high molecular weight diblock copolymers of the PS-b-PI
type “grafted from” SWCNTs or MWCNTs, employing in-situ anionic
sequential polymerization under high vacuum using purified reagents.
The specific technique has not yet been utilized for copolymers, due to
the sensitivity of the living anionic sites, however the adopted synthetic
route showcased promising results. In order to determine the molecular
characteristics as well as the successful synthesis, all samples were
E. Kasapis et al.
Fig. 4. Bright-field HR-TEM images of all samples casted in toluene after thermal annealing at 130 ◦ C/2 days followed by cryo-ultramicrotoming and staining of the
PI domains with vapors of OsO4 for approximately 90 min corresponding to the composite materials of the: (a) SWCNTs-g-PS-b-PI_1 type, (b)–(c) SWCNTs-g-PS-b-PI_2
type, (d)–(e) MWCNTs-g-PS-b-PI_3 type, (f) MWCNTs-g-PS-b-PI_4 type. (g) Bright-field HR-TEM image of pristine MWCNTs.
characterized through SEC, while Raman spectroscopy was conducted
for the validation of the successful grafting of the diblock copolymers
from the relative CNTs. Furthermore, XPS studies were performed in
order to identify the bonds nature formed by the surface atoms of the
composite materials. The structure/properties relationship of such ma­
terials synthesized exclusively via in-situ anionic polymerization has not
been yet studied, to the best of our knowledge, leading to different
properties when studied in bulk. The presence of SWCNTs in the ob­
tained morphology resulted in less organized areas or induced local
disorientation, while MWCNTs led to domains predominately lacking
periodicity. The number of sidewalls evident on MWCNTs could also be
calculated from the HR-TEM images and the self-assembly behavior of
the diblock copolymers could be observed in conjunction either with the
SWCNTs or the MWCNTs respectively.
CRediT authorship contribution statement
Evangelos Kasapis: Methodology, Conceptualization, Validation,
Formal analysis, Investigation, Resources, Data curation, Writing –
original draft, Writing – review & editing, Visualization. Konstantina
Tsitoni: Validation, Formal analysis, Data curation, Writing – review &
editing. Gkreti-Maria Manesi: Validation, Formal analysis, Data cura­
tion, Writing – review & editing. Ioannis Moutsios: Validation, Formal
analysis, Data curation, Writing – review & editing. Dimitrios
Moschovas: Validation, Formal analysis, Data curation, Writing – re­
view & editing. Dmitry V. Vashurkin: Validation, Formal analysis,
Writing – review & editing. Denis S. Kotlyarskiy: Validation, Formal
analysis, Writing – review & editing. Dimitri A. Ivanov: Validation,
Formal analysis, Writing – review & editing, Supervision, Project
administration. Apostolos Avgeropoulos: Methodology, Conceptuali­
zation, Validation, Formal analysis, Investigation, Resources, Writing –
original draft, Writing – review & editing, Visualization, Supervision,
Project administration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
6
Polymer 235 (2021) 124243
the work reported in this paper.
Acknowledgements
E.K., K.T., G.-M.M., I.M., D.M. and A.A. would like to acknowledge
the Network of Research Supporting Laboratories at the University of
Ioannina for using the Electron Microscopy Facility. D.V.V., D.S.K., D.A.
I. and A.A. acknowledge financial support from the Ministry of Science
and Higher Education of the Russian Federation within State Contract
075-15-2019-1889.
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