2004-2011

Topics

1. Electrochemical and corrosion properties of metallic glasses and their components,
2. Electrocatalytic processes,
3. Local phenomena at electrodes,
4. High resolution characterization of nonhomogeneous functional and construction materials.

* High resolution morphological and microchemical analysis (SEM and SAM)
Characterization of surfaces of new materials including nanomaterials is an important task for both chemists and material scientists interested in understanding and improving their performance as functional and/or structural materials. The most suitable techniques for such an analysis are Scanning Auger Microanalysis (SAM) combined with Scanning Electron Microscopy (SEM). Chemical analysis of a selected nano-area or a thin surface film can be performed with the aid of a Scanning Auger Microprobe.

Apparatus
The Physical Chemistry of Materials Center is equipped with the Microlab 350 (Thermo VG Scientific, UK). This is a high resolution Auger system also capable of performing multi-technique analysis, with the option of being fitted with a range of preparation facilities. Its key features are:

• Spatial resolution: 7 nm SEM-Scanning Electron Microscopy, 12 nm SAM-Scanning Auger Microscopy
• High sensitivity
• User selectable energy resolution 0.6% - 0.06%
• Multi-technique capability (AES-Auger Electron Spectroscopy, XPS-X-ray Photoelectron Spectroscopy)
• Avantage, a Windows based data system

• X-ray gun (twin anode source: AlK_a, MgK_a) for XPS measurements (spatial distribution: average value from all sample surface area); this extends the use of this instrument to (X-ray Photoelectron Spectroscopy) dielectric materials,
• ion gun for sputter etching; usually ion gun is used for depth profiling, sample cleaning and charge compensation.

Sample preparation for surface analysis
Samples cannot exceed 10x10 mm surface area and 10 mm thickness. AES technique is limited to conducting materials: metals and semiconductors of sufficient conductivity. The stability of samples in the ultra-high vacuum conditions is required (the pressure lower than 10^-10 mb).

Restrains
Samples containing elements such as Hg, Te, Cs, K, Na, As, J, Zn, Se, P, S, etc. or their compounds cannot be analysed because of a possibility of analyser damage. The same concerns the samples which decompose with emission of compounds such as H₂O, HCl and H₂S under conditions of ultra-high vacuum and/or X-ray radiation.

Local chemical analysis
The following surface information can be obtained:

1. Chemical composition maps of the surface with nano-scale resolution
   • M.Janik-Czachor, J.Bukowska, A.Szummer, A.Molnar, P.Mack, S.M.Filipek, P.Kędzierzawski, A.Kudelski, M.Pisarek, M.Dolata, M.Varga: Modification of Surface Activity of Cu-based Amorphous Alloys by Chemical Processes of Metal Degradation, App. Catal. A, 235 (2002) 157, and 253 (2003) 539
     
   • A. Szummer, M. Janik-Czachor, P. Mack, M. Pisarek: High resolution electron probe characterization of modified Cu-based amorphous alloys, Microsc. & Microanal., 9 (4) (2003) 359
     
   • M. Pisarek, M. Janik-Czachor: Microstructural and Auger microanalytical characterization of Cu-Hf and Cu-Ti catalysts, Microsc. & Microanal., 12 (2006) 228
   • M.Pisarek, M.Janik-Czachor, T.Płociński, M.Łukaszewski: Characterization of catalysts obtained from rapidly quenched alloy precursors by electrochemical/chemical process of material degradation - selected examples, J. Mater. Sci. 44 (2009) 5701-5712 (review)
2. Local information on surface composition and on chemical state of the surface components in nano areas
   • M. Pisarek, M. Janik-Czachor, A. Molnar and K. Hughes: Catalytic Activity of Cu-Based Amorphous Alloy Ribbons Modified by Cathodic Hydrogen Charging, Appl. Catal. A, General, 283 (2005) 177
     
   • Pisarek M., Janik-Czachor M., Molnar A., Rac B.: Cathodic hydrogen charging as a tool to activate Cu-Ti amorphous alloy catalysts, Electrochim. Acta, 50, 5111 (2005)
     
   • M. Janik-Czachor, M. Pisarek, A. Molnar: Activation of Cu-based amorphous alloys ribbons for catalytic applications, ECS Transaction, 1(4) (2006) 479
     
