"PLASMA FUNCTIONALIZATION OF CARBON NANOWALLS FOR THE CONTROL OF SUPERHYDROPHOBICITY AND THE ATTACHMENT OF NANOPARTICLES AND BIOLOGICAL ENTITIES"
TE_228

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Research contract no.: 92/2010, cod Proiect TE_228
Project director: Dr. Sorin Vizireanu, s_vizi@infim.ro

 

Financing Authority: Executive Unit for Financing Higher Education, Research, Development and Innovation (UEFISCDI)

 

Institutions involved in the project:

National Institute for Lasers, Plasma and Radiation Physics (NILPRP)
Low Temperature Plasma Laboratory
Plasma Processes for Funtional Materials and Surfaces

 

Project objectives

Carbon is the most representative among the materials with high-potential for developing the "nano" areas. For understanding the nanostructured carbon (NC) term, there is necessary to point the difference between carbon nanostructures and carbon nanostructured materials. At nanometric scale, carbon nanostructures are the of following types: fullerenes, carbon nanofibres (CNF), carbon nanotubes (CNT) (with one or more walls), nanolayers / graphene flakes, carbon nanowalls (CNWs) [1]. Instead, at micrometer scale, these nanostructures may be presented as being closely interconnected one with each other or / and the substrate, forming the so named nanostructured carbon materials. Depending on applications, studies may focus on individual nanostructures (nanometric scale) or nanostructured materials (nanometric and micrometric scale). In the last years, special attention was payed to two-dimensional nanostructures assembled from carbon materials (carbon nanowalls-CNWs), the newest member of the nanostructured carbon materials family. Carbon nanowalls are represented as an interconnected network of two dimensional lamelar nanostructures [1], placed perpendicular to the substrate, consisting of superimposed nano-crystalline graphite domains. CNW specific features recommend them for high technology applications. Thus, recent research in the field presents nanowalls as efficient materials for field emission at low voltages [2], to achieve superhydrophobic surfaces [3], as materials for gas sensors, templates and supports for catalysts [1,4] and membranes for fuel cells [5].
The project team is part of a research group from the National Institute for Laser, Plasma and Radiation Physics, which developed an original procedure to synthesize carbon nanostructures, in particular "carbon nanowalls" [6,7]. This procedure combines two plasma deposition techniques in a single reactor: magnetron sputtering for substrate catalytic activation and chemical vapor deposition assisted by a plasma beam for carbonaceous material deposition. In the project we will use plasma as working tool. Plasma induced changes has become one of the most used techniques for nanomaterials treatment [8]; this is often superior to other techniques based on wet chemistry (liquid) or dry chemistry using neutral gases. Thus, using plasma there can be achieved activation, functionalization, purification and separation / disagglomeration of carbon nanostructures.
The present project aims the development of CNW plasma functionalization techniques in order to promote superhydrophobicity and the control of nanoparticles or biological entities attachment to such material. Superhydrophobicity, nanoparticles and biological entities (biomolecules, cells, micro-organisms) attachment to nanostructured carbon are major themes of current research in nanoscience and nanotechnology.
The presented researches will be continued by the proposed project by performing studies of cells interaction with nanostructured materials, with emphasis on interaction with carbon nanowalls. This study will take into account the degree of nanostructuration and the chemical nature of the surface. The degree of nanostructuration will be controlled by means of material synthesis method while the surface chemistry will be controlled by plasma functionalization, in order to add amino and carboxyl radicals to the surface.The results regarding this type of interactions will be obtained from biological investigations, which will be carried out on stabilized cell lines, performing  evaluation tests of the cellular energy metabolism (MTT test - 3 - (4,5-dimetiltiazol-2-yl) -2,5 -difeniltetrazol), and by examination of cell morphology by means of optical microscopy and scanning electron microscope.
The main project objective is the development of nanostructured materials plasma processing techniques for obtaining functional nanostructured materials based on carbon nanowalls.
Research will be focussed on CNW plasma treatment for use and integration of this material in applications connected with superhydrophobicity, sensors development, nanoporous catalytic materials and plaftorms / architectures for biology.
Specifically, the topic of proposed research points on achieving the following specific scientific objectives:
A) - Plasma functionalization of carbon nanowalls for obtaining  superhydrophobic surfaces.
B) - Carbon nanowalls functionalization for controlling the metallic nanoparticles attachment.
C) - Carbon nanowalls functionalization for functional groups attachment/grafting, in order to control the cellular growth.

