In-situ diagnostics and

dynamic protection studies by

Gracing Incidence X-Ray Diffractometry
Fourier Transform IR-Spectroscopy, and
novel Laser-electrochemical approaches

Wolfgang Kautek

University of Vienna
Department of Physical Chemistry
Währinger Strasse 42
A-1090 Vienna
Austria
University of Vienna - Department of Physical Chemistry – W. Kautek
 Coworkers

S. Arif A. Cortona
M. Forster D. Daminelli
K. Klingan S. Dieluweit
T. Nagy U. Hasbach
G. Trettenhahn M. Geuß
C. Zafiu M. Handrea
G. Nauer
M. Nauer
M. Sahre
P. Zhao

University of Vienna - Department of Physical Chemistry – W. Kautek

 Outline

In-situ Quartz Microbalance

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)
In-situ Atomic Force Microscopy (AFM)
In-situ Fourier Transfer Infrared Spectrometry (FTIR)
In-situ Nanotribology
In-situ Laser Electrochemical Activation

University of Vienna - Department of Physical Chemistry – W. Kautek

 Electrochemical Quartz Microbalance

2 f 0 Δm
electrode
2

Δf = −
holder

solution

holes for the electrodes

additional holes
Solution holder
A μq ρq
working electrode

quartz
base plate
quartz holder

connection to the oscillator

Acc. Zafiu et al.

University of Vienna - Department of Physical Chemistry – W. Kautek

 Electrochemical Quartz Microbalance

elektrochemische Quarz-Mikrowaage

University of Vienna - Department of Physical Chemistry – W. Kautek

 EQMB: Double Layer Structure

Au, 0.5 M NaOH W. Kautek, M. Sahre, and D.M. Soares, Ber. Bunsenges. Phys. Chem. 99 (1995) 667

University of Vienna - Department of Physical Chemistry – W. Kautek

 EQMB:
Au oxide monolayer,
Place exchange

Au, 0.5 M NaOH

W. Kautek, M. Sahre, and D.M. Soares, Ber. Bunsenges. Phys. Chem. 99 (1995) 667

University of Vienna - Department of Physical Chemistry – W. Kautek

 EQMB: Copper (pH 12)
0.1 M Na2SO4 (pH 12), scan rate 0.02 V/s

W. Kautek, M. Geuß, M. Sahre, P. Zhao, S. Mirwald, Surf. Interface Anal. 25 (1997) 548
University of Vienna - Department of Physical Chemistry – W. Kautek
 In situ grazing incidence x-ray diffractogram
(GIXD)

University of Vienna - Department of Physical Chemistry – W. Kautek

 In situ grazing incidence x-ray diffractogram
(GIXD):
Copper in 0.1 M Na2SO4 (pH 12)

W. Kautek, M. Geuß, M. Sahre, P. Zhao, S. Mirwald, Surf. Interface Anal. 25 (1997) 548
University of Vienna - Department of Physical Chemistry – W. Kautek
 Outline

In-situ Quartz Microbalance

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)
In-situ Fourier Transfer Infrared Spectrometry
(FTIR)
In-situ Atomic Force Microscopy (AFM)
In-situ Nanotribology
In-situ Laser Electrochemical Activation

University of Vienna - Department of Physical Chemistry – W. Kautek

 In situ FTIR

University of Vienna - Department of Physical Chemistry – W. Kautek

 In situ FTIR
Ag/AgCl reference electrode

Ar gas line

Pt counter electrode

Thin layer
Au working electrode
IR beam

ZnSe window
Acc. Zafiu et al.
µm screw
University of Vienna - Department of Physical Chemistry – W. Kautek
 Ex situ and in situ FTIR data of Cu in
fluoride and sulphate electrolytes (pH 12)

W. Kautek, M. Geuß, M. Sahre, P. Zhao, S. Mirwald, Surf. Interface Anal. 25 (1997) 548

University of Vienna - Department of Physical Chemistry – W. Kautek

 Ex situ and in situ FTIR data of Cu in
fluoride and sulphate electrolytes (pH 12)

W. Kautek, M. Geuß, M. Sahre, P. Zhao, S. Mirwald, Surf. Interface Anal. 25 (1997) 548

University of Vienna - Department of Physical Chemistry – W. Kautek

 In situ FTIR: Zn, Zn-Fe Alloy
on Steel

University of Vienna - Department of Physical Chemistry – W. Kautek

 In situ FTIR: Zn
0.1 M Na2SO4 (pH 12)

