Carbon and coal based materials of high added value

- research at CMPW PAN

Andrzej Dworak

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

Anthracite

Semi-graphite Graphite

Diamond

Natural carbon materials

High rank bituminous coal

Turbostratic structure

Graphite-like and graphitic structure

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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

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

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

Synthetic carbon

materials

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]

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

• 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

- 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 (

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

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

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

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

• 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

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

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

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

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