Kautek, W. in Situ Diagnostic and Laser. 2010

8/7/2019 Kautek, W. in Situ Diagnostic and Laser. 2010

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University of Vienna - Department of Physical Chemistry W . Kautek

InIn--situ diagnostics andsitu diagnostics and

dynamic protection studies bydynamic protection studies by

Gracing Incidence XGracing Incidence X--RayRay DiffractometryDiffractometry

Fourier Transform IRFourier Transform IR--Spectroscopy, andSpectroscopy, andnovel Lasernovel Laser--electrochemical approacheselectrochemical approaches

Wolfgang KautekWolfgang Kautek

University of ViennaUniversity of ViennaDepartment of Physical ChemistryDepartment of Physical Chemistry

WWhringerhringer StrasseStrasse 4242

AA--1090 Vienna1090 Vienna

AustriaAustria


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CoworkersCoworkers

A. CortonaA. Cortona

D.D. DaminelliDaminelliS.S. DieluweitDieluweit

U.U. HasbachHasbach

M.M. GeuGeu

M.M. HandreaHandreaG.G. NauerNauer

M.M. NauerNauer

M.M. SahreSahre

P. ZhaoP. Zhao

S. ArifS. Arif

M. ForsterM. ForsterK. KlinganK. Klingan

T. NagyT. Nagy

G. TrettenhahnG. Trettenhahn

C. ZafiuC. Zafiu


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OutlineOutline

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 NanotribologyIn-situ Laser Electrochemical Activation


4/45University of Vienna - Department of Physical Chemistry W . Kautek

Electrochemical Quartz MicrobalanceElectrochemical Quartz Microbalance

additional holes

holes for the electrodes

electrode

holder

Solution holder

working electrode

base platequartz holder

quartz

connection to the oscillator

solution

qqA

mff

=

2

02

Acc. Zafiu et al.



elektrochemische Quarz-Mikrowaage

Electrochemical Quartz MicrobalanceElectrochemical Quartz Microbalance



EQMB: Double Layer StructureEQMB: Double Layer Structure

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


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EQMB:EQMB:

Au oxide monolayer,Au oxide monolayer,Place exchangePlace exchange

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

Au, 0.5 M NaOH


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EQMB: Copper (pH 12)EQMB: Copper (pH 12)

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

0.1 M Na2SO

4(pH 12), scan rate 0.02 V/s


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In situ grazing incidence xIn situ grazing incidence x--rayray diffractogramdiffractogram

(GIXD)(GIXD)


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In situ grazing incidence xIn situ grazing incidence x--rayray diffractogramdiffractogram

(GIXD):(GIXD):Copper in 0.1 M NaCopper in 0.1 M Na22SOSO44 (pH 12)(pH 12)



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OutlineOutline



In-situ Fourier Transfer Infrared Spectrometry(FTIR)


In-situ Nanotribology

In-situ Laser Electrochemical Activation


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In situ FTIRIn situ FTIR


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Au working electrode

Pt counter electrode

Ar gas line

ZnSe window

IR beam

Ag/AgCl reference electrode

m screw

Thin layer

In situ FTIRIn situ FTIR

Acc. Zafiu et al.


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Ex situ and in situ FTIR data of Cu inEx situ and in situ FTIR data of Cu in

fluoride andfluoride and sulphatesulphate electrolytes (pH 12)electrolytes (pH 12)



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Ex situ and in situ FTIR data of Cu inEx situ and in situ FTIR data of Cu in

fluoride andfluoride and sulphatesulphate electrolytes (pH 12)electrolytes (pH 12)



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In situ FTIR: Zn, ZnIn situ FTIR: Zn, Zn--Fe AlloyFe Alloyon Steelon Steel


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In situ FTIR: ZnIn situ FTIR: Zn

0.1 M Na0.1 M Na22SOSO44 (pH 12)(pH 12)

22(-OH,bend)

2(-OH,bend)

Sulfate

Zn(OH)2

Exchange OH- for SO4-


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InIn--situ GIXD: Znsitu GIXD: Zn

0.1 M Na0.1 M Na22SOSO44 (pH 12)(pH 12)

-Zn(OH)2, Wulfingite, orthorombic


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OutlineOutline




In-situ Fourier Transfer Infrared Spectrometry (FTIR)



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NanotribologyNanotribology::

Ag inAg in KBrKBr

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

(b, d) 0.001 M(b, d) 0.001 M KBrKBr, 0.1 M KF,, 0.1 M KF,

0.010.01 NaOHNaOH

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


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InIn--situ 1D lateral force:situ 1D lateral force:Specific adsorption of bromide. Ag inSpecific adsorption of bromide. Ag in KBrKBr electrolyteelectrolyte

(0.1 M KF, 0.01 M(0.1 M KF, 0.01 M NaOHNaOH, 0.001, 0.001 KBrKBr))



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NanotribologyNanotribology



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OutlineOutline



In-situ Atomic Force Microscopy (AFM)In-situ Fourier Transfer Infrared Spectrometry (FTIR)



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LaserLaser CleaningCleaning

-- a Phase Separation Problema Phase Separation Problem


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Synagogue of Triest, by Otto Wagner, Vienna, Austria"Wettbewerb fr den Israelischen Tempel in Triest