2ν2(-OH,bend)
Exchange OH- for SO4-

ν2(-OH,bend) Zn(OH)2

Sulfate

University of Vienna - Department of Physical Chemistry – W. Kautek

 In-situ GIXD: Zn
0.1 M Na2SO4 (pH 12)

ε-Zn(OH)2, Wulfingite, orthorombic

University of Vienna - Department of Physical Chemistry – W. Kautek

 Outline

In-situ Quartz Microbalance

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)
In-situ Atomic Force Microscopy (AFM)
In-situ Fourier Transfer Infrared Spectrometry (FTIR)
In-situ Nanotribology
In-situ Laser Electrochemical Activation

University of Vienna - Department of Physical Chemistry – W. Kautek

 Nanotribology:
Ag in KBr

(a, c) 0.1 M KF, 0.01 NaOH,

(b, d) 0.001 M KBr, 0.1 M KF,
0.01 NaOH

W. Kautek, S. Dieluweit, and M. Sahre, J. Phys. Chem. 101 (1997) 2709.

University of Vienna - Department of Physical Chemistry – W. Kautek

 In-situ 1D lateral force:
Specific adsorption of bromide. Ag in KBr electrolyte
(0.1 M KF, 0.01 M NaOH, 0.001 KBr)

W. Kautek, S. Dieluweit, and M. Sahre, J. Phys. Chem. 101 (1997) 2709.

University of Vienna - Department of Physical Chemistry – W. Kautek

 Nanotribology

W. Kautek, S. Dieluweit, and M. Sahre, J. Phys. Chem. 101 (1997) 2709.

University of Vienna - Department of Physical Chemistry – W. Kautek

 Outline

In-situ Quartz Microbalance

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)
In-situ Atomic Force Microscopy (AFM)
In-situ Fourier Transfer Infrared Spectrometry (FTIR)
In-situ Nanotribology
In-situ Laser Electrochemical Activation

University of Vienna - Department of Physical Chemistry – W. Kautek

 Laser Cleaning
- a Phase Separation Problem

University of Vienna - Department of Physical Chemistry – W. Kautek

 High Precision Non - Contact Rubber

Synagogue of Triest, by Otto Wagner, Vienna, Austria

"Wettbewerb für den Israelischen Tempel in Triest„
Laser-cleaned, F = 1.0 J cm-1, 1Hz, 0.2 mm s-1

University of Vienna - Department of Physical Chemistry – W. Kautek

 Precision Laser Cleaning – Printed Paper

W. Kautek, S. Pentzien, Springer Proceedings in Physics, Vol. 100, Dickmann, K.; Fotakis, C.; Asmus, J.F. (Eds.), 2005, 403

University of Vienna - Department of Physical Chemistry – W. Kautek

 Recent Review Literature on
Laser Cleaning in Cultural Heritage
[1] C. Fotakis, W. Kautek, M. Castillejo (eds.),
Laser Chemistry, Special Issue,
Lasers in the Preservation of Cultural Heritage
(Hindawi Publishing Corporation New York 2006)
[2] C. Fotakis, D. Anglos, V. Zafiropulos, S. Georgiou, V. Tornari,
Lasers in the Preservation of Cultural Heritage:
Principles and Applications
(Taylor & Francis, New York, USA 2006).
[3] D.M. Kane (ed.),
Laser Cleaning II
(World Scientific, New Jersey, London, Singapore 2006)
[4] J. Nimmrichter, W. Kautek, M. Schreiner (eds.),
Springer Proceedings in Physics, Vol. 116,
Lasers in the Conservation of Artworks VI
(Springer-Verlag Heidelberg 2007)
[5] M. Schreiner, M. Strlic, R. Salimbeni (eds.)
Handbook on the Use of Lasers in Conservation and Conservation Science
(COST Office, Brussels 2008)
University of Vienna - Department of Physical Chemistry – W. Kautek
 Model System: AlOx Layers

HC TE
Anodization: Hard Coating Technical Eloxal
electrolyte sulphuric and oxalic acid sulphuric acid
potential 50 V 15 V
Properties: porous oxide porous oxide
total thickness, 70 µm 30 µm
Colour Black Transparent
W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249.
"Electrochemical reactivity of laser machined microcavities on anodised aluminium alloys".

