Nanocarbon in microwaves: electromagnetic properties and applications P'P' Kuzhir, S'A' Maksimenko,

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Nanocarbon in microwaves electromagnetic
properties and applicationsP.P. Kuzhir, S.A.
Maksimenko, Institute for Nuclear Problem of
Belarus State University, Belarus V.L.
Kuznetsov, I. Mazov, S.I. Moseenkov Boreskov
Institute of Catalysis SB RAS, Russia A.
Romanenko, Institute of Inorganic Chemistry SB
RAS O. Shenderova International Technology
Center, USA Ph. LambinFUNDP University of
Namur, Belgium
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Motivation

• Design of wide-band electromagnetic coatings with
  controlled properties.
• New materials with high shielding effectiveness
  and suitable mechanical and physical-chemical
  properties (weight, corrosive resistance,
  mechanical properties, etc) can significantly
  increase Electromagnetic compatibility prevent
  unauthorized access to information networks
  reduce impact on electronic devices from EM pulse
  attack reduce parasitic radiation from
  junctions, trailers, transmission lines improve
  technical characteristics of microwave elements,
  circuits and devices.

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CARBON NANOTUBE
(m-n)3 metal CNT armchair CNT (n,n) Zigzag
CNT (n,0)
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• Nano-sized inhomogeneities of different nature
  and geometry in dielectric media
• These dimensions are about one or two orders of
  magnitude bigger than the characteristic
  interatomic distance, so that spatial confinement
  of charge carriers is fully developed, thereby
  providing a discrete spectrum of energy states in
  one or several directions.

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• ballisticity of the electron motion over a
  typical CNT length, and
• extremely high electron current density reachable
  in CNTs.
• a strong slowing down of surface electromagnetic
  waves (low frequency plasmon-polariton modes)

G.Ya. Slepyan, S.A. Maksimenko, A. Lakhtakia,
O.M. Yevtushenko, and A.V. Gusakov,
Electrodynamics of carbon nanotubes Dynamic
conductivity, impedance boundary conditions and
surface wave propagation, Phys. Rev. B 60,
17136-17149 (1999).

• CARBON NANOTUBE in the THz range
• Electromagnetic slow-wave line vph/c0.02
• Dispersionless surface wave nanowaveguide
• Monomolecular traveling wave tube
• Terahertz nanoantenna

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Geometrical resonances
Clearly, although the cross-sectional radius is
electrically small, the length is electrically
large - conditions that are characteristic of
wire antennas Thus, an isolated CNT is a wire
nano-antenna
Slowing-down
Geometrical resonances are shifted from the
optics to IR and GHz range
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THz spectral range
A strong slowing down of surface electromagnetic
waves (low frequency plasmon-polariton modes)
Finite length effect in CNT nanoantenna
Comparison between experimentally observed
normalized absorbance of a CNT film 4, and
calculated normalized absorption cross-section
of CNT bundle. The 1.2 µm length CNT bundle
consists of three zigzag tubes with chiral
vectors (13,0), (12,0) and (11,0), respectively.
(a) t 2.210-14 s, (b) t 1 10-13 s M.
Shuba, et al., arXiv0806.2954v1
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MWCNT powders

SEM micrographs of purified carbon nanotubes. A)
large agglomerates of tangled nanotubes, B)
internal structure of nanotube agglomerate.
TEM images of MWCNT produced with Fe-Co
catalysts. ?) low magnification general view,
B) low defect MWCNT, C) Fe-Co particle
inside MWCNT, D) Fe-Co particle on the MWCNT
tip.
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Methodology of MWCNT/PMMA fabrication
MWNCT/PMMA composites were prepared via
coagulation technique.
Optical micrographs of MWCNT/PMMA composite
powder with 1 wt. MWCNT content 140 (A), 630
(B) (molten powder). MWCNT agglomerates in molten
PMMA particles are shown by arrows.
SEM micrographs of MWCNT/PMMA composite powders
with MWCNT content (by weight) 0.1 (A), 0.5 (B),
1.0 (C), and 10 wt. (D). Arrows on figures A-C
show individual nanotubes in the bulk volume of
polymer matrix. Inset on figure A shows small
agglomerated particles of polymer matrix. Each
scale bar corresponds to 1 ?m.
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Methodology of MWCNT/PMMA fabrication

