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Carbon and coal based materials of high added value
- research at CMPW PAN
Andrzej Dworak
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CMPW PAN (previously Institute of Coal Chemistry PAS)
Structure and properties of coals and basic methods of their processing
1986-2002- Brown coals- Hard coals
1997- 2008- Anthracites- Cokes- Pyrolysed vascular plants
Development of the basis of technology for obtaining carbon materials with specific properties
2006 – currently
– non-energetic application of natural carbon materials(carbon fillers of polymer composites, catalyst carriers, sorbents)
– synthetic carbon materials from various precursors (natural and others) preparation and application
Two-phase model of coal structure
/A. Marzec, 1985/
Cross-links
Acceptor-donor
bonds
Molecular
phase
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Anthracite
Semi-graphite Graphite
Diamond
Natural carbon materials
High rank bituminous coal
Turbostratic structure
Graphite-like and graphitic structure
http://www.google.pl/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&docid=Q_uVrb08ylmgMM&tbnid=tQ0hPKuthdC7TM:&ved=0CAUQjRw&url=http%3A%2F%2Fpl.wikinews.org%2Fwiki%2F2009-08-14%3A_Naukowcy_odkryli_now%25C4%2585_odmian%25C4%2599_w%25C4%2599gla&ei=FGfPU4fAHsnFPZn8gdAF&bvm=bv.71667212,d.ZWU&psig=AFQjCNF_u7_SJQU2Z_EOTt5izYgFOvZ7zg&ust=1406187643409531http://www.google.pl/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&docid=Q_uVrb08ylmgMM&tbnid=tQ0hPKuthdC7TM:&ved=0CAUQjRw&url=http%3A%2F%2Fpl.wikinews.org%2Fwiki%2F2009-08-14%3A_Naukowcy_odkryli_now%25C4%2585_odmian%25C4%2599_w%25C4%2599gla&ei=FGfPU4fAHsnFPZn8gdAF&bvm=bv.71667212,d.ZWU&psig=AFQjCNF_u7_SJQU2Z_EOTt5izYgFOvZ7zg&ust=1406187643409531
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HTT 2000oC
5 mm
Raw anthracite
• Increase of XY dimensions of carbon planes
• Decrease of interlayer spacing
• Increase of true density
• Appearance of electrical conductivity
5 mm3 mm
C~83%
C~93% C~95,5%
HTT, graphite-like anthracite
Increasing structural order
Bituminous coal
Natural carbon materials
S. Pusz et al. Fuel Proc. Tech., (2002) 77-78, 173-180
M. Krzesinska et al. Energy Fuels (2005) 19, 1962-1970
M. Krzesinska et al. Energy Fuels (2006) 20, 1103-1111
M. Krzesinska et al. IJCG (2009) 77, 350-355
S. Pusz et al. IJCG (2014), 131, pp. 147-161
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OH
O
OO
O
HO
OH
OOH
O
O
OH
OHO
OH
O
HO
OH
O
OH
HO
OH
O
O
O
HOO
OH
OHOH
NCH3
N
OH
OH
CH3
OH
N
CH3
O
OH
O
HO
O
Thermalreduction
Reduced anthraciteoxide
Anthracite oxide
HTT anthracite
Functionalizedanthracite
NanoplateletsXY: 10-20 mm (AFM)
Z: 6-30 nm
NanoplateletsXY: < 200 nm (AFM)
Z: 2-3 nm
Functionalization of anthracite
B. Kumanek, et al. Fullerenes, Nanotubes and Carbon Nanostructures, 2018, DOI: 1-.1080/1536383X.2018.1441827
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Polymer/carbon composites
Potential benefits of application of carbonfillers to polimer composites:
• better stiffness
• better thermal resistance
• better chemical resistance
• better mechnical strength
• low density
Polymer/carbon composites = polymer matrix + different kinds of carbon fillers
Hybrid polimer composite withtwo different carbon fillers
Matrices:
Thermosetting polymers
Termoplastic polymers
Elastomers
Fillers:
Carbon fibresCarbon blackGraphite
Carbon nanotubesGrapheneFulerenes
Other carbon materials
Carbon nanofillers
-
5 mm
+ bituminous coal (BC) + raw anthracite (RA) + HTT anthracite (A2000) Epoxy Matrix EP/TETA
20% mas.
