Transcript Plasma chemistry research at Faculty of Chemistry Brno

Plasma chemistry research
at Faculty of Chemistry
Brno University of Technology
František Krčma
Zdenka Stará
BUT location
Central Europe
BUT location
Central Europe
Czech Republic, Brno
BUT location
Central Europe
Brno – north part of city
BUT location
Central Europe
Brno – faculty campus
BUT structure
Faculty
of Architecture
Faculty
of Chemistry
Faculty of
Electrical
Engineering and
Communication
Faculty
of Civil
Engineering
Faculty of
Information
Technology
Faculty of
Business and
Management
Faculty of
Mechanical
Engineering
Faculty of
Fine Arts
FCH structure
IPAC
Institute of Physical
and Applied Chemistry
IMC
Institute of Material Chemistry
PLASMA CHEMISTRY
LABORATORY
microbiology
IFCBT
Institute of Food Chemistry
and Biotechnology
analytical methods
ICTEP
Institute of Chemistry
and Technology of
Environmental Protection
Plasma chemistry research fields
• Deposition of organosilicone layers
• Diaphragm discharge in liquids
• Destruction of pollutants in
atmospheric discharges
• Surface treatment and sterillization
• Plasma chemical removal of corrosion
• Discharge and post-discharge kinetics
Deposition of organosilicone layers
• Tetravinylsilane and vinyltriethoxysilane monomers
• Influence of deposition conditions on plasma polymer
mechanical and optical properties
• Study of the role of reactive bounds during the thin
films preparation
Deposition of organosilicone layers
• System equipped with mass spectroscopy and in situ
spectroscopic ellipsometry
• Multilayer preparation and characterization
• Application in glass based composites
Deposition of organosilicone layers
main publications
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Čech V., Vaněk J., Drzal L.: Deposition of Single Plasma-Polymerized
Vinyltriethoxysilane Films and their Layered Structure, Jap. J. Appl. Phys. 45
(2006) 8440
Čech V., Inagaki N., Vaněk J., Přikryl R., Burešová A., Zemek J.: PlasmaPolymerized Versus Polycondensed Thin Films of Vinyltriethoxysilane, Thin
Solid Film 502 (2006)181
Čech V.: Plasma Polymer Film as a Model Interlayer for Polymer
Composites, IEEE Transactions on Plasma Science 34 (2006) 1148
Čech V., Vaněk J., Jones F., Goruppa A.: RF-Power-Controlled Young's
Modulus of Plasma-Polymerized Organosilicon Films, J. Material. Sci. 40
(2005) 5099
Čech V., Vaněk J., Studýnka J., Přikryl R.: Plasma Polymer Films Prepared
in RF Inductive Coupling System, Chem. Papers 99 (2005) S446
Rašková Z., Brandejs K., Vaněk J., Krčma F.: Plasma Diagnostic During
Deposition Processes of Silane Based Thin Films, Czech. J. Phys. 54 (2004)
C1036
Diaphragm discharge in liquids
negative streamers
(negative discharge)
positive streamers
(positive discharge)
discharge reactor
Experimental conditions:
High voltage: 1-3 kV
Discharge current: 90-250 mA
Input power: 90-300 W
Solution: water + electrolyte (+ dye)
Optimal solution conductivity: 100-1000 μS∙cm-1
Diaphragm discharge in liquids
Investigated processes:
• generation of reactive species from water
- OH, H, O and some other radicals (det. by OES)
- hydrogen peroxide (det. by colorimetric method)
• excitation of metal elements from alkaline solutions (det. by OES)
• degradation of organic compounds dissolved in water
- organic dyes
- humic acids
• behaviour of solution properties (pH, conductivity)
Diaphragm discharge in liquids
main publications
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Procházková J., Stará Z., Krčma F.: Optical Emission Spectroscopy of
Diaphragm Discharge in Water Solutions, Czech J. Phys. 56 (2006) B1314
Stará Z., Krčma F.: Treatment of Humic Acids Solutions by Diaphragm
Discharge, Czech. J. Phys. 56 (2006) B1351
Stará Z., Krčma F.: Degradation of Organic Dyes Versus H2O2 Generation
During the DC Diaphragm Discharge Treatment in Water Solutions, Acta
Phys. Slovaca 55 (2005) 515
Stará Z., Krčma F.: The Study of H2O2 Generation by DC Diaphragm
Discharge in Liquids, Czech. J. Phys. 54 (2004) C1050
Stará Z., Krčma F., Nejezchleb M., Skalný J.D.: Organic Dye Decomposition
by DC Diaphragm Discharge in Water: Effect of Solution Properties on Dye
Removal, J. Adv. Oxid. Technol. (2007), submitted
Stará Z., Krčma F., Slavíček P.: Creation and Stability of DC Diaphragm
Discharge Generated in Water Solutions of Electrolytes and Organic Dyes, J.