Laser-cleaned, F= 1.0 J cm-1, 1Hz, 0.2 mm s-1

HighHigh PrecisionPrecision NonNon -- ContactContact RubberRubber


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PrecisionPrecision LaserLaser CleaningCleaning PrintedPrinted PaperPaper

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


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Recent Review Literature onLaser 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)

Model SystemModel System: AlOAlO LayersLayers


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Model System:Model System: AlOAlOxx LayersLayers

HC TE

Anodization:electrolytepotential

Hard Coatingsulphuric and oxalic acid50 V

Technical Eloxalsulphuric acid15 V

Properties:total thickness,

Colour

porous oxide70 m

Black

porous oxide30 m

Transparent

W. Kautek, G. Daminelli, Electrochim. Acta 48 (2003) 3249."Electrochemical reactivity of laser machined microcavities on anodised aluminium alloys".


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

TransparentTransparent AlOAlOxx coating on absorbing Al substratecoating on absorbing Al substrate

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


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Transparent coating on absorbing substrateTransparent coating on absorbing substrate

MOx

MM

Defects

M

Defects

Spallation

MOx MOx



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AbsorbingAbsorbing AlOAlOxx coating on absorbing Al substratecoating on absorbing Al substrate

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



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Absorbing coating on absorbing substrateAbsorbing coating on absorbing substrate

M M M

MOxMOx

Laser

Laser

MOx

Laser


InIn--situsitu MonitoringMonitoring of Laserof Laser CleaningCleaning of Metalsof Metals


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InIn--situsitu MonitoringMonitoring of Laserof Laser CleaningCleaning of Metalsof Metals

Electrolyte


MolecularMolecular inin--situsitu probe ofprobe of laserlaser cleaningcleaning


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MolecularMolecular inin situsitu probe ofprobe of laserlaser cleaningcleaning

Molecular in-situ probe:

Charging of ElectrochemicalHelmholtz plane


ElectrochemicalElectrochemical


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currentcurrent

measurementsmeasurements

-3 -2 -1 0 1 2 3

-40

-20

0

20

40

OCP

Applied potential

TE

C

urrent(A)

Potential (VMSE

)

-40

-20

0

20

40

HC

Cu

rrent(A)



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currentcurrent

measurementsmeasurements

2Al + 3H2O Al2O3 + 3H22Al + 6H2O 2Al

3+ + 3H2 + 6OH-

0 20 40 60 80 100 120 140

0

20

40

60

80

Imax

Ncrit

Nin

HC

6,62 Jcm-2

Curren

t(A)

Number of pulses


ElectrochemicalElectrochemical Evaluation of the Shock Affected ZoneEvaluation of the Shock Affected Zone


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ElectrochemicalElectrochemical Evaluation of the Shock Affected ZoneEvaluation of the Shock Affected Zone

Electrolyte

d

SAZ

MOx

Laser beam

WE

CE

Ion Current


ActiveActive electrochemistry ofelectrochemistry of passivatingpassivating metalmetal


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ActiveActive electrochemistry ofelectrochemistry of passivatingpassivating metalmetal

10 12 14 16 18 20

0

5

10

15

20

25

Curr

ent/A

Time / ms

-1,25 V

N = 52

N = 73

Absorbing Al2O3 on Al substrateF = 20.5 Jcm-2 and U = -1.25 V (vs. MSE)

2Al + 3H2O Al2O3 + 3H22Al + 6H2O 2Al

3+ + 3H2 + 6OH-


R P i i f Pi2,5x10

5


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ReRe--PassivationPassivation of Pits:of Pits:

Impedance EvaluationImpedance Evaluation

from Current Transientsfrom Current Transients

0,0

5,0x104

1,0x105

1,5x105

2,0x105

2,5x10

Absorbing Al2O3 on Al substrate

F = 20.5 Jcm-2

Resistance/

50 60 70 80 90 100

0,0

1,0x10-7

2,0x10-7

3,0x10-7

4,0x10-7

Capacitance/F

-1,25 V

+0,25 V

Number of pulses

( )RC

t

eItI

= 0

thin

thick

thick

thin

.... Details about dielectric

and conductive properties

!!

Irradiation of Oxides with UV LaserIrradiation of Oxides with UV Laser


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Irradiation of Oxides with UV LaserIrradiation of Oxides with UV Laser

Sol C, Tilley RJD, J. Mater. Chem. 11 (2001) 815-820Ultraviolet laser irradiation induced chemical reactions of some metal oxides

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

El h i lEl t h i l II iit i iit i


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ElectrochemicalElectrochemical InIn--situsitu monitoringmonitoring

cleaning

micro-machining

corrosion

"etch-stop" of layer removal

"shock-affected-zone (laser-induced defects)

laser removal mechanismselectrochemical kinetics of active metal

repassivation kinetics

Physical Chemistry andPhysical Chemistry and NanotechnologyNanotechnology of Interfacesof Interfaces


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Femtosecond Laser technologyWorking Group Wolfgang KAUTEK

RamanScattering

HarmonicGeneration

Fluorescence

Fs-LaserExcitation

Scattering

MultiphotonMultiphoton Fluorescence and 3DFluorescence and 3D--Microscopy in CHMicroscopy in CH


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Documents

Kautek, W. in Situ Diagnostic and Laser. 2010