Table Of ContentEuropean Federation of Corrosion
Publications
NUMBER 12
Modifications of
Passive Films
Papers presented at the European Symposium on
Modifications of Passive Films
Paris, France, 15-17 February 1993
Edited by
P. MARCUSB,. BAROUX M. KEDDAM
AND
Published for the European Federation of Corrosion
by The Institute of Materials
THE INSTITUTE OF MATERIALS
1994
European Symposium on Modifications of Passive Films, Paris, France, 15-1 7 February 1993.
Book Number 577
Published in 1994 by The Institute of Materials
1 Carlton House Terrace, London SWlY 5DB
0 1994 The Institute of Materials
All rights reserved
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Available on request
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ISBN 0-901716-52-9
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for any views expressed which are the sole responsibility of the authors
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Made and printed in Great Britain
Contents
Series Introduction ............................................................................................................................... xii
Preface .................................................................................................................................................. xiv
I Chemical and Electronic Properties of Passive Films
1 Influence of Ternary Elements on the Chloride Composition of Passive .................1
Films on Iron-Chromium Alloys
C. HUBSCHMID, H. 1. MATHIEU and D. LANDOLT
2 Composition of Passive Films on Stainless Steels Formed in Neutral ...................... 6
Sulphate Solutions
B. ELSENER, D. DEFILIPPO and A. ROSSI
3 Characterisation of Surface Films on FeCrPC Alloys by XPS and X-ray ................ 12
Excited Auger Peaks
A. ROSSI and B. ELSENER
4 Modifications of Passive Films formed on Ni-Cr-Fe Alloys with ........................... 17
Chromium Content in the Alloy and Effects of Adsorbed or
Segregated Sulphur
D. COSTA and P. MARCUS
5 Influence of Fe and Mo Alloying Elements on the Composition of ........................ 26
Passive Films Formed on Ni-Cr Alloys in an Acidic Chloride Solution
N. JALLERAT, S. MISCHLER and D. LANDOLT
6 Depth Composition of Passive Films Grown on Fe-Cr Alloys in Borate ...............3 5
So1utions:Influenceo f the Chromium Bulk Concentration
S. BOUDIN, C. BOMBART, G. LORANG and M. DA CUNHA BEL0
7 Chemical Composition of Naturally Formed Oxide on MgAl Alloys ..................... 41
T. H. NORDLIEN and K. NISANCIOGLU
8 Examination of Passive Layers on Fe/Cr, Fe/Ni and Cu/Ni Alloys with .............4 6
Ion Scattering Spectroscopy (ISS)
H.-H. STREHBLOW, C. CALINSKI, S. SIMSON, P. DRUSKA, H. W.H OPPE
and A. ROSSI
vii
Modifications of Passive Films
9 In Situ Xanes Studies of the Passive Film on Fe and Fe-26Cr .................................. 57
ALISON J. DAVENPORT, JENNIFER A. BARD WELL, H. S. ISAACS
and B. MACDOUGALL
10 Scanning Tunnelling Microscopy Study of the Atomic Structure of the ..............6 2
Passive Film Formed on Nickel Single Crystal Surfaces
V. MAURICE, H. TALAH and P. MARCUS
11 Atomic-Resolution STM of Passive Films on Fe-Cr Alloys .................................... 66
M. P. RYAN, R. C. NEWMAN, S. FUJIMOTO, G. E. THOMPSON,
S. G. CORCORAN and K. SIERADZKI
12 AFM Studies of EFC Round Robin Alloy 516 Relating to the Role of Mo ............7 0
in Passivation
J. E. CASTLE, X. F. YANG,J , H. QIU and P. A. ZHDAN
13 Photoelectrochemical Study of Passive Films ........................................................... 76
F. DI QUARTO, S. PIAZZA and C. SUNSERI
14 Modifications of the Structural and Electronic Properties of .................................. 85
Thermochemically Formed Passive Films on Fe-Cr Alloys
during Long Term Ageing: Influence of Silicon Addition
D. LIU, D. GORSE and B. BAROUX
15 Polarisation and pH Effects on the Semiconducting Behaviour of ........................ 91
Passive Films Formed in Chloride Containing Aqueous Solutions
J. P. PETIT, L. ANTONI and B. BAROUX
16 Modification of the Passivating Film on Copper in the Presence of ...................... 96
Benzotriazole: Photoelectrochemical Characterisation
E. SUTTER, D. LINCOT and C. FIAUD
11 Kinetics of Passivation and Electrochemical Properties
of Passive Films
17 Kinetics of Film Formation on Fe-Cr Alloys ........................................................... 102
R. KIRCHHEIM
18 Influence of Anions on the Electrochemical Behaviour of Passive Iron... ........... lo8
K. E. HEUSLER, L. JAECKEL and F. J. NAGIES
19 Modifications of Passive Films on 304 Stainless Steel Investigated by ............... 114
Capacitance Measurements
