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InIn--situsitu diagnosticsdiagnostics andand dynamicdynamic protectionprotection studiesstudies byby GracingGracing IncidenceIncidence XX--RayRay DiffractometryDiffractometry FourierFourier TransformTransform IRIR--Spectroscopy,Spectroscopy, andand novelnovel LaserLaser--electrochemicalelectrochemical approachesapproaches

WolfgangWolfgang KautekKautek

UniversityUniversity ofof ViennaVienna DepartmentDepartment ofof PhysicalPhysical ChemistryChemistry WWäähringerhringer StrasseStrasse 4242 AA--10901090 ViennaVienna AustriaAustria

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

A A - - 1090 1090 Vienna Vienna Austria Austria University of Vienna - Department of

CoworkersCoworkers

S.S. ArifArif M.M. ForsterForster K.K. KlinganKlingan T.T. NagyNagy G.G. TrettenhahnTrettenhahn C.C. ZafiuZafiu

A.A. CortonaCortona D.D. DaminelliDaminelli S.S. DieluweitDieluweit U.U. HasbachHasbach M.M. GeuGeußß M.M. HandreaHandrea G.G. NauerNauer M.M. NauerNauer M.M. SahreSahre P.P. ZhaoZhao

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

Nauer Nauer M. M. Sahre Sahre P. P. Zhao Zhao University of Vienna - Department of

OutlineOutline

In-situ Quartz MicrobalanceOutline Outline In-situ Grazing Incidence X-Ray Diffractometry (GIXD) In-situ Atomic Force Microscopy (AFM) In-situ

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)Outline Outline In-situ Quartz Microbalance In-situ Atomic Force Microscopy (AFM) In-situ Fourier Transfer Infrared

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

In-situ Fourier Transfer Infrared Spectrometry (FTIR)Diffractometry (GIXD) In-situ Atomic Force Microscopy (AFM) In-situ Nanotribology In-situ Laser Electrochemical

In-situ Nanotribology(AFM) In-situ Fourier Transfer Infrared Spectrometry (FTIR) In-situ Laser Electrochemical Activation University of

In-situ Laser Electrochemical ActivationTransfer Infrared Spectrometry (FTIR) In-situ Nanotribology University of Vienna - Department of Physical Chemistry –

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

In-situ Laser Electrochemical Activation University of Vienna - Department of Physical Chemistry – W. Kautek

ElectrochemicalElectrochemical QuartzQuartz MicrobalanceMicrobalance

quartz
quartz

electrode

holder

solution

holes for the electrodes

Solution holder

additional holes

working electrode

base plate

quartz holder

connection to the oscillator

Δ f =−

2

2 f Δ m

0

A

A μρ q q

μρ

q

q

Acc. Zafiu et al.

f =− 2 2 f Δ m 0 A μρ q q Acc. Zafiu et al.
f =− 2 2 f Δ m 0 A μρ q q Acc. Zafiu et al.

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

2 2 f Δ m 0 A μρ q q Acc. Zafiu et al. University of

ElectrochemicalElectrochemical QuartzQuartz MicrobalanceMicrobalance

Electrochemical Quartz Quartz Microbalance Microbalance elektrochemische Quarz-Mikrowaage University of Vienna -

elektrochemische Quarz-Mikrowaage

Microbalance Microbalance elektrochemische Quarz-Mikrowaage University of Vienna - Department of Physical Chemistry –
Microbalance Microbalance elektrochemische Quarz-Mikrowaage University of Vienna - Department of Physical Chemistry –
Microbalance Microbalance elektrochemische Quarz-Mikrowaage University of Vienna - Department of Physical Chemistry –
Microbalance Microbalance elektrochemische Quarz-Mikrowaage University of Vienna - Department of Physical Chemistry –
Microbalance Microbalance elektrochemische Quarz-Mikrowaage University of Vienna - Department of Physical Chemistry –