• The dispersion state of MWCNT in polymer matrix
  changes with increasing content of nanotubes.
• Only single isolated MWCNT are observed in the
  polymer body for composites with low
  concentration of MWCNT (0.1wt., 0.25 wt., 0.5
  wt.).
• Formation of nanotube straps in polymer matrix
  was observed for composites with medium content
  of MWCNT, for samples with 1.0 wt., 1.85 wt. of
  MWCNT.
• Increasing MWCNT loading up to 4.85 . leads to
  formation of the uniformly dispersed network of
  nanotubes in PMMA matrix.

SEM micrographs of MWCNT/PMMA composite films
with MWCNT content 0.25 (A), 0.5 (B), 1
(C), and 4.85 (D). Individual nanotubes on
figures A and B are indicated by arrows. Each
scale bar corresponds to 1 ?m.
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Electrical conductivity on MWCNT
The conductivity of initial MWCNT samples and
MWCNT/PMMA composites was measured using
four-point probe technique.
Dependence of electrical conductivity on MWCNT
loading in MWCNT/PMMA composites prepared via
coagulation technique

• The maximal value of electrical conductivity was
  observed for 4.85 wt. MWCNT loading.
• The significant increase of conductivity for
  MWCNT content changing from 0.5 to 1 wt.
  indicates a percolation threshold lower than
  1 wt..
• The reason is reaching the maximal number of
  electrical contacts between individual nanotubes,
  i.e. formation of the saturated conductive
  network in the bulk volume of the polymer
  matrix.

The percolation threshold was found to be approx
5wt for MWNT/PMMA composites, prepared via
liquid cast technique 1. 1 Slobodian P,
Lengálová A, Sáha P and Slouf M 2007 J. Reinf.
Plast. Compos. 26 1705-12
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Low-frequency analysis
J. Macutkevic, G. Valusis, P. Kuzhir et al,
Phys. Stat. Sol. C, accepted for publication
A) Low frequency conductivity spectra of
MWCNT/PMMA composites B) frequency dependence
of the dielectric permittivity of MWCNT/PMMA
composites.

• The composites show extremely high conductivity
  for 0.5 wt MWCNT content which is determined as
  percolation threshold.
• The increase of MWCNT loading leads to the
  drastic change in ? for composites which is
  changed from ca. 3-5 for 0.25 wt. to 10-100 for
  0.5-1.0 wt. of nanocarbon and even up to 106
  for higher loadings of MWCNT.
• This phenomenon can be attributed to the
  formation of the 3Dquasi-ordered structure of
  carbon nanotubes in the bulk volume of the
  polymer matrix.

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Microwave probing of MWCNT powders
Multi-Wall Carbon Nanotubes in Microwaves,  pp.
92-94, S. Moseenkov, V. Kuznetsov, P. Kuzhir et
al, Best Paper for the 1st WSEAS Int. Conf. on
NANOTECHNOLOGY

• EM response of MWCNT powders is found to be not
  very sensitive to the mean diameter of MWCNT, but
  dependent strongly on the purification degree and
  the metal content in MWCNT in 26-37GHz frequency
  range.
• The increase of the metal concentration leads to
  the decrease of the EM attenuation ability of the
  nanocarbon fillers.
• All well-purified samples demonstrate high level
  of EM aattenuation in Ka-band.
• MWCNT is found to be perspective candidate for
  applications in the microwave frequency range due
  to their high attenuation ability along with the
  low percolation threshold.

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Microwave probing of MWCNT/PMMA composites
Well-purified MWCNT with 24 nm mean outer
diameter were used for MW analysis.

• Strong correlation between EM transmission/reflect
  ance and electrical conductivity vs MWCNT content
  has been observed.

• The main reason of EM attenuation provided by
  MWCNT/PMMA composites is due to EM reflection,
  which is related to the conductive properties of
  the nanocarbon material.
• The increase of electrical conductivity with
  increase of MWCNT loading leads to simultaneous
  growth of reflection ability.
• Strong influence of absorbance mechanism (more
  than 30 of total incident EM power) on the
  shielding effectiveness of the composite
  materials takes place.
• The drastic change of the EM response takes place
  for the concentrations of MWCNT fillers lower
  than 1 wt.. Does it indicate the percolation
  nature of the microwaves interaction with
  MWCNT/PMMA composites?