   • M. Lewandowska, A. Roguska, M. Pisarek, B. Polak, M. Janik-Czachor, K.J. Kurzydłowski: Morphology and chemical characterization of Ti surfaces modified for biomedical applications, Biomol. Engin., 24 (2007) 438-442
   • M. Pisarek, M. - Lewandowska, A. Roguska, K.J. Kurzydłowski, M. Janik-Czachor: SEM, Scanning Auger and XPS characterization of chemically pretreated Ti surfaces intended for biomedical applications, Mater. Chem. Phys., 104 (2007) 93-97
     
   • M.Pisarek, M.Janik-Czachor, M.Donten: Local characterization of electrodeposited Ni-W amorphous alloy by Auger microanalysis, Surf. Coat. Tech., 202 (2008) 1980-1984
     
   • M. Pisarek, M. Łukaszewski, P. Winiarek, P. Kędzierzawski, M. Janik-Czachor: Influence of Cr addition to Raney Ni catalyst on hydrogenation of isoforone, Cat. Comm. 10 (2008) 213-216
   • M. Pisarek, M. Łukaszewski, P. Winiarek, P. Kędzierzawski, M. Janik-Czachor: Selective catalytic hydrogenation of isophorone on Ni-Al alloy modified with Cr, Mater. Chem. Phys., 114 (2009) 774-779
   • M.Pisarek, M.Łukaszewski, P.Winiarek, P.Kędzierzawski, M.Janik-Czachor: Catalytic activity of Cr or Co modified Ni-based rapidly quenched alloys in the hydrogenation of isophorone, Appl. Catal. A, 358 (2009) 240-248
   • M. Pisarek, M. Łukaszewski, M. Janik-Czachor: Auger Electron Spectroscopy for materials Science: Examples of Applications. Polish J. Chem., 83 (2009) 1393-1412 (review)
   • A. Roguska, A. Kudelski, M. Pisarek, M. Lewandowska, M. Dolata, M. Janik-Czachor: Raman investigations of TiO2 nanotube substrates covered with thin Ag or Cu deposits, J. Raman Spectr. 40, (2009) 1652-1656, DOI: 10.1002/jrs.2314
   • A. Roguska, A. Kudelski, M. Pisarek, M. Lewandowska, K.J. Kurzydłowski, M. Janik-Czachor: In situ spectroelectrochemical surface-enhanced Raman scattering (SERS) investigations on composite Ag/TiO2-nanotubes/Ti substrates, Surface Sci. 603 (2009) 2820-2824
   • M.Pisarek, M.Janik-Czachor, T.Płociński, M.Łukaszewski: Characterization of catalysts obtained from rapidly quenched alloy precursors by electrochemical/chemical process of material degradation - selected examples, J. Mater. Sci. 44 (2009) 5701-5712 (review)
   • A.Roguska, A.Kudelski, M.Pisarek, M.Opara, M.Janik-Czachor: Raman investigations of SERS activity of Ag nanoclusters on a TiO2-nanotubes/Ti substrate. Vibr. Spectr., 55 (2010) 38-43, doi:10.1016/j.vibspec.2010.07.003
   • M. Pisarek, A. Roguska, M. Andrzejczuk: Charakterystyka nanoporowatych warstw na Ti jako perspektywicznych podłoży dla zastosowań biomedycznych. Inżynieria Materiałowa 2011, XXXII, 71
   • M. Pisarek, A. Roguska, M. Andrzejczuk, L. Marcon, S. Szunerits, M. Lewandowska, M. Janik-Czachor: Effect of two-step functionalization of Ti by chemical processes on protein adsorption. Applied Surface Science 2011 , 257 (2011) 8196
   • A. Roguska, A. Kudelski, M. Pisarek, M. Opara, M. Janik-Czachor: Surface-enhanced Raman scattering (SERS) activity of Ag, Au and Cu nanoclusters on TiO2-nanotubes/Ti substrate. Applied Surface Science, 257 (2011) 8182 doi:10.1016/j.apsusc.2010.12.048 ,
   • A. Roguska, M. Pisarek, M. Andrzejczuk, M. Dolata, M. Lewandowska M. Janik-Czachor: Characterization of a calcium phosphate-TiO2 nanotube composite layer for biomedical applications. Materials Science and Engineering C, 31 (2011) 906 doi:10.1016/j.msec.2011.02.009
   • A. Roguska, S.Hiromoto, A. Yamamoto, M.J. Woźniak, M. Pisarek, M. Lewandowska: Collagen immobilization on 316L stainless steel surface with cathodic deposition of calcium phosphate. Applied Surface Science 257 (2011) 5037-5045
   • I.E.Malka, M.Pisarek, T.Czujko, J.Bystrzycki: A study of the ZrF4, NbF5, TaF5 and TiCl3 influences on the MgH2 sorption properties, Int. J. Hydrogen Energy 36 (2011) I2909-I2917
   • A.Lewera, L.Timperman, A.Roguska, N.Alonso-Vante: Metal-Support Interactions between Nanosized Pt and Metal Oxides (WO3 and TiO2) Studied using XPS, J. Phys. Chem. C 115 (2011) 20153-20159
   • M.Holdynski, M.Sintyureva, X.Liu, W.Wrobel, J.R.Dygas, M.Pisarek, R.M.Nix, F.Krok and I.Abrahams: Phase and Electrical Behaviour in Bi4NbO8.5, J. Phys.: Condens. Matter (2012), accepted
3. Composition profiles of thin surface films with a depth resolution below a nm
   • M. Janik-Czachor, A. Jaskiewicz, M. Dolata, Z. Werner, Passivity and its breakdown in Al-based amorphous alloys, Mater. Chem. Phys., 92 (2005) 348;
     