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

Microbalance elektrochemische Quarz-Mikrowaage University of Vienna - Department of Physical Chemistry – W. Kautek

EQMB:EQMB: DoubleDouble LayerLayer StructureStructure

Au, 0.5 M NaOH W. Kautek, M. Sahre, and D.M. Soares, Ber. Bunsenges. Phys. Chem.
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

Soares, Ber. Bunsenges. Phys. Chem. 99 (1995) 667 University of Vienna - Department of Physical Chemistry
EQMB:EQMB: AuAu oxideoxide monolayer,monolayer, PlacePlace exchangeexchange Au, 0.5 M NaOH W. Kautek, M. Sahre, and
EQMB:EQMB:
AuAu oxideoxide monolayer,monolayer,
PlacePlace exchangeexchange
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:EQMB: CopperCopper (pH(pH 12)12)

0.1 M Na 2 SO 4 (pH 12), scan rate 0.02 V/s

12) 12) 0.1 M Na 2 SO 4 (pH 12), scan rate 0.02 V/s W. Kautek,

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

S. Mirwald, Surf. Interface Anal. 25 (1997) 548 University of Vienna - Department of Physical Chemistry

InIn situsitu grazinggrazing incidenceincidence xx--rayray diffractogramdiffractogram (GIXD)(GIXD)

x x - - ray ray diffractogram diffractogram (GIXD) (GIXD) University of Vienna - Department of

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

ray ray diffractogram diffractogram (GIXD) (GIXD) University of Vienna - Department of Physical Chemistry – W.

InIn situsitu grazinggrazing incidenceincidence xx--rayray diffractogramdiffractogram (GIXD):(GIXD):

CopperCopper inin 0.10.1 MM NaNa 22 SOSO 44 (pH(pH 12)12)
CopperCopper inin 0.10.1 MM NaNa 22 SOSO 44 (pH(pH 12)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

OutlineOutline

In-situ Quartz MicrobalanceOutline Outline In-situ Grazing Incidence X-Ray Diffractometry (GIXD) In-situ Fourier Transfer Infrared Spectrometry

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)Outline Outline In-situ Quartz Microbalance In-situ Fourier Transfer Infrared Spectrometry (FTIR) In-situ Atomic Force

In-situ Fourier Transfer Infrared Spectrometry (FTIR) (FTIR)

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

In-situ NanotribologySpectrometry (FTIR) In-situ Atomic Force Microscopy (AFM) In-situ Laser Electrochemical Activation University of

In-situ Laser Electrochemical ActivationIn-situ Atomic Force Microscopy (AFM) In-situ Nanotribology University of Vienna - Department of Physical Chemistry –

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

In-situ Laser Electrochemical Activation University of Vienna - Department of Physical Chemistry – W. Kautek

InIn situsitu FTIRFTIR

In In situ situ FTIR FTIR University of Vienna - Department of Physical Chemistry – W.
In In situ situ FTIR FTIR University of Vienna - Department of Physical Chemistry – W.

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

In In situ situ FTIR FTIR University of Vienna - Department of Physical Chemistry – W.

InIn situsitu FTIRFTIR

Ag/AgCl reference electrode In In situ situ FTIR FTIR Ar gas line Pt counter electrode Thin layer Au working

Ar gas line Pt counter electrode Thin layer Au working electrode IR beam ZnSe window
Ar gas line
Pt counter electrode
Thin layer
Au working electrode
IR beam
ZnSe window

Acc. Zafiu et al.