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Theoretical predictions for THz spectral range

• Attenuation of EM radiation may be caused by
• complex impedance of carbon nanomaterials 1
• excitation of mechanical oscillation at
  eigenfrequency 2,3
• (iii) manifestation of far replica of antenna
  properties of MWCNTs in THz frequency range.

• A. Velez, J. Bonache, F. Martin, Proceedings of
  Metamaterials 2007 - Rome 22-24 October 2007,
  Editors F. Bilotti and L. Vegni - University
  "Roma Tre", Rome, Italy, 2007, p.53
• V. Sazonova, Yu. Yaish, H. Ustunel, D. Roundy,
  T.A. Arias, P.L. McEuen, Nature, 431, 2004, p.
  284.
• Poncharal, Z.L. Wang, D. Ugarte, W.A. de Heer,
  Science, 283, 1999, p.1513.

The experimentally observed 1-5 non-monotonic
frequency dependence of the reflectance and
transmittance of CNT-based composites in the
range 1-100 THz can be interpreted as
inhomogeneously broadened geometric
resonances. 1 Bommeli F., et al. Synt. Met.
86, 2307 (1997). 2 Ugawa A. et al. PRB 60,
R11305 (1999). 3 T.-I. Jeon, et. al. APL 80,
3403 (2002). 4 H. Hu, et. al. J. Am. Chem. Soc.
125, 14893 (2003) 5 C. Kang, et. al. Phys. Rev.
B. 75, 085410 (2007)
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Theoretical predictions for GHz spectral range
EM absorbance
EM transmision / reflection
MWCNT concentration, wt.
MWCNT concentration, wt.
Attenuation of EM radiation is caused mostly by
manifestation of antenna properties of MWCNTs in
GHz frequency range
Submitted to J Appl Phys
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Conclusions

• We found extremely low percolation threshold for
  MWCNT/PMMA pomposited prepared via coagulation
  technique.
• The study of EM response of MWCNT/PMMA composites
  in Ka-band demonstrates their high shielding
  effectiveness.
• The contributions of reflection and absorption
  mechanisms to EMI attenuation close to the ratio
  21 was observed for the composites with MWCNT
  content higher than 1 wt..
• MWCNT/PMMA composites offer good shielding
  performances in the microwave frequency range
  with the very low concentrations of nanocarbon
  fillers that cannot be achieved by classical EM
  materials.

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Methodology of OLC fabrication
V.M. Titov, I.L. Malkov, V.L. Kuznetsov, A.L.
Chuvilin, Method of production of onion like
carbon, RUS.PAT. No. 209370 (priority of
19.10.1993) reg 27.10.1997 V.L. Kuznetsov et al,
Chem. Phys. Lett., 222, 343 (1994).

• Onion-like carbon is detonation nanodiamond (ND)
  - derived subclass of carbon nano-onions.
• Nanodiamond is synthesized at the high
  pressure-high temperature conditions within a
  shock wave during detonation of carbon-containing
  explosives with a negative oxygen balance.
• Annealing of the ND powder in vacuum at high
  temperature results in the production of carbon
  nanoparticles with OLC structure.

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Methodology

• Onions produced by ND annealing at the
  intermediate temperature (14001900 K) have holes
  in their internal shells.
• The origin of such defects can be explained in
  terms of a deficit of diamond carbon atoms in the
  diamond/graphite interface forming therefore
  fullerene-like shells during ND annealing.

Figure. Schematic representation of the structure
of the OLC enclosed graphite-like shells
containing sparse surface groups on OLC surface
and structural defects such as holes within sp2
shells and surface steps of the curved nonclosed
shells (a). Atomic models of the holes with
zigzag arrangements of the carbon atoms at the
edges (b) and surface steps of curved nonclosed
shells (c) are also demonstrated. HRTEM picture
(d) illustrates nonclosed shells with surface
steps (indicated by arrows).
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Methodology
Figure. TEM images of OLC produced at 1800 K. A
and B correspond to HR images of marked regions
of low resolution image. Arrows show (C) common
shells united several onion cores, (H) holes, (Y)
y-junctions of graphene shells. Schematic
represents the structure of OLC.