Electrost. (2007), recieved
Destruction of pollutants
in atmospheric discharges
Experimental devices
• Gliding arc discharge
• Surface barrier discharge
Destruction of pollutants
in atmospheric discharges
• High-speed video camera measurements
Cycle duration, plasma channel length
• Destruction products analysis
Solid Phase Microextraction
(SPME) + GC-MS
TESTO 350 – simply gas analyser
• Optical measurements - OES
Destruction of pollutants
in atmospheric discharges
main publications
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Grossmannová H., Cigánek M., Krčma F.: High-Molecular Products
Analysis of VOC Destruction in Atmospheric Pressure Discharge,
J. Phys.: Conf. Ser. 63 (2007) Article No. 012011
Grossmannová H., Krčma F.: The Applicability of the Solid Phase
Microextraction Technique for the Analysis of the Gliding Arc
Discharge Products, Chem. Papers 99 (2005) S137
Grossmannová H., Vrajová J., Krčma F.: VOC Destruction in
Atmospheric Pressure Discharges – Analysis of the Low Molecular
Products, Proceedings of ISPC XVIII, Abstract 752, full 27P-170,
Kjoto 2007.
Grossmannová H., Krčma F.: VOC Abatement in Gliding arc Discharge
– Low Molecular Products Analysis, Proceedings of Frontiers in Low
Temperature Plasma Diagnostics VII, full text 4 pages on CD, Beverley
2007
Surface treatment and sterilization
DBD surface discharge
Hydrofility/hydrophobity
Plasma reactor UPS 100W
- Material: Paper, PE, PES
- Experimental conditions:
Atmospheric pressure
Plasma power input 130 – 190 W
Air
Treatment time 0 – 60 s
- Surface energy evaluation, Absorption, Spectrofotometer
Surface treatment and sterilization
DBD volume discharge
Sterilization
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B
Faculty of Science, Masaryk University
- Bioindicator – fungi Aspergillus Niger
- Experimental conditions:
Atmospheric pressure
Plasma power input 93 - 1080 mWcm-3
Nitrogen, Argon, Helium
Treatment time 0 – 240 s
C
Surface treatment and sterilization
main publications
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Janča J., Sťahel P., Buchta J., Subedi D., Krčma F., Pryčková J.:
A Plasma Surface Treatment of Polyester Textile Fibers Used for
Reainforcement of Car Tires, Polymers and Plasmas 6 (2001) 15
Vrajová J., Sťahel P., Novotný O., Buršíková V., Krčma F., Čech J.:
Plasma Based Removal of Microbial Contamination of Paper, Proc.
8th Internat. Balkan Workshop on Appl. Phys., Constanca 2007
Vrajová J., Prudíková I., Rašková Z., Krčma F.: Plasma Based Removal
of Microbial Contamination of Paper, Proceedings of ISPC XVIII,
Abstract 689, full 27P-121 (4 pages) on CD, Kjoto 2007
Čechová E., Klučáková M., Krčma F., Majzlík P., Vrajová J.:
Interaction of Humic Acids Thin Layers with Plasma at Atmospheric
Pressure, Proceedings of ISPC XVIII, Abstract 745, full 27P-163
(4 pages) on CD, Kjoto 2007.