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

µm screw

IR beam ZnSe window Acc. Zafiu et al. University of Vienna - Department of Physical Chemistry

ExEx situsitu andand inin situsitu FTIRFTIR datadata ofof CuCu inin fluoridefluoride andand sulphatesulphate electrolyteselectrolytes (pH(pH 12)12)

sulphate electrolytes electrolytes (pH (pH 12) 12) W. Kautek, M. Geuß, M. Sahre, P. Zhao, 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

S. Mirwald, Surf. Interface Anal. 25 (1997) 548 University of Vienna - Department of Physical Chemistry

ExEx situsitu andand inin situsitu FTIRFTIR datadata ofof CuCu inin fluoridefluoride andand sulphatesulphate electrolyteselectrolytes (pH(pH 12)12)

sulphate electrolytes electrolytes (pH (pH 12) 12) W. Kautek, M. Geuß, M. Sahre, P. Zhao, 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

S. Mirwald, Surf. Interface Anal. 25 (1997) 548 University of Vienna - Department of Physical Chemistry

InIn situsitu FTIR:FTIR: Zn,Zn, ZnZn--FeFe AlloyAlloy

onon SteelSteel

Zn, Zn, Zn Zn - - Fe Fe Alloy Alloy on on Steel Steel University of

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

Zn, Zn Zn - - Fe Fe Alloy Alloy on on Steel Steel University of Vienna

InIn situsitu FTIR:FTIR: ZnZn

0.10.1 MM NaNa 22 SOSO 44 (pH(pH 12)12)

2ν 2 (-OH,bend) ν 2 (-OH,bend)
2ν 2 (-OH,bend)
ν 2 (-OH,bend)

Exchange OH - for SO 4

-

Zn(OH) 2 Sulfate
Zn(OH) 2
Sulfate
2 (-OH,bend) Exchange OH - for SO 4 - Zn(OH) 2 Sulfate University of Vienna -

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

InIn--situsitu GIXD:GIXD: ZnZn

0.10.1 MM NaNa 22 SOSO 44 (pH(pH 12)12)

ε-Zn(OH) 2 , Wulfingite, orthorombic
ε-Zn(OH) 2 , Wulfingite, orthorombic

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

(pH 12) 12) ε-Zn(OH) 2 , Wulfingite, orthorombic University of Vienna - Department of Physical Chemistry

OutlineOutline

In-situ Quartz MicrobalanceOutline Outline In-situ Grazing Incidence X-Ray Diffractometry (GIXD) In-situ Atomic Force Microscopy (AFM) In-situ

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)Outline Outline In-situ Quartz Microbalance In-situ Atomic Force Microscopy (AFM) In-situ Fourier Transfer Infrared

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

In-situ Fourier Transfer Infrared Spectrometry (FTIR)Diffractometry (GIXD) In-situ Atomic Force Microscopy (AFM) In-situ Nanotribology In-situ Laser Electrochemical

In-situ Nanotribology(AFM) In-situ Fourier Transfer Infrared Spectrometry (FTIR) In-situ Laser Electrochemical Activation University of

In-situ Laser Electrochemical ActivationTransfer Infrared Spectrometry (FTIR) In-situ Nanotribology University of Vienna - Department of Physical Chemistry –

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

In-situ Laser Electrochemical Activation University of Vienna - Department of Physical Chemistry – W. Kautek

NanotribologyNanotribology::

AgAg inin KBrKBr

(a,(a, c)c) 0.10.1 MM KF,KF, 0.010.01 NaOHNaOH,, (b,(b, d)d) 0.0010.001 MM KBrKBr,, 0.10.1 MM KF,KF, 0.010.01 NaOHNaOH

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

S. Dieluweit, and M. Sahr e, J. Phys. Chem. 101 (1997) 2709. University of Vienna -

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

and M. Sahr e, J. Phys. Chem. 101 (1997) 2709. University of Vienna - Department of

InIn--situsitu 1D1D laterallateral force:force:

SpecificSpecific adsorptionadsorption ofof bromide.bromide. AgAg inin KBrKBr electrolyteelectrolyte (0.1(0.1 MM KF,KF, 0.010.01 MM NaOHNaOH,, 0.0010.001 KBrKBr))

KF, 0.01 0.01 M M NaOH NaOH , , 0.001 0.001 KBr KBr ) ) W.