University of Vienna - Department of Physical Chemistry – W. Kautek

 Transparent AlOx coating on absorbing Al substrate

(a) F = 1.7 Jcm-2, N = 20 (b) F = 2.9 Jcm-2, N = 1

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 Transparent coating on absorbing substrate

Defects Defects
Spallation

MOx MOx MOx

M M M

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 Absorbing AlOx coating on absorbing Al substrate

F = 4.3 J cm-2, N = 1000 F = 6.4 J cm-2; N = 1000

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 Absorbing coating on absorbing substrate

Laser

Laser
Laser

MOx MOx MOx

M M M

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 In-situ Monitoring of Laser Cleaning of Metals

Electrolyte

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 Molecular in-situ probe of laser cleaning

Molecular in-situ probe:

Charging of Electrochemical
Helmholtz plane

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek
 Electrochemical
40
current
HC
measurements 20

Current ( μ A)
0

-20

-40
40
TE
20

Current ( μ A)
0

-20

-40
-3 -2 -1 0 1 2 3

Potential (V MSE )
OCP
Applied potential

University of Vienna - Department of Physical Chemistry – W. Kautek

 Electrochemical 2Al + 3H2O → Al2O3 + 3H2
current 2Al + 6H2O → 2Al3+ + 3H2 + 6OH-

measurements

80
HC
-2
60 6,62 Jcm N crit

I max
Current (µA)

40

20
N in

0 20 40 60 80 100 120 140

Number of pulses

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 Electrochemical Evaluation of the Shock Affected Zone

CE Laser beam

Electrolyte
Ion Current

HAZ

MOx L

SAZ

WE
W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249
University of Vienna - Department of Physical Chemistry – W. Kautek
 “Active” electrochemistry of “passivating” metal
2Al + 3H2O → Al2O3 + 3H2
2Al + 6H2O → 2Al3+ + 3H2 + 6OH-

25
-1,25 V
20 N = 52
Current / µA N = 73
15

10

10 12 14 16 18 20

Time / m s
Absorbing Al2O3 on Al substrate
F = 20.5 Jcm-2 and U = -1.25 V (vs. MSE)

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249

University of Vienna - Department of Physical Chemistry – W. Kautek

 5
2,5x10
Re-Passivation of Pits:
5 thick
Impedance Evaluation 2,0x10

Resistance / Ω
from Current Transients 1,5x10
5

5
t 1,0x10
−
I (t ) = I 0 e RC
5,0x10
4
thin

0,0

.... Details about dielectric 4,0x10

-7
-1,25 V
and conductive properties +0,25 V thick

Capacitance / F
-7
3,0x10

ε!!
-7
2,0x10

thin
-7
1,0x10

0,0
Absorbing Al2O3 on Al substrate 50 60 70 80 90 100
F = 20.5 Jcm-2 Number of pulses

University of Vienna - Department of Physical Chemistry – W. Kautek

 Irradiation of Oxides with UV Laser

Discoloration due to stoichometric changes

1) TiO2, CeO2, Nb2O5, MoO3 and WO3:

blue-black

2) V2O5, Cr2O3, Fe2O3, NiO, CuO, CdO, Tl2O3:

silver-metallic

3) Al2O3, MgO, ZrO2, Ta2O5, ZnO, Ga2O3, Sb2O4, In2O3,

SnO2, Y2O3, Eu2O3, Sm2O3 : no significant change

Sol C, Tilley RJD, J. Mater. Chem. 11 (2001) 815-820

“Ultraviolet laser irradiation induced chemical reactions of some metal oxides”

University of Vienna - Department of Physical Chemistry – W. Kautek

 Electrochemical In-situ monitoring

cleaning
micro-machining
corrosion

"etch-stop" of layer removal

"shock-affected-zone“ (laser-induced defects)
laser removal mechanisms
electrochemical kinetics of active metal
repassivation kinetics

University of Vienna - Department of Physical Chemistry – W. Kautek

 Physical Chemistry and Nanotechnology of Interfaces
Femtosecond Laser technology
Working Group Wolfgang KAUTEK