Vrajová J., Rašková Z., Prudíková I., Krčma F.: Utilization of
Atmospheric Pressure Discharges for Paper Sterilization, Proceedings
of 16th Symposium on Application of Plasma Processes, 277-278,
Podbanské 2007
Plasma chemical removal of corrosion
• Method is known for about 20 year but there is only a very
limited knowledge about the mechanisms
• Empirically it is used mainly for iron and silver made
objects
Plasma chemical removal of corrosion
• Application on laboratory prepared samples with defined
process of corrosion layer preparation
• Use for iron, copper, bronze and brass samples with defined
surface raphness
• Analyse of the plasma during the process and all acessible
analyses of sample surface during whole process
Plasma chemical removal of corrosion
main publications
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Rašková Z., Krčma, F.: Plasmachemical Reduction for the
Conservation of Archaeological Artefacts, Publ. of Astronom. Observ.
Belgrade 82 (2007) 159
Krčma F., Cihlář M., Klíma M.: Diagnostic of Plasmachemical
Removal of Copper Based Corrosion Layers, Chem. Papers 99 (2005)
S583
Rašková Z., Krčma F., Klíma M., Kousal J.: Spectroscopy of Low
Pressure Discharges Used for Plasmachemical Treatment of
Archaeological Artifacts, Chem. Papers 96 (2002) S101
Rašková Z., Krčma F., Klíma M., Kousal J.: Characterisation of
Plasmachemical Treatment of Archaelogical Artifacts, Czech. J. Phys.
52 (2002) D927
Discharge and post-discharge kinetics
experimental
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flowing post-discharge in pure nitrogen and in nitrogen
mixtures with oxygen, argon and hydrogen
influence of hydrocarbon and metallic traces on nitrogen
post-discharge
fragmentation of organosilicone molecules in plasmas
Discharge and post-discharge kinetics
theoretical
• study of v-t and v-v processes in nitrogen post-discharge
• creation of nitrogen molecular ions during the postdischarge
• pooling reactions in pure nitrogen
• energy transfer reactions between near laying levels
• energy transfer between different molecular species,
mainly from nitrogen metastables to other particles
• estimation of reaction rates
• formation of organosilicone structures in plasma-gas
phase
• pulsed discharges as combination of ac active discharge
with its afterglow
Discharge and post-discharge kinetics
main publications
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Krčma F., Protasevich E. T.: Post-discharges in Pure Nitrogen and in
Nitrogen Containing Halogenated Hydrocarbon Traces, Tomsk Polytechnic
University Publishing, Tomsk 2003, pages 1 – 132, ISBN 189-8326-444.
Krčma F., Mazánková V., Soural I.: Short Live Afterglow in Pure Nitrogen
and Nitrogen Containing Traces of Methane and Oxygen, Publ. Astronom.
Observ. Belgrade 82 (2007) 133
Kanický V., Otruba V., Hrdlička A., Krásenský P., Krčma F.: Influence of
Metal Traces on Kinetics of a Nitrogen Glow Discharge in Post-Discharge
Period, J. Atom. Analyt. Spectrom. 22 (2007) 754
Krčma F., Mazánková V., Soural I.: Secondary "Pink Afterglow" in PostDischarge in Pure Nitrogen, Czech. J. Phys. 56 (2006) B871
Krčma F.: Pink Afterglow in Nitrogen - Hydrocarbon Mixtures, Acta Phys.