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

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

and M. Sahr e, J. Phys. Chem. 101 (1997) 2709. University of Vienna - Department of

NanotribologyNanotribology

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

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

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

and M. Sahr e, J. Phys. Chem. 101 (1997) 2709. University of Vienna - Department of

OutlineOutline

In-situ Quartz MicrobalanceOutline Outline In-situ Grazing Incidence X-Ray Diffractometry (GIXD) In-situ Atomic Force Microscopy (AFM) In-situ

In-situ Grazing Incidence X-Ray Diffractometry (GIXD)Outline Outline In-situ Quartz Microbalance In-situ Atomic Force Microscopy (AFM) In-situ Fourier Transfer Infrared

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

In-situ Fourier Transfer Infrared Spectrometry (FTIR)Diffractometry (GIXD) In-situ Atomic Force Microscopy (AFM) In-situ Nanotribology In-situ Laser Electrochemical

In-situ Nanotribology(AFM) In-situ Fourier Transfer Infrared Spectrometry (FTIR) In-situ Laser Electrochemical Activation University of

In-situ Laser Electrochemical ActivationTransfer Infrared Spectrometry (FTIR) In-situ Nanotribology University of Vienna - Department of Physical Chemistry –

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

In-situ Laser Electrochemical Activation University of Vienna - Department of Physical Chemistry – W. Kautek

LaserLaser CleaningCleaning

-- aa PhasePhase SeparationSeparation ProblemProblem

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

Phase Phase Separation Separation Problem Problem University of Vienna - Department of Physical Chemistry – W.

HighHigh PrecisionPrecision NonNon -- ContactContact RubberRubber

Precision Non Non - - Contact Contact Rubber Rubber Synagogue of Triest, by Otto Wagner, Vienna,

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

F = 1.0 J cm - 1 , 1Hz, 0.2 mm s - 1 University of
F = 1.0 J cm - 1 , 1Hz, 0.2 mm s - 1 University of

PrecisionPrecision LaserLaser CleaningCleaning PrintedPrinted PaperPaper

Cleaning Cleaning – – Printed Printed Paper Paper W. Kautek, S. Pentzien, Springe r Proceedings in

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

K .; Fotakis, C.; Asmus, J.F. (Eds.), 2005, 403 University of Vienna - Department of Physical

Recent Review Literature on Laser Cleaning in Cultural Heritage

[1]

[2]

[3]

[4]

C. Fotakis, W. Kautek, M. Castillejo (eds.), Laser Chemistry, Special Issue, Lasers in the Preservation of Cultural Heritage (Hindawi Publishing Corporation New York 2006)

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).

D.M. Kane (ed.), Laser Cleaning II (World Scientific, New Jersey, London, Singapore 2006)

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)

and Conservation Science (COST Office, Brussels 2008 ) University of Vienna - Department of Physical Chemistry

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

ModelModel System:System: AlOAlO xx LayersLayers

Model Model System: System: AlO AlO x x Layers Layers HC TE Anodization : electrolyte potential

HC

TE

Anodization:

electrolyte

potential

Hard Coating

sulphuric and oxalic acid

50

V

Technical Eloxal sulphuric acid

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

d microcavities on anodised aluminium alloys". University of Vienna - Department of Physical Chemistry – W.

TransparentTransparent AlOAlO xx coatingcoating onon absorbingabsorbing AlAl substratesubstrate

on on absorbing absorbing Al Al substrate substrate (a) F = 1.7 Jcm - 2 ,

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

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

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

Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry – W. Kautek (b)

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

Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry – W. Kautek (b)

TransparentTransparent coatingcoating onon absorbingabsorbing substratesubstrate

Defects MO x M
Defects
MO x
M

Defects

Spallation MO x M
Spallation
MO x
M

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

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

Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry –

MO x

MO x

M

Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry –

AbsorbingAbsorbing AlOAlO xx coatingcoating onon absorbingabsorbing AlAl substratesubstrate

on on absorbing absorbing Al Al substrate substrate F = 4.3 J cm - 2 ,

F = 4.3 J cm -2 , N = 1000

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

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

Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry – W. Kautek F

F = 6.4 J cm -2 ; N = 1000

Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry – W. Kautek F

AbsorbingAbsorbing coatingcoating onon absorbingabsorbing substratesubstrate

Laser

Laser MO x MO x M M
Laser
MO x
MO x
M
M

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

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

Laser

M MO x
M MO x
M MO x
M MO x
M MO x

M

M MO x

MO x

M MO x
Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry – W.