• The average ND particle size is 4 - 5 nm.
• The average particle size of primary OLC is about
  4-7 nm.
• OLC particles form agglomerates including the
  structures where the whole agglomerate of primary
  OLC particles can be enclosed by a graphite-like
  layer.

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Fullerene geometry

• and pod of peas fullerenes

radius
R. Langlet, A. Mayer, N. Geuquet, H. Amara, M.
Vandescuren, L. Henrard, S. Maksimenko and Ph.
Lambin Study of the polarizability of fullerenes
with a monopole-dipole interaction model,
Diamond and Related Materials  16, 21452149
(2007)
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Polarizability monopole-dipole-model A. Mayer
et al., Appl. Phys. Lett. 89 (2006) 063117

• The free charges delocalized through the
  molecule allow to reproduce a metallic behavior
• (delocalized p-electrons)
• The local electric field is perpendicular to
  the molecule surface
• Molecular dipole due to the displacement of
  free charges
• Charges are essentially located on the maximum
  curvature surface

? E
C540 with 48 Stone-Wales defects
C60
C60
without free charges
with free charges
Polarizability (ų)
Icosahedral onion Spherical
onion (defects) C1500 6078.3 6213.6 C960_at_C1
500 6087.6 6231.8 C540_at_C960_at_C1500 6087.7
6231.8 C240_at_C540_at_C960_at_C1500 6087.7 6231.8 C60
_at_C240_at_C540_at_C960_at_C1500 6087.7 6231.8
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Methodology

• Outer shells in primary aggregates can form
  common graphene layer.

R Langlet, Ph Lambin, A Mayer, S A Maksimenko and
P P Kuzhir, Dipole polarizability of onion-like
carbons and electromagnetic properties of their
composites, Nanotechnology, 19 (11) 115706 (8pp)
(2008)
Figure. Left axial polarizability vs L3. Right
pod of peas- fullerenes (a)  C1280  C720
inside, (b) C540  C240 inside.
Figure. (a) computer model of pod-of-peas
fullerenes structure C320 C80 balls inside
(b) OLC particles are marked O, elongated
particles with linked external graphite-like
layers and closed quasi-spherical internal
shells marked E. (c) Typical size distributions
of OLC and ND clusters in organosol matrix for
different samples.
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The cluster size and number of particles per
aggregate determine its polarizability, and
therefore govern the electromagnetic properties
of OLC-based material as a whole
Formation of primary aggregates
pod-of-peas-like structures and their
branching and chaining into extensive clusters
are in the nature of high electrical
conductivity of OLC
Charge carriers are concentrated in the inner
cores of OLCs, being preserved by outer
defect-free graphene shells, and can interact
effectively with external electromagnetic field
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Electron transport properties of OLC
V. Kuznetsov, S. Moseenkov, A. Ischenko, A.
Romanenko, T. Buryakov, O. Anikeeva, S.
Maksimenko, P. Kuzhir, D. Bychanok, A. Gusinski,
O. Ruhavets, O. Shenderova and P. Lambin,
Controllable electromagnetic response of
onion-like carbon based materials,phys. stat.
sol. (b) 245(10), 20512054 (2008)
Figure. 1. The temperature dependence of
conductivity s(T) of OLC series DC, annealed at
temperature 1400 K (DC1400), 1650 K (DC1650) and
1850 K (DC1850) in coordinates ln(s) - T-1/2.
Figure. 2. Dependence of density of states at
the Fermi level N(EF) calculated from the
temperature of annealing for samples of DA, DB,
DC and DH-series.

• The increase of the annealing temperature from
  1400 K up to 1900 K leads to the rise of the
  conductivity of OLC powder.
• The increase of the annealing temperature leads
  to increase of the density of states at Fermi
  level and consequently increasing of the carriers
  concentration.
• Some variation of density of states at the Fermi
  level is observed for OLC produce from ND of
  different vendors. That was attributed to the
  variation of size of agglomerate.