Slovaca 55 (2005) 453
Hubeňák J., Krčma F.: Determination of Hydrocarbon Concentration in the
N2 DC Flowing Afterglow, J. Phys. D: Appl. Phys. 33 (2000) 3121
Practical course from plasma chemical
processes and technologies
1. Low pressure measuring
2. EPR spectroscopy of plasma
3. RF discharge at low pressure
4. Optical emission spectroscopy of plasma
5. VOC destruction in atmospheric pressure plasma
6. Hydrogen peroxide generation by diaphragm discharge in liquids
7. Organic dyes degradation by diaphragm discharge in liquids
8. Study of ozone generation
9. Changes of polymer materials wettability by surface discharge
10. Permeability enhancement of non-wowen textile materials
International collaboration
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University Marne la Vallee, Paris region, France
Belgrade University, Serbia
Instituto Superior Tecnico de Lisboa, Portugal
Ecole Nationale Superiere du Chimie de Paris, France
Faculty of Mathematics, Physics and Informatics,
Comenius Univesrity Bratislava, Slovakia
• Physical Institut, Zemun, Serbia
National collaboration
• Faculty of Science, Masaryk University Brno
• Technical Museum, Brno
• Faculty of Mathematics and Physics, Charles University,
Prague
• Institut of Plasma Physics, Czech Academy of Science,
Prague
• Physical Institute, Czech Academy of Science, Prague
• Faculty of Electrical Engineering, Czech Technical
University, Prague
• HVM Plasma, Ltd, Prague
• Romill, Ltd, Brno
• Vacuum Praha, Ltd, Prague
• Zlín Precission, Ltd, Zlín
Actual projects
• Study of Kinetic Processes in Nitrogen Post-Discharge with Respect to their
Use in Chemical Analysis, Czech Science Foundation 202/05/0111 (20052007) – Krčma.
• Advanced Topics in Physics and Chemistry of Plasmas, Czech Science
Foundation 202/03/H162 (2003-2007) – Krčma.
• Study of Processes in Electrical Discharges in Water Solutions of Organic
Compounds, Czech Science Foundation 202/07/P371 (2007-2009) – Stará.
• Theoretic and Spectroscopic Study of Organosilicone Molecules and Their
Fragmentation, Barrande 2-07-27 (2007-2008) – Krčma.
• Research of Plasma Chemical Processes for Development of Inteligent
polymeric Nanostructures, Czech Science Foundation 104/06/0437 (20062008) – Čech.
• Structuring of plasma polymers, 1P05OC087 (2004-2007) – Čech.
• Participation at Research plan Multifunctional Heterogeneous Materials
based on Synthetic Polymers and Biopolymers, Ministry of Education, Youth
and Sport MSM 0021630501 (2005-2009).
Main closed projects
• Surface Activation of Synthetic Polymer Materials in Non-Isothermic Low
Temperature Plasma, Czech Science Foundation 104/99/0307 (1999-2001) –
Krčma.
• Study of the Processes in Post-discharge Plasma Created in Pure Nitrogen
with Chloro- and Fluoro-Carbons and Their Application in Determination
of the Plastic Materials Degradation, Czech Science Foundation
202/98/P258 (1998-2001) – Krčma.
• Plasma Surface Treatment of glass Fibers for Polymeric Composites, Czech
Science Foundation 104/00/0708 (2000-2002) – Čech.
• Functional Nanostructures for Composite Interfaces, ME 597 (2002-2006) –
Čech.
• Plasma Polymer Films Prepared in RF Inductive Coupling System, OC
527.110 (2001-2005) – Čech.
• 12 project of Czech Ministry of Education, Youth and Sports in program
Development of Universities.
IPAC
IMC
Scientific staff
Assoc. Prof. František Krčma, Ph.D.
Assoc. Prof. Ota Salyk, CSc.
Dr. Zdenka Stará, Ph.D.
Prof. Vladimír Čech, Ph.D.
Dr. Radek Přikryl, Ph.D.
Students
Bc
4
Mgr. 12
Ph.D. 6
Bc
2
Mgr. 3
Ph.D. 2
Finished students
Bc
3
Mgr. 18
Ph.D. 3
Bc
1
Mgr. 4
Ph.D. 2
Publications - overview