InIn--situsitu MonitoringMonitoring ofof LaserLaser CleaningCleaning ofof MetalsMetals

Electrolyte
Electrolyte

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

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

G. Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry

MolecularMolecular inin--situsitu probeprobe ofof laserlaser cleaningcleaning

Molecular in-situ probe:
Molecular in-situ probe:

Charging of Electrochemical Helmholtz plane

in-situ probe: Charging of Electrochemical Helmholtz plane W. Kautek, G. Daminelli, Electr ochim. Acta 48 (2003)

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

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

G. Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry

ElectrochemicalElectrochemical

currentcurrent

measurementsmeasurements

40 HC 20 0 -20 -40 ( μA)Current
40
HC
20
0
-20
-40
( μA)Current
40 TE 20 0 -20 -40 -3 -2 -1 0 1 2 3 Current (μA)
40
TE
20
0
-20
-40
-3
-2
-1
0
1
2
3
Current (μA)

Potential (V MSE )

OCP-2 -1 0 1 2 3 Current (μA) Potential (V M S E ) Applied potential

Applied potential-1 0 1 2 3 Current (μA) Potential (V M S E ) OCP University of

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

Potential (V M S E ) OCP Applied potential University of Vienna - Department of Physical

ElectrochemicalElectrochemical

currentcurrent

measurementsmeasurements

2Al + 3H 2 O Al 2 O 3 + 3H 2 2Al + 6H 2 O 2Al 3+ + 3H 2 + 6OH -

80 HC 6,62 Jcm -2 60 N crit I max 40 20 N in 0
80
HC
6,62 Jcm -2
60
N crit
I max
40
20
N in
0
0
20
40
60
80
100
120
140
Current (µA)

Number of pulses

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

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

G. Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry

ElectrochemicalElectrochemical EvaluationEvaluation ofof thethe ShockShock AffectedAffected ZoneZone

CE Laser beam Electrolyte Ion Current d HAZ MO x SAZ M WE
CE
Laser beam
Electrolyte
Ion Current
d
HAZ
MO x
SAZ
M
WE

L

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

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

G. Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry

ActiveActiveelectrochemistryelectrochemistry ofof passivatingpassivatingmetalmetal

2Al + 3H 2 O Al 2 O 3 + 3H 2 2Al + 6H 2 O 2Al 3+ + 3H 2 + 6OH -

25 -1,25 V N = 52 20 N = 73 15 10 5 0 10
25
-1,25 V
N
= 52
20
N
= 73
15
10
5
0
10
12
14
16
18
20
Current / µA

Time / ms

Absorbing Al 2 O 3 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

G. Daminelli, Electr ochim. Acta 48 (2003) 3249 University of Vienna - Department of Physical Chemistry

ReRe--PassivationPassivation ofof Pits:Pits:

ImpedanceImpedance EvaluationEvaluation fromfrom CurrentCurrent TransientsTransients

()

I t

=

I e

0

t

RC

Details about dielectric and conductive properties

Absorbing Al 2 O 3 on Al substrate F = 20.5 Jcm -2

2,5x10 5 thick 2,0x10 5 1,5x10 5 1,0x10 5 5,0x10 4 thin 0,0 4,0x10 -7
2,5x10 5
thick
2,0x10 5
1,5x10 5
1,0x10 5
5,0x10 4
thin
0,0
4,0x10 -7
-1,25
V
+0,25
V
thick
3,0x10 -7
2,0x10 -7
ε!!
thin
1,0x10 -7
0,0
50
60
70
80
90
100
Capacitance / F
Resistance / Ω