   • Werner Z., Jaskiewicz A., Pisarek M., Janik-Czachor M., Barlak M.: AES and RBS characterization of anodic oxide films on Al-Ta amorphous alloys, Z. Phys. Chem., 219, 1461 (2005)
     
   • M.Lewandowska, M.Pisarek, K.Rożniatowski, M.Grądzka-Dahlke, M. Janik-Czachor, K.J.Kurzydłowski: Nanoscale characterization of anodic oxide films on Ti-6Al-4V alloy, Thin Solid Films, 515 (2007) 646.
     
   • M.Pisarek: Characterization of metallic oxide thin-layer materials by Auger Electron Spectroscopy (AES) combined with Ar+ ion etching, Ann. Chim-Sci. Mat., 32 (4) (2007) 383-394
     
   • M.Pisarek, P.Kędzierzawski, M.Janik-Czachor, K.J.Kurzydłowski: The Effect of Hydrostatic Extrusion on the Corrosion Resistance of 316 Stainless Steel, Corrosion NACE, Vol. 64, No. 2 (2008) 131-137
   • M.Pisarek, P.Kędzierzawski, T.Płociński, M.Janik-Czachor, K.J.Kurzydłowski, Characterization of the Effects of Hydrostatic Extrusion on Grain Size, Surface Composition and the Corrosion Resistance of Austenitic Stainless Steels, Mat. Charact., 59 (9) (2008) 1292-1300
   • M.Pisarek, P.Kędzierzawski, M.Janik-Czachor, K.J.Kurzydłowski, Effect of Hydrostatic Extrusion on Passivity Breakdown on 303 Austenitic Stainless Steel in Chloride Solution, J. Solid State Electrochem. (Special Issue EMRS 2007), 13 (2009) 283-291
   • M. Pisarek, M. Łukaszewski, M. Janik-Czachor: Auger Electron Spectroscopy for materials Science: Examples of Applications. Polish J. Chem., 83 (2009) 1393-1412 (review)
4. Monographs
   • M.Janik-Czachor, M.Pisarek, Electrochemical, Microscopic and Surface Analytical Studies of Amorphous and Nanocrystalline Alloys, "Progres in Corrosion Science and Enegineering I" , Chapter 3 in: Modern Aspects of Electrochemistry, Su-Il Pyun, Jong-Won Lee (Eds.), Vol. 46 (2009) 175-230 pp. 175-230, Springer, New York 2009 (invited paper)

Scanning Electrochemical Microscopy
The Scanning Electrochemical Microscope designed by dr M. Dolata and dr P. Kędzierzawski and built in the Institute of Physical Chemistry PAS is a scanning probe instrument, which makes it possible to measure a distribution of some quantities as potential, current or pH over a surface of metal or semiconductor electrode. The instrument consists of an X-Y stage propelled by stepper motors and used to move a microsensor near the surface of the electrode, a motor controller, a potentiostat, a low noise and high input impedance signal conditioning system and a data acquisition system. Both microsensor movement and measurements are computer-controlled with a program developed at the Institute. The SEM has a step size of 0.3 mm and lateral resolution of the order of mms depending on sensor size, distance from the electrode and an electrode roughness.