+ reduced anthraciteoxide (AF1)
0,5% mas.
10 mm
+ HTT anthraciteafter cycloaddition (AF2)
Microcomposites
0
20
40
60
80
100
120
EP WK Awyj A2000 AF1 AF2
Me
chan
ical
stre
ngt
h[M
Pa]
Functionalized fillers
0,5%
Epoxy composites with natural carbon fillers
Raw fillersFunctionalized fillers
BC RA A2000
Ma
trix
U. Szeluga et al. Journal of Thermal Analysis and Calorimetry, 92 (2008) 813
U. Szeluga et al. Polymer Bulletin 60 (2008) 555
S. Pusz et al. Polymer Composites, (2015), 36, pp. 336-347
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Synthetic carbon
materials
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Carbon foam Glassy carbon
Carbon nanotubesGraphene sheets
and multi-layered nanoplatellets
Graphene sheet variously arranged
Weakly ordered or amorphous structure, nongraphitized
Carbon black
Fulerenes
Synthetic carbon materials
Heterogeneous structure, partly graphitized
Synthetic graphite
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Pyrolysis of phenol-formaldehyde resin to 1000 °C, heating rate 0.5 °C/h.
Structural model
Functional groups
Structural order
Morphology
ID/IG= 1,4
Glassy carbon
T – tetrahedral domains sp3
G – graphitic domains sp2
XPS
IR
GC: content C – 92%, O – 7%; true density – 1.45 g/cm3; electrical resistance – 4.2 x 10 -6 Ω mm
Inte
nsi
ty[a
.u.]
Tran
smit
ance
[a.u
.]
Inte
nsi
ty[a
.u.]
Wavenumber [cm-1]
Binding energy [eV]
Raman shift [cm-1]
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3 mm
Binary cmposite with GC Hybrid composites with GC and MWCNT
Properties of hybrid composites:
• Good dispersion of GC i MWCNT
• Perfect adhesion of GC to matrix
• Good mechanical strength
• Good electrical conductivity
• Big hardness and wear-resistance
• Thermal resistance
• Density comparable to pure epoxy matrix
Epoxy MatrixEP/TETA
Epoxy composites with glassy carbon
COMPOSITE sy Ef sf r (Ω cm)
EP47.18 MPa 2.77 GPa 72.92 MPa 4.82 x 10
14
EP-MWCNT (0.25%) +5% -8% -11% 4.05 x 104
EP-GC (10%) +29% +16% +30% 3.02 x 107
EP-GC10-MWCNT +32% +19% +33% 1.68 x 103
C H A N G ES
U. Szeluga et al. Composites Science and Technology, (2016) 134, 72-80
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• Percolation threshold of a segregated system much lower than for randomly distributed
• High local concentration of filler in a segregated system
in segregated system
Segregated vs random anthracite compositesCollaboration with IMC
National Academy of Sciences
of Ukraine
Percolation treshold of electricalconductivity for composites with anthracite filler
segregated system
randomly distributedsystem
O.V. Maruzhenko et al. Polymer Journal (Ukraine) (2018) 39, 219-226
Filler distribution
randomly oriented
Matrix: UHMWPE; Filler: HTT Antracite
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- carbon materials (pitch, tar, coals)
- thermosetting and thermoplastic
polymers
- by-products in production of polymers and polymer
waste
Precursors:
Carbon foams
Carbon content: 70 - > 95%
Bulk density: 0.02 – 0.5 g/cm3
True (helium) density: 1.5 – 2 g/cm3
Porosity: 82 – 95 %
Young modulus: 30 - 100 MPa
Compression strength: ~4 MPa
Electric conductivity: 2×10-3 [S cm]
Properties:
Preparation:
Pyrolysis at 900 oC, 2 oC/min
Graphitization > 2000 oC
Thermal stability of carbon foams
Collaboration with IOCBulgarian Academy of Sciences
Carbon foam
Polymerprecursor
„Carbon foams are porous carbon products containing regularly shaped, homogeneously dispersed cells, which
interact to form a three-dimensional array throughout a continuum material of carbon, predominantly in the non-
graphitic state.” /J. Klett, 2005/
B. Tsyntsarski et al. Carbon, (2010) 48 3523–3530
B. Nagel et al. Journal of Materials Sciences, (2014) 49 (1), 1-17
U. Szeluga et al. Journal of Thermal Analysis and Calorimetry, (2015) 122, 271-279
Temperature [oC]
Mas
s [m
g]
-
100 mm
+ epoxy
CF particles (