R. DEVAUX, C. MASSON, D. VOUAGNER, A. M. DE BECDELIEVRE,
C. DURET-THUAL and M. KEDDAM
20 Passive Characteristics of Amorphous Ni-P Alloys .............................................. 119
A. KROLIKO WSKI
viii
Contents
21 Passivity of Chromium in Concentrated and Anhydrous Solutions of ..............1 23
Sulphuric Acid
B. STYPULA and J. BANAS
22 Influence of Electrochemical Formation Conditions on the Stability of ............. 128
Passive Layers Formed on Fel7%Cr Stainless Steel in Sulphuric Acid
F. LECRAS, G. BARRAL and S. MAXZMOVITCH
23 Identifiability and Distinguishability of Passivation Mechanisms by ................ .134
Electrochemical Impedance Spectroscopy and Electrogravimetric
Transmittance
F. BERTHIER, J. P. DZARD and B. LE GORREC
24 Electrochemical Dissolution of Fe,,Co,,Si,,B,, Amorphous Alloy and ............. .139
h. e. r. Investigation on the Anodically Activated Alloy
M. EYRAUD, F. BELLUCCI and J. CROUSZER
25 Growth/dissolution Processes of Anodic Films Formed on Titanium ...............1 44
under a-irradiation, Studied by Coupling Electrochemistry and
Inductively Coupled Plasma Atomic Emission Spectrometry
T. SAKOUT, J. C. ROUCHAUD, M.F EDOROFF and D. GORSE
26 Characterisation of Passive Layers of Bronze Patinas (Cu-Sn Alloys) in ........... 150
Relation with the Tin Content of the Alloy
L. ROBBIOLA, C. FlAUD and A. HARCH
27 Hydrogen Permeation Through Passive Films on Iron ......................................... 155
K. SCHOMBERG, E. RIECKE and H. J. GRABKE
28 Hydrogen and Iron Transport Through Passive Oxide Films on ........................ 161
Electropolished Iron
P. BRUZZONZ and E. RIECKE
Ill Surface Treatments and Film Modifications
29 Electrode Reaction Inhibition by Surface Modification and Localised ............... 168
Corrosion Resistance of Stainless Steels in Aqueous Solution
Y.C . LU and M. B. IVES
30 Modification of Passive Zinc by Alloying Elements .............................................. 173
W.P AATSCH and W.J . LORENZ
31 Modification of Passive Films on 304L by Cyclic Polarisation Influence ............ 176
on Film Stability in Acidic Environments
C. DURET-THUAL and F. BARRAU
32 Surface Modification of Stainless Steel by an Alternating Voltage Process ........1 83
F. MANSFELD, S. H. LZNand L. KWIATKOWSZU
ix
Modifications of Passive Films
33 Modification of Passive Films Composition due to Water Ageing ...................... 188
B. LEGRAND, C. GOUX, C. SENILLOU and J. C. JOUD
34 Chromate-free Surface Treatment: MolyPhos - A New Surface ........................ 195
Conversion Coating for Zinc. Optimising the Treatment by
Corrosion Testing
G. BECH-NIELSEN, I. CHORKENDORFF and P. T. TANG
35 Passive Film Evolution on Stainless Steels with the Medium .............................. 198
Composition: Electrochemical Studies in the Presence of
Chloride and Molybdate Ions
L. FARAH, C. LEMAITRE and G. BERANGER
36 Passive films on Glassy FeCrPC Alloy-The Role of Phosphorus ..................... .202
in Stability
B. ELSENER and A. ROSSI
37 Modification of Ta/Ta,O, Films by Platinum Deposits ........................................ 206
0. KERREC, D. DEVILLIERS, C. HINNEN, P. MARCUS, H. CACHET
and M. FROMENT
38 The Effect of Pretreatments on the Corrosion Behaviour of Aluminium ...........2 14
H. J. W. LENDERINK and J. H. W. DE WIT
39 The Effect of Hydrostatic Pressure on the Modification of Passive Films .......... 220
Formed on 316L Stainless Steel in Sea Water
A. M. BECCARIA, G. POGGI, E. TARTACCA and P. CASTELLO
40 Effect of Laser Surface Remelting on Passivity and its Breakdown on ...............2 25
AI-Si Alloys
S. VIRTANEN and H. BOHNI
41 Laser Pulsed Irradiation of Passive Films ................................................................ 230
R. OLTRA, G. M. INDRIANJAFY and I. 0.E FIMOV
42 Irradiation Effects in Anodic Oxide Films of Titanium ......................................... 234
D. GORSE, T. SAKOUT and Y. SERRUYS
43 Modification of Oxide Films by Ion-Implantation and its Influence on .............2 40
the Corrosion Behaviour
J. W. SCHULTZE, A. MICHAELIS, 0.K ARSTENS and Ch. BUCHAL
44 Simulation of y-Ray Effects on Passive Films by Laser Irradiation ...................... 246
A. MICHAELIS and 1. W. SCHULTZE
45 Passivation of Metals by Plasma-Polymerised Films ............................................ .253
W. J. VAN OOIJ,A . SABATA and IH-HOUNG LOH
X
Con tents
/V Passivity Breakdown
46 Fundamental Aspects in the Design of Passive Alloys ......................................... .262
D. D. MACDONALD and MIRNA URQUIDI-MACDONALD
47 In Situ A M I nvestigation of Pitting ......................................................................... 274