Number of pulses

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

Capacitance / F Resistance / Ω Number of pulses University of Vienna - Department of Physical

IrradiationIrradiation ofof OxidesOxides withwith UVUV LaserLaser

Discoloration due to stoichometric changes

1)

TiO 2 , CeO 2 , Nb 2 O 5 , MoO 3 and WO 3 :

blue-black

2)

V 2 O 5 , Cr 2 O 3 , Fe 2 O 3 , NiO, CuO, CdO, Tl 2 O 3 :

silver-metallic

3)

Al 2 O 3 , MgO, ZrO 2 , Ta 2 O 5 , ZnO, Ga 2 O 3 , Sb 2 O 4 , In 2 O 3 , SnO 2 , Y 2 O 3 , Eu 2 O 3 , Sm 2 O 3 : 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

induced chemical reactio ns of some metal oxides” University of Vienna - Department of Physical Chemistry

ElectrochemicalElectrochemical InIn--situsitu monitoringmonitoring

cleaningElectrochemical In In - - situ situ monitoring monitoring micro-machining corrosion "etch-stop" of layer

micro-machiningIn In - - situ situ monitoring monitoring cleaning corrosion "etch-stop" of layer removal

corrosion- situ situ monitoring monitoring cleaning micro-machining "etch-stop" of layer removal

"etch-stop" of layer removalmonitoring monitoring cleaning micro-machining corrosion "shock-affected-zone“ (laser-induced defects) laser

"shock-affected-zone“ (laser-induced defects)corrosion "etch-stop" of layer removal laser removal mechanisms electrochemical kinetics of active

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

electrochemical kinetics of active metal(laser-induced defects) laser removal mechanisms repassivation kinetics University of Vienna - Department of

repassivation kineticsremoval mechanisms electrochemical kinetics of active metal University of Vienna - Department of Physical Chemistry –

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

kinetics of active metal repassivation kinetics University of Vienna - Department of Physical Chemistry – W.

PhysicalPhysical ChemistryChemistry andand NanotechnologyNanotechnology ofof InterfacesInterfaces

Femtosecond Laser technology Working Group Wolfgang KAUTEK

Femtosecond Laser technology Working Group Wolfgang KAUTEK Raman Scattering Harmonic Generation Fluorescence Fs-Laser
Femtosecond Laser technology Working Group Wolfgang KAUTEK Raman Scattering Harmonic Generation Fluorescence Fs-Laser
Femtosecond Laser technology Working Group Wolfgang KAUTEK Raman Scattering Harmonic Generation Fluorescence Fs-Laser
Femtosecond Laser technology Working Group Wolfgang KAUTEK Raman Scattering Harmonic Generation Fluorescence Fs-Laser

Raman

Scattering

Harmonic

Generation

Fluorescence

Fs-Laser Excitation Scattering
Fs-Laser
Excitation
Scattering
Generation Fluorescence Fs-Laser Excitation Scattering University of Vienna - Department of Physical Chemistry –

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

Fluorescence Fs-Laser Excitation Scattering University of Vienna - Department of Physical Chemistry – W. Kautek

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

and 3D 3D - - Microscopy Microscopy in in CH CH University of Vienna - Department

Literature

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W. Kautek, Corrosion Sci. 28 (1988) 173, "The Galvanic Corrosion of Steel Coatings: Aluminium in Comparison to Cadmium and Zinc".

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".

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".

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".

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".

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".

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”.

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”.

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”.

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”.

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".

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".

W. Kautek, G. Daminelli Electrochim. Acta 48 (2003) 3249-3255. "Electrochemical reactivity of laser machined microcavities on anodised aluminium alloys".

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".

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".

by low angle of incidence X-ray diffractometry" . University of Vienna - Department of Physical Chemistry

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

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

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

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