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Graphene studies at CMPW PAN
• 2D graphene structures
• Control of graphene layers order
• Graphene as a suport for 2D metalic layers
• 3D graphene structures
• Graphene in batteries
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Graphene synthesis in 2D form
Chemical vapor deposition (CVD)
Metallic substrates(Cu, Ni)
Oxide substrates(SixOy, MgO, Al2O3, SrO)
Methane, Ethanol, Acetylene
SEM AFM TEMLM and Raman
Collaboration with IFW Dresden
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ACS Nano, 2012, 6 (10), pp 9110–9117
Scheme of the graphene growth mechanism over Cu substrate
Important parameters
• Precursors
• Substrates, catalysts
• Temperature
• Reaction time
• Large area
• High quality
• Homogenous
• Stacking controllable
• Low cost, simple
Graphene synthesis in 2D form
Scheme of an APCVD system for graphene synthesis
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Huy Q. Ta, et al. Nano Letters 2016, 16, 6403-6410.
Seed
2L
40s
1L
Volmer – Weber(VW) growth
2L3L 1L
60s
3L 1L
5s
2L2L3L 1L
3s
Stranski – Krastanov(SK) growth AB- stacked bilayer
• Thermal CVD synthesis• Stacking control through optimized CH4:H2• Two growth modes• Homogeneous over large areas
• Twisted Bi-layer: - for chemical reactivity enhancement
• AB stacked Bi-layer :- for transistor applications etc.
Twisted bilayer
SK
VW
Stacking order control of graphene layers
-
Zhao, Science, 343 (2014) 1228
In situ freestanding Fe membrane formation
A variety of e-beam reactions between graphene and Fe atoms can be explored in situ
-
All scale bars = 1nm
Huy Q. Ta et al., ACS Nano, 2015, 9 (11), 11408–11413
Electron beam driven in situ chemistry over graphene
Formation of mono-layer ZnO in graphene pore under electron beam irradiation
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• Electron irradiation leads to Cr atom diffusion at graphene edges
• New graphene forms after Cr atom movement (always growth)
• Synthesis at room temperature
Cr
SYNTHESIS:• Cr from decomposing chromium (III)
acetylacetonate
• Electron irradiation Cr atoms
Electron beam driven in situ chemistry over graphene
Single Cr atom catalytic synthesis of graphene
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22
Graphene coated oxide nanoparticles:a) alumina, b) titania, c) magnesia,d) carbon shells after magnesia removal
Bachmatiuk, et al., ACS Nano, 7 (2013) 10552
Potential use of graphene coated oxide nanoparticles: - batteries, - functionalization, - bioapplications
3D graphene synthesis over oxides via CVD
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3D graphene potential for electrochemical storage
Batteries studies using carbon materials
Racks for coin batteries cycling
Collaboration with IFW Dresden
Equipment for coin cells preparation
Graphene coated nanoparticles
Cycling rates studies
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Carbon and coal based materials of high added value
- research at CMPW PAN
For closer data, see our papers in
Science, ACS Nano, Nano Letters,
Composites, Carbon, J. Material Science,
other
-
Carbon and coal based materials of high added value
- research at CMPW PAN
Contributions from CMPW PAN:
Prof. Barbara Trzebicka, head of the
laboratory
Composites
Prof. Sławomira Pusz
Dr. Urszula Szeluga
Dr. Bogumiła Kumanek
Graphene structures
Prof. Mark Rummeli
Prof. Alicja Bachmatiuk
Ph.D. students
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Carbon and coal based materials of high added value
- research at CMPW PAN
Cooperation:
• Quang-Zhou University, China
• Leibniz-Institute for Solid State Research and
Material Studies
• Institute of Macromolecular Chemistry, National
Academy of Science of Ukraina
• Institute of Organic Chemistry, Bulgarian
Academy of Sciences
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