Figure 1: SEM image of CNW, in right corner a image of water drop (contact angle 150)	Figure 2: Diagram set-up for CNW syntheses

The originality of the project is based primarily on novelty of the material that follows to be functionalized with plasma. This material, that we recently obtained and characterized [7,8], combining the magnetron sputtering for catalytic activation (catalyst: Ni, Fe) of the substrate with chemical deposition of carbon from vapor phase (precursor acetylene mixed with hydrogen) assisted by RF plasma jet, is accessible to a small number of research groups worldwide. The set-up used for synthesis of the CNWs is a powerful equipment, previously achieved via appropriate effort in the NILPRP laboratories, by completing and successive endowment with elements of automatization, control and monitoring. The equipment (figure 1) consists of a plasma reaction stainless steel chamber, on which is mounted an RF plasma source and a magnetron sputtering source, aimed towards the same substrate. The configuration allows sequential or simultaneous exposure of the substrate to plasma sources, ensuring activation of catalytic metal and carbonic material growth.
The proposed approach, plasma functionalization is also innovative. The use of low temperature plasmas to change the physical - chemical properties of the CNW is prefered, having the advantage of not involving energic particles that induce severe modifications on the surface. Low temperature plasmas have instead a high content of chemically active radicals (atomic, molecular), resulted from the dissociation by electronic collision of gas molecules introduced into the RF electric discharge which generate the plasma. Using the experimental approaches proposed below, the CNW functionalization will be done during or after the process of synthesis of CNW, using post synthesis treatments of activation and incorporation of functional groups or metal nanoparticles in plasma. Physical and chemical characteristics of the material resulted after the functionalization and applications are also of maximum scientific and technological interest.

Bibliography:
1. Y. Wu, B. Yang, B. Zong, H. Sun, Z. Shen, Y. Feng, J. Mater. Chem., 14, 469-477, 2004
2. A.Malesevic, R. Kemps, A.Vanhulsel, M P. Chowdhury, A. Volodin, C. van Haesendonck, J. Appl. Phys., 104, 084301, 2008 
3. X. Xiao, Y. T. Cheng, B. W. Sheldon, J. Rankin, Journal of Materials Research 23, 8, 2174-2178, 2008
4. Young Joon Hong, Hye Seong Jung, Jinkyoung Yoo, Yong-Jin Kim, Chul-Ho Lee, Miyoung Kim, and Gyu-Chul Yi, Adv. Mater. , 21, 222-226, 2009
5. L. Giorgi, Th. Dikonimos Makris, R. Giorgi, N. Lisi and E. Salernitano, Sensors and Actuators B: Chemical, Vol 126, p 144-152, 2007
6. A. Malesevic, S. Vizireanu, R. Kemps, A. Vanhulsel. C. van Haesendonck , G. Dinescu, Carbon 45, 2932-2937, 2007
7. S. Vizireanu, L. Nistor, M. Haupt, V. Katzenmaier, C. Oehr, G. Dinescu, Plasma Processes and Polymers, Volume 5, Issue 3, 263-268, 2008
8. K. Ostrikov, Rev. Mod. Phys. 77, 489, 2005

 

The list with the members of the research team:

• Dr. Vizireanu Sorin - Project Manager
• Dr. Stancu Elena-Claudia
• Dr. Ionita Eusebiu-Rosini
• Dr. Stoica Silviu-Daniel

 

Working plan. Objectives and activities (scientific and complementary)

Stage I. Functionalization of carbon nanowalls layers using fluorinated plasmas. Study regarding wetting properties of the functionalized CNW surfaces in relation to morphology, nano-roughness and chemical composition induced by plasma treatment
Deadline: December 2010
Stage II. Synthesis of carbon nanowall layers decorated with metal nanoparticles. Study of metallic nanoparticle attachment to carbon nano-structures
Deadline: December 2011
Stage III. Synthesis, patterning and functionalization of carbon nanowalls for interaction with cells. Investigation of cell attachment on CNW and functionalized CNW surfaces
Deadline:December 2012
Stage IV. Assessment of the integration of plasma functionalization techniques and CNW for applications
Deadline: July 2013