G. GUGLER, J. D. NEUVECELLE, P. METTRAUX, E. ROSSET and D. LANDOLT
48 Passivity of Non-metallic Inclusions in Stainless Steels and their Effect ............2 80
on Resistance Against Pitting
A. SZUMMER, M. JANIK-CZACHOR and S. HOFMANN
49 Inclusions in Stainless Steels - Their Role in Pitting Inititation ......................... 290
E. F. M. JANSEN, W. G. SLOOF and J. H. W. DE WIT
50 Influence of Ion Implanted Molybdenum or Molybdate Solution on ................2. 96
Pitting Corrosion of 304 Stainless Steel in Chloride Solutions. Statistical
Study by Digital Image Analysis of Pit Initiation and Propagation
I. LACOME, P. FIEVET, Y.R OQUES and F. DABOSI
51 The Effect of pH and Potentiostatic Polarisation on the Pitting ........................... 300
Resistance of Stainless Steels: Relation to Non-metallic Inclusions
or Passive Film Modifications
B. BAROUX and D. GORSE
52 Localised Corrosion of Laser Surface Alloyed 7175-T7351 Aluminium .............3 08
Alloy With Chromium
R. LI, M. G. S. FERREIRA, A. ALMEIDA, R. VILAR, K. WATKINS
and W. STEEN
53 The Problem of Convective Diffusion in Laser Pit Initiation ................................ 313
I. 0.E FIMOV and V.A . BENDERSKII
54 Pitting Corrosion of Heat-tinted Stainless Steel ...................................................... 316
P. C. PISTORIUS and T. VON MOLTKE
55 Pitting Corrosion Susceptibility of Oxide Layers in the Amorphous .................. 322
Alloy (FexNil-x)oJXW, o,2
M. L. ESCUDERO, A. R. PIERNA, J. C. GALVAN and F. FERNANDEZ
56 Influence of the Energetic p- Flux on the Corrosion Behaviour of Zr Alloys .....3 26
R. SALOT, F. LEFEBVRE and C. LEMAIGNAN
57 Influence of Ion Implantation on Corrosion and Stress Corrosion ...................... 330
Cracking of 304L Stainless Steel
R. KARRAY, C. SARRAZIN, D. DESJARDINS and B. DARRIET
58 Development of a Neural Network Model for Predicting Damage .................... 336
Functions for Pitting Corrosion in Condensing Heat Exchangers
M. URQUIDI-MACDONALD, M. N. EIDEN and D. D. MACDONALD
xi
European Federation of Corrosion Publications
Series Introduction
The EFC, incorporated in Belgium, was founded in 1955 with the purpose of promoting
European co-operation in the fields of research into corrosion and corrosion prevention.
Membership is based upon participation by corrosion societies and committees in technical
Working Parties. Member societies appoint delegates to Working Parties, whose membership is
expanded by personal corresponding membership.
The activities of the Working Parties cover corrosion topics associated with inhibition,
education, reinforcement in concrete, microbial effects, hot gases and combustion products,
environment sensitive fracture, marine environments, surface science, physico-chemical meth-
ods of measurement, the nuclear industry, computer based information systems, corrosion in
the oil and gas industry, and coatings. Working Parties on other topics are established as
required.
The Working Parties function in various ways, e.g. by preparing reports, organising sympo-
sia, conducting intensive courses and producing instructional material, including films. The
activities of the Working Parties are co-ordinated, through a Science and Technology Advisory
Committee, by the Scientific Secretary.
The administration of the EFC is handled by three Secretariats: DECHEMA e. V. in Germany,
the Soci6t6 de Chimie Industrielle in France, and The Institute of Materials in the United
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or results of experimental work, may be published in scientific and technical journals in one or
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In 1987 the, then, Institute of Metals was appointed as the official EFC publisher. Although
the arrangement is non-exclusive and other routes for publication are still available, it is expected
that the Working Parties of the EFC will use The Institute of Materials for publication of reports,
proceedings etc. wherever possible.
The name of The Institute of Metals was changed to The Institute of Materials with effect from
1 January 1992.
A. D. Mercer
EFC Scientific Secrefary,
The Institute of Materials, London, UK
Series Introduction
EFC Secretariats are located at:
Dr J A Catterall
European Federation of Corrosion, The Institute of Materials, 1 Carlton House Terrace, London,
SWlY 5DB, UK
Mr R Mas
Federation Europeene de la Corrosion, Societe de Chimie Industrielle, 28 rue Saint-Dominique,
F-75007 Paris, FRANCE
Professor Dr G Kreysa
Europaische Foderation Korrosion, DECHEMA e. V., Theodor-Heuss-Allee 25, P.O.B. 150104,
D-6000 Frankfurt M 15, GERMANY
xiii