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The increase of the annealing temperature leads
to increase the conductivity of OLC powder
OLC samples with larger average size of OLC
agglomerate show more pronounced OLC conductivity
We can operate density of states at Fermi level
N(EF) via variation of the annealing temperature
and separation of the large fraction of OLC,
providing metal-like behavior of OLC fillers
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Electromagnetic properties of OLC
The complex elements of the scattering matrix,
s11 and s21, have been measured with high
accuracy within 26-37GHz frequency range
(Ka-band) by free space technique.

• OLC powders display non-monotonous frequency
  dependence of the EM attenuation.
• Peculiarities of the EM response of OLC powders
  are provided by the agglomeration of OLC
  particles (giving new characteristic sizes).

P. Kuzhir, S. Maksimenko, D. Bychanok, V.
Kuznetsov, S. Moseenkov, I. Mazov, O.
Shenderova and Ph. Lambin, Nano-scaled onion-like
carbon prospective material for microwave
coatings. Metamaterials, accepted for publication
2009
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Electromagnetic properties of OLC
Absorption provided by OLC powders has been found
to be strongly dependent on the OLC cluster size
and ND annealing temperature
Table. EM response properties of ND and OLC
annealed at different temperatures in Ka-band
(26-37 GHz) band.
Large OLC fraction
Small OLC fraction
Figure. Frequency dependence of absorption
coefficient for OLC powders of Da-3 and Db-3
types.
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The complex dielectric function of OLC is found
to be strongly dependent on the agglomerate size
The rise of the annealing temperature leads to
enhanced absorption ability of OLC
Manipulating the OLC cluster size (chousing
large-size OLC fraction) and ND annealing
temperature, we can manage EM response of OLC
fillers
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Electromagnetic response of OLC-based polymer
composite
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Electromagnetic response of OLC-PMMA to microwaves

• Different OLC types have different surface
  chemistry different content of defects (holes),
  sp2/sp3 ratio, different amount of metallic
  impurities thus the EM response of OLC-PMMA
  films is related to the origin of precursor.
• ND and OLC synthesis conditions results on
  the EM attenuation varies from film to film.

• EM attenuation is much more pronounced for small
  OLC fraction.
• EM response of OLC-PMMA films at a given
  frequency is a monotonous function of the OLC
  concentration.
• All EM curves show well-defined peak near 30 GHz.

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EM response of OLC-based suspensions to microwaves
Dependence of transparency on concentration for
the system vaseline - OLC(sample Da1850)
and OLC(sample Db1850).
The percolation threshold is measureded for
OLC-based suspensions and found to be strongly
dependent on the primary OLC particles size
formed cluster. Manipulating the OLC cluster
size (chousing large-size OLC fraction) and ND
annealing temperature, we can manage EM response
of OLC fillers.
D.S. Bychanok, S.I. Moseenkov, V.L. Kuznetsov,
P.P. Kuzhir, S.A. Maksimenko, O.V.Ruhavets, A.V.
Gusinski, O. Shenderova and Ph. Lambin, Onion
Like Carbon In Microwaves Electromagnetic
Absorption Bands And Percolation Effect,
submitted to Nanoelectronics and
Optoelectronics, 2009, accepted for publication
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Influence of binding matrix
Figure. Frequency dependence of EM absorption,
provided by OLC-PMMA and OLC-PDMS composites.
OLC inclusions of (a) Dh-1 and (b) Dice-2 type.

• EM absorption in OLC-based PDMS samples shows
  much more pronounced frequency dependence than
  that for PMMA samples.
• The EM response provided by Dh-1 OLCs is higher
  when they are embedded in PDMS host, while Dice-2
  type of OLC inclusions demonstrates higher EM
  absorption when being incorporated in PMMA
  matrix.
• The reason is that OLCs of different types,
  depending on the synthesis conditions, have
  different affinity to the host matrix.

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The peculiarity of the EM response of OLC-based
polymer films is related to agglomeration of OLC
particles, ND origin and OLC synthesis conditions
and concentration
The influence of host matrix to the EM response
of OLC-based polymer composites is very important
Manipulating the OLC type and concentration, havin
g different host matrix, the EM coatings with
different EM properties can be designed
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The research is supported by

• NATO Science for Peace Program
• SfP-981051,
• INTAS
• 06-1000013-9225
• Belarusian Republican Foundation of Fundamental
  Research F06R-091

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Thank you for attention!