 

Results. Scientific output: ISI papers , Proceedings , Oral presentation , Posters

ISI papers

1. S. Vizireanu, M. D. Ionita, G. Dinescu, I. Enculescu, M. Baibarac, I. Baltog, Post-synthesis Carbon Nanowalls Transformation under Hydrogen, Oxygen, Nitrogen, Tetrafluoroethane and Sulfur Hexafluoride Plasma Treatments, Plasma Processes and Polymers, 9, 363, 2012

2. S. Vizireanu, B. Mitu, C.R. Luculescu L.C. Nistor, G. Dinescu, PECVD synthesis of 2D nanostructured carbon material, Surface and Coatings Technology, 211, 2, 2012

3. M Teodorescu, M Bazavan, E R Ionita, G Dinescu, Characterization of an argon radiofrequency plasma jet discharge continuously passing from low to atmospheric pressure, Plasma Sources Sci. Technol. 21, 055010, 2012

4. Z. Gonzalez, S. Vizireanu, Gheorghe Dinescu, C. Blanco, R. Santamaria, Carbon Nanowalls thin films as nanostructured electrode materials in Vanadium Redox Flow Batteries, Nano Energy, 1, 833, 2012

5. A. Achour, B. Belkerk, K. A. Aissa, S. Vizireanu, E. Gautron, M. Carette, P-Y. Jouan, G. Dinescu, L. Le Brizoual, Y. Scudeller, M-A. Djouadi, Thermal properties of carbon nanowalls layers measured by pulsed photothermal technique, Applied Physics Letters, 102, 061903, 2013. 

6. S. Vizireanu; A. Lazea Stoyanova; M.. Filipescu; D. Cursaru; G. Dinescu, Carbon nanowalls as suitable layers for lubricity improvement, Digest Journal of Nanomaterials and Biostructures, accepted for publication, July 2013.

 

Conference Proceedings 

1. B. Mitu, S. D. Stoica, S. Vizireanu, Plasma deposition of carbon-based materials: diagnostic studies , 2 pag. proceedings ESCAMPIG XXI, Portugal, July 10-14, TL7, 2012

2. Vizireanu S.; Stoica S.D.; Mitu B.; Lazea A.; Dinescu G.; Dependence of Carbon Nanowalls quality upon plasma and substrate conditions ; 3 pag.; proceedings Conferinta Carbon, Poland, June 17-22, 2012

3. Z. González; Vizireanu S.; Dinescu G.; Roldán S; Blanco C.; Santamaría R.; Carbon Nanowalls as active electrode materials in. Vanadium Redox Flow Batteries ; 4 pag.; proceedings Conferinta Carbon, Poland, June 17-22, 2012

 

Oral presentations

1. "Plasma jet treatment of carbon nanowalls layers", S. Vizireanu1, S.D. Stoica, M. D. Ionita, A. Lazea Stoyanova, L. Nistor, G. Dinescu, 16 th International Conference on Plasma Physics and Applications:, Magurele, Romania, 20-25.06.2013

2. “Carbon nanowalls: plasma synthesis, properties and application, S. Vizireanu, S. D. Stoica, E.C. Stancu, B. Mitu, G. Dinescu,.Diaspora in Cercetarea Stiintifica si Invatamantul Superior, 25-28/10/2012, Bucuresti, Romania

3. "Carbon Nanowalls as active electrode materials in Vanadium Redox Flow Batteries Carbon for Energy Storage", Z. Gonzalez, S. Vizireanu, G.Dinescu, S. Roldan, C. Blanco, R. Santamaria, Carbon 2012, Krakowia, Polonia, 17.06.2012 -22.06.2012