Application areas
Local corrosion studies, galvanic and paint coatings studies, corrosion and electrocatalysis studies of composite materials, electrode mechanisms, microstructure deposition using Scanning Counter Electrode technique.

Sample limitations
The instrument will accommodate plain samples of conducting material of the diameter of 8 mm and the height of 10 mm.

* Electrochemical System for Corrosion Studies
Autolab PGSTAT302N - for electrochemical investigations, providing major electrochemical methods including Electrochemical Impedance Spectroscopy (EIS).

Other activities

• 2011 - the Center celebrated its 7-th anniversary, see details, photogallery
• Prof. M.Janik-Czachor was a member of the Scientific Committee of the Conference Corrosion 2011, in Rytro (Poland) and was an invited speaker there.
• M.Warczak M.Sc. and A.Roguska M.Sc. won in the Iuventus Programme (see details)
• In 2010 the Physical Chemistry of Materials Center, in co-operation with the Faculty of Chemistry of the University of Warsaw and Hokkaido University in Sapporo, organized 10th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials (cyclic Symposia) within the frame of EMRS Fall Meeting 2010. See details and photo gallery: Opening and lectures, Social events.
• Prof. M.Janik-Czachor was a member of the International Scientific Committee of the Corrosion and Material Protection Conference in Prague, 19 - 22.04.2010, and an invited speaker there.
• Prof. K. Hashimoto, prof. M. Janik-Czachor and prof. P. Kulesza are the guest editors of a special issue of J. Solid State Electrochem. 13, 2 (2009), where the electrochemistry oriented papers from "E-MRS 2007, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials", Warsaw, 17th-21st September, 2007 are published.
• In 2009 Physical Chemistry of Materials Center celebrated its 5th anniversary, see details
• Dr. M.Pisarek is participating, since 2009, in UE research project "CORRAL" ( in Ecole Nationale Superieure de Chimie de Paris, Prof. Ph.Marcus).
  Dr. M.Pisarek presented following lectures in the scientific centres in France:
  - Electrochemical, Microscopic and Surface Analytical Studies of Structural and Functional Materials ( in Ecole Nationale Superieure de Chimie de Paris, Prof. Ph.Marcus),
  - Auger Electron Spectroscopy for Materials Science: Examples of Application (in Interdisciplinary Research Institute, Villenevue d'Ascq, Prof. S.Szunertis).
• Prof. dr. M.Janik-Czachor was an invited speaker at the International Stefan Mroz Sympozjum at the University of Wroclaw.
• Prof. dr. M.Janik-Czachor was an invited speaker at the International Symposium "Diffusion and Reaction: Multiscale Phenomena - on the Occasion of the 80th birthday anniversary of Prof. Stanisław Mrowec" at the University of Science and Technology, AGH, Kraków.
• In 2007 the Physical Chemistry of Materials Center, in co-operation with the Faculty of Chemistry of the University of Warsaw, organized 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials (cyclic Symposia) within the frame of EMRS Fall Meeting 2007. See details
• Dr. Kędzierzawski is involved since 2007 in a cooperation with Nano Material Laboratories, Materials Engineering Department, Tatung University. Taipei, Taiwan. The cooperation is focused on the application of carbon nanotubes as a support of catalysts for fuel cells (Direct Formic Acid Fuel Cell).
  

Consultants
Prof. A. Szummer, Prof. K. Sikorski, Prof. Z. Werner.

Information available:
Department of Electrochemistry, Corrosion and Applied Surface Science
Institute of Physical Chemistry, Polish Academy of Sciences
Kasprzaka 44/52
01-224 Warszawa
tel.: +48 (22) 343 3325
fax: +48 (22) 632 5276
e-mail: maria@ichf.edu.pl or marcinp@ichf.edu.pl

Staff:

• Piotr Kędzierzawski, Ph.D.
• Andrzej Sadkowski, D.Sc.
• Marcin Pisarek, Ph.D.
• Agata Roguska, M.Sc.
• Magdalena Warczak, M.Sc.