Raman
Scattering

Fs-Laser Harmonic
Excitation Generation

Fluorescence
Scattering

University of Vienna - Department of Physical Chemistry – W. Kautek

 Multiphoton Fluorescence and 3D-Microscopy in CH

University of Vienna - Department of Physical Chemistry – W. Kautek

 Literature
o W. Kautek, Corrosion Sci. 28 (1988) 173, "The Galvanic Corrosion of Steel Coatings: Aluminium in Comparison to Cadmium and Zinc".
o A.E. Bohe, J.R. Vilche, K. Jüttner, W.J. Lorenz, W. Kautek, and W. Paatsch, Corros. Sci. 32 (1991) 621.
"An Electrochemical Impedance Spectroscopy Study of Passive Zinc and Low Alloyed Zinc Electrodes in Alkaline and Neutral Aqueous Solutions".
o D.M. Soares, W. Kautek, C. Fruböse, and K. Doblhofer, Ber. Bunsenges. Phys. Chem. 98 (1994) 219.
"The Electrochemical Quartz-Microbalance in Media of Changing Viscoelastic Properties, and the Design and Characterization of Suitable Driver Electronics".
o W. Kautek, M. Sahre, and D.M. Soares, Ber. Bunsenges. Phys. Chem. 99 (1995) 667.
"In-situ Monitoring of Electrochemical Double Layer Structure Changes at Gold with a Phase-Controlled Quartz Microbalance".
o W. Kautek, S. Dieluweit, and M. Sahre, J. Phys. Chem. 101 (1997) 2709.
"Combined In-situ-Scanning Force Microscopy and Electrochemical Quartz Microbalance Investigation of Specific Adsorption and Phase Change Processes at the
Silver/Halogenide Interface".
o W. Kautek, M. Geuß, M. Sahre, P. Zhao, S. Mirwald, Surf. Interface Anal. 25 (1997) 548.
"Multi-Method Analysis of the Metal-Electrolyte Interface: Scanning Force Microscopy (SFM), Quartz-Microbalance Measurements (QMB), Fourier-Transform
Infrared Spectroscopy (FT-IR) and Grazing Incidence X-Ray Diffractometry (GIXD) at a Polycrystalline Copper Electrode".
o W. Kautek, S. Mirwald, M. Sahre, and G. Nauer, Electrochim. Acta 43 (1998) 2979.
”In-situ Grazing Incidence X-Ray Diffractometry of
Polycrystalline Copper in alkaline Chloride and Sulphate Electrolytes”.
o S. Sathiyanarayanan, M. Sahre, W. Kautek, Electrochim. Acta 43 (1998) 2985.
”Grazing Incidence X-Ray Diffractometry Investigation of Phase Change Processes at the Silver/Aqueous-Halogenide Interface”.
o S. Sathiyanarayanan, M. Sahre, and W. Kautek, Fresenius J. Anal. Chem. 363 (1999) 197.
"Influence of surface morphology on the oxidation of metal electrodes studied by
in-situ grazing incidence x-ray diffractometry”.
o S. Sathiyanarayanan, M. Sahre, W. Kautek, Corros. Sci. 41 (1999) 1899 - 1909.
”In-situ Grazing Incidence X-Ray Diffractometry Observation of Pitting Corrosion of Copper in Chloride Solutions”.
o M. Sahre, R. M. Souto, and W. Kautek, Microchim. Acta 133 (2000) 137-142.
"Chromate-Free Zinc Conversion Coatings Characterised by Grazing Incidence X-Ray Diffractometry".
o A. Cortona and W. Kautek, Phys. Chem. Chem. Phys. 3 (2001) 5283-5289.
"Microcorrosion and Shock-Affected Zone Investigation at Anodic Films on Aluminium Alloys by Pulse Laser Depassivation".
o W. Kautek, G. Daminelli Electrochim. Acta 48 (2003) 3249-3255.
"Electrochemical reactivity of laser machined microcavities on
anodised aluminium alloys".
o Hasbach, U. Retter, K. Siegler, and W. Kautek, J. Electroanal. Chem. 561 (2004) 29-35.
"On the impedance of porous electrodes – double-layer charging and charge transfer on an inhomogeneous inside electrode surface".
o M. Nauer, K. Ernst, W. Kautek, M. Neumann-Spallart, Thin Solid Films 489 (2005) 86-93.
"Depth profile characterization of electrodeposited multi-thin-film structures by low angle of incidence X-ray diffractometry".

University of Vienna - Department of Physical Chemistry – W. Kautek

University of Vienna - Department of Physical Chemistry – W. Kautek