4. "Hybrid Nanostructures Based on Aluminium Nitride and CNTs /CNWs as Thermal Interface Materials Carbon–based Composites and Nanocomposites" A. Achour, B. Belkerk, K, S. Vizireanu, J-F. Colomer, M. Carrette, P-Y. Jouan, G. Dinescu, L. Le Brizoual, Y. Scudeller and M-A. Djouadi, Carbon 2012, Krakowia, Polonia, 17.06.2012 -22.06.2012

5. “Modifications of Carbon nanowalls by Plasma Treatment” S. Vizireanu, S. D. Stoica, E.C. Stancu, B. Mitu, G. Dinescu, The 8th General Conference of Balkan Physical Union, Universitatea Ovidius din Constanta, Romania, 5–7/07/2012, (5 iulie 2012, locatie E8, sectiunea Plasma Physics)

 

Poster contributions

16 ^th International Conference on Plasma Physics and Applicatio ns:, Magurele, Romania, 20-25/06/2013
-The influence of nozzle dimensions upon the carbon nanowalls obtained by RF plasma jet,  S.D. Stoica, S. Vizireanu, B. Mitu, M. Bazavan, G. Dinescu
-Femtosecond laser processing of carbon nanowalls thin films deposited by radiofrequency plasma jet , I. Anghel, M. Zamfirescu, S.D. Stoica, M.D. Ionita, S. Vizireanu, G. Dinescu
-Response of malignant cells to the presence of carbon nanowalls structures, E.C. Stancu, S. Vizireanu, A.M. Stanciuc, L. Moldovan, G. Dinescu.

Third International Conference on Multifunctional, Hybrid and Nanomaterials, Sorento, Italia, 3-7/3/2013
Decoration of carbon nanowalls with metal nanoparticles for hybrid electrodes in electrochemistry, S. Vizireanu, A. Stoyanova, S.D. Stoica, L. Nistor, G. Dinescu

E-MRS Strasbourg-Franta, 14-18/05/ 2012:
-Stability of carbon nanowalls against chemical attack with acid solutions, autori: S. Vizireanu, G. Dinescu, L.C. Nistor, G. Ruxanda, M. Stancu, D. M. Ciuparu.
-Functionalization of carbon nanowalls surfaces for interaction with biological cells, autori: E.C. Stancu, A.M. Stanciuc, S. Vizireanu, L. Moldovan, G. Dinescu
-Nanoparticle -Nanowire Interface Influence on ZnO Nanostructure Luminescence Shifting, autori: A.Marcu, R.Zamani, I.Enculescu, S.Vizireanu, J.R.Morante, R.Birjega, C.P. Lungu, C.Grigoriu, J.Arbiol.

Carbon 2012, Krakowia, Polonia, in perioada 17-22/06/2012:
-Dependence of Carbon Nanowalls quality upon plasma and substrate conditions, autori: S. Vizireanu, S.D. Stoica, B.Mitu, A. Lazea, G. Dinescu,

13th International Conference on Plasma Surface Engineering Garmisch, Germania, 10-14/09/ 2012
-Plasma functionalization of carbon nanowalls, S. Vizireanu, S. D. Stoica, A.Lazea, E. C. Stancu, L. Nistor, G. Dinescu.

European Materials Reasearch Symposium, E-MRS 2011, Nisa, France, 8-15/05/2011
-Super-hydrophobic/super-hydrophilic layers of carbon nanowalls obtained by post-synthesis plasma treatments, S. Vizireanu, M.D. Ionita, E.R. Ionita, I. Enculescu, B. Mitu, G. Dinescu

ImageNano 2011 on Nanoscience & Nanotechnology Energy, Bio/medicine, Optics, Graphene, Bilbao, Spania, 11-14/04/2011
-Carbon nanowalls functionalization for controlling the metallic nanoparticles attachment, S. Vizireanu , S. D. Stoica, B. Mitu, L. Nistor, G. Dinescu

NT11 International Conference on the Science and Application of Nanotubes”,  Cambridge, United Kingdom, 10-16/07/2011
-Plasma post-synthesis treatment of carbon nanowalls and their characteristics, S. Vizireanu, S Stoica, E. Stancu, B. Mitu, C. R. Luculescu, L. Nistor, G. Dinescu